WO2012002696A2 - Method for preparing adhesive material for aqueous paint - Google Patents

Method for preparing adhesive material for aqueous paint Download PDF

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Publication number
WO2012002696A2
WO2012002696A2 PCT/KR2011/004695 KR2011004695W WO2012002696A2 WO 2012002696 A2 WO2012002696 A2 WO 2012002696A2 KR 2011004695 W KR2011004695 W KR 2011004695W WO 2012002696 A2 WO2012002696 A2 WO 2012002696A2
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WIPO (PCT)
Prior art keywords
monomer
methacrylate
acrylate
starch
methacrylic
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PCT/KR2011/004695
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French (fr)
Korean (ko)
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WO2012002696A3 (en
Inventor
한민
함충현
전영승
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대상 주식회사
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Application filed by 대상 주식회사 filed Critical 대상 주식회사
Priority to CN201180032782.1A priority Critical patent/CN102971387B/en
Priority to JP2013518243A priority patent/JP5733394B2/en
Publication of WO2012002696A2 publication Critical patent/WO2012002696A2/en
Publication of WO2012002696A3 publication Critical patent/WO2012002696A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to a method for producing an adhesive material for an aqueous paint, and more particularly, to include a core-shell copolymer having a core composed of a starch copolymer which is a natural polymer and a double layer of a shell composed of a hydrophobic polymer. It relates to a method for producing an adhesive material for an aqueous paint in the form of an emulsion.
  • the adhesive material for water-based paints obtained according to the production method of the present invention is particularly excellent in water resistance, coating film properties and viscosity properties.
  • the adhesive material for paint which accounts for most of the adhesive material applied to buildings, uses raw materials extracted from petrochemical organic solvents containing heavy metals and TVOCs, which are harmful to the human body. Therefore, eco-friendly adhesive materials and natural adhesive materials are compatible with environmental regulations. Attention is focused. For example, research on the method of reducing the relative amount of solvent used by increasing the solid component ratio in paint (high solidification), and the development of powder coating without using a solvent is being conducted, but there is a limit to fundamentally reducing environmental pollution. It is pointed out that there is.
  • starch has attracted much attention as an environmentally friendly adhesive material due to its good adhesiveness and low price, and excellent heat resistance.
  • starch-copolymers using starch have been used in various fields such as plastic materials, food containers, packaging materials, cushioning sheets, agricultural films, and the like.
  • an environmentally friendly adhesive material in particular, an adhesive material for water-based paints, when starch is used, durability and weather resistance may be deteriorated due to the biodegradable properties of the starch.
  • Japanese Patent Laid-Open No. 2004-224887 discloses a curable starch composition containing a curing agent having an isocyanate functional group which undergoes curing reaction with starch and starch.
  • the said curable starch composition has a problem that water resistance falls because the carboxyl group introduced for the purpose of hydrophilization remains in a coating film.
  • Japanese Patent Laid-Open No. 2004-224887 Japanese Patent Laid-Open No.
  • aqueous coating composition containing a curing agent has been disclosed. However, this is simply a suitable mixture of modified starch and petrochemical acrylic emulsion with a curing agent, which is different from starch-copolymer acrylic emulsion.
  • Japanese Patent Application Laid-Open No. 2001-40267 discloses a composition containing a starch ester, a hydrophobic plasticizer and water having an ester component of 2 to 8 carbon atoms and a degree of substitution of 1.0 to 2.2 as a peeling or moisture proof coating composition.
  • the hydrophobic character of the esterified starch there is a problem in that the water dispersibility of the resulting paint is poor and the film stability is poor at room temperature.
  • Korean Patent Laid-Open No. 10-2009-0061597 discloses 10-170 mgKOH / hydroxyl group obtained by copolymerizing starch and / or modified starch (a), and a polymerizable monomer mixture containing 40 to 95 mass% of aromatic polymerizable unsaturated monomers.
  • the coating composition containing the resin composition (A) obtained by making g hydroxyl-containing acrylic resin (b) and a polyisocyanate compound (c) react is disclosed.
  • the composition of the polyisocyanate compounds such as isophorone diisocyanate is toxic to the human body to check the remaining amount during the reaction from time to time, and also the drying time of the coating film may cause contamination during the drying process.
  • Korean Patent Publication No. 10-2009-0066567 discloses a starch-based coating composition using a resin (A) having a vinyl polymer bonded to starch and / or modified starch by graft polymerization; And a product (B) having an isocyanate group formed by reacting a polyisocyanate compound (b1) with a polyhydric alcohol (b2) to a resin (A) having a vinyl polymer bonded to starch and / or modified starch by graft polymerization.
  • the starch coating composition which uses resin (C) which consists of as a binder was disclosed.
  • an organic solvent such as toluene, xylene, cyclohexane, n-hexane, etc. should be used, so that the environmentally friendly effect is halved, and a toxic polyisocyanate compound should be used.
  • the Republic of Korea Patent Publication No. 10-2010-0029533 is a copolymer of 30 to 90% by weight starch and 70 to 10% by weight monomer, the monomer comprises a vinyl compound and 1,3-butadiene, the monomer 100 Starch copolymers are characterized in that 1,3-butadiene is contained in an amount of less than 10 parts by weight to 10 parts by weight, and the starch copolymer has improved water resistance, It has been disclosed that it can be used in fields such as cardboard adhesive, paper surface sizing agent, environmentally friendly woodworking adhesive. However, since 1,3-butadiene, which is present in the gaseous phase at room temperature, must be used, an expensive high pressure reaction facility is required.
  • a method of preparing an emulsion through copolymerization of acrylic or methacrylic polymer and starch may be considered, but workability is degraded due to high viscosity of starch, and existing synthetic acrylic emulsion Compared to the weak adhesive strength, in particular, problems such as weakening of water resistance due to the hydrophilic characteristics of the starch is still a problem to be solved.
  • the present invention is not only environmentally friendly, but also provides a method for producing an adhesive material for an aqueous paint having excellent adhesion, film stability and stable dispersion in aqueous solution, especially water resistance.
  • the present invention provides a method for preparing an adhesive material for an aqueous coating of an emulsion type containing a starch core and a copolymer having a core-shell structure having a double layer of hydrophobic enhanced shell.
  • an object of the present invention is to provide a method for producing an adhesive material for an aqueous paint of an emulsion type containing a copolymer having a core-shell structure excellent in water resistance and coating film formation.
  • an acrylic or methacrylic monomer hereinafter referred to as 'first monomer'
  • a polymerization initiator is added to an aqueous starch gelatin solution and polymerized to form a core copolymerized with starch and monomer.
  • step (b) at least one monomer selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene in the reaction obtained in step (a) (hereinafter referred to as 'second monomer') And adding a polymerization initiator to polymerize to form an emulsion containing a copolymer of a core-shell structure formed by polymerization of a second monomer on the core, thereby providing an adhesive material for an aqueous coating material.
  • the first monomer is acrylic acid, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl meth 1 type from the group consisting of acrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, and N-methylol acrylamide Functional acrylic or methacrylic monomer selected above; Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate , Lauryl methacrylate, cyclohexy
  • the mixing ratio (weight ratio) of the functional acrylic or methacrylic monomer and the non-functional acrylic or methacrylic monomer may be in the range of 1: 3 to 30, wherein the functional acrylic or methacrylic monomer is methacrylic acid ;
  • the nonfunctional acrylic or methacrylic monomer may be methyl methacrylate, n-butyl acrylate, or a mixture thereof.
  • the amount of the first monomer may be in the range of 0.3 to 3.0 parts by weight based on 1 part by weight of the starch.
  • step (a) may be preferably carried out in the presence of a phosphate ester emulsifier or a sulfate ester emulsifier
  • the emulsifier is ammonium salts of nonylpropenylethoxyether sulfate, polyoxyethylene alkylphenyl allyl It can be selected from the group consisting of esters of sodium sulfate, sulfonic acid esters of polyoxyethylene allyl glycidyl nonyl phenyl ether, and ammonium salts of sulfonic acid ester of polyoxyethylene nonyl propenyl ether.
  • step (a) may be carried out in the presence of a nonionic emulsifier containing ethylene oxide or polypropylene oxide units, the nonionic emulsifier is polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene ste It may be selected from the group consisting of aryl amines, polyethylene sorbitan, and alkylpolyoxyethylene-propylene copolymers.
  • the second monomer may be at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, styrene, and 2-ethylhexyl methacrylate, preferably the second monomer is methyl methacrylate. , a mixture of n-butyl acrylate, and styrene; Or a mixture of methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl methacrylate.
  • the amount of the second monomer may be in the range of 1.0 to 9.0 parts by weight based on 1 part by weight of the first monomer.
  • an adhesive material for water-based coatings having excellent adhesion, coating film stability and stable dispersion in aqueous solution, especially water resistance. That is, since the manufacturing method of the present invention does not use a petrochemical organic solvent, it is possible to fundamentally block the release of volatile organic compounds (TVOC) released from various chemical adhesives, especially by using starch as an aqueous paint adhesive material. Problems such as water resistance and coating film formation problems, workability due to high viscosity phenomenon, the adhesion can be effectively solved.
  • TVOC volatile organic compounds
  • the present invention comprises the steps of: (a) adding an acrylic or methacryl-based monomer (hereinafter referred to as 'first monomer') and a polymerization initiator to the aqueous starch gelatinization solution to form a core copolymerized starch and monomer; And (b) at least one monomer selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene in the reaction obtained in step (a) (hereinafter referred to as 'second monomer') And adding a polymerization initiator to polymerize to form an emulsion containing a copolymer of a core-shell structure formed by polymerization of a second monomer on the core, thereby providing an adhesive material for an aqueous coating material.
  • 'first monomer' an acrylic or methacryl-based monomer
  • a polymerization initiator to polymerize to form an emulsion containing a copo
  • the 'starch' includes all types of starch including natural starch derived from conventional plants, physical or chemical modified starch and the like.
  • the natural starch may include corn, waxy corn, potato, sweet potato, wheat, rice, tapioca, sago, waxy maize, sorghum, etc. ), And the starch may be obtained from the above-ground part of the plant, underground part, and the like.
  • the modified starch includes starch in which the unmodified starch is modified by a method such as etherification, esterification, oxidation, acid treatment, oxidative esterification, oxidative etherification, and enzyme treatment.
  • the said starch can also use the unmodified starch and the modified starch individually or in mixture of 2 or more types.
  • the 'aqueous starch liquor' is added to the starch in an aqueous medium (e.g., conventional water, purified water, or deionized water (i.e. ion-exchanged water)), and a conventional gelatinization method, for example starch degrading enzyme
  • an aqueous medium e.g., conventional water, purified water, or deionized water (i.e. ion-exchanged water)
  • a conventional gelatinization method for example starch degrading enzyme
  • starch degrading enzyme for example starch degrading enzyme
  • the aqueous starch gelatinized liquid can be obtained by an intermittent method.
  • starch decomposition may be performed by reacting at 20 to 150 ° C, preferably 50 to 120 ° C, for 30 to 300 minutes, preferably 60 to 200 minutes.
  • the starch degrading enzymes include alpha-amylase, beta-amylase, gluco-amylase, iso-amylase, and the like, and preferably, mesophilic alpha-amylase or heat-resistant alpha-amylase may be used.
  • the starch degrading enzyme is commercially available.
  • Part, preferably, may be in the range of 0.01 to 8 parts by weight, but is not particularly limited.
  • the "aqueous starch gelatinized liquid" can also be obtained dextrin as raw materials. If dextrin is used, it does not require the use of starch degrading enzymes. In the case of using dextrin as a raw material, the 'aqueous starch gelatinized liquid' can proceed at atmospheric pressure, for example, and usually 20 to 150 ° C, preferably 50 to 120 ° C, 30 to 300 minutes, preferably 60 to This can be done by reacting for 200 minutes.
  • gelatinized starch ie, an aqueous starch gelatinized liquid
  • the obtained gelatinized starch can be used directly in the subsequent copolymerization reaction by cooling to 70 to 90 ° C if necessary.
  • step (a) a mixture of a functional acrylic or methacrylic monomer with a non-functional acrylic or methacrylic monomer may be preferably used.
  • the functional acrylic or methacrylic monomers are acrylic acid, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl meta Acrylate, t-butylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate (2 -hydroxypropyl acrylate), acrylamide, and N-methylol acrylamide (N-methylol acrylamide) may be selected from one or more kinds, preferably methacrylic acid may be used.
  • non-functional acrylic or methacrylate monomers are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2 Ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acryl It may be selected from one group from the group consisting of latex, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, and cyclohexyl acrylate, preferably Methyl methacrylate, n-butyl acrylate, or mixture
  • the mixing ratio (weight ratio) of the functional acrylic or methacrylic monomer and the nonfunctional acrylic or methacrylic monomer may be in the range of 1: 3 to 30, preferably in the range of 1: 5 to 20.
  • the content of the functional acrylic or methacrylic monomers is too small, cracking of the coating film formed by the paint adhesive may occur, and when too much, the copolymer is not sufficiently formed, resulting in polymerization with the second monomer. This can be difficult.
  • the first monomer may be a mixture of 1: 4: 4 (weight ratio) of methacrylic acid, methyl methacrylate, and n-butyl acrylate.
  • the amount of the first monomer may be in the range of 0.3 to 3.0 parts by weight based on 1 part by weight of the starch (ie, gelatinized starch). If the amount of the first monomer is less than 0.3 parts by weight, the viscosity may be too high, and subsequent polymerization with the second monomer may be difficult. If it exceeds 3.0 parts by weight, it may be difficult to form a copolymer of the starch and the first monomer. .
  • the polymerization initiator used in step (a) may use a thermal dissociation initiator or an oxidation-reduction initiator capable of radical polymerization, for example sodium persulfate, potassium persulfate, t-butyl hydroperoxide, 2,2-azo Bisbutyronitrile, 2,2'-azobis-2-methylbutyronitrile, cumene hydroperoxide, etc. can be used, Preferably it is water-soluble, such as sodium persulfate, potassium persulfate, t-butyl hydroperoxide, etc. Initiators can be used. If necessary, reducing agents such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite, and the like may be added.
  • reducing agents such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite, and the like may be added.
  • the polymerization initiator may be added before 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 based on 100 parts by weight of the monomer (ie, the first monomer). have.
  • the content of the polymerization initiator is less than 0.1 parts by weight, the time required for polymerization may be increased, and when it exceeds 8 parts by weight, browning of the obtained starch-copolymer emulsion may be caused and discolored.
  • step (a) ie the polymerization of starch and the first monomer, may be carried out at a temperature of 60 to 100 ° C., preferably 70 to 90 ° C .; And from 0.01 to 10 bar, preferably from 0.1 to 5 bar. In addition, the polymerization may be carried out for 10 to 60 minutes, preferably 20 to 50 minutes. After the completion of the polymerization reaction, the obtained reactant is preferably carried out for 10 minutes to 120 minutes, preferably 20 minutes to 80 minutes, while maintaining the above temperature under nitrogen filling conditions and aging. By the aging step, the unreacted monomer can be minimized and sufficient polymerization can be achieved.
  • the reactant obtained in step (a) can be adjusted to a temperature in the range from 70 to 90 ° C., to carry out the polymerization of the subsequent second monomer.
  • the polymerization may be preferably carried out in the presence of a phosphate ester emulsifier or a sulfate ester emulsifier and / or a nonionic emulsifier containing ethylene oxide or polypropylene oxide units, that is, through emulsion polymerization.
  • the kind of the phosphate ester emulsifier or the sulfate ester emulsifier is not particularly limited, and a reactive emulsifier commonly used in emulsion polymerization may be used.
  • Representative examples include ammonium salts of nonylpropenylethoxyether sulfate (eg, Aquaron HS-10 (DKS, Japan), SE-10 (Adeca, Japan), etc.), polyoxyethylene alkylphenyl allyl sodium sulfate Esters (e.g., HA-100 (Hanseong, Korea), etc.), sulfonic acid esters of polyoxyethylene allyl glycidyl nonyl phenyl ether (e.g., SETM (adeka, Japan), etc.), poly Ammonium salts of sulfonic acid esters of oxyethylene nonyl propenyl ethers (e.g., HITENOL HSTM (DKS, Japan, etc.)).
  • the amount of the reactive emulsifier may be used in the range of 0.4 to 3.2 parts by weight, more preferably 1.2 to 2.4 parts by weight based on 100 parts by weight of the first monomer, but is not particularly limited.
  • the type of the nonionic emulsifier containing the ethylene oxide or polypropylene oxide unit is not particularly limited, and nonionic emulsifiers commonly used in emulsion polymerization may be used.
  • Representative examples include polyoxyethylene polyoxypropylene alkyl ethers (eg, FN-8 (Hanungseong, Korea), etc.), polyoxyethylene stearyl amines (eg, SN-2 (Hanongseong, Korea), etc. ), Polyethylene sorbitan (for example, SFT-10 (Hanongseong, Korea), etc.), alkyl polyoxyethylene-propylene copolymers (for example, MONOPOL PE etc.) can be mentioned.
  • the polymerization is carried out in the presence of the nonionic emulsifier, it is possible to control the particle size of the core obtained in an appropriate range (for example, 50nm to 300nm).
  • the nonionic emulsifier may be used in the range of 0.1 to 0.8 parts by weight based on 100 parts by weight of the first monomer.
  • the second monomer may be at least one selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene, specifically methyl methacrylate, ethyl Methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate , Cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, iso Can be selected from the group consisting of carbonyl acrylate,
  • the second monomer may be a mixture of methyl methacrylate, n-butyl acrylate, and styrene. In another embodiment, the second monomer may be a mixture of methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl methacrylate.
  • the amount of the second monomer may be in the range of 1.0 to 9.0 parts by weight, preferably 1.5 to 5.0 parts by weight based on 1 part by weight of the first monomer (total monomers in the case of a mixture of monomers).
  • the amount of the second monomer is less than 1.0 parts by weight, the particle size may be huge and may not be suitable as an adhesive material for coating.
  • the amount of the second monomer is greater than 9.0 parts by weight, the starch use effect may be weak and environmentally friendly properties may be reduced.
  • a chain transfer agent may be added to the second monomer to perform a polymerization reaction.
  • the chain transfer agent may use n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, C 1 -C 5 alcohol, or a mixture thereof.
  • step (b) The type and amount of the polymerization initiator and optionally the reducing agent used in step (b) may be appropriately selected within the range of the type and amount of the polymerization initiator described in connection with step (a).
  • the secondary polymerization reaction by the second monomer is a temperature of 60 to 100 °C, preferably 70 to 90 °C; And from 0.01 to 10 bar, preferably from 0.1 to 5 bar.
  • the polymerization may be performed for 60 minutes to 600 minutes, preferably 120 minutes to 480 minutes.
  • the obtained reactant is preferably carried out for 10 minutes to 120 minutes, preferably 20 minutes to 80 minutes, while maintaining the above temperature under nitrogen filling conditions and aging. The aging process can minimize the unreacted monomer.
  • step (b) when the second polymerization reaction is performed by the second monomer, a copolymer of starch and the first monomer, that is, the second monomer is polymerized on the core to form a shell, and thus a copolymer having a core-shell structure An emulsion containing is formed.
  • the reactant obtained in step (b) may be adjusted to a temperature in the range from 40 to 65 ° C., to carry out a conventional post treatment process.
  • the post-treatment process includes a conventional unreacted monomer removal process, for example, a chemical method, a wet removal method, or a hot steam method.
  • the unreacted monomer removal process may use a chemical method using an oxidizing agent and a reducing agent.
  • the oxidizing agent may be used t-butyl hydroperoxide (t-butyl hydroperoxide), cumenehydroperoxide (cumenehydroperoxide) and the like
  • the reducing agent is sodium hydrosulfite (sodium hydrosulfite), sodium metabisulfite (sodium metabisulfite) ) Can be used.
  • the amount of the oxidizing agent and the reducing agent may be in the range of 0.001 to 1 part by weight, preferably 0.002 to 0.8 part by weight based on 100 parts by weight of the obtained emulsion, and the post-treatment process using the oxidant and the reducing agent is 10 to 300 minutes, preferably Can be carried out for 20 to 250 minutes.
  • the post-treatment process using the oxidant and the reducing agent is 10 to 300 minutes, preferably Can be carried out for 20 to 250 minutes.
  • at a temperature of 40 to 60 °C, preferably 50 to 60 °C, 10 to 120 minutes, preferably 30 to 90 minutes maintaining the temperature under nitrogen filling conditions while carrying out the process of aging You may.
  • the product obtained as described above is an emulsion containing a copolymer of a core-shell structure, and if necessary, additives such as an antifoaming agent and a thickener commonly used in the paint field may be further added.
  • the emulsion obtained according to the production method of the present invention can be usefully used as an adhesive material for water-based paints, for example, can be used as an aqueous paint by mixing with pigments, other paint additives and the like.
  • aqueous starch liquor obtained in the above (1) 6.4 g of a reactive emulsifier (HA-100, Hannong, Korea), 1.6g of a nonionic emulsifier (FN-8, Hannong, Korea), and 147.7g of ion-exchanged water were added thereto.
  • the reactor was filled with nitrogen. Under nitrogen atmosphere, a solution of 0.5 g of potassium persulfate and 0.03 g of sodium bisulfite was dissolved in 9.0 g of ion-exchanged water, 20.0 g of methyl methacrylate, 5.0 g of methyl methacrylic acid, and 20.0 g of n-butyl acrylate.
  • the copolymerization reaction was carried out by dropwise addition of the monomer mixture at 80 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was aged by stirring at 80 ° C. for 1 hour to obtain an emulsion containing a starch-first monomer copolymer.
  • the emulsion obtained in (3) was cooled to 55 ° C, a solution obtained by dissolving 0.9 g of t-butyl hydroperoxide in 16 g of ion-exchanged water and 0.6 g of sodium hydrosulfite in 8.0 g of ion-exchanged water. The solution was added dropwise for 30 minutes. The reaction was aged at 55 ° C. for 30 minutes and then cooled to room temperature to prepare an adhesive material for an aqueous paint in emulsion form. As a result of measuring the solids content of the prepared emulsion, the solids content was about 50% by weight.
  • Example 1 (2) Except for using SRg (Adeka, Japan) 6.5g as a reactive emulsifier in Example 1 (2) was prepared in the same manner as in Example 1 to prepare an adhesive coating material for water-based emulsion.
  • Example 3 (3) a monomer mixture of 132.4 g of methyl methacrylate, 102.6 g of n-butyl acrylate, and 40.0 g of 2-ethylhexyl methacrylate was used as the second monomer.
  • an adhesive material for an aqueous paint in emulsion form was prepared.
  • a copolymer emulsion of a single structure was prepared by one polymerization. That is, 6.4 g of reactive emulsifier (HA-100, Hannong-Sung, Korea), 1.6g of nonionic emulsifier (FN-8, Hannong-Sung, Korea) to the aqueous starch gelatinized liquid obtained in Example 1 (1), and ion exchange Water 147.7g was added and nitrogen was charged to the reactor.
  • reactive emulsifier HA-100, Hannong-Sung, Korea
  • FN-8 nonionic emulsifier
  • a monomer mixture of a solution of 0.5 g of potassium persulfate dissolved in 9.0 g of ion-exchanged water and a monomer mixture of 117.7 g of methyl methacrylate, 157.2 g of n-butyl acrylate, and 40.0 g of styrene was prepared at 80 ° C.
  • the copolymerization reaction was carried out by dropwise addition for 30 minutes. After completion of the dropwise addition, the mixture was aged by stirring at 80 ° C. for 1 hour to obtain an emulsion containing a starch-monomer copolymer.
  • Example 1 The physical properties of the emulsions obtained in Example 1 and Comparative Example 1 were evaluated.
  • Non-volatile content, viscosity, Tg, coating state, adhesion, drying time, water resistance as an evaluation property items were measured as follows according to the KS certification test method, the results are shown in Table 1 below.
  • the emulsions obtained according to the present invention are particularly excellent in water resistance and viscosity, and also suitable in adhesion (i.e. adhesion).
  • adhesion i.e. adhesion
  • the viscosity is greatly increased, which is not suitable as an adhesive material for water-based coatings, but also in the state of coating and water resistance. It was inappropriate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The present invention provides a method for preparing an emulsion type adhesive material for an aqueous paint, containing a core-shell structured copolymer having a dual layer with a core comprising a starch-based copolymer, a natural polymer, and a shell comprising a hydrophobic polymer. The adhesive material for an aqueous pain obtained through the preparation method of the present invention has particularly excellent water-resisting qualities, film characteristics, and viscosity characteristics.

Description

수성 도료용 접착 소재의 제조방법Manufacturing method of adhesive material for waterborne paint
본 발명은 수성 도료용 접착 소재의 제조방법에 관한 것으로, 더욱 상세하게는, 천연 고분자인 전분계 공중합체로 구성된 코어 및 소수성 고분자로 이루어진 쉘의 이중층을 갖는, 코어-쉘 구조의 공중합체를 함유하는 에멀젼 형태의 수성 도료용 접착 소재의 제조방법에 관한 것이다. 본 발명의 제조방법에 따라 얻어진 수성 도료용 접착 소재는 내수성, 도막특성 및 점도 특성이 특히 우수하다.The present invention relates to a method for producing an adhesive material for an aqueous paint, and more particularly, to include a core-shell copolymer having a core composed of a starch copolymer which is a natural polymer and a double layer of a shell composed of a hydrophobic polymer. It relates to a method for producing an adhesive material for an aqueous paint in the form of an emulsion. The adhesive material for water-based paints obtained according to the production method of the present invention is particularly excellent in water resistance, coating film properties and viscosity properties.
현대인들이 하루의 80% 이상을 실내에서 생활하고 있음을 고려할 때 쾌적하고 건강한 실내공기질의 확보는 매우 중요하다. 현재 우리가 살고 있는 일반적인 공동주택은 에너지 절약과 단열강화에 따른 환기부족으로 실내 공기관리 여건은 점점 더 악화되고 있고, 특히 신축 건물에서 인체에 해로운 화학물질이 많이 나와 입주자가 피부염이나 두통, 신경성 질병 등 각종 질환에 시달리는 새집 증후군이 사회적 이슈가 되고 있다. 새집증후군은 건축내장재에 사용되는 각종 화학접착제에 포함된 휘발성 유기화합물(TVOC, Total Volatile Organic Compounds) 및 포름알데히드가 실내공간에서 방출되면서 발생된다. 따라서 접착제에 대한 환경규제가 점점 더 강화되고 있으며 이에 기존의 석유화학 소재를 대체하는 친환경 접착소재 및 천연 원료를 활용한 접착소재에 대한 관심이 급증하고 있다. Considering that modern people live more than 80% of the day indoors, securing a pleasant and healthy indoor air quality is very important. Currently, the common apartments we live in are lacking in ventilation due to energy savings and thermal insulation, and the indoor air management conditions are getting worse.In particular, new buildings have a lot of harmful chemicals. New house syndrome, suffering from various diseases, is becoming a social issue. Sick house syndrome is caused by the release of volatile organic compounds (TVOC) and formaldehyde from various chemical adhesives used in building interior materials. Therefore, environmental regulations for adhesives are increasingly strengthened, and interest in environmentally friendly adhesive materials and natural adhesives using natural materials is rapidly increasing.
건축물에 적용되는 접착소재의 대부분을 차지하는 도료용 접착소재는 인체에 유해한 중금속 성분과 TVOC를 다량 함유한 석유화학계 유기용매에서 추출한 원료를 사용하므로 환경규제에 대응가능한 친환경 접착소재 및 천연 접착소재에 대한 관심이 집중되고 있다. 예를 들어, 도료 중의 고형 성분비를 높여 상대적인 용제 사용량을 감소시키는 방법(하이솔리드화), 및 용제를 사용하지 않는 분체도료의 개발 등에 대한 연구가 진행되고 있으나, 환경오염을 근본적으로 감소시키기에는 한계가 있는 것으로 지적되고 있다.The adhesive material for paint, which accounts for most of the adhesive material applied to buildings, uses raw materials extracted from petrochemical organic solvents containing heavy metals and TVOCs, which are harmful to the human body. Therefore, eco-friendly adhesive materials and natural adhesive materials are compatible with environmental regulations. Attention is focused. For example, research on the method of reducing the relative amount of solvent used by increasing the solid component ratio in paint (high solidification), and the development of powder coating without using a solvent is being conducted, but there is a limit to fundamentally reducing environmental pollution. It is pointed out that there is.
환경친화형 도료를 개발하기 위한 시도로서, 기존의 석유화학 유기용매를 수성 용매로 대체시킨 아크릴 에멀젼 기술을 적용한 친환경 접착소재가 개발되고 있다. 예를 들어, 대한민국 특허공개 제10-2006-0076234호 및 제10-2006-0072480호, 대한민국 특허등록 제591,801호 및 제584,285호는 아크릴 에멀젼 기술을 활용한 친환경 도료용 접착소재를 개시한 바 있다. 그러나, 여전히 용매는 수성화 되었어도 일부 석유화학 유기용매를 사용하고 있으므로, 여전히 만족스러운 수준에는 미치지 못하고 있다.In an attempt to develop environmentally friendly paints, eco-friendly adhesive materials using acrylic emulsion technology, which replaces conventional petrochemical organic solvents with aqueous solvents, have been developed. For example, Korean Patent Laid-Open Publication Nos. 10-2006-0076234 and 10-2006-0072480, and Korean Patent Registration Nos. 591,801 and 584,285 have disclosed adhesive materials for environmentally friendly paints using acrylic emulsion technology. . However, even though the solvent is aqueous, some petrochemical organic solvents are used, and still are not satisfactory.
한편, 천연 원료를 활용한 접착소재에 대한 연구가 이루어지고 있으며, 이 중 전분은 접착성이 좋고 가격이 저렴하며, 열에 대한 저항성이 뛰어나 친환경 접착소재로 많은 주목을 받고 있다. 또한 전분의 친환경 특성에 주목하여 전분을 활용한 전분-공중합체를 플라스틱 소재, 식품용기, 포장재, 완충재 시트, 농업용 필름 등 폭넓은 분야에서 활용하고 있다. 그러나, 친환경 접착소재, 특히 수성 도료용 접착소재로서, 전분을 사용할 경우 전분의 생분해성 특성으로 인해 내구성 및 내후성 저하 문제가 발생할 수 있다.On the other hand, research on adhesive materials using natural raw materials is being made, and among these, starch has attracted much attention as an environmentally friendly adhesive material due to its good adhesiveness and low price, and excellent heat resistance. In addition, starch-copolymers using starch have been used in various fields such as plastic materials, food containers, packaging materials, cushioning sheets, agricultural films, and the like. However, as an environmentally friendly adhesive material, in particular, an adhesive material for water-based paints, when starch is used, durability and weather resistance may be deteriorated due to the biodegradable properties of the starch.
도료로서 전분을 사용하는데 따른 문제점을 해결하기 위하여, 일본 특허공개 제2004-224887호는 전분과 전분의 수산기와 경화반응을 하는 이소시아네이트 관능기를 갖는 경화제를 함유한 경화형 전분 조성물을 개시한 바 있다. 그러나, 상기 경화형 전분 조성물은 친수화의 목적으로 도입된 카르복실기가 도막중에 잔존함으로써, 내수성이 저하되는 문제가 있다. 또한, 일본 특허공개 제2004-224887호에 따른 경화형 전분 조성물의 단점을 해결하기 위하여, 일본 특허공개 제2010-53281호는 카르복실기 함유 수성 수지, 카르복실기 함유 변성 전분, 및 카르복실기와 경화반응하는 관능기를 갖는 경화제를 함유하는 수성 도료 조성물을 개시한 바 있다. 그러나, 이는 단순히 변성 전분과 석유화학계 아크릴 에멀젼을 경화제와 적절히 혼합한 것으로, 전분-공중합체 아크릴 에멀젼와는 상이하다. 기타, 일본 특허공개 제2001-40267호는 박리 또는 방습 도료 조성물로서, 2∼8개의 탄소원자의 에스테르 성분 및 1.0∼2.2의 치환도를 갖는 전분에스테르, 소수성 가소제 및 물을 함유한 조성물을 개시한 바 있으나, 에스테르화 전분의 소수성 특징 때문에 생성된 도료의 물 분산도가 떨어지고 상온에서 도막안정성이 떨어지는 문제가 있다.In order to solve the problem of using starch as a coating, Japanese Patent Laid-Open No. 2004-224887 discloses a curable starch composition containing a curing agent having an isocyanate functional group which undergoes curing reaction with starch and starch. However, the said curable starch composition has a problem that water resistance falls because the carboxyl group introduced for the purpose of hydrophilization remains in a coating film. In addition, in order to solve the shortcomings of the curable starch composition according to Japanese Patent Laid-Open No. 2004-224887, Japanese Patent Laid-Open No. 2010-53281 has a carboxyl group-containing aqueous resin, a carboxyl group-containing modified starch, and a carboxyl group-functional group An aqueous coating composition containing a curing agent has been disclosed. However, this is simply a suitable mixture of modified starch and petrochemical acrylic emulsion with a curing agent, which is different from starch-copolymer acrylic emulsion. In addition, Japanese Patent Application Laid-Open No. 2001-40267 discloses a composition containing a starch ester, a hydrophobic plasticizer and water having an ester component of 2 to 8 carbon atoms and a degree of substitution of 1.0 to 2.2 as a peeling or moisture proof coating composition. However, due to the hydrophobic character of the esterified starch, there is a problem in that the water dispersibility of the resulting paint is poor and the film stability is poor at room temperature.
대한민국 특허 공개 제10-2009-0061597호는 전분 및/또는 변성 전분 (a), 방향족계 중합성 불포화 단량체를 40 내지 95 질량％ 함유하는 중합성 단량체 혼합물을 공중합함으로써 얻어지는 수산기가 10 내지 170 mgKOH/g의 수산기 함유 아크릴 수지 (b), 및 폴리이소시아네이트 화합물 (c)를 반응시켜 얻어지는 수지 조성물 (A)를 함유하는 도료 조성물을 개시한 바 있다. 그러나, 상기 조성물은 이소포론디이소시아네이트 등의 폴리이소시아네이트 화합물이 인체에 유독하여 반응 중 잔존량을 수시로 확인하여야 하며, 또한 도막의 건조 시간이 길어 건조과정에서 오염이 발생할 수 있다. Korean Patent Laid-Open No. 10-2009-0061597 discloses 10-170 mgKOH / hydroxyl group obtained by copolymerizing starch and / or modified starch (a), and a polymerizable monomer mixture containing 40 to 95 mass% of aromatic polymerizable unsaturated monomers. The coating composition containing the resin composition (A) obtained by making g hydroxyl-containing acrylic resin (b) and a polyisocyanate compound (c) react is disclosed. However, the composition of the polyisocyanate compounds such as isophorone diisocyanate is toxic to the human body to check the remaining amount during the reaction from time to time, and also the drying time of the coating film may cause contamination during the drying process.
또한, 대한민국 특허공개 제10-2009-0066567호는 전분 및/또는 변성전분에 그래프트 중합에 의해 비닐폴리머를 결합시킨 수지(A)를 바인더로서 사용하는 전분계 도료조성물; 및 전분 및/또는 변성전분에 그래프트 중합에 의해 비닐폴리머를 결합시킨 수지(A)에, 폴리이소시아네이트 화합물(b1)과 다가 알코올(b2)을 반응시켜 이루어지는 이소시아네이트기를 가지는 생성물(B)을 부가반응시켜 이루어지는 수지(C)를 바인더로서 사용하는 전분계 도료조성물을 개시한 바 있다. 그러나, 상기 그래프트 중합을 수행하기 위해서는 톨루엔, 크실렌, 시클로헥산, n-헥산 등의 유기용매를 사용하여야 하므로, 친환경적인 효과가 반감되며, 또한, 유독성의 폴리이소시아네이트 화합물을 사용하여야 한다는 단점이 있다. In addition, Korean Patent Publication No. 10-2009-0066567 discloses a starch-based coating composition using a resin (A) having a vinyl polymer bonded to starch and / or modified starch by graft polymerization; And a product (B) having an isocyanate group formed by reacting a polyisocyanate compound (b1) with a polyhydric alcohol (b2) to a resin (A) having a vinyl polymer bonded to starch and / or modified starch by graft polymerization. The starch coating composition which uses resin (C) which consists of as a binder was disclosed. However, in order to perform the graft polymerization, an organic solvent such as toluene, xylene, cyclohexane, n-hexane, etc. should be used, so that the environmentally friendly effect is halved, and a toxic polyisocyanate compound should be used.
최근, 대한민국 특허공개 제10-2010-0029533호는 전분 30 내지 90 중량% 및 단량체 70 내지 10 중량%의 공중합체로서, 상기 단량체는 비닐계 화합물 및 1,3-부타디엔을 포함하며, 상기 단량체 100 중량부에 대하여 1,3-부타디엔이 1 중량부에서 10 중량부 미만의 비율로 함유된 것을 특징으로 하는 전분 공중합체를 개시한 바 있으며, 상기 전분 공중합체는 내수성이 개선됨으로써 종이 코팅 바인더뿐만 아니라 골판지 접착제, 종이 표면 사이징제, 친환경 목공 접착제 등의 분야에서 사용될 수 있음을 개시한 바 있다. 그러나, 상온에서 기체상으로 존재하는 1,3-부타디엔을 사용하여야 하기 때문에 고가의 고압 반응 설비가 요구되는 단점이 있다.Recently, the Republic of Korea Patent Publication No. 10-2010-0029533 is a copolymer of 30 to 90% by weight starch and 70 to 10% by weight monomer, the monomer comprises a vinyl compound and 1,3-butadiene, the monomer 100 Starch copolymers are characterized in that 1,3-butadiene is contained in an amount of less than 10 parts by weight to 10 parts by weight, and the starch copolymer has improved water resistance, It has been disclosed that it can be used in fields such as cardboard adhesive, paper surface sizing agent, environmentally friendly woodworking adhesive. However, since 1,3-butadiene, which is present in the gaseous phase at room temperature, must be used, an expensive high pressure reaction facility is required.
전분의 내구성 및 내후성 저하의 문제를 해결하기 위하여, 아크릴계 혹은 메타크릴계 고분자와 전분의 공중합을 통하여 에멀젼으로 제조하는 방법을 고려할 수 있으나, 전분의 고점도 현상으로 인하여 작업성의 저하되고, 기존 합성 아크릴 에멀젼에 비해 접착력이 약하고, 특히 전분의 친수성 특징으로 인한 내수성 약화 등의 문제는 여전히 해결해야 될 숙제이다.In order to solve the problem of deterioration of durability and weather resistance of starch, a method of preparing an emulsion through copolymerization of acrylic or methacrylic polymer and starch may be considered, but workability is degraded due to high viscosity of starch, and existing synthetic acrylic emulsion Compared to the weak adhesive strength, in particular, problems such as weakening of water resistance due to the hydrophilic characteristics of the starch is still a problem to be solved.
따라서, 친환경의 수성 도료용 접착 소재로서, 접착력, 도막 안정성 및 수용액상에서 안정적인 분산도, 특히 내수성이 우수한 수성 도료용 접착 소재를 개발하는 것이 당업계에 요구되고 있다.Accordingly, there is a need in the art to develop an adhesive material for an aqueous coating material which is excellent in adhesion strength, coating film stability, and stable dispersion in aqueous solution, particularly water resistance, as an environmentally friendly adhesive material for an aqueous coating material.
본 발명은 친환경적일 뿐만 아니라, 접착력, 도막 안정성 및 수용액상에서 안정적인 분산도, 특히 내수성이 우수한 수성 도료용 접착 소재의 제조방법을 제공한다. 특히, 본 발명은 전분계 코어 및 소수성이 강화된 쉘의 이중층을 갖는 코어-쉘 구조를 갖는 공중합체를 함유한 에멀젼 형태의 수성 도료용 접착 소재의 제조방법을 제공한다.The present invention is not only environmentally friendly, but also provides a method for producing an adhesive material for an aqueous paint having excellent adhesion, film stability and stable dispersion in aqueous solution, especially water resistance. In particular, the present invention provides a method for preparing an adhesive material for an aqueous coating of an emulsion type containing a starch core and a copolymer having a core-shell structure having a double layer of hydrophobic enhanced shell.
따라서, 본 발명은 내수성 및 도막형성이 우수한, 코어-쉘 구조를 갖는 공중합체를 함유한 에멀젼 형태의 수성 도료용 접착 소재의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a method for producing an adhesive material for an aqueous paint of an emulsion type containing a copolymer having a core-shell structure excellent in water resistance and coating film formation.
본 발명의 일 태양에 따라, (a) 수성 전분 호화액에 아크릴계 또는 메타크릴계 단량체(이하, '제1 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 전분과 단량체가 공중합된 코어를 형성시키는 단계; 및 (b) 단계(a)에서 얻어진 반응물에 스티렌, 프로필렌, 아크릴산 에스테르, 메타크릴산 에스테르, 아크릴로니트릴, 및 에틸렌으로 이루어진 군으로부터 1종 이상 선택된 단량체(이하, '제2 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 상기 코어 상에 제2 단량체가 중합되어 형성된 코어-쉘 구조의 공중합체를 함유한 에멀젼을 형성시키는 단계를 포함하는, 수성 도료용 접착 소재의 제조방법이 제공된다.According to one aspect of the present invention, (a) an acrylic or methacrylic monomer (hereinafter referred to as 'first monomer') and a polymerization initiator are added to an aqueous starch gelatin solution and polymerized to form a core copolymerized with starch and monomer. Making a step; And (b) at least one monomer selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene in the reaction obtained in step (a) (hereinafter referred to as 'second monomer') And adding a polymerization initiator to polymerize to form an emulsion containing a copolymer of a core-shell structure formed by polymerization of a second monomer on the core, thereby providing an adhesive material for an aqueous coating material.
본 발명의 제조방법에 있어서, 상기 제1 단량체는 아크릴산, 메타크릴산, 2-하이드록시프로필 메타크릴레이트, 2-하이드록시에틸 메타크릴레이트, 디메틸아미노에틸 메타아크릴레이트, t-부틸아미노에틸메타아크릴레이트, 디에틸아미노에틸 메타크릴레이트, 글리시딜 메타아크릴레이트, 2-하이드록시에틸 아크릴레이트, 2-하이드록시프로필 아크릴레이트, 아크릴아마이드, 및 N-메틸올 아크릴아미드로 이루어진 군으로부터 1 종 이상 선택된 관능성 아크릴계 또는 메타크릴계 단량체와; 메틸 메타크릴레이트, 에틸 메타크릴레이트, 이소부틸 메타크릴레이트, n-부틸 메타크릴레이트, t-부틸 메타크릴레이트, n-헥실 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 이소보닐 메타크릴레이트, 라우릴 메타아크릴레이트, 시클로헥실 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 이소부틸 아크릴레이트, n-부틸 아크릴레이트, t-부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, n-옥틸 아크릴레이트, 이소보닐 아크릴레이트, 및 시클로헥실 아크릴레이트로 이루어진 군으로부터 1 종이상 선택된 비관능성 아크릴계 또는 메타크릴계 단량체와의 혼합물을 바람직하게 사용할 수 있다. In the production method of the present invention, the first monomer is acrylic acid, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl meth 1 type from the group consisting of acrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, and N-methylol acrylamide Functional acrylic or methacrylic monomer selected above; Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate , Lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n Mixtures with non-functional acrylic or methacryl-based monomers selected from the group consisting of -octyl acrylate, isobonyl acrylate, and cyclohexyl acrylate can be preferably used.
상기 관능성 아크릴계 또는 메타크릴계 단량체와 상기 비관능성 아크릴계 또는 메타크릴계 단량체의 혼합비(중량비)는 1 : 3∼30 의 범위일 수 있으며, 상기 관능성 아크릴계 또는 메타크릴계 단량체는 메타크릴산이고; 상기 비관능성 아크릴계 또는 메타크릴계 단량체는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 또는 이들의 혼합물일 수 있다.The mixing ratio (weight ratio) of the functional acrylic or methacrylic monomer and the non-functional acrylic or methacrylic monomer may be in the range of 1: 3 to 30, wherein the functional acrylic or methacrylic monomer is methacrylic acid ; The nonfunctional acrylic or methacrylic monomer may be methyl methacrylate, n-butyl acrylate, or a mixture thereof.
상기 제1 단량체의 사용량은 상기 전분 1 중량부에 대하여 0.3∼3.0 중량부의 범위일 수 있다. The amount of the first monomer may be in the range of 0.3 to 3.0 parts by weight based on 1 part by weight of the starch.
또한, 단계(a)의 상기 중합은 인산 에스테르계 유화제 혹은 황산염 에스테르계 유화제의 존재하에서 바람직하게 수행될 수 있으며, 상기 유화제는 노닐프로페닐에톡시에테르 술페이트의 암모늄염류, 폴리옥시에틸렌 알킬페닐 알릴 소듐설페이트의 에스테르류, 폴리옥시에틸렌 알릴 글리시딜 노닐 페닐에테르의 술폰산 에스테르류, 및 폴리옥시에틸렌 노닐 프로페닐 에테르의 술폰산 에스테르의 암모늄염류로 이루어진 군으로부터 1 종 이상 선택될 수 있다.In addition, the polymerization of step (a) may be preferably carried out in the presence of a phosphate ester emulsifier or a sulfate ester emulsifier, the emulsifier is ammonium salts of nonylpropenylethoxyether sulfate, polyoxyethylene alkylphenyl allyl It can be selected from the group consisting of esters of sodium sulfate, sulfonic acid esters of polyoxyethylene allyl glycidyl nonyl phenyl ether, and ammonium salts of sulfonic acid ester of polyoxyethylene nonyl propenyl ether.
또한, 단계(a)의 상기 중합은 에틸렌 옥사이드 또는 폴리프로필렌 옥사이드 단위체가 함유된 비이온성 유화제의 존재하에서 수행될 수 있으며, 상기 비이온성 유화제는 폴리옥시에틸렌 폴리옥시프로필렌 알킬 에테르류, 폴리옥시에틸렌 스테아릴 아민류, 폴리에틸렌 솔비탄류, 및 알킬폴리옥시에틸렌-프로필렌 공중합체류로 이루어진 군으로부터 1 종 이상 선택될 수 있다.In addition, the polymerization of step (a) may be carried out in the presence of a nonionic emulsifier containing ethylene oxide or polypropylene oxide units, the nonionic emulsifier is polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene ste It may be selected from the group consisting of aryl amines, polyethylene sorbitan, and alkylpolyoxyethylene-propylene copolymers.
상기 제2 단량체는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 스티렌, 및 2-에틸헥실 메타크릴레이트로 이루어진 군으로부터 1종 이상 선택될 수 있으며, 바람직하게는 상기 제2 단량체는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 스티렌의 혼합물; 또는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 2-에틸헥실 메타크릴레이트의 혼합물일 수 있다. 상기 제2 단량체의 사용량은 상기 제1 단량체 1 중량부에 대하여 1.0∼9.0 중량부의 범위일 수 있다.The second monomer may be at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, styrene, and 2-ethylhexyl methacrylate, preferably the second monomer is methyl methacrylate. , a mixture of n-butyl acrylate, and styrene; Or a mixture of methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl methacrylate. The amount of the second monomer may be in the range of 1.0 to 9.0 parts by weight based on 1 part by weight of the first monomer.
본 발명의 제조방법에 따르면, 친환경적일 뿐만 아니라, 접착력, 도막 안정성 및 수용액상에서 안정적인 분산도, 특히 내수성이 우수한 수성 도료용 접착 소재를 제조할 수 있다. 즉, 본 발명의 제조방법은 석유화학계 유기용매를 사용하지 않으므로, 각종 화학접착제에서 방출되는 휘발성 유기화합물(TVOC)의 방출을 근본적으로 차단할 수 있으며, 특히 수성 도료 접착소재로서 전분을 사용함으로써 발생할 수 있는 문제점인 내수성 문제와 도막형성 문제, 고점도 현상으로 인한 작업성의 저하, 접착력 문제를 효과적으로 해결할 수 있다.According to the production method of the present invention, in addition to being environmentally friendly, it is possible to produce an adhesive material for water-based coatings having excellent adhesion, coating film stability and stable dispersion in aqueous solution, especially water resistance. That is, since the manufacturing method of the present invention does not use a petrochemical organic solvent, it is possible to fundamentally block the release of volatile organic compounds (TVOC) released from various chemical adhesives, especially by using starch as an aqueous paint adhesive material. Problems such as water resistance and coating film formation problems, workability due to high viscosity phenomenon, the adhesion can be effectively solved.
본 발명은 (a) 수성 전분 호화액에 아크릴계 또는 메타크릴계 단량체(이하, '제1 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 전분과 단량체가 공중합된 코어를 형성시키는 단계; 및 (b) 단계(a)에서 얻어진 반응물에 스티렌, 프로필렌, 아크릴산 에스테르, 메타크릴산 에스테르, 아크릴로니트릴, 및 에틸렌으로 이루어진 군으로부터 1종 이상 선택된 단량체(이하, '제2 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 상기 코어 상에 제2 단량체가 중합되어 형성된 코어-쉘 구조의 공중합체를 함유한 에멀젼을 형성시키는 단계를 포함하는, 수성 도료용 접착 소재의 제조방법을 제공한다.The present invention comprises the steps of: (a) adding an acrylic or methacryl-based monomer (hereinafter referred to as 'first monomer') and a polymerization initiator to the aqueous starch gelatinization solution to form a core copolymerized starch and monomer; And (b) at least one monomer selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene in the reaction obtained in step (a) (hereinafter referred to as 'second monomer') And adding a polymerization initiator to polymerize to form an emulsion containing a copolymer of a core-shell structure formed by polymerization of a second monomer on the core, thereby providing an adhesive material for an aqueous coating material.
본 발명의 제조방법에 있어서, 상기 '전분'은 통상의 식물 유래의 천연 전분, 물리적 혹은 화학적 변성 전분 등을 포함한 모든 형태의 전분을 포함한다. 상기 천연 전분으로는 옥수수, 찰옥수수, 감자, 고구마, 밀, 쌀, 타피오카, 사고(sago), 왁시 마즈(waxy maize), 수수(sorghum) 등을 포함한 다양한 식물 유래의 전분(즉, 미변성 전분)을 포함하며, 상기 전분은 상기 식물의 지상부, 지하부 등으로부터 얻어질 수 있다. 상기 변성 전분으로는 상기 미변성 전분을 에테르화, 에스테르화, 산화, 산처리, 산화 에스테르화, 산화 에테르화, 효소처리 등의 방법으로 개질화시킨 전분을 포함한다. 또한, 본 발명의 제조방법에서, 상기 전분으로서 미변성 전분, 변성전분을 단독으로 혹은 2 종 이상 혼합한 것을 사용할 수도 있다.In the production method of the present invention, the 'starch' includes all types of starch including natural starch derived from conventional plants, physical or chemical modified starch and the like. The natural starch may include corn, waxy corn, potato, sweet potato, wheat, rice, tapioca, sago, waxy maize, sorghum, etc. ), And the starch may be obtained from the above-ground part of the plant, underground part, and the like. The modified starch includes starch in which the unmodified starch is modified by a method such as etherification, esterification, oxidation, acid treatment, oxidative esterification, oxidative etherification, and enzyme treatment. Moreover, in the manufacturing method of this invention, the said starch can also use the unmodified starch and the modified starch individually or in mixture of 2 or more types.
상기 '수성 전분 호화액'은 수성 매질(예를 들어, 통상의 물, 정제수, 또는 탈이온수(즉, 이온교환수) 등) 중에 전분을 가하고, 통상의 호화방법, 예를 들어 전분 분해효소를 사용하여 상압상태에서 진행하는 단속식(batch-cooking) 방법 혹은 고온 고압상태에서 진행하는 연속식(jet-cooking) 방법에 의해 얻을 수 있다. 바람직하게는 단속식 방법에 의해 수성 전분 호화액을 얻을 수 있다. 상기 단속식 방법은 20∼150 ℃, 바람직하게는 50∼120 ℃에서, 30∼300 분, 바람직하게는 60∼200분 동안 반응시킴으로써, 전분 분해를 수행할 수 있다.The 'aqueous starch liquor' is added to the starch in an aqueous medium (e.g., conventional water, purified water, or deionized water (i.e. ion-exchanged water)), and a conventional gelatinization method, for example starch degrading enzyme It can be obtained by the batch-cooking method which proceeds at atmospheric pressure, or by the jet-cooking method which proceeds at high temperature and high pressure. Preferably, the aqueous starch gelatinized liquid can be obtained by an intermittent method. In the intermittent method, starch decomposition may be performed by reacting at 20 to 150 ° C, preferably 50 to 120 ° C, for 30 to 300 minutes, preferably 60 to 200 minutes.
상기 전분 분해효소는 알파-아밀라제, 베타-아밀라제, 글루코-아밀라제, 이소-아밀라제 등을 포함하며, 바람직하게는 중온성 알파-아밀라제 혹은 내열성 알파-아밀라제 등을 사용할 수 있다. 상기 전분 분해효소는 상업적으로 구입할 수 있다. 예를 들어, 단속식 방법에 의해 전분 분해를 수행할 경우, 전분 호화액의 pH는 4∼8 의 범위로 조절하는 것이 바람직하며, 전분 분해효소의 사용량은 전분 100 중량부에 대하여 0.001∼10 중량부, 바람직하게는 0.01∼8 중량부의 범위일 수 있으나, 특별히 제한되는 것은 아니다. The starch degrading enzymes include alpha-amylase, beta-amylase, gluco-amylase, iso-amylase, and the like, and preferably, mesophilic alpha-amylase or heat-resistant alpha-amylase may be used. The starch degrading enzyme is commercially available. For example, when performing starch decomposition by the intermittent method, it is preferable to adjust the pH of the starch gelatinized liquid in the range of 4 to 8, and the amount of starch degrading enzyme is 0.001 to 10% by weight based on 100 parts by weight of starch. Part, preferably, may be in the range of 0.01 to 8 parts by weight, but is not particularly limited.
또한, 상기 '수성 전분 호화액'은 덱스트린을 원료로 얻을 수도 있다. 덱스트린을 사용하는 경우, 전분 분해효소의 사용을 필요로 하지 않는다. 덱스트린을 원료로 할 경우, '수성 전분 호화액'은 예를 들어, 상압 상태에서 진행할 수 있으며, 통상 20∼150 ℃, 바람직하게는 50∼120 ℃에서, 30∼300 분, 바람직하게는 60∼200분 동안 반응시킴으로써 수행할 수 있다.In addition, the "aqueous starch gelatinized liquid" can also be obtained dextrin as raw materials. If dextrin is used, it does not require the use of starch degrading enzymes. In the case of using dextrin as a raw material, the 'aqueous starch gelatinized liquid' can proceed at atmospheric pressure, for example, and usually 20 to 150 ° C, preferably 50 to 120 ° C, 30 to 300 minutes, preferably 60 to This can be done by reacting for 200 minutes.
얻어진 호화 전분(즉, 수성 전분 호화액)은 필요할 경우, 70∼90 ℃로 냉각하여 이어지는 공중합 반응에 직접 사용할 수 있다.The obtained gelatinized starch (ie, an aqueous starch gelatinized liquid) can be used directly in the subsequent copolymerization reaction by cooling to 70 to 90 ° C if necessary.
단계(a)에서, 상기 제1 단량체는 관능성 아크릴계 또는 메타크릴계 단량체와 비관능성 아크릴계 또는 메타크릴계 단량체와의 혼합물을 바람직하게 사용할 수 있다. In step (a), a mixture of a functional acrylic or methacrylic monomer with a non-functional acrylic or methacrylic monomer may be preferably used.
상기 관능성 아크릴계 또는 메타크릴계 단량체는 아크릴산, 메타크릴산, 2-하이드록시프로필 메타크릴레이트(2-hydroxypropyl methacrylate), 2-하이드록시에틸 메타크릴레이트(2-hydroxyethyl methacrylate), 디메틸아미노에틸 메타아크릴레이트, t-부틸아미노에틸메타아크릴레이트, 디에틸아미노에틸 메타크릴레이트, 글리시딜 메타아크릴레이트, 2-하이드록시에틸 아크릴레이트(2-hydroxyethyl acrylate), 2-하이드록시프로필 아크릴레이트(2-hydroxypropyl acrylate), 아크릴아마이드, 및 N-메틸올 아크릴아미드(N-methylol acrylamide)로 이루어진 군으로부터 1 종 이상 선택될 수 있으며, 바람직하게는 메타크릴산을 사용할 수 있다.The functional acrylic or methacrylic monomers are acrylic acid, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl meta Acrylate, t-butylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate (2 -hydroxypropyl acrylate), acrylamide, and N-methylol acrylamide (N-methylol acrylamide) may be selected from one or more kinds, preferably methacrylic acid may be used.
또한, 상기 비관능성 아크릴계 또는 메타크릴계 단량체는 메틸 메타크릴레이트, 에틸 메타크릴레이트, 이소부틸 메타크릴레이트, n-부틸 메타크릴레이트, t-부틸 메타크릴레이트, n-헥실 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 이소보닐 메타크릴레이트(isobornyl methacrylate), 라우릴 메타아크릴레이트, 시클로헥실 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 이소부틸 아크릴레이트, n-부틸 아크릴레이트, t-부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, n-옥틸 아크릴레이트, 이소보닐 아크릴레이트(isobornyl acrylate), 및 시클로헥실 아크릴레이트로 이루어진 군으로부터 1 종이상 선택될 수 있으며, 바람직하게는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 또는 이들의 혼합물을 사용할 수 있다. In addition, the non-functional acrylic or methacrylate monomers are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2 Ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acryl It may be selected from one group from the group consisting of latex, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, and cyclohexyl acrylate, preferably Methyl methacrylate, n-butyl acrylate, or mixtures thereof can be used.
상기 관능성 아크릴계 또는 메타크릴계 단량체와 상기 비관능성 아크릴계 또는 메타크릴계 단량체의 혼합비(중량비)는 1 : 3∼30 의 범위, 바람직하게는 1 : 5∼20 의 범위일 수 있다. 관능성 아크릴계 또는 메타크릴계 단량체의 함량이 너무 소량일 경우 도료용 접착제에 의해 형성되는 도막의 갈라짐 현상이 발생할 수 있고, 너무 과량일 경우 공중합물이 충분히 형성되지 않아, 이어지는 제2 단량체와의 중합이 곤란할 수 있다. 일 구현예에서, 상기 제1 단량체는 메타크릴산, 메틸 메타크릴레이트, 및 n-부틸 아크릴레이트의 1 : 4 : 4 (중량비)의 혼합물일 수 있다.The mixing ratio (weight ratio) of the functional acrylic or methacrylic monomer and the nonfunctional acrylic or methacrylic monomer may be in the range of 1: 3 to 30, preferably in the range of 1: 5 to 20. When the content of the functional acrylic or methacrylic monomers is too small, cracking of the coating film formed by the paint adhesive may occur, and when too much, the copolymer is not sufficiently formed, resulting in polymerization with the second monomer. This can be difficult. In one embodiment, the first monomer may be a mixture of 1: 4: 4 (weight ratio) of methacrylic acid, methyl methacrylate, and n-butyl acrylate.
상기 제1 단량체의 사용량은 상기 전분(즉, 호화된 전분) 1 중량부에 대하여 0.3∼3.0 중량부의 범위일 수 있다. 제1 단량체의 사용량이 0.3 중량부 미만일 경우 점도가 너무 높아져 이어지는 제2 단량체와의 중합반응이 곤란할 수 있고, 3.0 중량부를 초과할 경우에는 전분과 제1 단량체와의 공중합물 형성이 곤란해질 수 있다.The amount of the first monomer may be in the range of 0.3 to 3.0 parts by weight based on 1 part by weight of the starch (ie, gelatinized starch). If the amount of the first monomer is less than 0.3 parts by weight, the viscosity may be too high, and subsequent polymerization with the second monomer may be difficult. If it exceeds 3.0 parts by weight, it may be difficult to form a copolymer of the starch and the first monomer. .
단계(a)에서 사용되는 중합개시제는 라디칼 중합이 가능한 열해리 개시제 또는 산화-환원 개시제 등을 사용할 수 있으며, 예를 들어 소듐 퍼설페이트, 포타슘 퍼설페이트, t-부틸 하이드로퍼옥사이드, 2,2-아조비스부티로니트릴, 2,2'-아조비스-2-메틸부티로니트릴, 큐멘하이드로퍼옥사이드 등을 사용할 수 있으며, 바람직하게는 소듐 퍼설페이트, 포타슘 퍼설페이트, t-부틸 하이드로퍼옥사이드 등의 수용성 개시제를 사용할 수 있다. 또한, 필요할 경우, 아스코르브산, 소듐 포름알데하이드 술폭시레이트, 소듐 바이설파이트 등의 환원제를 가할 수도 있다. The polymerization initiator used in step (a) may use a thermal dissociation initiator or an oxidation-reduction initiator capable of radical polymerization, for example sodium persulfate, potassium persulfate, t-butyl hydroperoxide, 2,2-azo Bisbutyronitrile, 2,2'-azobis-2-methylbutyronitrile, cumene hydroperoxide, etc. can be used, Preferably it is water-soluble, such as sodium persulfate, potassium persulfate, t-butyl hydroperoxide, etc. Initiators can be used. If necessary, reducing agents such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite, and the like may be added.
상기 중합개시제는 단량체 투입전에 투입하거나 단량체와 동시에 투입할 수 있으며, 그 사용량은 단량체(즉, 제1 단량체) 100 중량부에 대해 0.1 내지 8 중량부, 바람직하게는 0.2 내지 5 중량부의 범위일 수 있다. 중합개시제의 함량이 0.1 중량부 미만일 경우 중합에 필요한 시간이 증가될 수 있으며, 8 중량부를 초과할 경우 얻어지는 전분-공중합체 에멀젼의 갈변이 야기되어 변색될 수 있다.The polymerization initiator may be added before 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 based on 100 parts by weight of the monomer (ie, the first monomer). have. When the content of the polymerization initiator is less than 0.1 parts by weight, the time required for polymerization may be increased, and when it exceeds 8 parts by weight, browning of the obtained starch-copolymer emulsion may be caused and discolored.
단계(a)의 상기 중합 즉, 전분과 제1 단량체와의 중합은 60 내지 100℃, 바람직하게는 70 내지 90℃의 온도; 및 0.01 내지 10 bar, 바람직하게는 0.1 내지 5 bar의 압력 조건에서 수행할 수 있다. 또한, 상기 중합은 10분 내지 60분, 바람직하게는 20분 내지 50분 동안 수행될 수 있다. 중합반응을 종료한 후, 얻어진 반응물은 10분 내지 120분, 바람직하게는 20분 내지 80분 동안, 질소 충진 조건에서 상기 온도를 유지하며 숙성시키는 공정을 수행하는 것이 바람직하다. 상기 숙성 공정에 의해 미반응 단량체를 최소화할 수 있고, 또한 충분한 중합을 도모할 수 있다. 단계(a)에서 얻어진 반응물은 70∼90 ℃ 범위의 온도로 조절하여, 이어지는 제2 단량체의 중합을 수행할 수 있다.The polymerization of step (a), ie the polymerization of starch and the first monomer, may be carried out at a temperature of 60 to 100 ° C., preferably 70 to 90 ° C .; And from 0.01 to 10 bar, preferably from 0.1 to 5 bar. In addition, the polymerization may be carried out for 10 to 60 minutes, preferably 20 to 50 minutes. After the completion of the polymerization reaction, the obtained reactant is preferably carried out for 10 minutes to 120 minutes, preferably 20 minutes to 80 minutes, while maintaining the above temperature under nitrogen filling conditions and aging. By the aging step, the unreacted monomer can be minimized and sufficient polymerization can be achieved. The reactant obtained in step (a) can be adjusted to a temperature in the range from 70 to 90 ° C., to carry out the polymerization of the subsequent second monomer.
또한, 상기 중합은 인산 에스테르계 유화제 혹은 황산염 에스테르계 유화제 및/또는 에틸렌 옥사이드 또는 폴리프로필렌 옥사이드 단위체가 함유된 비이온성 유화제 존재하에서, 즉 유화 중합을 통하여, 바람직하게 수행할 수 있다. In addition, the polymerization may be preferably carried out in the presence of a phosphate ester emulsifier or a sulfate ester emulsifier and / or a nonionic emulsifier containing ethylene oxide or polypropylene oxide units, that is, through emulsion polymerization.
상기 인산 에스테르계 유화제 혹은 황산염 에스테르계 유화제의 종류는 특별히 한정되는 것은 아니며, 유화중합에 통상적으로 사용되는 반응성 유화제를 사용할 수 있다. 대표적인 예로는 노닐프로페닐에톡시에테르 술페이트의 암모늄염류(예를 들어, 아쿠아론 HS-10 (DKS, 일본), SE-10(아데카,일본) 등), 폴리옥시에틸렌 알킬페닐 알릴 소듐설페이트의 에스테르류(예를 들어, HA-100 (한농화성, 대한민국) 등), 폴리옥시에틸렌 알릴 글리시딜 노닐 페닐에테르의 술폰산 에스테르류(예를 들어, SETM(아데카, 일본) 등), 폴리옥시에틸렌 노닐 프로페닐 에테르의 술폰산 에스테르의 암모늄염류(예를 들어, HITENOL HSTM(DKS, 일본) 등)을 열거할 수 있다. 상기 반응성 유화제를 사용할 경우, 단계(a)를 수행하여 얻어지는 에멀젼의 중합안정성, 화학안정성 및 내수성을 더욱 향상시킬 수 있다. 상기 반응성 유화제의 사용량은 제1 단량체 100 중량부에 대하여 0.4∼3.2 중량부, 더욱 바람직하게는 1.2∼2.4 중량부의 범위로 사용할 수 있으나, 특별히 제한되는 것은 아니다.The kind of the phosphate ester emulsifier or the sulfate ester emulsifier is not particularly limited, and a reactive emulsifier commonly used in emulsion polymerization may be used. Representative examples include ammonium salts of nonylpropenylethoxyether sulfate (eg, Aquaron HS-10 (DKS, Japan), SE-10 (Adeca, Japan), etc.), polyoxyethylene alkylphenyl allyl sodium sulfate Esters (e.g., HA-100 (Hanseong, Korea), etc.), sulfonic acid esters of polyoxyethylene allyl glycidyl nonyl phenyl ether (e.g., SETM (adeka, Japan), etc.), poly Ammonium salts of sulfonic acid esters of oxyethylene nonyl propenyl ethers (e.g., HITENOL HSTM (DKS, Japan, etc.)). When using the reactive emulsifier, it is possible to further improve the polymerization stability, chemical stability and water resistance of the emulsion obtained by performing step (a). The amount of the reactive emulsifier may be used in the range of 0.4 to 3.2 parts by weight, more preferably 1.2 to 2.4 parts by weight based on 100 parts by weight of the first monomer, but is not particularly limited.
상기 에틸렌 옥사이드 또는 폴리프로필렌 옥사이드 단위체가 함유된 비이온성 유화제의 종류는 특별히 한정되는 것은 아니며, 유화중합에 통상적으로 사용되는 비이온성 유화제를 사용할 수 있다. 대표적인 예로는 폴리옥시에틸렌 폴리옥시프로필렌 알킬 에테르류(예를 들어, FN-8(한농화성, 대한민국) 등), 폴리옥시에틸렌 스테아릴 아민류(예를 들어, SN-2(한농화성, 대한민국) 등), 폴리에틸렌 솔비탄류(예를 들어, SFT-10(한농화성, 대한민국) 등), 알킬폴리옥시에틸렌-프로필렌 공중합체류(예를 들어, MONOPOL PE 등)을 열거할 수 있다. 상기 비이온성 유화제 존재하에서 중합반응을 수행할 경우, 얻어지는 코어의 입자 크기를 적절한 범위(예를 들어, 50nm∼300nm)로 제어할 수 있다. 상기 비이온성 유화제는 제1 단량체 100 중량부에 대하여 0.1∼0.8 중량부의 범위로 사용될 수 있다.The type of the nonionic emulsifier containing the ethylene oxide or polypropylene oxide unit is not particularly limited, and nonionic emulsifiers commonly used in emulsion polymerization may be used. Representative examples include polyoxyethylene polyoxypropylene alkyl ethers (eg, FN-8 (Hanungseong, Korea), etc.), polyoxyethylene stearyl amines (eg, SN-2 (Hanongseong, Korea), etc. ), Polyethylene sorbitan (for example, SFT-10 (Hanongseong, Korea), etc.), alkyl polyoxyethylene-propylene copolymers (for example, MONOPOL PE etc.) can be mentioned. When the polymerization is carried out in the presence of the nonionic emulsifier, it is possible to control the particle size of the core obtained in an appropriate range (for example, 50nm to 300nm). The nonionic emulsifier may be used in the range of 0.1 to 0.8 parts by weight based on 100 parts by weight of the first monomer.
단계(b)에서, 상기 제2 단량체는 스티렌, 프로필렌, 아크릴산 에스테르, 메타크릴산 에스테르, 아크릴로니트릴, 및 에틸렌으로 이루어진 군으로부터 1종 이상 선택될 수 있으며, 구체적으로는 메틸 메타크릴레이트, 에틸 메타크릴레이트, 이소부틸 메타크릴레이트, n-부틸 메타크릴레이트, t-부틸 메타크릴레이트, n-헥실 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 이소보닐 메타크릴레이트, 라우릴 메타아크릴레이트, 시클로헥실 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 이소부틸 아크릴레이트, n-부틸 아크릴레이트, t-부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, n-옥틸 아크릴레이트, 이소보닐 아크릴레이트, 시클로헥실 아크릴레이트, 스티렌, 프로필렌, 및 에틸렌으로 이루어진 군으로부터 1 종이상 선택될 수 있으며, 바람직하게는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 스티렌, 및 2-에틸헥실 메타크릴레이트로 이루어진 군으로부터 1종 이상 선택될 수 있다. 일 구현예에서, 상기 제2 단량체는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 스티렌의 혼합물일 수 있다. 또다른 구현예에서, 상기 제2 단량체는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 2-에틸헥실 메타크릴레이트의 혼합물일 수 있다.In step (b), the second monomer may be at least one selected from the group consisting of styrene, propylene, acrylic esters, methacrylic acid esters, acrylonitrile, and ethylene, specifically methyl methacrylate, ethyl Methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate , Cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, iso Can be selected from the group consisting of carbonyl acrylate, cyclohexyl acrylate, styrene, propylene, and ethylene And preferably at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, styrene, and 2-ethylhexyl methacrylate. In one embodiment, the second monomer may be a mixture of methyl methacrylate, n-butyl acrylate, and styrene. In another embodiment, the second monomer may be a mixture of methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl methacrylate.
상기 제2 단량체의 사용량은 제1 단량체(단량체의 혼합물인 경우 총 단량체) 1 중량부에 대하여 1.0∼9.0 중량부, 바람직하게는 1.5∼5.0 중량부의 범위일 수 있다. 상기 제2 단량체의 사용량이 1.0 중량부 미만일 경우 입자크기가 거대해져 도료용 접착소재로 적합하지 않을 수 있으며, 9.0 중량부를 초과하는 경우 전분 사용 효과가 미약하여 친환경성이 감소될 수 있다.The amount of the second monomer may be in the range of 1.0 to 9.0 parts by weight, preferably 1.5 to 5.0 parts by weight based on 1 part by weight of the first monomer (total monomers in the case of a mixture of monomers). When the amount of the second monomer is less than 1.0 parts by weight, the particle size may be huge and may not be suitable as an adhesive material for coating. When the amount of the second monomer is greater than 9.0 parts by weight, the starch use effect may be weak and environmentally friendly properties may be reduced.
또한, 필요에 따라, 얻어지는 공중합체의 분자량을 조절하기 위하여 연쇄 이동제를 상기 제2 단량체에 추가하여 중합반응을 수행할 수 있다. 상기 연쇄 이동제는 n-도데실 머캅탄, t-도데실 머캅탄, α-메틸스티렌다이머, C1∼C5 알코올, 또는 이들의 혼합물을 사용할 수 있다.In addition, if necessary, in order to control the molecular weight of the copolymer obtained, a chain transfer agent may be added to the second monomer to perform a polymerization reaction. The chain transfer agent may use n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, C 1 -C 5 alcohol, or a mixture thereof.
단계(b)에서 사용되는 중합개시제 및 선택적으로 가해지는 환원제의 종류 및 사용량은 단계(a)와 관련하여 기술한 중합개시제의 종류 및 사용량의 범위내에서 적절하게 선택될 수 있다.The type and amount of the polymerization initiator and optionally the reducing agent used in step (b) may be appropriately selected within the range of the type and amount of the polymerization initiator described in connection with step (a).
상기 제2 단량체에 의한 2차 중합반응은 60 내지 100℃, 바람직하게는 70 내지 90℃의 온도; 및 0.01 내지 10 bar, 바람직하게는 0.1 내지 5 bar의 압력 조건에서 수행할 수 있다. 또한, 상기 중합은 60분 내지 600분, 바람직하게는 120분 내지 480분 동안 수행될 수 있다. 중합반응을 종료한 후, 얻어진 반응물은 10분 내지 120분, 바람직하게는 20분 내지 80분 동안, 질소 충진 조건하에서 상기 온도를 유지하며 숙성시키는 공정을 수행하는 것이 바람직하다. 상기 숙성 공정에 의해 미반응 단량체를 최소화할 수 있다. 상기와 같이 제2 단량체에 의한 2차 중합반응을 수행하면, 전분과 제1 단량체의 공중합물 즉, 코어 상에 상기 제2 단량체가 중합되어 쉘을 형성하게 되고, 따라서 코어-쉘 구조의 공중합체를 함유한 에멀젼이 형성되게 된다. 단계(b)에서 얻어진 반응물은 40∼65 ℃ 범위의 온도로 조절하여, 통상의 후처리 공정을 수행할 수 있다.The secondary polymerization reaction by the second monomer is a temperature of 60 to 100 ℃, preferably 70 to 90 ℃; And from 0.01 to 10 bar, preferably from 0.1 to 5 bar. In addition, the polymerization may be performed for 60 minutes to 600 minutes, preferably 120 minutes to 480 minutes. After the completion of the polymerization reaction, the obtained reactant is preferably carried out for 10 minutes to 120 minutes, preferably 20 minutes to 80 minutes, while maintaining the above temperature under nitrogen filling conditions and aging. The aging process can minimize the unreacted monomer. As described above, when the second polymerization reaction is performed by the second monomer, a copolymer of starch and the first monomer, that is, the second monomer is polymerized on the core to form a shell, and thus a copolymer having a core-shell structure An emulsion containing is formed. The reactant obtained in step (b) may be adjusted to a temperature in the range from 40 to 65 ° C., to carry out a conventional post treatment process.
상기 후처리 공정은 통상의 미반응 단량체 제거 공정, 예를 들어 화학적 방법, 습윤제거 방법, 또는 고온 스팀 방법 등을 포함한다. 바람직하게는, 상기 미반응 단량체 제거 공정은 산화제 및 환원제를 사용한 화학적 방법을 사용할 수 있다. 상기 산화제로는 t-부틸 하이드로퍼옥사이드(t-butyl hydroperoxide), 쿠멘하이드로퍼옥사이드(cumenehydroperoxide) 등을 사용할 수 있으며, 상기 환원제로는 소듐 하이드로설파이트(sodium hydrosulfite), 소듐 메타비설파이트(sodium metabisulfite) 등을 사용할 수 있다. 상기 산화제 및 환원제의 사용량은 얻어지는 에멀젼 100 중량부에 대하여 0.001∼1 중량부, 바람직하게는 0.002∼0.8 중량부의 범위일 수 있으며, 상기 산화제 및 환원제를 사용한 후처리 공정은 10∼300 분, 바람직하게는 20∼250 분 동안 수행할 수 있다. 또한, 필요에 따라, 40 내지 60℃, 바람직하게는 50 내지 60℃의 온도에서, 10 내지 120분, 바람직하게는 30 내지 90분 동안, 질소 충진 조건하에서 상기 온도를 유지하며 숙성시키는 공정을 수행할 수도 있다. 상기 숙성 공정에 의해, 산화제 및 환원제와 미반응 단량체와의 충분한 반응을 유도할 수 있다.The post-treatment process includes a conventional unreacted monomer removal process, for example, a chemical method, a wet removal method, or a hot steam method. Preferably, the unreacted monomer removal process may use a chemical method using an oxidizing agent and a reducing agent. The oxidizing agent may be used t-butyl hydroperoxide (t-butyl hydroperoxide), cumenehydroperoxide (cumenehydroperoxide) and the like, the reducing agent is sodium hydrosulfite (sodium hydrosulfite), sodium metabisulfite (sodium metabisulfite) ) Can be used. The amount of the oxidizing agent and the reducing agent may be in the range of 0.001 to 1 part by weight, preferably 0.002 to 0.8 part by weight based on 100 parts by weight of the obtained emulsion, and the post-treatment process using the oxidant and the reducing agent is 10 to 300 minutes, preferably Can be carried out for 20 to 250 minutes. In addition, if necessary, at a temperature of 40 to 60 ℃, preferably 50 to 60 ℃, 10 to 120 minutes, preferably 30 to 90 minutes, maintaining the temperature under nitrogen filling conditions while carrying out the process of aging You may. By the above aging step, it is possible to induce a sufficient reaction between the oxidizing agent and the reducing agent and the unreacted monomer.
상기와 같이 얻어진 생성물은 코어-쉘 구조의 공중합체를 함유한 에멀젼으로서, 필요할 경우 도료 분야에서 통상적으로 사용되는 소포제, 증점제 등의 첨가제를 추가로 가할 수 있다. 본 발명의 제조방법에 따라 얻어진 상기 에멀젼은 수성 도료용 접착 소재로서 유용하게 사용될 수 있으며, 예를 들어, 안료, 기타 도료용 첨가제 등과 혼합하여 수성 도료로서 사용될 수 있다.The product obtained as described above is an emulsion containing a copolymer of a core-shell structure, and if necessary, additives such as an antifoaming agent and a thickener commonly used in the paint field may be further added. The emulsion obtained according to the production method of the present invention can be usefully used as an adhesive material for water-based paints, for example, can be used as an aqueous paint by mixing with pigments, other paint additives and the like.
이하, 본 발명을 실시예를 통하여 더욱 상세히 설명한다. 그러나 이들 실시예는 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited to these examples.
실시예 1. 코어-쉘 구조의 공중합체를 함유한 에멀젼의 제조Example 1 Preparation of an Emulsion Containing a Core-Shell Structured Copolymer
(1) 수성 전분 호화액의 제조(1) Preparation of Aqueous Starch Gelatinate
이온교환수 178.0g에 전분(DS-SyncSTA S100, 대상㈜, 대한민국) 90.6g을 투입하여 분산시킨 후, 7% HCl을 사용하여 pH를 6으로 조절하였다. 99g의 이온교환수에 1g의 내열성 알파-아밀라제(Liquozyme supra, Novozyme, 덴마크)를 희석시켜 제조한 전분 분해효소액 1.2g을 상기 반응물에 가하였다. 얻어진 반응물을 1L 용량의 4구 플라스크 반응조에 가하고, 90℃에서 2시간 동안 교반하였다. 반응물에 차아염소산 0.6g을 가하여 효소 활성을 저해시킨 후, 80℃로 냉각하여 수성 전분 호화액을 제조하였다. After dispersing 90.6 g of starch (DS-SyncSTA S100, Daesang, Korea) in 178.0 g of ion-exchanged water, the pH was adjusted to 6 using 7% HCl. 1.2 g of starch degrading enzyme solution prepared by diluting 1 g of heat-resistant alpha-amylase (Liquozyme supra, Novozyme, Denmark) in 99 g of ion-exchanged water was added to the reaction. The resulting reaction was added to a 1 L four-necked flask reactor and stirred at 90 ° C. for 2 hours. 0.6 g of hypochlorous acid was added to the reaction to inhibit the enzyme activity, and then cooled to 80 ° C. to prepare an aqueous starch gelatinizer.
(2) 전분계 코어의 제조(2) Preparation of Starch Core
상기 (1)에서 얻어진 수성 전분 호화액에 반응성 유화제(HA-100, 한농화성, 대한민국) 6.4g, 비이온성 유화제(FN-8, 한농화성, 대한민국) 1.6g, 및 이온교환수 147.7g을 가하고, 반응기에 질소를 충진하였다. 질소 분위기하에서, 9.0g의 이온교환수에 포타슘 퍼설페이트 0.5g 및 소듐 바이설파이트 0.03g을 용해시킨 용액과 메틸 메타크릴레이트 20.0g, 메틸 메타크릴산 5.0g, 및 n-부틸 아크릴레이트 20.0g의 단량체 혼합물을 80℃에서 30분 동안 적가하여 공중합 반응을 수행하였다. 상기 적가 완료 후, 80℃에서 1시간 동안 교반함으로써 숙성시켜, 전분-제1 단량체 공중합물을 함유한 에멀젼을 얻었다.To the aqueous starch liquor obtained in the above (1), 6.4 g of a reactive emulsifier (HA-100, Hannong, Korea), 1.6g of a nonionic emulsifier (FN-8, Hannong, Korea), and 147.7g of ion-exchanged water were added thereto. The reactor was filled with nitrogen. Under nitrogen atmosphere, a solution of 0.5 g of potassium persulfate and 0.03 g of sodium bisulfite was dissolved in 9.0 g of ion-exchanged water, 20.0 g of methyl methacrylate, 5.0 g of methyl methacrylic acid, and 20.0 g of n-butyl acrylate. The copolymerization reaction was carried out by dropwise addition of the monomer mixture at 80 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was aged by stirring at 80 ° C. for 1 hour to obtain an emulsion containing a starch-first monomer copolymer.
(3) 코어-쉘 이중구조를 갖는 공중합물의 제조(3) Preparation of Copolymer Having Core-Shell Dual Structure
상기 (2)에서 얻어진 에멀젼에, 55.0g의 이온교환수에 포타슘 퍼설페이트 2.8g 및 소듐 바이설파이트 0.23g을 용해시킨 용액과 메틸 메타크릴레이트 97.7g, n-부틸 아크릴레이트 137.2g, 스티렌 40.0g, 및 n-도데실 머캅탄 1.0g의 단량체 혼합물을 80℃에서 270분 동안 적가하여 중합반응을 수행하였다. 상기 적가 완료 후, 80℃에서 1시간 동안 교반함으로써 숙성시켜, 코어-쉘 구조의 공중합체를 함유한 에멀젼을 얻었다.In the emulsion obtained in the above (2), a solution obtained by dissolving 2.8 g of potassium persulfate and 0.23 g of sodium bisulfite in 55.0 g of ion-exchanged water, 97.7 g of methyl methacrylate, 137.2 g of n-butyl acrylate, and 40.0 styrene The polymerization reaction was carried out by dropwise addition of g, and a monomer mixture of 1.0 g of n-dodecyl mercaptan at 80 ° C. for 270 minutes. After completion of the dropwise addition, the mixture was aged by stirring at 80 ° C. for 1 hour to obtain an emulsion containing a core-shell structured copolymer.
(4) 후처리 공정(4) post-treatment process
상기 (3)에서 얻어진 에멀젼을 55℃로 냉각시키고, t-부틸 하이드로퍼록사이드 0.9g을 16g의 이온교환수에 용해시킨 용액과 소듐 하이드로설파이트 0.6g을 8.0g의 이온교환수에 용해시킨 용액을 30분 동안 적가하였다. 반응물을 55℃에서 30분 동안의 숙성시킨 후, 실온으로로 냉각시켜, 에멀젼 형태의 수성 도료용 접착 소재를 제조하였다. 상기 제조된 에멀젼의 고형분 함량을 측정한 결과, 고형분의 함량은 약 50 중량%이었다.The emulsion obtained in (3) was cooled to 55 ° C, a solution obtained by dissolving 0.9 g of t-butyl hydroperoxide in 16 g of ion-exchanged water and 0.6 g of sodium hydrosulfite in 8.0 g of ion-exchanged water. The solution was added dropwise for 30 minutes. The reaction was aged at 55 ° C. for 30 minutes and then cooled to room temperature to prepare an adhesive material for an aqueous paint in emulsion form. As a result of measuring the solids content of the prepared emulsion, the solids content was about 50% by weight.
실시예 2. 코어-쉘 구조의 공중합체를 함유한 에멀젼의 제조Example 2 Preparation of an Emulsion Containing a Core-Shell Structured Copolymer
상기 실시예 1의 (2)에서 반응성 유화제로서 SR-10(아데카, 일본) 6.5g을 사용한 것을 제외하고는 실시예 1과 동일하게 하여 에멀젼 형태의 수성 도료용 접착 소재를 제조하였다. Except for using SRg (Adeka, Japan) 6.5g as a reactive emulsifier in Example 1 (2) was prepared in the same manner as in Example 1 to prepare an adhesive coating material for water-based emulsion.
실시예 3. 코어-쉘 구조의 공중합체를 함유한 에멀젼의 제조Example 3 Preparation of Emulsions Containing Core-Shell Structured Copolymers
상기 실시예 1의 (3)에서 제2 단량체로서 메틸 메타크릴레이트 132.4g, n-부틸 아크릴레이트 102.6g, 및 2-에틸헥실 메타크릴레이트 40.0g의 단량체 혼합물을 사용한 것을 제외하고는, 실시예 1과 동일하게 하여 에멀젼 형태의 수성 도료용 접착 소재를 제조하였다.Except that in Example 3 (3), a monomer mixture of 132.4 g of methyl methacrylate, 102.6 g of n-butyl acrylate, and 40.0 g of 2-ethylhexyl methacrylate was used as the second monomer. In the same manner as in 1, an adhesive material for an aqueous paint in emulsion form was prepared.
비교예 1. 단일 구조의 공중합체 에멀젼의 제조Comparative Example 1. Preparation of Copolymer Emulsion of Single Structure
실시예 1의 (2) 및 (3)의 구분 없이, 1회의 중합에 의한 단일 구조의 공중합체 에멀젼을 제조하였다. 즉, 실시예 1의 (1)에서 얻어진 수성 전분 호화액에 반응성 유화제(HA-100, 한농화성, 대한민국) 6.4g, 비이온성 유화제(FN-8, 한농화성, 대한민국) 1.6g, 및 이온교환수 147.7g을 가하고, 반응기에 질소를 충진하였다. 질소 분위기하에서, 9.0g의 이온교환수에 포타슘 퍼설페이트 0.5g을 용해시킨 용액과 메틸 메타크릴레이트 117.7g, n-부틸 아크릴레이트 157.2g, 및 스티렌 40.0g의 단량체 혼합물의 단량체 혼합물을 80℃에서 30분 동안 적가하여 공중합 반응을 수행하였다. 상기 적가 완료 후, 80℃에서 1시간 동안 교반함으로써 숙성시켜, 전분-단량체 공중합물을 함유한 에멀젼을 얻었다.Without the division of (2) and (3) of Example 1, a copolymer emulsion of a single structure was prepared by one polymerization. That is, 6.4 g of reactive emulsifier (HA-100, Hannong-Sung, Korea), 1.6g of nonionic emulsifier (FN-8, Hannong-Sung, Korea) to the aqueous starch gelatinized liquid obtained in Example 1 (1), and ion exchange Water 147.7g was added and nitrogen was charged to the reactor. Under a nitrogen atmosphere, a monomer mixture of a solution of 0.5 g of potassium persulfate dissolved in 9.0 g of ion-exchanged water and a monomer mixture of 117.7 g of methyl methacrylate, 157.2 g of n-butyl acrylate, and 40.0 g of styrene was prepared at 80 ° C. The copolymerization reaction was carried out by dropwise addition for 30 minutes. After completion of the dropwise addition, the mixture was aged by stirring at 80 ° C. for 1 hour to obtain an emulsion containing a starch-monomer copolymer.
시험예. 물성 평가Test example. Property evaluation
실시예 1 및 비교예 1에서 얻어진 에멀젼의 물성을 평가하였다. 평가 물성 항목인 불휘발분, 점도, Tg, 도막상태, 밀착성, 건조시간, 내수성을 KS 인증 시험방법에 따라 다음과 같이 측정하였으며, 그 결과는 다음 표 1과 같다.The physical properties of the emulsions obtained in Example 1 and Comparative Example 1 were evaluated. Non-volatile content, viscosity, Tg, coating state, adhesion, drying time, water resistance as an evaluation property items were measured as follows according to the KS certification test method, the results are shown in Table 1 below.
* 불휘발분(고형분) - KS M 6010: 2009* Nonvolatile matter (solids)-KS M 6010: 2009
* 점도 - KS M ISO 2555: 2009 (#3, 60rpm)* Viscosity-KS M ISO 2555: 2009 (# 3, 60rpm)
* 도막상태 - KS M 5000: 2009* Coating condition-KS M 5000: 2009
* 밀착성 - KS M ISO 2409* Adhesion-KS M ISO 2409
* 건조시간 - KS M 6010: 2009* Drying time-KS M 6010: 2009
* 내수성 - KS M 5605* Water resistance-KS M 5605
표 1
구분 실시예 1 비교예 1
고형분 50.0 50.1
점도(CPS) 820 10,000 이상
도막상태 양호 불량
밀착성(ISO Class) ○ ○
건조시간(고화, 분) 30 30
내수성 ○ X
Table 1
division Example 1 Comparative Example 1
Solid content 50.0 50.1
Viscosity (CPS) 820 More than 10,000
Coating state Good Bad
Adhesiveness (ISO Class) ○ ○
Drying time (solid, min) 30 30
Water resistance ○ X
※ ○: 이상 없음* ○: no abnormality
△: 기포 및 백화 약간 발생   △: slight bubble and whitening
×: 도막 전체에 걸쳐 기포 및 백화 발생   ×: bubbles and whitening occur throughout the coating film
표 1의 결과로부터, 본 발명에 따라 얻어진 에멀젼은 특히 내수성 및 점도에 있어서 매우 우수하며, 밀착성(즉, 접착력)에 있어서도 적합함을 알 수 있다. 이에 반하여, 코어-쉘 구조가 아닌 단순 중합에 의해 얻어진 공중합물의 경우(즉 비교예 1의 에멀젼의 경우), 점도가 크게 증가하여 수성 도료용 접착 소재로서 부적합할 뿐만 아니라, 도막상태 및 내수성에 있어서도 부적합하였다.From the results in Table 1, it can be seen that the emulsions obtained according to the present invention are particularly excellent in water resistance and viscosity, and also suitable in adhesion (i.e. adhesion). In contrast, in the case of a copolymer obtained by a simple polymerization rather than a core-shell structure (that is, in the case of the emulsion of Comparative Example 1), the viscosity is greatly increased, which is not suitable as an adhesive material for water-based coatings, but also in the state of coating and water resistance. It was inappropriate.

Claims (12)

  1. (a) 수성 전분 호화액에 아크릴계 또는 메타크릴계 단량체(이하, '제1 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 전분과 단량체가 공중합된 코어를 형성시키는 단계; 및(a) adding an acrylic or methacrylic monomer (hereinafter referred to as 'first monomer') and a polymerization initiator to the aqueous starch gelatinization solution and polymerizing to form a core copolymerized with starch and monomer; And
    (b) 단계(a)에서 얻어진 반응물에 스티렌, 프로필렌, 아크릴산 에스테르, 메타크릴산 에스테르, 아크릴로니트릴, 및 에틸렌으로 이루어진 군으로부터 1종 이상 선택된 단량체(이하, '제2 단량체'라 함) 및 중합개시제를 가하고 중합시켜, 상기 코어 상에 제2 단량체가 중합되어 형성된 코어-쉘 구조의 공중합체를 함유한 에멀젼을 형성시키는 단계(b) at least one monomer selected from the group consisting of styrene, propylene, acrylic esters, methacrylic esters, acrylonitrile, and ethylene in the reaction obtained in step (a) (hereinafter referred to as 'second monomer') and Adding a polymerization initiator and polymerizing to form an emulsion containing a core-shell copolymer formed by polymerization of a second monomer on the core;
    를 포함하는, 수성 도료용 접착 소재의 제조방법.A method of producing an adhesive material for an aqueous paint, comprising a.
  2. 제1항에 있어서, 상기 제1 단량체가 아크릴산, 메타크릴산, 2-하이드록시프로필 메타크릴레이트, 2-하이드록시에틸 메타크릴레이트, 디메틸아미노에틸 메타아크릴레이트, t-부틸아미노에틸메타아크릴레이트, 디에틸아미노에틸 메타크릴레이트, 글리시딜 메타아크릴레이트, 2-하이드록시에틸 아크릴레이트, 2-하이드록시프로필 아크릴레이트, 아크릴아마이드, 및 N-메틸올 아크릴아미드로 이루어진 군으로부터 1 종 이상 선택된 관능성 아크릴계 또는 메타크릴계 단량체와; 메틸 메타크릴레이트, 에틸 메타크릴레이트, 이소부틸 메타크릴레이트, n-부틸 메타크릴레이트, t-부틸 메타크릴레이트, n-헥실 메타크릴레이트, 2-에틸헥실 메타크릴레이트, 이소보닐 메타크릴레이트, 라우릴 메타아크릴레이트, 시클로헥실 메타크릴레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 이소부틸 아크릴레이트, n-부틸 아크릴레이트, t-부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, n-옥틸 아크릴레이트, 이소보닐 아크릴레이트, 및 시클로헥실 아크릴레이트로 이루어진 군으로부터 1 종이상 선택된 비관능성 아크릴계 또는 메타크릴계 단량체와의 혼합물인 것을 특징으로 하는 제조방법.The method of claim 1, wherein the first monomer is acrylic acid, methacrylic acid, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate At least one selected from the group consisting of diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, and N-methylol acrylamide Functional acrylic or methacrylic monomers; Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate , Lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n -A process with a nonfunctional acrylic or methacrylic monomer selected from the group consisting of octyl acrylate, isobonyl acrylate, and cyclohexyl acrylate.
  3. 제2항에 있어서, 상기 관능성 아크릴계 또는 메타크릴계 단량체와 상기 비관능성 아크릴계 또는 메타크릴계 단량체의 혼합비(중량비)가 1 : 3∼30 의 범위인 것을 특징으로 하는 제조방법.The method according to claim 2, wherein the mixing ratio (weight ratio) of the functional acrylic or methacrylic monomer and the nonfunctional acrylic or methacrylic monomer is in the range of 1: 3 to 30.
  4. 제2항에 있어서, 상기 관능성 아크릴계 또는 메타크릴계 단량체가 메타크릴산이고; 상기 비관능성 아크릴계 또는 메타크릴계 단량체가 메틸 메타크릴레이트, n-부틸 아크릴레이트, 또는 이들의 혼합물인 것을 특징으로 하는 제조방법.The method of claim 2, wherein the functional acrylic or methacrylic monomer is methacrylic acid; The non-functional acrylic or methacryl-based monomer is methyl methacrylate, n-butyl acrylate, or a mixture thereof.
  5. 제1항에 있어서, 상기 제1 단량체의 사용량이 상기 전분 1 중량부에 대하여 0.3∼3.0 중량부의 범위인 것을 특징으로 하는 제조방법.The method according to claim 1, wherein the amount of the first monomer is in the range of 0.3 to 3.0 parts by weight based on 1 part by weight of the starch.
  6. 제1항에 있어서, 단계(a)의 상기 중합이 인산 에스테르계 유화제 혹은 황산염 에스테르계 유화제의 존재하에서 수행되는 것을 특징으로 하는 제조방법.The process according to claim 1, wherein the polymerization in step (a) is carried out in the presence of a phosphate ester emulsifier or a sulfate ester emulsifier.
  7. 제6항에 있어서, 상기 유화제가 노닐프로페닐에톡시에테르 술페이트의 암모늄염류, 폴리옥시에틸렌 알킬페닐 알릴 소듐설페이트의 에스테르류, 폴리옥시에틸렌 알릴 글리시딜 노닐 페닐에테르의 술폰산 에스테르류, 및 폴리옥시에틸렌 노닐 프로페닐 에테르의 술폰산 에스테르의 암모늄염류로 이루어진 군으로부터 1 종 이상 선택되는 것을 특징으로 하는 제조방법.The method of claim 6, wherein the emulsifier is ammonium salts of nonylpropenylethoxyether sulfate, esters of polyoxyethylene alkylphenyl allyl sodium sulfate, sulfonic acid esters of polyoxyethylene allyl glycidyl nonyl phenyl ether, and poly At least one member selected from the group consisting of ammonium salts of sulfonic acid esters of oxyethylene nonyl propenyl ether.
  8. 제1항 또는 제6항에 있어서, 단계(a)의 상기 중합이 에틸렌 옥사이드 또는 폴리프로필렌 옥사이드 단위체가 함유된 비이온성 유화제의 존재하에서 수행되는 것을 특징으로 하는 제조방법.The process according to claim 1 or 6, wherein the polymerization in step (a) is carried out in the presence of a nonionic emulsifier containing ethylene oxide or polypropylene oxide units.
  9. 제8항에 있어서, 상기 비이온성 유화제가 폴리옥시에틸렌 폴리옥시프로필렌 알킬 에테르류, 폴리옥시에틸렌 스테아릴 아민류, 폴리에틸렌 솔비탄류, 및 알킬폴리옥시에틸렌-프로필렌 공중합체류로 이루어진 군으로부터 1 종 이상 선택되는 것을 특징으로 하는 제조방법.The nonionic emulsifier is selected from the group consisting of polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene stearyl amines, polyethylene sorbitan, and alkylpolyoxyethylene-propylene copolymers. Manufacturing method characterized in that.
  10. 제1항에 있어서, 상기 제2 단량체가 메틸 메타크릴레이트, n-부틸 아크릴레이트, 스티렌, 및 2-에틸헥실 메타크릴레이트로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 제조방법.The method according to claim 1, wherein the second monomer is selected from the group consisting of methyl methacrylate, n-butyl acrylate, styrene, and 2-ethylhexyl methacrylate.
  11. 제10항에 있어서, 상기 제2 단량체가 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 스티렌의 혼합물; 또는 메틸 메타크릴레이트, n-부틸 아크릴레이트, 및 2-에틸헥실 메타크릴레이트의 혼합물인 것을 특징으로 하는 제조방법.The compound of claim 10, wherein the second monomer is a mixture of methyl methacrylate, n-butyl acrylate, and styrene; Or a mixture of methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl methacrylate.
  12. 제1항에 있어서, 상기 제2 단량체의 사용량이 상기 제1 단량체 1 중량부에 대하여 1.0∼9.0 중량부의 범위인 것을 특징으로 하는 제조방법.The method according to claim 1, wherein the amount of the second monomer used is in the range of 1.0 to 9.0 parts by weight based on 1 part by weight of the first monomer.
PCT/KR2011/004695 2010-06-30 2011-06-28 Method for preparing adhesive material for aqueous paint WO2012002696A2 (en)

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