WO2016084624A1 - Procédé de production d'une résine d'émulsion de peinture - Google Patents

Procédé de production d'une résine d'émulsion de peinture Download PDF

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Publication number
WO2016084624A1
WO2016084624A1 PCT/JP2015/081969 JP2015081969W WO2016084624A1 WO 2016084624 A1 WO2016084624 A1 WO 2016084624A1 JP 2015081969 W JP2015081969 W JP 2015081969W WO 2016084624 A1 WO2016084624 A1 WO 2016084624A1
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Prior art keywords
emulsion
monomer
emulsion resin
mass
parts
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PCT/JP2015/081969
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English (en)
Japanese (ja)
Inventor
雅志 林
山本　正治
尾田　浩
伸太郎 桑原
隆治 川合
梓 宮原
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日本ペイントホールディングス株式会社
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Publication of WO2016084624A1 publication Critical patent/WO2016084624A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a method for producing an emulsion resin for paint.
  • Liquid coating compositions can generally be roughly classified into two types: solvent-type coating compositions containing organic solvents and aqueous coating compositions.
  • water-based paint compositions are widely used because they contain a small amount of organic solvent and have a low environmental impact.
  • Many of such aqueous coating compositions contain an emulsion resin.
  • By including an emulsion resin in the aqueous coating composition it is possible to prepare a coating composition having a high solid content compared to an aqueous coating composition containing only a water-soluble resin, and the design range of the coating composition. There are advantages such as spreading.
  • water-based paint compositions are required to be dried and cured more quickly while ensuring paint stability. Therefore, a method for producing an emulsion resin having a higher solid content is required.
  • Patent Document 1 a monomer or a monomer mixture mainly composed of (meth) acrylic acid ester is emulsion-polymerized while continuously or intermittently adding a surfactant.
  • a method for producing an acrylic emulsion characterized by the above is described (claim 1). It is described that this production method can produce an acrylic emulsion having a high solid content, high particle stability, low viscosity, and excellent mechanical stability (paragraph [0010] etc. ).
  • the acrylic emulsion obtained by the method of Patent Document 1 has no explanation for blending a high concentration of styrene.
  • the configuration is different from the present invention in that the styrene content is low in Examples and the like.
  • Patent Document 2 a basic compound is added to a monomer mixture mainly composed of (meth) acrylic acid ester and an acidic monomer to neutralize or partially neutralize and then emulsify.
  • a method for producing an acrylic emulsion characterized by polymerization is described (claim 1). It is described that an acrylic emulsion having a low viscosity and a high solid content can be produced very easily by this production method (paragraph [0010]).
  • the acrylic emulsion obtained by the method of Patent Document 2 also has no explanation for high-concentration styrene blending.
  • the configuration is different from the present invention in that the styrene content is low in Examples and the like.
  • An emulsion resin having a low styrene content has a drawback of poor alkali resistance.
  • the blending amount of styrene is small, it is difficult to obtain the effect of improving the mechanical strength of the coating film due to the rigid structure derived from the aromatic ring. For this reason, it is difficult to obtain durability improvement effects such as excellent wear resistance, washing resistance and adhesion.
  • Cited Document 3 Japanese Patent Application Laid-Open No. 2001-342201 (Cited Document 3) is characterized in that a vinyl monomer is emulsion-polymerized in an aqueous medium in which an electrolyte substance is dissolved while reducing the concentration of the electrolyte substance. And a method for producing a resin emulsion (claim 1 and the like). It is described that an emulsion having a high concentration, a low viscosity, and extremely reduced generation of aggregates can be produced by this method ([0006] paragraph, etc.). However, when the concentration of the electrolyte substance in the resin emulsion increases, the electrolyte concentration in the coating film increases, and the water resistance of the coating film may be inferior.
  • the acrylic emulsion obtained by the method of Patent Document 3 is also different from the present invention in that the styrene content is low.
  • the present invention solves the above-mentioned conventional problems, and its object is to provide a coating emulsion resin having a high solid content even in the case of emulsion polymerization of a monomer mixture having a high styrene monomer content. It is to provide a method that can be manufactured.
  • a method for producing an emulsion resin for paint The above method Preparing a pre-emulsion solution comprising a monomer mixture comprising styrene monomer (a) 20-50% by weight, and ⁇ , ⁇ -ethylenically unsaturated monomer (b) 50-80% by weight copolymerizable with (a).
  • the emulsion resin for paints obtained by the above production method has a number average particle size of 500 nm or less and a solid content concentration of 50% by mass or more.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer (b) includes a (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less,
  • the content of the (meth) acrylic monomer (b1) in the monomer mixture is 10 to 60% by mass
  • the surfactant is added in several portions. Manufacturing method of emulsion resin for paint.
  • the addition of the surfactant multiple times in the emulsion resin formation step is preferably performed in an amount that is increased by 20% by mass or more with respect to the amount of the surfactant added in the subsequent surfactant addition.
  • the monomer (b) includes an ⁇ , ⁇ -ethylenically unsaturated monomer having an acid group,
  • the neutralization rate of the monomer mixture (b) in the pre-emulsion solution is preferably 1.5 to 30%.
  • the emulsion resin for paints obtained by the above production method preferably has a residual monomer concentration of less than 1000 ppm.
  • the oil-soluble polymerization initiator preferably has a water solubility at 20 ° C. of 1 g / L or less.
  • the total amount of the surfactant added in the emulsion resin forming step is preferably 10 to 40% by mass with respect to the total amount of the surfactant used in the method for producing the emulsion resin for paint.
  • a coating emulsion resin having a high solid content can be produced even when a monomer mixture having a high styrene monomer content is subjected to emulsion polymerization.
  • a coating composition using the emulsion resin for coating obtained by the production method of the present invention it becomes possible to blend many rigid styrene skeletons derived from aromatic rings. Thereby, the mechanical strength of the coating film obtained can be improved.
  • the production method of the present invention it is possible to prepare a coating composition that provides a highly durable coating film having excellent wear resistance, alkali resistance, washing resistance, adhesion, and the like.
  • the background to the present invention will be described.
  • the present inventors have shown that in the preparation of an aqueous coating composition, by increasing the styrene content contained in the emulsion resin for coating, the performance such as alkali resistance of the resulting coating composition can be improved. I found it.
  • the production of an emulsion resin if the styrene monomer content in the monomer mixture used for the preparation is high, the production of the emulsion resin becomes difficult, especially the production of an emulsion resin for paints having a high solid content. It has been found through experiments that it becomes very difficult.
  • a monomer mixture is first dispersed / dissolved in water, and then the monomer is copolymerized through a process of being absorbed in micelles or particles as a polymerization reaction field. Since styrene monomer generally has low solubility in water, when the content of styrene monomer is high, in the copolymerization under the condition of low water content, it is difficult for the monomer mixture to be dispersed / dissolved in water, and the polymerization reaction The amount of monomer mixture absorbed into the field micelles or particles is significantly reduced.
  • Method for producing emulsion resin for paint is as follows. Preparing a pre-emulsion solution comprising a monomer mixture comprising styrene monomer (a) 20-50% by weight, and ⁇ , ⁇ -ethylenically unsaturated monomer (b) 50-80% by weight copolymerizable with (a). A pre-emulsion solution preparation step, and an emulsion resin formation step of forming an emulsion resin by emulsion polymerization of the monomer mixture, Is included.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer (b) includes a (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less, and the monomer The content of the (meth) acrylic monomer (b1) in the mixture is 10 to 60% by mass.
  • the surfactant is added in a plurality of times after the polymerization rate of the monomer mixture is in the range of 45% to 90%.
  • Pre-emulsion solution preparation step In the pre-emulsion solution preparation step, a pre-emulsion solution containing a monomer mixture is prepared.
  • the “pre-emulsion solution” means a solution containing the monomer mixture used for preparing the emulsion resin.
  • This pre-emulsion solution can be prepared by mixing the monomer mixture, a solvent, and additives such as a neutralizing agent and a surfactant as necessary.
  • the monomer mixture is composed of 20 to 50% by mass of styrene monomer (a) and 50 to 80% by mass of ⁇ , ⁇ -ethylenically unsaturated monomer (b) copolymerizable with styrene monomer (a).
  • the mass ratio is more preferably 25 to 50% by mass of the styrene monomer (a) and 50 to 75% by mass of the ⁇ , ⁇ -ethylenically unsaturated monomer (b), and the styrene monomer (a) 30 to 50% by mass. More preferably, it is 50% by mass and 50% to 70% by mass of the ⁇ , ⁇ -ethylenically unsaturated monomer (b).
  • the content of the styrene monomer (a) exceeds 50% by mass, the reactivity of the monomer mixture is lowered, the stability of the resulting emulsion resin is lowered, and the residual monomer amount may be increased.
  • the content of the styrene monomer (a) is less than 20% by mass, the effect of improving the mechanical strength derived from the rigid skeleton derived from styrene cannot be expressed sufficiently, and the coating composition containing the emulsion resin is used. The effect of improving durability such as alkali resistance, washing resistance, and adhesion in the formed coating film cannot be sufficiently obtained.
  • styrene monomer (a) examples include styrene and styrene derivatives.
  • styrene derivatives include ⁇ -alkylstyrene (eg, ⁇ -methylstyrene), p-alkylstyrene (eg, p-methylstyrene, t-butylstyrene), p-alkyloxystyrene (eg, p-methoxystyrene). , P-chlorostyrene, 4-hydroxystyrene, and the like.
  • the styrene content in the styrene monomer (a) is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass. More preferably, only styrene is used as the styrene monomer.
  • ⁇ -ethylenically unsaturated monomer (b) copolymerizable with a styrene monomer for example, Acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth ) (Meth) acrylic such as dicyclopentadienyl acrylate, dihydrodicyclopentadienyl (meth)
  • the ⁇ , ⁇ -ethylenically unsaturated monomer (b) includes a (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less.
  • the content of the (meth) acrylic monomer (b1) in the monomer mixture is 10 to 60% by mass (10 to 60 parts by mass with respect to 100 parts by mass of the monomer mixture).
  • the content of the (meth) acrylic monomer (b1) is more preferably 15 to 55% by mass.
  • the monomer reactivity ratio r1 with styrene is the reaction in the case where M1 and M2 are copolymerized when monomer M1 is styrene and monomer M2 is another monomer such as a (meth) acrylic monomer. It is an index showing the ease of doing it. When r1 is 1 or more, it indicates that the monomers M1 are easily polymerized. Moreover, when r1 is less than 1, it shows that M1 and M2 are easily copolymerized.
  • This reactivity ratio r1 can be obtained as a literature value. For example, POLYMER HANDBOOK, fourth edition, volume 1, WILLY-INTERSCIENCE, A John Wiley & Sons, Inc. The reactivity ratio r1 is described.
  • the (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less include, for example, methacrylic acid (r1: 0.21), acrylic acid (r1: 0.25), Methyl methacrylate (r1: 0.5), n-butyl methacrylate (r1: 0.56), i-butyl methacrylate (r1: 0.55), ethyl methacrylate (r1: 0.55), glycidyl methacrylate (r1: 0) .54), cyclohexyl methacrylate (r1: 0.58), benzyl methacrylate (r1: 0.45), phenyl methacrylate (r1: 0.25), and the like.
  • (meth) acrylic monomers (b1) methacrylic acid, acrylic acid, methyl methacrylate, n-butyl methacrylate, etc. have high copolymerizability with styrene, and Tg design of the resulting coating film is easy. In view of ease of material acquisition, product price, and the like.
  • the (meth) acrylic monomer (b1) only one type may be used, or two or more types may be used in combination.
  • the reactivity ratio r1 in the (meth) acrylic monomer (b1) is more preferably 0.6 or less, and further preferably 0.5 or less.
  • the (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less is contained in the above mass range, whereby styrene
  • the reactivity of the monomer (a) with the ⁇ , ⁇ -ethylenically unsaturated monomer (b) is in the optimum range for the preparation of the emulsion resin, and the polymerization reaction proceeds well, resulting in stability over time, etc. There is an advantage that an excellent emulsion resin can be obtained.
  • a monomer mixture containing 20 to 50% by mass of styrene monomer (a) and 50 to 80% by mass of ⁇ , ⁇ -ethylenically unsaturated monomer (b) is used, where ⁇ ,
  • the ⁇ -ethylenically unsaturated monomer (b) contains a (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less, and further the (meth) in the monomer mixture.
  • a coating emulsion resin having a high styrene monomer (a) content and a solid content concentration of 50% by mass or more is preferable because the acrylic monomer (b1) content is 10 to 60% by mass.
  • the pre-emulsion solution contains a solvent and, if necessary, a neutralizing agent and a surfactant in addition to the monomer mixture.
  • Water is preferably used as the solvent contained in the pre-emulsion solution. If necessary, an organic solvent that does not react with the monomer mixture can also be used as a solvent.
  • the pre-emulsion solution preferably contains a neutralizing agent.
  • the neutralizing agent here means a basic substance that can be contained in the monomer mixture and neutralizes the acid group of the ⁇ , ⁇ -ethylenically unsaturated monomer having an acid group.
  • ⁇ , ⁇ -ethylenically unsaturated monomers having acid groups include acrylic acid, methacrylic acid, and ⁇ , ⁇ -ethylenic acids having acid groups exemplified in the above ⁇ , ⁇ -ethylenically unsaturated monomers (b). Examples include unsaturated monomers.
  • Specific examples of the neutralizing agent include ammonium hydroxide, aqueous ammonia, potassium hydroxide, calcium hydroxide, aluminum hydroxide, sodium hydrogen carbonate and the like.
  • the neutralization rate of the monomer mixture (b) in the pre-emulsion solution is preferably 1.5 to 30%, more preferably 2 to 30%, still more preferably 3 to 30%. . If the neutralization rate is less than 1.5%, the neutralization stabilization effect of the emulsion may not be obtained. On the other hand, if it exceeds 30%, the viscosity of the emulsion increases, which may make the production difficult.
  • the neutralization rate of the monomer mixture (b) refers to the amount of the ⁇ , ⁇ -ethylenically unsaturated monomer having an acid group and the neutralizing agent (basic substance) contained in the monomer mixture. It can be determined by calculating from the amount (molar ratio).
  • the pre-emulsion solution contains a neutralizing agent, there is an advantage that the viscosity of the pre-emulsion solution can be designed to be low and the manufacturing workability is improved.
  • the pre-emulsion solution may contain a surfactant as necessary.
  • a surfactant By including the surfactant in the pre-emulsion solution, there are advantages that the monomer dispersion performance is improved and the polymerization reaction proceeds well in the polymerization of the monomer mixture.
  • the surfactant include an anionic surfactant, a nonionic surfactant, and a polymerizable surfactant.
  • anionic surfactant a commonly used anionic surfactant can be used.
  • anionic surfactants include, for example, alkyl fatty acid salts, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, polyoxyethylene aryls.
  • Examples thereof include ether sulfates, alkylbenzene sulfonates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, sulfosuccinic acid alkyl disalts, polyoxyethylene sulfosuccinic acid alkyl disalts, and acylmethyl taurine.
  • the salt include ammonium salt, alkali metal salt, alkaline earth metal salt, alkanolamine salt and the like.
  • these surfactants polyoxyethylene alkylphenyl ether ammonium sulfate and polyoxyethylene polycyclic phenyl ether ammonium sulfate are more preferable.
  • nonionic surfactant a commonly used nonionic surfactant can be used.
  • specific examples of nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, alkyl fatty acid diethanolamide, alkyldimethylamine. And oxides.
  • polymerizable surfactant examples include a polymerizable surfactant having a double bond having radical polymerization ability in the molecule.
  • polymerizable surfactants include, for example, alkylallylsulfosuccinate, methacryloyl polyoxyalkylene sulfate, polyoxyethylene nonylpropenyl phenyl ether sulfate, and the like.
  • the content of the polymerizable surfactant is incorporated as part of the ⁇ , ⁇ -ethylenically unsaturated monomer (b) copolymerizable with (a). .
  • surfactants may be used alone or in combination of two or more. Moreover, you may use a commercial item as surfactant.
  • the amount of the surfactant contained in the pre-emulsion solution is preferably 0.05 to 8 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the pre-emulsion solution. .
  • Emulsion resin forming step In the emulsion resin forming step, the monomer mixture is subjected to emulsion polymerization to form an emulsion resin.
  • the method for emulsion polymerization of the monomer mixture include a method of sequentially dropping a pre-emulsion solution containing the monomer mixture into a polymerization reaction vessel.
  • the polymerization reaction vessel into which the pre-emulsion solution is dropped preferably contains an aqueous medium in advance.
  • the aqueous medium that can be contained in the polymerization reaction vessel include an aqueous medium containing water and a polymerization initiator as necessary.
  • Persulfate polymerization initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis [2-methyl-N— Water-soluble azo polymerization initiators such as (2-hydroxyethyl) propionamide], Organic peroxidation such as t-butyl
  • the pre-emulsion solution is successively dropped into the polymerization reaction vessel and the polymerization reaction is performed, for example, at room temperature to 95 ° C., more preferably 70 to 90 ° C., for 1 to 24 hours, more preferably 2 to 12 hours, and still more preferably. May include a mode in which the pre-emulsion solution is dropped over 2 to 6 hours.
  • conditions, such as these temperature and dripping time can be suitably changed according to the reactor used, reaction scale, etc.
  • the surfactant is added in a plurality of times. “The surfactant is added after the polymerization rate of the monomer mixture exceeds 45%” means that the surfactant is not added in the emulsion resin formation step in a state where the polymerization rate of the monomer mixture is less than 45%. Means that.
  • the surfactant contained in the pre-emulsion solution as needed does not correspond to the “addition of surfactant in the emulsion resin forming step” referred to herein.
  • the upper limit of the polymerization rate when starting the addition of the surfactant is 90%.
  • the surfactant after the polymerization rate of the monomer mixture exceeds 50%.
  • the upper limit of the polymerization rate when starting the addition of the surfactant is more preferably 85%.
  • “adding the surfactant in a plurality of times” is in contrast to the state of “adding the surfactant continuously”, and the surfactant is added in 2 or It means a state where it is added in divided portions.
  • the surfactant may be added separately in 2 to 20 times.
  • the surfactant is preferably added in 2 to 10 times, preferably in 2 to 7 times. Is more preferable.
  • the term “one time” as used herein means a state in which a predetermined amount of surfactant is added in one shot, and does not mean a state of continuous dripping.
  • the polymerization rate means a ratio (mass%) in which the monomer mixture is polymerized to become a polymer. This polymerization rate can be determined by sampling the reaction mixture and measuring the mass of the polymer produced.
  • the surfactant to be added in the emulsion resin forming step can be used.
  • the surfactant polyoxyethylene alkylphenyl ether ammonium sulfate, polyoxyethylene polycyclic phenyl ether ammonium sulfate, or the like is more preferably used.
  • the addition of the surfactant multiple times in the emulsion resin formation step is preferably performed in an amount that is increased by 20% by mass or more with respect to the amount of the surfactant added in the subsequent surfactant addition. More specifically, for example, when the addition amount of the first surfactant is z parts by mass, the addition amount of the second surfactant is z ⁇ 1.2 parts by mass or more. .
  • the upper limit of the amount of addition of the surfactant in the subsequent addition is not particularly limited, but may be, for example, 5 times or less, more preferably 3 times or less, and 2 times or less. Is more preferable.
  • the amount of the surfactant added in a plurality of times is increased as the amount is added later.
  • the particle size of the emulsion resin changes according to the reaction time, thereby forming an emulsion resin having a high solid content concentration and better storage stability. There is an advantage that becomes possible.
  • the total amount of the surfactant (active ingredient amount) added in the emulsion resin forming step is preferably 0.05 to 10 parts by mass, and preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture. More preferably, the amount is 0.2 to 3 parts by mass.
  • the total amount of the surfactant added in the emulsion resin forming step is 0.55 to 1.5 parts by mass with respect to 100 parts by mass of the monomer mixture, and this surfactant is added in four portions.
  • the first addition amount is 0.1 parts by mass
  • the second addition amount is 0.12 to 0.2 parts by mass
  • the third addition amount is 0.15 to 0.4 parts by mass
  • the amount added in the second round is 0.18 to 0.8 parts by mass.
  • the total amount of the surfactant added in the emulsion resin forming step is preferably 10 to 40% by mass, and preferably 15 to 30% by mass with respect to the total amount of the surfactant used in the method for producing the emulsion resin for paints. % Is more preferred.
  • total amount of surfactant used in the method for producing emulsion resin for paint refers to the amount of surfactant contained in the pre-emulsion solution and the total amount of surfactant added in the emulsion resin forming step. Means the total amount.
  • the emulsion resin obtained by the production method of the present invention has a number average particle size of 500 nm or less.
  • the number average particle diameter of the emulsion resin in the present specification can be determined by a dynamic and / or electrophoretic light scattering method using a particle size measuring device (for example, ELS-Z manufactured by Otsuka Electronics Co., Ltd.).
  • the number average particle size of the emulsion resin is more preferably 450 nm or less, and still more preferably 400 nm or less.
  • the solid content concentration of the emulsion resin is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and further preferably 65% by mass or more.
  • the emulsion resin obtained by the production method of the present invention is characterized by containing a large amount of a styrene component.
  • the production stability and the dispersion stability are excellent.
  • Such a feature is more preferable in that the number average molecular weight is 500 nm or less as described above, and the particle size distribution is, for example, a bimodal distribution.
  • the particle size distribution can be determined by measuring the particle size distribution using the particle size measuring apparatus as described above.
  • the solid content is measured by determining the difference in mass before and after drying when dried at 150 ° C. for 1 hour.
  • a residual monomer polymerization step After adding the oil-soluble polymerization initiator, further adding a reducing agent to polymerize the residual monomer, a residual monomer polymerization step, The embodiment including is more preferable. By including this step, the amount of residual monomer derived from the monomer mixture can be reduced, and problems such as odor can be solved.
  • the concentration of the residual monomer contained in the obtained emulsion resin is preferably less than 1000 ppm, and more preferably less than 900 ppm. In the present specification, the concentration of the residual monomer can be measured using a liquid chromatograph / mass spectrometer.
  • the oil-soluble polymerization initiator preferably has a water solubility at 20 ° C. of 1 g / L or less.
  • an oil-soluble polymerization initiator for example, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxybenzoate, t-butyl hydroperoxide, t-butylperoxy-3,5,5-trimethylhexanoate, di- organic peroxides such as t-butyl peroxide, and 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (N-butyl-2
  • oil-soluble polymerization initiator for example, it is more preferable to use one or more selected from the group consisting of t-butylperoxy-2-ethylhexanoate.
  • the amount of the oil-soluble polymerization initiator added in the residual monomer polymerization step is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer mixture.
  • the amount is preferably 0.2 to 2 parts by mass.
  • reducing agent for example, Reducing organic compounds such as L-ascorbic acid, L-ascorbate (such as sodium ascorbate), tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salts, and sodium thiosulfate, sodium sulfite, sodium acid sulfite, Reducing inorganic compounds such as sodium metabisulfite and ferrous chloride, Etc.
  • Reducing organic compounds such as L-ascorbic acid, L-ascorbate (such as sodium ascorbate), tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salts, and sodium thiosulfate, sodium sulfite, sodium acid sulfite, Reducing inorganic compounds such as sodium metabisulfite and ferrous chloride, Etc.
  • Reducing organic compounds such as L-ascorbic acid, L-ascorbate (such as sodium ascorbate), tart
  • the reducing agent for example, one kind selected from the group consisting of L-ascorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate metal salt, sodium thiosulfate, sodium sulfite, sodium acid sulfite, sodium metabisulfite, or It is more preferable to use more than that.
  • the amount of the reducing agent added in the residual monomer polymerization step is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer mixture. More preferably, it is 2 to 2 parts by mass.
  • the oil-soluble polymerization initiator is added first, and the reducing agent is added after a certain period of time.
  • the reducing agent is added after 10 minutes or more have elapsed since the oil-soluble polymerization initiator is added.
  • This elapsed time is more preferably 15 minutes or more, and further preferably 20 minutes or more.
  • an additive in addition to the above components, an additive as necessary may be used in any step.
  • the additive include a polymerization regulator such as a chain transfer agent and a buffer.
  • the polymerization regulator may be added in advance to the pre-emulsion solution in the pre-emulsion solution preparation step, or may be added by an arbitrary procedure in the emulsion resin formation step.
  • chain transfer agents include alcohols such as methanol, ethanol, propanol and butanol; carboxylic acids having 2 to 8 carbon atoms such as acetone, methyl ethyl ketone, cyclohexane, acetophenone, acetaldehyde, propionaldehyde, n-butyraldehyde, furfural, benzaldehyde and the like.
  • mercaptans such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octyl thioglycolate, and thioglycerol. Two or more of these may be used in combination.
  • the buffer include sodium acetate, ammonium acetate, dibasic sodium phosphate, and the like. Two or more of these may be used in combination.
  • the production method of the present invention makes it possible to produce a coating emulsion resin having a high solid content even in the case of emulsion polymerization of a monomer mixture having a high styrene monomer content.
  • the mechanical strength of the coating film obtained is improved by preparing a coating composition using a coating emulsion resin obtained by the production method of the present invention and having a high content of rigid styrene component derived from an aromatic ring. To do.
  • cleaning resistance, adhesiveness, etc. which has the outstanding durability can be prepared.
  • the emulsion resin obtained by the production method of the present invention has a solid content of 50% or more.
  • the solid content may be an emulsion resin having a very high solid content, for example, a solid content of 60% or more, and further a solid content of 65% or more.
  • a solid content of 60% or more for example, a solid content of 60% or more, and further a solid content of 65% or more.
  • the emulsion resin has a high solid content, there is an advantage that the degree of design freedom in the preparation of the coating composition is significantly improved.
  • the solid content of the emulsion resin used for the preparation of the coating composition is high, there is also an advantage that the energy required in the production and transportation of the coating composition can be reduced.
  • Coating Composition also relates to a coating composition containing an emulsion resin obtained by the above production method.
  • the coating composition include the emulsion resin and, if necessary, a pigment, a design material (such as sand, cinnabar, color sand, beads, color chips, mineral chips, glass chips, wood chips, and color beads), pigments
  • a coating composition containing a dispersant, other resin components, a thickener, a pH adjuster, a solvent and additives.
  • the pigment is not particularly limited, for example, an azo chelate pigment, an insoluble azo pigment, a condensed azo pigment, a monoazo pigment, a disazo pigment, a diketopyrrolopyrrole pigment, a benzimidazolone pigment, a phthalocyanine pigment, Indigo pigment, thioindigo pigment, perinone pigment, perylene pigment, dioxane pigment, quinacridone pigment, isoindolinone pigment, naphthol pigment, pyrazolone pigment, anthraquinone pigment, anthorapyrimidine pigment, metal complex Organic color pigments such as pigments: yellow lead, yellow iron oxide, chromium oxide, molybdate orange, bengara, titanium yellow, zinc white, carbon black, titanium dioxide, cobalt green, phthalocyanine green, ultramarine, cobalt blue, phthalocyanine blue, Cobalt buy Inorganic pigments such as lettuce; mica pigments (titanium dioxide-coated mica,
  • a pigment When a pigment is contained in the coating composition, it is preferable to improve the pigment dispersion performance using a pigment dispersant.
  • a pigment dispersant for example, DISPERBYK (trademark) -102, 180, 184, 185, 187, 190, 191, 192, 193, 194N, 198, 199, 2010, 2012, 2015, 2096, etc. Agents and the like.
  • the pigment mass concentration (PWC) with respect to the solid content of the coating composition is preferably in the range of 5 to 70% by mass.
  • the PWC is less than 5% by mass, the base concealing property is inferior, and when the PWC exceeds 70% by mass, the weather resistance may be lowered.
  • the pigment mass concentration (PWC) is more preferably 20 to 45% by mass.
  • resin components include, for example, epoxy resins; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate resins; polyurethane resins; cellulose derivatives such as nitrocellulose, cellulose acetate, and cellulose acetate butyrate; polyvinyl chloride; Vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, acrylonitrile-butadiene Copolymers, copolymers such as acrylonitrile-butadiene-styrene copolymer; polybutadiene; chlorinated rubber; petroleum resin; polyvinyl butyral; polyvinyl alcohol; polyethylene, poly Polyolefins such as propylene; polyvinylidene fluoride;
  • thickeners examples include inorganic thickeners such as colloidal silica, bentonite, montmorillonite and colloidal alumina; acrylic thickeners such as polyacrylic acid and acrylic copolymers; urethane-associated thickeners; alkali swelling thickeners Agents; Copolymer thickeners such as modified polyoxyethylene / urethane block copolymers; Cellulose thickeners such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydrophobic group-modified hydroxycellulose; polyethylene glycol ethers, nonionic surfactants Surfactants such as alginate; polysaccharides such as alginate, guar gum and mannan; water-soluble resins such as polyacrylic acid, polyvinyl alcohol and polyvinylpyrrolidone;
  • Examples of the pH adjuster include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, tributylamine and other alkylamines, diethanolamine, Alkanolamines such as diisopropanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, ethylenediamine, propylenediamine, diethylenetriamine, alkylenepolyamines such as triethylenetetramine, ammonia, ethyleneimine, pyrrolidine, piperidine, piperazine, morpholine, and Alkaline such as sodium hydroxide and potassium hydroxide Such as metal salts.
  • Examples of the solvent include water and various organic solvents.
  • Examples of organic solvents include coating compositions such as alcohol, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monophenyl ether, and the like.
  • Organic solvents generally used in the field are mentioned.
  • additives for example, in the field of coating compositions, such as film-forming aids, surface conditioners, preservatives, fungicides, antifoaming agents, light stabilizers, ultraviolet absorbers, antioxidants, pH adjusters, etc. Commonly used additives are listed.
  • the method for preparing the coating composition is not particularly limited, and can be prepared by stirring the above-described components with a stirrer or the like.
  • pigments or design materials are included in the coating composition, those having good dispersibility can be mixed with a stirrer, and as another method, a sand grind mill is added to a vehicle containing water, a surfactant or a dispersant. It is also possible to add a material that has been dispersed in advance using, for example.
  • the coating composition of the present invention can be applied to various substrates.
  • the base material include various cements, ceramic building materials, lightweight foamed concrete, mortar, slate plates, roofs, tiles, ALC and other inorganic building materials; various glasses; metal base materials such as steel plates, aluminum and stainless steel; It is done.
  • any appropriate method can be used according to the type and shape of the object (base material) to be coated.
  • a method of coating the aqueous coating composition for example, commonly used coating methods such as dipping, brushing, flow coating, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, die coater, etc. Etc. can be used.
  • the coating composition of the present invention can be used as an undercoating composition that forms an undercoating film by coating the substrate and leaving it to stand.
  • the base pretreatment include a method of coating a base conditioner such as a sealer.
  • the coating composition of the present invention can also be used as an undercoat coating composition for coating on an old coating film.
  • the coating composition of the present invention can be applied by a general coating method such as brushing, spraying or roller so that the coating amount is 50 to 500 g / m 2 , for example. . This painting may be performed in a plurality of times.
  • the coating composition of the present invention can be used as a top coating composition in which a top coating film is formed by coating and leaving on a base coating film formed as needed.
  • the coating composition can be applied by a general coating method such as brushing, spraying or roller so that the coating amount is 50 to 500 g / m 2 , for example. This painting may be performed in a plurality of times.
  • the coating composition of the present invention includes an emulsion resin obtained by emulsion polymerization of a monomer mixture having a high styrene monomer content. Therefore, a coating film having excellent alkali resistance, water resistance, chemical resistance, weather resistance, etc. can be formed by drying after coating the coating composition of the present invention. Since the coating composition of the present invention has excellent alkali resistance, weather resistance, etc., it is suitable for, for example, coating of inorganic building materials such as concrete, wall surfaces such as inner walls or outer walls of buildings, roofs, etc. Can be used.
  • Production Example 1 A glass Kolben was charged with 15.0 parts by weight of water (hereinafter sometimes referred to simply as “parts”) and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., the monomer emulsion (pre-emulsion solution) described in the following table was added at a constant rate over 5 hours. It was dripped at. * Monomer concentration in pre-emulsion solution: 80%
  • the mixture was further maintained for 60 minutes, and then cooled to 60 ° C.
  • 0.3 part of t-butylperoxy-2-ethylhexanoate was added and held for 30 minutes.
  • a solution in which 0.4 part of ascorbic acid was dissolved in 1 part of water was added, and then kept at 60 ° C. for 90 minutes. Thereafter, the operation of addition was repeated twice, followed by cooling.
  • the obtained emulsion was a stable emulsion having a solid content of 69.3%, a viscosity of 3794 mPas, a pH of 1.8, and an average particle size of 248 nm.
  • Production Example 2 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • the obtained emulsion was a stable emulsion having a solid content of 69.3%, a viscosity of 400 mPas, pH 5.2, and an average particle size of 374 nm.
  • Production Example 3 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 81%
  • Production Example 4 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Production Example 5 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Production Example 6 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 81%
  • Production Example 7 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 81%
  • Production Example 8 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 81%
  • Production Example 9 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • the obtained emulsion was a stable emulsion having a solid content of 69.3%, a viscosity of 480 mPas, a pH of 5.2, and an average particle diameter of 310 nm.
  • Production Example 10 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 78%
  • the obtained emulsion was a stable emulsion having a solid content concentration of 69.2%, a viscosity of 1830 mPas, a pH of 5.2, and an average particle diameter of 322 nm.
  • Production Comparative Example 1 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Production Comparative Example 2 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Production Comparative Example 3 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • polymerization rate reached 84%. From this, it was divided into a total of 3 times every hour, and each time was added all at once in the following amounts. 1 hour (polymerization rate 84%): 0.17 parts 2 hours: 0.27 parts 3 hours: 0.33 parts After completion of the dropping, polymerization was carried out in the same manner as in Production Example 1.
  • the obtained emulsion was an emulsion having a solid content concentration of 65.1% and an average particle diameter of 323 nm. The obtained emulsion was in a very high viscosity state, and the viscosity could not be measured.
  • Production Comparative Example 4 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Production Comparative Example 5 Polymerization was carried out in the same manner as in Production Example 1 except that the surfactant to be added from Production Example 1 was added in advance.
  • the obtained emulsion was an emulsion having a solid content concentration of 58.6% and an average particle size of 194 nm.
  • the obtained emulsion was in a very high viscosity state, and the viscosity could not be measured.
  • Production Comparative Example 6 A total amount of 0.87 parts of the same surfactant as the above 30% polyoxyethylene alkylphenyl ether ammonium sulfate aqueous solution was divided into a total of 4 times every hour from the point when the polymerization rate of Production Example 4 reached 41%. The polymerization was carried out in the same manner as in Production Example 4 except that each time was added all at once in the following amounts. 1 hour (41% polymerization rate): 0.10 parts 2 hours: 0.17 parts 3 hours: 0.27 parts 4 hours: 0.33 parts The obtained emulsion was an emulsion having a solid content concentration of 61.0% and an average particle size of 210 nm. The obtained emulsion was in a very high viscosity state, and the viscosity could not be measured.
  • Production Comparative Example 7 A total amount of 0.6 parts of 30% aqueous solution of polyoxyethylene alkylphenyl ether ammonium sulfate, which is the same surfactant as described above, was divided into a total of 2 times every hour from the time when the polymerization rate of Production Example 4 reached 93%. The polymerization was carried out in the same manner as in Production Example 4 except that each time was added all at once in the following amounts. 1 hour (polymerization rate 93%): 0.27 parts 2 hours: 0.33 parts The obtained emulsion was an emulsion having a solid content concentration of 63.3% and an average particle size of 424 nm. The obtained emulsion was in a very high viscosity state, and the viscosity could not be measured.
  • Production Comparative Example 8 A glass Kolben was charged with 15.0 parts by weight of water and heated to 80 ° C. After adding a solution prepared by dissolving 0.5 part of ammonium persulfate in 2 parts of water while controlling the temperature at 80 ° C., a monomer emulsion (pre-emulsion solution) having the following composition was added at a constant rate over 5 hours. Added. * Monomer concentration in pre-emulsion solution: 80%
  • Solid content (%) (mass after drying) / (mass before drying) ⁇ 100
  • the number average particle diameter of the emulsion resin was measured using ELS-Z (manufactured by Otsuka Electronics Co., Ltd.). In addition, about the calculation of a number average particle diameter, it calculated by the cumulant analysis method from the obtained diffusion coefficient.
  • the amount of (meth) acrylic monomer having a monomer reactivity ratio r1 with styrene of 0.7 or less in the monomer mixture is less than 10% by mass. Therefore, the emulsions obtained by these production comparative examples were in a very high viscosity state, and the viscosity could not be measured.
  • the emulsion resin obtained in these production comparative examples also has a solid content concentration that is significantly lower than the solid content concentration of the emulsion resin obtained in the production example. This indicates that a large amount of unreacted monomer remains. Since such an emulsion resin has a very high viscosity, it cannot be made into a paint.
  • the amount of the (meth) acrylic monomer (b1) having a monomer reactivity ratio r1 with styrene of 0.7 or less exceeds 60% by mass. Therefore, the emulsion obtained by Production Comparative Example 3 was in a very high viscosity state, and the viscosity could not be measured.
  • the emulsion resin obtained in Production Comparative Example 3 also has a solid content concentration that is significantly lower than the solid content concentration of the emulsion resin obtained in Production Example. That is, many unreacted monomers remain. Further, since the obtained emulsion resin has a very high viscosity, it cannot be made into a paint. Therefore, it is not suitable as an emulsion resin for paint.
  • the viscosity was extremely high and the viscosity could not be measured.
  • the solid content concentration is also significantly lower than the solid content concentration of the emulsion resin obtained in Production Example. That is, many unreacted monomers remain. Furthermore, since such an emulsion resin has a high viscosity, it cannot be made into a paint. Therefore, it is not suitable as an emulsion resin for paint.
  • a surfactant is added before the polymerization rate of the monomer mixture exceeds 45% in the emulsion resin formation step.
  • the surfactant is added before the size of the emulsion resin particles reaches the optimum range.
  • the emulsion resin obtained in Production Comparative Example 6 also has a solid content concentration that is significantly lower than the solid content concentration of the emulsion resin obtained in Production Example. That is, many unreacted monomers remain. Furthermore, since such an emulsion resin has a high viscosity, it cannot be made into a paint. Therefore, it is not suitable as an emulsion resin for paint.
  • the surfactant is added after the polymerization rate of the monomer mixture exceeds 90% in the emulsion resin formation step. Therefore, it is considered that the surfactant was insufficient, the particles became unstable, and the interaction between the particles became strong, which resulted in a very high viscosity state and the viscosity could not be measured.
  • the emulsion resin obtained in Production Comparative Example 7 also has a solid content concentration that is significantly lower than the solid content concentration of the emulsion resin obtained in Production Example. That is, many unreacted monomers remain. Furthermore, since such an emulsion resin has a high viscosity, it cannot be formed into a paint. Therefore, it is not suitable as an emulsion resin for paint.
  • Production Comparative Example 8 is an example in which the content of styrene monomer is 10% by mass and the amount of styrene monomer is less than the range in the present invention. It was found that the emulsion resin obtained by this production example has poor alkali resistance. The results of this experiment are detailed below.
  • Manufacturing Comparative Example 9 is a manufacturing comparative example corresponding to Example 1 described in JP-A-7-233208.
  • the viscosity of the pre-emulsion solution containing the monomer mixture was very high, and the pre-emulsion solution could not be dropped using a commonly used dropping device.
  • the emulsion resin obtained in Production Comparative Example 9 also has a solid content concentration that is significantly lower than the solid content concentration of the emulsion resin obtained in Production Example.
  • the viscosity of the pre-emulsion solution is very high and an optimum particle size cannot be formed during the emulsion polymerization, a large amount of unreacted monomer remains. Furthermore, since it does not contain a rigid styrene unit, it is inferior in alkali resistance and washing resistance (an index of wear resistance), and film distortion is likely to occur, resulting in a significant decrease in adhesion. Therefore, it is not suitable as an emulsion resin for paint.
  • Example 1 Preparation of Top Coating Composition
  • thickener trade name “SP-600N”, manufactured by Daicel Chemical Industries, Ltd., hydroxyethylcellulose-based thick
  • top coating composition 100 parts by weight of emulsion resin obtained in Production Example 1, 30 parts by weight of pigment paste, 6 parts by weight of film-forming aid, 1 part by weight of ethylene glycol, 0.1 part by weight of pH adjuster, Aqueous top coating composition 1 by sufficiently mixing 0.6 parts by mass of foaming agent, 0.2 parts by mass of thickener 1, 0.4 parts by mass of thickener 2, and 11.2 parts by mass of ion-exchanged water.
  • Examples 2-4 An aqueous top coating composition was prepared in the same manner as in Example 1, except that the emulsion resin obtained in Production Example 2, 4 or 7 was used instead of the emulsion resin obtained in Production Example 1. 2-4 were obtained.
  • Example 1 is the same as Example 1 except that the emulsion resin used in the preparation of the aqueous top coating composition obtained in Example 1 was changed from that in Production Example 1 to the emulsion resin obtained in Production Comparative Example 8. In the same manner, an aqueous top coating composition 5 was obtained.
  • Film-forming aid Trade name “CS-12”, manufactured by Chisso Corporation, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (pH adjuster) pH adjuster: 25% aqueous ammonia, manufactured by Wako Pure Chemical Industries, Ltd.
  • the coating performance (coating appearance, water resistance, alkali resistance, washing resistance, accelerated weather resistance) of the aqueous top coating compositions obtained in the above Examples and Comparative Examples was examined.
  • the washing resistance was examined as an index of wear resistance.
  • the test method is as follows. The test results are shown in the following table.
  • Nippe Ultra Sealer III (manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin-based sealer with carboxyl group) is coated on the flexible coating plate (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m 2. After standing for 16 hours (temperature: 23 ° C., humidity: 50%), the evaluation paint was applied at a coating amount of 100 g / m 2 , using a brush with a paint interval of 3 hours, and applied twice. Then, after leaving it to stand for 24 hours, it was evaluated (visually). ⁇ : No abnormalities are observed in the coating film ⁇ : Abnormalities such as cracks, itchiness and pinholes are observed
  • Nippe Ultra Sealer III manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin-based sealer having a carboxyl group
  • a water-resistant flexible board JIS A 5430 compliant
  • the evaluation paint was applied at a coating amount of 100 g / m 2 , using a brush, with a paint interval of 3 hours, and applied twice. Then, it dried and cured for 7 days, the water-resistant test board was created, and it was immersed in 20 degreeC water for 7 days.
  • Nippe Ultra Sealer III manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin-based sealer having a carboxyl group
  • an alkali-resistant flexible board JIS A 5430 compliant
  • the evaluation paint was applied at a coating amount of 100 g / m 2 , using a brush, with a paint interval of 3 hours, and applied twice. Then, it dried for 7 days and produced the alkali-proof test board.
  • the obtained test plate was immersed in a 3% aqueous solution of sodium hydroxide at 20 ° C.
  • Washing resistance JIS K 5663 synthetic resin emulsion paint, 1 type
  • Equipment It has the function of 6.3 wet abrasion test equipment of JIS K 5600-5-11. It has a test tank, a soap bath, a brush, etc., and the brush reciprocates on the coating film of the test piece. thing.
  • Preparation of test piece An evaluation paint was applied to a hard vinyl chloride sheet (specified in JIS K 6734) using a 6 mil applicator, and dried for 7 days to prepare a wash resistance test plate. The test was conducted in accordance with JIS K 5663 7.12. operation: The test piece was fixed horizontally on the test stand of the test tank of the cleaning test apparatus with the coating surface facing upward.
  • Nippe Ultra Sealer III manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin-based sealer having a carboxyl group
  • JIS A 5430 compliant accelerated weathering flexible board
  • the evaluation paint was applied at a coating amount of 100 g / m 2 using a brush with a paint interval of 3 hours and applied twice.
  • All of the water-based top coating compositions of the examples prepared using the emulsion resins obtained by the manufacturing examples have a coating film appearance, water resistance, alkali resistance, washing resistance (abrasion resistance), and weather resistance acceleration. It was confirmed to be excellent. On the other hand, it was confirmed that the water-based top coating composition prepared using the emulsion resin obtained in Production Comparative Example 8 was greatly inferior in alkali resistance and washing resistance (abrasion resistance) and inferior in water resistance. It was done.
  • aqueous undercoat paint composition 100 parts by weight of the emulsion resin obtained in Production Example 3, 8 parts by weight of a film-forming aid, 14 parts by weight of titanium dioxide, 97 parts by weight of calcium carbonate, 1.6 parts by weight of a thickener, and 7.4 parts by weight of an additive Were mixed well to obtain an aqueous undercoat paint composition 1.
  • Example 6 An aqueous undercoat paint composition 2 was obtained in the same manner as in Example 5 except that the emulsion resin of the aqueous undercoat paint composition of Example 5 was changed from that of Production Example 3 to that of Production Example 5.
  • Example 7 An aqueous undercoat paint composition 3 was obtained in the same manner as in Example 5 except that the emulsion resin of the aqueous undercoat paint composition of Example 5 was changed from that of Production Example 3 to that of Production Example 6.
  • Example 8 An aqueous undercoat paint composition 4 was obtained in the same manner as in Example 5 except that the emulsion resin of the aqueous undercoat paint composition of Example 5 was changed from that of Production Example 3 to that of Production Example 8.
  • the coating performance (alkali resistance, water resistance, adhesion) was examined for the aqueous top coating compositions obtained in the above examples and comparative examples.
  • the test method is as follows. The test results are shown in the following table.
  • Evaluation test The above-mentioned aqueous undercoating compositions 1 to 5 were each applied at a coating amount of 300 mg / m 2 on a 70 ⁇ 150 mm slate plate prepared by applying a two-component urethane paint at a coating amount of 150 mg / m 2 to prepare a base. Thus, an evaluation test plate was obtained. The following various tests were performed on the obtained evaluation test plate and evaluated.
  • a coating emulsion resin having a high solid content can be produced even when a monomer mixture having a high styrene monomer content is subjected to emulsion polymerization.
  • a coating composition using the emulsion resin for coating obtained by the production method of the present invention it becomes possible to blend many rigid styrene skeletons derived from aromatic rings. Thereby, the mechanical strength of the coating film obtained can be improved.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le problème à la base de la présente invention concerne un procédé qui permet de produire une résine d'émulsion de peinture présentant une teneur élevée en matières solides, même lorsqu'un mélange de monomères présentant une teneur élevée en monomères de styrène est polymérisé en émulsion. La présente invention concerne un procédé de production d'une résine d'émulsion de peinture, le procédé de production d'une résine d'émulsion de peinture comprenant : une étape de préparation d'une solution de pré-émulsion pour la préparation d'une solution de pré-émulsion qui contient un mélange de monomères comprenant 20 à 50 % en masse de monomères de styrène (a) et 50 à 80 % en masse de monomères éthyléniquement α,β-insaturés (b) qui sont copolymérisables avec (a); et une étape de formation d'une résine en émulsion pour la formation d'une résine en émulsion par polymérisation en émulsion du mélange de monomères, la résine d'émulsion de peinture obtenue par ce procédé de production présentant un diamètre de particule numérique moyen de 500 nm ou moins et une concentration en matières solides de 50 % en masse ou plus, le monomère éthyléniquement α,β-insaturé (b) contenant un monomère (méth)acrylique (b1) qui présente un rapport de réactivité des monomères r1 de 0,7 ou moins par rapport au styrène, la teneur en monomère (méth)acrylique (b1) contenu dans le mélange de monomères étant de 10-60 % en masse et un agent tensioactif étant ajouté dans une pluralité de lots après que le taux de polymérisation du mélange de monomères a atteint la plage de 45 %-90 %.
PCT/JP2015/081969 2014-11-28 2015-11-13 Procédé de production d'une résine d'émulsion de peinture WO2016084624A1 (fr)

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WO2017170577A1 (fr) * 2016-03-30 2017-10-05 住友精化株式会社 Procédé de production d'une composition de polymère contenant des groupes carboxyle
JP7483260B2 (ja) 2020-09-07 2024-05-15 日本ペイントホールディングス株式会社 液膜吐出塗装用、液柱吐出塗装用または液滴吐出塗装用の塗料組成物
JP7483259B2 (ja) 2020-09-07 2024-05-15 日本ペイントホールディングス株式会社 液膜吐出塗装用、液柱吐出塗装用または液滴吐出塗装用の塗料組成物

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CN106543784A (zh) * 2016-11-25 2017-03-29 江苏环宇纺织科技有限公司 一种高感速高稳防火胶的制备方法
EP3587516B1 (fr) 2018-06-27 2024-05-22 Ricoh Company, Ltd. Encre, procédé de fabrication de particule de résine acrylique, procédé d'impression, unité de réception d'encre et imprimante à jet d'encre
KR102710676B1 (ko) * 2023-12-01 2024-09-26 주식회사 태웅산업 도로 노면표지용 상온 경화형 수용성 도료조성물의 제조방법과 도로 노면표지의 시공방법

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JP7483260B2 (ja) 2020-09-07 2024-05-15 日本ペイントホールディングス株式会社 液膜吐出塗装用、液柱吐出塗装用または液滴吐出塗装用の塗料組成物
JP7483259B2 (ja) 2020-09-07 2024-05-15 日本ペイントホールディングス株式会社 液膜吐出塗装用、液柱吐出塗装用または液滴吐出塗装用の塗料組成物

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