JP2009126855A - Polyglycidol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surfactant having high affinity to aromatic materials and having excellent emulsification dispersion and solubilization abilities to organic compounds such as an organic pigment. <P>SOLUTION: A polyglycidol compound represented by general formula (I) [L is a 1-5C alkylene group; R is an aryl group (the aryl group may have one or more substituent selected from the group consisting of a 1-18C alkyl group, a 1-18C alkoxy group or a halogen atom); m is an integer of 1-5; and n is an integer of 3-20] is provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polyglycidol compound useful for a surfactant and the like.

As a phenyl ether polyglycidol usable as a surfactant, a water-soluble compound in which a phenyl group is substituted with an alkyl chain having 8 to 18 is known (GB1022878). However, since the hydrophobic part of this compound is an alkyl chain, there is a problem that the affinity to aromatic organic substances is low, and since it has an alkylphenol structure, there is a great concern that it acts as an environmental hormone. Polyglycidol dodecyl ether is also known (Sagitani, H. et.al., JAOCS, Vol.66, pp.146-152, 1989). This compound is produced by linking glycidol one by one. Therefore, there is a problem that the synthesis takes a very long time and is not suitable for industrial application. Accordingly, there is a need to provide surfactants that replace these compounds.
GB1022878 Sagitani, H. et.al., JAOCS, Vol.66, pp.146-152, 1989

  An object of the present invention is to provide a surfactant having high affinity for aromatic substances and having high emulsification dispersion and solubilization ability for organic compositions such as organic pigments. . Another object of the present invention is to provide a surfactant that has no fear of acting as an environmental hormone.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained polyglycidol represented by the following general formula (I) obtained by bonding phenyl ether substituted with an alkylphenyl group to a glycidol chain. The compound has high adsorptivity and affinity for aromatic substances, has high solubilizing ability for organic compositions, and is useful as a surfactant that does not become turbid even when the temperature is raised. I found out. The present invention has been completed based on the above findings.

（式中、LはC₁-C₅アルキレン基を示し、Rはアリール基（該アリール基はC₁-C₁₈アルキル基、C₁-C₁₈アルコキシ基、又はハロゲン原子からなる群から選ばれる1又は2以上の置換基を有していてもよい）を示し、ｍは1〜5の整数を示し（mが2以上の整数を示す場合には、R-L-で表される基はそれぞれ同一でも異なっていてもよい）、nは3〜20の整数を示す）で表されるポリグリシドール化合物が提供される。 That is, according to the present invention, the following general formula (I):

Wherein L represents a C ₁ -C ₅ alkylene group, R is an aryl group (the aryl group is selected from the group consisting of a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₁₈ alkoxy group, or a halogen atom) 1 or 2 or more may be substituted), m represents an integer of 1 to 5 (when m represents an integer of 2 or more, the groups represented by RL- are the same) Or may be different), and n represents an integer of 3 to 20).

According to a preferred embodiment of the above invention, L is represented by —C (R ¹ ) (R ² ) — (wherein R ¹ and R ² each independently represents a hydrogen atom or a C ₁ -C ₄ alkyl group). The above-mentioned polyglycidol compound; L is a group represented by —C (R ¹ ) (R ² ) —, R ¹ is a hydrogen atom, and R ² is a hydrogen atom or a methyl group The polyglycidol compound described above; m is an integer of 1 to 3, preferably 2 or 3, particularly preferably 3; n is an integer of 5 to 18, preferably 8 to 16 Of polyglycidol compounds.

From another aspect, the present invention provides a surfactant comprising the polyglycidol compound represented by the above general formula (I).
Further, according to the present invention, there is provided a dry element having at least an adhesive layer and a porous spreading layer on a water-impermeable support, the dry element comprising a polyglycidol compound represented by the above general formula (I). Provided.

The polyglycidol compound of the present invention has high adsorptivity and affinity for aromatic substances, and has a feature of high solubilizing ability for organic compositions. Moreover, since the polyglycidol compound of this invention does not have an alkylphenol structure or a biphenyl structure, possibility of acting also as an environmental hormone is low.
The polyglycidol compound of the present invention is useful as a surfactant that does not become turbid even when the temperature is raised. In addition to detergents and biochemical surfactants, it can also be used as an oil solubilizer or coating stabilizer. Available.

In the above general formula (I), L represents a C ₁ -C ₅ alkylene group (the above-mentioned carbon number C ₁ -C ₅ represents the number of carbon atoms in the alkylene chain connecting R and the benzene ring). The alkylene group may be linear or branched. The methylene unit constituting L is represented by -C (R ¹ ) (R ² )-(wherein R ¹ and R ² each independently represents a hydrogen atom or a C ₁ -C ₄ alkyl group). A methylene unit is preferable, and an alkylene group containing 1 to 5 methylene units is preferable. In the methylene unit, R ¹ is preferably a hydrogen atom, and R ² is preferably a hydrogen atom or a methyl group. When the alkylene group contains two or more of the above methylene units, these methylene units may be the same or different. More specifically, examples include a methylene group, a methylmethylene group, an ethylene group, a methylethylene group, a propylene group, and a butylene group. The alkylene group represented by L preferably contains one methylene unit, and L is more preferably a group represented by -C (R ¹ ) (R ² )-. In this case, R ¹ is more preferably a hydrogen atom, and R ² is more preferably a hydrogen atom or a methyl group.

R represents an aryl group. As the aryl group, a monocyclic or condensed polycyclic aromatic hydrocarbon group can be used. For example, a phenyl group, a naphthyl group, and the like are preferable, and a phenyl group is most preferable. The aryl group may have one or more substituents selected from the group consisting of a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₁₈ alkoxy group, or a halogen atom. Also good. In this specification, the alkyl part of the alkyl group or the alkoxy group may be linear, branched, cyclic, or a combination thereof. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be used. Examples of the substituent of the aryl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, or an alkyl group. A decyl group etc. can be mentioned, As a halogen atom, a fluorine atom, a chlorine atom, or a bromine atom can be used. When the aryl group has a substituent, the position of the substituent is not particularly limited. When the aryl group has two or more substituents, they may be the same or different.

1 to 5 groups represented by RL- can be present at any position on the benzene ring, and when two or more groups represented by RL- are present, they are the same or different. May be. The number of groups represented by RL- present on the benzene ring is preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3.
n represents an integer of 3 to 20, preferably 5 to 18, and more preferably 8 to 16.

  The polyglycidol compound of the present invention may have one or more asymmetric carbons, and stereoisomers based on the asymmetric carbon (optical isomers or diastereoisomers) may exist. Any stereoisomer in pure form, any mixture of stereoisomers, racemates and the like are all included in the scope of the present invention. Moreover, although the polyglycidol compound of this invention may exist as arbitrary hydrates or solvates, these substances are also included in the scope of the present invention. In addition, the compound of the present invention has m groups represented by RL- at any position on the benzene ring (m is an integer of 1 to 5), and m is the same and m groups on the benzene ring. Any mixture of isomers having different substitution positions of RL, or any mixture of compounds having different m is also encompassed in the scope of the present invention.

  In the polyglycidol compound represented by the general formula (I), the group represented by RL- is an unsubstituted benzyl group, and 1 to 3 of the benzyl groups are present at any position on the benzene ring. It is preferable. It is also preferred that a methyl group is present on the methylene of the benzyl group in one or more of the benzyl groups. For example, the following polyglycidol compounds are preferred (there are no particular restrictions on the bonding position of the substituted benzyl group on the benzene ring).

Particularly preferred compounds (5) to (10) are shown below (in either case, the bonding position of the substituted benzyl group on the benzene ring is not particularly limited).

(式中、R、L、及びmは上記の定義と同義である)で表されるフェノール化合物に触媒の存在下でグリシドールを付加させることによって製造することができる。この反応において、原料化合物であるフェノール化合物とグリシドールとの比率を変えることで、グリシドール鎖長を変えることが可能である。 Examples of the polyglycidol compound represented by the general formula (I) include the following general formula (11):

(Wherein R, L, and m have the same definitions as above) and can be produced by adding glycidol in the presence of a catalyst. In this reaction, it is possible to change the glycidol chain length by changing the ratio of the phenol compound, which is a raw material compound, to glycidol.

  Examples of the catalyst include alkali catalysts such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. Sodium hydroxide, potassium hydroxide, and cesium hydroxide are preferable, and potassium hydroxide is particularly preferable. The amount of the catalyst used is, for example, 0.0001 to 1%, preferably 0.001 to 0.8%, particularly preferably 0.005 to 0.5% based on the raw material compound. The above reaction can usually be carried out without a solvent. The reaction temperature is room temperature to 200 ° C, preferably 50 to 200 ° C, more preferably 100 to 180 ° C. While the reaction time varies depending on the reaction temperature, it is 1 to 150 hours, more preferably 2 to 24 hours, and particularly preferably 2 to 10 hours.

  The target product can be isolated by returning the reaction solution to room temperature after the reaction and neutralizing with an acid, followed by a conventional treatment. Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, and phosphoric acid, and organic acids such as methanesulfonic acid, ethanesulfonic acid, acetic acid, and p-toluenesulfonic acid. Preferably, hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid and acetic acid can be used, and hydrochloric acid, phosphoric acid, methanesulfonic acid and acetic acid are particularly preferably used. If the target product is insoluble in water after neutralization, the target product can be isolated by filtration. When the target product has a high viscosity, water can be added to obtain the target product in the form of an aqueous solution. The polyglycidol compound of the present invention may be produced as a mixture of compounds having different n, and the mixture can be used for various applications as it is.

  The polyglycidol compound of the present invention can be used as a surfactant, an emulsion polymerization emulsifier, a metal processing emulsifier, a cosmetic emulsifier, a paint emulsifier, an agrochemical emulsifier, a resin emulsifier, a wax emulsifier, a pigment dispersant. It can also be used for solubilizers such as fragrances, household detergents for clothes and dishes, industrial detergents such as machine metal detergents, penetrants, wetting agents, antifoaming agents and the like. Furthermore, it can also be used for protein solubilizers, lipid solubilizers, blocking agents and the like in the biochemical field.

  One of the utilization forms of the polyglycidol of the present invention is a dry analytical element containing the polyglycidol of the present invention. The dry analytical element is an element having at least one adhesive layer and a porous spreading layer on a water-impermeable support. The porous layer may be either fibrous or non-fibrous, and functions as a spreading layer for a liquid sample, and is preferably a layer having a liquid metering action. The liquid metering action is an action that spreads the liquid sample spotted and supplied to the surface of the layer at a substantially constant rate per unit area in the surface direction of the layer without substantially uneven distribution of the components contained therein. It is. In the spreading layer, in order to adjust the spreading area, the spreading speed, etc., the hydrophilic high properties described in JP-A-60-222770, JP-A-63-119397, JP-A-62-182652 are disclosed. A molecule or a surfactant can be blended, and the polyglycidol compound of the present invention can be blended as a surfactant.

The fibrous porous layer is preferably made of polyester fiber, as typified by JP-A-55-164356, JP-A-57-66359, JP-A-60-222769, and the like. The non-fibrous porous layer is preferably an organic polymer such as polysulfonic acid.
The adhesive layer is a layer having a function of adhering the water-impermeable support and the porous layer, and gelatin and derivatives thereof (eg, phthalated gelatin), cellulose derivatives (eg, hydroxypropylcellulose), agarose Hydrophilic polymers such as acrylamide polymer, methacrylamide polymer, acrylamide or copolymers of methacrylamide and various vinyl monomers can be used.

An aqueous solution containing a hydrophilic polymer is uniformly applied by a known method, and a known method can be used as the application method. For coating, for example, dip coating, extrusion coating, doctor coating, hopper coating, curtain coating and the like can be appropriately selected and used.
The hydrophilic polymer can contain the polyglycidol compound of the present invention. The main effect is to lower the surface tension and increase the coating property, but it is not limited to this action.

  Although a porous layer can be applied on the adhesive layer, it is preferable to laminate a cloth or a porous film supplied in advance as a knitted fabric. As described in JP-A-55-164356, the laminating method involves uniformly moistening the surface of the adhesive layer containing a hydrophilic polymer with water, and then overlaying a cloth or porous film thereon. It can be made to adhere by applying lightly and almost uniformly pressure. The thickness of the adhesive layer is preferably 0.5 to 50 μm, more preferably 1 to 20 μm.

Preferred materials for the light-transmitting support are cellulose ethers such as polyethylene terephthalate, polystyrene, and cellulose triacetate. In order to firmly adhere the water-absorbing layer, the detection layer, the substantially non-porous reagent layer, etc. of the hydrophilic layer to the support, an undercoat layer can be usually provided on the support or subjected to a hydrophilic treatment. . The thickness of the support is not particularly limited, but is preferably 10 to 1000 μm, and more preferably 300 to 800 μm. In the case of a light-transmissive support, the final detection may be performed on either the support side or the porous layer side.
If necessary, a stabilizer, a pH buffer, a cross-linking agent (hardener or curing agent), a surfactant, a polymer, and the like can be contained, and these can be contained in the adhesive layer or the porous layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, the scope of the present invention is not limited to the following Example.
In the following Examples, the molecular weight was measured by MALDI-MS, the surface tension was measured with a 0.1% by mass aqueous solution, and the cloud point was measured with a 1% surfactant-10% sodium sulfate aqueous solution. HLB was calculated from an organic conceptual diagram. The reaction was carried out in a Pyrex (registered trademark) flask equipped with a stirrer and a condenser.

Example 1
1-1) TBG-14
Tribenzylphenol (TBP, (C ₆ H ₅ -CH ₂ ) ₃ -C ₆ H ₃ -OH, manufactured by Sanko Chemical Co., Ltd., including tri-substituted compounds as well as dibenzylphenol, etc.) Potassium was added and heated to 120 ° C. while mixing under a nitrogen atmosphere. While maintaining the temperature at 120 ± 5 ° C., 259 g (about 14 equivalents to TBP) glycidol (manufactured by Wako Pure Chemical Industries) was slowly added dropwise. The mixture was further aged with stirring for 3.5 hours to obtain the target product TBG-14 (yield 345 g). This compound had a molecular weight of 586 to 1325 (n = 3 to 13) and a hydroxyl value of 592.2 mgKOH / mg. The HLB was 13.3, the cloud point was> 90 ° C., and the surface tension (0.1 mass% aqueous solution) was 44.8 mN / m.

1-2) TBG-10
185 g of glycidol (about 10 equivalents to TBP) and 0.8 g of potassium hydroxide were added to 86 g of TBP and synthesized in the same manner as described above to obtain 271 g of TBG-10. This compound had a molecular weight of 586 to 1473 (n = 3 to 15), a hydroxyl value of 556.3 mgKOH / mg, an HLB of 11.9, a cloud point of> 90 ° C., and a surface tension of 44.1 mN / m.

1-3) TBG-12
Synthesis was performed in the same manner as described above by adding 222 g of glycidol (about 12 equivalents to TBP) and 0.9 g of potassium hydroxide to 86 g of TBP, to obtain 308 g of TBG-12. This compound had a molecular weight of 586 to 1104 (n = 3 to 10), a hydroxyl value of 573.7 mgKOH / mg, HLB of 12.7, a cloud point of> 90 ° C., and a surface tension of 44.2 mN / m.

1-4) TBG-16
249 g of glycidol (about 16 equivalents to TBP) and 1.0 g of potassium hydroxide were added to 72 g of TBP and synthesized in the same manner as above to obtain 321 g of TBG-16. This compound had a molecular weight of 586 to 1548 (n = 3 to 16), a hydroxyl value of 615.0 mgKOH / mg, an HLB of 13.9, a cloud point of> 90 ° C., and a surface tension of 44.7 mN / m.

Example 2
2-1) DSG-12
Add 0.9 g of potassium hydroxide to 76 g of distyrylphenol (DSP, [C ₆ H ₅ -CH (CH ₃ )] ₂ -C ₆ H ₄ -OH, manufactured by Sanko Chemical Co., Ltd.) and mix under nitrogen atmosphere While heating to 120 ° C. While maintaining a temperature of 120 ± 5 ° C., 222 g (about 12 equivalents to DSP) of glycidol (manufactured by Wako Pure Chemical Industries) was slowly added dropwise. The mixture was further aged with stirring for 3.5 hours to obtain the desired product DSG-12 (298 g). This compound had a molecular weight of 524 to 1042 (n = 3 to 13), a hydroxyl value of 602.1 mgKOH / mg, an HLB of 13.7, a cloud point of> 90 ° C., and a surface tension of 40.1 mN / m.

2-2) DSG-10
176 g of glycidol (about 10 equivalents to DSP) and 0.8 g of potassium hydroxide were added to 76 g of DSP and synthesized in the same manner as described above to obtain 261 g of DSG-10. This compound had a molecular weight of 524 to 1412 (n = 3 to 15), a hydroxyl value of 583.1 mgKOH / mg, an HLB of 12.9, a cloud point of> 90 ° C., and a surface tension of 39.7 mN / m.

2-3) DSG-14
249 g of glycidol (about 14 equivalents to DSP) and 1.0 g of potassium hydroxide were added to 73 g of DSP and synthesized in the same manner as described above to obtain 322 g of DSG-14. This compound had a molecular weight of 524 to 1338 (n = 3 to 14), a hydroxyl value of 620.8 mgKOH / mg, an HLB of 14.3, a cloud point of> 90 ° C., and a surface tension of 40.3 mN / m.

Example 3
3-1) MSG-8
Add 1.0 g of potassium hydroxide to 86 g of monostyrylphenol (MSP, C ₆ H ₅ —CH (CH ₃ ) —C ₆ H ₅ —OH, manufactured by Sanko Chemical Co., Ltd.) and mix while mixing in a nitrogen atmosphere. Warmed to ° C. While maintaining a temperature of 120 ± 5 ° C., 237 g (about 8 equivalents to MSP) of glycidol (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added dropwise. The mixture was further aged with stirring for 3.5 hours to obtain the desired product MSG-8 (323 g). This target product had a molecular weight of 420 to 1160 (n = 3 to 13), a hydroxyl value of 611.1 mgKOH / mg, an HLB of 14.3, a cloud point of> 90 ° C., and a surface tension of 39.7 mN / m.
3-2) MSG-10
296 g of glycidol (about 10 equivalents to MSP) and 1.1 g of potassium hydroxide were added to 86 g of MSP to obtain 382 g of MSG-10 in the same manner as described above. This compound had a molecular weight of 420 to 1234 (n = 3 to 14), a hydroxyl value of 630.4 mgKOH / mg, an HLB of 15.1, a cloud point of> 90 ° C., and a surface tension of 39.8 mN / m.

Example 4: Dry analytical element using the compound of the present invention A gelatin aqueous solution was coated on a 180 µm polyethylene terephthalate colorless and transparent smooth film coated with gelatin so that the thickness after drying was 14 µm and dried. Next, water was supplied over the entire surface at a supply rate of about 30 g / m ² and moistened, and then a tricot knitted fabric knitted with 36 gauge polyester spun yarn equivalent to 50 denier was laminated under light pressure. , Dried. Next, an aqueous solution having the following composition was applied and dried on the cloth.
MES buffer (pH 6.6) 84 mmol / m ²
Cholesterol esterase (derived from Schizophyllum commune) 1.8 kU / m ²
Cholesterol oxidase (derived from Pseudomonas sp.) 4.0 kU / m ²
Peroxidase 30 kU / m ²
4-Aminoantipyrine (Wako Pure Chemical Industries, Ltd.) 0.4 g / m ²
DAOS (Dojindo Laboratories) 0.4 g / m ²
Polyglycol triphenyl phenyl ether (n = 12) 2.0 g / m ²
Pluronic F-88 (Asahi Denka) 1.3 g / m ²
Dextran sulfate (5000,000) (Wako Pure Chemical Industries, Ltd.) 0.7 g / m ²
Magnesium chloride hexahydrate (Wako Pure Chemical Industries, Ltd.) 4.6 g / m ²

  Using a sample prepared by adjusting a purified HDL or LDL product to a cholesterol concentration of 100 mg / dL and a 7% HSA aqueous solution as a sample, 10 μL of the sample was spotted on the dry analytical element, and then incubated at 37 ° C. for 6 minutes. . The state of color development at 600 nm at this time was measured. As a result, as shown in FIG. 1, although HDL developed a complete color in about 6 minutes, the ODL of LDL hardly increased and it was confirmed that this element has specificity for HDL.

It is the figure which showed the result of having measured HDL or LDL using the dry analytical element containing the polyglycidol compound of this invention.

Claims (7)

The following general formula (I):

Wherein L represents a C ₁ -C ₅ alkylene group, R is an aryl group (the aryl group is selected from the group consisting of a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₁₈ alkoxy group, or a halogen atom) 1 or 2 or more may be substituted), m represents an integer of 1 to 5 (when m represents an integer of 2 or more, the groups represented by RL- are the same) Or n may be an integer of 3 to 20). L is a group represented by -C (R ¹ ) (R ² )-(wherein R ¹ and R ² each independently represents a hydrogen atom or a C ₁ -C ₄ alkyl group). The polyglycidol compound described. The polyglycidol compound according to claim 2, wherein R ¹ is a hydrogen atom, and R ² is a hydrogen atom or a methyl group. The polyglycidol compound according to any one of claims 1 to 3, wherein m is an integer of 1 to 3. The polyglycidol compound according to any one of claims 1 to 4, wherein n is an integer of 5 to 18. A surfactant comprising the polyglycidol compound according to any one of claims 1 to 5. A dry element having at least an adhesive layer and a porous spreading layer on a water-impermeable support, the dry element comprising the polyglycidol compound according to any one of claims 1 to 5.

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