TW202311233A - Reactive surfactant, copolymer obtained by using the reative surfactant, polymer emulsion containing the copolymer, and method of producing the copolymer - Google Patents

Abstract

Provided is a reactive surfactant represented by general formula (1). (In the formula, R1 represents a hydrocarbon group having 8-36 carbon atoms or an acyl group having 8-36 carbon atoms, A1 and A2 each independently represent an alkylene group having 2-4 carbon atoms, L represents a group represented by formula (2), p represents a number of 1-10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number of 0-100, and n represents a number of 0-100. However, when m represents 0, X represents an ionic hydrophilic group.).

Description

Reactive surfactant, copolymer obtained by using the reactive surfactant, polymer emulsion containing the copolymer, and method for producing the copolymer

The present invention relates to a reactive surfactant, a copolymer obtained by polymerizing the reactive surfactant and a reactive unsaturated compound other than the reactive surfactant, a polymer emulsion containing the copolymer, and the Copolymer production method.

The surfactant system has a wide range of properties such as emulsification, dispersion, cleaning, wetting, and foaming. Utilizing these various properties, it has been used in various fields such as fibers, paper, rubber, plastics, metals, paints, pigments, and civil engineering. Especially in recent years, terminal products using surfactants have gradually become more high-performance, and some people have pointed out the secondary disadvantages of surfactants.

For example, surfactants are contained in products when manufacturing products such as paints, printing inks, and adhesives, or as components that are indispensable for stabilization of products, and even in terms of workability. However, when products containing surfactants are actually used in coating, printing, bonding, adhesion, etc., the water resistance and oil resistance of the coating film, printing surface, adhesive film, etc. are often deteriorated due to the presence of surfactants.

Furthermore, it is known that the surfactant used as an emulsifier when producing a polymer by emulsion polymerization not only participates in the initiation reaction or formation reaction of polymerization, but also has an effect on the mechanical stability of the polymer emulsion containing the produced polymer, Chemical stability, freezing stability, storage stability, etc., and even affect the physical properties of polymer emulsions such as particle size, viscosity, and foaming properties, as well as water resistance, weather resistance, adhesiveness, and heat resistance when filming. The physical properties of the film are seriously affected. Specifically, it has been pointed out that the foaming of the polymer emulsion increases due to the presence of an emulsifier, and when a film is formed from a polymer emulsion, the physical properties of the film such as adhesion, water resistance, weather resistance, and heat resistance deteriorate. . Also, the same phenomenon as that caused by the surfactant used as a dispersant has been pointed out for polymer emulsions produced by suspension polymerization.

These problems are caused by the surfactant used as an emulsifier or dispersant remaining in the polymer as a free body. As a method of reducing the free surfactant, some people have developed a surfactant that does not remain in the polymer as a free body by reacting with the polymer during polymerization or forming a film, so-called reactive surfactant. Sexual surfactant (also known as polymeric surfactant).

Many structures have been proposed about a reactive surfactant, for example in patent documents 1-8 etc. However, when using the polymer emulsion obtained by using these copolymers as the main component for coatings, adhesives, etc., satisfactory coating properties such as water resistance, corrosion resistance, and adhesion cannot be obtained. Improvement of these physical properties is required. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 49-46291 [Patent Document 2] Japanese Patent Application Laid-Open No. 62-100502 [Patent Document 3] Japanese Patent Application Laid-Open No. 63-23725 [Patent Document 4] Japanese Patent Application Laid-Open No. 4-50204 [Patent Document 5] Japanese Patent Laid-Open No. 62-104802 [Patent Document 6] Japanese Patent Laid-Open No. 62-11534 [Patent Document 7] Japanese Unexamined Patent Publication No. 2002-301353 [Patent Document 8] Japanese Unexamined Patent Publication No. 2006-75808

[Problem to be Solved by the Invention]

Therefore, the problem to be solved by the present invention is to provide a reactive surfactant of a copolymer capable of providing a coating film having excellent physical properties such as water resistance, corrosion resistance, and adhesion. [Means to solve the problem]

Therefore, the inventors of the present case have devoted themselves to research and found that a specific compound is useful as a reactive surfactant used as an emulsifier or a dispersant, and the reactive surfactant is reacted with a reaction other than the reactive surfactant. Copolymers obtained by polymerizing permanent unsaturated compounds can provide coating films with excellent physical properties such as water resistance, corrosion resistance, and adhesion, and finally complete the present invention.

That is, the present invention provides a reactive surfactant represented by the following general formula (1).

(In the formula, R ¹ represents a hydrocarbon group with 8 to 36 carbons or an acyl group with 8 to 36 carbons, A ¹ and A ² independently represent an alkylene group with 2 to 4 carbons, and L represents the following formula (2) Represents the base, p represents a number from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number from 0 to 100, and n represents a number from 0 to 100; however, when m is 0, X is ionic hydrophilic group)

In addition, the present invention provides a copolymer and a method for producing the copolymer. The copolymer is obtained by polymerizing (A) and (B), wherein (A) is selected from the reactive interface represented by the general formula (1). At least one active agent, (B) is at least one reactive unsaturated compound selected from the component (A).

Furthermore, the present invention provides a polymer emulsion containing the obtained copolymer. [Effect of Invention]

According to the present invention, it is possible to provide a reactive surfactant that can provide a copolymer capable of providing a coating film that exhibits an excellent function as an emulsifier during emulsion polymerization and has excellent physical properties such as water resistance, corrosion resistance, and adhesion. Furthermore, according to the present invention, a copolymer of a reactive surfactant and a reactive unsaturated compound other than a reactive surfactant can form a coating film having excellent physical properties such as water resistance, corrosion resistance, and adhesion, and is useful as a Coatings and adhesives.

[Mode of Implementing the Invention]

The reactive surfactant of the present invention will be described below. That is, the reactive surfactant of the present invention is a compound represented by the following general formula (1).

(In the formula, R ¹ represents a hydrocarbon group with 8 to 36 carbons or an acyl group with 8 to 36 carbons, A ¹ and A ² independently represent an alkylene group with 2 to 4 carbons, and L represents the following formula (2) Represents the base, p represents a number from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number from 0 to 100, and n represents a number from 0 to 100; however, when m is 0, X is ionic hydrophilic group)

In the general formula (1), the hydrocarbon group having 8 to 36 carbon atoms represented by R ¹ includes an alkyl group, an alkenyl group and an aryl group.

The alkyl group is, for example, a straight-chain or branched alkyl group, such as octyl, isooctyl, 2-ethylhexyl, secondary octyl, nonyl, isononyl, secondary nonyl, decyl, isodecyl , Secondary Decyl, Undecyl, Isoundecyl, Secondary Undecyl, Dodecyl, Isododecyl, Secondary Dodecyl, Tridecyl, Isotridecanyl, Secondary Tridecyl , Tetradecyl, Isotetradecyl, Secondary Tetradecyl, Hexadecyl, Isohexadecyl, Secondary Hexadecyl, Stearyl, Isooctyl, Eicosyl, 2-Butyloctyl , 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, monomethyl isostearyl , 21 bases, 22 bases, 30 bases, 36 bases, etc.

Examples of the alkenyl group include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

Examples of the aryl group include cumyl, cumenyl, styryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, Heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, styrenated phenyl, etc. .

Also, in the general formula (1), the acyl group having 8 to 36 carbon atoms represented by ^R1 includes, for example, octyl, nonylcarbonyloxy, decanyloxy, undecyloxy, dodecyloxy Tridecyloxy, tetradecyloxy, neooctyloxy, isononyloxy, 3,4,4-trimethylhexyloxy, neononyloxy, isodecyl Acyloxy, 2-propylheptyloxy, neodecyloxy, isododecyloxy, isododecyloxy, 2-butyloctyloxy, isotridecyloxy Isotetradecyloxy, isomyristyloxy, 2-pentylnonyloxy, isopentadecyloxy, isohexadecanyloxy, isopalmityloxy, 2- Hexyldecyloxy, Isoheptadecyloxy, Isostearyloxy, Isostearyloxy, 2-Heptylundecyloxy, Isododecyloxy, Isodidecyloxy Decacyloxy, 2-octyldodecyloxy, 2-nonyltridecyloxy, 2-decyltetradecyloxy, 2-undecylpentadecanyloxy 2-dodecylhexadecanyloxy, 2-tridecylheptadecanyloxy, 2-tetradecyloctadecyloxy, 2-pentadecylnonadecanyl Acyloxy, 2-hexadecyleicosyloxy, isoleyloxy, etc.

Among the hydrocarbon groups having 8 to 36 carbons exemplified by R ¹ , a phenyl group substituted with an alkyl group having 8 to 36 carbons or an alkyl group having 3 to 18 carbons is preferred. Among the alkyl groups having 8 to 36 carbons, an alkyl group having 8 to 24 carbons is preferred, an alkyl group having 10 to 14 carbons is more preferred, and a branched alkyl group having 11 to 13 carbons is still more preferred. Also, among the alkyl-substituted phenyl groups having 3 to 18 carbon atoms, nonylphenyl or octylphenyl is preferred. It is also preferable to use these mixed alkyl groups for R ¹ .

The alkylene groups represented by ^A1 and ^A2 of the general formula (1) include groups such as ethylidene, propylidene, isopropylidene, butylidene, isobutylene, and second-level butylene. , (A ¹ O) _n and (A ² O) _m may be the same or different; moreover, in each of (A ¹ O) _n and (A ² O) _m , there may be two or more alkane The base is formed by random/block combination. m is a number of 0-100, preferably a number of 1-80, more preferably a number of 2-50, most preferably a number of 3-20. n is a number of 0-100, preferably a number of 0-80, more preferably a number of 0-50, most preferably a number of 0-20.

When A ¹ O and A ² O are each a single group or two or more types of groups, it is preferable to include an ethyleneoxy group. When the ratio of ethyleneoxy to the total molar amount of A ¹ O and A ² O is less than 50 mol%, the stability of the polymer emulsion will deteriorate, so it is preferably 50-100 mol%, more preferably It is 60-100 mol%, more preferably 80-100 mol%, most preferably 100 mol%.

X in the general formula (1) represents a hydrogen atom or an ionic hydrophilic group, and when m is 0, X represents an ionic hydrophilic group. When the ionic hydrophilic group represented by X is an anionic hydrophilic group, it is preferably -SO ₃ M, -R ⁴ -SO ₃ M, -R ⁵ -COOM, -PO ₃ M ₂ , -PO ₃ HM or -CO- R ⁶ -COOM (wherein, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom [however, since an alkaline earth metal atom is usually divalent, 1/2 molar system is equivalent to M] or a quaternary ammonium cation, R ⁴ and R ⁵ represents an alkylene group having 1 to 6 carbons, and R ⁶ represents an alkylene group having 1 to 12 carbons).

In the formula representing an anionic hydrophilic group, the alkali metal atom represented by M includes, for example, lithium, sodium, and potassium, and the alkaline earth metal atom includes, for example, magnesium and calcium. In addition, examples of the quaternary ammonium cations include those derived from ammonia, alkylamines, and alkanolamines.

In the formula representing an anionic hydrophilic group, the alkylene groups with 1 to 6 carbons represented by ^R4 and ^R5 include, for example, methylene, ethylidene, propylidene, butylene, pentenyl, Pentyl, hexyl, etc.

In the formula representing an anionic hydrophilic group, R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a residue obtained by removing two carboxyl groups from a dibasic acid. Examples of dibasic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc. Saturated aliphatic dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, methyl hexahydrophthalic acid and other saturated alicyclic dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, methylenedi Aromatic dicarboxylic acids such as carboxylic acid and extended dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and other unsaturated aliphatic dicarboxylic acids, tetrahydrophthalic acid, formaldehyde Methylnadic acid, nadic acid (endomethylene tetrahydrophthalic acid), methylnadic acid (methylnadic acid), methylbutenyl tetrahydrophthalic acid, methylpentenyl tetrahydrophthalic acid, etc. Unsaturated alicyclic dicarboxylic acids, etc.

Among the aforementioned anionic hydrophilic groups, a group represented by -SO ₃ M, -PO ₃ M ₂ or -PO ₃ HM is preferable, and a group represented by -SO ₃ M is more preferable. Also, M is preferably an alkali metal or quaternary ammonium, and is more preferably quaternary ammonium in terms of excellent water resistance.

In the general formula (1), p represents a number of 1 to 10, and in some production methods, a mixture of those different from p may be formed. In the case of a mixture, p represents the average value. p is preferably a number of 1-8, more preferably a number of 1-5, most preferably a number of 1-3.

The production method of the reactive surfactant of the present invention is not particularly limited, for example, as a method of synthesizing a reactive surfactant in which X in the general formula (1) is a hydrogen atom, for example, a diallyl group can be synthesized by a known method. It is obtained by adding ethylene oxide, propylene oxide, etc. to the reaction product of glycidyl ether with unsaturated alkyl such as glycerin and alcohol or alcohol alkoxylate with ^R1 group. Also, a catalyst may be used for the ring-opening reaction of the epoxy group of diallylglycerol having an alcohol or alcohol alkoxylate having an R ¹ group, if necessary. The catalyst is not particularly limited as long as it can be used in the ring-opening reaction of epoxy, and examples thereof include tertiary amines, quaternary ammonium salts, boron trifluoride or its ether zirconium salts, aluminum chloride, barium oxide, hydrogen Sodium oxide, potassium hydroxide, etc.

Also, X in the synthetic general formula (1) is -SO ₃ M, -R ⁴ -SO ₃ M, -R ⁵ -COOM, -PO ₃ M ₂ , -PO ₃ HM or -CO-R ⁶ -COOM The method of the reactive surfactant is not particularly limited, and it can be obtained by reacting a compound in which X in the general formula (1) is a hydrogen atom with an ionic hydrophilizing agent. The reaction conditions are not particularly limited, and usually the temperature is from room temperature to 150° C., and the pressure is from normal pressure to about 0.5 MPa, and the reaction time is about 1 to 10 hours. A catalyst such as urea can also be used as needed. Also, when M is a hydrogen atom, it can be neutralized with a base such as sodium hydroxide or potassium hydroxide, ammonia, an alkylamine, or an alkanolamine such as monoethanolamine or diethanolamine.

The ionic hydrophilizing agent for introducing an anionic hydrophilic group represented by -SO ₃ M includes, for example, sulfanilic acid, sulfuric acid, anhydrous sulfuric acid, oleum, chlorosulfonic acid, and the like.

Examples of the ionic hydrophilizing agent for introducing an anionic hydrophilic group represented by -R ⁴ -SO ₃ M include propane sultone, butane sultone, and the like.

As an ionic hydrophilizing agent for introducing an anionic hydrophilic group represented by -R ⁵ -COOM, for example, chloroacetic acid (R ⁵ corresponds to a methylene group), chloropropionic acid (R ⁵ corresponds to an ethylidene group), or salts thereof can be used wait.

As an ionic hydrophilizing agent for introducing an anionic hydrophilic group represented by -CO-R ⁶ -COOM, for example, maleic acid, phthalic acid, or salts thereof can be used.

As the ionic hydrophilizing agent for introducing an anionic hydrophilic group represented by -PO ₃ M ₂ or -PO ₃ HM, for example, phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, phosphorus oxychloride, etc. can be used. During phosphorylation, a monoester compound in which X is represented by -PO ₃ HM and a diester compound in which two residues of X are removed from the general formula (1) and bonded to -PO ₂ M are obtained as a mixture. These can be separated, and when separation is difficult, they can also be used as a mixture as it is.

When the ionic hydrophilic group represented by X in the general formula (1) is a cationic hydrophilic group, examples thereof include -R ⁷ -NR ⁸ R ⁹ R ¹⁰ ·Y, or -Z-NR ⁸ R ⁹ R ¹⁰ ·Y The basis of representation and so on. In the above formula representing a cationic hydrophilic group, Y represents a halogen atom or methyl sulfate (CH ₃ SO ₄ ). Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Also, ^R7 represents an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include the same alkylene groups as those exemplified for R ⁴ of the above-mentioned anionic hydrophilic group.

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

When introducing a cationic hydrophilic group represented by -R ⁷ -NR ⁸ R ⁹ R ¹⁰ ·Y, the general formula (1) is firstly converted to a halogenating agent such as thionyl chloride, thionyl bromide, or phosgene. The hydroxyl group of the compound in which X is a hydrogen atom is halogenated, and then introduced by reacting a tertiary amine compound. Moreover, after making a secondary amine compound react instead of a tertiary amine compound, you may make a halogenated alkyl group, dimethyl sulfate, etc. react. The reaction conditions for the halogenation of hydroxyl groups are not particularly limited, and usually the temperature is room temperature to 100°C, the pressure is about 0.5 MPa at normal pressure, and the reaction time is about 1 to 10 hours. Also, the reaction conditions for amination are not particularly limited, and usually the temperature is room temperature to 150° C., and the reaction time is about 1 to 10 hours under increased pressure of about normal pressure to 0.5 MPa. Alkalis such as sodium hydroxide and potassium hydroxide can also be used as catalysts as required.

When introducing a cationic hydrophilic group represented by -Z-NR ⁸ R ⁹ R ¹⁰ ·Y, first, epihalohydrin such as epichlorohydrin, epibromohydrin, and a compound in which X in the general formula (1) is a hydrogen atom are carried out. reaction, and then it can be introduced by further reacting a tertiary amine compound. Moreover, after making a secondary amine compound react instead of a tertiary amine compound, you may make a halogenated alkyl group, dimethyl sulfate, etc. react. The reaction conditions for reacting epihalohydrin are not particularly limited, but usually the temperature is room temperature to 100°C, the pressure is about normal pressure to 0.3 MPa, and the reaction time is about 1 to 10 hours. Alkaline catalysts such as sodium hydroxide and potassium hydroxide, or acid catalysts such as sulfuric acid, phosphoric acid, ferric chloride, boron fluoride, and tin chloride can also be used as required. Also, the reaction conditions for amination are not particularly limited, and usually the temperature is room temperature to 150° C., and the reaction time is about 1 to 10 hours under increased pressure of about normal pressure to 0.5 MPa. Alkalis such as sodium hydroxide and potassium hydroxide can also be used as catalysts as required.

Among the above-mentioned X, hydrogen atom, -SO ₃ M or -PO ₃ HM is preferable; hydrogen atom, -SO ₃ NH ₄ , -SO ₃ Na or -PO ₃ HNa is more preferable in terms of ease of manufacture.

Next, the copolymer of the present invention will be described in detail.

The copolymer of the present invention comprises (A) at least one type selected from reactive surfactants represented by general formula (1), and (B) at least one type selected from reactive unsaturated compounds other than (A) components. 1 kind of aggregation. The repeating unit of the copolymer of the present invention does not repeat, so that its structure and repeatability are extremely diverse. Therefore, the structure of the copolymer included in the present invention cannot be represented by a common general formula. Therefore, in the present invention, the invention including such a copolymer is defined based on the description of specifying the copolymer by the production method "obtained by polymerizing (A) component and (B) component."

As for the reactive unsaturated compound of (B) component used in this invention, an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, etc. are mentioned, for example.

Examples of unsaturated carboxylic acids include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; -Carboxyethyl acrylate, 2-carboxyethyl methacrylate, etc. Moreover, the ester compound of unsaturated carboxylic acid is mentioned as unsaturated carboxylic acid ester, For example, it is an ester compound which has the structure obtained by reaction of unsaturated carboxylic acid and alcohols. Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, heptanol, octanol, 2-ethyl Hexyl Alcohol, Nonyl Alcohol, Decyl Alcohol, Undecyl Alcohol, Dodecyl Alcohol, Tridecyl Alcohol, Myristyl Alcohol, Pentadecyl Alcohol, Cetyl Alcohol, Heptadecanyl Alcohol, Cetyl Alcohol, Vinyl Alcohol, Allyl Alcohol, Benzyl Alcohol wait. An unsaturated carboxylic acid or its ester compound can be used individually or in combination of 2 or more types.

Moreover, the unsaturated carboxylic acid ester which has 2 or more unsaturated bonds obtained from a polyhydric alcohol and an unsaturated carboxylic acid can also be used as an internal crosslinking agent. Examples of unsaturated carboxylic acid esters having two or more unsaturated bonds include (poly)ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, methylenebisacrylamide, divinylbenzene, etc.

Furthermore, other reactive unsaturated compounds may be used as monomer components of the copolymer. Examples of other unsaturated compounds include styrene, dichlorostyrene, chloromethylstyrene, methylstyrene, acrylamide, acrylonitrile, butadiene, maleinitrile and the like.

(A) The reactive surfactant represented by the general formula (1) of the component is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total amount of the components (A) and (B) . When used in an amount of less than 0.1% by mass, the function as an emulsifier is insufficient, and a polymer emulsion cannot be obtained. When it exceeds 3 mass %, there exists a possibility that the water resistance of the film etc. which consist of a polymer emulsion may deteriorate.

The method for producing a copolymer obtained by polymerizing components (A) and (B) includes adding water, a polymerization initiator, and a mixture of components (A) and (B) (hereinafter also referred to as "monomer mixture") etc., and carry out the polymerization reaction. In the polymerization reaction, component (A) tends to function as an emulsifier. Moreover, other emulsifiers other than (A) component may be added as needed.

The emulsifier that can be used here is preferably an anionic surfactant or a nonionic surfactant, more preferably an anionic surfactant, from the viewpoint of improving the dispersion stability and mechanical stability of the polymer emulsion .

Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, and ammonium lauryl sulfate; sodium lauryl polyglycol ether sulfate; Sodium castor oil alkylate; Alkali sulfonate such as alkali metal salt of sulfonated paraffin, ammonium salt of sulfonated paraffin; Fatty acid salt such as sodium laurate, triethanolamine oleate, triethanolamine rosinate; Sodium benzenesulfonate , Alkaliaryl sulfonates such as alkali metal sulfates of alkylphenol hydroxyethylene; high alkyl naphthalene sulfonate; naphthalene sulfonate formalin condensate; Ethylene alkyl sulfate; polyoxyethylene alkyl aryl sulfate; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate; N-acyl amino acid salt; N-acyl methyl taurine salt etc.

Examples of nonionic surfactants include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; Ethylene oxide and/or propylene oxide adducts of alcohols with numbers 1 to 18; ethylene oxide and/or propylene oxide adducts of alkylphenols; alkylene glycols and/or alkylenes Ethylene oxide and/or propylene oxide adducts of diamines, etc.

Alcohols having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, amyl alcohol, isoamyl alcohol, Pentyl alcohol, hexanol, octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, etc. Examples of alkylphenols constituting nonionic surfactants include phenol, methylphenol, 2,4-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4-(1,1,3 ,3-tetramethylbutyl)phenol, 4-isooctylphenol, 4-nonylphenol, 4-tertiary octylphenol, 4-dodecylphenol, 2-(3,5-dimethylheptylphenol base) phenol, 4-(3,5-dimethylheptyl)phenol, naphthol, bisphenol A, bisphenol F, etc. The alkylene glycol constituting the nonionic surfactant includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2- Methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl -1,5-pentanediol, 1,6-hexanediol, etc. Examples of the alkylenediamine constituting the nonionic surfactant include those in which the alcoholic hydroxyl group of alkylene glycol is substituted with an amino group. In addition, the ethylene oxide adduct and the propylene oxide adduct may be a random adduct or a block adduct.

As for other emulsifiers, since the reactive surfactant represented by the general formula (1) used in the invention of this case can play a role as an emulsifier, it is not necessary and depends on the demand; if used, the addition amount is The less the better. Specifically, it is preferably 0 to 12 parts by mass, more preferably 0 to 8 parts by mass, and still more preferably 0 to 6 parts by mass with respect to 100 parts by mass of the monomer mixture. Even if the addition amount of other emulsifiers is 0 part by mass, emulsion polymerization can be performed stably. On the other hand, when more than 12 parts by mass are added, unreacted emulsifier remains when forming a film, and there is a possibility that substrate adhesion and water whitening resistance may be deteriorated. In addition, the emulsifier may be directly added to a solution obtained by adding water to the monomer mixture, may be previously added to a polymerization vessel, or may be used in combination.

The polymerization initiator usable for polymerizing the monomer mixture is not particularly limited, and may be either water-soluble or oil-soluble. Specific polymerization initiators include, for example, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-amidinepropane)dihydrochloride, etc. Azo compounds, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, and hydrogen peroxide, and the like. Also, a redox initiator consisting of a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, or the like can also be used. These polymerization initiators can be used individually or in combination of 2 or more types. Among these, persulfate salts and redox initiators are preferred from the viewpoint of excellent polymerization stability.

The amount of the polymerization initiator added is preferably 0.01 to 6 parts by mass, more preferably 0.03 to 4 parts by mass, and even more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the monomer mixture from the viewpoint of accelerating the polymerization rate share.

The polymerization initiator can be added in advance in the reaction vessel, added immediately before the polymerization starts, or added several times after the polymerization starts. In addition, it may be added to the monomer mixture in advance. When adding a polymerization initiator, the polymerization initiator may be separately dissolved in a solvent or a monomer mixture and then added, or the dissolved polymerization initiator may be further brought into an emulsified state before adding.

Moreover, at the time of polymerization, you may further add a chain transfer agent or a pH buffering agent. Chain transfer agents include, for example, lauryl mercaptan, epoxypropyl mercaptan, thioglycolic acid, 2-mercaptoethanol, mercaptoglycolic acid, 2-ethylhexyl mercaptoglycolic acid, 2,3-dimercapto- 1-propanol, etc. The pH buffering agent is not particularly limited as long as it is a compound having a pH buffering effect. For example, sodium bicarbonate, potassium bicarbonate, monosodium phosphate, monopotassium phosphate, disodium phosphate, trisodium phosphate, sodium acetate, acetic acid Ammonium, sodium formate, ammonium formate, etc.

During the polymerization, the water used is preferably ion-exchanged water. The usage-amount of water is preferably 30-400 mass parts with respect to 100 mass parts of monomer mixtures, More preferably, it is 35-200 mass parts, More preferably, it is 40-150 mass parts. If the amount of water used is more than 30 parts by mass, the viscosity of the polymer emulsion of the obtained copolymer can be in an appropriate range, and the polymerization stability of the obtained copolymer is also good. On the other hand, if it is 400 parts by mass or less, the solid content concentration of the polymer emulsion containing the obtained copolymer can be in an appropriate range, and the coating film formation property when coating on a substrate or a release sheet to form a coating film is good. .

The copolymer in the present invention can be synthesized by adding a polymerization initiator to a monomer mixture containing a reactive surfactant, if necessary, in the presence of an emulsifier, and performing emulsion polymerization. The procedures for carrying out the emulsion polymerization include the following methods (1) to (3). From the viewpoint of easy control of the polymerization temperature, method (2) or (3) is preferred, and method (3) is more preferred. (1) Put the monomer mixture into a reaction vessel and raise the temperature, add dropwise or in portions a polymerization initiator dissolved in water or a solvent to carry out polymerization. (2) After putting part of the monomer mixture in the reaction vessel and heating it up, add the polymerization initiator dissolved in water or a solvent dropwise or in portions to make the polymerization reaction proceed, then add the rest of the monomer mixture dropwise or in stages and continue to aggregate. (3) After adding a polymerization initiator dissolved in water or a solvent into the reaction vessel in advance and raising the temperature, add the emulsion or solution composed of the monomer mixture and water or solvent dropwise or in portions to carry out polymerization.

The polymerization conditions in the above-mentioned polymerization method are not particularly limited, and are preferably carried out according to the following conditions. In the method (1), the temperature range is preferably 40 to 100° C., and the polymerization reaction is preferably carried out for about 1 to 8 hours. In method (2), it is advisable to polymerize 1-50% by mass of the monomer mixture at 40-90°C for 0.1-4 hours, then add the rest of the monomer dropwise or in portions for about 1-5 hours The mixture is then matured at this temperature for about 1 to 3 hours. In method (3), it is advisable to raise the temperature of the polymerization initiator dissolved in water to preferably 40-90°C, and add the monomer mixture and water in full amount dropwise or in portions for about 2-5 hours. emulsion. Moreover, after that, aging is preferably performed at this temperature for 1 to 5 hours.

Also, in the above-mentioned polymerization method, based on the viewpoint of polymerization stability, it is preferable to dissolve the emulsifier (or part of the emulsifier) in the monomer mixture in advance, or adjust it to an O/W emulsion state in advance. .

It is also possible to adjust the pH by further adding an aqueous alkaline solution such as ammonia water, various water-soluble amines, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. to the polymer emulsion containing the copolymer obtained by the above polymerization method. At this time, it is preferable to adjust to pH 5-9, and it is more preferable to adjust to pH 6-8.5. The aqueous alkali solution can be added during or after the polymerization, and from the perspective of polymerization stability and the viscosity stability of the obtained polymer emulsion over time, it is preferable to add a part or the whole amount after cooling to room temperature during the aging stage of the polymerization.

The solid content concentration in the polymer emulsion (copolymer aqueous dispersion) or solution containing the copolymer obtained from the (A) component and (B) component of the present invention is preferably 10 to 80% by mass, more preferably 25 to 80% by mass. 70% by mass. In addition, the solid content concentration here refers to the amount of residue obtained after drying the polymer emulsion or solution at 105° C. for 2 hours/the amount of the polymer emulsion or solution.

The viscosity of the polymer emulsion at 25°C is preferably 30-400 mPa·s, more preferably 50-300 mPa·s. The viscosity referred to here is the value measured at 25°C using a rotary viscometer.

The average particle diameter of the polymer particles in the polymer emulsion is preferably 100-900 nm, more preferably 200-600 nm. The average particle diameter referred to here refers to the value measured by the dynamic light scattering method.

The polymer emulsion containing the copolymer of the present invention is suitable for applications such as various paints, various adhesives, and coating materials. [Example]

The present invention will be specifically described below according to the examples, but the present invention is not limited to the following examples. In order to manufacture the reactive surfactant of this invention, first, the synthesis example for synthesizing the precursor compound which reacts diallyl glyceryl ether and alcohol is shown below.

[Synthesis Example 1] Add 220g (1mol) of nonanol and 2.2g of sodium hydroxide as a catalyst to a stainless steel pressurized reaction device equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, and replace the gas environment in the reaction device with nitrogen while stirring 172 g (1 mol) of diallylglycidylglycerol was fed at 90° C., and after the feeding was completed, aging was performed at 90° C. for 5 hours to synthesize the following compound (A).

[Synthesis Examples 2-3] The following compounds (B) and (C) were respectively synthesized according to the same method as in Synthesis Example 1, except that nonylphenol was changed to 300 g (1 mol) of styrenated phenol and 172 g (1 mol) of isoundecyl alcohol.

(In the formula, n represents a number of 1 to 3).

[Synthesis Example 4] Add 172 g (1 mol) of isoundecyl alcohol and sodium hydroxide as a catalyst to a stainless steel pressurized reaction device equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and replace the gas environment in the reaction device with nitrogen while stirring 315 g (1.5 mol) of diallylglycidylglycerol was fed at 90° C., and after the feeding was completed, aging was performed at 90° C. for 5 hours to synthesize the following compound (D).

[Synthesis Example 5] The following compound (E) was synthesize|combined by the method similar to synthesis example 4 except having changed the quantity of diallyl glycidyl glycerol into 420 g (2.0 mol).

Using the above-mentioned compounds (A) to (E), the following reactive surfactants 1 to 18 were produced. [Example 1] Compound (A) (1mol) was added to a pressurized reaction vessel equipped with a stirrer, a thermometer and a reflux tube, and potassium hydroxide was added under conditions of a pressure of 1.5kg/cm ² and a temperature of 130°C while stirring As a catalyst, ethylene oxide (10 mol) was fed, and aging was carried out for 2 hours after the feeding to obtain the reactive surfactant 1 of the present invention. In addition, in the following examples, in the structural formula, EO represents an oxyethylene group, and PO represents an oxypropylene group. In addition, the numerical value in the lower right of a parenthesis represents the average value of a mixture.

[Example 2] Reactive surfactant 2 of the present invention was obtained in the same manner as in Example 1, except that compound (A) was changed to compound (B) (1 mol).

[Example 3] Reactive surfactant 3 of the present invention was obtained in the same manner as in Example 1, except that compound (A) was changed to compound (C) (1 mol).

[Example 4] Add compound (C) (1mol) to a pressurized reaction vessel equipped with a stirrer, a thermometer and a reflux tube, and add potassium hydroxide under conditions of a pressure of 1.5kg/cm ² and a temperature of 130°C while stirring As a catalyst, ethylene oxide (10 mol) and propylene oxide (2 mol) were fed, and aging was carried out for 2 hours after the feeding to obtain the reactive surfactant 4 of the present invention.

[Example 5] Add compound (C) (1 mol) to a pressurized reaction vessel equipped with a stirrer, a thermometer and a reflux tube, and add potassium hydroxide under conditions of a pressure of 1.5kg/cm ² and a temperature of 130°C under stirring As a catalyst, ethylene oxide (30 mol) was fed, and aging was carried out for 2 hours after the feeding to obtain the reactive surfactant 5 of the present invention.

[Example 6] Reactive surfactant 6 of the present invention was obtained in the same manner as in Example 1, except that compound (A) was changed to compound (D) (1 mol).

[Example 7] Reactive surfactant 7 of the present invention was obtained in the same manner as in Example 1, except that compound (A) was changed to compound (E) (1 mol).

[Example 8] Esterification; Sulfamic acid Add the reactive surfactant 1 (0.5mol) prepared above to a pressurized reaction vessel equipped with a stirrer, a thermometer and a reflux tube. Under stirring, replace the gas environment in the reaction vessel with nitrogen, and then add sulfonamide Acid (0.5 mol) was stirred at 70° C. for 1 hour to obtain reactive surfactant 8 of the present invention.

[Embodiments 9-14] Reactive surfactants 9 to 14 of the present invention were obtained in the same manner as in Example 8, except that reactive surfactant 1 was changed to reactive surfactants 2 to 7, respectively.

[Example 15] Esterification: phosphorus pentoxide Add reactive surfactant 4 (0.5 mol) to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, add phosphorus pentoxide (0.25 mol) at 40°C under stirring, and then stir at 80°C for 2 hours . Thereafter, it was neutralized with an aqueous sodium hydroxide solution to obtain the reactive surfactant 15 (mixture) of the present invention. The weight ratio of the following compounds (a) and (b) is in the range of 7:3 to 3:7.

[Example 16] Esterification: maleic anhydride Add reactive surfactant 1 (0.5 mol) to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube, add maleic anhydride (0.5 mol) under stirring, and stir at 80° C. for 1 hour for esterification. Neutralize with aqueous sodium hydroxide to obtain the reactive surfactant 16 of the present invention.

[Example 17] Esterification: chlorosulfonic acid Add reactive surfactant 4 (0.5 mol) to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and cool to 0-5° C. while stirring. Chlorosulfonic acid (0.5 mol) was added dropwise using a dropping funnel. After the dropwise addition, stirring was carried out at the temperature for 1 hour, and the generated HCl was removed by blowing nitrogen gas. Thereafter, it was neutralized with an aqueous sodium hydroxide solution under stirring to form a sodium salt, thereby obtaining the reactive surfactant 17 of the present invention.

[Example 18] Reactive surfactant 18 was obtained by the same method as Example 17 except having changed reactive surfactant 4 into compound C.

Using the above-mentioned reactive surfactant and reactive unsaturated compound, a polymer emulsion containing a copolymer was produced according to the emulsion polymerization method shown below.

[Examples 1-1 to 1-14, Comparative Examples 1-1 to 1-3] ＜Preparation of styrene/methyl methacrylate/2-ethylhexyl acrylate/acrylic acid (30/35/33/2wt%) polymer emulsion＞ A mixed monomer liquid was prepared by mixing 27 g of styrene, 31.5 g of methyl methacrylate, 29.7 g of 2-ethylhexyl acrylate, and 1.8 g of acrylic acid as monomers. 85.5 g of the mixed monomer liquid, 2.18 g each of the reactive surfactant shown in Table 1 as an emulsifier, and 2.18 g of the comparative surfactant, and 51.35 g of ion-exchanged water were mixed with a homomixer to prepare a mixed monomer emulsion. In addition, 54.4 g of ion-exchanged water was added to a reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, a nitrogen gas introduction tube, and a dropping funnel, and the remaining mixed monomer liquid 4.5 g was mixed with the reactive compound shown in Table 1 as an emulsifier. Each 0.07g of surfactant and comparative surfactant was added to the reaction container, and it heated up to 75 degreeC. Thereafter, after continuing stirring for 15 minutes, 0.2 g of ammonium persulfate as a polymerization initiator was dissolved in 1.8 g of ion-exchanged water in a stirred state, and added thereto to initiate polymerization. Next, 139 g of the mixed monomer emulsion was dripped and polymerized over 3 hours after 15 minutes from the addition of the polymerization initiator. Furthermore, after aging for 2 hours, it was cooled and the pH was adjusted to 8 with aqueous ammonia to obtain the polymer emulsions of Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-3. The comparative surfactants 1-3 of the emulsifier used for comparison are the following compounds.

[Assessment experiment 1] For the polymer emulsions of Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-3, measure or evaluate polymerization stability, average particle size and mechanical stability, and evaluate water whitening resistance for polymer films ( ΔE) and corrosion resistance. The measurement method and evaluation method are as follows. The results are shown in Table 1 below.

[polymerization stability] Filter 200g of the polymer emulsion with a 200-mesh filter cloth, wash with water to remove the filter residue of the condensate generated in the emulsification polymerization step, and then dry it at 105°C for 2 hours. Indicated by mass % of ingredients. In addition, in this measurement, the smaller the amount of aggregates, the higher the polymerization stability in the emulsion polymerization step. In general, when the amount of aggregates is 0.1% by mass or more, it is said that industrial production is impossible.

[The average particle size] Part of the polymer emulsion was taken, and the average particle diameter of the polymer particles was measured using a dynamic light scattering type zeta potential-particle diameter-molecular weight measurement system (manufactured by Otsuka Electronics Co., Ltd., product name ELSZ-1000).

[Mechanical Stability] Weigh 50 g of the polymer emulsion, and use a MARLON type testing machine to treat the polymer emulsion with a load of 20 kg and a rotation speed of 1,000 rpm for 10 minutes. Filter the polymer emulsion with an 80-mesh metal mesh, and wash it with water. The resulting aggregate residue was dried at 105° C. for 2 hours, and its mass was expressed in mass % relative to the solid content of the polymer emulsion. In addition, in this measurement, the smaller the amount of aggregates, the higher the mechanical stability of the polymer emulsion under high shear conditions. Industrially, it is preferably at most 0.4% by mass, and particularly preferably at most 0.2% by mass.

[Water bleaching resistance] Add 10 parts by mass of 2,2,4-trimethyl-1,3-pentanediol 2-methyl propionate to 100 parts by mass of polymer emulsion, and apply it on a commercially available glass plate with a 2 mil applicator , and dried at 50°C for 0.5 hours. The test sample was immersed in ion-exchanged water at 50° C. for 72 hours, and the temporal color difference (ΔE) was measured with a spectrophotometer (manufactured by KONICA MINOLTA Co., Ltd., product name CM-3700d). The evaluation criteria are as follows: ◎: ΔE<5, ○: 5≦ΔE<10, △: 10≦ΔE<15, ×: ΔE≧15

[corrosion resistance] Add 10 parts by mass of 2,2,4-trimethyl-1,3-pentanediol 2-methyl propionate to 100 parts by mass of polymer emulsion, and apply it on a commercially available hot and cold steel plate with a 4mil coater , and dried at 50°C for 0.5 hours. The obtained coating film for evaluation was scratched with a utility knife to reach the substrate (cross-cut part), and based on the salt spray resistance test of JIS K 5600-7-9:2006, the salt spray tester made by Ascott Company ( S450iS type) was subjected to a salt spray test, and the rusted area after 72 hours was evaluated visually. The evaluation criteria are as follows: ⊚: No rust was observed on the peripheral portion of the cross-cut portion. ◯: A very small amount of rust was observed on the periphery of the cross-cut portion, but peeling or swelling of the coating film caused by this was not observed. △: A large area of rust was observed on the periphery of the cross-cut portion, and the peeling or swelling of the coating film caused by this was observed, but no flow rust was observed. ×: A large piece of rust can be seen on the periphery of the cross-cut part, and the peeling or swelling of the coating film caused by it can be seen, and even the coating film contamination caused by flow rust can be seen.

[Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-3] ＜Preparation of 2-ethylhexyl acrylate/butyl acrylate/acrylic acid (40/58/2wt%) polymer emulsion＞ 44 g of 2-ethylhexyl acrylate, 63.8 g of butyl acrylate, and 2.2 g of acrylic acid were mixed as monomers to prepare a mixed monomer liquid. 109.8 g of the mixed monomer liquid, 0.11 g of decylmercaptan as a chain transfer agent, 1.87 g of each of the reactive surfactant shown in Table 2 below as an emulsifier, and 1.87 g of a comparative surfactant and 30.8 g of ion-exchanged water were passed through Shake and mix to prepare an emulsion for dropwise addition. In addition, 55.22 g of ion-exchanged water was added to a reaction container equipped with a stirrer, a reflux cooler, a thermometer, a nitrogen gas introduction tube, and a dropping funnel, and the temperature was raised to 80° C. while stirring. After stabilization was achieved at 80° C., 0.22 g of ammonium persulfate as a polymerization initiator was dissolved in 1.98 g of ion-exchanged water, and added thereto. Next, 142.58 g of the mixed monomer emulsion was dropped and polymerized over 3 hours after 15 minutes from the addition of the polymerization initiator. Furthermore, after aging for 1 hour, it was cooled and the pH was adjusted to 7-8 with aqueous ammonia to obtain the polymer emulsions of Examples 2-1-2-14 and Comparative Examples 2-1-2-3.

[Assessment experiment 2] For the polymer emulsions of Examples 2-1 to 2-14 and Comparative Examples 2-1 to 2-3, the polymerization stability, average particle size, and mechanical stability were evaluated, and the retention force, peeling force, and residual strength were evaluated for the polymer film. glue. The evaluation of the polymerization stability, average particle size, and mechanical stability of the polymer emulsion was performed using the same method as the evaluation experiment 1, and for the polymer film, the holding force, peeling force, and adhesive residue were evaluated. The evaluation method is as follows. The results are shown in Table 2 below.

[Retention test] A film was formed on a 38 μm thick PET film cut into a size of 25 mm×150 mm with a 4 mil coater, and dried at 105° C. for 3 minutes. Paste the 25mm×25mm bonding surface on the SUS board with a 2kg crimping roller. After aging for 24 hours, hang a 1kg load to measure the time before the test piece falls. The evaluation criteria are as follows. The longer the time before the test piece falls, the higher the adhesiveness can be judged. ○: More than 48 hours △: More than 24 hours and less than 48 hours ×: Less than 24 hours

[Peel force test] Make a film on the PET film in the same way as the holding force, stick the adhesive surface on the SUS board with a pressure roller, and perform aging at room temperature for 24 hours, then measure the peeling force at a speed of 300mm/min and an angle of 180°. The evaluation criteria are as follows. The higher the peeling force, the higher the adhesiveness was judged to be. ○: 10N or more △: More than 5N and less than 10N ×: Less than 5N

[Evaluation of residual glue] Using the SUS board after the peel force test, the resin component (residual glue) remaining on the SUS board was colored with a pigment and evaluated visually. The evaluation criteria are as follows: ◎: Residual glue on the surface of the test panel does not reach 10% ○: Residual glue on the surface of the test panel is more than 10% and less than 30% △: Residual glue on the test panel surface is more than 30% and less than 80% ×: More than 80% of residual glue on the surface of the test panel

According to the above-mentioned examples, it has been confirmed that the reactive surfactant of the present invention contains a polymer emulsion with a copolymer of a reactive unsaturated compound because it can form an emulsion with stable polymerization stability and mechanical stability, and can exert excellent reactivity. The function of emulsifier. Also, in evaluation test 1, it was confirmed that the polymer emulsion containing the copolymer obtained by polymerizing the reactive surfactant of the present invention and a reactive unsaturated compound other than the reactive surfactant can form water resistance and corrosion resistance Excellent polymer film. Furthermore, in the evaluation experiment 2, it was confirmed that the polymer emulsion of the present invention has excellent adhesion and less adhesive residue. [industrial availability]

The novel compound of the present invention is useful as a reactive surfactant used as an emulsifier, and a coating film formed from a polymer emulsion containing a copolymer produced by using it is excellent in water resistance and corrosion resistance, and can Suitable for water-based coatings. In addition, the coating film has excellent adhesiveness and less adhesive residue after peeling off, so the polymer emulsion of the present invention can also be used as an adhesive for labels on beverage bottles, cosmetic bottles or recyclable bottles.

Claims (4)

A kind of reactive surfactant, it is represented by following general formula (1):

(In the formula, R ¹ represents a hydrocarbon group with 8 to 36 carbons or an acyl group with 8 to 36 carbons, A ¹ and A ² independently represent an alkylene group with 2 to 4 carbons, and L represents the following formula (2) Represents the base, p represents a number from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number from 0 to 100, and n represents a number from 0 to 100; however, when m is 0, X is ionic hydrophilic group)

. A copolymer obtained by polymerizing (A) and (B), wherein, (A) is selected from at least one of the reactive surfactants as in claim 1, (B) is at least 1 sort(s) chosen from the reactive unsaturated compound other than (A) component. A kind of polymer emulsion, it is to contain the copolymer as claim item 2. A method for producing a copolymer comprising polymerizing (A) and (B), wherein (A) is at least one selected from reactive surfactants represented by the following general formula (1), (B) It is at least one kind of reactive unsaturated compound selected from (A) component;

(In the formula, R ¹ represents a hydrocarbon group with 8 to 36 carbons or an acyl group with 8 to 36 carbons, A ¹ and A ² independently represent an alkylene group with 2 to 4 carbons, and L represents the following formula (2) Represents the base, p represents a number from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number from 0 to 100, and n represents a number from 0 to 100; however, when m is 0, X is ionic hydrophilic group)

.