JP2002301353A - Surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surfactant containing no phenylether group such as nonylphenyl group which are believed to be adversely influential on the environment, and having almost equal performance to that of a reactive surfactant containing phenylether group. SOLUTION: The surfactant is expressed by general by formula (1). In formula (1), R<1> represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, each of AO and AO' represents a 2-4C oxyalkylene group, L represents a group expressed by general formula (2), (z) is a number from 1 to 10, X represents hydrogen atom or an ionic hydrophilic group, (m) is a number from 0 to 1,000 and (n) is a number from 0 to 1,000. In formula (2), each of R<2> and R<3> represents hydrogen atom or methyl group, (x) is a number from 0 to 12, and (y) is a number of 0 or 1. The surfactant is used to prepare an emulsifier for emulsion polymerization, a dispersant for suspension polymerization and a resin modifying agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive surfactant having a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, and a specific use thereof.

[0002]

2. Description of the Related Art Surfactants have a wide range of properties such as emulsification, dispersion, washing, wetting and foaming. Utilizing these various properties, it has been used in various fields such as fiber, paper, rubber, plastic, metal, paint, pigment, civil engineering, and the like. In particular, recently, the trend toward higher performance of end products using surfactants has been active,
Accordingly, a secondary disadvantage of the surfactant has been pointed out.

[0003] For example, surfactants are contained in products such as paints, printing inks and adhesives at the time of production of the products or as components which are indispensable in terms of product stabilization and workability. ing. When products containing such surfactants are actually used in operations such as coating, printing or bonding and sticking, surfactants are not necessary in the first place. , Printing surface,
In many cases, the performance such as the water resistance and oil resistance of the adhesive film is deteriorated.

[0004] Further, an emulsifier for emulsion polymerization used when producing a polymer by emulsion polymerization not only participates in a polymerization initiation reaction or a formation reaction, but also has a mechanical stability, a chemical stability, It also contributes to freezing stability and storage stability, etc., and also to emulsion physical properties such as emulsion particle size, viscosity and foaming properties, and film physical properties such as water resistance, weather resistance, adhesion and heat resistance when formed into a film. Is also known to have a significant effect. As a problem in this case, the foaming of the emulsion-polymerized emulsion is increased by the existing emulsifier, adhesiveness, water resistance,
It has been pointed out that film properties such as weather resistance and heat resistance deteriorate. In addition, similar phenomena due to a dispersant for suspension polymerization have been pointed out in polymers produced by suspension polymerization.

[0005] These problems result from the fact that the surfactant remains free in the polymer. As a method of reducing free surfactant, a surfactant which reacts with a polymer at the time of polymerization or molding to be bonded and does not remain free in a polymer, that is, a reactive surfactant (also referred to as a polymerizable surfactant). Say) has been developed.

[0006] Many structures have been proposed for reactive surfactants.
JP-B-49-46291 discloses a sulfosuccinate having a hydrocarbon group;
JP, JP-A-63-23725, JP-A-4-5
JP-A No. 0202 and JP-A-4-50204 disclose an alkoxylate of a hydrocarbon-substituted phenol having an allyl group or a propenyl group;
JP-A-62-115 discloses an alkoxylate of a glycerin derivative having a hydrocarbon group or an acyl group;
No. 34, cross-linking with formaldehyde (substitution)
Phenol derivatives; JP-A-63-319035, JP-A-4-50204, and the like include, as a hydrophobic group, an alkyl group derived from an α-olefin oxide. In the above-mentioned conventional technology, the hydrocarbon group includes an alkyl group, an alkenyl group, an aryl group and the like.

Among such reactive surfactants, those having a phenyl ether group as a hydrophobic group are widely used because of their excellent emulsifiability, dispersibility, polymerization stability and the like. However, in recent years, concerns have arisen about the so-called endocrine problem that nonylphenol may exert a pseudohormonal effect on living organisms and disrupt the endocrine system. Even alternatives are being sought. However, a reactive surfactant having a hydrophobic group other than the phenyl ether group, for example, a normal alkyl group, an alkenyl group, or the like, has a disadvantage that the performance is lower than a reactive surfactant having a phenyl ether group.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned conventional problems and to contain a phenyl ether group such as a nonylphenyl group which is considered to have a large effect on the environment. An object of the present invention is to provide a surfactant having the same performance as a reactive surfactant containing a group.

[0009]

Means for Solving the Problems Accordingly, the present inventors diligently studied and found that a reactive surfactant having a branched aliphatic hydrocarbon group or a branched aliphatic acyl group as a hydrophobic group is a (substituted) phenyl ether. The present inventors have found that they have the same performance as a reactive surfactant having a group, and that they have almost no adverse effect on the environment. That is, the present invention provides the following general formula (1) [Wherein, R ¹ represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, and AO and A
O ′ represents an oxyalkylene group having 2 to 4 carbon atoms;
Represents a group represented by the following general formula (2), and z represents 1
Represents a number of 10 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number of 0 to 1,000, and n represents 0 to 1,000.
Represents a number of 1,000. ) (Wherein R ² and R ³ represent a hydrogen atom or a methyl group,
x represents a number of 0 to 12, and y represents a number of 0 or 1. )]. Further, the present invention is an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, or a resin modifier comprising a surfactant represented by the general formula (1).

[0010]

Next, the present invention will be described in detail with reference to embodiments of the present invention. In the general formula (1),
R ¹ represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group. A branched aliphatic hydrocarbon group or a secondary aliphatic hydrocarbon group is a residue of a corresponding branched aliphatic alcohol or a residue of a secondary aliphatic alcohol.

Examples of such a branched aliphatic alcohol include isobutyl alcohol, tertiary butyl alcohol, isopentyl alcohol, neopentyl alcohol, tertiary pentyl alcohol, isohexanol, 2-methylpentanol, isoheptanol, and the like.
Isooctanol, 2-ethylhexanol, isononanol, 3,4,4-trimethylhexanol, isodecanol, 2-propylheptanol, isoundecanol, isododecanol, 2-butyloctanol, isotridecanol, isotetradecanol , Isomyristyl alcohol, 2-pentylnonanol, isopentadecanol, isohexadecanol, isopalmityl alcohol, 2-hexyldecanol, isoheptadecanol, isooctadecanol, isostearyl alcohol, 2-heptylundecanol , Isononadecanol, isoeicosanol, 2-octyldodecanol,
2-nonyltridecanol, 2-decyltetradecanol, 2-undecylpentadecanol, 2-dodecylhexadecanol, 2-tridecylheptadecanol, 2
-Tetradecyl octadecanol, 2-pentadecyl nonadecanol, 2-hexadecyl eicosanol, 1,
1-dimethyl-2-propenol, 3-methyl-3-butenol, 3-methyl-2-butenol, isohexenol, isoheptenol, isooctenol, isononenol, isodecenol, isoundecenol, isododecenol, isotridecenol, isotetra Examples include decenol, isopentadecenol, isohexadecenol, isoheptadecenol, isooctadecenol, isooleyl alcohol, isononadecenol, and isoeicosenol.

[0012] Such secondary aliphatic alcohols include, for example, isopropanol, 2-butanol,
2-octanol, secondary decanol, secondary undecanol, secondary dodecanol, secondary tridecanol, isotridecanol, secondary tetradecanol, secondary pentadecanol, secondary hexadecanol, secondary heptadecanol,
Secondary octadecanol and the like can be mentioned.

A branched aliphatic acyl group is a residue of a corresponding branched fatty acid. Examples of branched fatty acids include, for example, isobutanoic acid, isopentanoic acid, neopentanoic acid, isohexanoic acid, 2-methylpentanoic acid, neohexanoic acid, isoheptanoic acid, neoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, neooctanoic acid, isononanoic acid 3,4,4-trimethylhexanoic acid, neononanoic acid, isodecanoic acid, 2-propylheptanoic acid, neodecanoic acid, isoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, isotridecanoic acid, isotetradecanoic acid, isomyristic acid, 2-pentylnonanoic acid, isopentadecanoic acid, isohexadecanoic acid, isopalmitic acid, 2-hexyldecanoic acid, isoheptadecanoic acid, isooctadecanoic acid, isostearic acid, 2-heptylundecanoic acid, isononadecanoic acid, isoeicosanoic acid, 2
Octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid,
2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid,
Isooleic acid and the like.

Among these branched aliphatic hydrocarbon groups, secondary aliphatic hydrocarbon groups and branched aliphatic acyl groups, those having 8 to 36 carbon atoms are preferred, and those having 10 to 28 carbon atoms are more preferred. Further, the one having a larger number of branches is preferable because the emulsifiability, dispersibility, polymerization stability and the like of the surfactant represented by the general formula (1) are improved, and particularly, the surfactant has three or more methyl groups in the molecule. Are preferred. Among the hydrocarbon group or an acyl group having such a large number of branches, for example, as a commercial isotridecanol, also be a mixture of many structural isomers, which are H ¹ -NMR etc. The number of methyl groups in a molecule can be measured by the spectrochemical analysis method described in (1).

In the general formula (1), (AO) _m and (A
O ′) _n represents ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-
It can be obtained by a method such as addition polymerization of an alkylene oxide having 2 to 4 carbon atoms such as butylene oxide).
When (AO) _m and (AO ′) _n are formed by addition polymerization of an alkylene oxide, AO and AO ′ are determined by the alkylene oxide to be added. The polymerization form of the alkylene oxide or the like to be added is not limited, and may be homopolymerization of one kind of alkylene oxide, random copolymerization of two or more kinds of alkylene oxides, block copolymerization, random / block copolymerization, or the like. The degree of polymerization m is 0
When X is a hydrogen atom, the number is preferably 1 to 200, more preferably 3 to 100, and still more preferably 10 to 50. When X is an ionic hydrophilic group, the degree of polymerization m is preferably 1 to 200, more preferably 2 to 100, and still more preferably 2 to 50.

AO is most preferably an oxyethylene group. When AO is two or more groups, one is preferably an oxyethylene group, and the (AO) _m portion preferably contains 50 to 100 mol% of oxyethylene groups, more preferably 60 to 100 mol%. It is preferred that the polyoxyalkylene chain contains mol%.

When R ¹ is a secondary aliphatic hydrocarbon group, AO ′ is preferably an oxyethylene group from the viewpoint of easy availability of raw materials. Further, when R ¹ is a branched aliphatic hydrocarbon group having about 3 to 10 carbon atoms, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, AO ′ has 3 or 4 carbon atoms.
Is preferably an oxyalkylene group. Degree of polymerization n
Is a number in the range of 0 to 1,000, preferably 0 to 1,000.
100, more preferably 0 to 50, still more preferably 0 to
30, particularly when R ¹ is a branched aliphatic hydrocarbon group having about 3 to 10 carbon atoms, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, the polymerization degree n is preferably 2 to 30. .
The surfactant represented by the general formula (1) can adjust hydrophilicity or hydrophobicity by the number of m and n, and preferably has an appropriate degree of polymerization according to the application.

In the general formula (1), L represents a group represented by the following general formula (2). The group represented by the general formula (2) is a reactive group in the surfactant of the present invention. R ² and R ³ each represent a hydrogen atom or a methyl group;
Represents a number of 2, and y represents a number of 0 or 1.

Examples of the group represented by the general formula (2) include vinyl, 1-propenyl, allyl, methallyl,
-Butenyl, 3-butenyl, 4-pentenyl, 3-methyl-3-butenyl, 5-hexenyl, 8-nonenyl, 1
Alkenyl groups such as 0-dodecenyl; acryl, methacryl, 2-butenoyl, 3-methyl-3-butenoyl, 2
-An unsaturated acyl group such as dodecenoyl. Among these, allyl, methallyl, acryl, and methacryl are preferable in terms of availability of raw materials and reactivity. Further, the group represented by the general formula (2) can be copolymerized (radical polymerization or ionic polymerization) with another radically polymerizable reactive group. Further, it can be reacted with a compound having a group other than a polymerizable reactive group, such as an organopolysiloxane having a Si—H group.

In the general formula (1), z represents a number from 1 to 10. Depending on the production method or the like, z may be a mixture of different ones. In the case of a mixture, z represents an average value. As z is closer to 1, the emulsifiability, dispersibility, polymerization stability and the like of the surfactant of the present invention tend to be improved. Therefore, when emphasis is placed on emulsifiability, dispersibility, polymerization stability, and the like, z is preferably a number of 1 to 8, and z is preferably 1 to 5.
Is more preferable, and the number of 1-3 is most preferable.

On the other hand, when z is a number greater than 1,
Water resistance and mechanical strength of a resin obtained by emulsion polymerization or suspension polymerization using the surfactant of the present invention tend to be improved. When z is a number greater than 10,
The polymerization stability or the like in emulsion polymerization or suspension polymerization is reduced, and, for example, aggregates are easily generated during the polymerization reaction. Therefore, when importance is attached to the water resistance and mechanical strength of the resin,
It is preferred that z is a number greater than 1, and when the surfactant of the present invention is a mixture of those having z of 1 and those having z of 2 or more, z has an average of 1.1. -8 is preferable.

In the general formula (1), X represents a hydrogen atom or an ionic hydrophilic group. Examples of the ionic hydrophilic group include an anionic hydrophilic group and a cationic hydrophilic group. Among them, as the anionic hydrophilic group, for example, -SO
^{_{3 M, -R 4 -SO 3 M}} , -R 5 -COOM, -PO 3 M 2,
And a group represented by -PO ₃ MH or -CO-R ⁶ -COOM and the like.

In the above formula representing an anionic hydrophilic group,
Is a hydrogen atom, an alkali metal atom such as lithium, sodium or potassium; an alkaline earth metal atom such as magnesium or calcium (alkaline earth metal atom is usually 2
1/2); or ammonium.
Examples of the ammonium include ammonium ammonium, alkylamine ammonium such as monomethylamine and dipropylamine, and alkanolamine ammonium such as monoethanolamine, diethanolamine and triethanolamine. R ⁴ and R
⁵ represents an alkylene group such as methylene, ethylene, propylene, butylene, pentene, pentamethylene, hexamethylene and the like. Among them, an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene, and butylene is preferable from the viewpoint of raw materials.

R ⁶ is a residue obtained by removing a carboxyl group from a dibasic acid or its anhydride. Examples of the dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, and tetradecandioic acid. Saturated aliphatic dicarboxylic acids such as;
Cyclopentanedicarboxylic acid, hexahydrophthalic acid,
Saturated alicyclic dicarboxylic acids such as methyl hexahydrophthalic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid , Unsaturated fatty dicarboxylic acids such as mesaconic acid; unsaturated fatty acids such as tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid (endmethylenetetrahydrophthalic acid), methylnadic acid, methylbutenyltetrahydrophthalic acid, methylpentenyltetrahydrophthalic acid; And a saturated alicyclic dicarboxylic acid. These may be used in the production stage in the form of an anhydride. These, among anionic hydrophilic _{group, -SO 3 M, -PO 3 M} 2 or -P
The group represented by O ₃ MH is preferred.

X may be a cationic hydrophilic group. The cationic hydrophilic group, e.g., -R ⁷ -NR ⁸ R ⁹ R
^And a group represented by ¹⁰ · Y or -Z-NR ⁸ R ⁹ R ¹⁰ · Y. In the above formula representing the cationic hydrophilic group,
Y represents a halogen atom or a methyl sulfate group (-CH ₃ SO _4). As the halogen atom, a chlorine atom, a bromine atom,
And iodine atoms. R ⁷ has 1 to 4 carbon atoms.
Represents an alkylene group. Examples of the alkylene group having 1 to 4 carbon atoms include the same alkylene groups as those described above for R ⁴ of the anionic hydrophilic group.

R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkanol group having 2 to 4 carbon atoms or a benzyl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl and the like. Examples of the alkanol group having 2 to 4 carbon atoms include a 2-hydroxyethyl group, a 2-hydroxypropyl group, and a 2-hydroxybutyl group. Further, Z is _{-CH 2 CH (OH) CH 2} - or -CH
(CH ₂ OH) CH ₂ — is a group represented by —.

The method for producing the surfactant represented by the general formula (1) is not particularly limited. For example, when X is a hydrogen atom, (a) glycidyl ether or glycidyl ester having a reactive group represented by the general formula (2):
It can be obtained by adding mmol of alkylene oxide to a reaction product with a branched aliphatic alcohol, a secondary aliphatic alcohol, a branched fatty acid, or the like by a known method. Alternatively, (b) a reaction product of a glycidyl ether of a branched aliphatic alcohol or a secondary aliphatic alcohol or a glycidyl ester of a branched fatty acid with an alcohol or carboxylic acid having a reactive group represented by the general formula (2): It can also be obtained by adding mmol of alkylene oxide by a known method. To confirm the completion of the reaction between the glycidyl ether or glycidyl ester and the alcohol or carboxylic acid, the end point can be confirmed by measuring, for example, IR absorption, epoxy equivalent and the like. In the production method (a), a reaction product of a glycidyl ether or glycidyl ester having a reactive group represented by the general formula (2) and a branched aliphatic alcohol, a secondary aliphatic alcohol, a branched fatty acid, or the like. In the case where unreacted branched aliphatic alcohol, secondary fatty alcohol or branched fatty acid remains,
If necessary, these unreacted substances may be removed and purified before adding the alkylene oxide.

In the above production, a catalyst can be used if necessary. The catalyst that can be used is not particularly limited as long as it is used for the ring opening reaction of epoxy. For example, a tertiary amine, a quaternary ammonium salt, boron trifluoride or an ether complex thereof, aluminum chloride, barium oxide, sodium hydroxide, potassium hydroxide and the like can be mentioned.

The reaction conditions for adding the alkylene oxide are not particularly limited. Usually between room temperature and 150 ° C,
At a pressure of 0.01 to 1 MPa, if necessary, sodium hydroxide, potassium hydroxide, boron trifluoride or the like can be used as a catalyst. When X is an ionic hydrophilic group, the compound obtained by the above reaction is further subjected to a reaction for introducing an ionic hydrophilic group.

In the formula representing an ionic hydrophilic group, -SO ₃ M
In the case of carrying out a sulfate esterification to introduce an anionic hydrophilic group represented by the following formula, as the anionic hydrophilizing agent, for example, sulfamic acid, sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid and the like can be used. The reaction conditions in the case of sulfuric esterification are not particularly limited, but the reaction temperature is usually from room temperature to 150 ° C., the pressure is from normal pressure to about 0.5 MPa, and the reaction time is about 1 to 10 hours.

In the formula representing an ionic hydrophilic group, -R ⁴ -S
When an anionic hydrophilic group represented by O ₃ M is introduced, for example, propane sultone, butane sultone or the like can be used as the anionic hydrophilizing agent. The reaction conditions for sulfonation are not particularly limited,
Normal temperature is from room temperature to 100 ° C, pressure is from normal pressure to 0.5MPa
The reaction time is about 1 to 10 hours under the moderate pressure. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst. Moreover, you may add a solvent as needed.

In the formula representing an ionic hydrophilic group, -R ⁵ -C
When carboxylating to introduce an anionic hydrophilic group represented by OOM, as an anionic hydrophilizing agent,
For example, chloroacetic acid (R ⁵ corresponds to a methyl group), chloropropionic acid (R ⁵ corresponds to an ethyl group), or salts thereof can be used. The reaction conditions for carboxylation are not particularly limited, but usually, the temperature is from room temperature to 15
The reaction time is about 1 to 10 hours at 0 ° C. under a pressure of normal pressure to about 0.5 MPa. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst.

In the formula representing an ionic hydrophilic group, -PO ₃ M ₂
Alternatively, when phosphoric acid esterification is performed to introduce an anionic hydrophilic group represented by —PO ₃ MH, examples of the anionic hydrophilizing agent include diphosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, and phosphorus oxychloride. Can be used. In the case of phosphorylation, a monoester-type compound and a diester-type compound are obtained as a mixture. These may be separated or, if separation is difficult, may be used as a mixture as it is. The reaction conditions for the phosphorylation are not particularly limited, but the temperature is usually room temperature to 150 ° C., the pressure is normal pressure, and the reaction time is about 1 to 10 hours.

In the formula representing an ionic hydrophilic group, -CO-R
^When dibasic oxidation is carried out to introduce an anionic hydrophilic group represented by ^6- COOM, the above-mentioned dibasic acid or anhydride thereof can be used as the anionic hydrophilizing agent.
For example, maleic acid (R ⁶ corresponds to a CH ＝ CH group), phthalic acid (R ⁶ corresponds to a phenyl group), a salt thereof, or an anhydride thereof may be used. The reaction conditions for dibasic oxidation are not particularly limited, but the temperature is usually room temperature to 150 ° C., the pressure is normal pressure, and the reaction temperature is about 1 to 10 hours. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst. Also,
When anionic hydrophilicization is performed, neutralization may be performed thereafter with an alkali such as sodium hydroxide or potassium hydroxide, ammonia, an alkylamine, or an alkanolamine such as monoethanolamine or diethanolamine.

In the formula representing an ionic hydrophilic group, -R ⁷ -N
When introducing a cationic hydrophilic group represented by R ⁸ R ⁹ R ¹⁰ .Y, first, a halogenating agent such as thionyl chloride, thionyl bromide or phosgene is used to obtain a compound represented by the general formula (1) in which X is a hydrogen atom. The hydroxyl group of the compound represented can be halogenated and then introduced by reacting a tertiary amine compound. Also, instead of the tertiary amine compound, 2
After reacting the secondary amine compound, an alkyl halide, dimethyl sulfate or the like may be reacted. The reaction conditions for halogenating the hydroxyl group are not particularly limited, but the temperature is usually from room temperature to 100 ° C., and the pressure is from normal pressure to 0.5 MPa.
The reaction temperature is about 1 to 10 hours under a moderate pressure. The reaction conditions for amination are also not particularly limited, but the temperature is usually from room temperature to 150 ° C., and the pressure is from normal pressure to 0.5.
Under a pressure of about MPa, the reaction temperature is about 1 to 10 hours. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst.

In the formula representing an ionic hydrophilic group, -Z-NR
^When introducing a cationic hydrophilic group represented by ⁸ R ⁹ R ¹⁰ .Y, first, epihalohydrin such as epichlorohydrin and epibromohydrin is represented by general formula (1) wherein X is a hydrogen atom. The compound is reacted with
It can be introduced by reacting a secondary amine compound. Alternatively, after reacting a secondary amine compound instead of the tertiary amine compound, an alkyl halide, dimethyl sulfate, or the like may be reacted. The reaction conditions for reacting epihalohydrin are not particularly limited, but usually,
The temperature is from room temperature to 100 ° C., the pressure is from normal pressure to about 0.3 MPa, and the reaction temperature is about 1 to 10 hours. If necessary, an alkali catalyst such as sodium hydroxide or potassium hydroxide, or an acid catalyst such as sulfuric acid, phosphoric acid, iron chloride, boron fluoride, or tin chloride may be used. The reaction conditions for amination are also not particularly limited, but usually the temperature is from room temperature to 150 ° C., the pressure is from normal pressure to about 0.5 MPa, and the reaction temperature is about 1 to 10 hours. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst.

The surfactant of the present invention can be used in applications where a reactive surfactant having a phenyl ether group has been used, that is, an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, and a modification for resin (repellent). Water-improving, hydrophilicity-adjusting, compatibility-improving, antistatic-improving, anti-fog-improving, water-resistance-improving, adhesion-improving, dyeing-improving, film-forming-improving, weather-resistance-improving, blocking-resistance-improving, It can be used as a fiber processing aid, a drip-free agent, a fiber antifouling agent and the like. In addition, a raw material of a copolymerizable surfactant (for example, described in JP-A-10-120712) or a surfactant-modified organopolysiloxane (for example, described in JP-A-6-65379). )) Can also be used as a raw material.

When the surfactant of the present invention is used as an emulsifier for emulsion polymerization, it can be used arbitrarily within the usual range of the conventionally used emulsifier for emulsion polymerization. , Preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass. It is also possible to use the emulsifier for emulsion polymerization of the present invention in combination with another reactive or non-reactive emulsifier. Further, the monomer to be subjected to emulsion polymerization is not particularly limited, but is preferably an acrylate emulsion, a styrene emulsion,
Vinyl acetate emulsion, SBR (styrene / butadiene) emulsion, ABS (acrylonitrile / butadiene / styrene) emulsion, BR (butadiene)
Emulsion, IR (isoprene) emulsion, NB
It can be used for R (acrylonitrile / butadiene) emulsion and the like.

Examples of the acrylate emulsion include (meth) acrylic acid (ester),
Acrylic acid (ester) / styrene, (meth) acrylic acid (ester) / vinyl acetate, (meth) acrylic acid (ester) / acrylonitrile, (meth) acrylic acid (ester) / butadiene, (meth) acrylic acid (ester) / Vinylidene chloride, (meth) acrylic acid (ester) / allylamine, (meth) acrylic acid (ester)
/ Vinylpyridine, (meth) acrylic acid (ester) /
Alkylolamide, (meth) acrylic acid (ester)
/ N, N-dimethylaminoethyl ester, (meth) acrylic acid (ester) / N, N-diethylaminoethyl vinyl ether and the like.

Examples of the styrene-based emulsion include styrene alone, styrene / acrylonitrile, styrene / butadiene, styrene / fumaronitrile, styrene / maleonitrile, styrene / cyanoacrylate, styrene / phenylvinyl acetate, styrene /
Chloromethylstyrene, styrene / dichlorostyrene,
Styrene / vinyl carbazole, styrene / N, N-diphenylacrylamide, styrene / methyl styrene,
Acrylonitrile / butadiene / styrene, styrene /
Acrylonitrile / methylstyrene, styrene / acrylonitrile / vinylcarbazole, styrene / maleic acid and the like can be mentioned.

Examples of the vinyl acetate emulsion include vinyl acetate alone, vinyl acetate / styrene, vinyl acetate / vinyl chloride, vinyl acetate / acrylonitrile, and the like.
Vinyl acetate / maleic acid (ester), vinyl acetate / fumaric acid (ester), vinyl acetate / ethylene, vinyl acetate /
Propylene, vinyl acetate / isobutylene, vinyl acetate /
Examples include vinylidene chloride, vinyl acetate / cyclopentadiene, vinyl acetate / crotonic acid, vinyl acetate / acrolein, and vinyl acetate / alkyl vinyl ether.

When the surfactant of the present invention is used as a dispersant for suspension polymerization, it can be used arbitrarily within the usual range of the amount of a conventionally known dispersant for suspension polymerization. The amount can be preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, based on the monomer. It is also possible to use the dispersant for suspension polymerization of the present invention in combination with another reactive or non-reactive dispersant such as polyvinyl alcohol. The monomer to be subjected to suspension polymerization is not particularly limited, and can be used for homopolymerization and copolymerization of the above-mentioned monomer having a polymerizable carbon-carbon double bond, but is preferably a halogenated olefin type, a vinyl acetate type or the like. Can be used for polymerization.

Examples of the halogenated olefin polymerization include:
For example, vinyl chloride, vinylidene chloride, vinyl chloride / maleic acid (ester), vinyl chloride / fumaric acid (ester), vinyl chloride / vinyl acetate, vinyl chloride / vinylidene chloride, vinylidene chloride / vinyl acetate, vinylidene chloride / vinyl benzoate And the like.

When the surfactant of the present invention is used as a resin modifier, the properties of the resin to be modified include, for example, adjustment of hydrophilicity, improvement of compatibility, improvement of antistatic property, and improvement of antifogging property. , Improvement of adhesion, improvement of dyeability, improvement of film forming property, improvement of weather resistance, improvement of blocking resistance, and the like. The resin to be modified is not particularly limited, and can be used for any polymer produced by polymerization of the monomer.
Further, for example, it can be used for polyester resin, polyamide resin, polyimide resin, polyaryl ether resin, epoxy resin, urethane resin and the like. Particularly preferred resins that can be used are polyhalogenated olefins such as vinyl chloride and vinylidene chloride, and poly-α-olefins such as ethylene and propylene.

The resin modifier of the present invention can be added to the resin by applying it to the surface of the resin or kneading the resin during processing. Further, when polymerized with another monomer as one of the monomer components during the production of the resin, the resin modifier of the present invention is incorporated in the molecule of the resin, and a permanent modification effect such as permanent antistatic can be obtained. . The resin modifier of the present invention,
Since it has an ether chain in its chemical structure, it exhibits excellent compatibility with monomers. AO and AO '
When necessary, the degree of polymerization (m and n) of the oxyalkylene group and the type of the oxyalkylene group to be constituted are selected according to the purpose of the modification and the compatibility with the monomer, so that the hydrophilicity is improved. Can be easily adjusted. Therefore, the resin modifier of the present invention can simultaneously improve the compatibility with the monomer and the effect of modifying the polymer. Also, by using the resin modifier of the present invention,
It is possible to impart permanent antistatic and antifogging properties to the used resin.

The amount of the resin modifier of the present invention can be variously changed depending on the kind of the monomer, the purpose of the modification, the required performance, and the like.
It can be used in an amount of 1 to 80% by mass. In particular, when a water-soluble resin having insufficient hydrophilicity is to be used as a highly hydrophilic resin, it is more preferable to use 1 to 80% by mass based on the monomer. Other uses, such as water resistance, adhesion,
In order to improve the antistatic properties, antifogging properties, dyeing properties, film forming properties, weather resistance, blocking resistance, etc., or to impart compatibility to a polymer for a polymer alloy, the monomer It is preferable to use 0.1 to 60% by mass.

When the resin modifier of the present invention is used,
Crosslinkable divinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, and methylenebisacrylamide can be arbitrarily used in the usual range for improving the resin properties. Furthermore, when used as an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, or a resin modifier, the resin polymer can be crosslinked by the presence of a metal oxidizing agent, for example.

[0048]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples and the like,% and parts are based on mass unless otherwise specified. (Production Example 1) Isotridecanol (methyl number: 4.3: measured by ¹ H-NMR) in a 3 L stainless steel pressurized reactor equipped with a stirrer, thermometer and nitrogen inlet tube. After charging 1,000 g (5 mol) and 10 g of sodium hydroxide as a catalyst and replacing the atmosphere in the reactor with nitrogen, 570 g (5 mol) of allyl glycidyl ether was fed at 90 ° C. After aging for 5 hours, compound (A) was obtained. Compound (A) 9
At 130 ° C., 42 g (3 mol) of ethylene oxide 1,
Feed 320 g (30 mol), and after the feed,
After aging for 2 hours, the surfactant (1) of the present invention was obtained.

(Production Example 2) Surfactant (1) 377 g
(0.5 mol), further feed 440 g (10 mol) of ethylene oxide at 130 ° C.
After aging for 2 hours, a surfactant (2) of the present invention was obtained.

(Production Example 3) 157 g (0.5 mol) of the compound (A) was placed in a 500 mL glass four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, and cooled to 0 to 5 ° C. . To this, 115 g of chlorosulfonic acid was dropped using a dropping funnel. After the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and HCl generated was removed by blowing nitrogen.
Thereafter, the resultant was neutralized with an aqueous sodium hydroxide solution to form a sodium salt, thereby obtaining a surfactant (3) of the present invention.

(Production Example 4) Surfactant (1) was treated with chlorosulfonic acid to form a sulfate ester in the same manner as in Production Example 3, and then neutralized with an aqueous ammonia solution. ) Got.

(Production Example 5) Into the same flask as in Production Example 3, 452 g (0.6 mol) of the surfactant (1) was added.
After adding 28.4 g (0.6 mol) of diphosphorus pentoxide at 40 ° C. over 1 hour, the mixture was aged at 80 ° C. for 2 hours. Thereafter, the resultant was neutralized with an aqueous sodium hydroxide solution to obtain a surfactant (5) of the present invention.

(Production Example 6) The surfactant (1) 37 of the present invention obtained in Production Example 1 was placed in the same flask as in Production Example 3.
7 g (0.5 mol) and maleic anhydride 49 g (0.5
Mol), stirred at 80 ° C. and esterified, and then neutralized with an aqueous potassium hydroxide solution to obtain a surfactant (6) of the present invention.

(Production Example 7) The same pressure reactor as in Production Example 1 was charged with 377 g (0.5 mol) of the surfactant (1), and ethylene oxide 440 was added under the same conditions as in Production Example 1.
g (10 mol) and a mixture of 290 g (5 mol) of propylene oxide were reacted to obtain a surfactant (7) of the present invention.

(Production Example 8) The same flask as in Production Example 3 was charged with 377 g (0.5 mol) of the surfactant (1) and 5 g of boron trifluoride / ether complex, and 38 g (0.5 mol) of epichlorohydrin. Was added dropwise, and the mixture was reacted with ammonium and triethanolamine (75 g, 0.5 mol) to obtain a surfactant (8) of the present invention.

(Production Examples 9 and 10) Instead of isotridecyl alcohol, 5,7,7-trimethyl-2-
Production Examples 1 and 2 except that (1,3,3-trimethylbutyl) octanol (methyl group number 8) and methallyl glycidyl ether were used instead of allyl glycidyl ether.
Surfactants (9) and (10) of the present invention were obtained in accordance with the following.

(Production Example 11) The surfactant (9) was treated with chlorosulfonic acid to form a sulfate ester in the same manner as in Production Example 3, and then neutralized with potassium hydroxide. 11) was obtained.

(Production Example 12) In a 3 L glass four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, softanol 30 (trade name, manufactured by Nippon Shokubai Co., Ltd., having 12 to 14 carbon atoms)
3 mol adduct of ethylene oxide with a secondary alcohol (number of methyl groups: 2), hydroxyl value: 168 mg KOH / g) 668
g (2 mol) and 5 g of a boron trifluoride-ether complex as a catalyst, and at a temperature of 30 to 80 ° C., 153 g (2 mol) of epichlorohydrin was added dropwise over 1 hour,
Aged at 80 ° C for 2 hours. Thereafter, 250 g (3 mol) of 48% sodium hydroxide was added dropwise at 80 ° C. over 30 minutes, and after completion of the addition, the mixture was aged at 80 ° C. for 2 hours. Thereafter, 800 g of toluene was added as a solvent, and the resultant was washed with 1,000 g of water three times, and then heated and reduced in pressure to remove toluene, thereby obtaining a compound (B).

The same pressure reactor as in Production Example 1 was charged with 108 g (2 mol) of allyl alcohol and 4.8 g of potassium hydroxide as a catalyst, and the atmosphere in the reactor was replaced with nitrogen. (1 mole) at 90 ° C. After completion of the feed, the mixture was aged at 90 ° C. for 5 hours. Then, after the excess allyl alcohol was distilled off under reduced pressure, the pressure of the apparatus was returned to normal pressure with nitrogen, and 290 g (5 mol) of propylene oxide and then 440 g (10 mol) of ethylene oxide were fed at 130 ° C. After completion, the mixture was aged for 2 hours to obtain a surfactant (12) of the present invention.

(Production Example 13) The surfactant (12) was treated with diphosphorus pentoxide to form a phosphate ester in the same manner as in Production Example 5, and then neutralized with potassium hydroxide. Agent (13) was obtained.

(Production Example 14) Isomyristyl alcohol (with 4 methyl groups) in place of isotridecyl alcohol, methacryl glycidyl ester in place of allyl glycidyl ether, boron trifluoride ether complex in place of sodium hydroxide as a catalyst, Surfactant (14) of the present invention was obtained according to Production Example 1, except that a mixture of ethylene oxide and tetrahydrofuran was used instead of ethylene oxide.

(Production Example 15) The surfactant (14) was treated with chlorosulfonic acid to form a sulfate ester in the same manner as in Production Example 3, and then neutralized with sodium hydroxide. 15) was obtained.

(Production Example 16) Isotridecyl alcohol
In place of isotridecanoic acid (with 4.3 methyl groups: ¹H
-Value measured by NMR. ), Hydroxyl as catalyst
Boron trifluoride ether complex instead of sodium fluoride
The surfactant (1) of the present invention was prepared according to Production Example 1 except that
6) was obtained.

(Production Example 17) Isoundecyl alcohol (methyl group number: 3.
5: Value measured by ¹ H-NMR. ) Except that the surfactant (1) of the present invention was prepared according to Production Examples 1 and 4.
7) was obtained.

(Production Example 18) The surfactant (18) of the present invention was obtained in the same manner as in Production Example 1 except that the amount of allyl glycidyl ether was increased from 570 g (5 mol) to 1,140 g (10 mol). . Incidentally, the surfactant (18) corresponds to the one in which z is 2 in the general formula (1).

(Production Example 19) Isotridecanol 1,0
860 g (5 mol) of isoundecyl alcohol was used instead of 00 g (5 mol), and the amount of allyl glycidyl ether was increased from 570 g (5 mol) to 855 g (7.5 mol) according to Production Example 1. Thus, a surfactant (19) of the present invention was obtained. The surfactant (19) corresponds to the general formula (1) in which z is 1.5.

(Production Example 20) A surfactant (20) of the present invention was obtained in the same manner as in Production Example 4, except that the surfactant (19) was used instead of the surfactant (1). (Production Example 21) A surfactant (21) of the present invention was obtained according to Production Example 5, except that surfactant (19) was used instead of surfactant (1). (Production Example 22) The amount of allyl glycidyl ether was adjusted to 855.
The surfactant (22) of the present invention was obtained according to Production Examples 19 and 20, except that the amount was increased from g (7.5 mol) to 1,710 g (15 mol). Incidentally, the surfactant (22) corresponds to the one in which z is 3 in the general formula (1).

(Production Example 23) 172 g (1 mol) of isoundecanol and 2 g of sodium hydroxide as a catalyst were charged into a 3 L stainless steel pressurized reactor equipped with a stirrer, a thermometer, and a nitrogen inlet tube. After replacing the atmosphere in the apparatus with nitrogen, 171 g of allyl glycidyl ether (1.
5 mol) at 90 ° C.
Aged at ℃ for 5 hours. Thereafter, 360 g (5 mol) of butylene oxide was fed at 130 ° C., and then 1,320 g (30 mol) of ethylene oxide was fed. After the feed was completed, the mixture was aged for 2 hours to obtain a surfactant (2) of the present invention.
3) was obtained. The surfactant (23) has the general formula (1)
, Z corresponds to 1.5.

(Production Example 24) The surfactant (1) of the present invention
A mixture obtained by mixing the same amount of 7) and the surfactant (20) of the present invention in a mass ratio was designated as a surfactant (24) of the present invention. In the surfactant (24), in the general formula (1), z is 1.2.
Fall under

The surfactants of the present invention obtained in the above production examples are as follows. In the structural formula, EO represents an oxyethylene group, and PO represents an oxypropylene group. THF is a tetrahydrofuran residue (1,4-
(Butylene oxide residue).

[0071]

[0072]

[0073]

[0074]

[0075]

The comparative products in the following examples are as follows.

<< Example 1 >> With respect to the surfactants (1) to (24) of the present invention, the surface tension of each aqueous solution was measured by the Wilhelmy method. Table 1 shows the results. The test conditions are as follows. Measurement conditions: 0.1% aqueous solution Measurement temperature: 25 ° C

[0078]

<< Example 2 >> For each of the surfactants (1) to (24) of the present invention and the comparative products 1 to 4, the dispersion performance of carbon black and the emulsification performance of toluene were measured. Table 2 shows the results. The test method is as follows. <Carbon black dispersion performance test method> Capacity 100mL
1 g of the above surfactant and 10 g of carbon black were placed in a graduated cylinder with a stopper, and dissolved and dispersed in water.
Adjusted to 00 mL. Next, the measuring cylinder was shaken 100 times per minute, and then left at 25 ° C. for 1 hour.
Thereafter, 30 mL was withdrawn from the upper surface of the liquid, filtered through a glass filter, and then dried at 105 ° C., the weight of the residue on the glass filter was measured, and the dispersion performance (%) was calculated by the following equation. did. Dispersion performance (%) = ｛Residual mass of glass filter (g) / 3
(g)｝ × 100

<Test Method for Emulsifying Performance of Toluene> Capacity 20
5 mL of a 0.5% aqueous solution of the above surfactant and 5 mL of toluene were added to a mL test tube with a stopper and a scale. Next, the test tube was shaken 100 times per minute,
For 1 hour. Thereafter, the capacity (mL) of the emulsified layer was measured, and the emulsification performance (%) was calculated by the following equation. Emulsification performance (%) = {Emulsion layer volume (mL) / 10 (mL)} x
100

[0081]

<< Example 3 >> The surfactants (1), (12), (16) and (22) of the present invention and comparative products 2 and 4 were biodegraded according to the method of JIS-K-0102. A sex test was performed. That is, BOD is the biochemical oxygen consumption, the amount of dissolved oxygen consumed by aerobic microorganisms in water. Here, it is the amount of dissolved oxygen consumed when the sample was diluted with dilution water and left at 20 ° C. for 5 days. TOD is a constant determined from the chemical structure of each sample. The results are shown in Table 3 below.

[0083]

<< Example 4 >> For the surfactants (1) to (24) of the present invention and comparative products 1 to 4, in order to see the performance as an emulsifier for emulsion polymerization, 2-ethylhexyl acrylate / acryl was used. Emulsion polymerization was performed using the acid mixture as a monomer. About the obtained polymer emulsion, the particle size, the amount of aggregates, mechanical stability, foamability, and the water resistance of the film obtained from the polymer emulsion were measured. Table 4 shows the results.

<Polymerization method> 120 g of deionized water was placed in a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer.
And the system was replaced with nitrogen gas. Separately, a mixed monomer (2-ethylhexyl acrylate / acrylic acid = 97)
/ 3: mass ratio) 100 g of the surfactant (1) of the present invention to
(24) or 4 g of comparative products 1-4 was dissolved, and 10
g and ammonium persulfate 0.08 g to the reaction vessel,
Polymerization was started at 60 ° C. Then, the remaining mixture of the monomer and the surfactant was continuously dropped into the reactor over a period of 2 hours. After completion of the dropping, the mixture was aged for 2 hours to obtain a polymer emulsion.

<Particle Size> The particle size of the above polymer emulsion after polymerization was measured using an electrophoretic light scattering photometer (ELS-800, ELS-800).
The measurement was performed at 25 ° C. using Otsuka Electronics Co., Ltd. <Agglomerate amount>
The mixture was filtered through a 5-mesh wire net, and the residue was washed with water and then washed with 1 mesh.
After drying at 05 ° C. for 2 hours, the mass was measured and represented by mass% based on the solid content. <Mechanical stability> After stirring the above polymer emulsion after polymerization at 2,000 rpm for 2 minutes with a disper,
The amount of aggregate was measured by the above method, and the mechanical stability was evaluated.

<Foamability> The above polymer emulsion after polymerization was diluted twice with water.
L was placed in a 100 mL graduated test tube, vigorously shaken up and down for 10 seconds, and the foam amount was measured immediately after shaking and after 5 minutes. <Water resistance of the film> The polymer emulsion after polymerization is applied to a glass plate to form a coating film having a thickness of 0.2 mm, and the glass plate having the coating film is immersed in water at 50 ° C.
The time until eight-point characters could not be distinguished through the whitened coating film was measured, and the water resistance was evaluated. The evaluation criteria are as follows. A: Characters could be identified even after 48 hours. ：: Characters could be identified even after 24 hours, but characters could not be identified after 48 hours. Δ: Characters could not be identified after one hour or more. X: Characters could not be identified in less than one hour.

[0088]

<< Example 5 >> For the surfactants (1) to (24) of the present invention and comparative products 1 to 4, in order to see the performance as a dispersant for emulsion polymerization, ethyl acrylate / acrylic acid was used. Emulsion polymerization was carried out using a butyl / styrene mixture as a monomer. With respect to the obtained polymer emulsion, the particle diameter, the amount of aggregates, the mechanical stability, and the water resistance and impact resistance of the coating film obtained from the polymer emulsion were measured. Table 5 shows the results.

<Polymerization method> Ethyl acrylate / butyl acrylate / styrene = 49/49 /
A polymer emulsion was obtained in the same manner as in Example 4, except that the mixture had a mass ratio of 2: <Impact resistance> The above polymer emulsion after polymerization was applied to a mild steel plate (200 mm x 100 mm x 4 mm) to prepare a test piece having a 0.5 mm thick coating film, and the test piece was subjected to JIS-K- 5400 (General paint test method)
An impact resistance test was conducted in accordance with the impact resistance A method.
The test was performed 10 times, and the cracks and peeling of the coating film caused by the impact of the weight (falling steel ball) were visually determined.
Evaluation was made according to the following criteria. ：: Cracking or peeling due to weight was not observed, or was observed once. Δ: Cracking or peeling due to weight was observed two or three times. X: Cracking or peeling due to weight was observed 4 times or more.

[0091]

<< Example 6 >> Surfactants (1) to (7), (9) to (13), (17) to (2)
4) In order to observe the performance as a dispersant for suspension polymerization of the comparative products 1 to 4, suspension polymerization was performed using vinyl chloride as a monomer, and the obtained resin was tested by the following test method. Was. Table 6 shows the results.

<Polymerization Method> 100 g of deionized water and a surfactant (1) of the present invention were placed in a 500 mL stainless steel pressurized reactor equipped with a stirrer, thermometer, and nitrogen inlet tube.
2 g of (7), (9) to (13), (17) to (24) or Comparative Products 1 to 4 and 0.2 g of di-2-ethylhexyl peroxycarbonate were charged, and the inside of the reactor was set to 7 k.
After removing oxygen by degassing until Pa was reached, 100 g of a vinyl chloride monomer was charged, and the temperature was raised to 57 ° C. with stirring at a rotation speed of 500 rpm to carry out polymerization. At the start of the polymerization, the pressure in the autoclave was 0.8 MPa, but after 7 hours from the start of the polymerization, the pressure became 0.4 MPa. At this point, the polymerization was stopped, and the unreacted vinyl chloride monomer was purged. The material was taken out and dehydrated and dried.

<Particle Size Distribution> Of the obtained resin particles, 25
The mass ratio of particles that did not pass through a 0-mesh sieve (wire mesh based on Tyler mesh) was measured. <Water resistance test> The sol was prepared with the following composition,
A sheet having a thickness of 5 mm and heated at 190 ° C. for 10 minutes was immersed in water at 23 ° C. for 24 hours, and the light transmittance (%) was measured. -50 parts of resin obtained-30 parts of di-2-ethylhexyl phthalate-1 part of Ba / Zn-based stabilizer <Thermal stability test> The same sol as that used in the water resistance test was poured into an aluminum mold. The change in color tone after 30 minutes in a hot air atmosphere at 190 ° C. was evaluated on a scale of A (small change) to E (large change).

[0095]

<< Example 7 >> For the surfactants (1) to (24) of the present invention and the comparative products 1 to 4, solution polymerization of styrene was carried out in order to see the performance as a resin modifier. The obtained resin was tested by the following test methods. In addition, the thing which did not add a resin modifier was made into the blank. Table 7 shows the results.

<Polymerization method> 100 g of xylene was charged into the same reaction vessel as in Example 4, and the system was purged with nitrogen gas. Separately, 150 g of styrene and the surfactant (1) of the present invention
(24) or a mixed solution of 15 g of comparative products 1 to 4, 2 g of benzoyl peroxide, and 1 g of di-tert-butyl peroxide was prepared, and the mixed solution was continuously fed into the reactor at a reaction temperature of 130 ° C. for 2 hours. Was dripped. Further, a mixed solution of 10 g of xylene, 0.5 g of benzoyl peroxide, and 0.5 g of di-tert-butyl peroxide was added dropwise and reacted for 2 hours. Thereafter, the mixture was cooled to obtain a polymer solution. <Anti-fogging property> The above-mentioned polymer solution was applied on a glass plate to prepare a polymer film having a thickness of 0.2 mm. The anti-fogging property was evaluated by measuring a contact angle (°) of water with respect to the polymer film. .

<Antistatic Property> The above-mentioned polymer film was allowed to stand in an atmosphere at a temperature of 20 ° C. and a humidity of 50% for 24 hours, and then the surface resistivity was measured.

<Period of antistatic effect and antifogging property> The polymer film after the above antistatic effect and antifogging property test was wiped 50 times with absorbent cotton soaked in water, and then heated to a temperature of 20 ° C. After being left in an atmosphere of 35% humidity for 30 minutes, the surface resistivity and the contact angle of water were measured.

[0100]

[0101]

The effect of the present invention is that an interface which does not contain a phenyl ether group such as a nonylphenyl group, which is considered to have a large effect on the environment, and has the same performance as a reactive surfactant containing a phenyl ether group. In providing an activator.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 305/10 C07C 305/10 C07F 9/09 C07F 9/09 K C08F 2/20 C08F 2/20 2 / 24 2/24 A C08G 65/331 C08G 65/331 (72) Inventor Kaoru Komiya 7-35-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kako Kogyo Co., Ltd. (72) Inventor Masahide Tsuzuki Higashiohisa, Arakawa-ku, Tokyo 7-2-35 Asahi Denka Kogyo Co., Ltd. (72) Inventor Takeaki Mizuashi 7-2-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kagaku Co., Ltd. (72) Inventor Koji Beppu Arakawa, Tokyo 7-35 Higashio-ku, Asahi Denka Kogyo Co., Ltd. F-term (reference) 4D077 AB14 AB15 AC01 BA03 BA14 DC02X DC06X DC19X DC26X DC59X DC67X DC75X DD04X DD29X DD33X DE02X DE09X DE29X DE32X DE37X 4 H006 AA03 AB68 BN10 BP10 GP01 GP10 4H050 AA01 AB68 4J005 AA11 AA14 BD05 BD06 BD07 4J011 JA13 JB26 KA03 KA04 KA05 KA06 KB29

Claims (10)

[Claims] 1. The following general formula (1) [Wherein, R ¹ represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, and AO and A
O ′ represents an oxyalkylene group having 2 to 4 carbon atoms;
Represents a group represented by the following general formula (2), and z represents 1
Represents a number of 10 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number of 0 to 1,000, and n represents 0 to 1,000.
Represents a number of 1,000. ) (Wherein R ² and R ³ represent a hydrogen atom or a methyl group,
x represents a number of 0 to 12, and y represents a number of 0 or 1. )]. 2. In the general formula (1), R ¹ is a branched aliphatic hydrocarbon group or a branched aliphatic acyl group having 8 to 36 carbon atoms and having three or more methyl groups. 2. The surfactant according to 1. 3. The surfactant according to claim 1, wherein X in the general formula (1) is an anionic hydrophilic group. 4. In the general formula (1), X represents —SO _{3
^{M, -R 4 -SO 3 M,}} -R 5 -COOM, -PO 3 M 2,
—PO ₃ MH or —CO—R ⁶ —COOM (wherein M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or ammonium (provided that the alkaline earth metal atom is）), and R ⁴ And R ⁵ represents an alkylene group, and R ⁶ represents a residue obtained by removing a carboxyl group from a dibasic acid or its anhydride.)). 5. The surfactant according to claim 1, wherein in the general formula (1), X is a cationic hydrophilic group. 6. In the general formula (1), X represents —R ⁷ —
^{NR 8 R 9 R 10 · Y} , or ^{-Z-NR 8 R 9 R 10} · Y ( wherein, R ⁷ represents an alkylene group, R ⁸ to R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, carbon atoms represents 2-4 alkanol group or benzyl group, Y represents a halogen atom or a methyl sulfate group, Z is _{-CH 2 CH (OH) CH 2} - or -
_{CH (CH 2 OH) CH 2} - represents a group of the. The surfactant according to claim 5, which is a cationic hydrophilic group represented by the formula: 7. The surfactant according to claim 1, wherein z is a number of 1 to 8 in the general formula (1). 8. An emulsifier for emulsion polymerization, comprising the surfactant according to any one of claims 1 to 7. 9. A dispersant for suspension polymerization, comprising the surfactant according to claim 1. 10. A resin modifier comprising the surfactant according to any one of claims 1 to 7.