KR101823499B1 - Saccharides-based polymer particle emulsion and manufacturing method thereof - Google Patents
Saccharides-based polymer particle emulsion and manufacturing method thereof Download PDFInfo
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Abstract
The present invention provides a saccharide-based polymer particle emulsion comprising water as a dispersion medium and a dispersion medium-based polymer particle and a dispersion medium. The saccharide mixture-based polymer particles have a core-shell structure comprising a core formed by polymerization of a saccharide mixture and a core-forming monomer, and a shell formed on the core by polymerization of a shell-forming monomer. The saccharide-based polymer particle emulsion according to the present invention can form a coating film on the surface of the metal base, which has excellent adhesion strength and minimizes the phenomenon of sticking to each other as compared with the starch decomposition-based polymer particle emulsion. In addition, the saccharide-based polymer particle emulsion according to the present invention has a quality reliability because the composition ratio and the size of the polymer particles are uniform as compared with the starch decomposition-based polymer particle emulsion. Accordingly, the saccharide-based polymer particle emulsion according to the present invention can be used as a coating material or a coating material for forming a protective layer on the surface of a metal sheet which needs to be stacked.
Description
The present invention relates to a sugar-based polymer particle emulsion, and more particularly to a sugar-based polymer particle emulsion containing a saccharide-based polymer particle having a core-shell structure as a dispersion medium and a combination of monomers forming a core and a combination of monomers forming a shell Based polymer particle emulsion capable of forming a coating film having a strong adhesive force on the surface of a metal substrate and minimizing the phenomenon of sticking to each other between coating films, and a method for producing the same.
Coatings are commonly used to impart aesthetics to the surface of building materials or metallic materials, but they are now mainly used to protect the surface of building materials or metallic materials from external factors such as water, dust, air, oil and the like. For example, a steel sheet having a plated layer composed of a mixture of zinc, nickel, aluminum, and silica or a single composition maintains a high-quality appearance, but contamination due to fingerprints may easily occur, there is a problem. Therefore, an organic resin such as a water-dispersible acrylic resin, a water-dispersible epoxy resin, and a water-dispersible urethane resin is applied to the surface of a metal such as a zinc alloy plated steel sheet or an aluminum alloy steel sheet to form a coating film having a certain thickness, Efforts to improve the quality of life are continuing. In this connection, Korean Patent Registration No. 10-0774957 (Prior Art 1) discloses that 38 to 60% by weight of a water-soluble urethane acrylic hybrid resin; 1 to 3% by weight of an additive comprising antifoaming agents, wetting agents and rust inhibitors; Wherein the water-soluble urethane acrylic hybrid resin comprises 40 to 70 parts by weight of a water-soluble urethane dispersion and 30 to 40 parts by weight of an acrylic monomer containing an acetoacetoxy monomer in the presence of an acrylic reaction initiator Disclosed is a water-dispersed urethane acrylic hybrid coating for metal coating.
On the other hand, conventional metal-based coating agents are made of petrochemical raw materials, which causes a problem of poor environment-friendliness. To solve this problem, coating materials using natural raw materials have been studied. In particular, starch has attracted much attention as an eco-friendly coating material because it has good adhesiveness, low cost, and excellent heat resistance. In this connection, Korean Patent Registration No. 10-1473916 (Prior Art 2) discloses an aqueous emulsion for a paint containing dispersed, starch-based polymer particles and water as a dispersion medium. The starch-based polymer particles disclosed in the above-mentioned Reference 2 include a core made of a starch-based copolymer formed by polymerization of a starch-decomposed material and a core monomer mixture comprising a hard monomer and a soft monomer; And a shell formed of a copolymer formed on the core by polymerization of a shell monomer mixture comprising a hard monomer, a soft monomer, and a silane-based unsaturated monomer, wherein the hard monomer is a core- Wherein the soft monomer has an ethylenic unsaturated bond and the glass transition temperature of the homopolymer is 10 ° C to -80 ° C, and the glass transition temperature of the homopolymer is 30 ° C to 250 ° C. The silane-based unsaturated monomer includes at least one silane skeleton and at least one unsaturated bonding functional group capable of polymerizing with a hard monomer or a soft monomer. However, when a coating film is formed by applying the aqueous emulsion for coating to the surface of a metal substrate disclosed in the above-mentioned prior art document 2, the adhesion of the coating film is excellent but the coating films stick together. Particularly, when a plurality of metal sheets are laminated and stored for a long period of time, when the coated films formed on the surface of the metal sheet are stuck to each other, there is a problem that the coating film is damaged or the operation is delayed in the process of separating the metal sheet. In the prior art 2, a starch hydrolyzate obtained by decomposing seed starch to alpha-amylase to form a core is used. Since the starch hydrolyzate has a very large molecular weight distribution, the composition ratio of the starch-based polymer particles constituting the final emulsion And the size becomes uneven.
SUMMARY OF THE INVENTION The present invention has been made under the background of the prior art, and it is an object of the present invention to provide a coating film having excellent adhesion to the surface of a metal substrate and minimizing the phenomenon of sticking to each other, Based polymer particle emulsion and a process for producing the same.
The inventors of the present invention found that when the constituents and the content of the saccharide mixture acting as a seed for forming a core are controlled by preparing a sugar-mixture-based polymer particle having a core-shell structure by aqueous emulsion polymerization, the phase stability of the final emulsion And that when the coating film is formed on the surface of the metal substrate by the excellent and final emulsion, the coating strength of the coating film is excellent and the coating film does not stick to each other.
In order to achieve the above object, an embodiment of the present invention is an aqueous emulsion comprising water as dispersion medium based on polymer particles based on a saccharide mixture and water as a dispersion medium, wherein the saccharide mixture based polymer particles are prepared by polymerizing a saccharide mixture and a core- And a core-shell structure comprising a shell formed on the core by polymerization of a shell-forming monomer, wherein the saccharide mixture comprises 2-15 weight percent saccharides having a hexose-based degree of polymerization of 4 based on the total weight of the saccharide mixture % And a hexose-based polymer having a degree of polymerization of 4 or more, wherein the core-forming monomer comprises a carboxylic monomer having a hard monomer, a soft monomer and an ethylenically unsaturated bond, The forming monomer includes a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenically unsaturated bond, and a reactive emulsifier It provides a sugar-based emulsion polymer particles. In the sugar-based polymer particle emulsion according to an example of the present invention, the hard monomer has a ethylenically unsaturated bond and the homopolymer has a glass transition temperature of 30 ° C to 250 ° C, and the soft monomer has an ethylenically 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.
In order to solve the above-mentioned object, one example of the present invention is a method for producing a water-based emulsion comprising a mixture of a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water, adding a core- ; And a step of adding a shell-forming monomer and a polymerization initiator to an aqueous emulsion containing the core and polymerizing to form a shell on the core. The present invention also provides a method for producing a sugar-based polymer particle emulsion. In the method for preparing a sugar-based polymer particle emulsion according to an embodiment of the present invention, the saccharide mixture may contain 2-15% by weight of saccharides having a hexose-based degree of polymerization of 4 based on the total weight of the saccharide mixture, 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 is a soft monomer, a soft monomer, Monomers, carboxylic acid monomers having ethylenically unsaturated bonds, and reactive emulsifiers. The hard monomer has a ethylenically unsaturated bond and the homopolymer thereof has a glass transition temperature of 30 ° C to 250 ° C. The soft monomer has an ethylenically unsaturated bond and the glass transition temperature of the homopolymer is 10 ° C to -80 < 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.
The saccharide-based starch-based polymer particle emulsion according to the present invention has a half-life of the biomass-derived saccharide mixture which is repeatedly regenerated, so that it is more environmentally friendly than the emulsion for metal-based coatings based on conventional petroleum raw materials, Reliability can be secured. In addition, the saccharide-based polymer particle emulsion according to the present invention can form a coating film on the surface of a metal substrate, which has excellent adhesion strength and minimizes the phenomenon of sticking to each other as compared with the starch decomposition-based polymer particle emulsion. In addition, the saccharide-based polymer particle emulsion according to the present invention has a quality reliability because the composition ratio and the size of the polymer particles are uniform as compared with the starch decomposition-based polymer particle emulsion. Accordingly, the saccharide-based polymer particle emulsion according to the present invention can be used as a coating material or a coating material for forming a protective layer on the surface of a metal sheet which needs to be stacked.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of measurement of the molecular weight distribution of the starch hydrolyzate contained in the starch liquefied liquid by high performance liquid chromatography (HPLC).
Hereinafter, the present invention will be described in detail.
One aspect of the present invention relates to a sugar-based polymer particle emulsion that can be used for surface coating applications such as metal substrates. The saccharide-based polymer particle emulsion according to the present invention is an aqueous emulsion containing water as dispersion medium and a dispersion medium based on saccharide mixture. In addition, the saccharide mixture-based polymer particles according to the present invention, which is a dispersion of the saccharide-based polymer particle emulsion, comprises a core formed by polymerization of a saccharide mixture and a core monomer mixture, and a shell formed on the core by polymerization of the shell monomer mixture. - Has a shell structure. 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. The saccharide mixture contains 2 to 15% by weight of a saccharide having a hexose-based degree of polymerization of 4 based on the total weight of the saccharide mixture, Based polymer having a degree of polymerization of 4 or more. In addition, in the present invention, the saccharide mixture preferably comprises 4 to 10% by weight of sugars having a glucose-based degree of polymerization of 4 based on the total weight of the saccharide mixture and 65 to 85% by weight of saccharides having a glucose- %. Further, in the present invention, the saccharide mixture preferably comprises 20 to 35% by weight of saccharides having a glucose-based degree of polymerization of 3 or less, 4 to 10% by weight of saccharides having a glucose-based degree of polymerization of 4, And 70 to 80% by weight of saccharides having a degree of polymerization of 4 or more. The saccharide mixture in the present invention most preferably comprises 1 to 6% by weight of glucose, 7 to 15% by weight of saccharides having a polymerization degree of 2 based on glucose, a degree of polymerization of glucose- (Glucose) based sugar, 4 to 10% by weight of saccharides having a degree of polymerization based on glucose of 4, 6 to 14% by weight of saccharides having a degree of polymerization based on glucose of 5, and glucose Glucose-based polymerization degree is 13 to 21% by weight of saccharides having a degree of polymerization of 6, 4 to 10% by weight of saccharides having a degree of polymerization based on glucose of 7, glucose having a polymerization degree of 8 based on glucose, To 5% by weight of a saccharide having a degree of polymerization based on glucose of 9 and saccharides having a polymerization degree based on glucose of 10 or more with a balance of glucose and sucrose.
The core-forming monomers include 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. The type of the hard monomer constituting the core-forming monomer in the present invention is not particularly limited as long as it satisfies the above-mentioned characteristics, and preferable examples thereof include styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, And may be at least one member selected from the group consisting of methacrylonitrile, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyltoluene, vinyl acetate and vinyl chloride, It is more preferable that it is acrylate. 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, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate and hydroxybutyl acrylate. More preferably, it is butyl acrylate. 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 acrylic acid or methacrylic acid. 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 n-dodecyl mercaptan, t-dodecyl mercaptan More preferable.
The content of the hard monomer in the core-forming monomer is preferably 15 to 40% by weight, more preferably 20 to 35% by weight. The content of the soft monomer in the core-forming monomer is preferably 50 to 80% by weight, more preferably 55 to 75% by weight. The content of the carboxylic acid monomer having an ethylenically unsaturated bond in the core-forming monomer is preferably 2 to 10% by weight, more preferably 3 to 8% by weight. The content of the chain transfer agent in the core-forming monomer is preferably 0.5 to 5% by weight, more preferably 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: 4, more preferably 1: 2 to 1: 3.
The weight ratio of the saccharide mixture to the core-forming monomer in the core is preferably 1: 0.5 to 1: 4, more preferably 1: 1 to 1: 3, most preferably 1: 1.5 to 1: 2.5 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 styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, And may be at least one member selected from the group consisting of methacrylonitrile, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyltoluene, vinyl acetate and vinyl chloride, It is preferable that the combination of acrylate and styrene. 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 preferably includes methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, Acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate and hydroxybutyl acrylate. More preferably, it is butyl acrylate. 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, and preferably, Acrylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and more preferably acrylic acid or 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 n-dodecyl mercaptan, t-dodecyl mercaptan More preferable.
The content of the hard monomer in the shell-forming monomer is preferably 40 to 70% by weight, more preferably 45 to 65% by weight. The content of the soft monomer in the shell-forming monomer is preferably 15 to 35% by weight, more preferably 20 to 30% by weight. The content of the carboxylic acid monomer having an ethylenically unsaturated bond in the shell-forming monomer is preferably 10 to 30% by weight, more preferably 15 to 25% by weight. The content of the reactive emulsifier in the shell-forming monomer is preferably 0.1 to 2% by weight, more preferably 0.2 to 1% by weight. The content of the chain transfer agent in the shell-forming monomer is preferably 0.1 to 2% by weight, more preferably 0.2 to 1% 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: 0.8, more preferably 1: 0.3 to 1: 0.6.
Within the saccharide mixture-based polymer particles, Shell Content relationship
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: 6, more preferably from 1: 2 to 1: 5, : 2.5 to 1: 4.5.
Sugar-based polymer particles In the emulsion Explanation of the ingredients involved
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 20 to 60% by weight, more preferably 35 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 includes, for example, anionic emulsifiers such as alkylbenzenesulfonate, alkyldiphenyloxide disulfonate and the like; 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 anionic emulsifier is not limited in its kind and includes, for example, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate (CAS registration number: 69227-09-4); 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 0.5 to 15 parts by weight, more preferably 1 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 in the step of forming the core or shell of the saccharide-based polymer particles, and serves to disperse the other components evenly on the aqueous phase in the step of preparing the pre-emulsion of the shell- . 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 4 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 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 for the shell-forming monomer. In addition, 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.
Another aspect of the present invention relates to a method for preparing a sugar-based polymer particle emulsion which can be used for surface coating of metal substrates and the like. A method for producing a sugar-based polymer particle emulsion according to an embodiment of the present invention includes mixing a saccharide mixture, an anionic emulsifier, a nonionic emulsifier and water, adding a core-forming monomer and a polymerization initiator thereto, To obtain a water-based emulsion; And a step of adding a shell-forming monomer and a polymerization initiator to an aqueous emulsion containing the core and polymerizing to form a shell on the core. The saccharide mixture comprises 2-15% by weight of saccharides having a hexose-based degree of polymerization of 4 and 55-90% by weight of saccharides having a hexose-based degree of polymerization of 4 or higher based on the total weight of the saccharide mixture. In addition, the core-forming monomer includes a hard monomer, a soft monomer, and a carboxylic acid monomer having an ethylenic unsaturated bond. In addition, the shell-forming monomer includes a hard monomer, a soft monomer, a carboxylic acid monomer having an ethylenic unsaturated bond, and a reactive emulsifier. The hard monomer has a 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 glass transition temperature of the homopolymer is 10 ° C to - 80 < 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. The specific types and amounts of the saccharide mixture, the core-forming monomer, the shell-forming monomer and the various emulsifiers mentioned in the preparation method of the sugar-based polymer particle emulsion of the present invention are described above.
In the method for producing a sugar-based polymer particle emulsion according to an example of the present invention, the step of forming a core comprises the steps of adding an emulsifier (preferably an anionic emulsifier and a nonionic emulsifier) and water to a solution containing a saccharide mixture, Adding a core-forming monomer and a polymerization initiator to a polymerization reaction, and further adding a process of aging. An aqueous emulsion comprising a core consisting of a saccharide mixture based copolymer can be obtained by the formation step of the core. For the matters relating to the core-forming monomer used in the step of forming the core, refer to the above description. The polymerization initiator may be a thermal decomposition initiator or an oxidation-reduction initiator capable of radical polymerization, and examples thereof include sodium persulfate, potassium persulfate, t-butyl hydroperoxide, 2,2-azobisbutyronitrile, , 2'-azobis-2-methylbutyronitrile, cumene hydroperoxide and the like can be used, and water-soluble initiators such as sodium persulfate, potassium persulfate, and t-butyl hydroperoxide can be preferably used. If necessary, a reducing agent such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite and the like may be added. The polymerization initiator may be added before the addition of the monomer or simultaneously with the monomer. The amount of the polymerization initiator may be in the range of 0.1 to 8 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of the core-forming 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, a core composed of a saccharide mixture-based copolymer and an emulsion containing it can be obtained.
After preparing an aqueous emulsion of a core consisting of a saccharide mixture-based copolymer, a shell is formed on the core. The step of forming the shell on the core may include a step of adding a shell-forming monomer and a polymerization initiator to the emulsion containing the core and performing a polymerization reaction, and may further include a step of further aging. 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. On the other hand, in the step of forming the shell, the polymerization initiator may be added before the addition of the monomer or simultaneously with the monomer, and the amount thereof may be in the range of 0.1 to 8 parts by weight, preferably 0.2 to 5 parts by weight per 100 parts by weight of the shell- . 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 method
(1) Measurement of solid content of emulsion
The solids content of the emulsion was determined using the KS M ISO 3251 test method.
(2) Measurement of viscosity of emulsion
The viscosity of the emulsion was measured at 25 ° C using the KS M ISO 2555 (2009) test method.
(3) Evaluation of adhesion of coating film formed on metal substrate by emulsion
An emulsion was applied on the surface of an aluminum sheet to a thickness of about 100 mu m and dried in an oven at 130 DEG C for about 3 minutes to form a coating film. Thereafter, the adhesive strength between the film and the metal substrate was measured by a "Cross cut" test according to DIN EN ISO 2409, and the results were shown as scores from 0 (worst) to 5 (best).
(4) Evaluation of adhesion between coats formed by emulsion
An emulsion was applied on the surface of an aluminum sheet to a thickness of about 100 mu m and dried in an oven at 130 DEG C for about 3 minutes to form a coating film. Thereafter, the aluminum sheet on which the coated film was formed was cut into a size of 5 cm x 5 cm to prepare 30 sheets. Then, 30 sheets of aluminum sheets were stacked in sequence and stored for 24 hours under a pressure of 250 kgf at a temperature of 50 캜 using a heat press. Then, the case where the aluminum sheets adhered to each other was evaluated as "defective ", and the case where the aluminum sheets were not stuck together was evaluated as" good ".
2. Analysis of components of starch hydrolyzate containing starch hydrolyzate or product containing saccharide mixture
(1) Products containing a mixture of saccharides
Syncsta L20 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company, Korea), Syncsta L21 product (solid content of the saccharide mixture: 35% (HPLC: 1200 series, manufactured by Agilent Co., Ltd.), and the composition of Syncsta L22 (solid content of the saccharide mixture: 35% by weight; supplier: Target Co., Ltd.)) was measured by high performance liquid chromatography Respectively. The separation column used herein was Aminex HPX 42A (manufacturer: Bio-Rad, USA). The composition analysis results of the Syncsta L20 product are shown in the following Table 1, and the results of composition analysis of the Syncsta L21 product are shown in the following Table 2, and the results of composition analysis of the Syncsta L22 product are shown in the following Table 3, The results of the analysis are shown in Table 4 below.
DP2 in the above Tables 1 to 4 is a dissacchride having a degree of polymerization of 2 based on hexose and glucose and DP3 is a trisaccharide having a degree of polymerization of 3 based on hexose, ), DP4 is a tetrasaccharide based on hexose (especially glucose), DP5 is pentasaccharide with a degree of polymerization of 5 based on hexose (especially glucose), DP6 DP7 is a heptasaccharide with a degree of polymerization of 7 based on hexose (especially glucose), DP8 is a hexasaccharide 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 (especially glucose), DP10 + is a hexose (especially glucose) -based polymer having a degree of polymerization of 8, ) Based polysaccharide having a degree of polymerization of 10 or more, The.
As shown in Table 1, in the case of the saccharide mixture constituting the Syncsta L20 product, the content of the DP4 saccharides was about 6.8% by weight, the content of the saccharides having a degree of polymerization of hexose (especially glucose) of 4 or more was about 73.1% . On the other hand, as shown in Table 2, the saccharide mixture constituting Syncsta L21 product contained 0.04% by weight of DP4 saccharides and the content of saccharides having a degree of polymerization of 4 or more based on hexose (especially glucose) was 0.0% . Also, as shown in Table 3, in the case of the saccharide mixture constituting the Syncsta L22 product, the content of the DP4 saccharides was very low as 0.8% by weight, and the content of the saccharides having the degree of polymerization of hexose (especially glucose) Was much lower than the saccharide mixture comprising the Syncsta L20 product in weight percent. Also, as shown in Table 4, in the case of the saccharide mixture constituting the Syncsta L23 product, the content of the DP4 saccharide was very low as 0.8% by weight, and the content of the saccharide having the degree of polymerization of hexose (especially glucose) Was much lower than the saccharide mixture comprising the Syncsta L20 product in weight percent.
(2) Preparation and composition analysis of starch liquefied liquid containing starch hydrolysates
90.6 g of oxidized starch was added to 178.0 g of deionized water and dispersed to prepare a starch suspension. The pH of the starch suspension was adjusted to about 6.0 using a hydrochloric acid aqueous solution having a concentration of 7% by weight. In addition, 1 g of the heat-resistant alpha-amylase (Liquozyme supra, Novozyme, Denmark) was diluted with 99 g of deionized water to prepare a starch hydrolyzate solution. Then, 1.2 g of starch hydrolyzate was added to the starch suspension, and the mixture was reacted at about 95 캜 for about 90 minutes. After the reaction was completed, 0.6 g of hypochlorous acid was added to the reaction product to inactivate the enzyme and cooled to about 80 캜 to obtain a starch liquefied liquid containing the starch lysate. At this time, the dextrose equivalent (DE) value of the starch hydrolyzate was about 27, and the solid content of the starch hydrolyzate was about 35% by weight. Further, the molecular weight distribution of the starch hydrolyzate contained in the starch liquefied liquid was measured by high performance liquid chromatography (HPLC 1200 series, Agilent). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of measurement of the molecular weight distribution of the starch hydrolyzate contained in the starch liquefied liquid by high performance liquid chromatography (HPLC). The weight average molecular weight of the starch hydrolyzate was about 10,540. In FIG. 1, the peak detected when the retention time is about 30 minutes is a tetrasaccharide having a degree of polymerization of 4 based on hexose (especially glucose) based on a standard calibration curve. Also, the peak that is detected for more than about 30 minutes of staying time is a polysaccharide having a degree of polymerization based on hexose (especially glucose) of 5 or more. Therefore, the starch hydrolyzate contained in the starch hydrolyzate was composed of polysaccharide having almost no DP4 saccharide and having a degree of polymerization of 5 or more based on hexose (especially glucose).
3. Sugar mixture based or starch resolvent Preparation of aqueous emulsion containing polymer-based polymer particles
Production Example 1
The reactor was charged with 148 g of Syncsta L20 product (solids content of the mixture of saccharides: 35% by weight; supplier: Target Company, Korea), 6.5 g of an anionic emulsifier (trade name: RHODACAL DS 4; supplier: Solvay USA Inc., US) (Trade name: Disponil A1080; supplier: BASF, DE) and 142.9 g of deionized water were added and filled 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.
Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, and a polymerization initiator solution (a solution in which 1.0 g of potassium persulfate and 0.08 g of sodium persulfate were dissolved in 11.0 g of deionized water) and a core monomer mixture were stirred for 60 minutes Followed by dropwise addition 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 completing the dropwise addition of the polymerization initiator solution and the core monomer mixture, the copolymerization reaction product was stirred at about 80 캜 for about 60 minutes and aged to obtain a core composed of a saccharide mixture-based copolymer and an emulsion containing the same.
2.0 g of an anionic reactive emulsifier (component: 1-allyloxy-3-alkyl phenoxy-2-polyoxyethylene sulfate (trade name: Adeka Reasoap SE-10N; supplier: Asahi Denka Co., Ltd.) 2.0 g of an emulsifier (trade name: Disponil A1080; supplier: BASF, DE) was added and dissolved. Then, 95.0 g of styrene, 105.0 g of methyl methacrylate, 93.0 g of n-butylacrylate, 2.0 g of n-dodecyl mercaptan were slowly added dropwise in order to prepare a pre-emulsion of the shell monomer mixture.
The temperature of the reactor containing the emulsion containing the core was maintained at about 80 DEG C, and the pre-emulsion of the mixture of the polymerization initiator solution (3.5 g of sodium persulfate dissolved in 66.5 g of deionized water) and the shell monomer mixture was stirred for about 120 minutes And the copolymerization reaction was allowed to proceed on the core surface to form a shell. After completing the dropwise addition of the pre-emulsion of the polymerization initiator solution and the shell monomer mixture, the copolymerization reaction product was stirred at about 80 캜 for about 60 minutes and aged to obtain an emulsion containing the core-shell structure saccharide mixture- .
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 added dropwise for 30 minutes and reacted to remove unreacted monomers. After the addition of the oxidizer solution and the reducing agent solution was completed, 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
Except that the Syncsta L21 product (the solid content of the saccharide mixture: 35% by weight; Supplier: Target Company) was used in place of the Syncsta L20 product. A final emulsion containing particles was obtained.
Production Example 3
Except that a Syncsta L22 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company) was used in place of Syncsta L20 product, and a core-shell structure of a saccharide mixture- A final emulsion containing particles was obtained.
Production Example 4
Except that a Syncsta L23 product (solid content of the saccharide mixture: 35% by weight; supplier: Target Company) was used in place of Syncsta L20 product. A final emulsion containing particles was obtained.
Production Example 5
(Solid content of starch hydrolyzate: 35% by weight), 6.5 g of an anionic emulsifier (trade name: RHODACAL DS 4; supplier: Solvay USA Inc., US), 5 g of a nonionic emulsifier : Disponil A 1080; supplier: BASF, DE) and 142.9 g of deionized water were added and filled 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.
Thereafter, the reactor in a nitrogen atmosphere was heated to about 80 DEG C, and a polymerization initiator solution (a solution in which 1.0 g of potassium persulfate and 0.08 g of sodium persulfate were dissolved in 11.0 g of deionized water) and a core monomer mixture were stirred for 60 minutes Followed by dropwise addition 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 completing 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 a core composed of a starch degradation-based copolymer and an emulsion containing the same.
2.0 g of an anionic reactive emulsifier (component: 1-allyloxy-3-alkyl phenoxy-2-polyoxyethylene sulfate (trade name: Adeka Reasoap SE-10N; supplier: Asahi Denka Co., Ltd.) 2.0 g of an emulsifier (trade name: Disponil A1080; supplier: BASF, DE) was added and dissolved. Then, 95.0 g of styrene, 105.0 g of methyl methacrylate, 93.0 g of n-butylacrylate, 2.0 g of n-dodecyl mercaptan were slowly added dropwise in order to prepare a pre-emulsion of the shell monomer mixture.
The temperature of the reactor containing the emulsion containing the core was maintained at about 80 DEG C, and the pre-emulsion of the mixture of the polymerization initiator solution (3.5 g of sodium persulfate dissolved in 66.5 g of deionized water) and the shell monomer mixture was stirred for about 120 minutes And the copolymerization reaction was allowed to proceed on the core surface to form a shell. After the addition of the pre-emulsion of the polymerization initiator solution and the shell monomer mixture is completed, the copolymerization reaction product is agitated at about 80 캜 for about 60 minutes and aged to obtain an emulsion containing the core-shell structure starch hydrolyzate- .
Thereafter, the emulsion containing the starch decomposition-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 added dropwise for 30 minutes and reacted to remove unreacted monomers. After the addition of the oxidizer solution and the reducing agent solution was completed, 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 starch hydrolyzate-based copolymer particles.
4. Sugar mixture based or starch resolvent Based polymer particles Emulsion Property Analysis
A final emulsion comprising the core-shell structure starch degradation-based copolymer particles obtained in Production Examples 1 to 4 or a final emulsion comprising the core-shell structure starch decomposition-based copolymer particles obtained in Production Example 1 The emulsion was evaluated for color, precipitate generation, solid content, viscosity, adhesion of the coating formed on the metal substrate, and adhesion between the coating formed on the metal substrate. The results are shown in Table 5 below.
When the Syncsta L21 product, the Syncsta L22 product, and the Syncsta L23 product were used to form the core as shown in Table 5 above, the resulting final emulsion was in a gel state, making it impossible to uniformly coat the emulsion on the metal substrate . In addition, when the starch-decomposing liquid containing starch hydrolyzate was used to form cores as described above, the adhesion of the coating film formed on the metal substrate was not high, and the coating films formed on the metal substrate stuck to each other.
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 (10)
The saccharide mixture-based polymer particles have a core-shell structure comprising a core formed by polymerization of a saccharide mixture and a core-forming monomer, and a shell formed on the core by polymerization of a shell-
Wherein the saccharide mixture comprises 2-15% by weight of a saccharide having a hexose-based degree of polymerization of 4 and 55-90% by weight of a saccharide having a hexose-based degree of polymerization of 4 or higher based on the total weight of the saccharide mixture,
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,
The hard monomer may be selected from the group consisting of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, At least one member selected from the group consisting of propyl methacrylate, vinyl toluene, vinyl acetate, and vinyl chloride,
The soft monomer may be selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, ethylhexyl methacrylate, lauryl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, And at least one member selected from the group consisting of
The carboxylic acid monomer having an ethylenically unsaturated bond is at least one member selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid,
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 content of the hard monomer in the core-forming monomer is 15 to 40 wt%, the content of the soft monomer is 50 to 80 wt%, the content of the carboxylic acid monomer having the ethylenically unsaturated bond is 2 to 10 wt%
In the shell-forming monomer, the content of the hard monomer is 40 to 70 wt%, the content of the soft monomer is 15 to 35 wt%, the content of the carboxylic acid monomer having an ethylenically unsaturated bond is 10 to 30 wt% Wherein the content of the saccharide-based polymer particles is 0.1 to 2% by weight.
Wherein the saccharide mixture comprises 2-15% by weight of a saccharide having a hexose-based degree of polymerization of 4 and 55-90% by weight of a saccharide having a hexose-based degree of polymerization of 4 or higher based on the total weight of the saccharide mixture,
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,
The hard monomer may be selected from the group consisting of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, At least one member selected from the group consisting of propyl methacrylate, vinyl toluene, vinyl acetate, and vinyl chloride,
The soft monomer may be selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, ethylhexyl methacrylate, lauryl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, And at least one member selected from the group consisting of
The carboxylic acid monomer having an ethylenically unsaturated bond is at least one member selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid,
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 content of the hard monomer in the core-forming monomer is 15 to 40 wt%, the content of the soft monomer is 50 to 80 wt%, the content of the carboxylic acid monomer having the ethylenically unsaturated bond is 2 to 10 wt%
In the shell-forming monomer, the content of the hard monomer is 40 to 70 wt%, the content of the soft monomer is 15 to 35 wt%, the content of the carboxylic acid monomer having an ethylenically unsaturated bond is 10 to 30 wt% Is from 0.1 to 2% by weight based on the weight of the sugar-based polymer particle emulsion.
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| US8013042B2 (en) * | 2003-11-28 | 2011-09-06 | Daicel Chemical Industries, Ltd. | Process of producing a particle having a core-shell structure |
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| US8013042B2 (en) * | 2003-11-28 | 2011-09-06 | Daicel Chemical Industries, Ltd. | Process of producing a particle having a core-shell structure |
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