KR101855444B1 - Manufacturing method of saccharides-based polymer particle emulsion - Google Patents

Abstract

One embodiment of the present invention provides a method for manufacturing a saccharide-based polymer particle emulsion comprising the steps of: (a) mixing saccharide mixture, emulsifiers, and water, then adding a core forming monomer and a primary polymerization initiator to the mixture to polymerize the same, and obtaining an aqueous emulsion containing a core; and (b) adding a shell forming monomer and a secondary polymerization initiator to the aqueous emulsion containing the core and polymerizing the same to form a shell on the core. A gelling does not occur during a manufacturing process if a saccharide-based particle emulsion is manufactured by the method of the present invention. Moreover, the saccharide-based particle emulsion manufactured by the method of the present invention does not discolor even if the same is stored for a long time under an alkaline condition.

Description

Technical Field [0001] The present invention relates to a saccharide-based polymer particle emulsion,

The present invention relates to a method for producing a sugar-based polymer particle emulsion, and more particularly, to a method for producing a sugar-based polymer particle emulsion in which discoloration hardly occurs even under alkaline conditions.

The starch-based polymer particle emulsion or the sugar-based polymer particle emulsion is used for various purposes such as a binder component of a paper coating agent, a binder component of a paint, a binder component of an ink, and the like.

For example, Korean Patent Registration No. 10-1473916 discloses a starch-based polymer particle emulsion used as a binder component of a paint. Korean Patent Registration No. 10-1519515 discloses a starch-based polymer particle emulsion used as a binder component of an ink. Korean Patent Registration No. 10-1392326 discloses a starch-based polymer particle emulsion used as a binder component of a paper coating agent. Korean Patent Laid-Open Publication No. 10-2017-0074502 discloses a sugar-based polymer particle emulsion which can be used as a coating material or a coating material.

In the foregoing patents, starch-based polymer particle emulsions or saccharide-based polymer particle emulsions are all prepared through radical polymerization using initiators such as potassium persulfate, sodium bisulfite. The starch-based polymer emulsion or the saccharide-based polymer particle emulsion prepared in the above-mentioned patents tends to be discolored after the lapse of a certain period of time under an alkaline condition of pH 7 to 8 without maintaining the original color, , The binder component of the paint, the binder component of the ink, etc., there is a limit to the mixing conditions and there may be a problem in quality reliability.

The present invention has been made under the background of the prior art, and an object of the present invention is to provide a method for producing a sugar-based polymer particle emulsion capable of preventing discoloration in an alkali condition.

The inventors of the present invention have found that when a redox initiator consisting of a combination of specific components is used in the polymerization reaction step to form the core in the production of the sugar-based polymer particle emulsion, The discoloration can be minimized, and the present invention has been completed.

In order to solve the above-mentioned object, an embodiment of the present invention provides a method for producing a water-based emulsion comprising: (a) mixing a saccharide mixture, an anionic emulsifier and water, adding a core-forming monomer and a primary polymerization initiator thereto, ; And (b) adding a shell-forming monomer and a second polymerization initiator to the aqueous emulsion comprising the core and polymerizing to form a shell on the core. In addition, a preferred embodiment of the present invention is a method for producing a water-in-oil emulsion comprising (a ') mixing a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water and then adding a core-forming monomer and a primary polymerization initiator, ; And (b ') adding a shell-forming monomer and a secondary polymerization initiator to the aqueous emulsion comprising the core and polymerizing to form a shell on the core.

In the process for preparing a sugar-based polymer particle emulsion according to the present invention, the core-forming monomer comprises a hard monomer, a soft monomer and a carboxylic acid monomer having an ethylenically unsaturated bond, wherein the shell-forming monomer is a soft monomer, Carboxylic acid monomers having unsaturated bonds and reactive emulsifiers. Wherein the hard monomer has an ethylenically unsaturated bond and the homopolymer has a glass transition temperature of 30 ° C to 250 ° C, the soft monomer has an ethylenically unsaturated bond and the homopolymer has a glass transition temperature of 10 ° C to -80 ° C Lt; 0 > C. The reactive emulsifier may be selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and at least one functional group selected from a vinylene group.

In the method for producing a sugar-based polymer particle emulsion according to the present invention, the primary polymerization initiator is a redox-based polymerization initiator including sodium bisulfate and hydrogen peroxide. The weight ratio of sodium bisulfate to hydrogen peroxide constituting the first polymerization initiator is 3: 7 to 7: 3. The addition amount of the first polymerization initiator is 18 to 30 parts by weight per 100 parts by weight of the saccharide mixture.

When the saccharide-based polymer particle emulsion is prepared by the process according to the present invention, gelation does not occur during the production process. In addition, the saccharide-based polymer particle emulsion prepared by the method according to the present invention hardly causes discoloration even when stored in an alkaline condition for a long time. Therefore, when a sugar-based polymer particle emulsion prepared by the method according to the present invention is used as an adhesive component, a binder component of a paper coating agent, a binder component of a paint, a binder component of an ink, etc., .

1 is a photograph showing the state after adjusting the pH of the saccharide-based polymer particle emulsion prepared in Preparation Example 1 of the present invention to the pH of the alkaline condition (7.5 ± 2) and storing it at 60 ° C. for 6 days.
FIG. 2 is a photograph showing the state after adjusting the pH of the saccharide-based polymer particle emulsion prepared in Preparation Example 7 of the present invention to the pH of the alkaline condition (7.5 ± 2) and storing it at 60 ° C. for 6 days.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing a sugar-based polymer particle emulsion in which discoloration hardly occurs even under alkaline conditions.

A method for producing a sugar-based polymer particle emulsion according to the present invention comprises the steps of (a) mixing a saccharide mixture, an anionic emulsifier and water, adding a core-forming monomer and a primary polymerization initiator thereto, ; And (b) adding a shell-forming monomer and a secondary polymerization initiator to the aqueous emulsion containing the core and polymerizing to form a shell on the core. In addition, the method for producing a sugar-based polymer particle emulsion according to the present invention is preferably a method in which (a ') a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water are mixed and then a core- To obtain an aqueous emulsion containing the core; And (b ') adding a shell-forming monomer and a secondary polymerization initiator to an aqueous emulsion containing the core and polymerizing to form a shell on the core.

The saccharide-based polymer particle emulsion prepared by the method of the present invention is an aqueous emulsion containing water as a dispersion medium and a dispersion medium-based polymer particles and a dispersion medium. In addition, the saccharide mixture-based polymer particles have a core-shell structure comprising a shell formed on the core by polymerization of a core and shell monomer mixture formed by polymerization of a saccharide mixture and a core monomer mixture. Hereinafter, the saccharide mixture-based polymer particle is divided into a core and a shell.

core

In the saccharide mixture-based polymer particles of the present invention, the core consists of a copolymer formed by polymerization of a saccharide mixture and a core-forming monomer.

In the present invention, the saccharide mixture acts as a seed for forming a core. It is preferable that the starch hydrolyzate has a weight average molecular weight (Mw) of 300 to 2,000, As the enzyme hydrolyzate of starch, it is more preferable to have a weight average molecular weight (Mw) of 300 to 1,000, and more preferably to have a weight average molecular weight (Mw) of 350 to 800 as an enzyme hydrolyzate of starch. In the present invention, the saccharide mixture preferably comprises 1 to 20% by weight of glucose based on the total weight of the saccharide mixture, 10 to 65% by weight of saccharides having a glucose-based degree of polymerization of 2, Based sugar having 5 to 25% by weight of a sugar chain having a polymerization degree of 3 based on glucose, 0.1 to 10% by weight of saccharides having a glucose-based degree of polymerization of 4, glucose having a degree of polymerization of 5 based on 5 to 15% ) Based sugar (0.5 to 15% by weight), a glucose (glucose-based) polymerization degree of 7 to 0.5 to 15% by weight, a glucose-based polymer having a degree of polymerization of 8 to 0.5 to 15% Glucose-based polymer having a degree of polymerization of 9 is contained in an amount of 0.1 to 10% by weight, and the balance is a sugar-based polymer having a degree of polymerization of 10 or more based on the balance. More preferably, the saccharide comprises 1 to 10% by weight of glucose, 25 to 65% by weight of saccharides having a degree of polymerization of 2 based on glucose, (10 to 25% by weight of saccharides having a degree of polymerization of 3, 0.1 to 5% by weight of saccharides having a degree of polymerization based on glucose of 4, 0.5 to 10% by weight of saccharides having a degree of polymerization of 5 based on glucose, 0.5 to 10% by weight of a saccharide having a degree of polymerization of 6, 0.5 to 10% by weight of saccharides having a glucose-based degree of polymerization of 7, 0.5 to 10% by weight of saccharides having a degree of polymerization of 8 based on glucose, And a sugar residue having a degree of polymerization of 10 or more based on glucose as the balance and most preferably 2 to 8% by weight of glucose and a glucose-based polymerization degree of 0.1 to 5% (Glucose) -based polymer having a degree of polymerization of 3 is 12 to 24% by weight, a glucose-based polymer having a degree of polymerization of 4 is 0.2 to 4% by weight, a glucose-based 0.5 to 5% by weight of saccharides having a degree of polymerization of 5, 1 to 6% by weight of saccharides having a degree of polymerization of 6 based on glucose, 1 to 6% by weight of saccharides having a glucose-based degree of polymerization of 7, 1 to 6% by weight of saccharides having a glucose-based degree of polymerization of 8, 0.2 to 4% by weight of saccharides having a glucose- And a glucose having a degree of polymerization based on glucose of 10 or more as the balance.

In the present invention, the core-forming monomer includes a hard monomer, a soft monomer, and a carboxylic acid monomer having an ethylenic unsaturated bond. The term " hard monomer " refers to a monomer containing an ethylenic unsaturated bond such as a vinyl group, an allyl group or an acryl group, and the homopolymer is not tacky at room temperature. In the present invention, the light-weight monomer has such a characteristic, and at the same time, the homopolymer is a monomer having a glass transition temperature of 30 ° C to 250 ° C, preferably 40 ° C to 200 ° C. In the present invention, the type of the hard monomer constituting the core-forming monomer is not particularly limited as long as it satisfies the above-mentioned characteristics, and preferably styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate Acrylonitrile, methacrylonitrile, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyltoluene, vinyl acetate and vinyl chloride. More preferably at least one kind selected from glycidyl methacrylate, styrene or methyl methacrylate, and most preferably at least one selected from glycidyl methacrylate or methyl methacrylate . Also, the soft monomer refers to a monomer containing an ethylenic unsaturated bond such as a vinyl group, an allyl group or an acryl group, and the homopolymer is tacky at room temperature. In the present invention, the soft monomer has such a characteristic, and at the same time, the homopolymer is a monomer having a glass transition temperature of from 10 캜 to -80 캜, preferably from 5 캜 to -60 캜. The type of the soft monomer constituting the core-forming monomer in the present invention is not particularly limited as long as it satisfies the above-mentioned characteristics, and is preferably selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, Acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, butyl acrylate or ethylhexyl acrylate, And more preferably at least one kind selected from the group consisting of: In the present invention, the carboxylic acid monomer having an ethylenically unsaturated bond constituting the core-forming monomer may have an ethylenic unsaturated bond such as a vinyl group, an allyl group or an acrylic group for polymerization with other monomers, And is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and more preferably at least one selected from acrylic acid and methacrylic acid.

Further, in the present invention, the core-forming monomer may preferably further comprise a reactive emulsifier. In the present invention, the reactive emulsifier acts as an emulsifier for dispersing the other components evenly in the aqueous phase in the step of preparing the pre-emulsion of the core-forming monomer described later, and forms a core by polymerization with other monomers in the core formation step. The reactive emulsifier may be selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and a propenyl group for polymerization with other monomers. , A vinylidene group and a vinylene group, the type of the unsaturated bond functional group is not particularly limited. The reactive emulsifier is generally classified into an anionic emulsifier and a nonionic emulsifier. The reactive emulsifier used in the present invention is preferably an anionic emulsifier. Examples of the anionic reactive emulsifier usable in the present invention include bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate (bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate; Commercial products include "ANTOX MS-60" from Nippon Nyukazai Co., Ltd., propenyl-alkylsulfosuccinate, (meth) acrylic acid (meth) acrylic acid polyoxyethylene sulfonate; Commercial products include "ELEMINOLRS-30" from Sanyo Chemical Industries, Ltd.], allyloxymethyl alkyloxy polyoxyethylene sulfonate (commercially available from DAI-ICHI KOGYO SEIYAKU CO., LTD. ADEKA REASOAP SR-10 ", "ADEKA REASOAP SR-20 ", Asahi Denka Co., Ltd., which is a commercial product, , "ADEKA REASOAP SR-30"), and polyoxyalkylene alkenyl ether ammonium sulfate (commercially available product "LATEMUL PD-104" available from Kao Corp.). Other anionic emulsifiers that can be used in the present invention include "LATEMUL S-120", "LATEMUL S-120A", "LATEMUL S-180" and "LATEMUL S-180A" , "ELEMINOL JS-2 ", and the like; And alkenyl succinate-based anionic emulsifiers such as "LATEMUL ASK " from Kao Corp., and the like. Examples of other anionic emulsifiers which can be used in the present invention include 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium salt [ (Meth) acrylic acid sulfoalkyl ester salt] such as 3-sulfopropyl (meth) acrylate ammonium salt; Sulfopropylmaleic acid alkyl ester sodium salt, sulfopropylmaleic acid polyoxyethylene alkyl ester ammonium salt, sulfoethylfumaric acid alkyl ester ammonium salt, sulfoethylfumaric acid alkyl ester sodium salt, alkyl ester ammonium salts); alkylsulfosuccinates; Maleic acid dipolyethylene glycol alkylphenol ether sulfate, phthalic acid dihydroxyethyl ester (meth) acrylate sulfate; phthalic acid dihydroxyethyl ester (meth) acrylate sulfate; 1-allyloxy-3-alkyl phenoxy-2-polyoxyethylene sulfate; Commercial products include "ADEKA REASOAP SE-10N" and "ADEKA REASOAP SE-20N" from Asahi Denka Co., Ltd.); And polyoxyethylene alkylalkenylphenol sulfate (commercially available as "AQUALON" from DAI-ICHI KOGYO SEIYAKU CO., LTD.). Examples of the nonionic reactive emulsifier that can be used in the present invention include allyloxymethyl alkoxy ethyl hydroxy polyoxyethylene, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl ether (ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER, etc.) of Asahi Denka Kogyo KK are commercially available, and include polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenyl ether. ADEKA REASOAP NE-30 "," ADEKA REASOAP NE-40 "," ADEKA REASOAP NE-10 "," ADEKA REASOAP NE-20 " "; "LATEMULPD-420 "," LATEMULPD-430 " And "AQUALON RS-20" of DAI-ICHI KOGYO SEIYAKU CO., LTD.).

Further, in the present invention, the core-forming monomer may preferably further include a chain transfer agent. The chain transfer agent is not limited in its kind by controlling the molecular weight of the copolymer and is preferably selected from n-dodecyl mercaptan, t-dodecyl mercaptan, 1,5-pentanediol, 1,6- Dithiol, 2-ethylhexyl-3-mercaptopropionate, butyl 3-mercaptopropionate, dodecyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, ethyl 3-mercaptopropionate (3-mercaptopropionate), 2-ethylhexyl mercaptoacetate, ethyl 2-mercaptoacetate, 2-hydroxymethyl-2- Methyl-1,3-propanediol, and pentaerythritol tetrakis (2-mercaptoacetate), and may be at least one selected from the group consisting of n-dodecyl mercaptan or t-dodecyl mercaptan More preferably, it is more than the species.

The content of the hard monomer in the core-forming monomer is preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight. The content of the soft monomer in the core-forming monomer is preferably 50 to 99% by weight, more preferably 55 to 97% by weight. The content of the carboxylic acid monomer having an ethylenically unsaturated bond in the core-forming monomer is preferably 1 to 10% by weight, more preferably 2 to 8% by weight. The content of the reactive emulsifier in the core-forming monomer is preferably 0.1 to 4% by weight, more preferably 0.2 to 2% by weight. The content of the chain transfer agent in the core-forming monomer is preferably 0.1 to 5% by weight, more preferably 0.1 to 4% by weight. The weight ratio of the hard monomer to the soft monomer constituting the core-forming monomer is preferably 1: 1 to 1: 500, more preferably 1: 2 to 1: 400. The weight ratio of the saccharide mixture to the core-forming monomer in the core is preferably 1: 0.1 to 1: 1, more preferably 1: 0.1 to 1: 0.9, most preferably 1: 0.2 to 1: desirable.

Shell

In the saccharide mixture-based polymer particles of the present invention, the shell consists of a copolymer formed on the core by polymerization of a shell-forming monomer.

The shell-forming monomers include a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenic unsaturated bond, and a reactive emulsifier. In the present invention, the hard monomer constituting the shell-forming monomer includes the content of the hard monomer constituting the core-forming monomer, preferably at least one selected from glycidyl methacrylate, styrene or methyl methacrylate . In the present invention, the soft monomer constituting the shell-forming monomer includes the content of the soft monomer constituting the core-forming monomer, and is preferably at least one selected from hydroxyethyl acrylate, butyl acrylate or ethylhexyl acrylate have. In addition, the carboxylic acid monomer having an ethylenically unsaturated bond constituting the shell-forming monomer in the present invention contains the content of the carboxylic acid monomer having an ethylenically unsaturated bond constituting the core-forming monomer, preferably acrylic acid or methacrylic acid And may be at least one selected from the group consisting of acrylic acid and methacrylic acid. In the present invention, the reactive emulsifier acts as an emulsifier to disperse the other components evenly in the aqueous phase in the step of preparing the pre-emulsion of the shell-forming monomer to be described later, and forms a shell by polymerizing with other monomers in the shell forming step. The reactive emulsifier may be selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and a propenyl group for polymerization with other monomers. , A vinylidene group and a vinylene group, the type of the unsaturated bond functional group is not particularly limited. The reactive emulsifier is generally classified into an anionic emulsifier and a nonionic emulsifier. The reactive emulsifier used in the present invention is preferably an anionic emulsifier. Examples of the anionic reactive emulsifier usable in the present invention include bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate (bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate; Commercial products include "ANTOX MS-60" from Nippon Nyukazai Co., Ltd., propenyl-alkylsulfosuccinate, (meth) acrylic acid (meth) acrylic acid polyoxyethylene sulfonate; Commercial products include "ELEMINOLRS-30" from Sanyo Chemical Industries, Ltd.], allyloxymethyl alkyloxy polyoxyethylene sulfonate (commercially available from DAI-ICHI KOGYO SEIYAKU CO., LTD. ADEKA REASOAP SR-10 ", "ADEKA REASOAP SR-20 ", Asahi Denka Co., Ltd., which is a commercial product, , "ADEKA REASOAP SR-30"), and polyoxyalkylene alkenyl ether ammonium sulfate (commercially available product "LATEMUL PD-104" available from Kao Corp.). Other anionic emulsifiers that can be used in the present invention include "LATEMUL S-120", "LATEMUL S-120A", "LATEMUL S-180" and "LATEMUL S-180A" , "ELEMINOL JS-2 ", and the like; And alkenyl succinate-based anionic emulsifiers such as "LATEMUL ASK " from Kao Corp., and the like. Examples of other anionic emulsifiers which can be used in the present invention include 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium salt [ (Meth) acrylic acid sulfoalkyl ester salt] such as 3-sulfopropyl (meth) acrylate ammonium salt; Sulfopropylmaleic acid alkyl ester sodium salt, sulfopropylmaleic acid polyoxyethylene alkyl ester ammonium salt, sulfoethylfumaric acid alkyl ester ammonium salt, sulfoethylfumaric acid alkyl ester sodium salt, alkyl ester ammonium salts); alkylsulfosuccinates; Maleic acid dipolyethylene glycol alkylphenol ether sulfate, phthalic acid dihydroxyethyl ester (meth) acrylate sulfate; phthalic acid dihydroxyethyl ester (meth) acrylate sulfate; 1-allyloxy-3-alkyl phenoxy-2-polyoxyethylene sulfate; Commercial products include "ADEKA REASOAP SE-10N" and "ADEKA REASOAP SE-20N" from Asahi Denka Co., Ltd.); And polyoxyethylene alkylalkenylphenol sulfate (commercially available as "AQUALON" from DAI-ICHI KOGYO SEIYAKU CO., LTD.). Examples of the nonionic reactive emulsifier that can be used in the present invention include allyloxymethyl alkoxy ethyl hydroxy polyoxyethylene, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl ether (ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER, etc.) of Asahi Denka Kogyo KK are commercially available, and include polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenyl ether. ADEKA REASOAP NE-30 "," ADEKA REASOAP NE-40 "," ADEKA REASOAP NE-10 "," ADEKA REASOAP NE-20 " "; "LATEMULPD-420 "," LATEMULPD-430 " And "AQUALON RS-20" of DAI-ICHI KOGYO SEIYAKU CO., LTD.).

Further, in the present invention, the shell-forming monomer may preferably further include a chain transfer agent. The chain transfer agent is not limited in its kind by controlling the molecular weight of the copolymer and is preferably selected from n-dodecyl mercaptan, t-dodecyl mercaptan, 1,5-pentanediol, 1,6- Dithiol, 2-ethylhexyl-3-mercaptopropionate, butyl 3-mercaptopropionate, dodecyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, ethyl 3-mercaptopropionate (3-mercaptopropionate), 2-ethylhexyl mercaptoacetate, ethyl 2-mercaptoacetate, 2-hydroxymethyl-2- Methyl-1,3-propanediol, and pentaerythritol tetrakis (2-mercaptoacetate), and more preferably at least one selected from the group consisting of n-dodecyl mercaptan or t-dodecyl mercaptan And the like.

The content of the hard monomer in the shell-forming monomer is preferably 0.1 to 65% by weight, more preferably 0.2 to 55% by weight. The content of the soft monomer in the shell-forming monomer is preferably 15 to 99% by weight, more preferably 20 to 97% by weight. The content of the carboxylic acid monomer having an ethylenically unsaturated bond in the shell-forming monomer is preferably 1 to 30% by weight, more preferably 2 to 25% by weight. The content of the reactive emulsifier in the shell-forming monomer is preferably 0.1 to 4% by weight, more preferably 0.2 to 1% by weight. In addition, the content of the chain transfer agent in the shell-forming monomer is preferably 0.1 to 4% by weight, more preferably 0.1 to 2% by weight. The weight ratio of the hard monomer to the soft monomer constituting the shell-forming monomer is preferably 1: 0.2 to 1: 500, more preferably 1: 0.3 to 1: 400.

Content Relationship of Core to Shell in Sugar Mixture-Based Polymer Particles

The weight ratio of core forming monomer to shell forming monomer used to form the saccharide mixture based polymer particles of the present invention is preferably from 1: 2 to 1:15, more preferably from 1: 2 to 1:12, : 3 to 1:10. In addition, the weight ratio of core to shell within the saccharide mixture based polymer particles of the present invention is preferably from 1: 1 to 1: 5, more preferably from 1: 1 to 1: 4.

Description of the ingredients contained in the sugar-based polymer particle emulsion

The saccharide mixture-based polymer particles, which are the main constituents of the saccharide-based polymer particle emulsion according to an example of the present invention, include all of the above-mentioned contents. The content of the saccharide mixture-based polymer particles in the emulsion according to the present invention is not particularly limited, but is preferably 30 to 65% by weight, more preferably 45 to 60% by weight based on the total weight of the emulsion.

The saccharide-based polymer particle emulsion according to one embodiment of the present invention comprises an emulsifier. The emulsifier may be added at the time of the polymerization reaction for producing the saccharide mixture-based polymer particles of the core-shell structure or may be added at the time of emulsifying the saccharide mixture-based polymer particles of the core-shell structure into the dispersion medium. The emulsifier can improve the dispersibility of the core-forming monomer, the shell-forming monomer or the mixture of the saccharide-based polymer particles, minimize the occurrence of aggregates during the production of the saccharide mixture-based polymer particles, and improve the phase stability of the emulsion . Such an emulsifier is not limited in its kind, and examples thereof include anionic emulsifiers such as sulfosuccinates, alkylbenzenesulfonates, and alkyldiphenyloxide disulfonates; Nonionic emulsifiers such as nonionic emulsifiers or alcohol alkoxylates containing ethylene oxide or propylene oxide units; And a reactive emulsifier containing an unsaturated bonding functional group capable of polymerization, and these may be used alone or in combination. In the present invention, the anionic emulsifier is preferably added in the step of forming the core of the saccharide mixture-based polymer particles. The type of the anionic emulsifier is not particularly limited and includes, for example, sodium bistridecyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate For example, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, monoester form Sulfosuccinates such as Mono-ester Sulfosuccinates and the like; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate (CAS registration number: 69227-09-4) (Alkylbenzene sulfonate); Sodium decyl diphenyl ether disulfonate (CAS registration no. 65143-89-7), sodium n-hexadecyl diphenyl disulfonate (CAS registration no. 65143-89-7), sodium dodecyl diphenyl ether disulfonate 7), sodium dodecyl diphenyl ether disulfonate (CAS registration no. 119345-04-9), and the like. The alkyldiphenyl oxide disulfonate may be selected from the group consisting of sodium dodecyl ether, The amount of the anionic emulsifier is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight per 100 parts by weight of the core-forming monomer, but is not limited thereto. In the present invention, the nonionic emulsifier may be added at the stage of forming the core or shell of the saccharide-based polymer particle, and may be added at the stage of producing the preemulsion of the core-forming monomer described later or at the stage of producing the preemulsion of the shell- It serves to disperse the components evenly on the water system. The nonionic emulsifier is not limited in its kind and includes, for example, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene stearyl amines, polyethylene sorbitanates, alkyl polyoxyethylene-propylene copolymers, alcohol alkoxylates , And among these, alcohol alkoxylates are preferable. Specific examples of the alcohol alkoxylates include ethoxylated propoxylated 2-ethyl-1-haxanol (CAS registration number: 64366-70-7), ethoxylated linear aliphatic alcohols Alcohols, C12-14, ethoxylated; CAS registration number: 68439-50-9). The amount of the nonionic emulsifier is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight, per 100 parts by weight of the core-forming monomer, but is not limited thereto. In addition, the amount of the nonionic emulsifier is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight, per 100 parts by weight of the shell-forming monomer in the shell forming step, but is not limited thereto. In the present invention, most of the reactive emulsifier forms a shell by polymerizing with other monomers in the step of forming the core or the step of forming the shell, and only the unreacted portion is present in a form dispersed in the emulsion. The description of the reactive emulsifier is the same as that described in the core-forming monomer or the shell-forming monomer. In addition, the saccharide-based polymer particle emulsion according to the present invention may further comprise a polymerization initiator added during the production of the saccharide mixture-based polymer particle. The technical characteristics of the polymerization initiator are described later.

The process for preparing a sugar-based polymer particle emulsion according to the present invention consists largely of obtaining an aqueous emulsion comprising a core and forming a shell on the core.

Water containing core Emulsion  Step of obtaining

In the method for producing a sugar-based polymer particle emulsion according to the present invention, the step of obtaining an aqueous emulsion containing a core comprises mixing a saccharide mixture, an anionic emulsifier and water, adding a core-forming monomer and a primary polymerization initiator thereto, . The step of obtaining an aqueous emulsion containing the core may be performed by mixing a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water, adding a core-forming monomer and a first polymerization initiator, and performing a polymerization reaction have. In addition, the step of obtaining the aqueous emulsion containing the core may further include a step of aging the core particles formed by the polymerization reaction. At this time, the core-forming monomer is preferably added in the form of a pre-emulsion comprising a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenic unsaturated bond, a chain transfer agent, a reactive emulsifier, a nonionic emulsifier and water. The pre-emulsion of the core-forming monomer can be formed by dissolving an emulsifier in water and then adding a core-forming monomer thereto. Generally, emulsion polymerization using a pre-emulsion is known to have an advantage of minimizing the amount of emulsifier used. In the present invention, when the core-forming monomer is added in the form of pre-emulsion, not only the amount of emulsifier used is minimized but also the occurrence of aggregates is minimized, Can be improved. An aqueous emulsion comprising core particles consisting of a saccharide mixture-based copolymer can be obtained by forming the core. For the saccharide mixtures, anionic emulsifiers, nonionic emulsifiers and core-forming monomers used in the step of obtaining the aqueous emulsion containing the core, refer to the above. The primary polymerization initiator used in the step of obtaining the water-based emulsion containing the core includes sodium bisulfate and hydrogen peroxide as redox-based polymerization initiators. The weight ratio of sodium bisulfate to hydrogen peroxide constituting the first polymerization initiator is preferably 3: 7 to 7: 3, more preferably 4: 6 to 6: 4 in view of a smooth polymerization reaction. The addition amount of the first polymerization initiator is preferably 18 to 30 parts by weight per 100 parts by weight of the saccharide mixture in view of preventing gelation during the polymerization reaction and preventing color change in the alkali condition of the final emulsion More preferably 19 to 25 parts by weight per 100 parts by weight of the saccharide mixture. The primary polymerization initiator may be added before the addition of the core monomer or simultaneously with the monomer. The polymerization reaction temperature, the polymerization reaction pressure and the polymerization reaction time in the step of forming the core are not particularly limited, and may be, for example, from 60 to 100 ° C, preferably from 70 to 90 ° C, from 0.01 to 10 bar, At a pressure of ~ 5 bar for 20 to 120 minutes, preferably 30 to 90 minutes. The reaction product obtained by the polymerization reaction is aged for minimizing unreacted monomers and for progressing a sufficient polymerization reaction. The aging temperature is kept the same as the polymerization reaction temperature, and the aging time is not limited to a great extent. By aging the reaction product, core particles composed of a saccharide mixture-based copolymer and an emulsion containing the same can be obtained.

On the core Shell  Forming step

In the method for producing a sugar-based polymer particle emulsion according to the present invention, the step of forming a shell on the core comprises adding a shell-forming monomer and a secondary polymerization initiator to an aqueous emulsion containing the core and performing a polymerization reaction. The step of forming the shell on the core may include mixing a nonionic emulsifier with an aqueous emulsion containing the core, adding a shell forming monomer and a secondary polymerization initiator thereto, and performing a polymerization reaction. In addition, the step of forming the shell on the core may further include a step of aging the saccharide-based polymer particles formed by the polymerization reaction. In this case, the shell-forming monomer is preferably added in the form of a pre-emulsion comprising a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, a chain transfer agent, a reactive emulsifier, a nonionic emulsifier and water. The pre-emulsion of the shell-forming monomer can be formed by dissolving the emulsifier in water and then adding a shell-forming monomer thereto. Generally, emulsion polymerization using a pre-emulsion is known to have an advantage of minimizing the amount of emulsifier used. In the present invention, when the shell-forming monomer is added in the form of pre-emulsion, not only the amount of emulsifier used is minimized but also the occurrence of aggregates is minimized, Can be improved. For the matters concerning the shell-forming monomer used in the step of forming the shell, refer to the above description. The secondary polymerization initiator may be a thermal decomposition initiator or oxidation-reduction initiator capable of radical polymerization, and examples thereof include sodium persulfate, potassium persulfate, t-butyl hydroperoxide, 2,2-azobisbutyronitrile , 2,2'-azobis-2-methylbutyronitrile, cumene hydroperoxide, and the like, and water-soluble initiators such as sodium persulfate, potassium persulfate, and t-butyl hydroperoxide can be used have. On the other hand, in the step of forming the shell, the secondary polymerization initiator may be added before the addition of the monomer or simultaneously with the monomer, and the amount thereof may be 0.1 to 4 parts by weight, preferably 0.2 to 2 parts by weight per 100 parts by weight of the shell- Lt; / RTI > The polymerization reaction temperature, the polymerization reaction pressure and the polymerization reaction time in the step of forming the shell are not particularly limited and may be, for example, from 60 to 100 ° C, preferably from 70 to 90 ° C, from 0.01 to 10 bar, At a pressure of ~ 5 bar for 60 to 240 minutes, preferably 100 to 200 minutes. The reaction product obtained by the polymerization reaction is aged for minimizing unreacted monomers and for progressing a sufficient polymerization reaction. The aging temperature is kept the same as the polymerization reaction temperature, and the aging time is not limited to a great extent. By aging the reaction product, a polymer-based polymer particle based on a core-shell structure of a saccharide and an aqueous emulsion containing the same can be obtained.

The emulsion comprising the core-shell structure saccharide mixture-based polymer particles obtained by the formation of the core and shell is then cooled to 45-65 캜 and is preferably post-treated to remove unreacted monomers. The post-treatment step for removing unreacted monomers can be carried out by a chemical method, a wet-removing method, or a high-temperature steam method, and is preferably carried out by a chemical method using an oxidizing agent and a reducing agent. The post-treatment step using the oxidizing agent and the reducing agent is constituted by adding an oxidizing agent and a reducing agent to the emulsion containing the polymer-based polymer particles based on the core-shell structure to induce and aging the oxidation reaction and the reduction reaction. At this time, t-butyl hydroperoxide, cumene hydroperoxide and the like can be used as the oxidizing agent. Examples of the reducing agent include sodium hydrosulfite, sodium metabisulfite ) Can be used. The amount of the oxidizing agent and the reducing agent used in the post-treatment step is not particularly limited, and may be, for example, 0.001 to 1 part by weight, preferably 0.002 to 0.8 part by weight per 100 parts by weight of the emulsion. In the post-treatment step, the oxidation reaction and the reduction reaction may be carried out at about 40 to 60 DEG C for 10 to 100 minutes, preferably 20 to 40 minutes. In addition, the emulsion subjected to the oxidation reaction and the reduction reaction is aged to induce a sufficient reaction between the oxidizing agent and the reducing agent and the unreacted monomer. The aging is carried out at about 40 to 60 ° C for 20 to 150 minutes, preferably 30 to 100 minutes .

Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples are intended to clearly illustrate the technical features of the present invention and do not limit the scope of protection of the present invention.

1. Analysis of components of starch-containing saccharide mixture products

The sugar composition of Syncsta L22 product (the solid content of the saccharide mixture: 35% by weight; the weight average molecular weight Mw: about 400; supplier: Kanto Kagaku Co., Ltd.), an enzymatic hydrolysis product of starch, was subjected to high performance liquid chromatography (HPLC 1200 series, Agilent) . The separation column used herein was Aminex HPX 42A (manufacturer: Bio-Rad, USA). The compositional analysis results of the Syncsta L22 product are shown in Table 1 below.

Sugar separation of Syncsta L22 product Sugar content (wt% based on peak area) Glucose 4.0 DP2 55.2 DP3 18.7 DP4 0.8 DP5 1.3 DP6 2.0 DP7 2.3 DP8 2.0 DP9 0.8 DP10 + 12.9

DP2 is a dissacchride having a degree of polymerization of 2 based on hexose (especially glucose), DP3 is a trisaccharide having a degree of polymerization of 3 based on hexose (particularly glucose) DP4 is a tetrasaccharide with a hexose (especially glucose) -based degree of polymerization of 4, DP5 is pentasaccharide with a degree of polymerization of 5 based on hexose (especially glucose), DP6 is a hexasaccharide DP7 is a heptasaccharide with a degree of polymerization of 7 based on hexose (especially glucose), DP8 is a hexoseaccharide with a degree of polymerization of 6 based on hexose (especially glucose) DP9 is a nonasaccharide having a degree of polymerization of 9 based on hexose and glucose and the DP10 + is a hexose (especially glucose) -based oligosaccharide It is a polysaccharide with a degree of polymerization of 10 or more.

2. An aqueous system comprising a saccharide mixture-based polymer particle Emulsion  Produce

Production Example 1

The reactor was charged with 388 g of Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), anionic emulsifier (component: sulfosuccinate composition; trade name: AEROSOL EF-800; supplier: Cytec Industries, USA) and 200 g of deionized water were added, and the mixture was stirred with nitrogen. Further, 14.25 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 40.72 g of an aqueous hydrogen peroxide solution (about 14.25 g in terms of hydrogen peroxide) of 35% concentration was prepared as the oxidation initiator solution. To 100 g of deionized water was added 4 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), a nonionic emulsifier (component: alcohol ethoxylate; 4 g of Disponil A 1080 (supplier: BASF, DE) was added to dissolve, and then 6.6 g of 2-hydroxyethyl acrylate, 1.1 g of glycidyl methacrylate, 253 g of n-butyl acrylate, 168 g of ethylhexyl acrylate, 11 g of acrylic acid and 0.6 g of n-dodecyl mercaptan were slowly added dropwise in this order and mixed to prepare a pre-emulsion of the monomer mixture.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, 10% of a pre-emulsion of a reducing initiator solution, an oxidizing initiator solution and a monomer mixture was added dropwise thereto over about 30 minutes to conduct a copolymerization reaction, To obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

Thereafter, the temperature of the reactor containing the emulsion containing core particles was maintained at about 80 DEG C, 90% of the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the preemulsion of the monomer mixture Followed by dropping for about 120 minutes to promote the copolymerization reaction on the core surface, agitate for about 60 minutes and aged to obtain an emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Thereafter, the emulsion containing the saccharide mixture-based copolymer particles of the core-shell structure was cooled to about 55 캜, and an oxidizing agent solution (a solution in which 0.9 g of t-butyl hydroperoxide was dissolved in 16 g of deionized water) (A solution prepared by dissolving 0.6 g of sodium hydrosulfite in 8.0 g of deionized water) was dropped for 30 minutes and reacted to remove unreacted monomers. After completion of the dropwise addition of the oxidant solution and the reducing agent solution, the reaction product was aged at about 55 캜 for 30 minutes and then cooled to room temperature to obtain a final emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Production Example 2

The reactor was charged with 388 g of Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), anionic emulsifier (component: sulfosuccinate composition; trade name: AEROSOL EF-800; supplier: Cytec Industries, USA) and 200 g of deionized water were added, and the mixture was stirred with nitrogen. Further, 12.85 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 36.72 g (about 12.85 g in terms of hydrogen peroxide) of an aqueous hydrogen peroxide solution having a concentration of 35% was prepared as the oxidation initiator solution. To 100 g of deionized water was added 4 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), a nonionic emulsifier (component: alcohol ethoxylate; 4 g of Disponil A 1080 (supplier: BASF, DE) was added to dissolve, and then 6.6 g of 2-hydroxyethyl acrylate, 1.1 g of glycidyl methacrylate, 253 g of n-butyl acrylate, 168 g of ethylhexyl acrylate, 11 g of acrylic acid and 0.6 g of n-dodecyl mercaptan were slowly added dropwise in this order and mixed to prepare a pre-emulsion of the monomer mixture.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, 10% of a pre-emulsion of a reducing initiator solution, an oxidizing initiator solution and a monomer mixture was added dropwise thereto over about 30 minutes to conduct a copolymerization reaction, To obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

Thereafter, the temperature of the reactor containing the emulsion containing core particles was maintained at about 80 DEG C, 90% of the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the preemulsion of the monomer mixture Followed by dropping for about 120 minutes to promote the copolymerization reaction on the core surface, agitate for about 60 minutes and aged to obtain an emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Thereafter, the emulsion containing the saccharide mixture-based copolymer particles of the core-shell structure was cooled to about 55 캜, and an oxidizing agent solution (a solution in which 0.9 g of t-butyl hydroperoxide was dissolved in 16 g of deionized water) (A solution prepared by dissolving 0.6 g of sodium hydrosulfite in 8.0 g of deionized water) was dropped for 30 minutes and reacted to remove unreacted monomers. After completion of the dropwise addition of the oxidant solution and the reducing agent solution, the reaction product was aged at about 55 캜 for 30 minutes and then cooled to room temperature to obtain a final emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Production Example 3

The reactor was charged with 388 g of Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), anionic emulsifier (component: sulfosuccinate composition; trade name: AEROSOL EF-800; supplier: Cytec Industries, USA) and 200 g of deionized water were added, and the mixture was stirred with nitrogen. Also, 11.47 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 32.77 g of an aqueous hydrogen peroxide solution (about 11.47 g in terms of hydrogen peroxide) at a concentration of 35% was prepared as the oxidation initiator solution. To 100 g of deionized water was added 4 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), a nonionic emulsifier (component: alcohol ethoxylate; 4 g of Disponil A 1080 (supplier: BASF, DE) was added to dissolve, and then 6.6 g of 2-hydroxyethyl acrylate, 1.1 g of glycidyl methacrylate, 253 g of n-butyl acrylate, 168 g of ethylhexyl acrylate, 11 g of acrylic acid and 0.6 g of n-dodecyl mercaptan were slowly added dropwise in this order and mixed to prepare a pre-emulsion of the monomer mixture.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, 10% of a pre-emulsion of a reducing initiator solution, an oxidizing initiator solution and a monomer mixture was added dropwise thereto over about 30 minutes to conduct a copolymerization reaction, To obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

Thereafter, the temperature of the reactor containing the emulsion containing core particles was maintained at about 80 DEG C, 90% of the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the preemulsion of the monomer mixture The copolymerization reaction was carried out on the core surface by dropping for about 120 minutes, but gelation occurred and further experiments could not be carried out.

Production Example 4

The reactor was charged with 388 g of Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), anionic emulsifier (component: sulfosuccinate composition; trade name: AEROSOL EF-800; supplier: Cytec Industries, USA) and 200 g of deionized water were added, and the mixture was stirred with nitrogen. Also, 7.14 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 20.4 g (about 7.14 g in terms of hydrogen peroxide) of an aqueous hydrogen peroxide solution having a concentration of 35% was prepared as the oxidation initiator solution. To 100 g of deionized water was added 4 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), a nonionic emulsifier (component: alcohol ethoxylate; 4 g of Disponil A 1080 (supplier: BASF, DE) was added to dissolve, and then 6.6 g of 2-hydroxyethyl acrylate, 1.1 g of glycidyl methacrylate, 253 g of n-butyl acrylate, 168 g of ethylhexyl acrylate, 11 g of acrylic acid and 0.6 g of n-dodecyl mercaptan were slowly added dropwise in this order and mixed to prepare a pre-emulsion of the monomer mixture.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, 10% of a pre-emulsion of a reducing initiator solution, an oxidizing initiator solution and a monomer mixture was added dropwise thereto over about 30 minutes to conduct a copolymerization reaction, To obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

Thereafter, the temperature of the reactor containing the emulsion containing core particles was maintained at about 80 DEG C, 90% of the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the preemulsion of the monomer mixture The copolymerization reaction was carried out on the core surface by dropping for about 120 minutes, but gelation occurred and further experiments could not be carried out.

Production Example 5

The reactor was charged with 388 g of Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), anionic emulsifier (component: sulfosuccinate composition; trade name: AEROSOL EF-800; supplier: Cytec Industries, USA) and 200 g of deionized water were added, and the mixture was stirred with nitrogen. In addition, 4.28 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 12.23 g (about 4.28 g in terms of hydrogen peroxide) of an aqueous hydrogen peroxide solution having a concentration of 35% was prepared as the oxidation initiator solution. To 100 g of deionized water was added 4 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), a nonionic emulsifier (component: alcohol ethoxylate; 4 g of Disponil A 1080 (supplier: BASF, DE) was added to dissolve, and then 6.6 g of 2-hydroxyethyl acrylate, 1.1 g of glycidyl methacrylate, 253 g of n-butyl acrylate, 168 g of ethylhexyl acrylate, 11 g of acrylic acid and 0.6 g of n-dodecyl mercaptan were slowly added dropwise in this order and mixed to prepare a pre-emulsion of the monomer mixture.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, 10% of a pre-emulsion of a reducing initiator solution, an oxidizing initiator solution and a monomer mixture was added dropwise thereto over about 30 minutes to conduct a copolymerization reaction, To obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

Thereafter, the temperature of the reactor containing the emulsion containing core particles was maintained at about 80 DEG C, 90% of the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the preemulsion of the monomer mixture The copolymerization reaction was carried out on the core surface by dropping for about 120 minutes, but gelation occurred and further experiments could not be carried out.

Production Example 6

388 g of the Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), an anionic emulsifier (trade name: RHODACAL DS 4, supplied by Solvay USA Inc., US), 1.0 g of a nonionic emulsifier (trade name: Disponil A 1080; supplier: BASF, DE) and 142.9 g of deionized water were added and charged with nitrogen. The anionic emulsifier is an aqueous solution having about 22 to 23% by weight of sodium dodecyl benzene sulfonate (CAS registration number: 69227-09-4). In addition, the nonionic emulsifier is an aqueous solution having a concentration of ethoxylated linear aliphatic alcohol (Alcohols, C12-14, ethoxylated; CAS registration number: 68439-50-9) of about 40 to 70% by weight. Further, 12.85 g of sodium bisulfate (NaHSO ₄ ) and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a reduction initiator solution. Further, 36.72 g (about 12.85 g in terms of hydrogen peroxide) of an aqueous hydrogen peroxide solution having a concentration of 35% was prepared as the oxidation initiator solution.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, and a reduction initiator solution, an oxidation initiator solution, and a core monomer mixture were added dropwise thereto for about 60 minutes to proceed the copolymerization reaction. The core monomer mixture was prepared by adding 28.0 g of methyl methacrylate, 5.0 g of methacrylic acid, 65.0 g of n-butyl acrylate and 2.0 g of t-dodecyl mercaptan in this order. After completion of the dropwise addition of the initiator solution and the core monomer mixture, the copolymerization reaction product was agitated at about 80 캜 for about 60 minutes and aged to obtain a core particle composed of a saccharide mixture-based copolymer and an emulsion containing the same.

2 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), 100 g of a nonionic emulsifier (component: alcohol ethoxylate; 2 g of Disponil A 1080 supplied by BASF, DE) was added and dissolved. Then, 95 g of styrene, 105 g of methyl methacrylate, 93 g of n-butyl acrylate, 75 g of methacrylic acid and 2.0 g of n-dodecyl mercaptan In order, and mixed to prepare a pre-emulsion of the shell monomer mixture.

Thereafter, the temperature of the reactor containing the emulsion containing the core particles was maintained at about 80 DEG C, and the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the pre-emulsion of the shell monomer mixture The copolymerization reaction was allowed to proceed dropwise over 120 minutes to allow the copolymerization reaction to proceed on the core surface and agitated for about 60 minutes and aged to obtain an emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Thereafter, the emulsion containing the saccharide mixture-based copolymer particles of the core-shell structure was cooled to about 55 캜, and an oxidizing agent solution (a solution in which 0.9 g of t-butyl hydroperoxide was dissolved in 16 g of deionized water) (A solution prepared by dissolving 0.6 g of sodium hydrosulfite in 8.0 g of deionized water) was dropped for 30 minutes and reacted to remove unreacted monomers. After completion of the dropwise addition of the oxidant solution and the reducing agent solution, the reaction product was aged at about 55 캜 for 30 minutes and then cooled to room temperature to obtain a final emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Production Example 7

388 g of the Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea) (135.8 g in terms of solid content of the saccharide mixture), an anionic emulsifier (trade name: RHODACAL DS 4, supplied by Solvay USA Inc., US), 1.0 g of a nonionic emulsifier (trade name: Disponil A 1080; supplier: BASF, DE) and 142.9 g of deionized water were added and charged with nitrogen. The anionic emulsifier is an aqueous solution having about 22 to 23% by weight of sodium dodecyl benzene sulfonate (CAS registration number: 69227-09-4). In addition, the nonionic emulsifier is an aqueous solution having a concentration of ethoxylated linear aliphatic alcohol (Alcohols, C12-14, ethoxylated; CAS registration number: 68439-50-9) of about 40 to 70% by weight. Further, 1.28 g of sodium persulfate and 0.08 g of sodium sulfite (NaHSO ₃ ) were added to 11 g of deionized water and dissolved to prepare a polymerization initiator solution.

Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, and the polymerization initiator solution and the core monomer mixture were added dropwise thereto over about 60 minutes to proceed the copolymerization reaction. The core monomer mixture was prepared by adding 28.0 g of methyl methacrylate, 5.0 g of methacrylic acid, 65.0 g of n-butyl acrylate and 2.0 g of t-dodecyl mercaptan in this order. After completion of the dropwise addition of the polymerization initiator solution and the core monomer mixture, the copolymerization reaction product was agitated at about 80 캜 for about 60 minutes and aged to obtain core particles composed of a saccharide mixture-based copolymer and an emulsion containing the same.

2 g of an anionic emulsifier (component: allyloxy methylalkoxyethyl polyoxyethylene sulfate; trade name: Adeka Reasoap SR-10; supplier: Asahi Denka Co., Ltd.), 100 g of a nonionic emulsifier (component: alcohol ethoxylate; 2 g of Disponil A 1080 supplied by BASF, DE) was added and dissolved. Then, 95 g of styrene, 105 g of methyl methacrylate, 93 g of n-butyl acrylate, 75 g of methacrylic acid and 2.0 g of n-dodecyl mercaptan In order, and mixed to prepare a pre-emulsion of the shell monomer mixture.

Thereafter, the temperature of the reactor containing the emulsion containing the core particles was maintained at about 80 DEG C, and the polymerization initiator solution (a solution in which 1.2 g of sodium persulfate was dissolved in 60 g of deionized water) and the pre-emulsion of the shell monomer mixture The copolymerization reaction was allowed to proceed dropwise over 120 minutes to allow the copolymerization reaction to proceed on the core surface and agitated for about 60 minutes and aged to obtain an emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

Thereafter, the emulsion containing the saccharide mixture-based copolymer particles of the core-shell structure was cooled to about 55 캜, and an oxidizing agent solution (a solution in which 0.9 g of t-butyl hydroperoxide was dissolved in 16 g of deionized water) (A solution prepared by dissolving 0.6 g of sodium hydrosulfite in 8.0 g of deionized water) was dropped for 30 minutes and reacted to remove unreacted monomers. After completion of the dropwise addition of the oxidant solution and the reducing agent solution, the reaction product was aged at about 55 캜 for 30 minutes and then cooled to room temperature to obtain a final emulsion containing the core-shell structure of the saccharide mixture-based copolymer particles.

3. Sugar mixture-based polymer particles Emulsion  Property Analysis

(1) General property analysis

The solid content, viscosity and average particle size of the saccharide mixture-based copolymer particles of the final emulsion prepared in Preparation Example 1, Preparation Example 2, Production Example 5, Production Example 6 and Production Example 7 were measured, Respectively.

Analysis item Final emulsion classification Production Example 1 Production Example 2 Production Example 6 Production Example 7 Solid content (% by weight) 50.1 50.2 50.4 50.1 Viscosity (cPs) 110 115 202 180 Average particle size (nm) 160 160 140 142

On the other hand, in the case of the final emulsion prepared in Preparation Examples 3 to 5, gelation occurred and no further analysis was performed. In the case of Production Example 1, Production Example 2 and Production Example 6, the content of the reducing initiator sodium bisulfate and the oxidizing initiator hydrogen peroxide used in forming the core particles was 9.5 to 10.5 parts by weight, respectively, relative to 100 parts by weight of the solid mixture of saccharides, In Production Example 5, the content of the reducing initiator sodium bisulfate and the oxidizing initiator hydrogen peroxide used in the core particle formation was 3.1 to 8.5 parts by weight, respectively, relative to 100 parts by weight of the solid mixture of the saccharide mixture. It has been found that the gelation is determined depending on the content of initiator relative to the solids content of the saccharide mixture even though the same reducing initiator and oxidation initiator system are used in the core particle formation step in the production of the saccharide mixture based polymer particle emulsion.

(2) Stability analysis under alkaline conditions

The pH of the final emulsion prepared in Preparation Example 1, Preparation Example 2, Preparation Example 5, Preparation Example 6 and Preparation Example 7 was adjusted to 7.3 ± 2 and stored in an oven at 60 ° C. for 6 days, The color change was measured using a difference meter. The results are shown in Table 3 below.

Final emulsion classification 0 Analysis of primary color difference meter 6th color difference analysis value ΔE (0th day → 6th day) L a b L a b Production Example 1 90 -2.06 -10.87 87.17 -2.08 -10.97 6.1 Production Example 2 88 0.58 -0.06 85.68 -3.07 1.56 7.2 Production Example 6 88.32 -1.78 -10.25 87.94 -2.00 -10.87 6.1 Production Example 7 76.17 -4.82 -10.38 68.19 0.83 -2.16 17.17

1 is a photograph showing the state after adjusting the pH of the saccharide-based polymer particle emulsion prepared in Preparation Example 1 of the present invention to the pH of the alkaline condition (7.5 ± 2) and storing it at 60 ° C. for 6 days. 2 is a photograph showing the state after adjusting the pH of the saccharide-based polymer particle emulsion prepared in Production Example 7 of the present invention to the pH of the alkaline condition (7.5 ± 2) and storing it at 60 ° C. for 6 days. As shown in Table 3 and FIG. 1 to FIG. 2, the saccharide-based polymer particle emulsion prepared in Preparation Example 1 showed almost no color change even after storage for a long time under alkaline conditions. However, Color changed significantly when stored for long periods under alkaline conditions.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the scope of protection of the present invention should not be limited to the specific embodiments disclosed as the best mode, but should be construed as including all embodiments belonging to the claims attached hereto.

Claims (12)

(a) mixing a saccharide mixture, an anionic emulsifier and water, adding a core-forming monomer and a primary polymerization initiator thereto, and polymerizing to obtain an aqueous emulsion comprising the core; And
(b) adding a shell-forming monomer and a secondary polymerization initiator to an aqueous emulsion containing the core and polymerizing to form a shell on the core,
Wherein the core-forming monomer comprises a hard monomer, a soft monomer, and a carboxylic acid monomer having an ethylenically unsaturated bond,
Wherein the shell-forming monomer comprises a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, and a reactive emulsifier,
Wherein the hard monomer has an ethylenic unsaturated bond and the homopolymer has a glass transition temperature of 30 ° C to 250 ° C,
Wherein the soft monomer has an ethylenic unsaturated bond and the homopolymer has a glass transition temperature of from 10 캜 to -80 캜,
The reactive emulsifier may be selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, And at least one functional group selected from a vinylene group,
The first polymerization initiator is a Redox-based polymerization initiator containing sodium bisulfate and hydrogen peroxide,
The weight ratio of sodium bisulfate to hydrogen peroxide constituting the first polymerization initiator is 3: 7 to 7: 3,
Wherein the amount of the first polymerization initiator added is 18 to 30 parts by weight per 100 parts by weight of the saccharide mixture.
(a ') mixing a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water, adding a core-forming monomer and a primary polymerization initiator thereto, and polymerizing to obtain an aqueous emulsion comprising the core; And
(b ') adding a shell-forming monomer and a secondary polymerization initiator to an aqueous emulsion containing the core and polymerizing to form a shell on the core,
Wherein the core-forming monomer comprises a hard monomer, a soft monomer, and a carboxylic acid monomer having an ethylenically unsaturated bond,
Wherein the shell-forming monomer comprises a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, and a reactive emulsifier,
Wherein the hard monomer has an ethylenic unsaturated bond and the homopolymer has a glass transition temperature of 30 ° C to 250 ° C,
Wherein the soft monomer has an ethylenic unsaturated bond and the homopolymer has a glass transition temperature of from 10 캜 to -80 캜,
The reactive emulsifier may be selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, And at least one functional group selected from a vinylene group,
The first polymerization initiator is a Redox-based polymerization initiator containing sodium bisulfate and hydrogen peroxide,
The weight ratio of sodium bisulfate to hydrogen peroxide constituting the first polymerization initiator is 3: 7 to 7: 3,
Wherein the amount of the first polymerization initiator added is 18 to 30 parts by weight per 100 parts by weight of the saccharide mixture.
The method according to claim 1 or 2, wherein the saccharide mixture has a weight average molecular weight (Mw) of 300 to 2,000 as a hydrolyzate of starch.
The saccharide mixture according to claim 1 or 2, wherein the saccharide mixture comprises 1 to 20% by weight of glucose based on the total weight of the saccharide mixture, 10 to 65% by weight of saccharides having a glucose-based degree of polymerization of 2, Glucose-based polymer having a degree of polymerization of 5 to 25% by weight, a glucose-based polymer having a degree of polymerization of 4 to 0.1 to 10% by weight, a glucose-based polymer having a degree of polymerization of 5 to 0.5 to 15% 0.5 to 15% by weight of saccharides having a degree of polymerization (glucose) -based polymerization degree of 6, 0.5 to 15% by weight of saccharides having a degree of polymerization based on glucose of 7, 0.5 to 15% by weight of saccharides having a degree of polymerization of 8 based on glucose, A process for producing a sugar-based polymer particle emulsion, which comprises a saccharide having a glucose degree of 9 based on glucose and 0.1 to 10% by weight of a saccharide having a glucose degree-based degree of polymerization of 10 or more.
The method according to claim 1 or 2, wherein the hard monomer is selected from the group consisting of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, isobornyl acrylate Characterized in that the saccharide-based polymer particle emulsion is at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium carbonate, potassium carbonate, sodium carbonate, potassium carbonate, sodium carbonate, potassium carbonate, Gt;
The composition of claim 1 or 2, wherein the soft monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, ethylhexyl methacrylate, lauryl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate. The method of producing a sugar-based polymer particle emulsion according to claim 1,
[Claim 4] The method according to claim 1 or 2, wherein the carboxylic acid monomer having an ethylenically unsaturated bond is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid A process for producing a sugar-based polymer particle emulsion.
3. The composition of claim 1 or 2, wherein the core-forming monomer or shell-forming monomer is selected from the group consisting of n-dodecyl mercaptan, t-dodecyl mercaptan, 1,5-pentanediol, Mercaptopropionate, ethyl 3-mercaptopropionate, butyl 3-mercaptopropionate, dodecyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, ethyl 3-mercaptopropionate, methyl Mercaptopropionate, pentaerythritol tetrakis (3-mercaptopropionate), 2-ethylhexyl mercaptoacetate, ethyl 2-mercaptoacetate, 2-hydroxymethyl- Wherein the sugar chain-based polymer particle emulsion further comprises at least one chain transfer agent selected from the group consisting of 3-propanediol, and pentaerythritol tetrakis (2-mercaptoacetate).
The process for producing a sugar-based polymer particle emulsion according to claim 1 or 2, wherein the core-forming monomer comprises a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenic unsaturated bond and a reactive emulsifier .
The core-forming monomer as claimed in claim 1 or 2, wherein the core-forming monomer is in the form of a pre-emulsion comprising a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, a chain transfer agent, a reactive emulsifier, a nonionic emulsifier, ≪ / RTI > by weight of the polymeric emulsion.
The composition of claim 1 or 2, wherein the shell-forming monomer is in the form of a pre-emulsion consisting of a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, a chain transfer agent, a reactive emulsifier, a nonionic emulsifier, ≪ / RTI > by weight of the polymeric emulsion.
The method according to claim 1 or 2, wherein the second polymerization initiator is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, 2,2- azobisbutyronitrile, 2,2'- Azobis-2-methylbutyronitrile, and cumene hydroperoxide. 2. The method according to claim 1, wherein the saccharide-based polymer particle emulsion is at least one selected from the group consisting of azobis-2-methylbutyronitrile and cumene hydroperoxide.

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