JPH0253091B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides spicrisporic acid [] (4,5
-dicarboxy-4-pentadecanolide) and an open ring acid formed by ring opening of its lactone ring [ ] (3-hydroxy-1,3,4-tetradecanetricarboxylic acid). (hereinafter also simply referred to as a stabilizer). Microbial surfactants such as polybasic acids and glycolipids with long-chain alkyl groups have various functional groups, so
Unique performance is expected. In particular, those with carboxyl groups can be called biosoaps, and in addition to their original surface activities such as dispersion, emulsification, solubilization, wetting, penetration, and cleaning, they also have physiological activity, pharmacological activity, metal ion trapping action, thickening, and A major feature is that it can also exhibit useful effects such as oxidation-reduction, rust prevention, sterilization, and heat retention. Traditionally, organic liquids and organic or inorganic fine powders have been emulsified, dispersed, and dispersed in organic or aqueous media in fields such as dyes, pigments, and paints, civil engineering, agricultural materials, medicine, agrochemicals, cosmetics, and the textile industry. Surfactants are used for solubilization. For example, in recent years, in the development of water-based paints, the development of suitable pigments and dispersants has become an important issue. However, while the surfactants according to conventional techniques are excellent as dispersants, their dispersion systems lack stability. Furthermore, emulsified fuel, which is obtained by emulsifying fuel such as kerosene with an emulsifier, is useful as a low-pollution, safe fuel. However, problems often occurred such as loss of stabilizing effect due to changes in coexisting additives, pH, and temperature. The present inventors have conducted various studies to overcome the drawbacks of conventional surfactant-based stabilizers, and as a result, the above-mentioned spicrisporic acid and an open ring acid formed by opening the lactone ring thereof have been developed. The present inventors have discovered that various alkylamine salts have an excellent stabilizing effect on solid fine powders and various liquids, and have completed the present invention. The spicrisporic acid used is made from Penicillium through a microbial industrial process using glucose as a raw material.
It can be produced in large quantities with high yield as a metabolite of spiculisporum. In the present invention, spicrisporic acid having different degrees of neutralization and an alkylamine salt of an open ring acid obtained by ring opening of its lactone ring are provided as water-soluble or oil-soluble stabilizers. The emulsification and dispersion stabilizer of the present invention can be obtained by neutralizing spicrisporic acid (S acid) or its open ring acid (O acid) with an alkylamine in a solvent. In this case, the alkylamine includes not only a chain alkylamine but also a cyclic cycloalkylamine and an alkylamine having a hydroxyl group, and the number of carbon atoms is not particularly limited, but is preferably 4 to 8. The proportion of the alkylamine used is such that at least one carboxyl group contained in spicrisporic acid or its open ring acid undergoes a neutralization reaction. If there is an unreacted carboxyl group in the neutralized product, the carboxyl group may be left in a free form or reacted with another alkali to form a neutralized salt (e.g., sodium salt). You can also. The stabilizer of the present invention can be directly applied to fine powders such as organic or inorganic pigments and magnetic powders in the form of aqueous solutions, water-containing organic solvent solutions, and organic solvent solutions, or liquids such as cottonseed oil and kerosene. It is added to oil-based resins (eg, maleic anhydride-modified water-based resins, polyamide resins, polyurethane resin solutions, and other general vehicles) in the minimum required amount and used as a stabilizer. The concentration used as a solution is usually 0.01 to 3.0% by weight, preferably 0.1 to 1.5% by weight. The characteristics of the stabilizer of the present invention are as follows. (1) It has an excellent stabilizing effect on various dispersion systems and emulsion systems such as solid fine powder dispersion systems and water or oil emulsion systems. (2) It has good long-lasting effects (lasting for several weeks to several months) (3) It has good compatibility with water, oil, and water-containing organic solvents, so it can be used in a very wide range of applications. (4) A stabilizing effect can be achieved even when several kinds of dispersoids, emulsified oils, and solubilized oils are mixed. (5) It is economical because it is effective at low concentrations. (6) Since it is colorless or pale yellow, it rarely colors objects. (7) It has low toxicity and can be used over a wide range of areas. Next, the present invention will be explained in more detail based on Examples and Reference Examples. Dispersion force and dispersion stability tests for various solid fine powders were conducted as follows. [Dispersion test method] Place 50mg of finely powdered pigment in a 30ml graduated test tube.
Add 20ml of biosoap solution, bring to 30°C, and let stand for 4 hours. Then, shake horizontally with a shaker (400 times for 5 min, amplitude 4 cm) and leave at 30°C for 4 hours.
Next, insert the tip of the pipette up to the 5 ml graduation line from the liquid level in the test tube, and suck up 2 ml from that area.
Transfer to another test tube. Add 25 ml of water to this solution (A) and use an integrating sphere haze meter manufactured by Nippon Denshoku Co., Ltd.
Colorimetric measurements were performed using NDH-20D model (based on JISK-6714), and the dispersion force was determined according to the following formula. Dispersion force = To−Ts/To×100 Where, To: Transmittance of an aqueous solution obtained by adding 25 ml of water to 2 ml of the test solution. Ts: Transmittance of (A) above. [Dispersion stability test] Take 50 mg of solid fine powder in a 30 ml graduated test tube with a stopper, add biosoap solution, and let stand at 30°C for 4 hours. Next, the mixture was shaken horizontally using a shaker (400 times for 5 minutes, amplitude 4 cm), then stood in a test tube and the scale at the sedimentation interface was read every 15 minutes until 240 minutes. I also read the surface after 24 hours. Example 1 1, 0, 0.5, 0.1 and 0.05% aqueous solutions of various alkylamine salts of S-acid and O-acid were prepared,
The dispersion power and dispersion stability after 4 and 24 hours with respect to the hydrophilic pigment Red Garlic and the hydrophobic pigment α-phthalocyanine blue were measured. The results are shown in Tables 1 and 2, respectively. S-1n-HA, O-2C-HA and O- in water
2EHA etc. are hydrophilic pigments (α-
It has excellent dispersibility compared to Fe ₂ O ₃ ). For the hydrophobic pigment α-phthalocyanine blue, S-
In-HA, S-2n-HA, O-2n-HA, O-
It can be seen that 2EHA has excellent dispersibility and dispersion stability. These dispersions were stable for weeks to months. In addition, even when 1 equivalent of NaOH was added to O-1EHA released in water to make it water-soluble, the dispersion force and dispersion stabilizing effect on the red pepper were also great. Further, O-2MEA has extremely high hydrophilicity and is insoluble in organic solvents such as benzene other than methanol, but an aqueous solution showed a dispersing effect on red pepper and α-phthalocyanine blue. Note that the symbols shown in Table 1, Table 2, and the following description have the following meanings. S-1n-HA...S acid (spicrisporic acid) 1
Neutralized n-hexylamine salt S-2n-HA...2-neutralized n-hexylamine salt of S acid S-2c-HA...2-neutralized cyclohexylamine salt of S-acid S-2EHA...2-neutralized ethylhexyl of S acid Amine salt O-1n-HA...1 Neutralization of O acid (open ring acid) n-hexylamine salt O-2n-HA...2 Neutralization of n-hexylamine salt O-2c-HA...O acid 2 Neutralized cyclohexylamine salt O-2EHA...2 Neutralized ethylhexylamine salt of O acid O-2MEA...2 Neutralized monoethalamic acid O-1EHA-1Na...1 Neutralized ethylhexylamine salt of O acid Neutralized with 1 equivalent of NaOH NP-9...Polyoxyethylene (9) nonyl phenyl ether A・OT...Sodium 1,2-bis(2-ethylhexyloxycarbonyl)-1-ethanesulfonate

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[Table] Example 2 In the same manner as in Example 1, γ-iron oxide (γ-
Table 3 shows the dispersion force and dispersion stability test results for Fe ₂ O ₃ ) and magnetite (triiron tetroxide). γ-Fe ₂ O ₃ particles tend to aggregate, but O-
2EHA showed excellent dispersion and dispersion stabilizing effects on γ-Fe ₂ O ₃ . For magnetite, O-2EHA and S-1n-HA showed a dispersion stabilizing effect. The dispersion remained stable for weeks to months. Polyoxyethylene (9) nonyl phenyl ether (NP-9) and 1,2-bis(2-
Sodium ethylhexyloxycarbonyl)-1-ethanesulfonate (aerosol OT, A.OT)
etc. did not exhibit any dispersion or dispersion stabilizing effect.

[Table] Example 3 200mg of γ-Fe ₂ O ₃ was added to 1% O-2EHA aqueous solution.
ml (γ-Fe ₂ O ₃ :O-2EHA=2:1)
It was left to stand for 4 hours. After shaking for 5 minutes using a shaker, the mixture was transferred to a 18 cm diameter tray and air-dried. In this way, the γ-Fe ₂ O ₃ coated with biosoap is preserved in a solid state without coalescence between particles, and if necessary, for example, by adding water, the γ-Fe ₂ O ₃ can be stabilized again. A clear suspension was given. Example 4 O-2EHA is soluble in water and various organic solvents, and in a 50:50 mixed solvent of water and methyl cellosolve.
At a concentration of 0.1%, the dispersibility against red pepper was 42%. Regarding dispersion stability, 4
The scale of the sedimentation interface after hours was 28.1, and after 24 hours it was 19.4. Example 5 Some long chain alkylamine salts of S-acids and O-acids are soluble in various organic solvents. The results of the dispersion stability test are shown in the drawing. The blank is the case where no stabilizer is added to methyl ethyl ketone.
S-1EHA, S-2EHA and O-2DA (2 of O acid
Neutralized dodecylamine salt) etc. showed a dispersion stabilizing effect. Example 6 Add 5 ml of a 1% aqueous solution of O-2EHA and 0.5 ml of kerosene to a 30 ml graduated test tube, shake horizontally with a shaker (5 minutes, 400 times, amplitude 4 cm), and then place in a constant temperature water bath at 95°C. When placed in the container and measuring the time it took for a separated oil layer to form, a slight separated oil layer was formed after 65 minutes, but a cloudy emulsified layer persisted for more than 5 hours. On the other hand, 1% sodium lauryl sulfate (SDS) aqueous solution and 1% polyoxyethylene (15) nonyl phenyl ether (NP-15) aqueous solution both have approx.
The emulsified state was completely destroyed in 15 minutes. Example 7 3 ml of O-2EHA aqueous solution and 7 ml of kerosene were added to a 30 ml graduated test tube, mixed in the same manner as in Example 5, and left to stand at room temperature (25°C) for 24 hours, but the emulsion system was completely stable. It was hot. This emulsion system remained stable even after two months. On the other hand, the emulsification system using 3 ml of 1% aqueous solution of SDS and 2 ml of kerosene was used after 24 hours.
A 2.6 ml aqueous layer was separated, and a 2.1 ml aqueous layer was separated from the emulsion system using 3 ml of a 1% aqueous solution of polyoxyethylene (9) nonyl phenyl ether (NP-9) and 2 ml of kerosene. Example 8 O-
The great dispersion stabilizing effect of an aqueous solution of an acid or a neutralized salt of an S-acid on pigments, and the stabilizing effect of an emulsion system,
It is related to the chemical structure of the positively charged counterion of these neutralized salts and the hydrophilic and lipophilic balance (HLB) of the entire molecule, and the 22-ethylhexylamine salt of O-acid has the greatest stabilizing effect. Comparative Example An experiment was conducted in the same manner as in Example 1, except that a single neutralized sodium salt of S acid (S-1Na) and a double neutralized sodium salt of O acid (O-2Na) were used as the biosoap. As a result, regarding the dispersion of α-phthalocyanine blue, a dispersion force of 5% was obtained for S-1Na and 6% for O-2Na at a biosoap concentration of 0.1%. These dispersion systems are highly unstable;
In either case, the dispersion stability during the 4 hours was 0.

[Brief explanation of drawings]

The drawing is a graph showing the results of the dispersion stability test in Example 5.

Claims (1)

[Claims] 1 Spicrisporic acid (4,5-dicarboxy-4-pentadecanolide) or an alkylamine salt of 3-hydroxy-1,3,4-tetradecanetricarboxylic acid with its lactone ring opened (the alkylamine salt has a cycloalkyl An emulsification and dispersion stabilizer containing amine salts and alkylamine salts having a hydroxyl group as active ingredients.