JPS59162541A - Heat development type diazo copying material - Google Patents

Abstract

PURPOSE:To improve the raw stock preservability of a heat development type diazo copying material by forming a layer contg. a product produced by reacting 2-hydroxy-3-naphthoic acid hydrazide with aldehyde or ketone as a coupling component and a layer contg. a diazo compound. CONSTITUTION:A coupling layer contg. a Schiff base represented by the formula as a coupling component and a layer contg. a diazo compound are formed to manufacture a heat development type diazo copying material. One or both of the layers contain heat-meltable paraffin wax and higher fatty acid (amide) as an auxiliary coupler. In the formula, each of R1 and R2 is H, 1-20C alkyl, an aromatic group such as (substituted) phenyl or naphthyl, (substituted) aralkyl or heterocyclic group such as (substituted) thienyl or pyridyl, R1 and R2 may bond to each other to form a ring, and the substituent is alkyl, alkoxy, halogen, NO2, CN or the like. The diazo copying material can be developed at a low temp., has high preservability, and can give an image causing hardly the yellowing of the ground due to aging.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-developable diazo copying material which can also be used as a recording material.

[Prior art]

Heat-developable diazo copying materials generally have a coloring layer containing a diazo compound, a coupling component, and a coloring aid as main components on a support such as paper or film.

In such heat-developable diazo copying materials, in order to perform heat development at as low a temperature as possible, coloring aids such as
A thermofusible substance such as higher fatty acid amide is also used.

However, when attempting to improve the low-temperature developability of copying materials, there is a problem in that the shelf life (hereinafter referred to as raw shelf life) of the copying materials decreases. In order to improve this shelf life, it is known that the coupling component and the diazo compound are supported on a support as separate layers.
I still couldn't say that I was satisfied. For example, a 2-hydroxy-3-naphthosonic acid anilide compound such as naphthol As, which develops a blue color, is known as a coupling component. Although it develops a blue color, it has poor storage stability and has the disadvantage that the skin turns yellow over time.

〔the purpose〕

The present invention provides a heat-developable diazo copying material in which a coupling component and a diazo compound are supported as separate layers on a support, and at least one of the layers contains a thermofusible substance as a coloring aid. The object of the present invention is to provide a product with improved shelf life and significantly reduced yellowing of the skin over time.

〔composition〕

According to the present invention, a coupling component layer and a diazo compound layer are provided on a support, and at least one of the coupling component layer and the diazo compound layer contains a thermofusible substance, There is provided a heat-developable diazo copying material characterized in that a compound obtained by the reaction of 2-hydroxy-3-naphthoic acid hydrazide and an aldehyde or ketone is used as the coupling component.

The present invention is characterized in that a compound obtained from 2-hydroxy-3-naphthoic acid hydrazide and an aldehyde or ketone is used as a coupling component, and such a compound is known as a Schiff base and is , according to a conventionally known method, 2-hydroxy-3-naphthoic acid hydrazide and an aldehyde or ketone, for example,
It can be easily synthesized by boiling and refluxing for 1 to 2 hours in an alcoholic solvent. The reaction in this case is
It is expressed by the following formula.

In the above formula, R1 and R2 are hydrogen, a lower or higher alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted fe2 group,
Aromatic groups such as naphthyl group, anthryl group, pyrenyl group,
It represents a substituted or unsubstituted aralkyl group such as a benzyl group, a substituted or unsubstituted chenyl group, a pyridyl group, a heterocyclic group such as a carbazoyl group, and R1 and R2 may be the same or different, and R1 and R2 may be combined to form a ring.

Further, examples of the substituent include alkyl, alkoxy, nitro group, nitro group, cyan group, and the like.

Specific examples of the compound (hereinafter simply referred to as Schiff base) used in the present invention are shown below.

Note that the symbol [A+] shown in the above-mentioned coating-1 represents a 2-hydroxy-3-naphthyl group.

In the present invention, first, a coupling component layer containing the above-described Schiff base is provided on the support. in this case,
A binder is used in combination, and water-soluble resins or emulsion-type resins are used as the binder. Examples of water-soluble resins include polyvinyl alcohol, hydroxyethyl cellulose, calxexymethylcellulose, methylcellulose, gelatin, and arabic. Water-soluble polymers commonly used as this type of binder such as rubber and starch are used, and emulsion type resins include thermoplastic resins such as polyvinyl acetate, polyvinyl chloride, and styrene/maleic acid copolymers. can be mentioned.

This binder binds the dispersion of the coupling component to the support and at the same time coats the dispersion to prevent contact reaction with the diazo compound.

In the present invention, a diazo compound layer is provided on the coupling component layer, and in this case, a conventionally known azo compound can be used, such as one represented by the following general formula. .

L 2 In the above formula, Yl and Y2 represent hydrogen, a lower alkyl group, a lower alkoxy group, or a nitrogen. 2 is a general formula (wherein R1+R2 represents a substituted or unsubstituted lower alkyl group or aralkyl group, and R1 and R2 are bonded to each other as a methylene group via a carbon, oxygen, nitrogen, or sulfur atom. or a substituted or unsubstituted amine group represented by the formula (wherein R3 is hydrogen, a lower alkyl group or a lower alkoxy group) Represents the aromatic group represented. X is an acid residue or an acid residue forming a double salt with a metal salt, and examples of the acid residue include a dichloride ion, a sulfate ion, a tetrafluoroborate ion, a tetrafluorophosphate ion, etc. Metal salts that form double salts with acid residues include zinc chloride, cadmium chloride, tin chloride, and the like.

Specific examples of the diazo compound include those shown below.

4-N-morpholinoamino-2,5-jethoxybenzenediazonium, 4-N-benzyl-N-ethylamino-2,5-dibutoxybenzenediazonium, 4-N,
N-dimethylaminobenzenediazonium, 4-N-pyrrolidinoamino-2゜5-dibutoxybenzenediazonium, 4-N-piperazinoamino-2,5-dipropoxybenzenediazonium, 4-N-ethyl-N-hydroxyethylamino Benzenediazonium, 4-N-morpholinoamino-2-chlorobenzenediazonium, 4-
p-1ruylmerkabuto-2,5-jethoxybenzenediazonium, 4-N-benzoylamino-2,5-jethoxybenzenediazonium, 4-N-morpholinoamino-3-chlorobenzenediazonium, and the like.

In the present invention, one or both of the coupling component layer and the diazo compound layer contains a thermofusible substance. This thermofusible substance melts when heat is applied and brings the coupling component and diazo compound into contact to cause a coloring reaction, and has the property of dissolving one or both of the coupling component and the diazo compound. It is preferable to use one having a certain amount, and the coloring reaction is significantly accelerated by its use. In this case, the thermofusible substance has a melting point of 50 to 15
Those with a melting point of 0°C are preferable, and those with a melting point lower than 50°C are
It exhibits some melting properties during storage, reducing its shelf life. On the other hand, if the melting point is higher than 150° C., a large amount of heat is required to cause the coloring reaction, which is undesirable. Specific examples of such thermofusible substances include various waxes such as ξ rough-in wax, microcrystalline wax, carnano ζ wax, montan wax, and low-molecular polyethylene wax, as well as higher fatty acids, Examples include various organic compounds such as higher fatty acid amides and higher aliphatic alcohols.

In the present invention, 0.5 to 2 moles of the coupling component is applied to 1 mole of the diazo compound, and the ratio of the binder and the thermofusible substance used is as follows: The ratio is 0.5 to 5.0 parts by weight of the binder and 0.5 to 10 parts by weight of the thermofusible substance.

In addition to the above materials, various conventionally used auxiliary components can be added to the diazo copying material of the present invention.

For example, sodium naphthalene mono (or di- or tri-) sulfonate, aluminum sulfate, magnesium sulfate, zinc chloride, etc. can be used as a preservability improver, and thiourea, urea, etc. can be used as an antioxidant. Citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, birophosphoric acid, etc. can be used as acid stabilizers, and saponin etc. can also be used.

To produce the copying material of the present invention, first, the coupling component is added to water together with a dispersant, subjected to sol-milling treatment, then a binder is mixed, and the resulting mixture is applied onto a support and dried. . Next, a photosensitive liquid containing a diazo compound as a main component is applied thereon and dried. In addition, the addition of a thermofusible substance is
When adding it to the coupling component layer, it is sufficient to disperse it together with the coupling component using a sol mill.When adding it to the diazo compound layer, the thermofusible substance is dispersed together with a dispersant in water using a sol mill. This dispersion may be mixed with photosensitive paper.

〔effect〕

The heat-developable diazo copying material of the present invention uses the above-mentioned special Schiff base as a coupling component, so that it has excellent p1 shelf life and has significantly reduced background yellowing.

〔Example〕

Next, the present invention will be explained in more detail using examples. Note that all departments and sections shown below are based on weight.

Example 1 Compound of Table 1, A1 1 part Stearic acid amide 1 10% hydroxyethyl cellulose 2 Water

16 After dispersing the dispersion of the above formulation in a sail mill for 24 hours, 10 parts polyvinyl alcohol aqueous solution, 10 parts
and stirred thoroughly. Apply the solution to white base paper for diazo photosensitive paper for about 30 minutes. A photosensitive solution having the following formulation was coated and dried in a thickness of about 1.21-7 m'' to obtain diazo photosensitive paper A.

4-N-(4'-methoxybenzoyl)aminebenzenediazonium chloride-zinc chloride double salt
1 part citric acid 0.5
〃Saponin 0.1〃
water
100 Next, overlap the diazo-sensitive paper with the original,
A copy with a blue image was obtained by exposure and development using Ricobee Hydry (manufactured by Ricoh).

Example 2 Compound of Table 146 1 part Karte, Uno Wax 2
1 oz 641 J vinyl alcohol aqueous solution
2〃Water
15. After dispersing the dispersion of the above formulation in a sail mill for 24 hours, 10 parts of a 10% polyvinyl acetate emulsion was added and stirred well. The solution was applied to a white base paper for diazo photosensitive paper at a rate of about 3,000 P/m" and dried. A photosensitive solution having the following formulation was applied to this at a rate of about 1.2 P/rn" and dried to obtain diazo photosensitive paper B. Ta.

4-p'-)ruylmerkabuto 2.5-jethoxybenzenediazonasium chloride zinc chloride double salt
1 part tartaric acid
0.5〃Saponin 0.1
〃water
100 Next, overlap the diazo-sensitive paper with the original,
A copy with a blue image was obtained by exposure and development using Ricobi 1 High Try [■ Ricobi].

Example 3 Compound of Table 1, &3 8 1 part 10
Hydroxyethyl cellulose aqueous solution 2
〃water
17〃After dispersing the dispersion of the above formulation by applying Seel Mill K for 24 hours, add 10 parts of Gum Arabica aqueous solution 10
and stirred thoroughly. The solution was applied to white base paper for diazo photosensitive paper at a concentration of about 1.5 f/ml and dried.

Next, on this coating layer, apply a photosensitive liquid of the following formulation to approximately 3.0
p/m'' and dried.

4-N, N-1-n-furobylaminebenzenediazonium chloride zinc chloride double salt
1 part tartaric acid, 5 parts Montana wax dispersion, 1 part water
90 The component composition of the Montana wax dispersion is as follows.

Montana wax 2 parts 10%
Hydroxyethylcellulose aqueous solution 1
water
7 (Dispersed for 24 hours in a Gill Mill) Next, the original was layered on this diazo photosensitive paper, and a copy with a blue image was obtained by exposing and developing it using Ricobee Hydry (manufactured by Ricoh). It was done.

Examples 4 to 12 Products were obtained in the same manner as in Example 1, except that the following compounds were used in place of compound No. 1 in the coupling dispersion.

(1) Compound 11 shown in Table IK (Example 4) (2
) Compound of Grave 20 shown in Table-1 (Example 5) (3) Compound of A22 shown in Table-1 (Example 6) (4) Table-1
Compound of A28 shown in Table-1 (Example 7) (5) Compound of N30 shown in Table-1 (Example 8) (6) Compound of A32 shown in Table-1 (Example 9) (Force Table-1 A33 shown in
(Example 10) (8) Compound of A35 shown in Table 1 (Example 11) (9) Compound of A37 shown in Table 1 (Example 12) Comparative Example In Example 1, Ya 1 The same procedure was carried out except that 2-hydroxy-3-naphthoic acid anilide was used instead of the compound.

Next, the fading resistance of the image area and background area of the copies obtained in the above Examples and Comparative Examples was tested for 3 hours using a fade meter model FA-'3 manufactured by Suga Test Instruments KK. In addition, a phototilt is used for density measurement, and a clean filter is used for the image area.
The skin area was measured once using a blue filter. The measurement results are shown in the table below.

Claims (1)

[Claims] (1) A coupling component layer and a diazo compound layer are provided on a support, and at least one of the coupling component layer and the diazo compound layer contains a thermofusible substance. As a coupling component,
A heat-developable diazo copying material characterized in that it uses a compound obtained by the reaction of 2-hydroxy-3-naphthoic acid hydrazide and an aldehyde or ketone.