JPS5885847A - 2-naphthol-1-diazonium lewis acid salt and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI[R1, R2, R3, R4, R5 and R6 are H, alkyl, sulfonic acid group, carboxylic acid group or its derivative; X is an anion group (Lewis acid salt) such as BF<->4, PF<->6, AsF<->6, SbF<->6, SnCl<-2>6, FeCl<->4, BiCl<-2>5, etc. which generates a Lewis acid by light irradiation]. EXAMPLE:2-Naphthol-1-diazonium boron tetrafluoride. USE:Raw material for the preparation of photo-sensitive resin. PROCESS:The compound of formulaIcan be prepared by (1) reacting aminonaphthol of formula II, or an aminonaphthol salt derived from said aminonaphthol and hydrochloric acid or the above Lewis acid salt, with sodium nitrite or an alkyl nitrite, and (2) reacting the product with a Lewis acid and a compound composed of the complex of the acid and its salt (e.g. fluoboric acid or its K or Na salt).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 2-naphthol-1-diazonium Lewis acid salts useful as raw materials for producing photosensitive resins and a method for producing the same.

Conventional photosensitive resins are known to have a diazo group, an azide group, a cinnamoyl group, or a chalcone group as a photosensitive group. The sensitization mechanism of these photosensitive groups involves a photodimerization reaction or the generation of radicals, and these reaction mechanisms are used to generate crosslinks between macromolecules. However, these photosensitive groups have problems with low quantum yield to light and selectivity of photoreactivity. This is the result of intensive research to solve these problems.

It has been found that 2-naphthol-1-diazonium Lewis acid salt i) is suitable for that purpose. That is, 2 of the present invention
-Naphthol-1: ``When diazonium Lewis acid salt is irradiated with light, selective and highly reactive ketene is generated, which reacts with the epoxy compound to produce a compound with a high degree of polymerization. It has been discovered that the Lewis acid generated at the same time acts as a catalyst to facilitate and speed up the reaction, and has completed the present invention.

, that is, 9 The present invention is applicable to 2-naphthol-1=diazonium Lewis acid salts represented by the general formula % (R1, R2, R3, , R4, R5, Re have the same meanings as above). The present invention provides a method for manufacturing the same.

The 2-naphthol-1-diazonium Lewis acid salts of the present invention are prepared by mixing aminonaphthols or their Lewis acid hydrochloride and sodium nitrite or alkyl nitride in an organic solvent (according to the solubility of the amine naphthols, zinc chloride may be added). A compound consisting of a Lewis acid and a combination of its acids and salts, such as fluoroboric acid or its K, Na salt, is added.

This reaction is as follows.

R6NH2 The aminonaphthols in the present invention include 1-amino-2
- Naphthol and its inorganic acid salts.

Examples include 1-amino-2-naphthol-4-sulfonic acid or carboxylic acid and its derivatives, 1-amino-2-naphthol-7-sulfonic acid or carboxylic acid and its derivatives. - Lewis acid salt and soo are BF4,
PF; , AsF; , St+C'l; , F
ecl; , BiCl3, etc. Sodium nitrite, inbutyl nitride, as a diazotizing agent
Examples include isopropyl nitrite, propyl nitride, etc. As the reaction solvent, a solvent with good solubility of aminonaph tols is used. Examples include, but are not limited to, solvents such as methanol, ethanol, isopchelic alcohol, benzene, dioxane, tetrahydrofuran, dimethylformamide, and dimethylacetamide.

The reaction temperature is preferably about 0 to -5°C.

In this case, the molar ratio of aminonaphthols and sodium nitrite or alkyl nitride is preferably 1, but it is not limited to this. The reaction product is purified by a recrystallization method.

The thus obtained 2-naphthol-1-diazonium Lewis acid salt, for example, the tetrafluoroborate salt, can be used as a photosensitive resin,
Used in applications such as printing inks, UV-curable adhesives, and paints.

Next, the present invention will be explained in detail based on examples.

Example 1. Synthesis of 2-naph-thol-1-diazonium boron tetrafluoride 5f of 1-amino-2-naphthol hydrochloride and 3.5t of zinc chloride were dissolved in 80% of ethanol. This reaction solution was cooled to below -5°C, and an aqueous solution of 1°8f sodium nitrite dissolved in 4++d distilled water was added dropwise over 20 to 30 minutes.After 40 to 50 minutes, 42 thioborhydrofluoric acid 11 - was added. The precipitated sodium tetrafluoroborate was separated from each other, and the P solution was concentrated under reduced pressure at room temperature. By cooling it, the precipitated material was taken off and recrystallized with 95% ethanol. It was purified by

A 3.3f purified product was obtained.

From the infrared absorption spectrum, 2100, 2190ffi-
Diazonium was confirmed in 1 and hydroxyl group was confirmed in 350-Oc++s. The melting point of the crystals is 115 (decomposition)°C. difference,
Furthermore, thermogravimetric analysis showed that the measured weight loss and the theoretical value agreed. Example 2. Synthesis of 2-naphthol-1-diazonium boron tetrafluoride 2.5f of 1-amino-2-naphthol hydrochloride was converted into 80-
of methanol, cooled to -5°C, and added 2f of isobutyl nitride in methanol solution (10
d)' dropwise over 30 minutes with stirring. After 1, 1
After an hour, 42-thioboric hydrofluoric acid (11) is gradually added dropwise. After this was left at room temperature for 1 hour, the two reaction solutions were concentrated under reduced pressure at room temperature, and upon cooling, crystals were precipitated. When this was collected in a furnace and recrystallized with 95% ethanol, 1
．． A 5f crystal is obtained.

Example 1 by infrared absorption spectrum. same as 2100
, diazonium-based absorption at 2190 cm-”, 35
Absorption based on hydroxyl groups was confirmed at 00tyn. Melting point 1
14-115 (decomposition) °C. 6 Examples 3.2-Naphthol-1 in which theoretical analytical results were obtained by thermogravimetric analysis
-Synthesis of diazonium tetrafluoroboron 5F 1-amino-2,-naphthol hydrochloride was dissolved in 80-methanol, 42% borohydrofluoric acid 11- was added, and 1-amino-2-naphthol borofluoride was dissolved in 5f. 3.52% of zinc chloride was added to the hydrochloride salt, and the reaction solution was heated to -5°C.
Below, 1.8 f of sodium and lithium nitrite dissolved in 4-g distilled water was cooled and added dropwise over 30 minutes. After the dropwise addition was completed, the precipitated sodium tetrafluoroborate was separated from each other, and the F solution was concentrated under reduced pressure at room temperature. By cooling this, the precipitated material was collected in a furnace and purified by recrystallization with 95% ethanol.3. Of obtained.

Infrared absorption spectrum Example 1. Same as 2Zoo,
Absorption based on diazonium was confirmed at 2190 crn and absorption based on hydroxyl group at 3500 cIn.
Ta.

Example 4. Synthesis of 2-naphthol-7-sulfonic acid-1-diazonium 47 boron fluoride ＼ 2.5 t of 1-amino-2-naphthol-7-sulfonic acid was dissolved in 80 fIi of methanol. After cooling to -5°C, add 2 tons of imbutylnatrilite methanol solution (10 m) dropwise over 30 minutes while stirring. After 1 hour, add 42% 42% borohydrofluoric acid lO- to the solution using a dropping funnel. Drip gradually. This-
After standing at 5° C. for 1 hour, the reaction solution was concentrated under reduced pressure at room temperature, and when cooled, crystals were precipitated. This was collected in F and washed with isopropyl alcohol to obtain 2.29 crystals.

Example 1 based on infrared absorption spectrum. Same as 2100.
7 azonium-based absorption in 2190cIgK, 35
Absorption based on hydroxyl groups was confirmed at 00crn-.

Although each of the above examples used tetrafluoroboric acid, similar results were obtained by using its salts, such as sodium salt and potassium salt, instead.

Also, other Lewis acids and their acids or salts, such as kelp v, kusuyoshi compounds HPF6, NaPF6, HSb
If F6, KSbF6, HAsF6, etc. are used in the same manner as in the example, the corresponding 2-naphthol-1
- Diazonium Lewis acid salts are obtained.

[Brief explanation of drawings]

FIG. 1 is a thermogravimetric analysis of 2-naphthol-1-diazonium boron 47tsride of Example 1.

Claims (2)

[Claims] (1) General formula (where R1tR2, R3tR4, R5, and R6 represent hydrogen, an alkyl group, a sulfonic acid group, a carboxylic acid group, and a derivative thereof. , PF; , A SF″; t
S b Fts + S uCl a −, FeCl
; , representing an anion group such as B1C1:2, i.e., a Lewis acid salt),] is the basic component, and the mutual ortho positions are hydro-! f-
Sil group! 2- substituted with a diazonium acid group
Derivatives of naphthol-1-diazonium cytriate salts (2) General formula % formula % (R1, R, 2, R3, 几4 + R5+ R6'+・
has the same meaning as (1)), or the aminonaphthol and hydrochloric acid, or (1)
The method consists of reacting the aminonaphthol salt produced from the Lewis acid salt with sodium nitrite or an alkyl nitride, and further reacting the Lewis acid with a compound consisting of a complex of the acid and its salt. 2-naphthol-1 represented by the general formula % formula % (It, , R2, R3, R4, R5, R6 have the same meanings as above)
-Production method of diazonium Lewis acid salt