WO2012002696A2 - 수성 도료용 접착 소재의 제조방법 - Google Patents

수성 도료용 접착 소재의 제조방법 Download PDF

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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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Prior art keywords
monomer
methacrylate
acrylate
starch
methacrylic
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PCT/KR2011/004695
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English (en)
French (fr)
Korean (ko)
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WO2012002696A3 (ko
Inventor
한민
함충현
전영승
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대상 주식회사
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Priority to CN201180032782.1A priority Critical patent/CN102971387B/zh
Priority to JP2013518243A priority patent/JP5733394B2/ja
Publication of WO2012002696A2 publication Critical patent/WO2012002696A2/ko
Publication of WO2012002696A3 publication Critical patent/WO2012002696A3/ko

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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)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)
PCT/KR2011/004695 2010-06-30 2011-06-28 수성 도료용 접착 소재의 제조방법 WO2012002696A2 (ko)

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