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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
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  • 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
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • 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
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

• Aqueous polyolefin-based wax emulsions are generally used in a wide array of fields as ink, adhesive, aqueous coating material, floor polish, fiber processing agent, paper processing agent, mold releasing agent, and the like, either alone or in combination with other resin emulsions.
• the aqueous polyolefin wax emulsion is produced by methods such as a method of mechanical pulverization, a method of blasting and pulverizing under high pressure, a method of spraying from a pore, a method in which wax is dissolved in a solvent, which is then emulsified by a high pressure homogenizer, and the solvent is removed, a method in which wax is heated to not less than its melting point, which is then emulsified by a high pressure homogenizer, and the like.
• aqueous resin compositions obtained by these conventional production methods contain surfactants, and thus have the problem that the aqueous resin compositions after dried do not realize their expected properties such as water-resistance.
• Patent Document 1 JP 2001-253946A
• Patent Document 2 JP 2002-69302A
• the present invention was arrived at in light of the above matters, and it is an object thereof to provide a polyolefin wax-containing aqueous resin composition that can provide excellent properties without the use of a surfactant.
• the inventors of the present application performed intense investigation regarding the foregoing issue, and found that it is possible to solve the foregoing issue by mixing a carboxyl group-containing polyolefin wax, a compound that satisfies general formula (1) shown below, and water, while heating, and then adding a predetermined amount of a basic compound and dispersing the resin. Based on this finding, the present invention has been accomplished.
• the present invention provides an aqueous resin composition that is formed by heating and dissolving 100 parts by mass of a carboxyl group-containing polyolefin wax in the presence of 15 to 67 parts by mass of a compound that satisfies general formula (1) shown below, and 90 to 380 parts by mass of water, and then dispersing this with a basic compound that has been added at a ratio of 1 to 4 chemical equivalents per carboxyl group of the carboxyl group-containing polyolefin wax.
• n an integer from 1 to 4
• the carboxyl group-containing polyolefin wax that is used in the present invention is obtained by, for example, graft-copolymerizing at least one species selected from an ⁇ , ⁇ -unsaturated carboxylic acid and anhydrides thereof with at least one species selected from among a polypropylene wax, a propylene- ⁇ -olefin copolymer wax, a polyethylene wax, and an ethylene- ⁇ -olefin copolymer wax.
• the ethylene- ⁇ -olefin copolymer wax is a wax obtained by copolymerizing ethylene as the main component with ⁇ -olefin.
• the ⁇ -olefin include ⁇ -olefins with 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene.
• the ethylene content of the ethylene- ⁇ -olefin copolymer wax is preferably not less than 50 mol %. When the content of the ethylene component is less than 50 mol %, the adherence to polyethylene base becomes poor.
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof that are graft-polymerized with the olefin wax include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, and himic anhydride. Of these, maleic anhydride and itaconic anhydride are preferable.
• graft-copolymerization of at least one species selected from ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides thereof with a polyolefin wax well-known methods can be used, such as the method of heating and melting the polyolefin wax to not less than its melting point in the presence of a radical generator in order to effect the reaction (melting method), and the method of dissolving the polyolefin wax in an organic solvent and then heating and mixing the two in the presence of a radical generator in order to effect the reaction (solution method).
• the polyolefin wax may be those having been subjected to oxidation treatment in order to introduce a carboxyl group.
• oxidation treatment to introduce a carboxyl group into the polyolefin wax
• well-known methods can be used such as a method in which the polyolefin wax is heated and melted to not less than its melting point, and air, oxygen and ozone are blown thereinto for oxidation.
• the carboxyl group content of the carboxyl group-containing polyolefin wax obtained by the oxidation treatment is preferably 10 to 110 mgKOH/g.
• the content is over 110 mgKOH/g, the hydrophilicity of the resin is high and there is a risk that the water-resistance of the coating film that is obtained from the target composition will be poor.
• dispersion of the resin becomes difficult when the content is less than 10 mgKOH/g.
• the melt viscosity at 170° C. of the carboxyl group-containing polyolefin wax is preferably not more than 30,000 mPa ⁇ s.
• the melt viscosity is over 30,000 mPa ⁇ s, the resin solubility is poor and thus dispersion becomes poor.
• the glycol ether-based compound satisfying the general formula (1) that is used in the present invention is used in an amount of 15 to 67 parts by mass per 100 parts by mass of the carboxyl group-containing polyolefin wax.
• the amount is below 15 parts by mass, dispersion of the resin becomes difficult.
• the amount is greater than 67 parts by mass, drying of the target composition may require a high temperature and a longer length of time. Further, the original objective of dispersing the compound in an aqueous medium can be lost.
• These compounds can be used as a single species or in combination of two or more species.
• a basic compound is necessary to disperse the acid-modified chlorinated polyolefin.
• the dispersibility of the acid-modified chlorinated polyolefin can be increased by having a basic compound present in the system.
• the basic compound include: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonium carbonate; amines such as triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-
• the amount of water that is used when dispersing the polyolefin wax is 90 to 380 parts by mass. When the amount is less than 90 parts by mass, dispersion becomes difficult. On the other hand, when the amount is greater than 380 parts by mass, drying of the target composition may require high temperatures and a longer length of time.
• the aqueous resin composition of the present invention is produced by heating to dissolve 100 parts by mass of the carboxyl group-containing polyolefin wax in the presence of 15 to 67 parts by mass of the glycol ether-based compound that satisfies general formula (1), and 90 to 380 parts by mass of water, and then adding the basic compound at a ratio of 1 to 4 chemical equivalents per carboxyl group of the carboxyl group-containing polyolefin wax.
• the temperature when heating to dissolve the carboxyl group-containing polyolefin wax in the presence of the glycol ether-based compound that satisfies general formula (1) and water is 90 to 180° C., and preferably 100 to 160° C.
• the temperature when stirring is preferably 90 to 160° C.
• the stirring time is 30 minutes to 6 hours, preferably 1 to 4 hours.
• the resultant was then dried under reduced pressure, yielding a maleic anhydride-modified polypropylene wax with a carboxyl group content of 57 mgKOH/g and a melt viscosity at 170° C. of 25,800 mPa ⁇ s.
• aqueous resin composition (b) with a resin concentration (solid portion) of 30 mass % and a mean resin particle size of 77 nm was obtained in the same manner as in Working Example 1, except that the amount of each component was changed to the composition of Table 1.
• aqueous resin composition (c) with a resin concentration (solid content) of 30 mass % and a mean particle size of 35 nm was obtained in the same manner as in Working Example 1, except that the amount of each component was changed to the composition of Table 1.
• Example 1 Aqueous resin composition (a) (b) (c) (d) (e) Carboxyl Production 200 200 200 group-containing Example 1 polyolefin Polypropylene 200 wax [g] oxide wax 1) Polyethylene 200 oxide wax 2) Ethylene glycol 36 24 mono-n-butyl ether [g] Diethylene glycol 100 mono-n-butyl ether [g] Ethylene glycol 45 mono-n-ethylhexyl ether [g] Deionized water [g] 400 410 380 610 410 N,N-dimethylethanolamine 23 20 40 23 [g] Nonylphenol ethylene oxide 54 [g] 48% potassium hydroxide 21 aqueous solution [g] Sodium sulfite [g] 3 Mean particle size [nm] 48 77 35 180 No dispersion
• the aqueous resin composition was applied onto a glass plate using a 50 ⁇ m applicator, and then dried at room temperature for 12 hours, forming the test piece. This test piece was immersed in warm water held at 60° C. for 24 hours, and then the condition of the test piece was observed.
• aqueous resin composition Eighty g of the aqueous resin composition was sealed in a 100-mL container and left undisturbed for two weeks in a 50° C. atmosphere, and the change in its viscosity was assessed based on the following testing standards.
• aqueous resin composition (d) containing a surfactant is lacking in both adherence and water resistance.
• the aqueous resin composition containing polypropylene-based wax can be used as ink, adhesive, aqueous coating material, floor polish, fiber processing agent, paper processing agent, mold releasing agent, and various binders.

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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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• 2005
  • 2005-07-22 JP JP2005212536A patent/JP5011668B2/ja active Active
• 2006
  • 2006-07-21 KR KR1020087004035A patent/KR101287851B1/ko active IP Right Grant
  • 2006-07-21 CN CN200680026493XA patent/CN101228228B/zh not_active Expired - Fee Related
  • 2006-07-21 EP EP06781428A patent/EP1911804B1/de not_active Not-in-force
  • 2006-07-21 US US11/995,848 patent/US20090005483A1/en not_active Abandoned
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• 2010
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