JPS6320303A - Modified amine compound and surfactant comprising same - Google Patents

Abstract

PURPOSE:To obtain the title compound excellent in affinities for and adhesiveness to various polymers and useful for the production of an emulsion which can give films and coatings excellent in strength and water resistance, by reacting an amine compound with a vinyl polymer having NH2 group-reactive functional groups and a specified compound. CONSTITUTION:An amine compound (A) having NH2 groups in the molecule, such as a polyethyleneimine of MW <=5,000, obtained by polymerizing a monoamine such as dimethylamine with ethyleneimine is reacted with 0.01-1 equivalent (per equivalent of NH2 groups of component A) vinyl polymer (B) of MW of 100-10,000, having NH2 group-reactive functional groups such as halogen atoms, epoxy groups, isocyanate groups, vinyl groups or COOH groups on one or both ends and 0.01-1 equivalent of a compound (C) of the formula (wherein R is a 4-28C hydrocarbon, A is a 2-4C alkylene, X is an atomic group having an NH2 group-reactive functional group and n is 0-30) at room temperature to 200 deg.C in the presence of, optionally, an organic solvent as a diluent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel modified amine compound and a surfactant containing the same.

More specifically, it can be used as a surfactant such as an emulsifier 2 dispersant for emulsifying or dispersing each paper oil, resin, or organic or inorganic powder in an aqueous medium.
In particular, it relates to a novel modified amine compound useful as an emulsifier for emulsion polymerization of vinyl compounds and the like.

(Prior art and problems to be solved by the present invention) Various types of modified amine compounds have been synthesized in the past, but among these modified amine compounds, there are hydrophobic groups and hydrophilic groups in the molecule. And as a substance with surfactant ability,
A modified amine compound obtained by reacting polyethyleneimine with an α-olefin epoxide and a modified amine compound obtained by addition reacting epihalohydrin to a polyamide polyamine resin (Japanese Patent Publication No. 22922/1982) have been proposed. However, when a vinyl compound is emulsion polymerized using these modified amine compounds as an emulsifier, a film obtained by scattering water from the resulting emulsion polymer is a vinyl compound produced by a polymerization reaction with the modified amine compound used as an emulsifier. Since the affinity with the polymer component is low and microphase separation occurs, various physical properties such as water resistance and strength are poor.

The object of the present invention is to solve the above-mentioned drawbacks of conventional modified amine compounds and to provide a novel modified amine compound that has excellent surface activity and compatibility with various vinyl polymers.
It's about doing ilR.

(Means and effects for solving the problem) The present inventors have developed an amine compound using a vinyl polymer having a functional group capable of reacting with an amino group at one or both ends and a specific structure having a hydrophobic group. The present invention was achieved based on the discovery that a novel modified amine compound obtained by reacting a compound with a vinyl amine compound exhibits excellent surfactant ability and is also excellent in compatibility with vinyl polymers.

That is, the present invention provides an amine compound (A) containing an amine group in the molecule, a vinyl polymer (B) having a functional group capable of reacting with an amino group at one or both ends, and the general formula % ( In the formula, R is a hydrocarbon group having 4 to 28 carbon atoms, and A is a hydrocarbon group having 2 carbon atoms.
~4 alkylene group, X is an atomic group having a functional group capable of reacting with an amino group, and n is O or an integer of 1 to 30.

The present invention relates to modified amine compounds obtained by reacting the compound (C) represented by ), salts thereof, and surfactants containing them.

In the present invention, an amine compound (A) containing an amino group in the molecule (hereinafter referred to as amine compound<A). ), if the amine group is only a tertiary amine group, amines having two or more amino groups in the molecule or their Xs
When the amino group contains a primary amino group and/or a secondary amino group, amines or derivatives thereof having one or more amino groups in the molecule are used. Such amine compounds (A) include, for example, monoamines such as dimethylamine and diethylamine; polyethyleneimine obtained by polymerizing ethyleneimine; polyalkyleneimines such as copolymers of ethyleneimine and propyleneimine; ethylenediamine, diethylenetriamine; triethylenetetramine, tetraethylpentamine,
Poly)alkylenepolyamines such as pentaethylenehexamine: polyalkyleneimines and/or poly(poly))
Polyamide polyamine obtained by condensation of alkylene polyamine and polybasic acid such as adipic acid: polyalkylene imine and/or polyurea polyamine obtained by reaction of (poly)alkylene polyamine and/or alkylene imine with urea: alkylene imine and phthalate Examples include polyamide polyester polyamine obtained by copolymerization with an acid anhydride such as an acid. In addition, as derivatives of amines, the above-mentioned amines and alkylene oxides such as ethylene oxide and propylene oxide, (meth)acrylic acid esters, or (
Examples include addition reaction products of meth)acrylamide and α,β-unsaturated acid amide compounds. In the present invention, it is preferable to use polyethyleneimine or a derivative thereof as the amine compound (A) in order to obtain excellent surface activity. In addition, when using the obtained modified amine compound as a surfactant, the molecular weight should be 5.
It is preferable to use polyethyleneimine having a molecular weight of 000 or less.

Vinyl polymer B) having a functional group capable of reacting with an amino group at one or both ends used in the present invention (hereinafter referred to as
It is called a vinyl polymer (B). ) include vinyl polymers or oligomers having the functional group, which can be synthesized by various methods; It is preferably a group, a vinyl group or a carboxyl group. In order to obtain the vinyl polymer (B) having the above-mentioned functional group at the end, for example, the vinyl polymer (B) having a halogen atom at the end is prepared by using carbon tetrachloride or carbon tetrabromide as a chain transfer agent.

Halogenated methane such as trichlorobromomethane: Obtained by radical polymerization of a polymerizable monomer in the presence of a halogen-containing compound such as halogenated acetic acid such as monochloroacetic acid and monobromoacetic acid. The vinyl polymer (8) having an epoxy group at the end is obtained by radical polymerizing a polymerizable monomer using mercaptoethanol or the like as a chain transfer agent to synthesize a vinyl polymer or oligomer having a hydroxyl group at the end, and then further processing. It can be synthesized by modifying it with a polyepoxy compound. The vinyl polymer (B) having an isocyanate group at its terminal can be synthesized by modifying the terminal hydroxyl group-containing polymer or oligomer with a polyisocyanate compound.

In particular, it is preferable to use a polyisocyanate compound having two isocyanate groups with different reactivities in one molecule, such as isophorone diisocyanate. The vinyl polymer (B) having a vinyl group at the terminal is a polymer containing the above-mentioned terminal hydroxyl group-containing polymer or oligomer and an epoxy group-containing polymerizable monomer such as glycidyl methacrylate or an isocyanate group-containing polymer such as isocyanate ethyl methacrylate. or α
, can be synthesized by esterification with a β-unsaturated acid. In addition, after synthesizing a polymer or oligomer having a carboxyl group at the terminal by radical polymerization of a polymerizable monomer in the presence of thioglycolic acid as a chain transfer agent,
It can be synthesized by reacting glycidyl methacrylate, aziridinylethyl methacrylate, isoprobenyloxaprine, etc. The vinyl polymer (B) is not particularly limited to the synthesis method described above, and can be synthesized by various methods.

The polymerizable monomer that can be used when synthesizing the vinyl polymer (B) has the same reactivity toward amino groups as the functional group contained at one or both ends of the vinyl polymer (B). υ1 is not particularly limited, except in cases where it contains the above functional groups. For example, when using a polymerizable monomer having a side chain reactive with amino groups, such as butadiene, isoprene, chlorobrene, (meth)acrylic acid, itaconic acid, and maleic anhydride, A functional group such as an isocyanate group or an epoxy group with high properties must be introduced at the end of the vinyl polymer (B). If the polymerizable monomer contains a functional group that is as reactive to amino groups as the functional group contained at the end of the vinyl polymer (B), the amine compound (A) and the vinyl polymer During the reaction (B), it may gel or the surface activity of the resulting modified amine compound may decrease. Polymerizable for use! l W-isomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.

(meth)acrylic acid alkyl esters such as 2-ethylhexyl (meth)acrylate; alkenylbenzenes such as styrene, α-methylstyrene, and vinyltoluene; furthermore, vinyl acetate and vinylpyridine.

Butadiene, isoprene, chlorobrene, acrylonitrile, methacrylonitrile, acrylic acid.

Methacrylic acid, itaconic acid, maleic anhydride, acrylamide, methacrylamide, dimethylamine ethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide.

(meth)acrylic M-2-hydroxyethyl, (meth)
Examples include 2-hydroxypropyl acrylate.

One or more of these can be used.

The molecular weight and amount of the vinyl polymer (B) used to obtain the modified amine compound of the present invention can be varied widely depending on the use and purpose of the obtained modified amine compound, but 100 when used as an agent
~io, o o o between molecules is preferable, and it is preferable to use the vinyl polymer (B) in an amount of 0.01 to 1 equivalent per amino group of the amine compound (A).

A compound (C) represented by the general formula % (in the formula, R, A, X and n are the same as above) used in the present invention (hereinafter referred to as compound (C)).

), the hydrocarbon group having 4 to 28 carbon atoms corresponding to R in the formula includes a linear or branched alkyl group having 4 to 28 carbon atoms, an (alkyl)aryl group, and a (alkyl)hydrogenated aryl group. and (alkyl)aralkyl groups. In the formula, X may be any atomic group having a functional group that can react with an amino group, but from the viewpoint of ease of reaction with the amine compound (A), the functional group that can react with an amine group is a halogen atom, Preferably, it is an epoxy group, an isocyanate group, a vinyl group or a carboxyl group. The compound (C) is, for example, n-octyl polyoxyalkylene glycidyl ether having from 1 to 30 moles of alkylene oxide such as ethylene oxide, propylene oxide, and isobutylene oxide.

n-nonyl polyoxyalkylene glycidyl ether,
Lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2
-Primary alkyl polyoxyalkylene glycidyl ethers such as ethylhexyl polyoxyalkylene glycidyl ether: those obtained by adding 1 to 30 moles of fullkylene oxide to a mixture of secondary alcohols having 12 to 14 carbon atoms and further converting the mixture into glycidyl ether. , carbon number 1
Secondary alkyl polyoxyalkylene glycidyl ethers such as those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of 0 to 12 secondary alcohols and further glycidyl etherification; the number of moles of alkylene oxide added is 1 to 30 Alkylphenyl polyoxyalkylene glycidyl ethers such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether, etc.: Addition mole of alkylene oxide Octylcyclopentyl polyoxyalkylene glycidyl ether having a number of 1 to 30.

Octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, laurylcyclopentyl polyoxyalkylene glycidyl ether, laurylcyclohexyl polyoxyalkylene glycidyl ether, stearylcyclopentyl polyoxyalkylene glycidyl ether, stearylcyclohexyl Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as polyoxyalkylene glycidyl ether: octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether with an added mole number of alkylene oxide of 1 to 30 Ethers, alkylbenzyl polyoxyethylene glycidyl ethers such as stearylbenzyl polyoxyalkylene glycidyl ether; glycidyl ethers of higher alcohols such as octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether: octylphenyl Glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether.

Glycidyl ethers of alkylphenols such as stearyl phenyl glycidyl ether: octylcyclopentyl glycidyl ether, octylcyclohexyl glycidyl ether, nonylcyclopentyl glycidyl ether, nonylcyclohexyl glycidyl ether, lauryl cyclopentyl glycidyl ether, lauryl cyclohexyl glycidyl ether, stearyl shift 0 Glycidyl ethers of furkylcycloalkanols such as pentyl glycidyl ether and stearyl cyclohexyl glycidyl ether; Glycidyl ethers of furkylbenzyl alcohol such as octylbenzyl glycidyl ether, nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether, and stearyl benzyl glycidyl ether : 1,2-epoxy alkanes such as α-olefin epoxide having 12 or 14 carbon atoms, α-olefin epoxide having 16 or 18 carbon atoms: octyl isocyanate, decyl isocyanate.

Alkyl isocyanates such as octadecyl isocyanate: Monoisocyanate compounds obtained by reacting alcohols such as octanol, lauryl alcohol, stearyl alcohol, or alkylene oxide adducts of these alcohols with diisocyanates such as tolylene diisocyanate: octanol, lauryl Halides in which the terminal hydrogen group of alcohols, alcohols such as stearyl alcohol, or fullkylene oxide adducts of these alcohols is substituted with halogen atoms such as chlorine, bromine, and iodine; lauric acid.

Saturated fatty acids such as myristic acid, valmitic acid, stearic acid, nioleic acid, linoleic acid, and linolenic acid. Unsaturated fatty acids such as eleostearic acid 2-acrylic acid
Examples include acrylic acid alkyl esters such as ethylhexyl, lauryl acrylate, and stearyl acrylate, and one or more types selected from these groups can be used.

The amount of the compound (C) used is not particularly limited, but in order to develop sufficient surface activity, the amine compound < A
) per amino group of α01 to 1 compound (
C) is preferably used.

The reaction conditions for obtaining the modified amine compound of the present invention are not particularly limited, and for example, the amine compound (A), vinyl polymer (B), and compound (C) are used as they are, or if necessary, diluted with a solvent. and preferably at normal humidity
The reaction is carried out at a temperature of 200°C, more preferably 50 to 150°C. At this time, it is preferable that the solvent used if necessary be capable of dissolving the amine compound (A), the vinyl polymer (8), and the compound (C), and be inert to them. Furthermore, during the reaction, a catalyst may be freely used to accelerate the reaction.

The modified amine compound of the present invention thus obtained is
A modified amine salt can be prepared by blending with an acid. It is preferable to use a modified amine salt because the solubility in water may be improved. At this time, examples of acids that can be blended include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid;
Examples include organic acids such as acetic acid and (meth)acrylic acid.

Furthermore, the surfactant of the present invention contains the above-mentioned modified amine compound and/or its salt, and if necessary, a conventionally known cationic or nonionic emulsifier, water-soluble organic solvent, etc. Additives may be added within a range that does not impair the characteristics of the modified amine compound or its salt.

(Effect of the invention) The modified amine compound of the present invention is an amine compound (A
), a vinyl polymer (B) and a compound (C) are reacted, and both components form a graft structure on the amine compound (A). That is, when a modified amine compound is used as a surfactant, the amine compound <A) unit imparts hydrophilicity, the vinyl polymer (B) unit improves compatibility with various polymers, and the compound ( C) The unit exhibits the effect of adjusting the balance between hydrophilicity and hydrophobicity. Therefore, the modified amine compound has excellent surfactant ability, and when used as a surfactant, it can efficiently emulsify or disperse various oily substances, Sl fat piles, organic or inorganic powders in an aqueous medium. Can be done.

It is also useful as an emulsifier for emulsion polymerization of vinyl compounds, etc., and various emulsions can be stably produced. Films and coatings obtained from such emulsions have improved compatibility with polymer particles after emulsion polymerization because the modified amine compound used as an emulsifier has a graft chain of a vinyl polymer component. ing.

For this reason, the tendency of conventionally known cationic emulsifiers to be localized at the particle fusion interface of films and coatings after film formation is eliminated, and the emulsifiers provide high film strength and excellent water resistance.

In addition, the modified amine compound of the present invention has the hydrophilicity, rust prevention, antibacterial property, and reactivity of the amino group of the amine compound (A).
Because it combines cationic properties, hydrophobicity (in some cases hydrophilicity) of the vinyl polymer (B), film-forming ability, affinity with various polymers, and adhesiveness, it is used as a fiber treatment agent in addition to surfactants. 9 Paper processing agents, sizing agents, adhesives, coating agents, epoxy resin curing agents 9 Surface treatment agents, modifiers for various polymeric materials, etc. can also be suitably used.

(Example) Examples of the present invention are shown below, but these are given for the purpose of illustration and are not intended to limit the scope of the present invention. Further, in the following, parts 9% each represent parts by weight double ω%.

Reference example 1 Production of vinyl polymer (1) Stirrer, reflux condenser, nitrogen blowing tube, thermometer.

The monomer mixed solution (A) was charged into a flask equipped with a dropping funnel, and the temperature was raised to 80° C. while stirring under a nitrogen stream.

A catalyst solution prepared by dissolving 1.7 parts of azobisisobutyronitrile in 200 parts of isopropanol was added dropwise over 20 minutes, and stirring was continued for 30 minutes. Next, the monomer mixed solution (B) was added dropwise over 4 hours. To complete the reaction, a solution of 5.5 parts of azobisisobutyronitrile dissolved in 100 parts of methanol was added dropwise every 30 minutes in four portions as a post-catalyst. After the dropwise addition was completed, stirring was continued for 1 hour at the same temperature to complete the reaction. Yield 95.0%,
A solution (solid content 71.8%) of a vinyl polymer (1) having a bromine atom at one end of a number average molecule ω1000 was obtained.

Monomer mixed solution (△) Butyl acrylate 198 parts Styrene
66 parts methyl methacrylate
66 parts Bromotrichloromethane 110 parts Isopropanol 130 parts Monomer mixed solution (
B) Butyl acrylate 462 parts styrene
154 parts methyl methacrylate
154 parts Bromotrich 0 Lomethane 110
Part Azobisisobutyronitrile 3.8 parts Reference Example 2 Production of vinyl polymer (2) Reference Example 1 except that the monomer mixed solutions (A) and (B) had the following compositions. , the operation of Reference Example 1 was repeated to obtain a solution of vinyl polymer (2) having a bromine atom at one end of a number average molecule M of 5000 (with a yield of 97.0%).
A solids content of 70.7% was obtained.

Monomer mixed solution <A) Butyl acrylate 198 parts Styrene
66 parts methyl methacrylate
66 parts Bromotrichloromethane 22 parts Isopropanol 130 parts Monobase mixed solution (B) Butyl acrylate 462 parts Styrene
154 parts methyl methacrylate
154 parts Methane 22 parts Azobisisobutyronitrile 3.8 parts Reference Example 3 Production of vinyl polymer (3) Stirrer, reflux condenser, nitrogen blowing tube, thermometer.

The monomer mixed solution (A) was charged into a flask equipped with a dropping funnel, and the temperature was raised to 80° C. while stirring under a nitrogen stream.

A catalyst solution prepared by dissolving 17 parts of azobisisobutyronitrile in 200 parts of benzene was added dropwise thereto over 20 minutes, and stirring was continued for 30 minutes. Next, the monomer mixed solution (B) was added dropwise over 5 hours. To complete the reaction, azobisisobutyronitrile is used as a post-catalyst5.
A solution prepared by dissolving 5 parts in 100 parts of benzene was added dropwise in 4 portions every 30 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature (80°C) for 1 hour to complete the reaction. A solution (solid content: 72.5%) of a vinyl polymer having a number average molecular weight of 11,200 and a hydroxyl group at one end was obtained with a yield of 98.5%.

Single temperature solution (A) Butyl acrylate 198 parts Styrene
66 parts methyl methacrylate
66 parts Mercaptoethanol 44 parts Benzene 130 parts Single matrix mixed solution (
B) Butyl acrylate 462 parts styrene
154 parts methyl methacrylate
154 parts Mercaptoethanol 44 parts Azobisisobutyronitrile 3.8 parts Into a flask equipped with a stirrer, a reflux condenser, and a hygrometer, 250 parts of isophorone diisocyanate, 2110 parts of benzene, and 1 part of dibutyltin dilaurate as a catalyst. Prepare, 80
The temperature was raised to ℃. Here, a vinyl polymer solution 160 having a hydroxyl group at one end synthesized in advance is added.
0 parts were added dropwise over 1 hour. Stirring was continued at 80°C for 1 hour to complete the reaction. Number average molecular weight: 1400
A vinyl polymer with an isocyanate group at one end (
A solution of 3) (solid content 72.0%) was obtained.

Reference example 4 Production of 0 vinyl polymer (4) In Reference Example 3, monomer mixed solution (A).

52 parts of thioglycolic acid was used instead of 44 parts of mercaptoethanol used in each of (B), xylene was used instead of benzene as a solvent during the polymerization reaction, and the reaction with inphorone diisocyanate was not performed. Except for this, the procedure of Example 3 was repeated, and the polymerization yield was 96.3.
%, solution of vinyl polymer (4) having a carboxyl group at one end with a number average molecular weight of 900 (solid content 71.1%)
was gotten.

Reference Example 5 Production of 0-vinyl polymer (5) Bisphenol A diglycidyl needle 430 was placed in a flask equipped with a stirrer, a reflux condenser, and a thermometer.
1,992,190 parts and 4 parts of benzyltriethylammonium chloride as a catalyst were charged and heated to 110°C. To this, 1600 parts of a xylene solution of the vinyl polymer (4) having a carboxyl group at one end obtained in Reference Example 4 was added dropwise over 1 hour. Stirring was continued for an additional hour to complete the reaction. number average molecule ω13
A vinyl polymer with an epoxy group at one end of 00 (5
) solution (solid content 71.0%) was obtained.

Example 1 In a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, polyethyleneimine as the amine compound (A) (Evomin 3p-oo6. manufactured by Nippon Shokubai Kagaku Kogyo ■,
average molecular weight of about 600), 150 parts of the solution of the vinyl polymer (1) obtained in Reference Example 1, and the compound (C
) was charged with 15.5 parts of a mixture of α-olefin epoxides having 12 and 14 carbon atoms (AOE-X24. manufactured by Daicel Chemical Industries, Ltd., average molecular weight: 196.3) and heated at 80° C. for 40 minutes with stirring under a nitrogen stream. Allowed time to react. The volatile components were removed from the resulting reaction product under reduced pressure (<5111 mHg, heated to 80° C.) to obtain 11170 parts of a brown viscous modified amine compound. The surface tension (20°C) of an aqueous solution with a resin content of 0.1% is 43.9 dyne/
It was cm. In addition, the resin content of the amine salt obtained by adding acetic acid as an organic acid (1) adjusted to H = 5.0) is 0.
．． The surface tension of an aqueous solution (20°C) at 1% is 45.0
dyne/cm.

Examples 2 to 3 Same as Example 1 except that the sleeves of vinyl polymer (B) and the usage ratio thereof and the usage ratio of compound (C) were as shown in Table 1. Modified amine compounds [2] to [3] were obtained. Their properties were as shown in Table 1.

Example 4 Three parts of 47° polyethyleneimine (Evomin SP-006) were charged into a reaction vessel similar to that used in Example 1, and heated to 80°C. 210 parts of the solution of the vinyl polymer (3) obtained in Reference Example 3 was added dropwise thereto over 1 hour. Subsequently, 43.4 parts of octadecyl isocyanate as compound (C) was added dropwise over 30 minutes. After the dropwise addition was completed, stirring was continued for 1 hour at the same temperature to complete the reaction. Volatile components were removed in the same manner as in Example 1 to obtain 240 parts of modified amine compound [4]. Their properties were as shown in Table 1.

Example 5 Polyethyleneimine (Evomin SP-006) was placed in a flask equipped with a stirrer, a thermometer, and a product water separator for dehydration condensation.
47.3 parts, vinyl polymer (4) obtained in Reference Example 4
150 parts of a solution of
The condensed water was separated and removed.

It took three hours for a total of 13 catties of water to be removed.

Thereafter, the reaction was carried out for 1 hour, and after cooling, volatile components were removed in the same manner as in Example 1, and the modified amine compound [5] 1
Got 95 copies. The properties were as shown in Table 1.

Example 6 In a reaction vessel similar to Example 1, 47.3 parts of polyethyleneimine (Evomin SP-006), 195 parts of the solution of the vinyl polymer (5) obtained in Reference Example 5, and α-olefin epoxide ( 3 parts of AOE-X24>3 was charged and reacted at 80°C for 2 hours with stirring under a nitrogen stream.The reactant was heated to 80°C under reduced pressure (5mIIIHiJ).
Amine compound modified by removing volatile components [6] 216
I got the department. The properties were as shown in Table 1.

Comparative Example 1 In a reaction vessel similar to that used in Example 1, 47.3 parts of polyethyleneimine (Evomin SP-006) and AO were added.
75.5 parts of E-X24 was charged and reacted at 80°C for 2 hours with stirring under a nitrogen stream to obtain a comparative modified amine compound [
One solution was obtained. The properties are as shown in Table 1, and the surfactant ability was inferior to that of the modified amine compound of the present invention.

Comparative Example 2 In a reaction vessel similar to that used in Example 1, 112.5 parts of diethylenetriamine and adipine! 146.1 parts of polyamide polyamine synthesized by dehydration condensation from 42.1 parts.
7 parts, 634.1 parts of water was added, and further reacted with 27.8 parts of epichlorohydrin at 80°C for 5 hours to obtain a solution of comparative modified amine compound [2]. The properties are as shown in Table 1, and the surfactant ability was inferior to that of the modified amine compound of the present invention.

Example 7 Into a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, 133 parts of pure water was added, and a 10% aqueous solution of the modified amine compound [2] prepared in Example 2 (acetic acid) was added. Add 57 parts of (adjust to pH = s, o) and
It was heated to 65° C. while slowly blowing nitrogen gas. 6 parts of a 5% aqueous solution of 2,2'-azobis(2-amidinopropane) digroup M1 was injected therein. Subsequently, a monomer mixture consisting of 55 parts of butyl acrylate and 45 parts of methyl methacrylate was added dropwise over 2 hours. The temperature was maintained at 65-10°C during the dropping, and after the dropping was completed, the temperature was maintained at the same temperature for 1 hour.
The polymerization was terminated by stirring for an hour. Good stability during polymerization, very low lumps, non-volatile content 35.7%, p
An aqueous resin composition with H=5.2 was obtained. A film produced by 1q from this aqueous resin composition had high strength, little whitening in water, and good water resistance.

Example 8 A 10% aqueous solution of 1q of the modified amine compound [5] prepared in Example 5 as an emulsifier (adding acetic acid to pH=5.
The same procedure as in Example 7 was repeated except that 57 parts (adjusted to 0. An aqueous resin composition was obtained. The film obtained from this aqueous resin composition had little whitening in water, good water resistance, and excellent strength.

Comparative Example 3 The same operation as in Example 7 was repeated except that 57 parts of a 10% aqueous solution of the modified amine compound for comparative example [2] was used as an emulsifier, and an aqueous resin with a nonvolatile content of 35.1% was prepared. A composition was obtained. The film to be tested had a high water absorption rate and whitened in water.

Claims (1)

[Claims] 1. An amine compound (A) containing an amino group in the molecule, a vinyl polymer (B) having a functional group capable of reacting with an amino group at one or both ends, and the general formula R -(OA)-_nX (in the formula, R is a hydrocarbon group having 4 to 28 carbon atoms, A is a carbon number 2
~4 alkylene group, X is an atomic group having a functional group capable of reacting with an amino group, and n is 0 or an integer of 1 to 30. ) A modified amine compound and its salt obtained by reacting the compound (C). 2. The modified amine compound and its salt according to claim 1, wherein the functional group capable of reacting with an amino group is a halogen atom, an epoxy group, an isocyanate group, a vinyl group, or a carboxyl group. 3. The modified amine compound and its salt according to claim 1, wherein the amine compound (A) containing an amino group in the molecule is polyethyleneimine or a derivative thereof. 4. An amine compound (A) containing an amino group in the molecule, a vinyl polymer (B) having a functional group capable of reacting with an amino group at one or both ends, and the general formula R-(OA)-_nX (In the formula, R is a hydrocarbon group having 4 to 28 carbon atoms, and A is a hydrocarbon group having 2 carbon atoms.
~4 alkylene group, X is an atomic group having a functional group capable of reacting with an amino group, and n is 0 or an integer of 1 to 30. ) A surfactant comprising a modified amine compound obtained by reacting the compound (C) and/or a salt thereof. 5. The surfactant according to claim 4, wherein the functional group capable of reacting with an amino group is a halogen atom, an epoxy group, an isocyanate group, a vinyl group, or a carboxyl group. 6. The surfactant according to claim 4, wherein the amine compound (A) containing an amino group in the molecule is polyethyleneimine or a derivative thereof.