JPS59212454A - Novel 2-hydroxy-3-naphthoic acid amide derivative and utilization thereof for diazo copying material - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 and R2 are H or lower alkoxyl but not H at the same time). EXAMPLE:2-Hydroxy-3-naphthoic acid-O-ethoxybenzylamide. USE:Useful as a blue color coupling component in diazo copying materials, having improved color fastness to light, and scarcely oxidized with time. PREPARATION:2-Hydroxy-3-naphthoic acid chloride of formula II is reacted with an amine derivative of formula III in a solvent, e.g. ethanol or dioxane, in the presence of an acid neutralizing agent, e.g. sodium hydroxide or potassium carbonate, at 80-90 deg.C for 3-8hr to give the compound of formula I . The reaction is carried out using 1-2.5mol, based on one mole compound of formula I , compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to novel 2-hydroxy-3-naphthoic acid amide derivatives useful as blue color-forming coupling components in diazo copying materials.

PRIOR ART Conventionally, naphthalene group σ) polyhydroxy compounds, such as 2,3-dihydroxynaphthalene and its derivatives and 2-hydroxy-3-
Naphthoic acid amide derivatives and the like are known. In particular, 2-hydroxy-3-naphthoic acid amide derivatives are widely used because of their ability to form, together with general diazo components, azo dye images with a color tone close to pure blue and with high density. However, many of them have problems in terms of image stability over time. For example, 2-hydroxy-3-naphthoic acid (N-morpholinopropyl), which was proposed as a color-forming coupler in JP-A No. 43-3403, cannot form dye images with light fastness, and Widely used as a dye intermediate (known as naphtho-/I/
AS can form a dye image with good light fastness, but because it is easily oxidized, it may discolor the image area over time or cause the background area to fade.
There was a drawback that six colors were contaminated.

Purpose The first object of the present invention is to form an azo dye image that has a color tone close to pure blue, has high color density, has excellent light fastness, and does not change color over time. It is an object of the present invention to provide a new 2-hydroxy-3-naphthoic acid amide derivative which does not stain the background and is therefore extremely useful as a coupling component of diazo copying materials.

A second object of the present invention is the novel 2-hydroxy-3-
An object of the present invention is to provide a diazo photographic material containing a naphthoic acid amide derivative as a coupling component.

Structure The novel 2-hydroxy-3-f phthoic acid amide derivative of the present invention has the general formula (where R1 and R are hydrogen atoms or lower alkoxy groups, such as methoxy groups, ethoxy groups, etc.; ) is a compound represented by

Furthermore, the diazo copying material of the present invention is characterized in that it contains this new compound as a coupling component.

The novel compounds of the invention are generally 2-hydroxy-3-
1 mole of naphthoic acid chloride and 1 to 2.5 moles of the amine derivative represented by the general formula are mixed in a reaction solvent such as ethanol or dioxane in the presence of an acid neutralizer such as sodium hydroxide, sodium carbonate, or sodium acetate. to 8
It is synthesized by reacting at 0 to 90°C for 3 to 8 hours. Note that 2-hydroxy-3-naphthoic acid chloride is obtained by reacting 2-hydroxy-3-naphthoic acid and thionyl chloride at 50 to 80° C. for about 5 hours in a reaction solvent such as benzene.

The novel 2-hydroxy-3-naphthoic acid amide derivative is a dehydrated 2-hydroxy-3-naphthoic acid amide derivative using phosphorus trichloride as a dehydration catalyst.
It can also be synthesized by a method of subjecting naphthoic acid and the above-mentioned amine derivative to a dehydration condensation reaction, or by a method of subjecting a 2-hydroxy-3-7toic acid ester and the above-mentioned amine derivative to a dealcoholization condensation reaction.

Specific examples of the 2-hydroxy-3-naphthoic acid amide derivatives obtained as described above include 2-hydroxy-3-naphthoic acid amide derivatives.
-Naphthoic acid -〇-ethoxyhensylamide, 2-hydroxy-3-naphthoic acid-〇-methoxybenzylamide, etc. are suppressed.

The 2-hydroquine-3-naphthoamide derivative of the present invention can be used in diazo copying materials, especially Ki4 development type diazo copying materials.
It is useful as a coupling component for To prepare an uninvented heat-developable diazo copying material using such a coupling component, 2-hydroxy-3-
A photosensitive layer may be formed by applying a photosensitive liquid consisting of an aqueous dispersion containing a sulfthoic acid amide derivative, a diazo component, a water-soluble binder, and a development accelerator as main components onto a support such as paper or plastic film and drying it. . Here, the diazo component is one used in general diazo copying materials, e.g.
Y, 4-diazo2,5-dimethoxyphenylmorpholine, 4-diazo2e 5-jethoxyphenylmorpholine, 4-diazo-2,5-jethoxyphenylmorpholine, 4-diazo-2,5-')7' Toxifenoylmorpholine, 4-diazo-2-5-dibutoxy-N-
Benzyl-N-ethylaniline, 4-diazo-2,5-
Dibutoxy-N.

N-dibutylaniline, 4-diazo-2,5-diphthoxy-N-be/di-N-hydroxyethylaniline, 4
-Diazo-2,5-dibutoxyphenylhyperidine, 4
-Sia:/'-2,5-jethoxyphenylpyrrolidine, 4-diazo-2,5-dipropoxyphenylpiperazine, 4-diazo-N,N-dimethylaniline, 4-diazo-N,N-diethylaniline, 4-Diazo-N-ethyl-N-hydroxyethylaniline, 4-diazophenylmorpholine, 4-diazophenylpyrrolidine, 4-thiazo2-7ff-nylpyrrolidine, 4-di'7zo2
-Chloro-N.

N-diethylaniline, 4-diazo-2-chlorophenylmorpholine and other diazotized compounds and zinc chloride,
Double salts with metal chlorides such as cadmium chloride and tin chloride, and salts of the diazo compounds with strong acids such as sulfuric acid, boron tetrafluoride, and hexafluorophosphoric acid are recommended. The molar ratio of the diazo component to the coupling component in the photosensitive layer is 1=
About 0.2 to 5 moles! (is appropriate.

Examples of the development accelerator include waxy substances having a melting point of 50 to 150 DEG C., such as paraffin wax, microcrystalline wax, carnawapa wax, and higher fat-freezing amides. These are usually used in an amount of 0.1 to 5 parts by weight per part of the coupling component.

Examples of the water-soluble binder include 1"VA% hydrogen ethyl cellulose, methyl cellulose, starch, etc. These are usually 0.00% per 1 part by weight of the carboxylic component.
1 to 2 parts by weight are used.

In addition to the above-mentioned components, various additives commonly used in diazo copying materials can be added to the photosensitive layer. For example, sodium naphthalene mono-, di- or trisulfonate, aluminum sulfate,
Magnesium sulfate, cadmium chloride, zinc chloride, etc. are used as antioxidants, thiourea, urea, etc. are used, and as acid stabilizers, citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. are used. In addition, adding a small amount of saponin can help.

Effects The novel 2-hydroxy-3-naphthoic acid amide derivative of the present invention is extremely useful as a blue color-forming coupling component for diazo copying materials, and although it has a color tone that is close to pure and is highly concentrated, In addition to being able to form an azo dye image with excellent fastness to bright light, it is also resistant to oxidation over time, so it does not discolor the image area or stain the background area.

Synthesis examples and application examples of the compounds of the present invention are shown below.

Synthesis of 2-hydroxy-3-naphthoic acid-0-ethoxybenzylamide: 5.7 g (0,028 mol) of 2-hydroxy-3-naphthoic acid chloride was added to 50 g of dioxane.
Dissolved in 0-ethoxybenzylamine 5.0 at room temperature
g (0,034 mol) was added dropwise. Next, add this solution to 40
After warming to ~50°C, add 2.8 g of sodium acetate (0
,034 mol) dissolved in 28 m of water was added, and 80
After reacting at ℃ for about 5 hours and leaving it to cool, the reaction solution was poured into ice water lt, and the precipitated crystals were separated, dried, and then recrystallized with ethanol to obtain 2-hydroxy-3-naphthoic acid-0. 5.7 g of -hydroxybenzylamide were obtained as pale yellow fine needle crystals. m, p, 151
~152℃.

Elemental analysis results: ICN actual value (CH) 6.09 74,70 4.32
Calculated value (95,9774,744,36 Synthesis Example 2 Synthesis of 2-hydroxy-3-naphthoic acid-0-methoxybenzylamide = 10.3 g (0.05 mol) of 2-hydroxy-3-naphthoic acid chloride dioxane 70
m1, and to this, 0-methoxybenzylamine 8
, 2 g (0.06 mol) dissolved in 82 ml of water was added at room temperature, followed by reaction at 80° C. for about 5 hours. After cooling, the reaction solution was poured into ice-water IL, and the precipitated crystals were separated, dried, and recrystallized with toluene to yield 8.5 g of 2-hydroxy-3-naphthoic acid-0-methoxybenzylamide. Obtained as a pale yellow powder. m, p, 14
2-143℃.

Elemental analysis results: I (CN Measured value (CH) 5.65 74.49 4.4
9 Calculated value (%) 5.59 74.24 4.5
6 Compound 1 obtained in Synthesis Example 1
g Stearic acid amide 1g10Hydroxyethyl cellulose water i8 [1o & water
After dispersing 50 g of the mixture in a Zeel mill for 24 hours, 10 thioxide starch aqueous solution FII 09' was added and stirred thoroughly. The resulting dispersion was applied to base paper for diazo copying paper until the dry adhesion amount was approximately 3.
．． After coating and drying to form a pre-coat layer, add citric acid 0.5.9 Savoni 1 on top.
0.1y water 10
The dry adhesion amount of the photosensitive liquid consisting of 01f is approximately 1.2 fl/r.
A photosensitive layer was provided by coating and drying at RT to obtain heat-developable diazo copying paper A.

On the other hand, for comparison, heat-developable diazo copying paper B was prepared in exactly the same manner except that 2-hydroxy-3-naphthoic acid-(N-morpholinopropyl)amide was used instead of the compound obtained in Synthesis Example 1. It was created. Similarly, a heat-developable diazo copy, IC, was prepared using 2-hydroquine-3-naphthoic acid anilide in place of the compound obtained in Synthesis Example 1.

Next, when each of the above diazo copying papers was developed using a commercially available heat development type diazo copying machine, an image with a tone close to that of pure i't was formed in each case. In order to further examine light fastness, each copy was exposed to sunlight for 24 hours. The above results are shown in the table below.

Note) *: Based on Macbeth densitometer.

As can be seen from this table, diazo copying paper A using the compound of the present invention has light fastness of the image area and background area of 1 (1) compared to conventional diazo copying paper.

Procedural amendment July 1, 1982! IEI Kazuo Wakasugi, Commissioner of the Japan Patent Office, Novel 2-Hydroxy-3-Naphthoic Acid Amide Derivatives and Their Use in Diazo Copying Materials 3, Relationship with the Amendment Person Case Patent Applicant 1-3 Nakamagome, Ota-ku, Tokyo No. 6 (67ri Ricoh Co., Ltd. - Representative Hama 1) Hiro 4, Agent 5, "Detailed description of the invention" column 6 of the specification subject to amendment, Contents of the amendment Page 11 of the specification Lines 10-11 "After adding the solution dissolved in water 82- at room temperature" was changed to "Dropped.
After warming to 0°C, sodium acetate 4.9F (0,
Add a 10% aqueous solution of 0.06 mol) and build up the pressure to .

that's all

Claims (1)

[Scope of Claims] A 2-hydroxy-3-naphthoic acid amide derivative represented by the following formula (L R, ``horse'' represents a hydrogen atom or a lower alkoxy group, but is not a hydrogen atom at the same time). (However, R, , R, represents a hydrogen atom or a lower alkoxy group, but is not a hydrogen atom at the same time.) Diazocontaining a 2-hydroxy-3-naphthoic acid amide derivative represented by Copying materials.