JPS58212990A - Diazo heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To obtain the titled material, which has excellent shelf life and imparts excellent coloring, whose color is not faded by light, and wherein a specified naphthol blue coloring coupler and a new yellow coloring coupler are used at the same time together with a diazo compound and a heat fusible material. CONSTITUTION:A blue coloring coupler (e.g. naphthol AS or the like shown by the formula II) shown by the formula I (R1 is an aromatic group and alicylic group; X1 is H, halogen, acetyl, sulfonic acid, and alkoxyl) and a novel yellow coloring coupler (e.g. compounds shown by the formulas V and VI or the like) shown by the formula III or the formula VI (R2 and R3 are alkyl, alkoxyl, phenyl, and cyano; X and Y are halogen, alkyl, and alkoxyl; (n) is 0-4; and (m) is 0-5) are used as couplers at the same time. The couplers, a diazo compound, and a heat fusible material (material having 50-350 deg.C of a melting point and a softening point is recommended), and a binder, an acidic material, a basic material, a filler, and the like as required are provided on a supporting body as a heat sensitive layer, and an intended recording material is obtained.

Description

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

Diazo thermosensitive recording materials are widely known, in which a thermosensitive layer mainly composed of a diazo compound, Cassirer, or a thermofusible substance is provided on a support such as paper or a plastic film.

In this diazo thermosensitive recording material (or heat-developable diazo close-up material), it is difficult to develop a black color with Katuzolam 44Il, and the only practical coupler for this yuzu is phloroglucin. However, this material has problems with moisture resistance due to its water solubility and color tone changes due to fading. Therefore, in order to produce black color, it is generally necessary to use a combination of two or three yuzu cassillers.
For example, combinations of 2,3-dihydroxynaphthalene 6-sulfone sorta (blue) acetoacetate and anilide (yellow) resorcinol (sepia) are known. However, these also had the same problems as described above. In addition, a water-soluble type yellow coupler is disclosed in Japanese Patent Publication No. 45-36072, but it has the disadvantage of being susceptible to discoloration.

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 that provides excellent black color development, has good storage stability, and is resistant to photofading.

That is, the present invention provides diazo compounds, cassilla, and thermofusible U.
In a diazo-based heat-sensitive recording material in which a heat-sensitive IW having a heat-sensitive IW having a main component as a main component is provided on a support, the coupler is a blue color-forming coupler λ1 represented by the following general formula (I) (where R is an aromatic group or is an alicyclic group, and Xl is hydrogen, halogen, acetyl group, sulfonic acid group, or alkoxyl group. . represents an alkyl group, an alkoxyl group, a phenyl group, or a cyano group.

X and Y represent a halogen, an alkyl group, or an alkoxyl group.

n is an integer from θ to 4, and -1m is an integer from 0 to 5.

) It is characterized by being used in combination with.

-Ill1 The yellow couplers of formulas (II) and (Ill) are new materials that are resistant to photobleaching, and when combined with naphthol As thread (general formula (I)), excellent black coloring can be obtained. It is.

In the present invention, yellow cassiller having the structure of general formula (II) or (l[) is used in combination with blue cassiller having the structure (1) in a ratio of 1:5 to 5:1. . 5 to 50% of the thermofusible substance is added to 1 layer of the diazo compound and 1 part of the basket.
Add 30 parts.

Examples of the conjugate of general formula (I) include the following 0 Specific examples of the general formula (!l) include the following.

Specific examples of the general formula (Ill) include the following: O The thermofusible substance has a melting point or softening point of 50 to 25
A temperature range of 0C is adopted. Specific examples include the following:

Alcohol derivatives such as 2-tribromoethanol, 2,2-dimethyltrimethylene glycol, alcohol, 2-cyclohegysandiol, malonic acid, glutaric acid, maleic acid, methylmaleic acid, beeswax, shellac wax, etc. animal waxes such as carnano wax, vegetable waxes such as carnano wax, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and microcrystalline wax, and other synthetic waxes such as polyhydric alcohol esters of higher fatty acids, Higher amines, higher amides, condensates of fatty acids and amines, condensates of aromatics and amines, synthetic paraffins, rough-in chlorides, higher fatty acids with gold 4 salts, higher linear glycols, 3,4-epoxy hexa Dialkyl hydrophthalate, etc.

The thermally iJ-melting or thermally softening 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 5 Or, the shelf life of the product tends to deteriorate, 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-speed coloring property (high-speed recording property), these thermofusible or heat-softening substances used in the present invention should be used in an amount of 2 to 3 parts per 1 part of the diazo compound.
It is used in a proportion of 5 to 10 parts by weight. If the number of this one company is less than the range 11B, the color development will be insufficient, and the resulting product will be unsuitable as a recording material for high-speed recording. In the case of the present invention, especially for high-speed output recording such as facsimile, 5-fold h
It is preferable to use it in a proportion of h part or more.

On the other hand, if the amount of addition 1i is too large, it is not preferable that smearing occurs during heating and color development. Therefore,
In the case of the present invention, the temperature of the thermofusible material is preferably maintained within the above range.

In the present invention, in order to firmly support the lj8 thermochromic layer on the support, a heat-fusible or heat-softening binder is used as necessary. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, No.? Examples include acrylic cut ester, polystyrene, polybutadiene, polyacrylamide, styrene/citadiene/acrylic copolymer, and the like. These binders have a melting point or softening point of 50~
It is preferable to use one with an axis of 250C.

In the present invention, as the binder, the above-mentioned thermofusible or thermosoftening binder is preferably used, but these binders do not necessarily need to be used alone, and each component in the layer is Other binders may be used in combination to firmly bind to the support. Examples of such binders include the following.

Polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and its conductors, divinylpyrrolidone, Cal 11? Methylcellulose, methylcellulose, ethylcellulose, polyester (n of 100,000 or more), polystyrene (MW of 100,000 or more), chlorinated rubber, styrene maleic anhydride copolymer, iso(or diyne)zotylene-maleic anhydride branched copolymer, urea - Water dissolvable, organic solvent soluble, or aqueous dispersion type resin such as formalin resin 4, phenol m IJM , melamine resin.

Of course, these tying agents can be used alone depending on the case.

In addition, in the present invention, 1=thermochromic layer further contains an acidic substance, a basic substance, Jr. as an auxiliary component as necessary.
i ingredients and others may be included.

Acidic substance: An acidic substance is added as necessary to prevent a coupling reaction and for storage stability, and examples thereof include the following.

Cod acid, citric acid, boric acid, lactic acid, gluconate, sulfuric acid, etc.

Salt-based substances; The stone-based substances 'U are added as necessary to cause a coupling reaction during heating, and include, for example, the following.

Water Evk sodium sodium calcium oxide, charcoal potassium and other caustic alkalis and charcoal cutting alkalis. Substances that generate stone-based properties when heated include urea, thiourea and their donors, alkali salts of irichloroacetic acid, ammonium chloride, ammonium sulfate, and ammonium chloride. 66
Sodium benzoate and guanidines can be used to enhance color.

Filler: A filler is added to improve the matching property to a thermal head when heating is performed by a thermal head, etc., and examples of such fillers include the following.

Organic and inorganic solid particles such as styrene resin particles, urine-formalin butyrate resin particles, water-dispersed aluminum, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin, silica, and alumina.

Other auxiliary ingredients include M chloride, sodium citrate, guanidine sulfate, calcium gluconate, sorbitol, and saccharose to suppress or assist color development, and saponin and the like are used as solubilizers.

To obtain the heat-sensitive recording material of the present invention, the above-mentioned forming components are dissolved or dispersed in a suitable solvent to prepare a coating solution for forming each layer W4, and this coating solution is applied onto a support and dried. and the product.

In this case, 1. The solvent for dissolving or dispersing the layer-forming components is appropriately selected depending on the properties of the layer to be formed and the purpose of formation. Examples of such solvents include water or an aqueous medium in which an organic solvent is dissolved in water, benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, kerosene, methyl isobutyl ketone, methyl cephalic acid, and acetone. , methyl ethyl ketone, dimethyl ether, siloxane, and other nonpolar or polar organic solvents.

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 and computers that require high-speed recording. If so, the characters recorded on its surface or ll1
The II image can be fixed by removing the l1iII image by heating and decomposing the unreacted diazo compound by light. Furthermore, the heat-sensitive recording material of the present invention is
Utilizing this theorem, it can be applied to recording and creating necessary items for securities, gift certificates, admission tickets, certificates, slips, etc.

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

Example I Liquid A Stearic acid amide 9 parts A-chloride-vinyl-acetate copolymer 5 parts Methyl cellosolve 85 parts The above composition was milled in a ball mill to give [Liquid A] θ4 M L/.

B liquid N-stearylbenzamide 10 parts by weight Imidazole 5 parts Silica 5 parts Methyl cellulose 5 days water
70 parts by weight of the above composition was dispersed in 1F-Lumil to prepare [Liquid B]. 5
01//ni' high-quality paper was undercoated with calcium carbonate and F'VA to form a dry ht 2 &Ar/. On top of that, add [Liquid A] to dry type h4,0 &/ltj
Apply the following and then dry [Liquid B] on top of it:
ai 13k 4.0 l/m'', and prepared with a calender so as to have a Peck smoothness of Baa o o seconds.
When printed with 00, the color was black. Furthermore, when exposed with Ricobee High Start 100 and measured with -7 Kuves density set, the print density was 0.95 and the print density was 0.95. It was lO. Heat-sensitive paper before exposure is placed in a 40C-90% environment for 24 hours.
After standing for a period of time, the skin elasticity was measured and found to be 0.15.

After exposure (7), the thermal paper was pasted on the wall of a general office for one month, and the background density was 0.12.
The color tone was also the same as the color tone after exposure.

Example 2 Thermal writing paper was obtained in the same manner as the yellow coupler of [Liquid B] in Example 1. Printing power is 0.95, background density is 0.
10 o 40 tZ' = 90% lump ヱ Lower number 11ij Skin skin after 24 hours exposure 11 A 1 (i was 0.14).

After the wall test, the background color was 0.11, and there was no difference in color from the color tone of the textured area.

Comparative Example 1 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that phloroglucin was used instead of Blue Cassirer and Yellow Cassirer in [Liquid B] of Example 1. The print density was 1.05, and the background density was 0.45 after being left for 24 hours at 013°40C-90% +34. After the wall test, the skin area changed color.

Comparative Example 2 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the yellow cassiller of CB in Actual IM Example 1 was replaced with acetoacetanilide. Print density is 1.05, background density is 0.10
Met. Immediately after being exposed to a 40C-90% environment for 24 hours, the scalp 111X turned yellow.

Comparative Example 3 A thermosensitive recording paper was obtained in the same manner as in Example 1 using the yellow coupler (liquid B). Once printed, the density was 095, and the background density was 0.10. 2 in an environment of 40C-9Q%
The skin level after 4 hours of exposure was 0.15.

After storing the high-exposure thermal paper in a typical office room for one month, the background density was 0.12, but the color tone of the image area changed from black to bluish-purple.

Patent applicant: Rico Co., Ltd.

Claims (1)

[Scope of Claims] 1. In a diazo-based heat-sensitive recording material in which a single heat layer containing a diazo compound, a coupler, and a heat-fusible substance as main components is provided on a support, the cassiller is represented by the following general formula (1).
A blue-coloring Cassilla represented by (wherein R3 is an aromatic group or an alicyclic group, X, halogen, halogen, acetate/l/ group, sulfonic acid group, alkoxyl group) and the following general formula (11) or a yellow coloring coupler represented by the general formula (111) (where R2+ R6 is an argyl group, an alkoxyl group,
Does not represent phenyl or cyano groups. X and Y represent a halogen, an alkyl group, or an alkoxyl group. n is an integer of θ to 4, and m is an integer of 0 to 5. ) A diazo-based heat-sensitive recording material characterized in that it is used in combination with.