JPH01171628A - High polymer emulsifier - Google Patents

Abstract

PURPOSE:To form emulsion without unity of liq. drop and phase separation over a long time with the addition of a small amt. of a emulsifier, by prepg. a high polymer emulsifier with polymer having three kinds of constituent unit of specified formula. CONSTITUTION:The high polymer emulsifier is prepd. with the polymer (C) contg. the constituent unit (A) of formula I (where, R<1> is hydrogen atom. or methyl group, R<2> is hydrogen atom., methyl group, etc., and R<3> is hydrogen atom., methyl group, etc.) and the constituent unit (B) selected from constituent unit (b-1) of formula II (where, R<10> is hydrogen atom. or methyl group, R<11> is hydrogen atom., methyl group, etc., R<12> is hydrogen atom., methyl group, etc., and R<13> is 4-30C alkyl group, etc.) and constituent unit (b-2) of formula III (where, R<16> is hydrogen atom. or methyl group, R<17> is hydrogen atom., methyl group, etc., and R<18> is hydrogen atom., methyl group, etc.), as main constituent unit.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer emulsifier. More specifically, it is made of a polymer with a specific structural unit, and even with a small amount of O used, it acts on the two-phase liquid-liquid interface of water and oil, stably placing oil droplets in an aqueous medium or water droplets in an oil medium. The present invention relates to a polymer emulsifier that can be dispersed and obtain an extremely stable emulsion (hereinafter referred to as an emulsion) that does not cause droplet coalescence or two-phase separation even when left for a long time.

[Conventional technology] Traditionally, textile industry, synthetic rubber/synthetic resin industry, paper/pulp industry, civil engineering/architectural industry, paint/printing ink industry, machinery/
Various emulsions are manufactured or used in a wide range of fields such as metal industry, ceramic industry, a pharmaceutical industry, leather industry, pharmaceutical/cosmetic industry, food industry, and energy-related fields, but coalescence of droplets and two-phase separation occur. Emulsifiers are used to obtain stable emulsions.

However, emulsions are generally obtained by mixing two liquids that do not dissolve in each other, and one liquid is dispersed as droplets in the other liquid phase, so the area of the liquid-liquid interface is very large. They are large and thermodynamically extremely unstable, with a strong tendency to cause droplet coalescence and two-phase separation. In addition, emulsions have a wide variety of purposes, applications, and conditions of use, and the emulsifier to be added needs to satisfy a number of requirements depending on the composition, type, and conditions of use of the intended emulsion. For example, the type of oil used in emulsion production, the dissolved substances, the composition ratio of water and oil, and whether water or oil is in the form of droplets, whether it is oil-in-water type -〇/W type, or oil-in-oil type. It is required to provide an emulsion that does not cause coalescence of droplets or two-phase separation in response to a number of requirements such as water type - correction type 0), temperature conditions at which the emulsion is used, and mechanical conditions during use. Ru.

Conventionally, many emulsifiers have been proposed and used to meet the above requirements. For example, nonionic low-molecular emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid salts, alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates. anionic low-molecular emulsifiers such as alkylammonium salts, alkylbenzylammonium salts, alkylimidazolinium salts, amphoteric low-molecular emulsifiers such as alkylcarboxybetaine, alkylimidacillin, or polyoxyethylene, Proposals include nonionic polymer emulsifiers such as oxypropylene block polymers, anionic polymer emulsifiers such as (meth)acrylic H/(meth)acrylic acid alkyl ester copolymer salts, and maleic acid/styrene copolymer salts. has been done.

However, emulsions obtained using these emulsifiers have poor long-term stability and tend to cause coalescence of droplets and two-phase separation.Also, emulsions obtained using these emulsifiers are susceptible to coalescence of droplets and two-phase separation. There have been problems in that relatively stable emulsions can only be obtained within a limited range with respect to requirements such as composition, temperature during emulsification, and temperature at which the emulsion is used.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems that conventional emulsifiers have.

Therefore, an object of the present invention is to provide a polymeric emulsifier that can be used in a wide range of emulsification systems and can provide an emulsion that does not cause coalescence of droplets or two-phase separation over a long period of time simply by adding raw materials. .

[Means and Effects for Solving the Problems 1] The present inventors have conducted intensive research to achieve the above object, and as a result, have arrived at the present invention.

That is, the present invention provides - bottom (I) RI R3 -f-C= C-)-(I) R2R4 [where R1 is hydrogen or methyl group, R2 is hydrogen, methyl group, -COO- (-R5+]-R6, or -〇 ON-+R5→-R6, R3 is hydrogen, methyl group,
-CH2Coo-+R5→-R6 or -A-+R5→
-R6 (However, R5 is a carbon @.2 to 4 alkylene oxide residue containing a non-oxide residue, ! is a number from 1 to 300, R6 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an organic group having 2 to 5 carbon atoms and an unsaturated bond, or one group that exhibits ionicity when dissociated in the presence of water, R7 is hydrogen or +R8qR9 (R8 += 631-fold R1 of all alkylene oxide residues: carbon number 2 containing 50-fold ω% or more of ethylene oxide residue
~4 alkylene oxide residues, m is a number from 1 to 300,
R9 is hydrogen, an alkyl group having 1 to 3 carbon atoms, and 2 to 5 carbon atoms.
This refers to an organic group having an unsaturated bond or a group that dissociates in the presence of water and exhibits ionicity. ), and A is! -COO-, -CON- (R7 is the same as above) or -CH20-. ), and R2 is one COO+R
5≠-R6 or B is a methyl group and R4 is -COO+R5÷-R6! Or -CON+R5→-R6, R3 is one CH2
COO+R5←-R6 or ℃ element or methyl group, and R4 is -C O O- (-R 5-R6 or! ・-〇 〇 N-(-R 5-←]-R6.) At least one type of fS building unit (A>) and -Bottom (II) R10 R12 Effect-C□C→- (II) R11 R13 [However, in the formula, R10 is hydrogen or a methyl group, R11
is hydrogen, a methyl group, -C O O R f4 or R13 is an alkyl group having 4 to 3 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group,
Cyclic alkenyl group? ! A monovalent organic group derived from a dicyclic compound, -COOR14, (wherein R14 is an alkyl group having 4 to 30 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group, a cyclic alkenyl group, or a hetero A monovalent organic group derived from a cyclic compound, R15 is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group,
Indicates a monovalent organic group derived from a cyclic alkenyl group or a heterocyclic compound. ), R12 is hydrogen or a methyl group, and R13 is -CH2COOR1
4 or is a methyl group and R13 is a structural unit (b-1) represented by and -bottom (I[
1) R16Rlfl 1 ←C 820+T-R21, R1B is hydrogen, methyl group, -CH2COO+R20+T-R21 or -CH2C0NfR20TTrR21, R19
Lt-B+R20-)7R21 (However, R20 has 2 to 4 carbon atoms and the content of ethylene oxide residue is 30% by weight or less and 8% or less based on the total weight of all alkylene oxide residues.
alkylene oxide residue, n is a number from 1 to 300, R2
1 is hydrogen, a monovalent group derived from an alkyl group, alkenyl group, aryl group, aralkyl group, cyclic alkyl group, cyclic alkenyl group or polycyclic compound having 1 to 30 carbon atoms, R22 is hydrogen or +R23-)7-R”
(R23 is an alkylene oxide residue having 2 to 4 carbon atoms in which the content of ethylene oxide residue is 30% by weight or less based on the joint position of all alkylene oxide residues, p is 1 to 3
The number 00, R2A represents hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group, a cyclic alkenyl group, or a monovalent organic group derived from a heterocyclic compound. -0), and B is -CO
O-1 -CON- (R22 is the same as above) or -CH20-
shows. ), and R17 is -COO-+R2o-)-
-R21 or -〇〇N+R20÷1R21, R18 is hydrogen or methyl group, R19 is -COO+R20+-R21 or -CON +R20+-7,R21, and Rie is -
CH2COO+R20+7-R21 or -CH2CO
In the case of N-+R2O-)-7i-R21, R17 is hydrogen or a methyl group, and R19 is -COO-+R20←-R21 or -CON+R20->-R21T-. The present invention relates to a polymer emulsifier comprising a polymer (C) containing as a main constitutional unit at least one structural unit (8) selected from the group consisting of structural units (b-2) represented by the following.

In the general formula (I) representing the hydrophilic structural unit (A),
+R5← and +R8+T- each represent 1 or m alkylene oxide residues having 2 to 4 carbon atoms, and 50% by weight or more of all the alkylene oxide residues are ethylene oxide residues.

1 and m, which indicate the total number of moles of alkylene oxide added, are numbers from 1 to 300, preferably from 3 to 100. R
6 and R9 are the terminal groups of the polyoxyalkylene chain, such as hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, vinyl group, methylvinyl group, allyl group, (meth)acryloyl group, (isopropyl group), ) Crotonoyl group, dimethylacryloyl group, -CH2803e, -CH2CH2SO3e, -CH2CH2CH2803e, -CH2CHCH2SO3, -CH2CO2°, H -COCH2CH2CO2e, -COCH=CHCO2e, -CH2NH2, -CI-12 N(CH3)2,
-CH2N (CH2CH20H)2, -CH2N
■H3, -CH2N■(CH3)3, -CH2C1-l
CH2NH2, 薯H -CH2C1-lCH2N (CH3)2, H, etc. can be mentioned, and when the terminal group is an anionic group, the counter ions are: ■ 2■ 2■ Na, K■, NH4, Ca , MgN■H(CH
Examples include 2CH20H)s, N''H(CH3)5, etc., and counter ions when the terminal MW is a cationic group include:
Cj! , BrO, , e, CH3Cooe, etc.

Also, the general formula (If) representing the hydrophobic structural unit (b-1)
In, R14 is an alkyl group having 4 to 30 carbon atoms, an aryl group, etc., such as n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, 1,3.5 - Alkyl groups such as trimethylhexyl, decyl, dodecyl, and octadecyl; alkenyl groups such as nibtenyl, decenyl, and oleyl;
Phenyl group, methylphenyl group, octylphenyl group,
Aryl groups such as nonylphenyl group and naphthyl group; aralkyl groups such as benzyl group, methylbenzyl group and phenethyl group; cyclic alkyl groups such as dichlorohexyl group and dimethylcyclohexyl group; cyclic alkenyl groups such as cyclopentenyl group; pyridyl group, Examples include monovalent organic groups derived from heterocyclic compounds such as a thienyl group.

R15 includes all the specific examples listed for R14, but in addition to these, hydrogen, methyl group, ethyl group, propyl group, allyl group, and other hydrogen or organic groups having 1 to 3 carbon atoms can be mentioned.

Furthermore, the general formula (I[
In [), +R20←〒 and 1,000R23←" respectively indicate n or p alkylene oxide residues having 2 to 4 carbon atoms, but the content of ethylene oxide residues in all alkylene oxide residues is 30 to 8 % or less. Also, n and ρ indicating the total number of moles added of alkylene oxide are numbers from 1 to 300, preferably from 3 to 100. R 21 and R which are the terminal groups of the polyoxyalkylene chain
Specific examples of 2/L include those listed above for R15.

The content ratio of the structural unit (A) and the structural unit (B) that mainly constitute the polymer (C) that is effective as a polymer emulsifier of the present invention is not particularly limited, but as a range that can be applied to a wide range of water-oil compositions, The unit (A) is 5 to 95% by weight, preferably 10 to 90% by weight, and the positional unit <B) is preferably in the range of 95 to 5% by weight or 90 to 10% by weight,
Also, the structural unit (A) and the structural unit (B) in the polymer (C)
) is preferably 50% by weight or more, preferably 70% by weight or more. Therefore, within a range that does not impair the effects of the present invention, that is, less than 50% by weight in the polymer (C),
Other structural units may be included, preferably in an amount of less than 30% by weight.

When the structural unit <A> is less than 5% by weight, or when the structural unit (B) is less than 5% by weight, the hydrophobicity or hydrophilicity of the polymer (C) becomes too strong, and the polymer (C) becomes too hydrophobic or hydrophilic. Since the effect of the oxyethylene chain or hydrophobic chain is insufficient, a stable emulsion cannot be obtained over a long period of time.

The molecular weight of the polymer (C) may be in a wide range, but it is 1,000 to 500,000, preferably 3,000 to 30,000.
A range of 10,000 is desirable.

The polymer emulsifier of the present invention is made from a polymer (C) containing as main constituent units a specific hydrophilic structural unit (A) having a polyoxyethylene chain and a specific hydrophobic structural unit (B) having a hydrophobic chain. However, there are no particular limitations on the method for obtaining such a polymer, and any method can be used to produce it.

For example, (1) a vinyl monomer that produces a structural unit (A) represented by general formula (I) and a vinyl monomer that produces a structural unit (b-1) represented by general formula (IF) by polymerization; and at least one vinyl monomer selected from the vinyl monomers that produce the structural unit (b-2) represented by the general formula (III), if necessary in the coexistence of other monomers. How to copolymerize below.

■A raw material polymer that produces a polymer (C) containing structural units (A) and (B) as main constituent units through an esterification reaction with alcohol, etc. etherification reaction with
Examples include modification methods such as an addition reaction of alkylene oxide or a terminal modification reaction of a polyoxyalkylene chain.

In the method (2), examples of the vinyl monomer that produces the hydrophilic structural unit (A) include polyalkylene glycol derivatives or alkylene oxide adducts as shown below, but both of them have oxyalkylene chains. Contains 50% by weight or more of ethylene oxide units based on the total type 1, and these terminal alkoxides are monomers alkoxylated with an alkyl group having 1 to 3 carbon atoms, and the terminal alkenoxides are monomers alkoxylated with an alkyl group having 1 to 3 carbon atoms. It is a monomer alkenoxylated with ~3 alkenyl groups.

For example: 1) unsaturated carboxylic gI esters of (terminally alkoxylated or alkenoxylated) polyalkylene glycols such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid or citraconic acid; 2) ( meth) Alkylene oxide adducts of unsaturated carboxylic acid amides such as acrylamide, crotonamide, itaconamide, and maleamide, or compounds in which the terminals of these polyoxyalkylene chains are alkoxylated or alkenoxylated, 3) (Terminals are alkoxylated) or alkenoxylated) polyalkylene glycol;
A compound in which an alkylene oxide is further added to an ester of an unsaturated dicarboxylic acid such as itaconic acid, maleic acid, or fumaric acid with a monoamide, or a compound in which the terminal is alkoxylated or alkenoxylated, 4) (The terminal is alkoxylated or alkenoxylated) (alkenoxylated) polyalkylene glycol mono(meth)allyl ethers, etc., and one or more of these can be used. Among these, examples of monomers 1) include polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polyethylene glycol-polybrobylene glycol mono(meth)acrylate; methoxypolyethylene glycol ( meth)acrylate, methoxypolyethylene glycol-bolib, robylene glycol (meth)
Alkoxypolyalkylene glycol (meth)acrylate alkoxylated with an alkyl group having 1 to 3 carbon atoms such as acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol-polybrobylene glycol (meth)acrylate: Allyloxypolyethylene glycol Alkenoxypolyalkylene glycol (meth)acrylate alkenoxylated with an alkenyl group having 2 to 3 carbon atoms such as (meth)acrylate: bis(polyethylene glycol) maleate, bis(polyethylene glycol-polypropylene glycol) maley 1~, bis Maleic acid esters such as (MeI-xybolyethylene glycol) maleate;
Polyethylene glycol crotonate, methoxypolyethylene glycol crotonate: bis(polyethylene glycol) itaconate, bis(polyethylene glycol-polypropylene glycol) itaconate, bis(
Examples include ethoxypolyethylene glycol) itaconate. Examples of monomers in 2) include polyoxyalkylene unsaturated carboxylic acid amides such as polyoxyethylene (meth)acrylamide, polyoxyethylene-polyoxypropylene (meth)acrylamide, and ethylene oxide adducts of maleamide: methoxypolyoxy An alkyl group having 1 to 3 carbon atoms or an alkyl group having 2 to 3 carbon atoms as the terminal group of a polyoxyalkylene chain such as ethylene (meth)acrylamide, isopropoxypolyoxyethylene-polyoxypropylene (meth)acrylamide, allyloxypolyoxyethylene crotonamide, etc. Examples of monomers in 3) include terminal ether-type polyoxyalkylene unsaturated carboxylic acid amides having an alkenyl group, and examples of monomers in 3) include ethylene oxide adducts of maleic acid monoamide ceno(polyethylene glycol) ester. can. Also, as an example of the monomer in 4),
polyethylene glycol mono(meth)allyl ether,
Poly: [Thylene glycol-polypropylene glycol monoallyl ether, methoxypolyethylene glycol monoallyl ether, etc. Among the vinyl monomers that produce these structural units (A), polyalkylene glycol (terminally alkoxylated) is easily available and provides a copolymer with excellent emulsifying ability. At least one member selected from the group consisting of (meth)acrylic acid ester of Particularly preferred are the monomers.

In addition, in the method (2), examples of the vinyl monomer for producing the hydrophobic structural unit (b-1) include 1-hexene,
Fat h% such as 1-octene, isooctene, 1-nonene, 1-decene, 1-dodecene, vinylcyclohexane, etc.
Vinyl compounds: Aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, 3-phenyl-1-propene, vinylnaphthalene, etc. Vinyl compounds with heterocycles such as N-vinylcarbazole Nibutyl (meth)acrylate 1,2-Etherhexyl (meth)acrylate, n-octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate
Acrylic 1 note, p-methylphenyl (meth)acrylate, octylphenyl (meth)acrylate, 2nonylphenyl (meth)acrylate, dinonylphenyl (
meth)acrylate, benzyl(meth)acrylate,
Alkyl having 4 to 3 carbon atoms such as cyclohexyl (meth)acrylate, pyridyl (meth)acrylate, thienyl (dicita)acrylate, dibutyl-r,-4-, didodecyl maleate, dodecyl cromylate, didodecyl itaconate, etc. group, alkenyl group, aryl group, aralkyl group, cyclic alkyl group, cyclic alkenyl1.
Esters of alcohols with a monovalent right Oi group derived from polycyclic compounds and unsaturated carboxylic acids; (di)butyl (meth)acrylamide, (di)dodecyl (meth)
In addition to acrylamide, (di)stearyl (meth)acrylamide, etc., substituents derived from alkyl groups, alkenyl groups, aryl groups, aralkyl groups, cyclic alkyl groups, cyclic alkenyl groups, and heterocyclic compounds having 4 to 30 carbon atoms are used. (meth)acrylamide having a monovalent organic group,
Unsaturated carboxylic acid amides such as crotonamide, maleamide, itaconamide; alkyl groups having 4 to 30 carbon atoms such as dodecyl allyl ether, phenyl allyl ether, benzyl allyl ether, alkenyl groups, aryl groups, aralkyl groups, cyclic alkyl groups; cyclic alkenyl group,
Examples include furyl ether having a monovalent organic group derived from a heterocyclic compound, and one or more of these may be used. Among these monomers, (meth)acrylates having an alkyl group having 4 to 20 carbon atoms and 1 to 10 carbon atoms are easily available and provide a copolymer with excellent emulsifying ability. Particularly preferred is at least one monomer selected from the group consisting of alkylphenyl (meth)acrylate having an alkyl group as a substituent, styrene, α-methylstyrene, and α-olefin having 6 to 22 carbon atoms.

Examples of the vinyl monomer that generates the hydrophobic structural unit (b-2) include the following polyalkylene glycol derivatives and alkylene oxide adducts, but both of them have a large amount of oxyalkylene chains. for,
The content of ethylene oxide units is 30% by weight or less of the monomer.

For example, polypropylene glycol (meth)acrylate, polypropylene glycol-polyethylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol crotonate, bis(polypropylene glycol) maleate, bis(polypropylene glycol-polyethylene glycol) Esters of polyalkylene glycols such as itaconate and unsaturated carboxylic acids; methoxypolypropylene glycol (meth)acrylate, butoxypolypropylene glycol (meth)acrylate, octyloxypolypropylene glycol-polyethylene glycol (meth)acrylate, phenoxypolypropylene glycol-polyethylene glycol ( meth)acrylate, naphthoxypolypropylene glycol-polyethylene glycol (meth)acrylate, p-methylphenoxypolypropylene glycol (meth)acrylate, cyclohexoxypolypropylene glycol (meth)acrylate, pyrisiloxypolypropylene glycol (meth)acrylate, bis(
Methoxypolypropylene glycol) maleate, methoxypolypropylene glycol)
- such as xypolypropylene glycol crotonate,
A terminal ether type polyalkylene glycol having a monovalent organic group derived from a C1-C30 alkyl group, alkenyl group, aryl group, aralkyl group, cyclic alkyl group, cyclic alkenyl group, or heterocyclic compound as a terminal group. and unsaturated carboxylic acids: alkylene oxide adducts of unsaturated carboxylic acid amides, such as polyoxypropylene (meth)acrylamide, polyoxypropylene-polyoxyethylene (meth)acrylamide, propylene oxide adducts of maleamide; methoxy Alkyl groups, alkenyl groups, aryl groups, aralkyl groups, cyclic alkyl groups, and cyclic alkenyl groups having 1 to 30 carbon atoms as terminal groups of polyoxyalkylene chains such as polyoxypropylene (meth)acrylamide and phenoxypolyoxypropylene (meth)acrylamide. terminal ether type polyoxyalkylene unsaturated carboxylic acid amide having an organic group of 11ilIi derived from polycyclic compound; polypropylene glycol monoallyl ether, phenoxypolypropylene glycol allyl ether, benzyloxypolypropylene glycol-polyethylene glycol allyl ether Allyl ethers such as these can be mentioned, and one or more of these can be used.

By the method (2), a polymer (
As mentioned above, the ratio of monomers that can be used when producing C) is such that the content of the structural unit (A) in the polymer (C) after polymerization is 5 to 95% by weight, Preferably 1
0 to 90 weight percent, structural unit (B) 95 to 5 weight percent, preferably 90 to 10 weight percent, and the total weight of structural unit (A) and structural unit (B) is 50 weight percent or more It is necessary to carry out the polymerization using a proportion such that the amount is preferably 70% by weight or more.

Therefore, the monomers that produce structural units other than the structural unit (A) and the structural unit (B) after polymerization are limited to a range that does not impair the effects of the present invention, that is, the polymer of the structural units (
The monomer that produces the structural unit (A) and the monomer that produces the structural unit (B) are used in a range where the content m in C) is less than 50% by weight, preferably less than 30% by weight. can be copolymerized with the body. Examples of monomers that produce structural units other than structural unit (A> and structural unit (B)) include (meth)acrylic acid (salt), maleic acid (salt), fumaric acid (salt), Crotonic acid (salt), itaconic acid (
Various unsaturated carboxylic acid salts such as (meth)allylsulfonic acid (salt), sulfoethyl (meth)acrylate (salt), styrene sulfonic acid salt), vinylsulfonic acid (salt), 2-acrylamide- Various sulfonic acid salts such as 2-methylpropanesulfonic acid salts): (meth)
Acrylamide, various (meth)acrylamides such as N-methylol (meth)acrylamide, dimethylamine ethyl (meth)acrylamide; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)
Acrylate, various aminoalkyl (meth)acrylates such as dimethylaminopropyl (meth)acrylate; carbon number of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, methyl crotonate, diethyl maleate, etc. Esters of 1 to 3 alcohols and unsaturated carboxylic acids; Vinyl compounds having organic groups having 3 or less carbon atoms as substituents, such as ethylene, propylone, isobutene, and vinyl chloride;
Examples include acrylonitrile, and one of these
A species or two or more species can be used. .

Further, in order to produce the polymer (C) by the method (2), the monomer components may be copolymerized by a known method using a polymerization initiator. Copolymerization can be carried out by methods such as polymerization in a solvent or bulk polymerization.

Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used include, for example, water; lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; benzene, toluene, xylene, cyclohexane, Aromatic, aliphatic or polycyclic compounds such as n-hexane and dioxane; ethyl acetate;
Examples include ketone compounds such as acetone and methyl ethyl ketone. Examples of the polymerization initiator include persulfates such as ammonium pertarate and sodium persulfate, peroxides such as benzoyl peroxide and lauroyl peroxide, hydroperoxides such as cumene hydroperoxide, and azobisisobutyronitrile. Aliphatic azo compounds and the like are used.

At this time, a promoter such as an amine compound can also be used in combination. The polymerization temperature is adjusted appropriately depending on the solvent and polymerization initiator used, but it is usually carried out within the range of 0 to 120'C.

Bulk polymerization uses peroxides such as benzoyl peroxide and lauroyl peroxide, hydroperoxides such as cumene hydroperoxide, and aliphatic azo compounds such as azobisisobutyronitrile as polymerization initiators.
It is carried out within a temperature range of 50-150°C.

In addition, the copolymer obtained by copolymerization in this way can be used as an emulsifier as it is, but if necessary, the solvent used during polymerization may be separated and removed or replaced with another solvent or water. It can also be used. In addition, hydroxides, oxides, and carbonates of alkali metals or alkaline earths,
A basic substance such as ammonia or organic amine may be added as a pl+ regulator before use.

Next, when producing the polymer (C) by the method of
A method using an unsaturated carboxylic acid polymer as a raw material, and a method using an unsaturated carboxylic acid ester polymer as a raw material and a transesterification reaction with an alcohol that produces structural units (A> and B) after modification. , C) Polymerize 8
? An alkylene oxide is added to a raw material polymer obtained by copolymerizing a monomer and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid (A, amide) to form a structural intermediate (B). A> is introduced by the Zin method, and 2> is the addition of fullkylene oxide to the raw material ffl Z♂ obtained by copolymerizing the structural unit (monomer that becomes 8) and 7lyl alcohol by polymerization. , a method of introducing a structural unit (Δ).

e)■ () Mass, I, and body obtained by method () and (a) of ■
- Among the polymers obtained in step 2), the polymer in which the terminal Lt of the polyoxyalkylene chain is -C) l-1 group is combined with the raw material polymers, and the terminal +a -OH group is etherified, ionized,
(meth)acryloylation, (iso)chloro1henoylation,
Metamorphosis'・16 by methods such as dimethyl acryloylation
Examples include ノ′ノγ t+′.

When obtaining the small coalescence (C) using the method described by these authors, the following conditions must be met. That is, the content of the structural unit (A, ) in the modified polymer (C) is 5 to 95% by weight, preferably 10 to 90% by weight, and the content ω of the structural unit (B) is 95 to 5% by weight. %, preferably 90 to 10% by weight, and the )61 content of structural units (A) and structural units (B) in the polymer (C) is 50% by weight or more, preferably 70% by weight. In addition, when the structural unit (A) is introduced by adding alkynone oxide, the content of ethylene oxide units in the polyoxyalkylene compound after addition must be 50% or more. It is necessary to

To give a specific example of method (a), the raw material η that can be used is one or two unsaturated monocarboxylic acids such as (meth)acrylic acid and croton n-sana. These polymers and poly]
-ji (Non-glycol. Methoxypolyethylene Shiguri T)
~le, methoxyboriege
One or more types of alcohols capable of producing the structural unit (A) such as di-non-glycol, glycol, allyloxypoly-J-dilene glycol, and butanol, octanol, dodecanol, and oleyl alcohol. 1 q of polymer (C) can be obtained by esterifying one or more types of alcohols that produce structural units (B) such as phenol, nonylphenol, and benzyl alcohol by a known method.

To give a specific example of the method described above, raw material polymers include unsaturated monocarbons such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, methyl crotonate, and ethyl crotonate. Examples include polycarboxylic acid lower alkyl ester polymers obtained using one or more types of lower alkyl esters of acids, and these polymers and alcohols similar to those listed in (a) can be combined using known methods. An example of this method is to carry out a transesterification reaction.

Examples of raw material polymers that can be used in method (c) include unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid, (meth)acrylamide, and crotonic acid. At least one monomer selected from the group consisting of unsaturated carboxylic acid amides such as amide, itaconamide, and maleamide, and unsaturated carboxylic acid monoamides such as maleic acid t-amide, and Polymerizes to form structural units (
Examples include polymers obtained by copolymerizing with at least one monomer producing B), and these polymers include:
Polymer (C) can be obtained by adding ethylene oxide and, if necessary, alkylene oxide such as propylene oxide or butylene oxide by a known method.

Method 2) uses a polymer obtained by copolymerizing, for example, allyl alcohol and at least one monomer that can be polymerized to produce the structural unit (B) in the same manner as in method ①. This is a method of obtaining a polymer (C) by adding ethylene oxide and, if necessary, an alkylene oxide such as pro-ethylene oxide or butylene oxide by a known method.

The method (e) is a method in which a polymer having a polyoxyethylene chain having a terminal group of 10H is used as a raw material and terminal modification is performed. As an example of etherification modification, for example, the raw material polymer has an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms such as methyl chloride, methyl bromide, ethyl chloride, propyl chloride, allyl chloride, etc. Using one or more types selected from halogenated hydrocarbons,
Examples include a method of performing a Williamson reaction using a known method. (meth)acryloylation and (iso)
For modification such as crotonoylation, the 1iij
The 14 copolymer and one or more selected from (meth)acrylic acid, (iso)ly7cotonic acid, dimethylacrylic acid, etc. may be esterified by a known method. In addition, the divine method can be applied to perform terminal ionization modification using the raw material copolymer. For example, anionization modification methods include sulfuric acid esterification using fuming sulfuric acid, sulfuric anhydride, chlorosulfonic acid, sulfamic acid, etc., and sulfoethylation using isethionate, chloroethanesulfonate, vinylsulfonate, etc. A method for sulfopropylation using propane sultone, a method for sulfopropylation using allyl chloride and bisulfite,
A method of 1-sulfo-2-bitroxypropylation using epichlorohydrin and bisulfite, a method of carboxymethylation using monochloroacetic acid (salt), a method of carboxyprobionylation using succinic anhydride. , a method of producing a maleic acid half ester using maleic anhydride, a method of adding sulfite aqueous lA salt to the maleic acid half ester, a method of converting it into a phosphoric acid ester using phosphorus pentoxide, phosphorus oxychloride, etc. These modified products can be used as is, but if necessary, alkali metal or alkaline earth metal hydroxides, oxides, carbonates, ammonia, etc. Xi l
? It may be used after adding a basic substance such as amine as a pH adjuster.

Examples of cationization modification methods include aminomethylation using formaldehyde, hydrochloric acid and ammonia or various amine compounds, and 1-amino-2-hydroxypropylation using epichlorohydrin and ammonia or various amine compounds. These modified products can be used as is, but if necessary, acidic substances such as hydrochloric acid, hydrogen bromide, hydrogen iodide, acetic acid, etc. may be added as a H regulator before use. .

The polymer emulsifier of the present invention comprises a hydrophilic structural unit <A> having a polyoxyalkylene chain of a certain chain length or more and a hydrophobic structural unit (A) having a hydrophobic chain of a certain chain length or more.
B) is composed of the following polymer as the main constitutional unit,
It is a polymer that has a plurality of long-chain hydrophilic segments and a plurality of long-chain hydrophobic segments with the main chain as a boundary.

When this polymer is used as an emulsifier in the present invention, it strongly adsorbs to the water-oil interface due to its basic structure, resulting in an extremely strong water-oil interfacial film. Therefore, the polymer emulsifier of the present invention has basic properties not found in conventional emulsifiers, such as the ability to maintain the hydrophilic-hydrophobic balance even when external factors such as heat or dissolved electrolytes are applied to the resulting emulsion. As a result, it exhibits many extremely excellent functions as mentioned in the law.

(1) By appropriately selecting the hydrophilicity-hydrophobicity balance, droplet coalescence can be maintained over a long period of time for a wide range of compositions, regardless of the type of oil used or the composition ratio of water and oil.
Produces an extremely stable emulsion without phase separation.

(2) A stable W2O type or 07S type emulsion is produced regardless of the composition ratio of water and ura.

In particular, it is possible to easily obtain a W10 type emulsion in a water-rich system or a 07 type emulsion in an oil-rich system, which were conventionally difficult to produce or unstable. That is, in both water and oil, the component with a larger m can be stably formed into droplets, and both of the obtained emulsions are extremely stable.

(3) When obtaining any type of emulsion, it is possible to easily form a stable emulsion without the need for complicated operations such as stirring using a homogenizer or colloid mill, and also to add protective colloids. There is no particular need for the combined use of stabilizers or thickeners.

(4) Compared to conventional emulsifiers, a stable emulsion can be produced by using an extremely small amount of emulsifier.

(5) Conventional emulsifiers, especially nonionic emulsifiers, tend to lose their affinity with water and significantly reduce their emulsifying ability as the temperature rises or the amount of dissolved electrolyte increases. Even if the emulsifier of the invention is nonionic, it is hardly affected by heat or electrolytes and has extremely excellent heat resistance and salt resistance.

(6) Since it has a nonionic polyoxyethylene chain as a hydrophilic group, it can be widely applied regardless of the ionicity of the substances contained in the emulsion system.

(For example - for boat fishing, anionic emulsifiers are not suitable for emulsification systems containing cationic components, and cationic emulsifiers are not suitable for emulsification systems containing anionic components.) (7) Control of droplet size is possible. In other words, when used at a normal addition rate, it produces an extremely stable emulsion with small droplets, and when the addition rate is slightly reduced, conventional emulsifiers do not produce a stable emulsion. On the other hand, the polymer emulsifier of the present invention has an extremely strong film at the water-oil interface, and therefore produces a stable emulsion containing droplets with large particle sizes.

(8) Extremely low foaming property.

(9) The emulsion does not break even after repeated freezing and thawing, making it freeze resistant and F! 1.Produces emulsions with excellent solubility and qualitative properties.

(10) When used as an emulsifier for emulsion polymerization, the resulting resin has excellent water resistance, weather resistance, etc.

(11) Extremely safe with almost no skin irritation or eye mucosal irritation.

There are no particular limitations on the method of emulsifying and obtaining an emulsion using the polymer emulsifier of the present invention, and any method can be applied.

The type of oil that can be used or the composition of water and oil is not particularly limited as described above, and can be selected depending on the purpose and use of the polymer emulsifier.

For example, any type of oil can be used as long as it is liquid and does not have infinite solubility in water.
Specifically, various mineral oils such as crude oil, gasoline, diesel oil, kerosene, heavy oil, tar, spindle oil, liquid paraffin, and coal-based oil; beef tallow, lard, whale oil, fish oil, rapeseed oil, sesame oil, coconut oil, and Various animal and vegetable oils such as bean oil, palm oil, camellia oil, mustard oil, rosin, and sumac; hydrocarbons such as n-pentane, n-hexane, cyclohexane, benzene, toluene, and xylene; chloroform, carbon tetrachloride, and chloride. Ethylene, 1,1,1. - halogenated hydrocarbons such as trichloroethane and ethylene bromide, alcohols such as n-hexanol, n-pentanol, 2-heptatool, n-octatool, 2-octatool, polypropylene glycol, diethyl ether, isopropyl ether, Ethers such as n-hexyl ether and methylphenyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, and vinegar'fl-n
- Esters such as propyl, caproic acid, capric acid,
Various types of fatty acids such as oleic acid, phenols such as phenol and cresol, nitrogen compounds such as nido-Omethane, nitrobenzene, aniline, and n-hebutylamine, and sulfur and phosphorus compounds such as carbon disulfide and tri-butyl phosphate. Solvents; (meth)methyl acrylate, (meth)
Ethyl acrylate, styrene, α-methylstyrene, α
- Single carriers for polymerization such as olefins: Other special IA oils such as silicone oils, fluorine oils, and liquid polymers can be used alone or in combination.

Furthermore, dissolved substances or dispersed substances may be present on either side of the water or oil. For example, dissolved substances on the water side include sulfuric acid, sulfate, hydrochloric acid, hydrochloride, nitric acid, nitrate, sodium hydroxide, potassium hydroxide, ammonia, persulfate,
Overchlorine! Extremely hot mM salts, hydrogen peroxide, sulfites, nitrites, etc., bases and their salts: carboxylic acid salts such as (meth)acrylic acid salts), acetic acid (salts), maleic acid salts), t) - Sulfones (salts) such as toluenesulfonic acid (salts) and styrenesulfonic acid (salts), amines (salts)
Various organic acids and bases and their salts such as methanol,
Water-soluble organic solvents such as ethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and acetone; Water-soluble polymer compounds such as polyethylene glycol, polycarboxylic acid, polysulfonic acid, polyvinyl alcohol, and polysaccharides. be able to. In addition, dissolved substances on the oil side include various organic radical initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, penzoyl chloride, and dibutyl peroxide; polystyrene, polymethyl methacrylate, and polyacetic acid. Examples include oil-soluble polymer compounds such as silica. Examples of the dispersed substance include inorganic particles such as ceramic, lime, cement, silica, alumina, and carbon black; organic particles such as organic pigments and polymer latex.

Furthermore, there is no particular limitation on the method of mixing or adding water, oil, and the polymer emulsifier of the present invention, and water, oil, and emulsifier may be added at the same time, or they may be added and mixed in order to emulsify. good. If they are to be added at the same time, they may be added in their entirety first, or they may be mixed while being fed continuously. If the substances are added in order, they may be added in any order, and the substances to be added later may be added at once, or may be used continuously or in parts by being added and dispersed. Various forms can be adopted, such as those dissolved or dispersed in water or a solvent, or liquid or solid forms that do not contain water or solvent.7□The amount of the polymer emulsifier of the present invention added is not particularly limited. However, there are no particular limitations on the emulsification method, that is, the equipment used for emulsification, and a simple stirrer such as a propeller blade is sufficient, but a shaker, Emulsification can be carried out using any device such as a homogenizer, colloid mill, pressure homogenizer or ultrasonic homogenizer.

As mentioned above, the polymer emulsifier of the present invention has excellent heat resistance and produces an emulsion with excellent freeze-thaw stability, so there are no particular limitations on the temperature during emulsification or the temperature at which the produced emulsion is used. Can be used in a wide temperature range. For example, the temperature during emulsification may be within a temperature range where both the aqueous phase and the oil phase can maintain their liquid state, emulsification may be carried out at a low temperature by using additives that lower the freezing point, or emulsification may be carried out at a low temperature by applying pressure. It can also be emulsified.

Further, the polymer emulsifier of the present invention may be used in combination with various surfactants and polymers having emulsifying ability, stabilizers, thickeners, rust preventives, antioxidants, etc., as necessary.

〔Effect of the invention〕

The polymer emulsifier of the present invention is made of a polymer having a specific structural unit, and due to its basic structure, it can be applied to a wide range of emulsification systems.Moreover, by adding only a small amount of ω, droplets can be maintained for a long period of time. It is possible to provide an extremely stable emulsion that does not cause coalescence or two-phase separation.

Therefore, the polymer emulsifier of the present invention is an extremely high-performance emulsifier that can be applied to a wide range of uses as described below.

In other words, inorganic chemical industry, organic chemical industry, textile industry, synthetic rubber and synthetic resin industry, paper and pulp industry, civil engineering and construction industry, color materials, paint and printing ink industry, adhesive industry, machinery and
Metal industry, ceramic industry, agriculture, forestry and fisheries industry, oil and fat/detergent industry, petrochemical/fuel oil industry, leather industry, pharmaceutical/cosmetics industry, food industry, electrical/electronic industry, energy-related field, environmental conservation field, biochemistry field, etc. In a wide range of fields, for example, m
Ift oil, scouring agent, humectant, antistatic agent, water repellent,
Waterproofing agents, softening agents, dyeing aids, thread oil, emulsifiers for emulsion/suspension polymerization, emulsion adhesives, emulsion paints, abrasives, drilling oils, lubricating oils, hydraulic oils, cutting oils, rolling oils, cold electrodes Various mold release agents such as pressurized oil, rust preventive agent, metal rot surface treatment agent, mold release agent, leather fatliquoring agent, paper sizing agent, asphalt emulsion, emulsifier for agricultural chemicals and photography, emulsifier for flotation agent, demolition agent, etc. Base agent, antifogging agent, emulsifier for tertiary crude oil recovery, emulsion fuel, emulsion explosive, emulsifier for separated water in fuel oil, emulsifier for waste liquid treatment, emulsifier for extraction, spilled oil treatment agent, emulsifier for coating film production, microcapsule manufacturing Emulsifiers for manufacturing microparticles, emulsifiers for manufacturing inorganic hollow molded bodies, emulsifiers for various cosmetics such as emulsions and cold creams, ointments, emulsifiers for pharmaceuticals, various weighed dairy products, emulsion-type products, and various two-phase reactions. Liquid-liquid emulsifiers, emulsifiers for two-phase reactions using enzymes or catalysts, emulsifiers for various waxes, emulsifiers for shoe polish, kitchen cleaners, clothing cleaners, tank cleaners, gold plate surface cleaners, etc. It can be applied to all emulsification applications related to phase-based emulsification, such as various two-phase reactions, manufacturing of various emulsions, and various emulsion-type products, and is contributing to the development of industries in emulsifier and emulsion-related fields. It can greatly contribute to

[Example] Next, the polymer emulsifier of the present invention will be described in more detail with reference to comparative examples and examples, but the present invention is not limited thereto.

In addition, unless otherwise specified, parts represent parts by weight.

Reference Example 1 50 parts of toluene was charged into a flask equipped with a thermometer, a stirrer, two dropping funnels, a gas inlet tube, and a reflux condenser, and the inside of the flask was replaced with nitrogen while stirring, and 10 parts of toluene was charged under a nitrogen stream.
Heated to 0°C. Thereafter, while maintaining the same temperature under a nitrogen stream, polyethylene glycol monomethacrylate (containing an average of 8 ethylene oxide units per molecule, an average molecular f
A monomer mixture consisting of 20 parts of f1438), 80 parts of stearyl acrylate (monomer that produces the structural unit (b-1), molecule matrix 324) as a monomer that produces the structural unit (B), and 50 parts of toluene. The solution was added dropwise over 120 minutes, and at the same time, a polymerization initiator solution consisting of 5 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise from the other dropping funnel over 180 minutes. After the dropwise addition was completed, the same temperature was maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% as a result of GPC analysis for polyethylene glycol monomethacrylate, and 98% as a result of gas chromatography analysis for stearyl acrylate (also in the following reference examples, structural units (A) and ( b-2
) The polymerization rate was determined by GPC analysis for the monomer that produces , and by gas chromatography analysis for the other monomers. ), and the average molecular weight of the hand polymer obtained by 1q is 6,000 as a result of GPC analysis using polystyrene as a standard (in the following reference examples, the average molecular weight of the polymer obtained in the same manner was determined by GPC analysis. ). Thereafter, the solvent was distilled off under reduced pressure to obtain polymer (1).

Reference Example 2 50% of isopropyl alcohol was added to the same reactor as Reference Example 1.
The flask was purged with nitrogen while stirring, and heated to 80° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, a methacrylamide ethylene oxide adduct (containing an average of 6 ethylene oxide units per molecule, average molecular m349) 40 50 parts of dodecyl acrylate (monomer that produces structural unit (b-1), molecule ff1240) as a monomer that produces structural unit (B), and other than structural unit (A) and structural unit (8) Taking the monomer that produces the structural unit, methacrylamide (molecule ff185) 1
A monomer mixed solution consisting of 0 parts of azobisdimethylvaleronitrile and 50 parts of isopropyl alcohol was added dropwise over 120 minutes, and at the same time 18 parts of azobisdimethylvaleronitrile was added from the other dropping funnel.
A polymerization initiator solution consisting of 5 parts and 50 parts of isopropyl alcohol was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization.

The polymerization rate of each monomer at this time was 96% for methacrylamide ethylene oxide adduct and 9% for dodecyl acrylate.
8%, methacrylamide was 99%, and the average molecular weight of the obtained polymer was 10,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a true polymer (2).

Reference Example 3 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol acrylate (containing an average of 20 ethylene oxide units per molecule, average molecular f
A monomer mixed solution consisting of 50 parts of dodecyl acrylate (a monomer that produces structural unit (b-1), molecule ff1240) as a monomer that produces structural unit (B), and 50 parts of toluene. was added dropwise over 120 minutes, and at the same time, a polymerization initiator solution consisting of 1.5 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise from the other dropping funnel over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for methoxypolyethylene glycol acrylate and 9% for dodecyl acrylate.
9%, and the average molecular weight of the obtained polymer was 20,000. Thereafter, by distilling off the solvent under reduced pressure, the polymer (
3) was obtained.

Reference Example 4 Into a flask equipped with a thermometer, a stirrer, a dropping funnel, a gas introduction tube, and a reflux condenser, 100 parts of toluene and a structural unit (
Methoxypolyethylene glycol methacrylate (containing an average of 20 ethylene oxide units per molecule, average molecule FF 1980) as a monomer producing A)
30 parts, 50 parts of butyl methacrylate (monomer that produces structural unit (b-1), molecule fa142) as a single substance that produces structural unit (B), and structural units other than (A> and structural unit (B)) 20 parts of methyl acrylate (molecule f!86) was charged as a monomer to generate the structural unit of
The inside of the flask was replaced with nitrogen while stirring, and the atmosphere was heated to 100% under nitrogen flow.
heated to ℃. Then, while maintaining the same temperature under a nitrogen stream, 1.5 g of benzoyl peroxide was added from the dropping funnel.
30 parts of polymerization initiator solution consisting of 50 parts of toluene and 50 parts of toluene
It was added dropwise over 0 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. At this time, the polymerization rate of each car body was 100% for methoxypolyethylene glycol methacrylate, 99% for butyl methacrylate, and 99% for methyl acrylate, and the average molecular weight of the obtained polymer was 200,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (4).

Reference Example 5 50 parts of toluene was charged into the same reactor as Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, ethoxypolyethylene glycol acrylate (containing an average of 40 ethylene oxide units per molecule, average molecular m.
186o) 80 parts, 20 parts of α-methylstyrene (monomer that produces the structural unit (b-i>, molecule ff1118) as a monomer that produces the structural unit (B), and 5 parts of toluene.
A monomer mixed solution consisting of 0 parts was added dropwise over 120 minutes,
Simultaneously, from the other dropping funnel, a polymerization initiator solution consisting of 1.2 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for ethoxypolyethylene glycol acrylate and 99% for α-methylstyrene, and the average molecular weight of the obtained polymer was 50,000. Thereafter, the small polymer (5) was obtained by distilling off the solvent under reduced pressure.

Reference Example 6 50 parts of benzene was charged into a reactor similar to Reference Example 1, and the inside of the flask was replaced with nitrogen while stirring, and the reactor was heated under a nitrogen stream to reflux the benzene. Thereafter, while maintaining a reflux state under a nitrogen stream, n-propoxypolyethylene glycol-polypropylene glycol acrylate (on average 60 ethylene oxides and 10 propylene oxides per molecule) was used as a monomer to produce the structural unit (A). Containing unit, average molecule ω3334) 20 parts, structure/unit (
B) A monomer mixture solution consisting of 80 parts of nonylphenyl acrylate <4'if the monomer that produces the structural unit (b-1), molecule 1274) and 50 parts of benzene was added for 120 minutes. At the same time, a polymerization initiator solution consisting of 1.0 part of benzoyl peroxide and 50 parts of benzene was added dropwise from the other dropping funnel over 180 minutes.

After the dropwise addition was completed, the reflux state was maintained for another 60 minutes to complete the polymerization. At this time, the polymerization rate of each 1 part matrix was 100% for n-propoxypolyethylene glycol-polypropylene glycol acrylate and 98% for nonylphenyl acrylate, and the average molecular weight of the obtained polymer was 10%.
It was 10,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (6).

Reference Example 7 50 parts of toluene was charged into the same reactor as Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, bis(methoxypolyethylene glycol) maleate (containing an average of 10 ethylene oxide units per molecule, average molecular weight of 584 ) and 10 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule, average molecule FF 1498),
Styrene as a monomer that produces structural unit (B) (monomer that produces structural unit (b-1), molecule ff1104)
A monomer mixed solution consisting of 80 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 120 minutes, and at the same time a polymerization initiator solution consisting of 3.0 parts of azobisisobutyronitrile and 50 parts of toluene was added from the other dropping funnel. The mixture was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 95% for bis(methoxypolyethylene glycol) maleate;
96% polyethylene 1 non-glycol monoallyl ether
, styrene was 99%, and the average molecular weight of the obtained polymer was 20,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (7).

Reference Example 8 50% of isopropyl alcohol was placed in the same reactor as Reference Example 1.
The flask was purged with nitrogen while stirring, and heated to 80° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, ethoxypolyethylene glycol crotonate (containing an average of 20 ethylene oxide units per molecule, average molecular weight 1994) 70 N,N-dibutyl methacrylamide as a monomer that produces structural unit (B) (monomer that produces structural unit (b-1), molecule ff1197
) and 50 parts of isopropyl alcohol was added dropwise over 120 minutes, and at the same time, from the other dropping funnel, a polymerization consisting of 1.5 parts of azobisdimethylvaleronitrile and 50 parts of isopropyl alcohol was started. The agent solution was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization.

The polymerization rate of each polymer at this time was 96% for ethoxypolyethylene glycol crotonate and 96% for N,N-dibutylmethacrylamide, and the average molecular stiffness of the obtained polymer was 30,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (8).

Reference Example 9 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, bis(methoxypolyethylene glycol) itaconate (containing an average of 20 ethylene oxide units per molecule, average molecular ff 11038) was used as a monomer to produce the structural unit (A). ) 30 parts, octyl methacrylate (structural unit (
b-1) Produced by single fn, molecule ff1198)
A monomer mixed solution consisting of 70 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 120 minutes, and at the same time a polymerization initiator solution consisting of 1.5 parts of azobisisobutyronitrile and 50 parts of toluene was added from the other dropping funnel. It was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 96% for bis(methoxypolyethylene glycol) itaconate.
, octyl methacrylate was 98%, and the average molecular weight of the obtained polymer was 15,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (9).

Reference Example 10 50 parts of toluene was charged into the same reactor as in Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol acrylate (containing an average of 4 ethylene oxide units per molecule, average molecular ff
1262) 50 parts, styrene as a monomer that produces the structural unit (B) (a monomer that produces the structural unit (b-1),
Molecule ff1104) 40 parts and 1-decene (structural unit (b
A monomer mixed solution consisting of 10 parts of the monomer producing -1), molecular weight 140) and 50 parts of toluene was added dropwise over 120 minutes, and at the same time 1. A polymerization initiator solution consisting of 5 parts of toluene and 50 parts of toluene was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 99% for methoxypolyethylene glycol acrylate, 97% for styrene,
The content of 1-decene was 95%, and the average molecular weight of the obtained polymer was 30,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer 10).

Reference Example 11 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, 40 parts of methoxypolyethylene glycol methacrylate (containing an average of 10 ethylene oxide units per molecule, average molecular weight 540) as a monomer for forming the structural unit (A) , styrene as a monomer that produces the structural unit (B) (a monomer that produces the structural unit (b-1),
50 parts of molecule ff1104) and allylhexyl ether (
A molecule, molecule ff114, that produces structural unit (b-1)
2) A monomer mixed solution consisting of 10 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 120 minutes, and at the same time a polymerization initiator consisting of 1.5 parts of azobisisobutyronitrile and 50 parts of toluene was added from the other dropping funnel. The solution was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for methoxypolyethylene glycol methacrylate;
The polymer contained 96% styrene and 94% allylhexyl ether, and the average molecular weight of the obtained polymer was 40,000. Thereafter, the polymer (11) was obtained by distilling off the solvent under reduced pressure.
I got it.

Reference Example 12 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, 70 parts of methoxypolyethylene glycol methacrylate (containing an average of 10 ethylene oxide units per molecule, average molecular weight 540) as a monomer to produce structural unit (A) , polypropylene glycol monomethacrylate as a monomer that produces the structural unit (B) (a monomer that produces the structural unit (b-2), containing an average of 6 propylene oxide units per molecule, an average molecule of 1
434) A monomer mixed solution consisting of 30 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 120 minutes, and at the same time a polymerization initiator consisting of 1.5 parts of azobisisobutyronitrile and 50 parts of toluene was added to the other dropping funnel. The solution was added dropwise over 180 minutes. After the dropwise addition was completed, the polymerization was further maintained at the same temperature for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time is
98% methoxypolyethylene glycol acrylate
, polypropylene glycol monomethacrylate is 98
%, and the average molecular weight of the obtained polymer was 20,000. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (1
2) was obtained.

Reference Example 13 50% of isopropyl alcohol was placed in the same reactor as Reference Example 1.
The flask was purged with nitrogen while stirring, and heated to 80° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol acrylate (containing an average of 30 ethylene oxide units per molecule, average molecular fil 406) 20 1 part, methoxypolypropylene glycol-polyethylene glycol monomethacrylate as a monomer producing structural unit (B) (monomer producing structural unit (b-2), on average 1 per molecule)
containing 0g of glolene oxide and 3 ethylene oxide units, average molecular weight 812) 70 parts, structural unit (
A monomer mixed solution consisting of 10 parts of methacrylic acid molecule fa86) and 50 parts of isopropyl alcohol as a unit that produces structural units other than structural units A) and (B) was added dropwise over 120 minutes, and at the same time the other A polymerization initiator solution consisting of 1.5 parts of azobisdimethylvaleronitrile and 50 parts of isopropyl alcohol was added dropwise from the dropping funnel over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 100% for methoxypolyethylene glycol acrylate and 100% for methoxypolypropylene glycol.
Polyethylene glycol methacrylate was 97%, methacrylic acid was 100%, and the average molecular weight of the obtained polymer was 30,000. Thereafter, 7 parts of monoethanolamine were added and mixed, and then the solvent was distilled off under reduced pressure to obtain a polymer (13).

Reference Example 14 50 parts of toluene was charged in the same reactor as in Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol acrylate (containing an average of 10 ethylene oxide units per molecule, an average molecular f
f1526) 40 parts, benzyl acrylate (structural unit (b-
50 parts of monomer, molecule ff1162) that produces 1), 10 parts of dimethylamine ethyl methacrylate (molecule ff1157) as a monomer that produces structural units other than structural unit (A) and structural unit (B), and 50 parts of toluene. A monomer mixed solution consisting of 1.5 parts of azobisisobutyronitrile and 50 parts of toluene was added dropwise over 180 minutes from the other dropping funnel. did. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete one cup. The polymerization rate of each monomer at this time was 98% for methoxypolyethylene glycol acrylate, 97% for benzyl acrylate, and 98% for dimethylamine ethyl methacrylate, and the average molecular weight of the obtained polymer was 20,000. Ta. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymer (14).

Reference Example 15 In a flask equipped with a thermometer, a stirrer, and a gas introduction tube,
20 parts of the polymer (1) obtained in Reference Example 1, 1.1 parts of sulfamic acid, and 0.2 parts of urea were charged, the inside of the flask was replaced with nitrogen while stirring vigorously, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, by reacting for 180 minutes while maintaining the same temperature under a nitrogen stream, a polymer (15
) was obtained.

As a result of electrophoretic analysis, the conversion rate of sulfamic acid was 75%.

Reference Example 16 Into the same reaction vessel as in Reference Example 15, 20 parts of the polymer (1) prepared by 1!7 in Reference Example 1 and 1.1 parts of maleic anhydride were charged, and the inside of the flask was replaced with nitrogen while stirring. , heated to 100°C under nitrogen flow. Thereafter, the reaction was carried out for 180 minutes while maintaining the same temperature under a nitrogen stream. As a result of analyzing the reaction solution by liquid chromatography, the conversion rate of maleic anhydride was 72%. Thereafter, 1.5 parts of jetanolamine was added and mixed to obtain an m-coalescence (16) in which the terminal of the polyoxyethylene chain was modified to a maleic acid half ester salt.

Reference Example 17 In a flask equipped with a thermometer, a stirrer, and a reflux condenser with a water separator, 20 parts of the polymer (2) obtained in Reference Example 2, 20 parts of cyclohexane, 1.8 parts of acrylic acid, and 0 parts of sulfuric acid were added.
．． Two parts were charged, and the temperature was raised to the reflux temperature of cyclohexane while stirring. Thereafter, the reaction was carried out for 180 minutes while maintaining the same temperature and removing the produced water from the system. As a result of analyzing the reaction solution by liquid chromatography, the conversion rate of acrylic acid was 77%. Then, by adding and mixing 0.6 parts of monoethanolamine, a polymer (17
) was obtained.

Reference Example 18 In a reactor similar to Reference Example 1, 50% isopropyl alcohol was added.
The flask was purged with nitrogen while stirring, and heated to 80° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, 50 parts of octyl acrylate (monomer that produces structural unit (b-1), molecule ff1184) as a monomer that produces structural unit (B), and structural unit (A)
A monomer mixed solution consisting of 50 parts of acrylic M (molecule flfi72) and 50 parts of isopropyl alcohol as a molecule that produces structural units other than structural unit (8) was added dropwise over 120 minutes, and at the same time the other one was added dropwise. A polymerization initiator solution consisting of 1.5 parts of azobisdimethylvaleronitrile and 50 parts of isopropyl alcohol was added dropwise from the funnel over 180 minutes.

After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for octyl acrylate and 99% for acrylic acid, and the average molecular weight of the obtained m-coalescence was 20,000. Thereafter, 280 parts of a 10% aqueous sodium hydroxide solution was added and mixed, and then the solvent was distilled off under reduced pressure to obtain comparative m-coalescence (1).

Reference Example 19 50 parts of toluene was charged in the same reactor as Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, 50 parts of methoxypolyethylene glycol methacrylate (containing an average of 10 ethylene oxide units per molecule, average molecular weight 540) as m-coalescence to produce the structural unit (A), Structural unit (A) and structural unit (B
) A monoconvex mixed solution consisting of 50 parts of methyl acrylate (molecule ff186) and 50 parts of toluene was added dropwise over 120 minutes, and at the same time azobisisomer was added from the other dropping funnel. A polymerization initiator solution consisting of 1.5 parts of butyronitrile and 50 parts of toluene was added dropwise over 180 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 100% for methoxypolyethylene glycol methacrylate and 9% for methyl acrylate.
The average molecular weight of the obtained polymer was 10,000.

Thereafter, the comparative m-coalescence (
2) was obtained.

Reference Example 20 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol methacrylate (containing an average of 20 ethylene oxide units per molecule, an average molecular f
f1966) 50 parts, structural unit (A) and structural unit (
A monomer mixed solution consisting of 50 parts of vinyl acetate (molecular fa86) and 50 parts of toluene as monomers that produce structural units other than B) was added dropwise over 120 minutes, and at the same time, from the other dropping funnel, azobis Isobutyronitrile 1.
1 part of a polymerization initiator solution consisting of 5 parts of toluene and 50 parts of toluene.
The mixture was added dropwise over 80 minutes.

After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for methoxypolyethylene glycol acrylate and 90% for vinyl acetate, and the average molecular weight of the obtained polymer was 1,50,000. Thereafter, the solvent was distilled off under reduced pressure to obtain comparative polymer (3).

Reference Example 21 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol methacrylate (containing an average of 20 ethylene oxide units per molecule, average molecular mouth 980) was used as a monomer to produce the structural unit (A). , styrene as a monomer that produces the structural unit (B) (a monomer that produces the structural unit (b-1),
A monomer mixed solution consisting of 2 parts of molecule ff1104) and 50 parts of toluene was added dropwise over 120 minutes, and at the same time 1.
1 part of a polymerization initiator solution consisting of 5 parts of toluene and 50 parts of toluene.
It was added dropwise over 80 minutes.

After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 98% for methoxypolyethylene glycol methacrylate and 100% for styrene, and the average molecular weight of the obtained polymer was 30,000. Thereafter, the solvent was distilled off under reduced pressure to obtain comparative polymer (4).

Reference Example 22 50 parts of toluene was charged into a reactor similar to Reference Example 1, the inside of the flask was replaced with nitrogen while stirring, and the temperature was heated to 100°C under a nitrogen stream.
heated to. Thereafter, while maintaining the same temperature under a nitrogen stream, methoxypolyethylene glycol acrylate (containing an average of 10 ethylene oxide units per molecule, average molecular ω
526) 2 parts, 98 parts of butyl methacrylate (monomer that produces structural unit (b-1), molecule ff1142) as a monomer that produces structural unit (B), and 50 parts of toluene.
1.5 parts of azobisisobutyronitrile and 50 parts of toluene were added dropwise from the other dropping funnel over 180 minutes. did. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The polymerization rate of each monomer at this time was 100% for methoxypolyethylene glycol acrylate and 97% for butyl methacrylate.
The average molecular weight of the obtained polymer was 20,000.

Thereafter, the comparative polymer (
5) was obtained.

Examples 1 to 17 Using each of the polymers (1) to (17) obtained in Reference Examples 1 to 17 as an emulsifier, emulsions were prepared by the following method, and their standing stability was evaluated.

In a 200Id beaker, 60 parts of toluene, 60 parts of water, and each of the polymers (1) to (17) were placed in designated openings corresponding to the emulsifier addition ports shown in Table 1, and mixed for 10 minutes at room temperature to prepare an emulsion. The mixing was performed using a homomixer at 5.00 rpm.

20 parts of each of the obtained emulsions were placed in a test tube with a 25 mA stopper and a scale, and left to stand at room temperature. After 3 hours, 1 day, 3 days, 10 days, and 30 days, the upper layer (toluene layer) The standing stability of the emulsion was evaluated by measuring the separation status of the lower layer (aqueous layer) over time. The evaluation criteria were as follows. (However, the VO1% of the separated layer indicates the VO1% with respect to the capacity of each of the upper layer and the lower layer before emulsification.) ◎: Minute 11! t1m3vo less than 1%○: Separation layer 3v01% or more and less than 10vo1%Δ: Separation layer 10vo+% or more and less than 30vo1%×: Separation layer 3Qvo
Table 1 shows the emulsifier used in each example in an amount of 1% or more, the time of its addition, and the evaluation results over time of the standing stability of the resulting emulsion.

Comparative Examples 1 to 9 Comparative polymers (1) to (5) obtained in Reference Examples 18 to 22
, conventional product (A) is polyoxyethylene nonylphenyl ether with HLB of 13.0, conventional product (B) is H
Examples except that polyoxyethylene nonylphenyl ether with an LB of 8.0, sorbitan monooleate with an HLB of 4.3 as the conventional product (C), and sodium lauryl sulfate as the conventional product (D) were used as emulsifiers. An emulsion was prepared in the same manner as in Example 1, and the standing stability of the obtained emulsion was evaluated in the same manner as in Example 1. Table 1 shows the emulsifier used, its additive base, and the evaluation results.

Examples 18-25 In Example 1, polymers (1) and (2) were used as emulsifiers.
, (3), (4), (8), (11) or (14), respectively, except that kerosene, soybean oil, ethyl acrylate or 1,1.1-trichloroethane was used as the oil component. An emulsion was prepared in the same manner as in Example 1, and the standing stability of the obtained emulsion was evaluated.

Table 2 shows the type of oil, emulsifier, amount added, and evaluation results used in each example.

(In addition, when 1,1.1-trichloroethane was used, the upper layer was an aqueous layer and the lower layer was an oil layer.) Comparative Example 10
~17 In Example 1, the same method as in Example 1 was used except that one of the emulsifiers used in Comparative Examples 1 to 9 was used, and kerosene or 1,1.1-trichloroethane was used as the oil. An emulsion was prepared, and the standing stability of the obtained emulsion was evaluated. The evaluation results are shown in Table 2.

Examples 26 to 29 In Example 1, 1.2 parts each of polymers (1), (5), or (9) were used as emulsifiers, toluene or kerosene was used as oil, and the oil content was 36 parts or 84 parts, and water was 84 parts. part or 36 parts (however, the total amount of oil and water is 120 parts)
An emulsion was prepared in the same manner as in Example 1, except that the emulsion was measured using an electrical conductivity method.

As a result, it was clear that among the water and oil components, the component with a larger m was converted into droplets.

Furthermore, the static stability of the obtained emulsion was evaluated in Example 1.
It was evaluated using the same method. The evaluation results are shown in Table 3.

Comparative Examples 18-23 In Example 1, H was used as the conventional product (A) as an emulsifier.
3.7 parts each of polyoxyethylene nonylphenyl ether with L8 of 13.0 or sorbitan monooleate with HL B of 4.3 as conventional product (C);
Using toluene or kerosene as the oil, the oil content is 36
An emulsion was prepared in the same manner as in Example 1 except that the amount of water was 84 parts or 36 parts (however, the total of oil and water was 120 parts). The test was conducted in the same manner as in Example 26, and the standing stability was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Examples 30 to 32 Emulsions were prepared in the same manner as in Examples 1.3 and 12, and the resulting emulsions were allowed to stand at 60°C, and the standing stability was evaluated in the same manner as in Example 1. . However, the evaluation was performed after 3 hours, 1 day, and 10 days. The evaluation results are shown in Table M4.

Comparative Examples 24 to 26 Emulsions were prepared in the same manner as in Comparative Examples 6.7 and 8, and each of the 1q emulsions was prepared in Example 30.
It was left to stand still in the same manner as above, and the standing stability was evaluated. The evaluation results are shown in Table 4.

Examples 33 to 35 Emulsions were prepared in the same manner as in Examples 1.3 and 12, and the resulting emulsions were left in a freezer at -10°C for 24 hours, then returned to room temperature to freeze and freeze.
A melting process was performed.

Thereafter, the standing stability of the emulsion was evaluated in the same manner as in Example 30. The evaluation results are shown in Table 5.

Comparative Examples 27 to 29 Emulsions were prepared in the same manner as in Comparative Examples 6, 7 and 8, and the resulting emulsions were subjected to freezing and thawing treatment in the same manner as in Example 33. In all of these emulsions, the emulsions were destroyed by freezing and thawing treatment.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R^1 is hydrogen or a methyl group, R^2 is hydrogen or a methyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^3 is hydrogen, methyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. There is ▼, and R^4 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {However, R^5 is a carbon containing ethylene oxide residues in an amount of 50% by weight or more based on the total weight of all alkylene oxide residues. alkylene oxide residue having a number of 2 to 4, l is a number of 1 to 300, R^6 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an organic group having an unsaturated bond having 2 to 5 carbon atoms, or the presence of water A group that dissociates and shows ionicity, R^7 is hydrogen or ▲ has a mathematical formula, chemical formula, table, etc. an alkylene oxide residue having 2 to 4 carbon atoms, m is a number of 1 to 300, R^9
represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an organic group having 2 to 5 carbon atoms and an unsaturated bond, or a group that exhibits ionicity when dissociated in the presence of water. ), A is -COO-, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (R^7 is the same as above)
Or -CH_2O-. }, and R^2 is ▲ There is a mathematical formula, chemical formula, table, etc. ▼ or ▲ There is a mathematical formula, chemical formula, table, etc. ▼, then R^3 is hydrogen or a methyl group, and R^4 is ▲ Mathematical formula, chemical formula, etc. , there are tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and R^3 is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ 2 is hydrogen or a methyl group, and R^4 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] At least one structural unit (A) represented by general formula (II) ▲Mathematical formula, chemical formula, table, etc.▼(II) [However, in the formula, R^1^0 is hydrogen or a methyl group, R ^
1^1 is hydrogen, methyl group, -COOR^1^4 or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, R^1^2 is hydrogen,
Methyl group, -CH_2COOR^1^4 or ▲ formula,
There are chemical formulas, tables, etc. ▼ where R^1^3 is derived from an alkyl group, alkenyl group, aryl group, aralkyl group, cyclic alkyl group, cyclic alkenyl group, or heterocyclic compound having 4 to 30 carbon atoms. Monovalent organic group, -COOR^1^4, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ or -CH_2OR^1^4 (However, R^1^4 is an alkyl group with 4 to 30 carbon atoms,
A monovalent organic group derived from an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group, a cyclic alkenyl group, or a heterocyclic compound, R^1^5 is hydrogen, an alkyl group having 1 to 30 carbon atoms, It represents a monovalent organic group derived from an alkenyl group, an aryl group, an aralkyl group, a cyclic alkyl group, a cyclic alkenyl group, or a heterocyclic compound. )
If R^1^1 is -COOR^1^4 or ▲There is a mathematical formula, chemical formula, table, etc.▼, then R^1^2 is hydrogen or a methyl group, and R^1^3 is -COOR^ 1＾4 or ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1^2 is -CH_2COOR^1^4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, then R^1^1 is hydrogen or a methyl group, and R^1^3 is -COOR^1^4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] Structural unit (b-1) represented by general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [However, in the formula, R^1^6 is hydrogen or a methyl group, R^
1^7 is hydrogen, methyl group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, R^1^8
is hydrogen, methyl group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, and R^1^9
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^2^
0 is an alkylene oxide residue having 2 to 4 carbon atoms in which the content of ethylene oxide residue is 30% by weight or less based on the total weight of all alkylene oxide residues, n is a number from 1 to 300, R^2^
1 is hydrogen, a monovalent organic group derived from an alkyl group, alkenyl group, aryl group, aralkyl group, cyclic alkyl group, cyclic alkenyl group or heterocyclic compound having 1 to 30 carbon atoms, R^2^2 is Hydrogen or ▲Mathematical formulas, chemical formulas, tables, etc.▼
0% by weight or less of an alkylene oxide residue having 2 to 4 carbon atoms, p is a number from 1 to 300, R^2^4 is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group, an aralkyl group , represents a monovalent organic group derived from a cyclic alkyl group, a cyclic alkenyl group, or a heterocyclic compound. )
, B indicates -COO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^2^2 is the same as above) or -CH_2O-. ), and if R^1^7 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, then R^1^8
is a hydrogen or methyl group, and R^1^9 is ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼ and R^
If 1^8 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, then R^1^7
is hydrogen or a methyl group, and R^1^9 is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼. ] A polymer emulsifier comprising a polymer (C) containing at least one structural unit (B) selected from the group consisting of the structural unit (b-2) represented by the following as a main constitutional unit. 2. The content of the structural unit (A) and the structural unit (B) in the polymer (C) is 5 to 95% by weight, respectively,
A patent claim in which the structural unit (B) is in the range of 95 to 5% by weight, and the total content of the structural unit (A) and structural unit (B) in the polymer (C) is 50% by weight or more range 1
The polymer emulsifier described in section. 3. The polymer emulsifier according to claim 1 or 2, wherein the average molecular weight of the polymer (C) is in the range of 1,000 to 500,000. 4. In the general formula (I) representing the structural unit (A),
Patents where R^1, R^2 and R^3 are each independently hydrogen or methyl group, and R^4 is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼ The polymer emulsifier according to any one of claims 1 to 3. 5. In the general formula (I) representing the structural unit (A),
R^6 and R^9 are each independently hydrogen, carbon number 1-
3 alkyl group, alkenyl group having 2 to 3 carbon atoms, (meth)acryloyl group, (iso)crotonoyl group, dimethylacryloyl group, -SO_3X, -R^2^3SO_3
X, -R^2^3CO_2X, -COR^2^3CO_
2X, -PO_3(X)_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -PO_3(R^2^4)(X), ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^2^3 is an alkylene group with 1 to 3 carbon atoms,
Hydroxyalkylene group or alkenylene group, R^2
^4, R^2^5 and R^2^6 are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, X and Y are each independently hydrogen, an alkali metal, an alkaline earth metal, It is an ammonium or amine base, and Z^■ represents a counter anion. ) The polymer emulsifier according to any one of claims 1 to 4. 6. Any of claims 1 to 5, wherein in the general formula (II) representing the structural unit (b-1), R^1^1 and R^1^2 are each independently hydrogen or a methyl group. The polymer emulsifier described in Crab. 7. In the general formula (III) representing the structural unit (b-2), R^1^6, R^1^7 and R^1^8 are each independently hydrogen or a methyl group, Claim No. 1
The polymer emulsifier according to any one of items 1 to 6. 8. In the general formula (I) representing the structural unit (A),
l is a number from 3 to 100, and in general formula (III) representing the structural unit (b-2), n is a number from 3 to 100, according to any one of claims 1 to 7. polymer emulsifier.