JPS58210055A - Novel 2-hydroxy-3-naphthoic acid amide derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is group of formula II (n is 2 or 3) of formula III (R1, R2 are R3 are H, lower alkyl or aryl provided that at least one of them is not H)]. EXAMPLE:2-Hydroxyl-3-naphthoic acid 2'-phenylethylamide. USE:Useful as a blue-color developing coupling component of diazo photosensitive material. Excellent light-stability at the printed part and the highlighted part. PROCESS:The compound of formula I can be prepared by reacting 1mol of 2- hydroxy-3-naphthoic acid chloride of formula IV with 1.0-2.5mol of an amine derivative of formula V in the presence of an acid-neutralizing agent such as Na2CO3 at 80-90 deg.C for 3-8hr. The reaction solvent is preferably ethanol, dioxane, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly applicable to diazo-sensitized +41. The present invention relates to a novel 2-hydroxy-3-naphthoic acid amide derivative useful as a blue color-forming coupling component for i+.

Conventionally, naphthalene-based polyhydroxy compounds such as 2,3-dihydroxynaphthalene and its derivatives and 2,3-dihydroxynaphthalene have been used as coupling components to obtain blue diazo copies.
-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 color tone close to blue and high coloring temperature. However, many of them have problems in terms of image stability over time. For example, in Japanese Patent Publication No. 43-3403, the azo dye produced by 2-hydroxy-3-naphthoic acid-(N-morpholinopropyl)-amide represented by the following formula has a drawback of poor light fastness. In addition, naphthol S represented by the following formula, which is conventionally known as an intermediate for azo dyes, has the disadvantage that it becomes colored by oxidation, that is, it stains the background.

The present invention aims to eliminate the above-mentioned drawbacks and provide a novel compound useful as a coupling component in a diazo photosensitive material, which produces an azo dye that has excellent light fastness and does not change color over time due to the degree of oxidation. The gist thereof is a 2-hydroxy 3-naphtho, l1il amide derivative represented by the general formula.

To synthesize the 2-hydroxy-3-naphthoic acid amide derivative of the present invention, 2-hydroxy-3-naphthoic acid chloride shown below and an amine derivative represented by the following general formula are used, provided that n: 2
or 3) Or R1 82N -C-R2 ■ 3 (However, R+, R2, R3: H, lower alkyl group, or aryl group, and not 11 at the same time) and the molar ratio It is synthesized by reacting at a reaction temperature of 80 to 90° C. for 3 to 8 hours in the presence of an acid neutralizer at a ratio of 1:1.0 to 2.5.

As the acid neutralizing agent, helium hydroxide, sodium carbonate, sodium acetate, etc. can be used, and as the reaction solvent, ethanol, diochirin, etc. can be used. In addition, 2-hydroxy-3-naphthoic acid chloride is 2-hydroxy-3-naphthoic acid chloride.
Hydroxy-3-naphthoic acid and thionyl 11ide are reacted at 50 to 70°C for about 5 hours using benzene as a reaction solvent to synthesize τ.

Other methods for synthesizing the 2-hydroxy-3-nano-1 to engineered acid amide derivatives include a method of dehydration condensation from 2-hydroxy-3-naphthoic acid and an amine derivative using phosphorus trichloride as a catalyst, and -[12 There is a method of synthesizing an amine derivative from the ster form of -hydroxy-3-naphthoic acid by dealcoholization condensation reaction. can be synthesized.

The 2-hydroxy-3-naphthoic acid amide derivative of the present invention is useful as a coupling component in diazo-sensitive materials, and diazo-sensitive materials 1 to 1 using the same can be produced according to conventionally known methods. In particular, the compound of the present invention, a developability accelerator, a water-soluble resin, etc. are dispersed in water using a ball mill, and then coated on paper or film as a support, and then a photosensitive solution containing a diazo compound is coated. It can be applied to heat-developable diazo photosensitive sheets 1 to 1. As a development accelerator, M11+H is 50 to 15
0° C. substances such as paraffin wax, microcrystalline wax, carnauba wax, and fatty acid amides. Examples of water-soluble resins include polygonyl alcohol, hydroxyl cellulose, and starch. The mixing ratio of each material is
The weight pressure is 1:0.1 to 5.0:0.1 to 2.0.

As the diazo compound used in the photosensitive liquid, any of those used in general diazo photosensitive materials can be used. A specific example is as follows.

4-cyasylmorpholine, 4-diazo-2,5-dibutylmorpholine, 4-diazo-2,5-dibu] - xyphenylmorpholine, 4-diazo-2,5-
dibutoxy-N-benzyl-N-X thylaniline, 4-
Diazo-2,5-dibutoxy-N-N-dibutylaniline, 4-diazo-2,5-dibutoxy-N-benzyl-
N-H]-roxyethylaniline, 4-siacy 2.5
-dibutoxy7Tylpiperidine, 4-diazo-2.5
-jethoxyphenylgororidine, 4-diazo-2.5
-diproboxif nilpiperazine, 4-diazo-N-
N-dimethylaniline, 4-diazo-N-N-diethylaniline, 4-diazo-N-ethyl-N-didroxyedylaniline, 4-diazo-N-N-dipropylaniline, 4-diazophenylmorpholine , 4-diazophenylpyrrolidine, 4-diazo-2-methylnoenylpyrrolidine, 4-diazo-2-chloro-N-N-diethylaniline, 4-diazo-2-ethoxy-N-N-diethylaniline , 4-diazo-2-chlorophenylmorpholine and the like.

The coupling component is used in an amount of 0.2 to 5 moles per mole of these diazo compounds.

Additives used in conventional diazo-sensitive materials can be used in combination with the coupling component of the present invention. That is, naphthalene mono-,
Anti-oxidation products such as di- or trisulfone-resistant pttrium, aluminum sulfate, lilIM magnesium, cadmium chloride, zinc chloride, etc. Thia urine water, urine water, etc. are used as agents, and citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, birophosphoric acid, etc. are used as acid stabilizers.

Other saponins can be added in small amounts.

A diazo photosensitive material using the compound of the present invention as a coupling component has excellent light resistance in the image area and the background area.

Next, a typical synthesis example of the compound according to the present invention will be shown.

Synthesis Example 1 Synthesis of 2-hydroxy-3-naphthomonoacid 2-phenylethylamide: 2-hydroxy-3-nano 1-1 dichloride 10,3
G (0.05 mol) to 1 non 1
00 m, Q, and 2-phenylethylamine 12.1 (1 (0.In + of) was added dropwise at room temperature. After heating to 10 to 80 °C, A 10% aqueous solution of >0.06 mol was added and the reaction continued for about 5 hours.After cooling,
Pour the reaction solution into 700 nl of ice water, collect the precipitated crystals by filtration, dry and recrystallize with methanol to obtain 2-hydroxy-3-naphthoic acid 2.
6.8 g of ``-)1-nylethylamide was obtained as pale yellowish white crystals. Its melting point was 109-111°C.

The elemental analysis results are as follows.

1cN Actual value (%) 5.91 78.27 4.
83 total sieve value (%) 5.88 78,34
4.81 (as C I9 fl 17 N O 2 ) Synthesis Example 2 Synthesis of 2-hydroxy-3-naphthoic acid 3-phenylpropylamide: 2-hydroxy-3-naphthoic acid [1ride 10,3
(J(0.05 mol>) in dioxane 100m
2-7enylprobylamine 13 dissolved in β at room temperature
, 50 (0.1 mol) was added dropwise. 7
After heating to 0-80°C, 4.9 g of sodium acetate
A 10% aqueous solution of (0.06 mol) was added, and the reaction was continued for 5 hours. hk cold model, ice water 700
The reaction solution was heated to m℃, the precipitated crystals were collected by filtration, dried, and recrystallized with methanol to yield 2-hydroxy-3-naphthoic acid 3'-phenylpropylamide 5,0. Obtained as pale yellowish white crystals. Its melting point is 1
The temperature was 13.5-114°C.

Elemental analysis results are as arranged.

CN Actual value (%) 6.31 78, 71 4,
55 total value (%) 6,28 78,65 4.59 (
C201-1+ a NO2) Synthesis Example 3 Synthesis of 2-hydroxy-3-naphthoethyl tert-butyramide: 2-hydroxy-3-naphthyl-, T-If chloride 1
0.3 (1(0,05n1ol) to dioxane 10
7.39 (0.4 mol) of tert-butylamine was dissolved in 0 mA at room temperature. It was lowered. 40-50
After heating to °C, 4,9 g
A 10% aqueous solution of (0.06 mol) was added, and the reaction was continued (-) for about 5 hours. After cooling, soak in ice water for 700 m
The precipitated crystals were collected by filtration, dried, and recrystallized with methanol to obtain 4.1 g of 2-hydroxy-3-naphthoic acid tert-butylamide as light brown crystals. Its melting point was 164-166°C.

The elemental analysis results are as follows.

CN Actual value (%) 7.11 73.98 5.79
Total sieve value (%) 7,06 74.04 5,76
(as C+ 51-117 NO2) Synthesis Example 4 Synthesis of 2-hydroxy-3-naphthoic acid Schiffnyl methylamide: 2-hydroxy-3-naphthoic acid chloride 10.3
(J (0.05 mol) in dioxane 100 m
, dissolved in Q at room temperature, diphenylmethylamine 11.
5g (0,061'lol) was added dropwise. 70
After heating to ~80°C, 1 to 4,9 g of lithium acetate (
A 10% aqueous solution of 0.06 mol> was added, and the reaction was continued for about 5 hours. After cooling, the mixture was poured into ice water at 700 m°C, and the precipitated crystals were collected by filtration, dried, and recrystallized with methanol. , 6.8 g of 2-hydro-4-cy-3-naphtho-T acid diphenylmethylamide was obtained as pale yellow-white crystals.The melting point was 208-209°C, and the IJo elemental analysis results are as follows.

1cN Actual measurement + 1fT (%) 5.41 81.66
71.01 Calculated value (%) 5,43 81.56
3.96 (as C24t-l + s NO2) Synthesis Example 5 2-Human11:lC3-naphtho-r II Synthesis of l-rifr-nylmethylamide: 2-Human1]-1-C3-naph j to [acid chloride 6.4 Q (0.03 mol) dioxane 100
To m j2? 'll 'A'l (J, at room temperature, triphinylmethylamine 15.9 o (0,06 mof
) to diAquinone 50n1. A solution dissolved in e was added dropwise. After heating to 70-80°C, acetic acid 3. O
A 10% aqueous solution of g (0,036 mol) was added and the reaction continued for about 5 hours.

b' was cold-welded, poured into 700 mβ of ice water, the precipitated crystals were filtered, dried, and recrystallized with benzene to obtain 2-hydroxy-3-naphthoic acid triphenylmethylamide 4.4Q. was obtained as pale yellowish white crystals. Its melting point is 228-230°C.

The results of elemental analysis are as shown in 1.

1-I CN actual measurement value (%)! 1.43 83.9!3 3.
2131 calculated value (%) 5.41 83,88 3
．． 26 (as C30+-123N O2) Next, an application example of the compound of the present invention using the above synthetic compound will be described.

Application example 1 A heat-developable diazo photosensitive sheet was prepared in the following manner.

Compound of Synthesis Example 1 1g stearamide 1g 10% hydroxyethylcellulose 10g water
50 () After applying the dispersion of the above formulation to a ball mill for 24 hours, 10 g of a 10% oxidized starch aqueous solution was added and stirred well.The solution was coated on white base paper for diazo photosensitive paper at about 3.0 g/l112 and dried. Add about 1.2 g/n of photosensitive liquid of the following formulation to this.
Diazo photosensitive paper A was obtained by applying and drying the film at a temperature of +''.

4-Diazo-2,5-dibu] ~xyphenylmorpholine indide 1/2 7nC121g citric acid
O, 5g saponin
0.1 g water 100 m Q Next, this diazo photosensitive paper was overlapped with the original and exposed and developed using Ricopy Hydry (manufactured by Ricoh Co., Ltd.) to obtain a copy with a blue image.

For comparison, the compound of Synthesis Example 1 was replaced with 2-hydroxy-3-naphtho! Diazo-sensitized M
I got a B. Similarly, diazo-sensitive paper C was obtained using 2-hydroxy-3-naphthogolic acid anilide. In order to examine the light fastness of these diazo photosensitive papers, diazo photosensitive papers Δ, B and C were developed using Ricobee Hydry and exposed to sunlight for 24 hours. The results are summarized in the table below. The 'a degree was measured using a Macbeth (Macbeth) stratimeter.

Dma x 1) mill Test Test Test Before Test After Before After Photosensitive paper 1.
18 1,15 0.10 0,15 photosensitive paper 1
．． 1'll 1.61 0.11 0.15 Photosensitive paper 1.17 1.15 0.10 0.19
As can be seen from the results of the comparative test, the light-fastness of the image area and background of the photosensitive paper using the compound of the present invention is superior to that of conventional photosensitive paper.

Application example 2 A heat-developable diazo photosensitive sheet was prepared using the following method.

Compound of Synthesis Example 4 1g stearic acid amide 1 (110% hydroxybrolulerulose 10g water
509 A dispersion of the above formulation was added to 2411. After milling in a ball mill for 20 minutes, 101 J of a 10% oxidized starch aqueous solution was added and stirred well. Apply the solution to white base paper for diazo photosensitive paper at a density of approximately 3.0 (1/ n+'
It was coated and dried. Furthermore, about 1.2 liters of photosensitive liquid of the following formulation
A diazo-sensitive paper was obtained by coating and drying with R/T112.

4-Diazo-2,5-dibu1-xy-noenilmo/L/
Chloride-1/2 ZnC121 (] Citric acid 0.5g Saponin
o, i g water
100 l
1lj2 Next, this diazo photosensitive paper was placed on top of the original and exposed and developed using Ricoh Hydry (Ricoh! 11) to obtain a copy with a blue image.

For comparison, diazo photosensitive paper E was prepared in exactly the same manner using 2-hydroxy-3-def-1-technic acid 3--N-morpholamide and 1-viramide in place of the compound of Synthesis Example 4.
I got it. Similarly, diazo-sensitive paper F was obtained using 2-hydroxy-3-naphthoic acid anilide. To examine the light fastness of these diazo-sensitive papers, diazo-sensitive papers E and F were developed using Ricopy Hydry and exposed to sunlight for 24 hours. The results are summarized in the table below. The degree of a was measured using a Macbeth Ili II meter.

Dmax I) min test test 1- test before test after before after photosensitive paper 1
,18 1,15 0.10 0.14 Photosensitive paper
1.19 1. Old 0.11 0.15 photosensitive paper
1.17 1.15 0.10 0.19 As can be seen from the results of this comparative test, the light-fastness of the image area and background of the photosensitive paper using the compound of the present invention is superior to that of conventional photosensitive paper. ing.

Patent applicant: Ricoh Co., Ltd. Agent: Patent attorney: Hidetake Komatsu 330-

Claims (1)

[Claims] general formula Amide derivative.