JP3934167B2 - Surface active compound - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a novel surfactant compound, and in particular, to a surfactant having a low critical micelle concentration in an aqueous solution, excellent surface tension reducing ability, and strong adsorptive power to a hydrophobic surface.
The present invention also relates to a surfactant having excellent dispersibility, emulsifiability, and stability as a dispersant for a hydrophobic organic compound.
[0002]
[Prior art]
As an index representing the adsorption force or cohesion force of a surfactant, it is generally represented using a critical micelle concentration (CMC) or surface tension (γmin).
As a measure for improving the adsorptive power of a surfactant (reducing CMC and γmin), there is known a method of making a plurality of hydrophobic chains of surfactant molecules described in German Patent No. 1932299 and the like.
[0003]
In the production of fine particle dispersions, surfactants have been a very large governing factor in emulsification and dispersion, such as the size and stability of the resulting particles vary greatly depending on the type and amount of surfactant. Searching for surfactants for fine dispersion has been carried out and various emulsion stabilizers useful in silver halide photographic systems have been found. Examples of these emulsion stabilizers are described in JP-A Nos. 51-129229, 60-20251, US Pat. No. 3,428,456, US Pat. No. 3,963,688, and the like. However, a surfactant that gives a fine dispersion stably in a small amount with respect to a wide range of compounds has not been found.
Further, the dispersion prepared for the photographic light-sensitive material is refrigerated or stored at room temperature as necessary during the period from preparation to production. At this time, it is often a big problem that the deterioration of the dispersion such as oil separation and crystal precipitation proceeds with time. In this case, since the stability over time varies depending on the type and amount of the surfactant used, it has been desired to develop a surfactant having excellent storage stability over time of the dispersion.
Accordingly, in the field of photographic light-sensitive materials, it has been desired to develop a surfactant that gives a fine dispersion stably in a small amount with respect to a wide range of compounds. Here, it is not difficult to understand that the function required for the surfactant is synonymous with the improvement of the associating force and adsorption force of the active agent generally required for the above surfactants.
[0004]
[Problems to be solved by the invention]
The first object of the present invention is to provide a novel surfactant compound having a low critical micelle concentration and excellent surface tension reducing ability.
The second object of the present invention is to provide a novel surface active compound having excellent adsorption ability to a hydrophobic surface.
The third object of the present invention is to provide a novel surface active compound capable of stably providing fine dispersion particles in a small amount.
A fourth object of the present invention is to provide a novel surface active compound that can provide dispersion particles having excellent stability over time.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following.
(1) A surface active compound represented by the following general formula [ II ].
General formula [ II ]
[0008]
[Chemical formula 5]
[0009]
In the formula, R ₂ represents n-C ₁₂ H ₂₅ — , and L ₂ represents an alkylene group having 2 to 8 carbon atoms. Q represents a single bond or an oxygen atom. M represents a counter cation. m2 represents an integer value of 1 to 3.
(2) The surface active compound as described in (1 ) above, wherein m2 is 1 or 2.
(3) A surface active compound represented by the following general formula [III].
General formula [III]
[0010]
[Chemical 6]
[0011]
In the formula, n represents an integer of 2 to 5. Q represents a single bond or an oxygen atom. M represents a counter cation. m3 Represents 1 or 2 .
(4) The surfactant compound according to any one of (1) to (3) , wherein the Q is a single bond.
(5) The surface active compound according to any one of (1) to (4) , wherein the surface active compound is used for dispersing a hydrophobic organic compound .
Further explaining the present invention in detail, in the above general formula [II], Q can be arbitrarily selected from a single bond or an oxygen atom.
[0012]
M represents a counter cation, and preferably represents an alkali metal ion (eg, lithium ion, sodium ion, potassium ion, etc.), an alkaline earth metal ion (eg, magnesium ion, calcium ion, etc.) and an ammonium ion. Particularly preferred are sodium ion and potassium ion.
In the general formula [II], R ₂ represents nC ₁₂ H ₂₅ —.
L ₂ represents an alkylene group of from 2 to 8 carbon atoms (ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc.), of these, carbon An alkylene group of 2 to 6 (ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc.) is particularly preferred.
[0013]
m2 Represents an integer value of 1 to 3, preferably 1 or 2.
In the general formula [III ] , n is an integer of 2 to 5, particularly preferably an integer of 2 to 4. Q and M represent a counter cation. Q and M are the same as defined in the general formula [ II ]. m3 represents an integer value of 1 or 2, and is preferably 1. Specific examples of preferable surface active compounds used in the present invention are illustrated below, but the present invention is not limited to these specific examples.
[0014]
[Chemical 7]
[0015]
[Chemical 8]
[0016]
[Chemical 9]
[0017]
[Chemical Formula 10]
[0018]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples as long as the gist of the invention is not exceeded.
[0019]
Synthesis Example 1 Synthesis of Compound PW-1 1) Synthesis of di-dodecyl phosphoryl chloride Into a 1 l three-necked flask equipped with a condenser and a stirrer were placed 223.6 g (1.2 mol) of dodecyl alcohol and 500 ml of methylene chloride, and the mixture was stirred. While cooling with ice, 55.8 g (0.6 mol) of phosphorus oxychloride was added dropwise over 30 minutes so that the internal temperature did not exceed 10 ° C., and the mixture was stirred as such for 20 minutes after completion of the addition. The reaction solution was heated to room temperature, heated for 1 hour under reduced pressure of 80 to 120 mmHg, further raised to 50 ° C., and reacted for 3 hours under normal pressure. The reaction solution was cooled to room temperature to obtain 246.6 g of a transparent liquid (yield 87.6%).
[0020]
2) Synthesis of 2-hydroxyethyl-di-dodecyl phosphate Into a 200 ml three-necked flask equipped with a condenser and a stirrer, was charged 12.48 g (0.2 mol) of ethylene glycol and 15.2 g (0.15 mol) of triethylamine. While stirring under water cooling, 44.9 g (0.099 mol) of di-dodecyl phosphoryl chloride synthesized above was added dropwise over 30 minutes so that the internal temperature did not exceed 30 ° C., and the mixture was stirred for 1 hour after the completion of the addition. did. The reaction solution was heated to 50 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, 200 ml of ethyl acetate was added, the precipitate was filtered, the filtrate was concentrated under reduced pressure, and separated and purified by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane = 2/1). As a result, 21.9 g (yield: 46.3%) of the target compound was obtained.
[0021]
3) Synthesis of Compound PW-1 Into a 200 ml three-necked flask equipped with a cooling tube and a stirrer, 19.1 g (40 mmol) of 2-hydroxyethyl-di-dodecyl phosphate synthesized above and 10 ml of chloroform were placed, and ice-cooled. Under stirring, 9.3 g (80 mmol) of chlorosulfonic acid was added dropwise over 30 minutes so that the internal temperature did not exceed 15 ° C., and the mixture was stirred as it was at room temperature for 2 hours after completion of the dropwise addition. To this reaction solution, 20 ml of water was slowly added, and 50 ml of ethanol was further added to form a solution, and then the pH was adjusted to 7.1 with a 1N sodium hydroxide solution. The operation of adding 300 ml of toluene and azeotropic dehydration to this reaction solution was repeated 5 times, and then the solution was concentrated once, dissolved by adding 300 ml of ethyl acetate, and dehydrated by standing overnight using 80 g of anhydrous sodium sulfate. Insoluble matters were filtered off from this solution, and the filtrate was concentrated under reduced pressure to obtain 122.9 g (yield: 98.5%) of the desired compound PW of the present invention in the form of a white powder compound. The compound was identified by IR spectrum, 1H-NMR spectrum and elemental analysis.
[0022]
¹ H-NMR (CDCL ₃ , δ) 0.8 to 1.1 (hydrocarbon chain CH ₃ , 6H), 1, 2 to 1.5 (hydrocarbon chain CH ₂ , 40H), 3.8 to 4. 0 (hydrocarbon chain —CH ₂ O—, 4H), 4.0 to 4.4 (tetramethylene chain —CH ₂ O—, 4H)
[0023]
Synthesis Example 2 Synthesis of Compound PW-3 1) Synthesis of di-dodecyl phosphoryl chloride Di-dodecyl phosphoryl chloride was synthesized according to the same formulation as that of Synthesis Example 1.
2) Synthesis of 4-hydroxybutyl-di-dodecyl phosphate Into a 200 ml three-necked flask equipped with a condenser and a stirrer, 18.8 g (0.2 mol) of 1,4-butanediol and 15.2 g (0.2 mol) of triethylamine were added. 15 mol) was added, and 44.9 g (0.099 mol) of di-dodecyl phosphoryl chloride synthesized above was added dropwise over 30 minutes while stirring under water cooling so that the internal temperature did not exceed 30 ° C. The mixture was stirred for 1 hour. The reaction solution was heated to 50 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, 200 ml of ethyl acetate was added, the precipitate was filtered, the filtrate was concentrated under reduced pressure, and separated and purified by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane = 2/1). As a result, 21.1 g (yield 42.1%) of the target compound was obtained.
[0024]
3) Synthesis of Compound PW-3 Into a 200 ml three-necked flask equipped with a condenser tube and a stirrer, 20.3 g (40 mmol) of 4-hydroxybutyl-di-dodecyl phosphate synthesized above and 10 ml of chloroform were placed, and ice-cooled. Under stirring, 9.3 g (80 mmol) of chlorosulfonic acid was added dropwise over 30 minutes so that the internal temperature did not exceed 15 ° C. After completion of the addition, 20 ml of water was slowly added to the reaction solution, and 50 ml of ethanol was further added. Was added to make a homogeneous solution, and the pH was adjusted to 7.1 with 1N sodium hydroxide solution. The operation of adding 300 ml of toluene and azeotropic dehydration to this reaction solution was repeated 5 times, and then the solution was concentrated once, dissolved by adding 300 ml of ethyl acetate, and dehydrated by standing overnight using 80 g of anhydrous sodium sulfate. Insoluble matters were filtered off from this solution, and the filtrate was concentrated under reduced pressure to obtain 23.6 g (yield 97.1%) of the desired compound PW-3 of the present invention in the form of a waxy compound. The compound was identified by IR spectrum, ¹ H-NMR spectrum and elemental analysis.
[0025]
¹ H-NMR (CDCL ₃ , δ) 0.8 to 1.1 (hydrocarbon chain CH ₃ , 6H), 1, 2 to 1.5 (hydrocarbon chain CH ₂ , 40H), 1.7 to 1. 9 (tetramethylene chain CH ₂ , 4H), 3.8 to 4.0 (hydrocarbon chain —CH ₂ O—, 4H), 4.0 to 4.4 (tetramethylene chain —CH ₂ O—, 4H)
[0026]
Synthesis Example 3 Synthesis of Compound PW-7 1) Synthesis of Di-dodecyl phosphoryl chloride Di-dodecyl phosphoryl chloride was synthesized according to the same formulation as in Synthesis Example 1 above.
2) Synthesis of sodium-di-dodecyl phosphate 44.9 g (0.099 mol) of di-dodecyl phosphoryl chloride synthesized above was placed in a 200 ml three-necked flask equipped with a condenser and a stirrer, and the internal temperature exceeded 30 ° C. Then, 500 ml of distilled water was added dropwise over 30 minutes, and the mixture was stirred for 3 hours after completion of the addition. The reaction solution was filtered to take out a white waxy solid, washed with 1 liter of ice-cold water, and then air-dried overnight. The obtained solid and 200 ml of methanol were placed in a 1000 ml three-necked flask equipped with a condenser and a stirrer, dissolved by heating to 40 ° C., and then a 28% methanol solution of sodium methylate was added dropwise over 15 minutes. The mixture was heated to 0 ° C. and stirred for 30 minutes. The filtrate obtained by hot filtration of this solution was added to 8 liters of acetone for crystallization. The precipitate was collected by filtration and dried under reduced pressure to obtain 30.1 g (yield 66.6%) of the target compound.
[0027]
3) Synthesis of Compound PW-7 A 200 ml three-necked flask equipped with a condenser tube and a stirrer was charged with 13.7 g (30 mmol) of the sodium-di-dodecyl phosphate synthesized above, 30 ml of toluene and 30 ml of dimethylacetamide at room temperature. While stirring, 4.1 g (33 mmol) of butane sultone was added dropwise over 10 minutes. After completion of the addition, the temperature was raised to 150 ° C. and stirred for 6 hours. The reaction solution was cooled to room temperature and added to 300 ml of acetone, and then the precipitate was collected by filtration to obtain 13.8 g (yield 77.4%) of the target compound PW-7 as a pale yellow solid. Obtained in shape. The compound was identified by IR spectrum, ¹ H-NMR spectrum and elemental analysis.
[0028]
Other compounds of the present invention can also be easily synthesized by this synthesis example or a method similar thereto.
[0029]
Example 1 Surfactant CMC, γ _min
The adsorptive power of the surfactant of the present invention and the comparative compound to CMC, γ _min and hydrophobic surface was measured by the following method, and the results shown in Table 1 were obtained.
Measurement of CMC and γ _{min Using} a surface tension meter A3 manufactured by Kyowa Science Co., Ltd., the surface tension of each surfactant at 25 ° C. was measured at a concentration of 1 to 10 × ^{4 −4} wt%, It was determined from a graph plotting surface tension against concentration.
Measurement of adsorption force on hydrophobic surface Amberlite XAD-2000 (crosslinked polystyrene resin having a nonpolar hydrophobic surface with a specific surface area of 620 m ² / g) commercially available from Organo Co., Ltd. at an interface of 1 × 10 ⁻² mol / liter After adding to 100 ml of the activator solution and stirring at 25 ° C. for 10 hours, this was removed by filtration, and the amount of the surfactant in the solution was quantified by a liquid chromatogram. The amount of the surfactant adsorbed from the concentration of the activator at this time and decreased from the solution was calculated, and calculated and evaluated as the amount adsorbed per 1 g of the added polystyrene resin.
[0030]
[Table 1]
[0031]
Embedded image
[0032]
As can be seen from Table 1, the CMC and γ _min of the surfactant of the present invention are characterized by being able to take a very low value at the same time as compared with the conventional surfactant.
Furthermore, it can be seen that the surfactant of the present invention has a higher adsorptivity to a hydrophobic surface than a conventional surfactant.
[0033]
Example 2 Emulsifying power of surfactant: Dispersion of photographic coupler The following yellow coloring coupler was stirred and emulsified according to the following formulation to obtain dispersions 1 to 13 .
Liquid I: Gelatin solution (10%) 67g
Liquid II: 8 g of the following coupler C-1
15 ml of ethyl acetate
Surfactant 0.35g
Emulsification was dissolved mixed at 55 ° C. The solution I and solution II to obtain an emulsion is 3 times the line emulsification of 2 min at 17000rpm at homoblender.
[0034]
Embedded image
[0035]
The surfactant was dispersed for the comparative compound and the compound of the present invention as shown in Table 2, and the results of the dispersion particle size determined by the light scattering method using a Master Sizer manufactured by Malvern are also shown in Table 2.
Table 2 shows that the compound of the present invention can make the particle size finer even with the same amount of emulsifier. In particular, it can be seen that the emulsifiability is remarkably improved as compared with the conventional phosphate ester type surfactant of the comparative example.
[0036]
[Table 2]
[0037]
Example 3 Stability of emulsion over time After the emulsion prepared in Example 2 was refrigerated at 5 ° C. for 3 weeks, it was dissolved by heating at 40 ° C. and diluted with water, and the presence or absence of insoluble matter was confirmed.
The evaluation was conducted silently, and was classified into 5 grades in order from the evaluation with many insolubles x to ○ with no insolubles, and made x, ▲, Δ, ○, ◎.
The results are shown in Table 2 as in Example 2.
It can be seen that many of the compounds of the present invention are more easily dissolved than the comparative example sodium dodecylbenzenesulfonate having high emulsifying performance, and are excellent in stability over time of the emulsion due to refrigeration.
[0038]
【The invention's effect】
By using the compound of the present invention, it has become possible to obtain an aqueous solution having an extremely low surface tension with a very small amount of use. Furthermore, by using the compound of the present invention, an extremely fine emulsified dispersion can be stably obtained with a small amount of use.

Claims (5)

A surface active compound represented by the following general formula [II].
General formula [II]
In the formula, R ₂ represents nC ₁₂ H ₂₅ — , and L ₂ represents an alkylene group having 2 to 8 carbon atoms. Q represents a single bond or an oxygen atom. M represents a counter cation. m2 represents an integer value of 1 to 3. The surface active compound according to claim 1, wherein the m2 is 1 or 2. A surface active compound represented by the following general formula [III].
General formula [III]
In the formula, n represents an integer of 2 to 5. Q represents a single bond or an oxygen atom. M represents a counter cation. m3 Represents 1 or 2. The surface active compound according to any one of claims 1 to 3 , wherein the Q is a single bond. The surfactant compound, characterized in that it is used to disperse the hydrophobic organic compound, surface-active compounds according to any one of claims 1-4.