Classifications

• • 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
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • 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
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives

Definitions

• the present invention relates to an anionic surfactant composition for emulsion polymerization and a method for producing a polymer emulsion using the same.
• the polymer emulsion is obtained by emulsion polymerization of vinyl monomers such as vinyl acetate, (meth) acrylic acid ester, styrene and its derivatives, and is used as it is in the fields of paints, adhesives, adhesives, paper processing, fiber processing, etc. Alternatively, the polymer is separated and widely used industrially as plastic and rubber.
• an emulsifier an anionic interface such as linear alkyl sulfate salt, linear alkyl benzene sulfonate, alkyl diphenyl ether disulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, etc.
• Activators and nonionic surfactants such as polyoxyethylene linear alkyl ethers and polyoxyethylene alkylphenyl ethers are used.
• Emulsifiers in emulsion polymerization not only affect the initiation and growth reactions of polymerization, but also the stability of the polymer emulsion during polymerization (hereinafter also referred to as “polymerization stability”), and the mechanical stability of the polymer emulsion produced. It has a great influence on the chemical and chemical stability. Therefore, the performance required for the surfactant for emulsion polymerization is that the polymerization stability and chemical stability are good, the particle size of the polymer emulsion can be reduced, and the environmental load is small.
• Patent Document 1 discloses an anionic surfactant derived from a polyoxyalkylene alkyl ether in which the polydispersity and branching degree of a raw material nonionic surfactant are in a specific range.
• An emulsifier for emulsion polymerization is disclosed.
• Patent Document 2 JP 2001-72702 discloses an ether type obtained by adding an alkylene oxide to an alcohol having 13 carbon atoms synthesized by an oxo method as an emulsifier for emulsion polymerization or a dispersant for suspension polymerization.
• Nonionic or anionic surfactants are disclosed.
• JP-A-2000-256548 Patent Document 3 discloses a surfactant composition for emulsion polymerization in which two types of polyoxyalkylene alkyl ether sulfates having different critical micelle concentrations are used in combination.
• Patent Document 4 JP-T-2009-537688 discloses a method for producing an aqueous dispersion of a polymer using an emulsifier containing at least two half-esters of ethoxylated fatty alcohols having different number average number of ethoxy groups. An emulsion polymerization method is disclosed.
• the present invention relates to the following [1] to [4].
• Component A an anionic surfactant represented by the following formula I
• component B at least one selected from anionic surfactants represented by the following formulas II to IV
• An anionic surfactant composition for emulsion polymerization in which Component A / Component B, which is a mass ratio of Component A and Component B, is 1 or more and 35 or less.
• R 1 represents a hydrocarbon group having 6 to 26 carbon atoms
• m represents an average addition mole number of ethylene oxide
• M + represents a hydrogen ion or a cation
• m is 10 to 100.
• R 2 and R 3 each independently represent a hydrocarbon group having 8 to 26 carbon atoms
• R 4 each independently represents a hydrocarbon group having 6 to 18 carbon atoms
• Q + represents a hydrogen ion or a cation
• n represents the average number of moles of ethylene oxide added, and n is 0 or more and 3 or less.
• a method for producing a polymer emulsion comprising a step of emulsion-polymerizing a monomer capable of radical polymerization in the presence of the anionic surfactant composition for emulsion polymerization according to [1].
• a method for producing a coating composition comprising the method for producing a polymer emulsion according to [2] above in a production process.
• a method for producing a polymer coating film comprising the following steps 1 to 3 in this order.
• Step 1 Step of obtaining a polymer emulsion by emulsion polymerization of a radical polymerizable monomer in the presence of the anionic surfactant composition for emulsion polymerization described in [1]
• Step 2 Polymer emulsion obtained in Step 1
• Step 3 Obtaining a coating composition using a coating
• Step 3 Applying the coating composition obtained in Step 2 to a substrate and drying to form a polymer coating film
• the anionic surfactant composition for emulsion polymerization of the present invention includes component A: an anionic surfactant represented by the following formula I, and component B: At least one selected from the anionic surfactants represented by formula II to formula IV is blended, and component A / component B, which is a mass ratio of blended component A and component B, is 1 to 35. is there.
• R 1 represents a hydrocarbon group having 6 to 26 carbon atoms
• m represents an average addition mole number of ethylene oxide
• M + represents a hydrogen ion or a cation
• m is 10 to 100.
• R 2 and R 3 each independently represent a hydrocarbon group having 8 to 26 carbon atoms
• R 4 each independently represents a hydrocarbon group having 6 to 18 carbon atoms
• Q + represents a hydrogen ion or a cation
• n represents the average number of moles of ethylene oxide added, and n is 0 or more and 3 or less.
• excellent in polymerization stability means that the produced polymer emulsion (hereinafter also simply referred to as “emulsion”) contains few aggregates. Specifically, the polymerization stability can be evaluated by the method described in Examples.
• the emulsion particle size is small means that the average particle size of the produced emulsion is not large. Specifically, in the emulsion polymerization method of the examples, the average particle size of the emulsion is 100 nm to 300 nm. It means the following.
• the average particle diameter of the emulsion refers to the average particle diameter based on the scattering intensity distribution measured by the dynamic light scattering method, and can be specifically measured by the method described in the examples.
• excellent in mechanical stability means that the occurrence of agglomerates is suppressed even when a shear force is applied to the produced polymer emulsion using, for example, a Maron mechanical stability tester.
• Mechanical stability can be evaluated by the method described in Examples.
• excellent in chemical stability refers to the divalent metal aggregation resistance of the produced emulsion. Specifically, even when an aqueous calcium chloride solution and a polymer emulsion are mixed, aggregation occurs. It means not producing anything. Chemical stability can be evaluated by the method described in Examples.
• the polyoxyalkylene alkyl ether sulfate ester salt having sufficient chemical stability as described in Patent Documents 1 to 3 requires an addition mole number of alkylene oxide of about 13 moles or more, and has a large molecular weight. It becomes.
• this polyoxyalkylene alkyl ether sulfate ester salt is emulsion-polymerized in an amount of 1% by mass or less based on the monomer, the molecular weight is large, the number of molecules decreases, the stability of the particles is insufficient, and the polymerization stability is low. There was a problem that would be bad.
• the emulsifier described in Patent Document 4 it has been difficult to obtain sufficient polymerization stability and chemical stability.
• the present invention provides an emulsion capable of producing a polymer emulsion that is excellent in polymerization stability even when used in a low addition amount, has a small particle size, and is excellent in mechanical stability and chemical stability.
• the present invention relates to providing an anionic surfactant composition for polymerization, a method for producing a polymer emulsion using the same, a method for producing a coating composition, and a method for producing a polymer coating film.
• emulsion polymerization that can produce a polymer emulsion that is excellent in polymerization stability even when used in a low addition amount, has a small particle size, and has excellent mechanical stability and chemical stability.
• An anionic surfactant composition for use, a method for producing a polymer emulsion using the same, a method for producing a coating composition, and a method for producing a polymer coating film can be provided. The reason is not clear, but it is thought as follows. In general, when component A is used, the chemical stability is good, but at low addition amounts, the polymerization stability is poor and the emulsion particle size tends to be large.
• component B when Component B is used, a polymer emulsion having a small particle diameter can be obtained, but the polymerization stability tends to be slightly poor and the chemical stability tends to be poor.
• component A and component B are mixed and used at a specific ratio, component B having a small molecular weight has a large number of molecules per mass and a small critical micelle concentration (cmc). It is considered that those having insufficient stability are reduced in particle size by increasing the number of molecules and improving the stability of the emulsion and by having a low cmc.
• polymerization stability is better than when each of component A and component B is used alone, and the emulsion has a smaller particle size, mechanical stability, chemical stability. It is considered that an excellent effect is exhibited.
• the anionic surfactant composition for emulsion polymerization of the present invention comprises an anionic surfactant represented by the following formula I as component A.
• R 1 represents a hydrocarbon group having 6 to 26 carbon atoms
• m represents an average addition mole number of ethylene oxide
• M + represents a hydrogen ion or a cation
• m is 10 to 100.
• R 1 is a hydrocarbon group having 6 to 26 carbon atoms, preferably from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability.
• the carbon number of R 1 is preferably 7 or more, more preferably 8 or more from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability. From the viewpoint, it is preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less.
• m represents an average added mole number of ethylene oxide and is 10 or more and 100 or less.
• m is preferably 12 or more, more preferably 15 or more, and still more preferably 18 or more.
• m is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less, from the viewpoint of increasing the mechanical stability. , Preferably 50 or less, more preferably 30 or less, still more preferably 25 or less.
• ethylene oxide about 1 mol of propylene oxide which does not affect the performance may be added.
• M + represents a hydrogen ion (H + ) or a cation.
• the cation include alkali metal ions such as sodium ion (Na + ) and potassium ion (K + ), ammonium ion (NH 4 + ), ammonium ion substituted with an alkyl group having 1 to 4 carbon atoms, and the like.
• M + is preferably hydrogen ion, sodium ion, potassium ion, ammonium ion, more preferably sodium. Ion, ammonium ion, more preferably sodium ion.
• M + is a divalent or higher cation
• it may be present as a counter ion with an anion of —SO 3 — .
• the amount of —SO 3 — On the other hand, a 1 ⁇ 2 amount should be present.
• the anionic surfactant composition for emulsion polymerization of the present invention is obtained by blending an anionic surfactant represented by the following formulas II to IV as component B.
• R 2 is a hydrocarbon group having 8 to 26 carbon atoms, preferably from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability and chemical stability.
• the carbon number of R 2 is preferably 10 or more, more preferably 12 or more, still more preferably 16 or more, from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability and mechanical stability. In view of the above, it is preferably 24 or less, more preferably 22 or less, and still more preferably 20 or less.
• R 3 is a hydrocarbon group having 8 to 26 carbon atoms, and is preferably an alkyl group from the viewpoints of reducing the average particle size of the emulsion, polymerization stability, mechanical stability, and chemical stability.
• the carbon number of R 3 is preferably 9 or more, more preferably 10 or more, still more preferably 12 or more, from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability and mechanical stability. In view of the above, it is preferably 22 or less, more preferably 18 or less, and still more preferably 14 or less.
• n represents the average number of moles of ethylene oxide added and is 0 or more and 3 or less. From the viewpoint of increasing the polymerization stability and mechanical stability, n is preferably 1 or more, more preferably 2 or more, and from the viewpoint of reducing the average particle size of the emulsion, preferably 2 or less, more preferably 1. Hereinafter, it is more preferably 0. In addition, you may substitute a part of ethylene oxide to a propylene oxide to such an extent that performance is not affected.
• R 4 is a hydrocarbon group having 6 to 18 carbon atoms, preferably from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability.
• the number of carbon atoms of R 4 is preferably 7 or more, more preferably 8 or more from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability. From the viewpoint, it is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
• Q + represents a hydrogen ion (H + ) or a cation.
• the cation include alkali metal ions such as sodium ion (Na + ) and potassium ion (K + ), ammonium ion (NH 4 + ), ammonium ion substituted with an alkyl group having 1 to 4 carbon atoms, and the like.
• alkali metal ions such as sodium ion (Na + ) and potassium ion (K + ), ammonium ion (NH 4 + ), ammonium ion substituted with an alkyl group having 1 to 4 carbon atoms, and the like.
• mechanical stability and chemical stability preferably hydrogen ion, sodium ion, potassium ion, ammonium ion, more preferably sodium ion, ammonium ion. More preferably, it is a sodium ion.
• Q + When Q + is a divalent or higher cation, it may be present as a counter ion with an anion of —SO 3 — .
• Q + when Q + is a divalent cation, the amount of —SO 3 — On the other hand, a 1 ⁇ 2 amount should be present.
• Component B includes at least one selected from the group consisting of a compound represented by Formula II, a compound represented by Formula III, and a compound represented by Formula IV. What is necessary is just to mix
• Component B is preferably a compound represented by Formula II or a compound represented by Formula III from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability. In the emulsion polymerization using a highly hydrophobic monomer, the compound represented by the formula III is more preferable from the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability.
• the blended component A to component B mass ratio [component A / component B] is 1 from the viewpoint of increasing polymerization stability, mechanical stability, and chemical stability. Above, preferably 1.2 or more, more preferably 1.5 or more. From the viewpoint of increasing mechanical stability and chemical stability, it is more preferably 2.0 or more, still more preferably 2.5 or more, and still more preferably 3.5 or more. From the viewpoint of reducing the average particle size of the resulting emulsion and increasing the polymerization stability and mechanical stability, it is 35 or less, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and still more preferably 8 Hereinafter, it is more preferably 6 or less, and still more preferably 5 or less.
• the mass ratio of component A and component B is the mass ratio of the total amount of component A and the total amount of component B. When two or more types of component A and / or component B are used, the total amount The mass ratio of the amount may be within the above range.
• the surfactant composition of the present invention comprises component A and component B. Since component A has a distribution in the number of moles of ethylene oxide added, the component A includes compounds having a small number of moles of ethylene oxide added. Therefore, when Component B is a compound represented by Formula (III), some of the components formulated as Component A may overlap with the components formulated as Component B. By measuring, the component mix
• the surfactant composition of the present invention can further contain other components as long as the effects of the present invention are not impaired.
• other components include nonionic surfactants such as alcohol ethoxylates (polyoxyethylene monoalkyl ethers), alkyl polyglycosides, and alkanolamides, and anionic surfactants such as fatty acid soaps and alkyl ether carboxylates; Examples include water-soluble protective colloids.
• the anionic surfactant composition for emulsion polymerization of the present invention preferably contains water from the viewpoint of reducing environmental burden and workability.
• water ion-exchanged water, reverse osmosis membrane filtered water (RO water), distilled water, pure water, ultrapure water, etc. can be used, but the average particle size of the emulsion is reduced, polymerization stability, mechanical stability. From the viewpoint of increasing the property and chemical stability, high purity is preferable. What is necessary is just to adjust the compounding quantity of water so that the total compounding quantity of the component A and the component B may be 10 to 40 mass% from a viewpoint of workability
• the anionic surfactant composition for emulsion polymerization of the present invention is a blending method capable of producing a uniform composition
• any procedure and method may be used.
• the method for producing a polymer emulsion of the present invention is a method in which a radically polymerizable monomer is emulsion-polymerized in the presence of the anionic surfactant composition for emulsion polymerization.
• a radically polymerizable monomer is emulsion-polymerized in the presence of the anionic surfactant composition for emulsion polymerization.
• component A and component B are blended in the polymerization system, and component A and component B may be mixed and added in advance, or added separately.
• the monomer used in the present invention is a radical polymerizable monomer.
• styrene monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene
• acrylic acid such as acrylic acid and methacrylic acid
• Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like preferably having an alkyl group having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms
• acrylic acid esters vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides such as vinylidene chloride
• vinyl esters such as vinyl acetate and vinyl propionate.
• (meth) acrylic acid ester means 1 type or 2 types chosen from methacrylic acid ester and acrylic acid ester. The same applies to the following.
• the amount of the surfactant composition used in the method for producing a polymer emulsion of the present invention is as follows. From the viewpoint of reducing the average particle size of the emulsion and increasing the polymerization stability, mechanical stability, and chemical stability. From 100 parts by mass, the total amount of component A and component B is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the same viewpoint. , Preferably 20 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.
• radical polymerization initiator used in the method for producing a polymer emulsion of the present invention can be used as long as it is used for ordinary emulsion polymerization.
• the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; organic peroxides such as hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide; azobisdiisobutyronitrile, 2, Examples include azo initiators such as 2′-azobis (2-amidinopropane) dihydrochloride, and water-soluble radical polymerization initiators are preferable from the viewpoint of polymerization reactivity, workability, and economy. More preferred.
• a redox initiator in which a peroxide compound is combined with a reducing agent such as sodium sulfite, Rongalite, and ascorbic acid can be used.
• the emulsion polymerization conditions in the method for producing a polymer emulsion of the present invention are not particularly limited, but the amount of the monomer used is preferably 30% by mass or more, more preferably 40% by mass or more, based on the total system, and Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less.
• a monomer addition method it can be used in any emulsion polymerization method such as a monomer dropping method, a monomer batch charging method, a pre-emulsion method in which a monomer is previously prepared as an emulsion for dropping (pre-emulsion) and then dropped.
• the pre-emulsion method is preferable from the viewpoint of polymerization stability.
• the dropping time of the pre-emulsion is preferably 1 hour or more and 8 hours or less, and the aging time is preferably 1 hour or more and 5 hours or less.
• the polymerization temperature is adjusted by the decomposition temperature of the initiator, but is preferably 50 ° C. or higher and 90 ° C. or lower, and particularly 70 ° C. or higher and 85 ° C. or lower in the case of persulfate.
• the polymer emulsion of the present invention is obtained by the production method using the anionic surfactant composition for emulsion polymerization.
• the average particle size of the polymer emulsion of the present invention is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 190 nm or less, and still more preferably 180 nm or less, from the viewpoint of increasing mechanical stability and chemical stability. From the viewpoint of polymerization stability, it is preferably 100 nm or more, more preferably 110 nm or more, and further preferably 120 nm or more.
• the coating composition of the present invention contains the polymer emulsion. Moreover, the manufacturing method of the coating composition of this invention includes the manufacturing method of the polymer emulsion of this invention in a manufacturing process.
• the coating composition of the present invention can further contain a colorant (pigment or dye) and, if necessary, water, a viscosity control agent, an antifoaming agent, an antioxidant, an ultraviolet absorber and the like.
• colorants include extender pigments such as talc, kaolin, calcium carbonate, and barium sulfate; colored pigments such as bengara, carbon black, ultramarine, and yellow iron oxide; white pigments such as titanium dioxide and zinc oxide, titanium mica, and bismuth oxychloride. Inorganic pigments such as pearl pigments; dyes as organic synthetic dyes, organic pigments, and the like. These colorants may be used alone or in combination of two or more.
• the coating composition of the present invention can improve coating film gloss and coating film adhesion by containing the polymer emulsion.
• the content of the polymer emulsion in the coating composition of the present invention is preferably 5% by mass or more in terms of solid content with respect to the total solid content in the coating composition from the viewpoint of coating film gloss and coating film adhesion.
• it is 10 mass% or more, More preferably, it is 15 mass% or more,
• it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.
• the content (pigment weight concentration, PWC: Pigment Weight Concentration) of the pigment in terms of the solid content relative to the total solid content of the coating composition is the coating film gloss, and the coating film From the viewpoint of adhesion, it is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably. Is 70% by mass or less.
• PWC pigment solid content (mass) in coating composition / total solid content (mass) in coating composition ⁇ 100
• the polymer coating film of the present invention (hereinafter also simply referred to as “coating film”) is formed by applying the coating composition onto a substrate and drying it.
• the method for producing a polymer coating film of the present invention preferably includes the following steps 1 to 3 in this order.
• Step 1 Step of obtaining a polymer emulsion by emulsion polymerization of a radical polymerizable monomer in the presence of the anionic surfactant composition for emulsion polymerization of the present invention
• Step 2 Paint using the polymer emulsion obtained in Step 1
• Step 3 Step of applying the coating composition obtained in Step 2 to a substrate and drying to form a polymer coating film
• substrate which consists of glass, a metal (aluminum, stainless steel, etc.), ceramics (an insulator, a tile, etc.), a heat resistant polymer material, etc. is mentioned.
• the coating composition is applied to the substrate and then dried. By heating in the drying step, the drying time can be shortened and the hardness of the formed coating film can be improved.
• the heating temperature is preferably 40 ° C. or more, more preferably 100 ° C. or more, and preferably 300 ° C. or less, more preferably 150 ° C. or less.
• the heating time is preferably 30 seconds or more, more preferably 5 ° C. Minutes or more, and preferably 2 hours or less, more preferably 60 minutes or less.
• the thickness of the coating film varies depending on the application, etc., but from the viewpoint of productivity, coating film gloss, and coating film adhesion, it is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and the hardness. From the viewpoint of increasing, the thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more.
• the present invention further discloses the following anionic surfactant composition for emulsion polymerization, a method for producing a polymer emulsion, a method for producing a coating composition, and a method for producing a polymer coating film.
• Component A an anionic surfactant represented by the following formula I
• component B at least one selected from the anionic surfactants represented by the following formula II to formula IV
• R 1 represents a hydrocarbon group having 6 to 26 carbon atoms
• m represents an average addition mole number of ethylene oxide
• M + represents a hydrogen ion or a cation
• m is 10 to 100.
• R 2 and R 3 each independently represent a hydrocarbon group having 8 to 26 carbon atoms
• R 4 each independently represents a hydrocarbon group having 6 to 18 carbon atoms
• Q + represents a hydrogen ion or a cation
• n represents the average number of moles of ethylene oxide added, and n is 0 or more and 3 or less.
• R 1 is an alkyl group, an alkenyl group or an alkylphenyl group, preferably an alkyl group or an alkenyl group.
• R 1 has 7 or more carbon atoms, preferably 8 or more, and 22 or less, preferably 20 or less, more preferably 18 or less, ⁇ 1> or ⁇ 2>
• m is 12 or more, preferably 15 or more, more preferably 18 or more, and 50 or less, preferably 30 or less, more preferably 25 or less, ⁇ 1> to ⁇ 3 >
• M + is a hydrogen ion, a sodium ion, a potassium ion, or an ammonium ion, preferably a sodium ion or an ammonium ion, more preferably a sodium ion.
• R 2 is an alkyl group, an alkenyl group or an alkylphenyl group, preferably an alkenyl group or an alkylphenyl group, more preferably an alkylphenyl group.
• R 2 has 10 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 24 or less, preferably 22 or less, more preferably 20 or less, ⁇ 1
• R 3 is an alkyl group, an alkenyl group or an alkylphenyl group, preferably an alkyl group or an alkylphenyl group, more preferably an alkyl group.
• R 3 has 9 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 22 or less, preferably 18 or less, more preferably 14 or less, ⁇ 1 >- ⁇ 8> An anionic surfactant composition for emulsion polymerization.
• R 4 is an alkyl group, an alkenyl group or an alkylphenyl group, preferably an alkyl group or an alkenyl group Activator composition.
• R 4 has 7 or more, preferably 8 or more, and 14 or less, preferably 12 or less, more preferably 10 or less, from ⁇ 1> to ⁇ 10>
• Q + is a hydrogen ion (H + ), an alkali metal ion, an ammonium ion (NH 4 + ), or an ammonium ion substituted with an alkyl group having 1 to 4 carbon atoms, preferably Is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, more preferably a sodium ion, an ammonium ion, and still more preferably a sodium ion, ⁇ 1> to ⁇ 11> for anionic surfactant for emulsion polymerization Agent composition.
• Component A / Component B which is a mass ratio of component A and component B, is 1.2 or more, preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 2.5 or more. More preferably, it is 3.5 or more, and 20 or less, preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less, even more preferably 5 or less.
• ⁇ 1> to ⁇ 12> The anionic surfactant composition for emulsion polymerization according to any one of the above.
• ⁇ 14> The anionic surfactant composition for emulsion polymerization according to any one of ⁇ 1> to ⁇ 13>, further comprising water.
• ⁇ 15> The anionic surfactant composition for emulsion polymerization according to any one of ⁇ 1> to ⁇ 14>, wherein the total amount of component A and component B is 10% by mass or more and 40% by mass or less.
• a method for producing a polymer emulsion comprising a step of emulsion polymerization of a radical polymerizable monomer in the presence of the anionic surfactant composition for emulsion polymerization according to any one of ⁇ 1> to ⁇ 15>.
• the monomer capable of radical polymerization is a styrene monomer; (meth) acrylic acid; methyl (meth) acrylate, having 1 to 22 carbon atoms, preferably 1 to 12 or less, more preferably 1 to 8 or less.
• the method for producing a polymer emulsion according to ⁇ 16> selected from the group consisting of (meth) acrylic acid ester having an alkyl group, vinyl halide, vinylidene halide, vinyl ester, nitriles, and conjugated diene.
• the amount of the anionic surfactant composition for emulsion polymerization used is such that the total amount of component A and component B is 0.1 parts by mass or more, preferably 0.5 parts by mass with respect to 100 parts by mass of the monomer.
• a method for producing a polymer emulsion is performed in the presence of a radical polymerization initiator, and the radical polymerization initiator is selected from the group consisting of a persulfate, hydrogen peroxide, an organic oxide, and an azo initiator.
• the method for producing a polymer emulsion according to any one of ⁇ 16> to ⁇ 18>, which is preferably a persulfate.
• the amount of the monomer used is 30% by mass or more, preferably 40% by mass or more, and 70% by mass or less, preferably 60% by mass or less, based on the total system.
• ⁇ 16> to ⁇ 19 The manufacturing method of the polymer emulsion in any one of>.
• ⁇ 21> The method for producing a polymer emulsion according to any one of ⁇ 16> to ⁇ 20>, wherein the monomer addition method is a monomer dropping method, a monomer batch charging method, or a pre-emulsion method, preferably a pre-emulsion method.
• the monomer dropping method is a pre-emulsion method, the pre-emulsion dropping time is from 1 hour to 8 hours, and the aging time is from 1 hour to 5 hours, any of ⁇ 16> to ⁇ 21>
• the emulsion polymerization is performed in the presence of a radical polymerization initiator, the radical polymerization initiator is a persulfate, and the polymerization temperature is 70 ° C. or higher and 85 ° C.
• the average particle size of the polymer emulsion is 300 nm or less, preferably 200 nm or less, more preferably 190 nm or less, still more preferably 180 nm or less, and 100 nm or more, preferably 110 nm or more, more preferably 120 nm or more.
• polymer emulsion polymer emulsion.
• the coating composition according to ⁇ 28> further comprising at least one selected from the group consisting of a colorant, water, a viscosity control agent, an antifoaming agent, an antioxidant, and an ultraviolet absorber.
• the content of the polymer emulsion is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 90% by mass in terms of solid content with respect to the total solid content of the coating composition.
• the coating composition according to ⁇ 28> or ⁇ 29> which is preferably 85% by mass or less, more preferably 80% by mass or less.
• the coating composition contains a pigment, and the PWC is 5% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and 95% by mass or less, preferably 80% by mass.
• PWC pigment solid content (mass) in coating composition / total solid content (mass) in coating composition ⁇ 100
• ⁇ 32> A method for producing a coating composition, comprising the method for producing a polymer emulsion according to any one of ⁇ 16> to ⁇ 25> in a production process.
• ⁇ 33> A polymer coating film formed by applying and drying the coating composition according to any one of ⁇ 28> to ⁇ 31> on a substrate.
• ⁇ 34> The polymer coating film according to ⁇ 33>, wherein the coating film has a thickness of 40 ⁇ m or less, preferably 30 ⁇ m or less, and 1 ⁇ m or more, preferably 2 ⁇ m or more.
• ⁇ 35> A method for producing a polymer coating film, comprising the following steps 1 to 3.
• Step 1 Step of obtaining a polymer emulsion by emulsion polymerization of a radical polymerizable monomer in the presence of the anionic surfactant composition for emulsion polymerization according to any one of ⁇ 1> to ⁇ 15>
• Step 2 Step 1 A step of obtaining a coating composition using the polymer emulsion obtained in step 3, and a step 3: a step of applying the coating composition obtained in step 2 to a substrate and drying to form a polymer coating film ⁇ 36> 3, heating is performed in a drying step, the heating temperature is 40 ° C or higher, preferably 100 ° C or higher, and 300 ° C or lower, preferably 150 ° C or lower, and the heating time is 30 seconds or longer, preferably 5 minutes.
• the manufacturing method of the polymer coating film as described in ⁇ 35> which is 2 hours or less, Preferably it is 60 minutes or less.
• surfactant The surfactants (component A and component B) and surfactant compositions used in the following examples and comparative examples are shown in the following table.
• the ion-exchanged water was added so that the amount of the pre-emulsion was stirred at 500 r / min, the temperature was raised to 80 ° C., and the first stage polymerization was performed for 30 minutes. Thereafter, the remaining pre-emulsion was dropped from the dropping funnel over 3 hours while maintaining the temperature at 80 ° C., and after completion of dropping, the mixture was aged for another hour to obtain a polymer emulsion.
• the obtained polymer emulsion was cooled to 30 ° C. or lower and filtered through a 200 mesh stainless steel wire mesh to collect aggregates in the polymer emulsion. Furthermore, aggregates adhered to the flask and the stirring blade were also collected.
• the stability of the obtained polymer emulsion was evaluated by the following method. Moreover, the glossiness and adhesiveness of a polymer coating film formed by applying a coating composition obtained using a polymer emulsion on a substrate were evaluated by the following methods. The results are shown in Table 4.
• Examples 22 to 25 and Comparative Examples 9 to 10 A polymer emulsion was produced in the same manner as in Examples 1 to 21, except that the monomer used for production of the polymer emulsion was 110.8 g of butyl acrylate, 110.8 g of 2-ethylhexyl acrylate, and 3.4 g of acrylic acid. The resulting polymer emulsion was evaluated. The results are shown in Table 4.
• the emulsion obtained in the production of the polymer emulsion is neutralized with 25% by mass ammonia water, and the neutralized polymer emulsion using a sub-micron particle size distribution measuring device “ELSZ-1000” (manufactured by Otsuka Electronics Co., Ltd.). Was diluted about 30,000 times with distilled water, and the average particle size of the particles was measured. As the measurement analysis method, the cumulant average particle diameter obtained by cumulative measurement 70 times was employed.
• ⁇ Manufacture of coating composition > 50 g each of 1 mm diameter and 2 mm diameter glass beads in a polyethylene 250 mL wide-mouth bottle, and “PEIKE R-670” as a pigment (titanium dioxide (rutile titanium oxide), manufactured by Ishihara Sangyo Co., Ltd., average particle diameter of about 0.21 ⁇ m) 150 g, 3.75 g of water-soluble dispersant “Poise 530” (special polycarboxylic acid type surfactant, manufactured by Kao Corporation, 40 mass% aqueous solution) and 62 g of ion-exchanged water are stirred for 3 hours in a paint shaker and filtered.
• Poise 530 special polycarboxylic acid type surfactant, manufactured by Kao Corporation, 40 mass% aqueous solution
• a pigment aqueous dispersion having a pigment solid content of 70% by mass was prepared.
• 7.2 g of the pigment aqueous dispersion 11.0 g of each of the polymer emulsions of Examples 2, 3, 5, 10, 13 and Comparative Examples 2 and 3 obtained above, and ion-exchanged water 1 .8 g was weighed and mixed uniformly to obtain a coating composition having a finished paint solid content of 50 mass% and a PWC of 50 mass%.
• PWC is a value calculated by the following formula.
• PWC pigment solid content (mass) ⁇ (pigment dispersion solid content (mass) + polymer emulsion solid content (mass)) ⁇ 100
• the coating composition obtained above was used as a bar coater no. 8 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was coated on a polypropylene film and an acrylic plate as a base material, respectively, and then dried at room temperature for 24 hours to obtain a polymer coating film (film thickness: about 10 ⁇ m).
• the polymer emulsions obtained in Examples 1 to 21 and 26 were superior in polymerization stability and good compared to the polymer emulsions obtained in Comparative Examples 1 to 8 and 11 to 14. While maintaining the emulsion particle size, excellent mechanical stability and chemical stability were exhibited.
• the polymer emulsions obtained in Examples 22 to 25 were superior to the polymer emulsions obtained in Comparative Examples 9 to 10 in terms of polymerization stability and excellent mechanical particle size while maintaining a good emulsion particle size. It showed stability and chemical stability.
• the coating film formed with the coating composition prepared using the polymer emulsion obtained in the example is the coating film formed with the coating composition prepared using the polymer emulsion obtained in the comparative example. Compared with, the coating film gloss and coating film adhesion were excellent.
• the polymer emulsion obtained by the anionic surfactant composition for emulsion polymerization of the present invention has excellent polymerization stability and excellent mechanical stability and chemical stability while maintaining a good emulsion particle size. It is useful in the fields of paint, adhesive, paper processing, fiber processing, plastic, rubber and the like.

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