JP2007153965A - Emulsifier for emulsion polymerization, method for producing polymer emulsion and the resultant polymer emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive emulsifier for emulsion polymerization, comprising a compound free from a polyoxyalkylene chain as a hydrophilic group, making emulsion polymerization stability high, and giving a polymer and its film with markedly improved water resistance, adhesion, heat resistance and weatherability. <P>SOLUTION: The emulsifier comprises a compound of the general formula(1)( wherein, R<SP>1</SP>is a hydrocarbon group; R<SP>2</SP>is H or methyl; G is a monosaccharide's residue, wherein at least one of the -OH groups in (G)<SB>n</SB>is substituted with an anionic hydrophilic group; and n is 1-30 ). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an emulsifier for emulsion polymerization used in emulsion polymerization, a method for producing a polymer emulsion using the emulsifier for emulsion polymerization, and a polymer emulsion obtained by the method.

  Conventionally, as an emulsifier for emulsion polymerization, anionic surfactants such as dodecyl benzene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate ester salt, polyoxyalkylene alkyl (aryl) ether sulfate ester salt, polyoxyalkylene alkyl Nonionic surfactants such as (aryl) ethers and polyoxyethylene polyoxypropylene block copolymers are used alone or in combination, but the stability of the polymer emulsion and the properties of the polymer film obtained from the emulsion These are not always satisfactory, and many problems to be solved remain.

  Examples thereof include problems such as polymerization stability of the emulsion, mechanical stability of the obtained emulsion, chemical stability, freeze-thaw stability, pigment miscibility, and storage stability. In particular, the mechanical stability remains a problem to be improved. Furthermore, when a polymer film is prepared from the emulsion, the used emulsifier remains in the polymer film in a free state, causing problems such as poor water resistance and adhesion of the film. In addition, when the emulsion is destroyed by means such as salting out or aciding out and the polymer is taken out, a large amount of emulsifier is contained in the waste water, which causes river pollution. Become.

  In order to improve the problems of conventional emulsifiers from this point of view, many reactive emulsifiers that have copolymerizable unsaturated groups as reactive groups and polyoxyalkylene chains and ionic groups introduced into hydrophilic groups have been proposed. Has been.

  For example, JP-A-8-41112, JP-A-1-99638, JP-A-58-203960 and the like disclose an anionic reactive surfactant, and JP-A-2003-268021, JP-A-4 No.-50204, Japanese Patent Laid-Open No. 63-54927, and the like each describe a nonionic reactive surfactant, and emulsion polymerization is attempted for various monomers. Emulsions using these reactive emulsifiers as emulsifiers have good stability during polymerization, and the polymer films obtained from the emulsions showed excellent performance in water resistance, adhesiveness, heat resistance, and weather resistance. .

However, problems with reactive emulsifiers derived from such alkylene oxides include the fact that unreacted alkylene oxide remains in the product, and substances that are highly carcinogenic or irritating as by-products. It is done. For example, it is known that harmful dioxane is generated during synthesis and toxic aldehydes are generated by oxidative decomposition of alkylene oxide chains. In recent years, sick house syndrome and VOC (volatile organic compound) problems are noisy. It is not preferable to use an emulsifier containing aldehyde or the like for the production of the emulsion.
Japanese Patent Laid-Open No. 8-41112 JP-A-1-99638 JP 58-203960 A JP 2003-268021 A Japanese Patent Laid-Open No. 4-50204 JP-A-63-54927

  The present invention has been made in view of the above circumstances, and its purpose is not to have a polyoxyalkylene chain as a hydrophilic group, to improve stability during emulsion polymerization, and to improve the stability of polymers and polymer films. An object of the present invention is to provide an emulsifier for reactive emulsion polymerization, which is remarkably improved in water resistance, adhesiveness, heat resistance and weather resistance.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, have an allyl group or a methallyl group as an unsaturated group having copolymerizability, and various anions on polyglucoside as a hydrophilic group portion. The present inventors have found that the above-mentioned problems can be solved by using a polyglucoside compound into which a hydrophilic hydrophilic group is introduced as an emulsifier for emulsion polymerization.

That is, the emulsifier for emulsion polymerization of the present invention contains a compound represented by the following general formula (1).

In the formula, R ¹ is a hydrocarbon group, and R ² is a hydrogen atom or a methyl group. G represents a monosaccharide residue, and (G) at least one of —OH groups contained in _n is substituted with an anionic hydrophilic group. n is a number from 1 to 30.

  The method for producing a polymer emulsion of the present invention includes a step of adding the emulsifier for emulsion polymerization of the present invention together with a monomer in an aqueous medium to polymerize the monomer, or adding the monomer to the aqueous medium after monomer polymerization, and The amount of the emulsifier used for emulsion polymerization is 0.1 to 20% by weight with respect to the monomer amount.

  And the polymer emulsion of this invention is obtained by the manufacturing method of the said polymer emulsion.

  The emulsifier for emulsion polymerization according to the present invention has an allyl group or methallyl group which is a copolymerizable double bond in the hydrophobic group portion of the molecule and is excellent in copolymerizability with a polymerizable monomer. Easy to be incorporated into the composition. Therefore, it is useful as an emulsifier for copolymerizable reactive emulsion polymerization, and the amount of the emulsifier present in the polymer film obtained from the polymer emulsion polymerized using the emulsifier for emulsion polymerization of the present invention is in a free state. This reduces the water resistance, adhesiveness, heat resistance, and weather resistance of the film, and exhibits excellent effects. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved. Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.

  Embodiments of the present invention will be described below.

The emulsifier for emulsion polymerization of the present invention is characterized by containing a polyglucoside compound represented by the following general formula (1).

In the compound of the general formula (1), R ¹ in the formula represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, and the like.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, 2 Secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl , Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, - octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - and the like isostearyl group.

  Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like. As an aryl group, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, cumylphenyl, styrenated cresyl, benzylxylyl, α-naphthyl, β-naphthyl groups and the like can be mentioned. Examples of the cycloalkyl group and cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.

Further, R ¹ may contain two or more kinds of the hydrocarbon groups described above.

Among these, R ¹ is preferably an alkyl group or alkenyl group having 6 to 30 carbon atoms.

Usually, R ¹ is a residue obtained by removing a hydroxyl group from alcohol. These alcohols are naturally derived alcohols or industrially produced alcohols.

  Naturally occurring alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.

  Industrially produced alcohols are branched saturated primary alcohols produced by the oxo process via higher olefins derived from propylene or butene or mixtures thereof, such as isononanol, isodecanol, isoundecanol, isododecane. Nord, isotridecanol and the like. In addition, as a commercial product, there is Exxal series manufactured by Exxon Mobil, Inc. As a mixture of linear and branched alcohols produced by the oxo method via olefins derived from n-paraffins and ethylene oligomers, Shell There are Neodol series manufactured by the company, Diadol series manufactured by Mitsubishi Chemical Corporation, Safol series and Lial series manufactured by Sasol. Examples of Gerve alcohol obtained by dimerization of alcohol by Gerve reaction include 2-ethyl-1-hexanol, 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-octanol, 2-propyl There are -1-heptanol, 4-methyl-2-propyl-1-hexanol, 2-propyl-5-methyl-1-hexanol, etc., or it is produced by air oxidation of paraffin, and the hydroxyl group is other than the end of the carbon chain There are secondary alcohols that are randomly bonded.

  Moreover, it is also possible to mix and use two or more of these alcohols.

In the above general formula (1), R ² represents a hydrogen atom or a methyl group.

G represents a monosaccharide residue, and (G) at least one of the —OH groups contained in _n is substituted with an anionic hydrophilic group.

Examples of the anionic hydrophilic group include sulfate groups, phosphonate groups (3), carboxylate groups (4 or 5), and succinate groups (6) represented by the following general formulas (2) to (6). .

In the formula, R ³ represents a residue obtained by removing a carboxyl group from a dibasic acid. M and M ′ represent a hydrogen atom, a metal atom, ammonium, an alkanolamine or a hydrocarbon group, and M and M ′ may be different or the same.

R ³ is a residue obtained by removing a carboxyl group from a dibasic acid. Examples of such dibasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecane Saturated aliphatic dicarboxylic acids such as diacids; saturated alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid, hexahydrophthalic acid and methylhexahydrophthalic acid; phthalic acid, isophthalic acid, terephthalic acid, tolylene dicarboxylic acid, xylylene diene Aromatic dicarboxylic acids such as carboxylic acids; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid (endomethylenetetrahydrophthalic acid) , Methyl nadic acid, methylbutenyltetrahy Rofutaru acid, and unsaturated alicyclic dicarboxylic acids such as methyl pentenyl tetrahydrophthalic acid.

  M and M ′ represent a hydrogen atom, a metal atom, ammonium, or a hydrocarbon group. Examples of the metal atom include alkali metal atoms such as lithium, sodium and potassium, alkaline earth metal atoms such as magnesium and calcium (however, since alkaline earth metal atoms are usually divalent, 1/2), etc. Examples of ammonium include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N-methylmonoethanolamine, and N-ethylmonoethanol. Amine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′— Tetrakis (2-Hi Rokishipuropiru) ammonium, such as ethylenediamine. Examples of the hydrocarbon group include those described above. M and M ′ may be different or the same, and may contain two or more of the above-described ones.

(G) The anionic hydrophilic group contained in _n may contain two or more of the above groups.

  In General formula (1), n is a number of 1-30, Preferably it is 1-10.

[Synthesis method]
The reaction conditions for obtaining the emulsifier for emulsion polymerization of the present invention are not particularly limited. For example, a catalyst is present in which higher alcohol and allyl glycidyl ether, or alkyl glycidyl ether derived from higher alcohol and epichlorohydrin and allyl alcohol are present. After the bottom reaction, a polyglucoside moiety is introduced. And various anionic hydrophilic groups can be introduce | transduced into the polyglucoside part of the obtained reaction composition, and the emulsifier for emulsion polymerization of this invention can be obtained. Moreover, you may refine | purify by a well-known method as needed.

  Polyglucoside can be introduced into the hydrophobic group having a reactive group by applying a known production method of alkylpolyglucoside. Examples of the method for producing alkyl polyglucoside include, for example, JP-A No. 2001-278891, JP-A No. 11-209391, JP-A No. 8-269103, JP-A No. 64-47796, and JP-A No. 62-292789. It is disclosed in publications and the like. As a generally used method for producing an alkylpolyglucoside, a method of obtaining an alkylpolyglucoside by reacting a sugar and a fatty alcohol in the presence of an acid catalyst, or a reaction of sugar and butanol in the presence of an acid catalyst to form a butylpolyglucoside, There is a method of obtaining an alkylpolyglucoside in two stages by exchange reaction with a fatty alcohol.

  Examples of the sugar used for the production of the polyglucoside compound include a monosaccharide, a monosaccharide derivative, and an oligosaccharide. Monosaccharides include hexoses such as glucose, mannose, allose, altrose, galactose, talose, growth, idose, fructose, psicose, tagatose, sorbose and the like. Examples of pentoses include ribose, arabinose, xylulose, lyxose and ribulose.

  Monosaccharide derivatives include rhamnose, fucose and the like as deoxy sugars. Examples of uronic acid include glucuronic acid, galacturonic acid, mannuronic acid and the like. Examples of amino sugars include glucosamine and chondrosamine.

  Examples of the oligosaccharide include malto-oligosaccharides, cellooligosaccharides, manno-oligosaccharides, galactooligosaccharides and the like having a degree of polymerization of 2 to 10.

  Further, two or more kinds of the monosaccharides, monosaccharide derivatives or oligosaccharides described above can be blended and used.

  Introduction of an anionic hydrophilic group into the polyglucoside moiety can be carried out using a known method. For example, in order to introduce the anionic hydrophilic group of the general formula (2), it may be sulfated using sulfamic acid, chlorosulfonic acid, anhydrous sulfuric acid, or sulfuric acid. The anionic hydrophilic group of the general formula (3) can be introduced by phosphoric esterification using diphosphorus pentoxide or polyphosphoric acid. The anionic hydrophilic group of the general formula (4) can be introduced by ether carboxylation using a monohalogen lower carboxylic acid (monochloroacetic acid, monobromopropionic acid, etc.). The anionic hydrophilic group of the general formula (5) can be introduced by ester carboxylation using a dibasic acid (preferably an anhydride). The anionic hydrophilic group of the general formula (6) can be introduced by ester carboxylation with maleic anhydride and then sulfonation with sodium sulfite.

[Emulsion polymerization monomer]
Examples of monomers that can be applied to emulsion polymerization using the emulsifier for emulsion polymerization of the present invention include various monomers such as acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Acrylic monomers such as methyl, acrylonitrile, acrylamide and acrylic acid hydroxy ester, for example, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, butadiene In addition to conjugated diolefin monomers such as isoprene and chloroprene, there are ethylene, maleic anhydride, methyl maleate and the like. The emulsifier of the present invention can be used for emulsion polymerization or suspension polymerization of one or more of the above monomers.

[Polymerization conditions]
Emulsion polymerization using the emulsifier for emulsion polymerization of the present invention can be carried out by conventionally known methods and conditions. The polymerization initiator used for the reaction may be a conventionally known one, and for example, hydrogen peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, and the like can be used. As the polymerization accelerator, sodium bisulfite, ferrous ammonium sulfate, and the like can be used. Further, as a chain transfer agent, mercaptans such as α-methylstyrene dimer, n-butyl mercaptan, t-dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide may be used.

  The use amount of the emulsifier for emulsion polymerization of the present invention is usually suitably 0.1 to 20.0% by weight as a ratio to the total monomers. More preferably, it is used in the range of 0.2 to 10.0% by weight.

  The emulsifier for emulsion polymerization of the present invention alone can satisfactorily complete emulsion polymerization, but it further comprises at least one surfactant selected from the group of other anionic surfactants and nonionic surfactants. As a result, the polymerization stability during emulsion polymerization can be improved, and the processing characteristics in the subsequent steps can be improved. The anionic surfactant and the nonionic surfactant are not particularly limited. For example, examples of the anionic surfactant include fatty acid soap, rosin acid soap, alkylsulfonate, alkylarylsulfonate, alkylsulfosuccinate, polysulfone Examples of the nonionic surfactant include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, alkyl polyglucoside, and polyglycerin alkyl. Examples include ether, polyglycerin fatty acid ester, sorbitan fatty acid ester and the like. The amount used is preferably 0.5 to 100 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the emulsifier for emulsion polymerization of the present invention. More preferably, it is 10-30 weight part.

  Moreover, a well-known protective colloid agent can be used together in order to improve the polymerization stability at the time of emulsion polymerization. Examples of protective colloid agents that can be used in combination include fully saponified polyvinyl alcohol (PVA), partially saponified PVA, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.

  As another method of using the emulsifier for emulsion polymerization of the present invention, it can be added after completion of polymerization in order to improve the stability of the polymer emulsion.

[Action, other]
The emulsifier for emulsion polymerization of the present invention has an allyl group or methallyl group which is a copolymerizable double bond in the hydrophobic group portion of the molecule, and is copolymerizable with a polymerizable monomer, particularly a vinyl monomer. Excellent and easy to incorporate into polymer composition. Therefore, as a copolymerizable reactive emulsifier, the amount of the emulsifier present in the polymer film obtained from the polymer emulsion is remarkably reduced, and the water resistance, adhesiveness, heat resistance and weather resistance of the film are greatly improved. Exhibits excellent effects. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved.

  Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.

  Hereinafter, although an embodiment and an effect of the present invention are described according to an example and a comparative example, illustration is only for explanation and is not intended to limit or limit the inventive idea. In the text, “part” is based on mass unless otherwise specified.

[Production Example 1]
A reactor equipped with a stirrer, a nitrogen introduction tube, a distillation apparatus, and a thermometer was charged with 200 parts of isotridecyl alcohol and sodium hydroxide as a catalyst, and dehydrated under reduced pressure at 105 ° C. for 30 minutes. After cooling to 90 ° C., 114 parts of allyl glycidyl ether was added dropwise and aged at 90 ° C. for 5 hours to obtain Intermediate A.

  30 parts of butyl glucoside and p-toluenesulfonic acid were added as a catalyst to Intermediate A, and the temperature was raised to 130 ° C. and reacted for 3 hours. At that time, the pressure in the reactor was reduced to 10 mbar to distill off butanol as a by-product. Next, after neutralizing with sodium hydroxide, excess intermediate A was removed to obtain a polyglucoside compound of intermediate A.

  To 100 parts of the polyglucoside compound of Intermediate A, 18 parts of sulfamic acid was charged and reacted at 120 ° C. for 3 hours to carry out sulfate esterification. Unreacted sulfamic acid was removed to obtain the product A of the present invention.

[Production Example 2]
A reactor equipped with a stirrer, a nitrogen introducing tube, a distillation apparatus, and a thermometer was charged with 200 parts of isotridecyl alcohol and a boron trifluoride ether complex as a catalyst, and dehydrated under reduced pressure at 105 ° C. for 30 minutes. After cooling to 90 ° C., 128 parts of methallyl glycidyl ether was added dropwise and aged at 90 ° C. for 5 hours to obtain Intermediate B.

  To intermediate B, 60 parts of butyl glucoside and p-toluenesulfonic acid were added as catalysts, heated to 130 ° C. and reacted for 3 hours. At that time, the pressure in the reactor was reduced to 10 mbar to distill off butanol as a by-product. Next, after neutralizing with sodium hydroxide, excess intermediate B was removed to obtain a polyglucoside compound of intermediate B.

  13 parts of sulfamic acid was added to 100 parts of the polyglucoside compound of intermediate B and reacted at 120 ° C. for 3 hours to effect sulfate esterification. After removing the unreacted sulfamic acid, the product B of the present invention was obtained by neutralization with monoethanolamine.

[Production Example 3]
A reactor equipped with a stirrer, a nitrogen introduction tube, a distillation apparatus, and a thermometer was charged with 186 parts of lauryl alcohol and sodium hydroxide as a catalyst, and dehydrated under reduced pressure at 105 ° C. for 30 minutes. After cooling to 90 ° C., 114 parts of allyl glycidyl ether was added dropwise and aged at 90 ° C. for 5 hours to obtain Intermediate C.

  The intermediate C was added with 20 parts of glucose and alkylbenzenesulfonic acid as a catalyst and stirred, and then heated to 110 ° C. and reacted for 5 hours. At that time, the pressure in the reactor was reduced to 10 mbar, and water as a by-product was distilled off. Next, after neutralizing with sodium hydroxide, excess intermediate C was removed to obtain a polyglucoside compound of intermediate C.

  20 parts of sulfamic acid was added to 100 parts of the polyglucoside compound of Intermediate C, and reacted at 120 ° C. for 3 hours to carry out sulfate esterification. After removing unreacted sulfamic acid, it was dissolved in isopropyl alcohol, and neutralized equivalent amount of sodium hydroxide was added to form a sodium salt. Finally, vacuum topping was performed to obtain the product C of the present invention.

[Production Example 4]
The process until obtaining the intermediate polyglucoside compound is carried out in accordance with the method of Production Example 1, and after obtaining 192 parts of neodol 23 instead of isotridecyl alcohol to obtain intermediate D, 55 parts of butylglucoside As a result, a polyglucoside compound of Intermediate D was obtained.

  8 parts of anhydrous phosphoric acid was added to 100 parts of the polyglucoside compound of intermediate D, reacted at 80 ° C. for 3 hours, and converted to phosphoric ester to obtain the product D of the present invention.

[Production Example 5]
A reactor equipped with a stirrer, a nitrogen introduction tube, a distillation apparatus, and a thermometer was charged with 87 parts of allyl alcohol and sodium hydroxide as a catalyst. went. Next, the temperature was raised to 120 ° C., and excess allyl alcohol was removed under reduced pressure to obtain Intermediate E.

  To intermediate E, 40 parts of butyl glucoside and p-toluenesulfonic acid were added as catalysts, heated to 130 ° C., and reacted for 3 hours. At that time, the pressure in the reactor was reduced to 10 mbar to distill off butanol as a by-product. Next, after neutralizing with sodium hydroxide, excess intermediate E was removed to obtain a polyglucoside compound of intermediate E.

  After adding 21 parts of maleic anhydride to 100 parts of the polyglucoside compound of Intermediate E and reacting at 80 ° C. for 2 hours, the product was obtained by sulfonation with anhydrous sodium sulfite.

[Production Example 6]
The steps until obtaining an intermediate polyglucoside compound are reacted according to the method of Preparation Example 1 to obtain 172 parts of Exxal11 instead of isotridecyl alcohol to obtain intermediate F, and then 55 parts of glucose. A polyglucoside compound of body F was obtained.

  Into 100 parts of the polyglucoside compound of Intermediate F, 18 parts of sodium monochloroacetate and sodium hydroxide as a catalyst were charged, reacted at 80 ° C. for 3 hours to ether carboxylate, and purified to obtain the product F of the present invention.

[Production Example 7]
According to the method of Production Example 3, the reaction product was reacted under the same conditions except that 158 parts of 2-propyl-1-heptanol, 65 parts of glucose and 16 parts of sulfamic acid were used instead of lauryl alcohol. Got.

[Production Example 8]
The steps up to obtaining the intermediate polyglucoside compound are reacted according to the method of Production Example 2, and styrenated phenol (mono-, di-, tri-isomer mixture) 305 parts instead of isotridecyl alcohol After obtaining H, a polyglucoside compound of Intermediate H was obtained with 75 parts of butyl glucoside.

  6 parts of phosphoric anhydride was added to 100 parts of the polyglucoside compound of intermediate H, reacted at 80 ° C. for 3 hours, and converted to phosphoric ester to obtain the product H of the present invention.

[Production Example 9]
According to the method of Production Example 1, 185 parts of lauryl alcohol instead of isotridecyl alcohol, 128 parts of methallyl glycidyl ether instead of allyl glycidyl ether, and 90 parts of a mixture of maltose and maltotriose instead of butyl glucoside The product I of the present invention was obtained by reacting under the same conditions except that 9 parts of sulfamic acid was used.

  Table 1 shows emulsifiers for emulsion polymerization obtained in the above production examples and used in the following use examples (Examples and Comparative Examples).

<Usage example 1>
A mixed monomer emulsion was prepared by mixing 100 parts of butyl acrylate, 100 parts of styrene, 290 parts of ion-exchanged water and 10 parts of an emulsifier for emulsion polymerization, and dissolved oxygen was removed with nitrogen gas. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 100 parts of the above mixed monomer emulsion, heated to 80 ° C., and 0.5 parts of potassium persulfate was added for prepolymerization. I let you. Next, 400 parts of the remaining mixed monomer emulsion was added dropwise over 3 hours and polymerized over 3 hours from 10 minutes after the start of polymerization. Further, after aging for 2 hours at the polymerization temperature, the mixture was cooled to obtain a polymer emulsion.

  The emulsifiers for emulsion polymerization used are as shown in Table 2.

  The contents of dioxane and formaldehyde of the emulsifier for emulsion polymerization used, and the obtained polymer emulsion were evaluated for polymerization stability, mechanical stability, particle diameter, foaming property, and film glossiness, respectively. The evaluation method is as follows. The results are shown in Table 2.

[Contents of dioxane and formaldehyde]
The dioxane contained in the emulsifier for emulsion polymerization was determined by absorptiometry using GC (gas chromatography) and formaldehyde using the acetylacetone method. The results were evaluated according to the following criteria:
Dioxane amount less than −1 ppm: ○, 1 ppm or more and less than 10 ppm: Δ, 10 ppm or more: ×,
Formaldehyde amount: less than −1 ppm: ○, 1 ppm or more and less than 10 ppm: Δ, 10 ppm or more: ×.

[Polymerization stability]
The polymer emulsion after polymerization was filtered using an 80-mesh filter cloth, and the residue on the filter cloth was washed with water and dried, and the weight was expressed in% relative to the solid content of the emulsion.

[Machine stability]
50 g of the polymer emulsion was stirred for 5 minutes at a load of 10 kg and a rotation speed of 1000 rpm with a Marlon type tester, the resulting aggregate was filtered through an 80 mesh wire mesh, the residue was washed with water and dried, and its weight was determined as the solid content of the emulsion. In%.

[Particle size]
The particle size distribution was measured with a dynamic light scattering particle size distribution measuring apparatus (MICROTRAC UPA 9340 manufactured by Nikkiso) and displayed in units of μm.

[Foaming]
The emulsion was diluted 2-fold with water, put in 30 cc into a 100 ml Nessler tube, inverted 30 times, and then the amount of foam after 5 minutes of standing was measured.

[Glossiness of film]
A 0.5 mm (wet) emulsion film was formed on a glass plate and allowed to stand at room temperature for 24 hours to prepare a film. The glossiness of this film was visually confirmed and evaluated in three stages: ○ (excellent), Δ (possible), and × (impossible).

<Usage example 2>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 135 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C. Dissolved oxygen was removed. Separately, 75 parts of methyl methacrylate, 171 parts of ethyl acrylate, 4 parts of acrylic acid, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.

  The emulsifiers for emulsion polymerization used are as shown in Table 3.

  The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, VOC amount, unreacted emulsifier amount, and water resistance. The evaluation methods for polymerization stability and particle diameter are the same as described above. The amount of VOC, the amount of unreacted emulsifier, and the water resistance evaluation method are as follows. The results are shown in Table 3.

[VOC amount]
The amount of VOC contained in the polymer emulsion was measured by headspace GC. The results were evaluated according to the following criteria:
Less than 10 ppm: ○, 10 ppm or more and less than 50 ppm: Δ, 50 ppm or more: ×.

[Unreacted emulsifier amount]
Methanol was added to the polymer emulsion to coagulate the polymer, and after centrifugation, the supernatant was used to measure the amount of unreacted emulsifier by HPLC-MS (high performance liquid chromatography-mass spectrometry).

[Water resistance test]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, immersed in water, and the time until 4.5 point characters could not be read through the polymer film was measured. The results were evaluated according to the following criteria:
300 hours or more: ○, less than 300 hours 200 hours or more: Δ, less than 200 hours: ×.

<Usage example 3>
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 250 parts of ion-exchanged water, heated to 80 ° C., and dissolved oxygen in water was removed with nitrogen gas. Next, 50 parts of a mixed monomer solution prepared by dissolving 5 parts of an emulsifier for emulsion polymerization in 125 parts of butyl acrylate and 125 parts of 2-ethylhexyl acrylate was charged into the reactor, and then 0.5 part of ammonium persulfate was added to the reactor. Polymerization was performed, and the remaining 205 parts of the mixed monomer solution was added dropwise over 3 hours from 10 minutes after the start of the polymerization. Subsequently, the mixture was further aged for 2 hours at the polymerization temperature, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.

  The emulsifiers for emulsion polymerization used are as shown in Table 4. In addition, the inventive products A to D and the comparative products A, D, E, and F are used as a combined nonionic emulsifier, polyoxyethylene lauryl ether (EO 30 mol adduct), and the inventive products F to I are used as a combined anionic emulsifier. Lauryl sulfate sodium salt was used in an amount of 10% by weight of the emulsifier for emulsion polymerization.

  About the obtained polymer emulsion, polymerization stability, mechanical stability, the amount of unreacted emulsifier, heat-resistant coloring property, and adhesiveness were evaluated, respectively. The evaluation methods for polymerization stability, mechanical stability, and amount of unreacted emulsifier are the same as described above. The evaluation methods for heat resistant colorability and adhesiveness are as follows. The results are shown in Table 4.

[Adhesiveness]
The emulsion is applied to a thickness of 25 μm (dry) on a PET film cut to a width of 5 cm, heat-treated, then attached to a SUS plate, and roller-pressed. The film was peeled off so that the adhesive surface would be 5 cm × 5 cm, and a 200 g weight was suspended from the end of the film to measure the time until peeling.

[Heat resistant coloring]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, heat-treated for 30 minutes in a hot air dryer adjusted to 200 ° C., and the coloring of the polymer film was visually examined. Results were evaluated according to the following criteria:
No coloring is observed: ○,
It is colored pale yellow: △,
Colored dark brown: x.

<Usage example 4>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 70 ° C. Dissolved oxygen was removed. Separately, 250 parts of vinyl acetate, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.

  The emulsifiers for emulsion polymerization used are as shown in Table 5.

  The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, and adhesiveness. The polymerization stability and particle size evaluation method is the same as the above evaluation method. The evaluation method of adhesiveness is as follows. The results are shown in Table 5.

[Adhesiveness]
The emulsion is coated on a plywood cut to a width of 5 cm to a thickness of 25 μm (dry), heat-treated, and then a 5 cm wide cotton cloth is affixed and roller-pressed. The cloth was peeled off so that the adhesive surface was 5 cm × 5 cm, and a time until the piece was peeled off by hanging a weight of 1 kg on the edge of the peeled cloth was measured.

The polymer emulsion obtained by adding the emulsifier for emulsion polymerization of the present invention can be applied to, for example, wood, metal, paper, cloth, and other concrete as an adhesive, a coating agent, an impregnation reinforcing agent, and the like. Moreover, the polymer taken out from the emulsion or latex can be used for resins, rubbers, polymer modifiers, and the like.

Claims (3)

An emulsifier for emulsion polymerization comprising a compound represented by the following general formula (1).

In the formula, R ¹ represents a hydrocarbon group, and R ² represents a hydrogen atom or a methyl group. G represents a monosaccharide residue, and (G) at least one of —OH groups contained in _n is substituted with an anionic hydrophilic group. n is a number from 1 to 30. Adding the emulsifier for emulsion polymerization according to claim 1 together with a monomer in an aqueous medium to polymerize the monomer, or adding to the aqueous medium after monomer polymerization;
And the usage-amount of the said emulsifier for emulsion polymerization is 0.1 to 20 weight% with respect to the said monomer amount. The manufacturing method of the polymer emulsion characterized by the above-mentioned. A polymer emulsion obtained by the method for producing a polymer emulsion according to claim 2.