JP2604140B2 - Base generation method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a base. More particularly, the present invention relates to a method for producing a base upon use from a compound that is substantially neutral upon storage.

BACKGROUND OF THE INVENTION Bases are very versatile reagents used in various reactions (eg, hydrolysis reactions, polymerization reactions, color reactions, redox reactions, neutralization reactions, etc.). There are many common products in which a base component is incorporated, such as a conventional developer for silver salt photography, a photothermographic material, an adhesive, and various detergents.

However, bases (especially strong bases) have a problem in stability, such as absorption and inactivation of carbon dioxide in the air. It is also difficult to store a highly reactive strong base in contact with other components. Further, the base may irritate the skin, for example, and may harm the human body. When handling the base, it is necessary to pay attention to its toxicity and skin irritation.

Therefore, products incorporating a base component have the above-mentioned problems with respect to the stability over time of the base, the storage stability of other components in contact, and the handling properties.

As one means for solving the above problem,
No. 59-180537 discloses a base precursor represented by the formula (I) or (II) described below. As described in the above publication, the base precursor represented by the formula (I) or (II) described below is extremely stable at room temperature, and decomposes rapidly when heated to a certain temperature or higher to dissolve the basic component. Release. Therefore, this base precursor can be preferably used for a photothermographic material.

[Summary of the Invention] The present invention has been further studied on a method for producing a base using a base precursor represented by the following formula (I) or (II).

An object of the present invention is to use a base precursor represented by the following formula (I) or (II), which is extremely stable during storage, to produce a base more rapidly at the time when the base is required. Is to provide a method for generating

The present invention relates to the use of a base precursor represented by the following formula (I) or (II) by using a base precursor represented by the following formula (I) or (II):
Wherein a substance selected from the group consisting of metallic silver, a silver compound, metallic copper and a copper compound is accelerated by a base precursor represented by the following formula (I) or (II): An object of the present invention is to provide a method for producing a base, which is characterized by acting as an agent.

(R ¹ —C≡C—CO ₂ H) _x · B (I) R ² (—C≡C—CO ₂ H) ₂ · B _y (II) [In the above formula, R ¹ represents a hydrogen atom or an alkyl group. , a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue, an aralkyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, -CO ₂ M (M is an alkali metal atom), and -CO ₂ H · A monovalent group selected from the group consisting of B (each group may have one or more substituents), and R ² is a group consisting of an alkylene group, an arylene group, and a heterocyclic divalent residue. B is an organic base, x is 1 when B is a monoacidic group, and B is a divalent group selected from the group consisting of two or more divalent groups (each group may have one or more substituents). Is 2 if an acid base, and y is 1 if B is a monoacid base and 1 if B is a diacid base.

[Effect of the Invention] The method for producing a base according to the present invention is characterized in that
A substance selected from the group consisting of metallic silver, a silver compound, metallic copper and a copper compound is caused to act as a decomposition accelerator on the base precursor represented by I).

According to the research of the present inventors, metallic silver, silver compounds, metallic copper,
It has been found that the copper compound and the copper compound exhibit an excellent catalytic action on the decomposition reaction (base generation reaction) of the base precursor.

In the method for producing a base of the present invention, the base precursor is easily and rapidly produced by causing a substance selected from the group consisting of metallic silver, a silver compound, metallic copper and a copper compound to act as a decomposition accelerator. be able to. Therefore, according to the method for producing a base of the present invention, it has become possible to rapidly produce a base with a combination of only a substance that is very stable in a storage state (a decomposition accelerator and a base precursor).

In particular, by using the above-mentioned decomposition accelerator together with the heat treatment described in JP-A-59-180537, the base can be more rapidly generated at the time when the base is required. Further, by using the method for producing a base of the present invention, the heating temperature in the heat treatment can be set to a lower temperature.

[Detailed Description of the Invention] The method for producing a base according to the present invention uses a substance selected from the group consisting of metallic silver, a silver compound, metallic copper and a copper compound as a decomposition accelerator.

The silver and copper compounds may be ionic or covalent, and may be used without any particular limitation.
The valence of the copper atom of the copper compound may be monovalent or divalent. Silver and copper compounds may have one or more ligands or water of crystallization. Further, the silver and copper compounds may be soluble or insoluble in water or organic solvents. That is, as long as it is a compound of silver and copper, it can act as a base accelerator decomposition accelerator without any particular limitation.

Among the above-mentioned decomposition accelerators, silver and copper compounds selected from the group consisting of oxides, sulfides, halides, carboxylate salts and substituted acetylides are preferred. Further, metallic copper or a copper compound is more preferable than metallic silver or a silver compound from the viewpoint of the catalytic function and practically inexpensive.

Next, typical specific examples of substances that can be preferably used as a decomposition accelerator for a base precursor in the method for producing a base of the present invention are shown below.

(1) metallic silver, (2) metallic copper, (3) Ag ₂ O, (4) Cu ₂ O, (5) CuO, (6) Ag ₂ S, (7) Cu ₂ S, (8) CuS, (9) AgCl, (10) CuCl, (11) CuCl 2, (12) CuCl 2 · 2H 2 O, (13) AgBr, (14) CuBr, (15) AgI, (16) CuI, (17) AgNO ₃ , (18) Cu (NO ₃ ) ₂ , (19) AgOCOCH ₃ , (20) Cu (OCOCH ₃ ) ₂ , (21) AgCN, (22) CuCN, (23) C ₂₁ H ₄₄ CO ₂ Ag, _{(33) C 8 H 17 -C≡C} -Ag (35) copper ethylenediaminetetraacetate _{(36) CuSO 4 · 5H 2} O As described above, the decomposition accelerators for the base precursor may be used alone or in combination of two or more.

Hereinafter, the base precursor represented by the following formula (I) or (II) will be described.

(R ¹ -C≡C—CO ₂ H) _x · B (I) R ² (−C≡C—CO ₂ H) ₂ · B _y (II) The structural feature of the base precursor is that the acid moiety is propiol. It is an acid derivative having a triple bond at the α-position of the carboxyl group, which makes the carboxyl group much easier to decarboxylate. However, the propiolic acid derivative is extremely stable under storage conditions at room temperature and in the absence of a decomposition reaction catalyst, and decomposes to release a base component only by heating and / or the action of the decomposition reaction catalyst.

In the above formula (I), R ¹ is a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), a cycloalkyl group (preferably having 5 to 8 carbon atoms), or an alkenyl group (preferably having 5 carbon atoms). 2 to 5), alkynyl group (preferably 2 to 5 carbon atoms), aryl group (eg, phenyl group, naphthyl group, anthryl group), heterocyclic residue (eg, pyridyl group, thienyl group, thiazolyl group) ,
Benzoxazolyl group, benzothiazolyl group), aralkyl group (preferably having 7 to 10 carbon atoms), acyl group (preferably having 2 to 12 carbon atoms), alkoxycarbonyl group (preferably having 2 to 9 carbon atoms) Carbamoyl group (preferably 2 to 9 carbon atoms), -CO ₂ M
(M is an alkali metal atom; for example, —CO ₂ Na, —CO ₂ K) and —CO ₂ H · B (B is an organic base) and is a monovalent group (each group is It may have the above substituents).

In the above formula (II), R ² represents an alkylene group, an arylene group (eg, 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 9,10-arylene group), It is a divalent group selected from the group consisting of ring divalent residues (eg, a thienylene group) (each group may have one or more substituents).

In order for the base precursor represented by the formula (I) or (II) to have a sufficient decomposition rate in the method for producing a base of the present invention, R ¹ and R ² preferably have an appropriate electron-withdrawing property.

For the above reasons, R ¹ is an alkenyl group, alkynyl group, phenyl group, naphthyl group, anthryl group, pyridyl group, thienyl group, benzoxazolyl group, benzothiazolyl group, acyl group, alkoxycarbonyl group, carbamoyl group, -CO ₂ M, and is preferably a monovalent group selected from the group consisting of -CO ₂ H · B (each group may have one or more substituents).

Similarly, R ² is preferably a divalent group selected from the group consisting of a phenylene group, a naphthylene group, an arislene group, and a thienylene group (each group may have one or more substituents) .

Also, considering that the raw materials are easily available and that the synthesis is easy, R ¹ is a monovalent group selected from the group consisting of phenyl, naphthyl, anthryl, pyridyl, and thienyl groups. More preferably, each group may have one or more substituents.

In the above formulas (I) and (II), B is an organic base, x is 1 when B is a monoacid base, 2 when B is a diacid base, and y is B Is 2 when B is a diacid base, and 1 when B is a diacid base.

The organic base represented by B is not particularly limited and can be selected according to the purpose of use.

The base part B of the base precursor used in the present invention is described below.
The following shows a typical specific example.

Next, typical specific examples of the base precursor represented by the above formula (I) or (II) which can be preferably used in the method for producing a base of the present invention are shown below.

Hereinafter, a specific method of using the method for producing a base of the present invention will be described.

As described above, the method for producing a base according to the present invention includes, as described above, silver salt photography, image formation such as diazo photography, anionic polymerizable adhesives, coating film formation for coating, sealing and caulking agents,
For various chemical reaction systems that require base components such as detergents,
Can be applied effectively.

In silver salt photography, the development, that is, the oxidation-reduction reaction between silver halide and a developing agent, is carried out under alkaline conditions. According to the present invention, by adding the above-described base precursor and the decomposition accelerator in the photosensitive material in an isolated state,
After exposure, development can be induced by simply heating. In this case, the base precursor and the decomposition accelerator are respectively contained in at least one layer on separate supports,
It is desirable to add another layer on the same or the same support, or to isolate them from each other by emulsification dispersion, solid dispersion, microcapsules or the like. For example, the base precursor can be contained in the photosensitive material and the development accelerator can be contained in the developing sheet, and both can be superposed and heated during development.

In diazo photography, as shown in the following formula, the unreacted portion of the remaining diazonium salt and the coupler are subjected to a coupling reaction under alkaline conditions to form an azo dye.

When the present invention is applied to the above diazo photographic method, for example, in a dry method, a diazonium salt and a base precursor and a decomposition accelerator are added in an isolated state to diazo photosensitive paper, coated, exposed, and then thermally developed to form an azo dye. Images can be obtained. In the conventional thermal developing diazo photography, an alkali generator such as ammonium carbonate and hexamethylenetetramine was used, but the development time was long and the stability of the photosensitive paper was not good. On the other hand, by using the base generation method of the present invention, rapid image formation was made possible, and the stability of the photosensitive paper was also improved.

In addition, the base produced according to the present invention can be used as a basic catalyst for the polymerization reaction of an anionic polymerizable monomer. There is no particular limitation on the anionic polymerization,
It can be applied to various fields such as an adhesive, a coating agent, and a sealing and caulking agent.

In addition, the present invention can be applied to products that require a base component such as a detergent and a fungicide. When the present invention is applied to the above-mentioned products, it is preferable to use a two-component product comprising a component containing a base precursor and a component containing a decomposition accelerator. Then, a base can be generated by mixing (preferably heating after mixing) at the time of use. Therefore, these products can be made neutral, safe and stable by applying the present invention.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

Comparative Example 1 A 5 × 10 ⁻² mol / solution (solvent: butyl acetate and ethylene glycol monomethyl ether, volume ratio = 50: 50) of the following base precursor was heated to 80 ° C. to produce guanidine. The time change of the hydrogen ion index (pH) was measured.

Example 1 10 ml of the solution of the base precursor used in Comparative Example 1
In addition, the following decomposition accelerator 0.1 to the base precursor
After adding the equivalent amount, the mixture was heated to 80 ° C., and the time change of the hydrogen ion index due to the production of guanidine was measured.

Example 2 10 ml of the solution of the base precursor used in Comparative Example 1
Then, after adding 0.01 equivalent of the decomposition accelerator used in Example 1 to the base precursor, the mixture was heated to 80 ° C., and the time change of the hydrogen ion index due to the formation of guanidine was measured.

The above measurement results of Comparative Example 1 and Examples 1 and 2
Shown in the figure.

In FIG. 1, the horizontal axis represents time (minutes) after the completion of the heating to 80 ° C., and the vertical axis represents the hydrogen ion index of the solution.

The curve (-□-□-) is the measurement result of Comparative Example 1, the curve (− △ − △ −) is the measurement result of Example 1, and the curve (− ○ − ○ −) is the measurement result of Example 2. The result.

As is clear from the results shown in FIG. 1, the effect of the decomposition accelerator is remarkable when 0.01 equivalent is used relative to the base precursor, and the decomposition of the base precursor itself is extremely slow. It can be seen that when an accelerator is used in combination, it is rapidly decomposed.

[Application Example 1] Application to heat-developed thiazo photograph On a base paper, a mixture of the following components was applied at a wet thickness of 100 µm.

After drying, it was exposed through a transparent text original using a diazo exposure apparatus. 120 exposed samples
After heating at 5 ° C. for 5 seconds, a blue positive image having an optical density of 1.15 and a good S / N ratio was obtained.

[Reference Example 1] In place of the base precursor and the decomposition accelerator used in Application Example 1, 100 mg of hexamethylenetetramine was added, and the same treatment was carried out.
It was 50.

Example 3 10 ml of the solution of the base precursor used in Comparative Example 1
Then, 0.1 equivalent of the decomposition accelerator (4) of the present invention was added to the base precursor, and the mixture was heated to 80 ° C. Thirty seconds later, when the hydrogen ion concentration was measured, the pH value had risen to 11.5 due to the rapid formation of guanidine.

Example 4 10 ml of the solution of the base precursor used in Comparative Example 1
Then, 0.1 equivalent of the decomposition accelerator (5) of the present invention was added to the base precursor, and then heated to 80 ° C. Thirty seconds later, when the hydrogen ion concentration was measured, the pH value had risen to 12.0 due to the rapid formation of guanidine.

Example 5 10 ml of the solution of the base precursor used in Comparative Example 1
Then, 0.1 equivalent of the decomposition accelerator (30) of the present invention was added to the base precursor, and the mixture was heated to 80 ° C. Thirty seconds later, when the hydrogen ion concentration was measured, the pH value had risen to 12.2 due to the rapid formation of guanidine.

Example 6 10 ml of the solution of the base precursor used in Comparative Example 1
The decomposition accelerators (6), (7), (10), (2)
3), (24) and (26) were each added to the base precursor in an amount of 0.1 equivalent, and then heated to 80 ° C. After 30 seconds, the hydrogen ion concentration was measured. The above results are shown in Table 1 below. Table 1 shows Example 1 (decomposition accelerator 3).
7), Example 3 (4), Example 4 (5), Example 5 (3
The results of 0) are also shown together.

As is clear from the results shown in Table 1, when a copper catalyst or a silver catalyst is used as a decomposition accelerator, an organic base (guanidine) is rapidly generated, and the pH value (hydrogen ion concentration) increases.

[Brief description of the drawings]

FIG. 1 is a graph showing measurement results in Comparative Example 1 and Examples 1 and 2. The horizontal axis represents the time (minutes) after completion of the heating to 80 ° C., and the vertical axis represents the hydrogen ion index of the solution. -□-□-: Measurement result of Comparative Example 1-△-△-: Measurement result of Example 1-○-○-: Measurement result of Example 2

Claims (7)

(57) [Claims] 1. A method for preparing a compound represented by the following formula (I) or (II) using a base precursor represented by the following formula (I) or (II):
Wherein a substance selected from the group consisting of metallic silver, a silver compound, metallic copper and a copper compound is accelerated by a base precursor represented by the following formula (I) or (II): (R ¹ -C≡C—CO ₂ H) _x · B (I) R ² (−C≡C—CO ₂ H) ₂ · B _y (II Wherein R ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue, an aralkyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, —CO ₂ M (M is an alkali metal atom), and-
A monovalent group selected from the group consisting of CO ₂ H.B (each group may have one or more substituents), and R ² is an alkylene group, an arylene group, or a heterocyclic divalent residue. A divalent group selected from the group consisting of groups (each group may have one or more substituents), B is an organic base, and x is 1 when B is a monoacid base. , B is 2 when B is a diacid base, and y is 1 when B is a monoacid base and 1 when B is a diacid base.]. 2. The method according to claim 1, wherein said decomposition accelerator is copper metal or a copper compound. 3. The method according to claim 1, wherein said decomposition accelerator is a silver or copper compound selected from the group consisting of oxides, sulfides, halides, carboxylate salts and substituted acetylides. 4. The method according to claim 3, wherein said decomposition accelerator is a substituted acetylide of monovalent copper. 5. The method according to claim 1, wherein said decomposition accelerator is allowed to act on said base precursor under heating conditions. 6. The method according to claim 5, wherein said heating condition is 50 ° C. or higher. 7. The method according to claim 1, wherein B in the above formula is a substituted or unsubstituted guanidine.