JP7088815B2 - An agent for improving the action of a rust inhibitor, a composition for emulsion polymerization using the agent, and an emulsion containing a rust inhibitor. - Google Patents

Description

The present invention relates to an agent for improving the action of a rust preventive, a composition for emulsion polymerization using the same, and an emulsion containing a rust preventive.

Conventionally, as a rust preventive for iron-based metal materials such as steel materials and non-ferrous metal materials such as aluminum and titanium, especially aluminum and its alloys, phosphorus-based rust preventives such as phosphates, phosphate esters, and phosphonic acids, or Organic rust preventives such as organic acid amine salts, organic sulfonic acid metal salts, and heterocyclic compounds are widely used.

Here, the generation of rust occurs when the metal comes into contact with air and water, which is an electrolyte, and oxidizes. Therefore, in order to prevent the occurrence of rust, it is common to take a method of blocking the metal surface from air or water. For example, as a method of imparting rust resistance to a water-based paint, a method of using a pigment that reacts with air to form a film on the surface of a metal, or a method of using a resin having excellent adhesion and barrier properties has been conventionally used. and so on. As an example of the former, for example, a method using a phosphate or zinc powder has been proposed (see, for example, Patent Document 1). Further, as an example of the latter, a method using an epoxy resin or a vinylidene chloride-based resin having excellent adhesiveness and durability has been proposed (see, for example, Patent Documents 2 and 3).

By the way, in recent years, there has been an active shift from solvent-based paints to water-based paints due to the growing interest in global environment protection and the tightening of solvent regulations and heavy metal regulations for paints, which is equivalent to solvent-based paints. A water-based paint having excellent rust-proof and moisture-proof properties is strongly desired. In such a flow, as disclosed in Patent Document 2 and Patent Document 3, various water-based paints having the form of a resin emulsion such as a vinylidene chloride-based copolymer resin emulsion have been proposed.

The resin emulsion used for water-based paints is produced by emulsion polymerization of a monomer composition containing a polymerizable monomer and an emulsifier in water. Here, as a technique for imparting rust resistance to a resin emulsion, for example, in Patent Document 4, a reactive surfactant having a predetermined chemical structure (phosphoric acid ester structure) is used as an emulsifier for emulsion polymerization. Technology has been proposed. Further, for example, Patent Document 5 also proposes a technique of using a surfactant having a predetermined chemical structure (polyetheramine structure containing a primary amino group) as an emulsifier for emulsion polymerization.

Japanese Unexamined Patent Publication No. 2013-19546 Japanese Unexamined Patent Publication No. 2013-151598 Japanese Unexamined Patent Publication No. 2015-166436 Japanese Unexamined Patent Publication No. 11-309361 Japanese Unexamined Patent Publication No. 2003-29643

However, according to the studies by the present inventors, it has been found that there is still room for improvement in the conventional technique of imparting rust resistance to a resin emulsion by using an emulsifier for emulsion polymerization. Specifically, when a phosphoric acid ester-type surfactant as disclosed in Patent Document 4 is used, sufficient polymerization stability cannot be achieved, and when an electrolyte is mixed in the obtained resin emulsion. Emulsification stability was found to be inadequate. Further, as a result, when a pigment is blended in order to use the obtained resin emulsion as a paint, there is a problem that agglomerates are generated.

Further, it was found that even when a polyether amine type surfactant as disclosed in Patent Document 5 is used, sufficient emulsifying property cannot be obtained and it cannot be used as an emulsifier for emulsion polymerization.

The present invention has been made in view of the above-mentioned problems in the prior art, and provides a means capable of improving the rust resistance of the resin emulsion while sufficiently ensuring the polymerization stability of the resin emulsion. The purpose.

The present inventors have made diligent studies to solve the above problems. As a result, surprisingly, the ionic bond salt having a predetermined chemical structure has an action of improving the rust preventive action of the other rust preventive agent when used in combination with the other rust preventive agent. It was found that it had, and the present invention was completed.

That is, according to one embodiment of the present invention, it is an agent for improving the action of a rust preventive and has the following chemical formula (1):

In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and A represents a linear chain having 2 to 4 carbon atoms. Represents a shaped or branched alkylene group, m represents the average number of added moles of AO, which is a number from 1 to 150, l is an integer of 1 to 3, and n represents the atomic value of Q ⁺ , which is 1 or. 2, where Q ⁺ represents a monovalent metal cation, a divalent metal cation, or a nitrogen-containing compound cation.
An action improver containing an ionic bond salt represented by is provided.

Further, according to another aspect of the present invention, there is also provided a method for improving the action of the rust preventive agent, which comprises using the above-mentioned predetermined action improver in combination with the rust preventive agent.

Furthermore, according to still another embodiment of the present invention, an emulsion polymerization composition containing the above-mentioned predetermined action improver, a polymerizable monomer, and a solvent is also provided.

Further, according to still another embodiment of the present invention, a rust preventive-containing emulsion containing a rust preventive agent, the above-mentioned predetermined action improver, and a resin emulsion is also provided.

According to the present invention, it is possible to improve the rust preventive property of the resin emulsion while sufficiently ensuring the polymerization stability of the resin emulsion.

Hereinafter, embodiments of the present invention will be described.

One embodiment of the present invention relates to an agent for improving the action of a rust preventive. Here, in the present specification, the "rust inhibitor action improving agent" means an action of improving the rust preventive action of the other rust preventive agent when used in combination with the other rust preventive agent. Means. Further, in the present specification, the "effect improving agent for rust preventives" may be simply referred to as "action improving agent". Whether or not a compound has a use as an "effect improving agent for a rust preventive" is determined when the compound is used in combination with other rust preventives as compared with the case where the compound is not used in combination with other rust preventives. Whether or not the rust preventive action of the rust preventive agent is improved can be confirmed as an index. As the evaluation test for the rust preventive action, the test described in the column of Examples described later can be adopted.

[Structure of ionic bond salt]
The action improver according to this embodiment has the following chemical formula (1):

It contains an ionic bond salt represented by.

In the chemical formula (1), R ₁ represents a hydrogen atom or a methyl group.

In the chemical formula (1), R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples of the alkenyl group having 2 to 4 carbon atoms include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group and a 2-butenyl group. Among them, R ₂ is preferably a hydrogen atom, a methyl group or a 1-propenyl group, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.

In the chemical formula (1), A represents a linear or branched alkylene group having 2 to 4 carbon atoms. The linear or branched alkylene group having 2 to 4 carbon atoms includes ethylene group, methylmethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group and 1-methyltrimethylene. Examples include a group, a 2-methyltrimethylene group, a 1,1-dimethyldimethylene group, and a 1,2-dimethyldimethylene group. These alkylene groups form an oxyalkylene group together with an oxygen atom. The oxyalkylene group (AO group) may be the same or a heterogeneous mixture (block or random), preferably an oxyethylene group alone, an oxypropylene group alone, or a mixture of an oxyethylene group and an oxypropylene group (block or random). ), More preferably an oxyethylene group or an oxypropylene group, and particularly preferably an oxyethylene group (that is, A is an ethylene group).

In the chemical formula (1), m represents the average number of moles of substance added of AO, which is a number of 1 to 150, preferably a number of 5 to 120.

In the chemical formula (1), l is an integer of 1 to 3. The ion-binding salt represented by the chemical formula (1) is usually a compound in which l is 1 (1 mol adduct), a compound in which 1 is 2 (2 mol adduct), and a compound in which l is 3. It exists in the form of a mixture with (3 mol adduct).

In the chemical formula (1), n represents the valence of Q ⁺ and is 1 or 2. That is, if Q ⁺ is a monovalent cation, n is 1, and if Q ⁺ is a divalent cation, n is 2.

In the chemical formula (1), Q ⁺ represents a monovalent metal ion, a divalent metal ion or a nitrogen-containing compound ion.

Examples of monovalent metal cations include sodium ion, potassium ion, lithium ion and the like.

Examples of the divalent metal cation include calcium ion, magnesium ion and the like.

Nitrogen-containing compound cations include ammonium ion (NH ₄₊ ⁾ , organic ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolinium ion, piperidinium ion, pyrazinium ion, pyrimidinium ion, and tria. From the group consisting of zorium ion, triazinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalinium ion, piperazinium ion, oxazolinium ion, thiazolinium ion and morpholinium ion. At least one selected may be mentioned. Each of the above ions may have an ethylenically unsaturated bond such as a (meth) acryloyl group or a vinyl group.

Specific examples of the organic ammonium ion include the following ions. For example, dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, monopropylammonium ion, dipropylammonium ion, tripropylammonium ion, tetrapropylammonium ion, monobutylammonium. Ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, monopentylammonium ion, dipentylammonium ion, trypentylammonium ion, tetrapentylammonium ion, monohexylammonium ion, dihexylammonium ion, monoheptylammonium ion, diheptyl Ammonium Ion, Monooctyl Ammonium Ion, Dioctyl Ammonium Ion, Monononyl Ammonium Ion, Monodecyl Ammonium Ion, Monoundecyl Ammonium Ion, Monododecyl Ammonium Ion, Monotridecyl Ammonium Ion, Monotetradecyl Ammonium Ion, Monopentadecyl Ammonium Ion , Monohexadecylammonium ion, Monoheptadecylammonium ion, Monooctadecylammonium ion, Monononadesylammonium ion, Monoicosylammonium ion, Monohenicosylammonium ion, Monodocosylammonium ion, Monotricosylammonium ion, Methyl (Ethyl) ammonium ion, methyl (propyl) ammonium ion, methyl (butyl) ammonium ion, methyl (pentyl) ammonium ion, methyl (hexyl) ammonium ion, methyl (heptyl) ammonium ion, methyl (octyl) ammonium ion, methyl ( Nonyl) ammonium ion, methyl (decyl) ammonium ion, methyl (undecyl) ammonium ion, methyl (dodecyl) ammonium ion, methyl (tridecyl) ammonium ion, methyl (tetradecyl) ammonium ion, methyl (pentadecyl) ammonium ion, methyl (hexadecyl) ) Ammonium ion, Methyl (heptadecyl) ammonium ion, Methyl (octadecyl) ammonium ion, Methyl (nonadecil) ammonium ion, Methyl (icosyl) ammonium ion, Me Chill (henicosyl) ammonium ion, methyl (tricosyl) ammonium ion, ethyl (propyl) ammonium ion, ethyl (butyl) ammonium ion, ethyl (pentyl) ammonium ion, ethyl (hexyl) ammonium ion, ethyl (heptyl) ammonium ion, ethyl (Octyl) ammonium ion, ethyl (nonyl) ammonium ion, ethyl (decyl) ammonium ion, ethyl (undesyl) ammonium ion, ethyl (dodecyl) ammonium ion, ethyl (tridecyl) ammonium ion, ethyl (tetradecyl) ammonium ion, ethyl ( Pentadecyl) ammonium ion, ethyl (hexadecyl) ammonium ion, ethyl (heptadecyl) ammonium ion, ethyl (octadecyl) ammonium ion, ethyl (nonadecyl) ammonium ion, ethyl (icosyl) ammonium ion, ethyl (henicocil) ammonium ion, ethyl (tricosyl) ) Ammonium ion, dimethyl (ethyl) ammonium ion, dimethyl (propyl) ammonium ion, dimethyl (butyl) ammonium ion, dimethyl (pentyl) ammonium ion, dimethyl (hexyl) ammonium ion, dimethyl (heptyl) ammonium ion, dimethyl (octyl) Ammonium ion, dimethyl (nonyl) ammonium ion, dimethyl (decyl) ammonium ion, dimethyl (undecyl) ammonium ion, dimethyl (dodecyl) ammonium ion, dimethyl (tridecyl) ammonium ion, dimethyl (tetradecyl) ammonium ion, dimethyl (pentadecyl) ammonium Ions, dimethyl (hexadecyl) ammonium ions, dimethyl (heptadecyl) ammonium ions, dimethyl (octadecyl) ammonium ions, dimethyl (nonadesyl) ammonium ions, dimethyl (icosyl) ammonium ions, dimethyl (henicosyl) ammonium ions, dimethyl (tricosyl) ammonium ions , Trimethyl (ethyl) ammonium ion, trimethyl (propyl) ammonium ion, trimethyl (butyl) ammonium ion, trimethyl (pentyl) ammonium ion, trimethyl (hexyl) ammonium ion, trimethyl (heptyl) ammonium ion, trimethyl (octyl) Ammonium ion, trimethyl (nonyl) ammonium ion, trimethyl (decyl) ammonium ion, trimethyl (undecyl) ammonium ion, trimethyl (dodecyl) ammonium ion, trimethyl (tridecyl) ammonium ion, trimethyl (tetradecyl) ammonium ion, trimethyl (pentadecyl) ammonium Ions, trimethyl (hexadecyl) ammonium ions, trimethyl (heptadecyl) ammonium ions, trimethyl (octadecyl) ammonium ions, trimethyl (nonadecyl) ammonium ions, trimethyl (icosyl) ammonium ions, trimethyl (henicosyl) ammonium ions, trimethyl (tricosyl) ammonium ions Alkylammonium ions such as.

Monovinylammonium ion, divinylammonium ion, trivinylammonium ion, monopropenylammonium ion, dipropenylammonium ion, tripropenylammonium ion, monobutenylammonium ion, dibutenylammonium ion, tributenylammonium ion, monopentenylammonium ion, di Pentenylammonium ion, tripentenylammonium ion, monohexenylammonium ion, dihexenylammonium ion, monoheptenylammonium ion, diheptenylammonium ion, monooctenylammonium ion, dioctenylammonium ion, monononenylammonium ion, mono Decenylammonium ion, Monoundecenylammonium ion, Monododecenylammonium ion, Monotridecenylammonium ion, Monotetradecenylammonium ion, Monopentadecenylammonium ion, Monohexadecenylammonium ion Ions, monoheptadecenylammonium ions, monooctadecenylammonium ions, monononadesenylammonium ions, monoicosenylammonium ions, monohenicosenylammonium ions, monodocosenylammonium ions, monotricose Alkenylammonium ions such as nylammonium ions.

Dimethyl (vinyl) ammonium ion, dimethyl (propenyl) ammonium ion, dimethyl (butenyl) ammonium ion, dimethyl (pentenyl) ammonium ion, dimethyl (hexenyl) ammonium ion, dimethyl (heptenyl) ammonium ion, dimethyl (octenyl) ammonium ion, dimethyl (Nonenyl) ammonium ion, dimethyl (decenyl) ammonium ion, dimethyl (undecenyl) ammonium ion, dimethyl (dodecenyl) ammonium ion, dimethyl (tridecenyl) ammonium ion, dimethyl (tetradecenyl) ammonium ion, dimethyl (pentadecenyl) ammonium ion, dimethyl ( Hexadecenyl) ammonium ion, dimethyl (heptadecenyl) ammonium ion, dimethyl (octadecenyl) ammonium ion, dimethyl (nonadesenyl) ammonium ion, dimethyl (icosenyl) ammonium ion, dimethyl (henicosenyl) ammonium ion, dimethyl (tricosenyl) ammonium ion, bis (2) -A monoammonium ion having an alkyl group and an alkenyl group such as methoxyethyl) monoethylammonium ion, trimethyl (vinyl) ammonium ion, and bis (2-methoxyethyl) monomethylammonium ion.

Monobenzylammonium ion, (1-phenethyl) ammonium ion, (2-phenethyl) ammonium ion (also known as monophenethylammonium ion), dibenzylammonium ion, bis (1-phenethyl) ammonium ion, bis (2-phenethyl) ammonium Aromatically substituted alkylammonium ions such as ions (also known as diphenethylammonium ions); monocyclopentylammonium ion, dicyclopentylammonium ion, tricyclopentylammonium ion, monocyclohexylammonium ion, dicyclohexylammonium ion, monocycloheptylammonium ion, dicyclo Cycloalkylammonium ions with 5 to 16 carbon atoms such as heptylammonium ions; monoammonium ions having alkyl and cycloalkyl groups such as dimethyl (cyclopentyl) ammonium ion, dimethyl (cyclohexyl) ammonium ion, and dimethyl (cycloheptyl) ammonium ion. (Methylcyclopentyl) ammonium ion, bis (methylcyclopentyl) ammonium ion, (dimethylcyclopentyl) ammonium ion, bis (dimethylcyclopentyl) ammonium ion, (ethylcyclopentyl) ammonium ion, bis (ethylcyclopentyl) ammonium ion, (methylethylcyclopentyl) ) Ammonium ion, bis (methylethylcyclopentyl) ammonium ion, (diethylcyclopentyl) ammonium ion, (methylcyclohexyl) ammonium ion, bis (methylcyclohexyl) ammonium ion, (dimethylcyclohexyl) ammonium ion, bis (dimethylcyclohexyl) ammonium ion, (Ethylcyclohexyl) ammonium ion, bis (ethylcyclohexyl) ammonium ion, (methylethylcyclohexyl) ammonium ion, (diethylcyclohexyl) ammonium ion, (methylcycloheptyl) ammonium ion, bis (methylcycloheptyl) ammonium ion, (dimethylcyclo) Alkylcycloalkylammonium ions such as heptyl) ammonium ion, (ethylcycloheptyl) ammonium ion, (methylethylcycloheptyl) ammonium ion, (diethylcycloheptyl) ammonium ion.

Monomethanolammonium ion, dimethanolammonium ion, trimethanolammonium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, mono (n-propanol) ammonium ion, di (n-propanol) ammonium ion, tri (n) -Propanol) Ammonium ion, monoisopropanol ammonium ion, diisopropanol ammonium ion, triisopropanol ammonium ion, monobutanol ammonium ion, dibutanol ammonium ion, tributanol ammonium ion, monopentanol ammonium ion, dipentanol ammonium ion, tripen Tanol ammonium ion, monohexanol ammonium ion, dihexanol ammonium ion, monoheptanol ammonium ion, diheptanol ammonium ion, monooctanol ammonium ion, monononanol ammonium ion, monodecanol ammonium ion, monoundecanol ammonium ion, Monododecanolammonium ion, monotridecanolammonium ion, monotetradecanolammonium ion, monopentadecanolammonium ion, monohexadecanolammonium ion, monomethylmonoethanolammonium ion, monoethylmonoethanolammonium ion, monoethylmono Propanolammonium ion, monoethylmonobutanolammonium ion, monoethylmonopentanolammonium ion, monopropylmonoethanolammonium ion, monopropylmonopropanolammonium ion, monopropylmonobutanolammonium ion, monopropylmonopentanolammonium ion, monobutyl Monoethanolammonium ion, monobutylmonopropanolammonium ion, monobutylmonobutanolammonium ion, monobutylmonopentanolammonium ion, dimethylmonoethanolammonium ion, diethylmonoethanolammonium ion, diethylmonopropanolammonium ion, diethylmonobutanolammonium ion , Diethylmonopentanolammonium ion, dipropylmonoethanolammonium ion, dipropylmonopropa Nordammonium ion, dipropylmonobutanolammonium ion, dipropylmonopentanolammonium ion, dibutylmonoethanolammonium ion, dibutylmonopropanolammonium ion, dibutylmonobutanolammonium ion, dibutylmonopentanolammonium ion, monomethyldiethanolammonium ion, monomethyl Dipropanol ammonium ion, monomethyl dibutanol ammonium ion, monomethyl dipentanol ammonium ion, monoethyl diethanol ammonium ion, monoethyl dipropanol ammonium ion, monoethyl dibutanol ammonium ion, monoethyl dipentanol ammonium ion, monopropyl diethanol ammonium Ion, monopropyldipropanolammonium ion, monopropyldibutanolammonium ion, monopropyldipentanolammonium ion, monobutyldiethanolammonium ion, monobutyldipropanolammonium ion, monobutyldibutanolammonium ion, monobutyldipentanolammonium Ions, monocyclohexyl monoethanolammonium ion, monocyclohexyldiethanolammonium ion, monocyclohexylmonopropanolammonium ion, monocyclohexyldipropanolammonium ion, mono (β-aminoethyl) monoethanolammonium ion, monotert-butyl monoethanolammonium ion, Monotert-butyldiethanolammonium ion, mono (β-aminoethyl) isopropanolammonium ion diethylmonoisopropanolammonium ion, trimethylmonoethanolammonium ion, triethylmonoethanolammonium ion, triethylmonopropanolammonium ion, triethylmonobutanolammonium ion, triethylmono Pentanolammonium ion, tripropylmonoethanolammonium ion, tripropylmonopropanolammonium ion, tripropylmonobutanolammonium ion, tripropylmonopentanolammonium ion, diethylmonomethylethanolammonium ion, bis (2-methoxyethyl) monoethylmonomethyl Ammonium ion, monoethylmo Alkanolammonium ions such as nomethyldiethanolammonium ion and diethylmonomethylmonoethanolammonium ion. From the viewpoint of availability, monoethyl monoethanolammonium ion, diethyl monoethanolammonium ion, diethyl monomethylethanolammonium ion, bis (2-methoxyethyl) monoethylammonium ion, bis (2-methoxyethyl) monoethyl monomethylammonium ion , Monoethyl diethanolammonium ion, monoethyl monomethyl diethanolammonium ion is preferable, and monoethyl monoethanolammonium ion, diethyl monoethanolammonium ion, diethyl monomethyl monoethanolammonium ion are particularly preferable.

Also, ethylammonium dimethylmonoacrylate ion, ethylammonium dimethylmonoacrylate ion, ethylammonium diethylmonoacrylate ion, ethylammonium diethylmonomethacrylate ion, 1- (acrylamide ethyl) trimethylammonium ion, 1- (methacrylamide ethyl). ) Trimethylammonium ion, 1- (acrylamidepropyl) trimethylammonium ion, 1- (methacrylamidepropyl) trimethylammonium ion, 1- (acrylamide ethyl) dimethylammonium ion, 1- (methacrylamideethyl) dimethylammonium ion, 1-( Acrylamide propyl) dimethylammonium ion, 1- (methacrylamidopropyl) dimethylammonium ion, diethylmono (2-isocyanoethyl) ammonium ion, diethylmono (2-cyanopropyl) ammonium ion, diethylmono (1,2-epoxypropane) Reactive organic ammonium ions such as ammonium ions are also preferably used.

In the above ammonium ion, the description of "N-" or "N, N-" indicating that it is a substituent on N is omitted.

Specific examples of the imidazolium ion include, for example, imidazolium ion, N-isobutylimidazolium ion, 2-methylimidazolium ion, 2-ethylimidazolium ion, 2-n-propylimidazolium ion, 2-isopropyl. Imidazole ion, 2-n-butyl imidazolium ion, 2-phenylimidazolium ion, 4-methylimidazolium ion, 4-ethylimidazolium ion, 4-nitroimidazolium ion, 4-phenylimidazolium ion, 2- Methyl-4-phenylimidazolium ion, 4,5-dimethylimidazolium ion, 1-isobutyl-2-methylimidazolium ion, 1-isobutyl-2,3-methylimidazolium ion, 2,4,5-trimethylimidazolium ion Examples thereof include lithium ion, 2,4,5-triphenylimidazolium ion, benzimidazolium ion, 2-methylbenzimidazolium ion, 2-phenylbenzimidazolium ion and the like. From the viewpoint of availability, 1-isobutyl-2-methylimidazolium ion and 1-isobutyl-2,3-methylimidazolium ion are particularly preferable.

Specific examples of pyridinium ions include, for example, pyridinium ion, 2-isobutylpyridinium ion, 3-isobutylpyridinium ion, 3-methylpyridinium ion, 4-methylpyridinium ion, 2-ethylpyridinium ion, 3-ethylpyridinium ion. , 4-Ethylpyridinium ion, 4-propylpyridinium ion, 2-n-hexylpyridinium ion, 3-n-hexylpyridinium ion, 3,5-dimethylpyridinium ion, 3,5-diethylpyridinium ion, 2,6-di -Tert-Butylpyridinium ion, 2-benzylpyridinium ion, 4-benzylpyridinium ion, 2-phenylpyridinium ion, 3-phenylpyridinium ion, 4-phenylpyridinium ion, 2,6-diphenylpyridinium ion, 2- (3- (3-) Phenylpropyl) pyridinium ion, 4- (3-phenylpropyl) pyridinium ion, 2-benzoylpyridinium ion, 3-benzoylpyridinium ion, 4-benzoylpyridinium ion, 2-methoxypyridinium ion, 2-n-butoxypyridinium ion, 2 , 6-Dimethoxypyridinium ion, 2-methoxy-6-methylpyridinium ion, 4-methoxy-3-nitropyridinium ion, 3-ethoxy-2-nitropyridinium ion, 2-methoxy-3-nitropyridinium ion, 4-( 4-Nitrobenzyl) Pyridinium ion, 2-vinylpyridinium ion, 4-vinylpyridinium ion, 2-hydroxypyridinium ion, 3-hydroxypyridinium ion, 4-hydroxypyridinium ion, 2,4-dihydroxypyridinium ion, 2,6- Dihydroxypyridinium ion, 3-hydroxymethylpyridinium ion, 4-hydroxymethylpyridinium ion, 2- (2-hydroxyethyl) pyridinium ion, 2-hydroxy-6-methylpyridinium ion, 3-hydroxy-2-methylpyridinium ion, 5 -Hydroxy-2-methylpyridinium ion, 2-hydroxy-3-nitropyridinium ion, 2-hydroxy-5-nitropyridinium ion, 4-hydroxy-3-nitropyridinium ion, 3-hydroxy-2-nitropyridinium ion, 2 -Hydroxy-6-methyl-5-nitropyridinium ion, 2-ethenylpyridinium Dinium ion, 2-ethynylpyridinium ion, 2-methyl-5-ethylpyridinium ion, 4-ethyl-2-methylpyridinium ion, 5-butyl-2-methylpyridinium ion, 2-ethyl-6-isopropylpyridinium ion, 3 -Ethyl-4-methylpyridinium ion, 2-methyl-5-vinylpyridinium ion, 4- (phenylpropyl) pyridinium ion, 4- (1-piperidyl) pyridinium ion, 4-pyrrolidinopyridinium ion, 2-pyrrolidinium-2 -Ilpyridinium ion, 4-phenoxypyridinium ion, 2-methyl-3-ethylpyridinium ion, 2-methyl-5- (iso) propylpyridinium ion, 2-acetylpyridinium ion, 3-acetylpyridinium ion, 4-acetylpyridinium Ions, 2-methyl-5-acetylpyridinium ion, 2,6-diacetylpyridinium ion, 2-phenoxy-5-acetylpyridinium ion, 2,6-bis (hydroxymethyl) pyridinium ion, 2,2'-bipyridinium ion, 2,6-bis (p-tolyl) pyridinium ion, N-Boc-3-hydroxy-1,2,3,6-tetrahydropyridinium ion, N-Boc-1,2,3,6-tetrahydropyridinium ion, etc. Can be mentioned.

Specific examples of the pyrrolidinium ion include, for example, pyrrolidinium ion, N-methylpyrrolidinium ion, N-ethylpyrrolidinium ion, N-propylpyrrolidinium ion, N-butylpyrrolidinium ion, N-phenylpyrrolidinium. Um ion, N-nitrosopyrolidinium ion, 2-methylpyrrolidinium ion, 2-phenylpyrrolidinium ion, 3-phenylpyrrolidinium ion, 3-hydroxy-1-methylpyrrolidinium ion, 3- (4-methylphenyl) pyrrolyl Examples thereof include dinium ion, 3- (pyrrolidinium-1-ylmethyl) piperidine, 2-pyrrolidinium-2-ylpyridine and the like.

Specific examples of the pyrrolinium ion include, for example, pyrrolinium ion, N-methylpyrrolinium ion, 2-acetyl-5-methylpyrrolinium ion, methylpyrrolinium-1-carboxylate, 2-acetylpyrrolinium ion, and the like. 3-Acetylpyrrolinium ion, 2,5-dimethyl-1- (4-nitrophenyl) -1H-pyrrolinium ion, 1-furfurylpyrrolinium ion, 1- (2-nitrophenyl) pyrrolinium ion, 1, 2,5-trimethylpyrrolinium ion, 2,4-dimethylpyrrolinium-3,5-dicarboxylate diethyl, 4-methylpyrrolinium-3-carboxylate ethyl, 4-phenylpyrrolinium-3-carboxylate ethyl, 3 , 4,5-trimethylpyrrolinium-2-carboxylate ethyl, 2,5-dimethylpyrrolinium-3-carboxylate methyl, 1,2,5-trimethyl-1H-pyrrolinium-3-carboxylate methyl, N-tri Examples thereof include methoxysilylpyrrolinium ion, N-triethoxysilylpyrrolinium ion, N- (3-trimethoxysilylpropyl) pyrrolinium ion, N- (3-triethoxysilylpropyl) pyrrolinium ion and the like.

Specific examples of the piperidinium ion include, for example, 2,6-dimethylpiperidinium ion, 1,3-dimethyl-4-piperidonium ion, 2,2,6,6-tetramethylpiperidinium ion, 2 , 2,6,6-Tetramethyl-4-hydroxypiperidinium ion, 2,2-6-6-Tetramethyl-4-acetoxypiperidinium ion, 2,2,6,6-Tetramethyl-4-acetamidopipe Ridinium ion, 2,2,6,6-tetramethyl-4-oxopiperidinium ion, 2,2,6,6-tetramethyl-4-methoxypiperidinium ion, 2,2,6,6-tetramethyl- 4-propoxypiperidinium ion, 2,2,6,6-tetramethyl-4- (2-hydroxy-4-oxapentoxy) piperidinium ion, 2,2,6,6-tetramethyl-4-methacrylate pipete Lidinium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, 1,2,2,6,6-pentamethyl-4-oxycarbonyl-2-propenpiperidinium ion, 1,3- Dimethyl-4- [2-cyclopentyl-2-phenylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- (2-cyclopropyl-2-phenylpropanoyl) oxypiperidinium ion, 1,3-dimethyl -4- (2-Cyclopentyl-2-pyridine-3-ylpropanoyl) oxypiperidinium ion, 1,3-dimethyl-4- [2-cyclopentyl-2- (4-hydroxyphenyl) propanoyl] oxypiperidinium ion , 1,3-dimethyl-4- (2-cyclobutyl-2-phenylpropanol) oxypiperidinium ion, 1,3-dimethyl-4- [2-cyclopentyl-2- (4-methoxyphenyl) propanoyl] oxypipe Lidinium ion, 1,3-dimethyl-4- [2-cyclopentyl-2- (2-thienyl) propanoyl] Oxypiperidinium ion, 1,3-dimethyl-4- [2-cyclopentyl-2- (5-methyl-) 2-thienyl) propanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (3-bromophenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2 -(4-Bromophenyl) -2-cyclopentylpropanoyl] Oxypiperidinium ion, 1,3-dimethyl -4- [2- (4-Cyanophenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (3-cyanophenyl) -2-cyclopentylpropanoyl] oxypipe Lidinium ion, 1,3-dimethyl-4- [2- (3-methylthiophenyl) -2-cyclopentylpropanoyl] Oxypiperidinium ion, 1,3-dimethyl-4- [2- (4-methylthiophenyl)- 2-Cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (4-methylsulfonylphenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [ 2- (3-Methylsulfonylphenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (4-fluorophenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (4-chlorophenyl) -2-cyclopentylpropanoyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (3-fluorophenyl) -2-cyclopentylpropa Noyl] oxypiperidinium ion, 1,3-dimethyl-4- [2- (5-chloro-2-thienyl) -2-cyclobutylpropanoyl] oxypiperidinium ion and the like.

Specific examples of the pyrazinium ion include, for example, pyrazinium ion, methyl pyrazinium carboxylate, pyrazinium-2-carbonitrile, pyrazinenium carboxamide, 2-acetyl-3-ethylpyrazinium ion, 2-acetyl. -3-Methylpyrazinium ion, 2-Acetylpyrazinium ion, 2- (aminomethyl) -5-methylpyrazinium ion, 2-Amino-3- (phenylmethyl) pyrazinium ion, 2,3-bis (2) '-Pyridyl) -5,6-dihydropyrazinium ion, 2-cyanopyrazinium ion, 2,3-diethyl-5-methylpyrazinium ion, 2,3-diethylpyrazinium ion, 6,7-dihydro-5 -Methyl-5H-cyclopentapyrazinium ion, 3,5-dimethyl-2-ethylpyrazinium ion, 2,3-dimethyl-5-isopropylpyrazinium ion, 2,3-dimethylpyrazinium ion, 2,5- Dimethylpyrazinium ion, 2,6-dimethylpyrazinium ion, 2,3-diphenylpyrazinium ion, 2-ethoxy-3-ethylpyrazinium ion, 2-ethoxy-3-methylpyrazinium ion, 2-ethoxypyrazini Um ion, 5-ethyl-2,3-dimethylpyrazinium ion, 2-ethyl-3-methoxypyrazinium ion, 2-ethyl-3-methylpyrazinium ion, ethylpyrazinium ion, 2-flufurylthiopyrazinium ion, 5-Isobutyl-2,3-dimethylpyrazinium ion, 2-isobutyl-3-methoxypyrazinium ion, 2-isopropylpyrazinium ion, 2- (2-mercaptoethyl) pyrazinium ion, 2-methoxy-3-ethyl Pyrazinenium ion, 2-methoxy-3- (1-methylpropyl) pyrazinium ion, 2-methoxypyrazinium ion, 5-methyl-6,7-dihydrocyclopentapyrazinium ion, 2-methylmercapto-3-methyl Pyrazinenium ion, 2-methyl-3- (methylthio) pyrazinium ion, 2-methyl-3-n-propylpyrazinium ion, 2-methylpyrazinium ion, 2- (methylthio) -3-ethylpyrazinium ion, 2- (Methylthio) pyrazinium ion, 2-propylpyrazinium ion, 2- (1H-pyrazol-4-yl) pyrazinium ion, 2,3,5,6-tetramethylpyrazinium ion, 2,3,5 -bird Examples thereof include methylpyrazinium ion and 2-vinylpyrazinium ion.

Specific examples of the pyrimidinium ion include, for example, pyrimidinium ion, 4-methylpyrimidinium ion, 4-hydroxypyrimidinium ion, 4,6-dimethylpyrimidinium ion, 4,6-dihydroxy. Pyrimidinium ion, 2,4,5-trihydroxypyrimidinium ion, 4,6-dihydroxy-2-methylpyrimidinium ion, 4,6-dihydroxy-5-nitropyrimidinium ion, 2,4- Dimethyl-6-hydroxypyrimidinium ion, 4,6-dimethyl-2-hydroxypyrimidinium ion, 2- [4-n- (hexyloxy) phenyl] -5-n-octylpyrimidinium ion, 4- Hydroxypyrazolo [3,4-d] -pyrimidinium ion, 4,6-dihydroxypyrazolo [3,4-d] pyrimidinium ion and the like can be mentioned.

Specific examples of the triazolium ion include, for example, 1,2,3-triazolium ion, 1,2,4-triazolium ion, 3-mercapto-1,2,4-triazolium ion, 3-hydroxy. -1,2,4-triazolium ion, 3-methyl-1,2,4-triazolium ion, 1-methyl-1,2,4-triazolium ion, 1-methyl-3-mercapto-1,2 , 4-Triazolium ion, 4-Methyl-1,2,3-Triazolium ion, Benzotriazolium ion, Trilltriazolium ion, 1-Hydroxybenzotriazolium ion, 4,5,6,7-Tetrahydrotriazoli Um ion, 3-amino-1,2,4-triazolium ion, 3-amino-5-methyl-1,2,4-triazolium ion, carboxybenzotriazolium ion, 2- (2'-hydroxy-5' -Methylphenyl) benzotriazolium ion, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazolium ion, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl ) Bentriazolium ion, 2- (2'-hydroxy-4-octoxyphenyl) benzotriazolium ion and the like can be mentioned.

Specific examples of the triazinium ion include, for example, 1,2,3-triazinium ion, 1,2,4-triazinium ion, 1,3,5-triazinium ion, 3,4-dihydro-3. -Hydroxy-4-oxo-1,2,3-benzotriazinium ion, 3- (2-pyridyl) -5,6-diphenyl-1,2,4-triazinium ion, 5,6-diphenyl-1, 2,4-Triazinium ion, hexahydro-1,3,5-triethyl-s-triazinium ion, hexahydro-1,3,5-triphenyl-1,3,5-triazinium ion, 2- (4- (4-) Pyridinyl) -1,3,5-triazinium ion, 1,3,5-triacryloylhexahydro-1,3,5-triazinium ion, 2,4,6-triphenyl-s-triazinium ion, 2 , 4,6-tri (2-pyridyl) -s-triazinium ion, 2,4,6-tris (allyloxy) -1,3,5-triazinium ion, 1,3,5-tris (4-pyridyl) ) -2,4,6-triazinium ion, 2,4,6-tris (2-pyridyl) -1,3,5-triazinium ion, 1- (1,3,5-triazinium-2-yl) Examples thereof include piperazine, 2,4,6-tripyridyl-s-triazinium ion, 2,4,6-tris (allyloxy) -1,3,5-triazinium ion and the like.

Specific examples of the quinolinium ion include, for example, quinolinium ion, 2-methylquinolinium ion, 3-methylquinolinium ion, 4-methylquinolinium ion, and 8-methylquinolinium ion. , 2,8-dimethylquinolinium ion, 3,8-dimethylquinolinium ion, 4,8-dimethylquinolinium ion, 7-methylquinolinium ion, 2,7-dimethylquinolinium ion, 3, , 7-dimethylquinolinium ion, 4,7-dimethylquinolinium ion, 6-methylquinolinium ion, 2,6-dimethylquinolinium ion, 3,6-dimethylquinolinium ion, 4,6 -Dimethylquinolinium ion, 8-ethylquinolinium ion, 2-methyl-8-ethylquinolinium ion, 4-methyl-8-ethylquinolinium ion, 7-isopropyl-2-methylquinolinium ion , 6-tert-butyl-4-methylquinolinium ion and the like.

Specific examples of the isoquinolinium ion include, for example, isoquinolinium ion, 3-methylisoquinolinium ion, 4-methylisoquinolinium ion, 5-methylisoquinolinium ion, 6-. Methylisoquinolinium ion, 7-methylisoquinolinium ion, 8-methylisoquinolinium ion, 1,3-dimethylisoquinolinium ion, 5,8-dimethylisoquinolinium ion, 5,6 , 7,8-Tetramethylisoquinolinium ion, 3-tert-butylisoquinolinium ion, 4-tert-butylisoquinolinium ion, 6-tert-butylisoquinolinium ion, 7-tert- Examples include butylisoquinolinium ion.

Specific examples of the indolinium ion include, for example, indolinium ion, 3-methylindolinium ion, 2-methylindrinium ion, 1-methyl-3-methylindolinium ion, and 2,3-dimethylindolinium ion. , 3-Ethylindolinium ion, 2-phenylindolinium ion, 3-phenylindolinium ion, 2,3-phenylindolinium ion, 2,3-dimethyl-7-nitroindolinium ion, 2,3-dimethyl- 7-Chloroindrinium ion, 3-ethyl-7-methylindrinium ion, 2,3-dimethyl-7-methoxymethylindrinium ion, 7-methoxymethyl-3-methylindrinium ion, 3- (pyridine-2) -Il) Indoliunim ion, 3- (pyridine-2-yl) -2-methylindolinium ion, 3- (4,6-dimethoxypyrimidine-2-yl) -2-methylindrinium ion, 3- (4) , 6-Dimethoxypyrimidine-2-yl) -7-ethyl-2-methylindolinium ion, 3- (4,6-dimethoxypyrimidine-2-yl) -7-methoxymethyl-2-methylindolinium ion, 3 -(4,6-dimethoxypyrimidine-2-yl) -2-butoxymethylindolinium ion, 3- (4,6-diethoxypyrimidine-2-yl) -7-methoxymethylindolinium ion and the like can be mentioned.

Specific examples of the quinoxalinium ion include quinoxalinium ion, 2-methylquinoxalinium ion, 2,3-dimethylquinoxalinium ion and the like.

Specific examples of the piperazinium ion include, for example, piperadinium ion, N-methylpiperazinium ion, N-ethylpiperazinium ion, N- (iso) propylpiperadinium ion, N-butylpiperazinium ion, N-. Phenylpiperazinium ion, 2-methylpiperazinium ion, 2,5-dimethylpiperazinium ion, 2,6-dimethylpiperazinium ion, 1,4-diphenylpiperazinium ion, 1-acetylpiperazinium ion, 1-allylpipe Radinium ion, 1- (2-methylallyl) piperazineium ion, 1- (1-methylbutyl) piperazineium ion, 1-benzoylpiperazinium ion, 1-cyclopentylpiperazinium ion, 1-formylpiperazinium ion, 1-phenethylpipe Radinium ion, 1- (4-pyridyl) piperazinium ion, 1- (2-pyrrolidinoethyl) piperazinium ion, 1- (o-tolyl) piperazinium ion, 1,4-diethylpiperazinium ion, 1,4 -Diformylpiperazinium ion, 1- (1,3-dimethylbutyl) piperazinium ion, 1- (2,3-dimethylphenyl) piperazinium ion, 1- (2,6-dimethylphenyl) piperazinium ion, 1 -(3,4-dimethylphenyl) piperazinium ion, N, N'-dimethylpiperazinium ion, 1- (2-ethoxyethyl) piperazinium ion, 1- (2-ethoxyphenyl) piperazinium ion, 1-( 2-Methylethyl) piperazinium ion, 1- (2-methoxyphenyl) piperazinium ion, 1- (3-methoxyphenyl) piperazinium ion, 1- (4-methoxybenzyl) piperazinium ion, 1- (4- (4-methoxybenzyl) piperazinium ion Methylbenzoyl) piperazinium ion, 1- [2- (phenoxy) ethyl] piperazinium ion, N- (2-hydroxyethyl) piperazinium ion, N- (4-hydroxyphenyl) piperazinium ion, 1- (2-) Hydroxyethyl) -4-isopropylpiperadinium ion, N-4-benzyl-2-phenylpiperazinium ion, 1-benzyl-4- (piperidin-3-ylmethyl) piperazinium ion, 1- (3-biphenylyl) piperazini Um ion, 1- (4-biphenylyl) piperazinium ion, 1-cyclohexyl-4- (piperidin-3-ylmethyl) Piperazineium ion, 1- (2,3-dimethylphenyl) -4- (piperidine-3-ylmethyl) piperazineium ion, 1- (2,4-dimethylphenyl) -4- (piperidine-3-ylmethyl) piperazine Umion, 1- (2,5-dimethylphenyl) -4- (piperidine-3-ylmethyl) piperazineium ion, 1-ethyl-4- (piperidine-3-ylmethyl) piperazineium ion, 1- (1-ethylpropyl) ) Piperazineium ion, 1- (2-methoxyphenyl) -4- (piperidine-3-ylmethyl) piperazineium ion, 1- (2-methoxyphenyl) -4- (piperidine-4-ylmethyl) piperazineium ion, 1 -(3-Methylphenyl) -4- (piperidine-3-ylmethyl) piperazineium ion, 1- (3-methoxyphenyl) -4- (piperidine-4-ylmethyl) piperazineium ion, 2-methyl-1- ( 3-Methylphenyl) -4- (piperidine-3-ylmethyl) piperazineium ion, 2-methyl-1- (3-methylphenyl) -4- (piperidine-4-ylmethyl) piperazineium ion, 1-[(1) -Methylpiperidine-3-yl) methyl] piperazineium ion, 1-methyl-4- (piperidine-3-ylmethyl) piperazineium ion, 1- (3-methylpyridine-2-yl) piperazineium ion, 1- (1- (3-methylpyridin-2-yl) piperazineium ion Examples thereof include piperidine-3-ylmethyl) -4-propylpiperazinium ion, 1- (piperidine-4-ylmethyl) -4-propylpiperazinium ion, 1-acetyl-4- (4-hydroxyphenyl) piperazineium ion and the like. ..

Specific examples of the oxazolinium ion include, for example, oxazolinium ion, 4-methyloxazolinium ion, 5-methyloxazolinium ion, 4-phenyloxazolinium ion, and 4,5-diphenyloxazoli. Nium ion, 4-ethyloxazolinium ion, 4,5-dimethyloxazolinium ion, 5-phenyloxazolinium ion, benzoxazolinium ion, 5-chlorobenzoxazolinium ion, 5-methylbenzoxazoli Nium ion, 5-phenylbenzoxazolinium ion, 6-methylbenzoxazolinium ion, 5,6-dimethylbenzoxazolinium ion, 4,6-dimethylbenzoxazolinium ion, 6-methoxybenzoxazolinium Ion, 5-methoxybenzoxazolinium ion, 4-ethoxybenzoxazolinium ion, 5-chlorobenzoxazolinium ion, 6-methoxybenzoxazolinium ion, 5-hydroxybenzoxazolinium ion, 6-hydroxy Examples thereof include benzoxazolinium ion, naphtho [1,2] oxazolinium ion, naphtho [2,1] oxazolinium ion and the like.

Specific examples of the thiazolinium ion include, for example, thiazolinium ion, 2-aminothiazolinium ion, 2-methylthiazolinium ion, 2-methoxythiazolinium ion, and 2-ethoxythiazolinium ion. , 2-isobutylthiazolinium ion, 2-trimethylsilylthiazolinium ion, 5-trimethylsilylthiazolinium ion, 4-methylthiazolinium ion, 4,5-dimethylthiazolinium ion, 2-ethylthiazolinium ion , 2,4-dimethylthiazolinium ion, 2-amino-5-methylthiazolinium ion, 2-amino-4-methylthiazolinium ion, 2,4,5-trimethylthiazolinium ion, benzothiazoli Nium ion, 2-methylbenzothiazolinium ion, 2,5-dimethylbenzothiazolinium ion and the like can be mentioned.

Specific examples of the morpholinium ion include, for example, morpholinium ion, N-methylmorpholinium ion, N-ethylmorpholinium ion, N- (iso) propylmorpholinium ion, N- (iso). ) Butylmorpholinium ion, N-acetylmorpholinium ion, N- (2-nitrobutyl) morpholinium ion, N-phenylmorpholinium ion, 4-morpholinoacetophenone, N- (meth) acrylic morpholinium ion , N- (meth) acryloylmorpholinium ion, bis (2-morpholinium ethyl) ether, 4-morpholinium nitrobenzene, dimorpholinium methane, acetoacetmorpholid, 4-tert-butyl-2- (Phenoxymethyl) morpholinium ion, 2,6-dimethylmorpholinium ion, 4- (2,3-epoxypropyl) morpholinium ion, N-formylmorpholinium ion, N- (2-hydroxyethyl) Examples thereof include morpholinium ion, N- (4-nitrophenyl) morpholinium ion, and N-nonanoylmorpholinium ion. From the viewpoint of availability, N-methylmorpholinium ion and N-ethylmorpholinium ion are particularly preferable.

In the present invention, Q ⁺ is preferably a nitrogen-containing compound cation, more preferably an organic ammonium ion, and more preferably an organic ammonium ion having an ethylenically unsaturated bond. Q ⁺ is more preferably N, N-dimethylmonoacrylate ethylammonium ion, N, N-dimethylmonoethylammonium methacrylate ion, N, N-diethylmonoacrylate ethylammonium ion, N, N-diethylmono. Ethylammonium methacrylate ion, N, N-diethylmono (2-isocyanoethyl) ammonium ion, N, N-diethylmono (2-cyanopropyl) ammonium ion, N, N-diethylmono (1,2-epoxypropane) Ammonium ion. Q ⁺ is even more preferably N, N-dimethylmonoacrylate ethylammonium ion, N, N-dimethylmonoethylammonium methacrylate ion, N, N-diethylmonoacrylate ethylammonium ion, N, N-diethyl. It is a monoethylammonium methacrylate ion. Q ⁺ is particularly preferably N, N-dimethylmonoacrylate ethylammonium ion or N, N-dimethylmonoacrylate ethylammonium ion.

When Q ⁺ has an ethylenically unsaturated bond, the number of ethylenically unsaturated bonds possessed by the ionic unsaturated bond of the present invention is not particularly limited and can be arbitrarily selected depending on the intended use, but is preferably one.

Examples of the ion-binding salt represented by the chemical formula (1) as described above include the following compounds (all of which are exemplified as a mixture of 1 to 3 l).

1) Polyoxyethylene (7) [styrenated (methylphenyl ether)] sulfate ester ammonium salt (compound (A))
2) Polyoxypropylene (8) [styrenated (methylphenyl ether)] sulfate ester ammonium salt (compound (B))
3) Polyoxyethylene (30) [styrenated (methylphenyl ether)] sulfate ester ammonium salt (compound (C))
4) Polyoxyethylene (7) [styrenated (phenyl ether)] sulfate ester ammonium salt (compound (D))
5) Polyoxypropylene (8) [styrenated (phenyl ether)] sulfate ester ammonium salt (compound (E))
6) Polyoxyethylene (30) [styrenated (phenyl ether)] sulfate ester ammonium salt (compound (F))
7) Polyoxyethylene (12) [styrenated (methylphenyl ether)] sulfate ester dimethylmonoethylammonium methacrylate salt (compound (G))
8) Polyoxyethylene (12) [styrenated (methylphenyl ether)] sulfate ester ammonium salt (compound (H))
9) Polyoxyethylene (12) [styrenated (methylphenyl ether)] sulfate ester sodium salt (compound (I))
10) Polyoxyethylene (12) [styrenated (phenyl ether)] sulfate ester ammonium salt (compound (J))
11) Polyoxyethylene (12) [styrenated (butylphenyl ether)] sulfate ester sodium salt (compound (K))
12) Polyoxyethylene (10) [methylstyrene (methylphenyl ether)] sodium sulfate (compound (L))
13) Polyoxypropylene (20) [methylstyrene (methylphenyl ether)] sodium sulfate (compound (M))
14) [Polyoxypropylene (5) Polyoxyethylene (6)] Random [Styrene (methylphenyl ether)] Sulfate ester ammonium salt (Compound (N))
15) [Polyoxypropylene (10) polyoxyethylene (20)] block [styrenated methylphenyl ether)] sodium sulfate (compound (O)).

In the above description example, for example, polyoxyethylene (7) indicates that an average of 7 mol of oxyethylene group is added, and polyoxypropylene (8) indicates that an average of 8 mol of oxypropylene group is added. Others are similar to this.

The compound represented by the chemical formula (1) (ionic bond salt) is a phenol compound which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms (corresponding to _R2 ). , A styrated alkylphenol derivative obtained by reacting styrene or methylstyrene according to a conventional method is used as a starting material, and is produced according to a method known per se.

Specifically, first, a desired number of moles of alkylene oxide is added to the phenolic hydroxyl group of the styrene-alkylphenol derivative obtained by the above method in the presence of a base catalyst such as sodium hydroxide or potassium hydroxide. Then, sulfate esterification is performed using a sulfate agent such as anhydrous sulfuric acid, chlorosulfonic acid, sulfamic acid, and sulfuric acid, and the sulfate esterified product is neutralized with a base to convert it into a salt with a cation (Q ⁺ ). Then, the compound represented by the chemical formula (1) (ion-binding salt) can be obtained.

[Use of ion-binding salt]
In the present invention, the compound represented by the chemical formula (1) (ion-binding salt) is used as an action improving agent for a rust preventive as described above. That is, according to another aspect of the present invention, there is also provided a method for improving the action of the rust preventive agent, which comprises using the above-mentioned predetermined action improver in combination with the rust preventive agent.

(anti-rust)
In the present invention, there is no particular limitation on the specific form of the rust preventive agent whose rust preventive action is improved by the compound (ionic bond salt) represented by the chemical formula (1), and any conventionally known rust preventive agent can be used. Can be adopted. Examples of the rust preventive include zinc-based rust preventives and nitrogen-containing compound-based rust preventives.

Examples of the zinc-based rust preventive agent include zinc, zinc phosphate, calcium phosphite, zinc strontium phosphite, zinc cyanamide zinc polyphosphate, zinc calcium cyanamide, and hydrates thereof.

Examples of the nitrogen-containing compound-based rust preventive include alkylamines having an alkyl group having 1 to 24 carbon atoms, ethylene oxide (1 to 20 mol) adducts thereof, and alkylamines such as polyalkylamines; alkyl sulfonates and aryl sulfonates. , Alkylaryl sulfonates, amine salts of sulfonates such as petroleum sulfonates; acylsarcosines such as lauroyl sarcosine and oleoyl sarcosin; alkanols such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. Amines; ethylene oxide (1-20 mol) adducts of cyclic amines composed of 6 to 24 carbon atoms; amines with two or more nitrogen atoms such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine and theirs. Ethylene oxide (1-60 mol) adduct; imidazole series such as imidazole, methyl imidazole, ethyl methyl imidazole, benzo imidazole, aminobenzo imidazole, phenylbenzo imidazole, naphtho imidazole, triphenyl imidazole, imidazoline; polyether amine, alkenyl succinic acid And so on.

In addition to these, a phosphate-based rust preventive such as a rust preventive having a phosphate ester structure as disclosed in Patent Document 4, a gluconate and / or a mixture of a heptoglucontate and a saccharide compound, Phtalic acid esters, adipic acid esters, silicates, nitrites, chromates, oxyacids and the like may be used.

The action improver according to the present invention improves the rust preventive action of the other rust preventive agent by being used in combination with other rust preventive agents such as those described above. However, there is no particular limitation on the specific form of the combined use of the action improver and other rust preventives according to the present invention, and the environment in which the above other rust preventives are added to exert the rust preventive action. Therefore, it is considered that the action and effect of the present invention can be exhibited if the action improver according to the present invention is added so as to coexist. Hereinafter, as a preferred embodiment of the present invention, a mode of use of the action improver according to the present invention will be described when the rust preventive is added to the resin emulsion to exert a rust preventive action.

Here, the action improver according to the present invention has a property of being able to exhibit excellent emulsification performance as an emulsifier for emulsion polymerization. Therefore, extremely excellent polymerization stability can be achieved by performing emulsion polymerization using the action improver (ion-binding salt) according to the present invention as an emulsifier for emulsion polymerization. However, the usage mode of the action improving agent according to the present invention is not limited to this, and a usage mode in which the agent is added to a separately obtained resin emulsion together with a rust preventive agent can also be adopted. That is, in the embodiment of the resin emulsion as described above, the usage mode of the action improving agent according to the present invention is roughly classified into the following two.

(1) A form in which a polymerizable monomer is emulsion-polymerized using the action improver according to the present invention as an emulsifier for emulsion polymerization, and a rust inhibitor is added to the obtained resin emulsion to form an emulsion containing a rust inhibitor;
(2) A polymerizable monomer is emulsified and polymerized using an emulsifier for emulsion polymerization other than the action improver according to the present invention, and a rust preventive and an action improver according to the present invention are added to the obtained resin emulsion to prevent rust. A form of an agent-containing emulsion.

Of these, first, the form (1) will be described. In the form (1), first, a composition for emulsion polymerization containing an action improver according to the present invention, a polymerizable monomer, and a solvent is prepared. do. Here, in the present invention, the monomer (polymerizable monomer) that can be emulsified and polymerized using the emulsifying emulsifier is not particularly limited, and conventionally known polymerizable monomers can be used. For example, (meth) acrylic acid. Acrylic acids or methacrylic acids such as methyl, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate. Acid esters; Vinyl halides such as vinyl bromide, vinyl chloride, vinylidene chloride; Vinyl esters of fatty acids such as acetic acid, propionic acid, tertiary synthetic saturated carboxylic acid: styrene, α-methylstyrene, etc. Aromatic vinyls: Monoolefins such as ethylene and butadiene or conjugated diolefins: Vinyl cyanide such as acrylonitrile: α, β-unsaturated amides such as acrylamide: Acrylic acid, methacrylic acid, itaconic acid, maleic acid, Examples thereof include α and β-unsaturated carboxylic acids such as fumaric acid.

As the polymerization initiator, an initiator usually used for emulsion polymerization can be used without particular limitation, and for example, potassium, sodium, ammonium persulfate or perborate, hydrogen peroxide and other inorganic peroxides can be used. Organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, peracetic acid; 2,2-azobisisobutyronitrile, 4-azobis- (4-cyanopentanoic) acid or its alkali metal. A radical-forming polymerization initiator such as a salt can be used, and the amount thereof is preferably 0.01 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and further preferably 0.1. ~ 1.0% by mass.

Further, if it is necessary to use a peroxide as a polymerization initiator, the peroxide can be used in combination with a reducing agent such as ascorbic acid, soluble sulfite, hydrosulfite, and thiosulfate. It can also be used as a redox-based polymerization initiator in combination with a metal monomer that generates heavy metal ions in water or a metal compound that generates metal ions in water such as ferrous sulfate.

In addition, a chain transfer agent can also be used in combination, and as such, for example, t-dodecyl mercaptan, dodecyl mercaptan, carbon tetrachloride, chloroform, triphenylmethane and the like can be used.

Furthermore, conventional additives in emulsion polymerization techniques such as chelating agents, buffers, salts of organic acids and the like can be used.

As the solvent, in addition to water, an organic solvent such as alcohol, glycol or glycol ether can be used, but water is preferably used as the solvent.

In the form of (1), the amount of the action-improving agent according to the present invention in the composition for emulsion polymerization is preferably 0. It is 5 to 10% by mass, more preferably 1 to 7% by mass, and even more preferably 2 to 5% by mass. In the form of (1), the action improver (ion-binding salt) represented by the chemical formula (1) alone can sufficiently exert a function as an emulsifier for emulsification and polymerization, but if necessary, conventional methods can be used. Known surfactants, reactive emulsifiers (however, these concepts do not include the ion-binding salt according to the present invention), polymer emulsifiers, protective colloids and the like can also be used in combination. Examples of the surfactant that can be used in combination include a long-chain alkyl sulfate, a long-chain alkylbenzene sulfonate, a polyoxyethylene alkylphenyl ether sulfate, an alkyldiphenyl ether disulfonate, and the like as an anionic surfactant. Examples of the ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and pluronic type surfactant. Examples of reactive emulsifiers that can be used in combination include vinyl monomers having a sulfonic acid group or a sulfonate group, vinyl monomers having a sulfate ester group, and nonionic groups such as alkali metal salts, ammonium salts, and polyoxyethylene. Examples thereof include a vinyl monomer having a quaternary ammonium salt and a vinyl monomer having a quaternary ammonium salt.

Examples of polymer emulsifiers that can be used in combination include polyvinyl alcohol, poly (meth) acrylate, polyhydroxyalkylene (meth) acrylate, and examples of protective colloids that can be used in combination are anions such as sodium alginate. Examples thereof include sexual colloids and nonionic protective colloids such as hydroxyethyl cellulose.

When used in combination with anionic surfactants, nonionic surfactants, polymer emulsifiers and / or protective colloids, 0.05 to 10 parts by mass of each of the anionic surfactants according to the present invention. The degree is appropriate.

In the form of (1), by performing emulsion polymerization using the above-mentioned composition for emulsion polymerization, a resin emulsion containing the emulsion polymer of the composition for emulsion polymerization can be obtained. That is, according to another embodiment of the present invention, a rust preventive-containing emulsion containing a rust preventive agent, an action improver, and a resin emulsion is also provided. Here, the emulsion polymerization of the composition for emulsion polymerization can be carried out by a conventionally known emulsion polymerization method. As such a method, there are a batch charging method, a monomer addition method, a monomer emulsion addition method and the like, and a preferred method is a monomer emulsion addition method.

In the form of (1), a rust preventive-containing emulsion can be obtained by adding the above-mentioned other rust preventive to the resin emulsion obtained by the above-mentioned emulsion polymerization. However, if the action and effect of the present invention are not impaired, a part of the above other rust-preventive agents may be used for the composition for emulsion polymerization before emulsion polymerization or the reaction system during emulsion polymerization. All may be added all at once or in divided portions. The content of the other rust preventive is not particularly limited, but the content of the rust preventive is preferably 1 to 50% by mass with respect to 100% by mass of the resin emulsion (without the rust preventive). , More preferably 5 to 40% by mass, still more preferably 10 to 30% by mass.

On the other hand, in the form of (2), as the emulsifier for emulsion polymerization blended in the composition for emulsion polymerization, an emulsifier for emulsion polymerization other than the above-mentioned action improver is used instead of the above-mentioned action improver, and emulsion polymerization is used. A rust-preventive agent-containing emulsion can be obtained in the same manner as in the above-mentioned form (1) except that the action improving agent is post-added to the resin emulsion obtained in the above-mentioned method. Since the examples of the emulsifier for emulsion polymerization other than the action improver are as described above in the description of the form (1), duplicated description will be omitted here.

The rust inhibitor-containing emulsion thus obtained can be incorporated into, for example, a paint. Since the rust preventive-containing emulsion according to the present invention contains an action improver, the action of the rust preventive is improved. Therefore, the paint containing the rust inhibitor-containing emulsion according to the present invention can exhibit excellent rust preventive performance, and when applied on a substrate made of iron or the like, for example, rust on the substrate Occurrence can be effectively prevented.

Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to the following embodiments. In the following description, "part" represents a mass part and "%" represents a mass%.

[Ionic binding salt as an action enhancer]
In this example, the following ion-binding salts (1) to (4) were used as the action improver.

Ionic-binding salt (1): The above compound (G)
Ionic-binding salt (2): The above compound (H)
Ionic-binding salt (3): The above compound (I)
Ionic-binding salt (4): The above compound (J).

[Production example of resin emulsion]
(Manufacturing Example 1)
A polymerizable monomer was prepared by mixing 100 parts of butyl acrylate, 70 parts of methyl methacrylate, 30 parts of styrene, and 4 parts of acrylic acid.

On the other hand, 4.08 parts of the ion-binding salt (1) (2% by mass with respect to 100% by mass of the polymerizable monomer) was added to 105 parts of the ion-exchanged water and mixed. The polymerizable monomer prepared above was added thereto and emulsified. Then, 1.02 parts of ammonium persulfate (0.5% by mass with respect to 100% by mass of the polymerizable monomer) was added and mixed well to prepare a monomer emulsion.

Next, 100 parts of deionized water and 5% by mass (15.7 parts) of the monomer emulsion prepared above were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and stirring was started. The temperature was raised to 80 ° C. over 30 minutes in a nitrogen stream and maintained at 80 ° C. for 30 minutes for initial polymerization.

Subsequently, the remaining monomer emulsion was continuously added dropwise at 80 ° C. over 3 hours to polymerize, and after the completion of the addition, aging was carried out for 1 hour to obtain a resin emulsion.

(Manufacturing Example 2)
A resin emulsion was obtained by the same method as in Production Example 1 described above, except that the ion-binding salt (2) was used instead of the ion-binding salt (1).

(Manufacturing Example 3)
A resin emulsion was obtained by the same method as in Production Example 1 described above, except that the ion-binding salt (3) was used instead of the ion-binding salt (1).

(Manufacturing Example 4)
A resin emulsion was obtained by the same method as in Production Example 1 described above, except that the ion-binding salt (4) was used instead of the ion-binding salt (1).

(Manufacturing Example 5)
Emulsion polymerization was carried out using Adecaria Soap (registered trademark) SR10 (sulfate ester type reactive surfactant, manufactured by ADEKA Co., Ltd.) instead of the ion-binding salt (1), and the obtained emulsion polymer was subjected to emulsion polymerization. The resin emulsion was prepared by the same method as in Production Example 1 described above, except that 1.02 parts (0.5% by mass with respect to 100% by mass of the polymerizable monomer) of the ion-binding salt (1) was post-added. Obtained.

(Manufacturing Example 6)
Similar to Production Example 5 described above, except that the amount of the ion-binding salt (1) added to the obtained emulsion polymer was changed to 10.2 parts (5% by mass with respect to 100% by mass of the polymerizable monomer). A resin emulsion was obtained by the above method.

(Comparative Manufacturing Example 1)
A resin emulsion was obtained by the same method as in Production Example 5 described above, except that the ion-binding salt (1) was not post-added to the emulsion polymer obtained by emulsion polymerization.

(Comparative Manufacturing Example 2)
Instead of the ionic bond salt (1), Newcol (registered trademark) LA407 (polyoxyethylene alkylamine type surfactant, manufactured by Nippon Emulsifying Co., Ltd.) 1.02 parts (0 with respect to 100% by mass of the polymerizable monomer) A resin emulsion was obtained by the same method as in Production Example 5 described above, except that 5.5% by mass) was post-added.

(Comparative Manufacturing Example 3)
Instead of the ionic bond salt (1), Neucol® LA407 (polyoxyethylene alkylamine type surfactant, manufactured by Nippon Emulsifying Co., Ltd.) 10.2 parts (5 with respect to 100% by mass of the polymerizable monomer) A resin emulsion was obtained by the same method as in Production Example 6 described above, except that (% by mass) was post-added.

(Comparative Manufacturing Example 4)
With the above-mentioned Production Example 5 except that Neucol (registered trademark) 560-SF (polyoxyethylene alkylphenol type surfactant, manufactured by Nippon Emulsion Co., Ltd.) was post-added in place of the ionic bonding salt (1). A resin emulsion was obtained by the same method.

(Comparative Manufacturing Example 5)
With the above-mentioned Production Example 6 except that Neucol (registered trademark) 560-SF (polyoxyethylene alkylphenol type surfactant, manufactured by Nippon Emulsion Co., Ltd.) was added in place of the ionic bonding salt (1). A resin emulsion was obtained by the same method.

(Comparative Manufacturing Example 6)
Similar to Production Example 1 described above, except that Aqualon (registered trademark) KH10 (sulfate ester type reactive surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used instead of the ionic bonding salt (1). A resin emulsion was obtained by the method.

(Comparative Manufacturing Example 7)
A resin emulsion was obtained by the same method as in Production Example 1 described above, except that sodium dodecylbenzenesulfonate was used instead of the ion-binding salt (1).

(Comparative Manufacturing Example 8)
By the same method as in Production Example 1 described above, except that Neucor (registered trademark) 2607PCA (phosphate ester-type surfactant, manufactured by Nippon Emulsion Co., Ltd.) was used instead of the ionic bonding salt (1). , A resin emulsion was obtained.

(Comparative Manufacturing Example 9)
Similar to Production Example 1 described above, except that Neucol (registered trademark) LA407 (polyoxyethylene alkylamine type surfactant, manufactured by Nippon Emulsion Co., Ltd.) was used instead of the ionic bonding salt (1). A resin emulsion was obtained by the method.

(Manufacturing Example 7)
80 parts of butyl acrylate and 80 parts of methyl methacrylate were mixed to prepare a polymerizable monomer.

On the other hand, 4.8 parts of the ion-binding salt (1) (3% by mass with respect to 100% by mass of the polymerizable monomer) was added to 160 parts of the ion-exchanged water and mixed. The polymerizable monomer prepared above was added thereto and emulsified. Then, 0.8 parts of ammonium persulfate (0.5% by mass with respect to 100% by mass of the polymerizable monomer) was added and mixed well to prepare a monomer emulsion.

Next, 80 parts of deionized water and 5% by mass (8.0 parts) of the monomer emulsion prepared above were charged in a reactor equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and stirring was started. The temperature was raised to 80 ° C. over 30 minutes in a nitrogen stream and maintained at 80 ° C. for 30 minutes for initial polymerization.

Subsequently, the remaining monomer emulsion was continuously added dropwise at 80 ° C. over 3 hours to polymerize, and after the completion of the addition, aging was carried out for 1 hour to obtain a resin emulsion.

(Comparative Manufacturing Example 10)
Similar to Production Example 7 described above, except that Aqualon (registered trademark) KH10 (sulfate ester type reactive surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used instead of the ionic bonding salt (1). A resin emulsion was obtained by the method.

[Evaluation of resin emulsion]
The resin emulsions obtained in each of the above-mentioned production examples and each comparative production example were evaluated as follows. Here, the evaluation results of the resin emulsions obtained in Production Examples 1 to 6 are shown in Table 1 below. The evaluation results of the resin emulsions obtained in Comparative Production Examples 1 to 9 are shown in Table 2 below. Further, the evaluation results of the resin emulsions obtained in Production Example 7 and Comparative Production Example 10 are shown in Table 3 below.

(1) Measurement of solid content The evaporation residue after weighing 1 g of the resin emulsion, adding 5 g of pure water, and drying at 105 ° C. for 2 hours was expressed as the solid content.

(2) Polymerization stability (agglomeration amount)
The resin emulsion was filtered through 200 μm mesh nylon, and the polymerization stability was evaluated from the mass of the residue according to the following evaluation criteria.

⊚: The amount of the filtration residue was less than 0.1% by mass with respect to the solid content of the resin emulsion;
◯: The amount of the filtration residue was 0.1% by mass or more and less than 10% by mass with respect to the solid content of the resin emulsion;
X: The amount of the filtration residue was 10% by mass or more with respect to the solid content of the resin emulsion (in this example, the rust preventive performance could not be evaluated).

[Evaluation of rust preventive properties of emulsions containing rust preventives]
Using each of the above-mentioned production examples and the resin emulsions obtained in each comparative production example, the rust preventive-containing emulsions of Examples 1 to 7 and Comparative Examples 1 to 10 and the prevention of Comparative Example 11 were carried out by the following methods. A rust-free emulsion was prepared.

(Examples 1 to 6)
By using each of the resin emulsions obtained in Production Examples 1 to 6 described above and adding 20% by mass of a rust inhibitor (zinc phosphate tetrahydrate) to 100% by mass of the resin emulsion, The rust preventive-containing emulsions of Examples 1 to 6 corresponding to each production example were prepared.

(Example 7)
Using the resin emulsion obtained in Production Example 1 described above, by adding 15% by mass of a rust inhibitor (zinc phosphate tetrahydrate) to 100% by mass of the resin emulsion, the case of Example 7 An emulsion containing a rust inhibitor was prepared.

(Comparative Examples 1 to 7, 10)
By using each of the resin emulsions obtained in Comparative Production Examples 1 to 7 described above and adding 20% by mass of a rust inhibitor (zinc phosphate tetrahydrate) to 100% by mass of the resin emulsion. , The rust preventive agent-containing emulsions of Comparative Examples 1 to 7 and Comparative Example 10 corresponding to each Comparative Production Example were prepared. Since the resin emulsions obtained in Comparative Production Example 8 and Comparative Production Example 9 did not have sufficient polymerization stability, preparation of a rust preventive-containing emulsion by adding a rust preventive agent and rust preventive properties described later were obtained. Was not evaluated.

(Comparative Example 11)
The resin emulsion obtained in Production Example 1 described above was used as it was without adding a rust inhibitor to obtain a rust inhibitor-free emulsion of Comparative Example 11.

Subsequently, the rust preventive property was evaluated by the following method using the rust preventive agent-containing (or non-containing) resin emulsion obtained above.

(Evaluation method of rust prevention)
A rust inhibitor-containing emulsion was applied to a blast plate (150 x 70 x 2.3 [mm]) of SS400, which is a rolled steel material for general structure washed with acetone, using a 10 mil bar coater to apply a coating film. Formed. Then, the coating film was dried at 60 ° C. for 1 hour, and further left at room temperature for 24 hours. Then, a diagonal cut was made in this coating film. Immediately after cutting, the coating film portion below the intersection of the diagonal lines was immersed in a 5 mass% sodium chloride aqueous solution at room temperature for 5 days. After the immersion was completed, the width of rust generated from the cut line (inverted V-shape) was measured every 5 mm along the cut line, the average value of the obtained values was calculated, and evaluated according to the following criteria:
⊚: Rust generation width is less than 3 mm;
◯: Rust generation width is 3 mm or more and less than 5 mm;
Δ: Rust generation width is 5 mm or more and less than 10 mm;
X: Rust is generated in a width of 10 mm or more or rust is generated in the entire coating film.

The results of these evaluations are shown in Table 4 below.

From the results shown in Table 4, it can be seen that the rust preventive-containing emulsion of each example in which the action improver according to the present invention is used in combination with other rust preventives exhibits excellent rust preventive performance. On the other hand, sufficient rust preventive performance could not be achieved with the rust preventive agent-containing emulsions of each comparative example. It was also confirmed that the effect of improving the rust preventive property according to the present invention is exhibited regardless of the monomer composition.

Further, Examples 1 to 4 and Example 7 (corresponding to the above-mentioned form (1)) in which the action improver according to the present invention was used as an emulsifier for emulsion polymerization, and the action improver were post-added to the resin emulsion. It can be seen that in both Example 5 and Example 6 (corresponding to the above-mentioned embodiment (2)), the same excellent rust prevention performance is exhibited.

From the results of Comparative Example 11, it was also confirmed that the ion-binding salt according to the present invention does not exhibit rust preventive performance by itself. That is, it can be seen that the ionic bond salt according to the present invention has a function of improving the rust preventive action of the other rust preventive agent when used in combination with the other rust preventive agent.

Claims (14)

It is an action improver for rust preventives and
The following chemical formula (1):

In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and A represents a linear chain having 2 to 4 carbon atoms. Represents a shaped or branched alkylene group, m represents the average number of added moles of AO, which is a number from 1 to 150, l is an integer of 1 to 3, and n represents the atomic value of Q ⁺ , which is 1 or. 2, where Q ⁺ represents a monovalent metal cation, a divalent metal cation, or a nitrogen-containing compound cation.
An action enhancer containing an ion-binding salt represented by. The action improver according to claim 1, wherein Q ⁺ is an organic ammonium ion. The action improver according to claim 2, wherein Q ⁺ is an organic ammonium ion having an ethylenically unsaturated bond. The action improving agent according to any one of claims 1 to 3, wherein _R2 is a methyl group. The action improving agent according to any one of claims 1 to 4, wherein A is an ethylene group. The action improving agent according to any one of claims 1 to 5, wherein m is a number of 5 to 120. It is a method to improve the action of rust preventives.
A method comprising using the action enhancer according to any one of claims 1 to 6 in combination with a rust preventive. A composition for emulsion polymerization, which comprises the action improver according to any one of claims 1 to 6, a polymerizable monomer, and a solvent. The composition for emulsion polymerization according to claim 8, wherein the content of the action improving agent is 0.5 to 5% by mass with respect to 100% by mass of the polymerizable monomer (not containing the action improving agent). A rust preventive-containing emulsion comprising a rust preventive, the action enhancer according to any one of claims 1 to 6, and a resin emulsion. The rust preventive-containing emulsion according to claim 10, which comprises the emulsion polymer of the composition for emulsion polymerization according to claim 8 or 9. The tenth or eleventh claim, wherein the content of the action improver is 0.5 to 10% by mass with respect to 100% by mass of the resin emulsion (excluding the rust preventive and the action improver). Emulsion containing rust inhibitor. The rust preventive according to any one of claims 10 to 12, wherein the content of the rust preventive agent is 1 to 50% by mass with respect to 100% by mass of the resin emulsion (not including the rust preventive agent). Agent-containing emulsion. A paint comprising the rust inhibitor-containing emulsion according to any one of claims 10 to 13.