WO2021125122A1 - Aqueous polyamide dispersion - Google Patents
Aqueous polyamide dispersion Download PDFInfo
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- WO2021125122A1 WO2021125122A1 PCT/JP2020/046467 JP2020046467W WO2021125122A1 WO 2021125122 A1 WO2021125122 A1 WO 2021125122A1 JP 2020046467 W JP2020046467 W JP 2020046467W WO 2021125122 A1 WO2021125122 A1 WO 2021125122A1
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- polyamide
- aqueous
- alkylene oxide
- nylon
- dispersion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
- This disclosure relates to an aqueous polyamide dispersion and the like.
- the aqueous dispersion of polyamide can impart solvent resistance, chemical resistance, abrasion resistance, gas barrier property, adhesiveness, etc. by forming a polyamide coating coating on the base material.
- Water-based inks, paper treatment agents, binders, lubricants, steel plate surface treatment agents, surface modifiers, hot melt adhesives such as interlining adhesives, etc. are widely used.
- the aqueous dispersion of polyamide is used for the purpose of improving the adhesion with the matrix resin in the composite material in which the thermoplastic resin such as the polyamide resin is used as the matrix resin.
- the conventional polyamide aqueous dispersion is an anionic (for example, about pH 9 to 10) aqueous dispersion, and when the pH of the aqueous dispersion becomes low, for example, by adding an acidic substance, polyamide aggregates are formed. Therefore, the usable pH range has been limited.
- the present inventors can suppress the formation of polyamide agglomerates even in the neutral pH range if the aqueous polyamide dispersion contains a specific polyalkylene polyamine alkylene oxide adduct in addition to the polyamide.
- Item 1 A polyamide aqueous dispersion containing an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct having a melting point of 25 ° C. or higher.
- Polyamides are 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon, 6/11 copolymerized nylon, 6/12 copolymerized nylon.
- the aqueous polyamide dispersion liquid according to Item 1 which is at least one selected from the group consisting of elastomers.
- Item 3. Item 2.
- Item 4. The aqueous polyamide dispersion liquid according to any one of Items 1 to 3, wherein 1 to 20 parts by mass of the polyalkylene polyamine alkylene oxide adduct is contained with respect to 100 parts by mass of the polyamide.
- Item 5. The aqueous polyamide dispersion according to any one of Items 1 to 4, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a structure in which alkylene oxide is addition-polymerized to polyethyleneimine.
- Item 6. Item 2. The aqueous polyamide dispersion liquid according to any one of Items 1 to 5, wherein the volume average particle size of the polyamide is 1 ⁇ m or less.
- Item 7. Item 2. The aqueous polyamide dispersion according to any one of Items 1 to 6, wherein the amount of polyamide having a particle size of 2 ⁇ m or more is 15% by volume or less of the total amount of polyamide when the pH is lowered to 6.5.
- Item 8. A coating agent containing the polyamide aqueous dispersion according to any one of Items 1 to 7.
- Item 9. A molded body processed by using the coating agent according to Item 8.
- polyamide aqueous dispersion in which the formation of polyamide agglutinating is suppressed even in a region where the pH is neutral (for example, about 7).
- the present disclosure preferably includes, but is not limited to, a polyamide aqueous dispersion containing a specific polyalkylene polyamine alkylene oxide adduct, a coating agent containing the polyamide aqueous dispersion, and the like. Includes everything disclosed herein and recognizable to those skilled in the art.
- the polyamide aqueous dispersion included in the present disclosure includes an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct.
- the polyamide aqueous dispersion may be referred to as "the polyamide aqueous dispersion of the present disclosure”.
- Water is preferable as the aqueous medium, and various types of water such as tap water, industrial water, ion-exchanged water, deionized water, and pure water can be used. Deionized water and pure water are particularly preferable. Further, as the aqueous medium, a pH adjuster, a viscosity regulator, a fungicide and the like may be appropriately added to water, if necessary.
- polyamide a known one or one manufactured by a known method can be used. Commercially available products may be used.
- examples thereof include polyamides produced by a method such as polycondensation of diamine and dicarboxylic acid, polycondensation of ⁇ -amino- ⁇ 'carboxylic acid, or ring-opening polymerization of cyclic lactam. That is, examples thereof include polyamides in which diamine and dicarboxylic acid are polycondensed, polyamides in which ⁇ -amino- ⁇ 'carboxylic acid is polycondensed, and polyamides in which cyclic lactam is ring-opened polymerized.
- a dicarboxylic acid or a monocarboxylic acid can be used as a polymerization regulator.
- the polyamide in which diamine and dicarboxylic acid are polycondensed is, in other words, a polyamide having diamine and dicarboxylic acid as a monomer structural unit
- the polyamide in which ⁇ -amino- ⁇ 'carboxylic acid is polycondensed is, in other words, ⁇ .
- a polyamide having -amino- ⁇ 'carboxylic acid as a monomer structural unit, and a polyamide in which cyclic lactam is ring-open polymerized is, in other words, a polyamide having cyclic lactam as a monomer structural unit.
- diamine examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
- dicarboxylic acids examples include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, and xylylene dicarboxylic acid.
- dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, and xylylene dicarboxylic acid.
- acids and dimeric acids unsaturated dicarboxylic acids having 36 carbon atoms synthesized from unsaturated fatty acids
- ⁇ -amino- ⁇ 'carboxylic acid examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
- annular lactam examples include ⁇ -caprolactam, ⁇ -enantractum and ⁇ -lauryl lactam.
- the dicarboxylic acid used as the polymerization regulator is the same as the dicarboxylic acid used in the production of the polyamide, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandicarboxylic acid. , Decandicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, pimelic acid, dimeric acid and the like.
- Examples of the monocarboxylic acid include caproic acid, heptanic acid, nonanoic acid, undecanoic acid, dodecanoic acid and the like.
- polyamides examples include nylon, specifically 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon.
- 6/11 Copolymerized Nylon, 6/12 Copolymerized Nylon, 6/66/11 Copolymerized Nylon, 6/66/12 Copolymerized Nylon, 6/66/11/12 Copolymerized Nylon, or 6/66/610 / 11/12 Copolymerized nylon and the like are exemplified.
- "/" here is a symbol used to indicate that it is a copolymer of each nylon.
- 6/66 copolymerized nylon represents a copolymerized nylon of 6-nylon and 66-nylon.
- a dimer acid-based polyamide and a polyamide elastomer are also exemplified.
- the polyamide elastomer include a polyamide elastomer which is a copolymer of nylon and polyester or a copolymer of nylon and polyalkylene ether glycol.
- the polyalkylene ether glycol include polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol, polyhexamethylene oxide glycol and the like.
- the polyester include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene naphthalate, and polybutylene naphthalate.
- Polyamide can be used alone or in combination of two or more.
- the polyamide elastomer is not particularly limited, but a block copolymer containing a polyamide block and a polyether block is preferable.
- a block copolymer having a structure in which a polyamide and a polyether are copolymerized is preferable, and a block copolymer having a structure in which a polyamide and a polyether are copolymerized is particularly preferable.
- the constituent components of the polyether block include glycol compounds such as polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol and polyhexamethylene oxide glycol, and diamine compounds such as polyether diamine.
- polyamide elastomer two or more kinds of these constituents may be used.
- a polyamide elastomer several types having different molecular structures of the bonding portion between the polyamide block and the polyether block, that is, the bonding morphology, for example, "(polyamide block) -CO-NH- (polyamide block)"
- the bonding morphology for example, "(polyamide block) -CO-NH- (polyamide block)”
- examples thereof include a polyether block amide copolymer having a bonded form, a polyether ester block amide copolymer having a bonded form of "(polyamide block) -CO-O- (polyamide block)", and the like.
- polyalkylene polyamine alkylene oxide adduct for example, one having a structure in which an alkylene oxide is added to 1 to 3 active hydrogens in an amino compound is preferable.
- alkylene oxide is addition-polymerized with amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine are preferable, and ethylene oxide / propylene oxide is particularly preferable. Is more preferably blocked or randomly subjected to addition polymerization.
- the polyethyleneimine may be either linear or branched.
- the polyalkylene polyamine alkylene oxide adduct is not particularly limited, but a polyethyleneimine alkylene oxide adduct having a structure in which polypropylene oxide and polyethylene oxide are added as alkylene oxide components to polyethyleneimine in a block is particularly preferably used. ..
- AO represents an alkylene oxide and n represents an integer
- AO alkylene oxide
- n represents an integer
- AO alkylene oxide
- -CH 2 CH 2 O-, -CH 2 CH (CH 3 ) O-, or a block or a random copolymer thereof is preferably mentioned.
- the polyalkylene polyamine alkylene oxide adduct used in the aqueous polyamide dispersion of the present disclosure has a melting point of 25 ° C. or higher, preferably 25 to 100 ° C.
- the upper or lower limit of the range is, for example, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, It may be 97, 98, or 99 ° C.
- the range
- the number average molecular weight of the polyalkylene polyamine alkylene oxide adduct is preferably 5000 to 25000.
- the upper or lower limit of the range is, for example, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, or 24000. May be good.
- the range is, for example, more preferably 10,000 to 20,000.
- the number average molecular weight is 5000 or more, it works more preferably as a protective colloid around the particles as a polymer-type nonionic surfactant, and can preferably contribute to the stabilization of the aqueous dispersion.
- the number average molecular weight is 25,000 or less, not only contributes to the stabilization of the particles, but also the viscosity of the aqueous dispersion does not become too high, which can be a more practical and preferable viscosity.
- the value of the number average molecular weight here is a value obtained by the measurement method described below.
- Number average molecular weight measurement method A tetrahydrofuran solution containing a polyalkylene polyamine alkylene oxide adduct at a concentration of 0.2% by mass is prepared, and measurement is performed using a high performance liquid chromatograph. Then, a molecular weight marker (polystyrene) having a known molecular weight is measured under the same conditions, a calibration curve is created, and the number average molecular weight (Mn) is calculated.
- the measurement conditions are as follows.
- Measuring machine GPC-101 (Shodex) Column: TSK GEL Multipore HZ-N manufactured by Tosoh Corporation Column temperature: 40 ° C Outflow: tetrahydrofuran Flow rate: 0.25 ml / min
- the solubility of the polyalkylene polyamine alkylene oxide adduct in water is preferably 25% by mass or more, more preferably 26, 27, 28, or 29% by mass or more, and further preferably 30% by mass or more. Is.
- the solubility in water here is a value obtained as follows when examined using water at 25 ° C.
- Solubility (% by mass) A / (A + B) x 100
- A mass of polyalkylene polyamine alkylene oxide adduct
- B mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
- Such a polyalkylene polyamine alkylene oxide adduct is commercially available as a polymer type nonionic surfactant, and for example, "Discol N" which is a polyalkylene polyamine alkylene oxide adduct manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. -518 ”can be used.
- the polyalkylene polyamine alkylene oxide adduct can be used alone or in combination of two or more.
- the amount of the polyalkylene polyamine alkylene oxide adduct used in the aqueous polyamide dispersion of the present disclosure is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide.
- the upper or lower limit of the range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 parts by mass. Good.
- the range is, for example, more preferably 3 to 17 parts by mass, still more preferably 5 to 15 parts by mass.
- the aqueous polyamide dispersion containing no polyalkylene polyamine alkylene oxide adduct is usually anionic (for example, pH 9 to 10).
- anionic for example, pH 9 to 10.
- an acidic substance is added to the polyamide aqueous dispersion, polyamide agglomerates are likely to be formed, whereas the polyamide aqueous dispersion also containing a polyalkylene polyamine alkylene oxide adduct has a neutral region (for example, about pH 7 or more acidic). It can maintain a stable state up to pH). Therefore, not only the range of use of the aqueous polyamide dispersion can be expanded, but also it can be mixed with an acidic additive or the like, and various performance improvements and the like can be easily performed.
- the reason why the stable state can be maintained up to the neutral region by adding the polyalkylene polyamine alkylene oxide adduct to the aqueous polyamide dispersion is that it is a general polymer type non-ion.
- these polymer chains are only freely present around the particles and have a weak chemical stabilizing effect, whereas a polyalkylene polyamine alkylene oxide adduct having a nitrogen atom is used.
- nitrogen atoms are attracted to the carbonyl group on the surface of the polyamide particles, and the polyalkylene polyamine alkylene oxide adduct is present relatively close to the particle surface, which contributes to a greater stabilizing effect. Guess.
- the method for producing the aqueous polyamide dispersion liquid of the present disclosure is not particularly limited.
- it can be produced by a method including a step of mixing an aqueous dispersion in which polyamide is dispersed (hereinafter, also referred to as a polyamide aqueous dispersion precursor) and a polyalkylene polyamine alkylene oxide adduct.
- a polyamide aqueous dispersion precursor an aqueous dispersion in which polyamide is dispersed
- a polyalkylene polyamine alkylene oxide adduct a polyalkylene polyamine alkylene oxide adduct
- the method for producing the polyamide aqueous dispersion precursor is not particularly limited, and any method may be used as long as the polyamide can be uniformly dispersed in the aqueous medium.
- a method of dispersing polyamide powder obtained by pulverizing polyamide by a pulverization method such as a mechanical pulverization method, a freezing pulverization method, or a wet pulverization method in an aqueous medium, or emulsifying using polyamide and a basic substance.
- a pulverization method such as a mechanical pulverization method, a freezing pulverization method, or a wet pulverization method in an aqueous medium, or emulsifying using polyamide and a basic substance.
- a method of producing an aqueous dispersion such as a mechanical pulverization method, a freezing pulverization method, or a wet pulverization method in an aqueous medium, or emulsifying using polyamide and a basic substance.
- examples thereof include a method of producing an aqueous dispersion, a method of emulsifying polyamide using a surfactant, and producing an aqueous dis
- a polyamide, a basic substance, and an aqueous medium are put into a container to prepare a mixed solution thereof.
- the container used for preparing the mixture is a pressure-resistant container provided with a heating means for heating the polyamide to a temperature higher than the temperature at which it softens in an aqueous medium and a stirring means capable of applying a shearing force to the contents.
- a pressure resistant autoclave with a stirrer is preferable.
- the polyamide, basic substance and aqueous medium are mixed in this container to obtain a mixed solution.
- the mixed solution is heated to a temperature equal to or higher than the softening temperature of the polyamide and stirred to emulsify the mixture to obtain an emulsion. Cooling the emulsion to room temperature gives a polyamide aqueous dispersion precursor.
- the basic substance is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and amine compounds.
- the basic substance may be used alone or in combination of two or more.
- sodium hydroxide and / or potassium hydroxide are particularly preferably used from the viewpoint of excellent static stability of the dispersion.
- the amount of the basic substance used is 0.1 to 2 mol per 1 mol of the terminal carboxyl group of the polyamide from the viewpoint of excellent static stability such as little change in the viscosity of the obtained aqueous dispersion with time. It is preferably 0.4 to 1 mol, more preferably 0.4 to 1 mol.
- the amount of the polyamide used is not particularly limited, but is preferably set to 0.1 to 80 parts by mass, and set to 20 to 60 parts by mass with respect to 100 parts by mass of the obtained polyamide aqueous dispersion precursor. It is more preferable to do so.
- a polyamide aqueous dispersion precursor can be obtained by using a basic substance and a surfactant (dispersion stabilizer) in combination.
- a surfactant used to obtain a polyamide aqueous dispersion precursor (that is, to disperse polyamide in an aqueous medium)
- the effect of the obtained polyamide aqueous dispersion of the present disclosure can be used.
- Additives such as anionic surfactants, nonionic surfactants, and polymer-based dispersants can also be used as long as they are not impaired.
- anionic surfactant examples include aliphatic polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkylphenyl ether sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyldiphenyl sulfonates, and ⁇ -olefins.
- examples thereof include sulfonates, alkyl sulfates, naphthalene sulfonate formalin condensates, dialkyl sulfosuccinates, polyoxyethylene alkyl ether acetates, rosin salts and fatty acid salts.
- nonionic surfactant examples include polyethylene glycol, ethylene oxide / propylene oxide copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl thioether, polyoxyethylene sorbitan fatty acid monoester, and polyoxy.
- examples thereof include ethylene alkyl amide and polyglycerin ester.
- polymer-based dispersion stabilizer examples include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyacrylic acid salt, polyacrylic acid ester salt, alginate, and salts of ethylene / acrylic acid copolymers. (Especially ammonium salt), styrene / maleic anhydride copolymer salt, styrene-maleic acid monoester copolymer salt, isobutylene / maleic anhydride copolymer salt, carboxymethyl cellulose salt and the like can be mentioned.
- a nonionic surfactant and a polymer-based dispersion stabilizer are preferably used from the viewpoint of enhancing the stability of the obtained aqueous dispersion liquid of the present disclosure.
- the obtained aqueous dispersion of the present disclosure has excellent heat resistance, is not easily decomposed even when processed at a high temperature for a long time, and has good adhesion between the laminate treated with the aqueous dispersion and the matrix resin.
- Ethylene oxide / propylene oxide copolymer polyoxyethylene alkyl ether (eg polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene mi Listel ether, polyoxyethylene octyldodecyl ether, etc.), ethylene / acrylic acid copolymer ammonium salt, styrene / maleic anhydride copolymer ammonium salt, styrene-maleic acid monoester copolymer ammonium salt, isobutylene / maleic acid
- the ammonium salt of the ester copolymer is preferably used.
- additives can be used alone or in combination of two or more.
- the amount of the additive used is preferably less than 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyamide.
- the amount of the additive used is preferably less than 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyamide.
- the use of these additives may adversely affect the adhesiveness between the laminate treated with the obtained dispersion and the matrix resin, refer to the above amount and avoid using a relatively large amount. It is desirable to set it appropriately.
- additives may be further added after the polyamide aqueous dispersion precursor is obtained in the manufacturing process.
- the polyamide aqueous dispersion of the present disclosure can be obtained by mixing the polyalkylene polyamine alkylene oxide adduct with the polyamide aqueous dispersion precursor prepared as described above.
- the method for mixing the polyamide aqueous dispersion precursor and the polyalkylene polyamine alkylene oxide adduct is not particularly limited.
- the polyamide aqueous dispersion precursor and the polyalkylene polyamine alkylene oxide adduct are put into the same container and stirred. Then, a method of mixing and the like can be mentioned.
- the concentration (w / w%) of the polyamide in the aqueous polyamide dispersion of the present disclosure is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, and further preferably 5 to 50% by mass. It is mass%.
- concentration of polyamide is 80% by mass or less, the stability of the aqueous polyamide dispersion can be further improved. Further, when the concentration is 0.1% by mass or more, the polyamide can be more easily adhered to the adherend of the laminated body.
- the average particle size of the dispersed polyamide (particles) is, for example, preferably less than 2 ⁇ m.
- the lower limit of the average particle size is not particularly limited, but is, for example, 0.05 ⁇ m or more. For example, it is more preferably less than 2 ⁇ m and 0.05 ⁇ m or more.
- the upper or lower limit of the range is, for example, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0. It may be 9.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ⁇ m. Further, as described above, the lower limit does not have to be set.
- the average particle size of the polyamide is the volume average particle size measured by the laser diffraction type particle size distribution measurement method. That is, it is a volume average particle diameter value obtained when the polyamide aqueous dispersion is measured by a laser diffraction type particle size distribution measuring device.
- the aqueous polyamide dispersion liquid of the present disclosure is preferably one in which agglomerates of polyamide are unlikely to be formed when the pH is lowered by using an acidic substance.
- the degree of aggregation of polyamide can be indicated by, for example, the ratio (volume%) of the total polyamide amount (volume) to the polyamide amount (volume) having a particle size of 2 ⁇ m or more. The value is obtained by measuring the particle size distribution by the laser diffraction / scattering method. For example, when the pH is lowered to 6.5, the amount of polyamide having a particle size of 2 ⁇ m or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume or less.
- the amount of polyamide having a particle size of 2 ⁇ m or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume. It is more preferably 9, 8, 7, 6, 5, 4, or 3% by volume or less.
- the amount of polyamide having a particle size of 2 ⁇ m or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume. It is more preferably 9, 8, 7, 6, 5, 4, or 3% by volume or less.
- an acidic substance that does not affect the aggregation of the polyamide is preferable, and more specifically, for example, ammonium sulfate and the like are preferably mentioned.
- the aqueous polyamide dispersion liquid of the present disclosure preferably includes, for example, one having a pH of less than 6.7 and an average particle size of polyamide satisfying the above preferable range.
- the pH range is 6.65 or less, 6.6 or less, 6.55 or less, 6.5 or less, 6.45 or less, 6.4 or less, 6.35 or less, 6.3 or less, 6.25 or less, It may be 6.2 or less, 6.15 or less, or 6.1 or less.
- the lower limit of pH is not particularly limited. For example, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.
- the aqueous polyamide dispersion liquid of the present disclosure preferably includes, for example, one having a pH of less than 6.7 and containing no polyamide particles having an average particle diameter of 2 ⁇ m or more.
- the pH range is 6.65 or less, 6.6 or less, 6.55 or less, 6.5 or less, 6.45 or less, 6.4 or less, 6.35 or less, 6.3 or less, 6.25 or less, It may be 6.2 or less, 6.15 or less, or 6.1 or less.
- the lower limit of pH is not particularly limited as long as it does not contain polyamide particles having an average particle diameter of 2 ⁇ m or more. For example, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.
- the pH of the aqueous polyamide dispersion is a value measured at 25 ° C. using a pH meter.
- Various molded products can be processed by using the coating agent containing the aqueous polyamide dispersion liquid of the present disclosure.
- the coating agent is useful as a material for producing various molded products.
- the method for producing the molded product is not particularly limited, but the step of applying the aqueous polyamide dispersion liquid of the present disclosure to the base material or pouring it into a mold, and drying the aqueous dispersion of the coated or poured polyamide aqueous dispersion. It involves a step (ie, removing water).
- a method for producing a molded product including such a step it is possible to obtain a molded product having various forms such as a film, a film or a sheet containing an aqueous polyamide dispersion.
- the method for applying the aqueous polyamide dispersion liquid of the present disclosure to the substrate is not particularly limited, and for example, a coating method using a brush, a spatula, a roller, a caulking gun, a silk screen, an air spray, a nozzle spray, a roll coater, or the like. Can be mentioned.
- the amount of the polyamide aqueous dispersion applied to the base material is appropriately set according to the purpose, and for example, the film is applied so that the thickness of the film obtained from the polyamide aqueous dispersion of the present disclosure is 0.001 mm to 5 mm.
- the method of pouring the aqueous polyamide dispersion into the mold is not particularly limited.
- a method of applying a polyamide aqueous dispersion to a substrate or pouring it into a mold and then removing water can be mentioned.
- the drying temperature in the step of removing water is not particularly limited, but is usually set to 40 to 300 ° C.
- the drying time is not particularly limited, and for example, when drying at 100 ° C., it is 0.2 to 2 hours.
- the base material used for manufacturing the molded product is not particularly limited, but is, for example, metal such as aluminum or copper, glass, wood, rubber, thermoplastic resin, thermosetting resin, and further reinforced with reinforcing fibers or fillers. Manufactured from resin or the like.
- the thickness and shape of the base material are not particularly limited.
- the coating side of the aqueous polyamide dispersion in the molded product thus obtained (for example, a laminate obtained by coating on a base material and drying) and a further base material are combined, for example, hot pressing.
- a composite material in which base materials are bonded in layers can be produced by pressurizing the mixture at 120 to 300 ° C., if necessary, to 0.1 to 100 MPa and heating for 1 to 500 seconds.
- the base material to be bonded may be a different type of base material or the same type of base material.
- the polyamide aqueous dispersion of the present disclosure includes materials for manufacturing automobile parts, sports-related products, medical instruments, etc., coating agents for paper and films, adhesives, surface modifiers, raw materials for foam rubber, coating agents, etc.
- materials for manufacturing automobile parts, sports-related products, medical instruments, etc. coating agents for paper and films, adhesives, surface modifiers, raw materials for foam rubber, coating agents, etc.
- manufacturing materials such as hoses, tubes, belts, gaskets and packings, sealants for connectors and sensors, thermal adhesives, cord coatings, materials for manufacturing electrical and electronic parts such as antenna covers, etc. It can be utilized.
- the aqueous polyamide dispersion liquid of the present disclosure can form a film having excellent adhesiveness to the matrix resin on the substrate.
- a polyamide resin is preferable, and a good composite material can be obtained.
- Example 1 Production of aqueous polyamide aqueous dispersion
- the solubility of the polyalkylene polyamine alkylene oxide adduct (Discol N-518) in water was determined by drying Discol N-518, adding a predetermined amount to water, stirring at 25 ° C. for 5 hours, and then stirring the mixture. It was examined whether it would dissolve and calculated by the following formula.
- Solubility (% by mass) A / (A + B) x 100
- A mass of polyalkylene polyamine alkylene oxide adduct
- B mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
- the solution was fluid, while at 35% by mass, a gel-like substance was formed and there was undissolved residue. Therefore, the solubility in water was judged to be 30% by mass or more and less than 35% by mass. ..
- volume average particle size of the polyamide in the polyamide aqueous dispersion was measured using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name "SALD-2300") and found to be 0.53 ⁇ m.
- Example 2 An aqueous polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of "Discol N-518" used was 90 g and the amount of deionized water used was 47.8 g.
- the volume average particle size of polyamide in this aqueous dispersion was measured using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name "SALD-2300") and found to be 0.53 ⁇ m.
- Comparative Example 1 A polyamide dispersion was obtained in the same manner as in Example 1 except that 53 g of deionized water was added instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass).
- Comparative Example 2 Instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass), 24 g (number average molecular weight) of "Discol N-206" which is a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 33,000, melting point less than 25 ° C, solubility in water 20% by mass or more and less than 25% by mass), and the amount of deionized water used was 96 g.
- "Discol N-518” solid content concentration: 20% by mass
- 24 g number average molecular weight of "Discol N-206” which is a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 33,000, melting point less than 25 ° C, solubility in water 20% by mass or more and less than 25% by mass
- the amount of deionized water used was 96 g.
- the solubility of Discol N-206 in water is a value examined in the same manner as the method for examining the solubility of Discol N-518 in water.
- Example 3 Comparative Example 3 In Example 1, 24 g of an ethylene oxide / propylene oxide copolymer (Pluronic F108 ADEKA Corporation) was used as a nonionic surfactant instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass). A polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of deionized water used was 96 g.
- AO represents an alkylene oxide and n represents an integer. It is described as a polyalkylene polyamine alkylene oxide adduct consisting of repeating units represented by.
- aqueous polyamide dispersions (Examples 1 and 2 and Comparative Examples 1 to 3) obtained as described above were mixed with deionized water to have a polyamide concentration of 1 (w / w)%. 50 ml of the diluted polyamide aqueous dispersion was weighed out, and a 1 mol / L ammonium sulfate aqueous solution was gradually added as an acid component, and the amount of addition at which particle aggregation started was examined. Regarding the agglutination of particles, the agglutination state was confirmed by particle size distribution measurement using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name “SALD-2300”).
- agglomerates are formed at a pH of 7.2 in Comparative Example 1 and agglomerates are formed at a pH of 7.2 in Comparative Example 2.
- agglomerates were formed at a pH of 6.7, whereas in Example 1, the dispersed state could be maintained up to pH 6.2, that is, the dispersed state was maintained even at a pH of 6.4. It was found that the content of particles of 2 ⁇ m or more was 0% by volume, and in Example 2, the dispersed state could be maintained up to pH 6.4, and the content of particles of 2 ⁇ m or more was 0% by volume.
- Comparative Example 1 when 3 mmol of ammonium sulfate, which is an acidic component, was added to the polyamide dispersion, aggregates were formed, and in Comparative Example 2, when 3 mmol of ammonium sulfate, which was an acidic component, was added to the polyamide dispersion, aggregates were formed.
- Comparative Example 3 when 9 mmol of ammonium sulfate, which is an acidic component, was added to the polyamide dispersion, aggregates were formed at a pH of 6.7, whereas in Example 1, ammonium sulfate, which is an acidic component, was added to the polyamide dispersion up to 50 mmol.
- the dispersed state can be maintained even if it is added, and in Example 2, the dispersed state can be maintained even if ammonium sulfate, which is an acidic component, is added to the polyamide dispersion liquid up to 30 mmol.
- the “content (%) of particles of 2 ⁇ m or more" in Table 1 represents the volume% with respect to the total amount of polyamide contained in the dispersion liquid.
- aqueous polyamide dispersion containing the polyalkylene polyamine alkylene oxide adduct can maintain the dispersed state even in a low pH region (a region having a pH of about 7 or lower).
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Abstract
Provided is an aqueous polyamide dispersion that suppresses occurrence of polyamide agglomerates even in regions having a neutral pH (approximately 7, for example). More specifically, provided is an aqueous polyamide dispersion containing an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct having a melting point of 25°C or higher.
Description
本開示は、ポリアミド水性分散液等に関する。
This disclosure relates to an aqueous polyamide dispersion and the like.
ポリアミドの水性分散液は、基材に対してポリアミドのコーティング塗膜を形成することにより、耐溶剤性、耐薬品性、耐磨耗性、気体遮断性、接着性等を付与することができることから、水性インキ、紙処理剤、バインダー、潤滑剤、鋼板表面処理剤、表面改質剤、芯地接着剤等のホットメルト接着剤等に広く用いられている。
Since the aqueous dispersion of polyamide can impart solvent resistance, chemical resistance, abrasion resistance, gas barrier property, adhesiveness, etc. by forming a polyamide coating coating on the base material. , Water-based inks, paper treatment agents, binders, lubricants, steel plate surface treatment agents, surface modifiers, hot melt adhesives such as interlining adhesives, etc. are widely used.
とりわけ、ポリアミドの水性分散液は、ポリアミド樹脂などの熱可塑性樹脂をマトリックス樹脂とした複合材料において、マトリックス樹脂との密着性を高める目的で用いられている。
In particular, the aqueous dispersion of polyamide is used for the purpose of improving the adhesion with the matrix resin in the composite material in which the thermoplastic resin such as the polyamide resin is used as the matrix resin.
従来のポリアミド水性分散液は、アニオン性(例えばpH9~10程度)の水性分散液であり、例えば酸性物質を添加するなどして、水性分散液のpHが低くなると、ポリアミドの凝集物が生成するため、使用できるpH範囲が限定されていた。
The conventional polyamide aqueous dispersion is an anionic (for example, about pH 9 to 10) aqueous dispersion, and when the pH of the aqueous dispersion becomes low, for example, by adding an acidic substance, polyamide aggregates are formed. Therefore, the usable pH range has been limited.
本発明者らは、ポリアミドに加え、特定のポリアルキレンポリアミンアルキレンオキシド付加物をも含有するポリアミド水性分散液であれば、pHが中性の領域であってもポリアミド凝集物生成が抑制される可能性を見出し、さらに改良を重ねた。得られた知見を本明細書に開示する。
The present inventors can suppress the formation of polyamide agglomerates even in the neutral pH range if the aqueous polyamide dispersion contains a specific polyalkylene polyamine alkylene oxide adduct in addition to the polyamide. We found the sex and made further improvements. The findings obtained are disclosed herein.
本開示は例えば以下の項に記載の主題を包含する。
項1.
水性媒体と、前記水性媒体中に分散されたポリアミドと、融点が25℃以上であるポリアルキレンポリアミンアルキレンオキシド付加物とを含む、ポリアミド水性分散液。
項2.
ポリアミドが、6-ナイロン、66-ナイロン、610-ナイロン、11-ナイロン、12-ナイロン、6/66共重合ナイロン、6/610共重合ナイロン、6/11共重合ナイロン、6/12共重合ナイロン、6/66/11共重合ナイロン、6/66/12共重合ナイロン、6/66/11/12共重合ナイロン、6/66/610/11/12共重合ナイロン、ダイマー酸系ポリアミド、ナイロン系エラストマーからなる群より選ばれる少なくとも1種である項1に記載のポリアミド水性分散液。
項3.
ポリアルキレンポリアミンアルキレンオキシド付加物が、数平均分子量が5000~25000で、25℃における水への溶解性が25質量%以上のポリアルキレンポリアミンアルキレンオキシド付加物である、項1又は2に記載のポリアミド水性分散液。
項4.
ポリアミド100質量部に対して、ポリアルキレンポリアミンアルキレンオキシド付加物が1~20質量部含まれる、項1~3のいずれかに記載のポリアミド水性分散液。
項5.
ポリアルキレンポリアミンアルキレンオキシド付加物が、ポリエチレンイミンにアルキレンオキシドを付加重合した構造を有するポリアルキレンポリアミンアルキレンオキシド付加物である、項1~4のいずれかに記載のポリアミド水性分散液。
項6.
ポリアミドの体積平均粒子径が、1μm以下である、項1~5のいずれかに記載のポリアミド水性分散液。
項7.
pHを6.5まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下である、項1~6のいずれかに記載のポリアミド水性分散液。
項8.
項1~7のいずれかに記載のポリアミド水性分散液を含む塗工剤。
項9.
項8に記載の塗工剤を用いて加工された成型体。 The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
A polyamide aqueous dispersion containing an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct having a melting point of 25 ° C. or higher.
Item 2.
Polyamides are 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon, 6/11 copolymerized nylon, 6/12 copolymerized nylon. , 6/66/11 copolymerized nylon, 6/66/12 copolymerized nylon, 6/66/11/12 copolymerized nylon, 6/66/610/11/12 copolymerized nylon, dimer acid-based polyamide, nylon-based Item 2. The aqueous polyamide dispersion liquid according to Item 1, which is at least one selected from the group consisting of elastomers.
Item 3.
Item 2. The polyamide according to Item 1 or 2, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a number average molecular weight of 5000 to 25000 and a solubility in water at 25 ° C. of 25% by mass or more. Aqueous dispersion.
Item 4.
Item 2. The aqueous polyamide dispersion liquid according to any one of Items 1 to 3, wherein 1 to 20 parts by mass of the polyalkylene polyamine alkylene oxide adduct is contained with respect to 100 parts by mass of the polyamide.
Item 5.
Item 2. The aqueous polyamide dispersion according to any one of Items 1 to 4, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a structure in which alkylene oxide is addition-polymerized to polyethyleneimine.
Item 6.
Item 2. The aqueous polyamide dispersion liquid according to any one of Items 1 to 5, wherein the volume average particle size of the polyamide is 1 μm or less.
Item 7.
Item 2. The aqueous polyamide dispersion according to any one of Items 1 to 6, wherein the amount of polyamide having a particle size of 2 μm or more is 15% by volume or less of the total amount of polyamide when the pH is lowered to 6.5.
Item 8.
A coating agent containing the polyamide aqueous dispersion according to any one of Items 1 to 7.
Item 9.
A molded body processed by using the coating agent according to Item 8.
項1.
水性媒体と、前記水性媒体中に分散されたポリアミドと、融点が25℃以上であるポリアルキレンポリアミンアルキレンオキシド付加物とを含む、ポリアミド水性分散液。
項2.
ポリアミドが、6-ナイロン、66-ナイロン、610-ナイロン、11-ナイロン、12-ナイロン、6/66共重合ナイロン、6/610共重合ナイロン、6/11共重合ナイロン、6/12共重合ナイロン、6/66/11共重合ナイロン、6/66/12共重合ナイロン、6/66/11/12共重合ナイロン、6/66/610/11/12共重合ナイロン、ダイマー酸系ポリアミド、ナイロン系エラストマーからなる群より選ばれる少なくとも1種である項1に記載のポリアミド水性分散液。
項3.
ポリアルキレンポリアミンアルキレンオキシド付加物が、数平均分子量が5000~25000で、25℃における水への溶解性が25質量%以上のポリアルキレンポリアミンアルキレンオキシド付加物である、項1又は2に記載のポリアミド水性分散液。
項4.
ポリアミド100質量部に対して、ポリアルキレンポリアミンアルキレンオキシド付加物が1~20質量部含まれる、項1~3のいずれかに記載のポリアミド水性分散液。
項5.
ポリアルキレンポリアミンアルキレンオキシド付加物が、ポリエチレンイミンにアルキレンオキシドを付加重合した構造を有するポリアルキレンポリアミンアルキレンオキシド付加物である、項1~4のいずれかに記載のポリアミド水性分散液。
項6.
ポリアミドの体積平均粒子径が、1μm以下である、項1~5のいずれかに記載のポリアミド水性分散液。
項7.
pHを6.5まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下である、項1~6のいずれかに記載のポリアミド水性分散液。
項8.
項1~7のいずれかに記載のポリアミド水性分散液を含む塗工剤。
項9.
項8に記載の塗工剤を用いて加工された成型体。 The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
A polyamide aqueous dispersion containing an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct having a melting point of 25 ° C. or higher.
Item 2.
Polyamides are 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon, 6/11 copolymerized nylon, 6/12 copolymerized nylon. , 6/66/11 copolymerized nylon, 6/66/12 copolymerized nylon, 6/66/11/12 copolymerized nylon, 6/66/610/11/12 copolymerized nylon, dimer acid-based polyamide, nylon-based Item 2. The aqueous polyamide dispersion liquid according to Item 1, which is at least one selected from the group consisting of elastomers.
Item 3.
Item 2. The polyamide according to Item 1 or 2, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a number average molecular weight of 5000 to 25000 and a solubility in water at 25 ° C. of 25% by mass or more. Aqueous dispersion.
Item 4.
Item 2. The aqueous polyamide dispersion liquid according to any one of Items 1 to 3, wherein 1 to 20 parts by mass of the polyalkylene polyamine alkylene oxide adduct is contained with respect to 100 parts by mass of the polyamide.
Item 5.
Item 2. The aqueous polyamide dispersion according to any one of Items 1 to 4, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a structure in which alkylene oxide is addition-polymerized to polyethyleneimine.
Item 6.
Item 2. The aqueous polyamide dispersion liquid according to any one of Items 1 to 5, wherein the volume average particle size of the polyamide is 1 μm or less.
Item 7.
Item 2. The aqueous polyamide dispersion according to any one of Items 1 to 6, wherein the amount of polyamide having a particle size of 2 μm or more is 15% by volume or less of the total amount of polyamide when the pH is lowered to 6.5.
Item 8.
A coating agent containing the polyamide aqueous dispersion according to any one of Items 1 to 7.
Item 9.
A molded body processed by using the coating agent according to Item 8.
pHが中性(例えば約7)の領域であってもポリアミド凝集物生成が抑制されるポリアミド水性分散液が提供される。
Provided is a polyamide aqueous dispersion in which the formation of polyamide agglutinating is suppressed even in a region where the pH is neutral (for example, about 7).
本開示は、特定のポリアルキレンポリアミンアルキレンオキシド付加物を含むポリアミド水性分散液や、当該ポリアミド水性分散液を含む塗工剤等を好ましく包含するが、これらに限定されるわけではなく、本開示は本明細書に開示され当業者が認識できる全てを包含する。
The present disclosure preferably includes, but is not limited to, a polyamide aqueous dispersion containing a specific polyalkylene polyamine alkylene oxide adduct, a coating agent containing the polyamide aqueous dispersion, and the like. Includes everything disclosed herein and recognizable to those skilled in the art.
本開示に包含されるポリアミド水性分散液は、水性媒体と、前記水性媒体中に分散されたポリアミドと、ポリアルキレンポリアミンアルキレンオキシド付加物とを含む。なお、当該ポリアミド水性分散液を「本開示のポリアミド水性分散液」ということがある。
The polyamide aqueous dispersion included in the present disclosure includes an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct. The polyamide aqueous dispersion may be referred to as "the polyamide aqueous dispersion of the present disclosure".
水性媒体としては、水が好ましく、水道水、工業用水、イオン交換水、脱イオン水、純水などの各種の水を用いることができる。特に脱イオン水および純水が好ましい。また、水性媒体としては、必要に応じて、水にpH調整剤、粘度調整剤、防かび剤等が適宜添加されたものであってもよい。
Water is preferable as the aqueous medium, and various types of water such as tap water, industrial water, ion-exchanged water, deionized water, and pure water can be used. Deionized water and pure water are particularly preferable. Further, as the aqueous medium, a pH adjuster, a viscosity regulator, a fungicide and the like may be appropriately added to water, if necessary.
ポリアミドとしては、公知のもの、又は公知の方法で製造されたものを用いることができる。市販されているものを用いてもよい。
As the polyamide, a known one or one manufactured by a known method can be used. Commercially available products may be used.
より具体的には、例えば、ジアミンとジカルボン酸との重縮合、ω-アミノ-ω’カルボン酸の重縮合、又は環状ラクタムの開環重合、等の方法で製造されたポリアミドが挙げられる。つまり、ジアミンとジカルボン酸とが重縮合したポリアミド、ω-アミノ-ω’カルボン酸が重縮合したポリアミド、環状ラクタムが開環重合したポリアミド、等が挙げられる。ここでの重縮合または開環重合の際に、重合調節剤として、ジカルボン酸またはモノカルボン酸を用いることができる。
More specifically, examples thereof include polyamides produced by a method such as polycondensation of diamine and dicarboxylic acid, polycondensation of ω-amino-ω'carboxylic acid, or ring-opening polymerization of cyclic lactam. That is, examples thereof include polyamides in which diamine and dicarboxylic acid are polycondensed, polyamides in which ω-amino-ω'carboxylic acid is polycondensed, and polyamides in which cyclic lactam is ring-opened polymerized. At the time of polycondensation or ring-opening polymerization here, a dicarboxylic acid or a monocarboxylic acid can be used as a polymerization regulator.
なお、ジアミンとジカルボン酸とが重縮合したポリアミドは、換言すればジアミンとジカルボン酸をモノマー構造単位とするポリアミドであり、ω-アミノ-ω’カルボン酸が重縮合したポリアミドは、換言すればω-アミノ-ω’カルボン酸をモノマー構造単位とするポリアミドであり、環状ラクタムが開環重合したポリアミドは、換言すれば環状ラクタムをモノマー構造単位とするポリアミドである。
The polyamide in which diamine and dicarboxylic acid are polycondensed is, in other words, a polyamide having diamine and dicarboxylic acid as a monomer structural unit, and the polyamide in which ω-amino-ω'carboxylic acid is polycondensed is, in other words, ω. A polyamide having -amino-ω'carboxylic acid as a monomer structural unit, and a polyamide in which cyclic lactam is ring-open polymerized is, in other words, a polyamide having cyclic lactam as a monomer structural unit.
ジアミンとしては、例えば、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、フェニレンジアミン、メタキシリレンジアミン等が挙げられる。
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane. , Phenylenediamine, metaxylylenediamine and the like.
ジカルボン酸としては、例えば、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ノナンジカルボン酸、デカンジカルボン酸、テトラデカンジカルボン酸、オクタデカンジカルボン酸、フマル酸、フタル酸、キシリレンジカルボン酸、ダイマー酸(リノール酸やオレイン酸を主成分とする不飽和脂肪酸より合成される炭素数36の不飽和ジカルボン酸)等が挙げられる。
Examples of dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, and xylylene dicarboxylic acid. Examples thereof include acids and dimeric acids (unsaturated dicarboxylic acids having 36 carbon atoms synthesized from unsaturated fatty acids containing linoleic acid and oleic acid as main components).
ω-アミノ-ω’カルボン酸としては、例えば、6-アミノカプロン酸、7-アミノヘプタン酸、9-アミノノナン酸、11-アミノウンデカン酸、12-アミノドデカン酸等が挙げられる。
Examples of the ω-amino-ω'carboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
環状ラクタムとしては、例えば、ε-カプロラクタム、ω-エナントラクタムおよびω-ラウリルラクタム等が挙げられる。
Examples of the annular lactam include ε-caprolactam, ω-enantractum and ω-lauryl lactam.
前記重合調節剤として用いられるジカルボン酸としては、前記のポリアミドの製造に用いられるジカルボン酸と同様であり、例えば、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ノナンジカルボン酸、デカンジカルボン酸、テトラデカンジカルボン酸、オクタデカンジカルボン酸、フマル酸、フタル酸、キシリレンジカルボン酸、ダイマー酸等が挙げられる。また、モノカルボン酸としては、例えば、カプロン酸、ヘプタン酸、ノナン酸、ウンデカン酸、ドデカン酸等が挙げられる。
The dicarboxylic acid used as the polymerization regulator is the same as the dicarboxylic acid used in the production of the polyamide, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonandicarboxylic acid. , Decandicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, phthalic acid, pimelic acid, dimeric acid and the like. Examples of the monocarboxylic acid include caproic acid, heptanic acid, nonanoic acid, undecanoic acid, dodecanoic acid and the like.
本発明においては、ポリアミドの中でも、特に、-[NH(CH2)5CO]-、-[NH(CH2)6NHCO(CH2)4CO]-、-[NH(CH2)6NHCO(CH2)8CO]-、-[NH(CH2)10CO]-、-[NH(CH2)11CO]-、および-[NH(CH2)2NHCO-D-CO]-(式中Dは炭素数34の不飽和炭化水素を示す)からなる群より選択される少なくとも1種又は2種以上を構造単位とするポリアミドが、好ましく用いられる。
In the present invention, among the polyamides,-[NH (CH 2 ) 5 CO]-,-[NH (CH 2 ) 6 NHCO (CH 2 ) 4 CO]-,-[NH (CH 2 ) 6 NHCO (CH 2 ) 8 CO]-,-[NH (CH 2 ) 10 CO]-,-[NH (CH 2 ) 11 CO]-, and-[NH (CH 2 ) 2 NHCO-D-CO]-( In the formula, D represents an unsaturated hydrocarbon having 34 carbon atoms), and a polyamide having at least one or two or more selected from the group consisting of structural units is preferably used.
かかるポリアミドの例としては、ナイロンが挙げられ、具体的には、6-ナイロン、66-ナイロン、610-ナイロン、11-ナイロン、12-ナイロン、6/66共重合ナイロン、6/610共重合ナイロン、6/11共重合ナイロン、6/12共重合ナイロン、6/66/11共重合ナイロン、6/66/12共重合ナイロン、6/66/11/12共重合ナイロン、又は6/66/610/11/12共重合ナイロン等が例示される。なお、ここでの「/」は各ナイロンの共重合体であることを示すため用いた記号である。例えば、6/66共重合ナイロンは、6-ナイロンと66-ナイロンの共重合ナイロンを表す。
Examples of such polyamides include nylon, specifically 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon. , 6/11 Copolymerized Nylon, 6/12 Copolymerized Nylon, 6/66/11 Copolymerized Nylon, 6/66/12 Copolymerized Nylon, 6/66/11/12 Copolymerized Nylon, or 6/66/610 / 11/12 Copolymerized nylon and the like are exemplified. In addition, "/" here is a symbol used to indicate that it is a copolymer of each nylon. For example, 6/66 copolymerized nylon represents a copolymerized nylon of 6-nylon and 66-nylon.
またさらに、用い得るポリアミドの例として、ダイマー酸系ポリアミドや、ポリアミドエラストマーも例示される。ポリアミドエラストマーとしては、具体的には、ナイロンとポリエステルとの共重合体、又はナイロンとポリアルキレンエーテルグリコールとの共重合体である、ポリアミドエラストマーが例示される。当該ポリアルキレンエーテルグリコールとしては、ポリエチレンオキシドグリコール、ポリプロピレンオキシドグリコール、ポリテトラメチレンオキシドグリコール、ポリヘキサメチレンオキシドグリコール等が例示される。また、当該ポリエステルとしては、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンナフタレート、ポリブチレンナフタレート等が例示される。
Further, as an example of the polyamide that can be used, a dimer acid-based polyamide and a polyamide elastomer are also exemplified. Specific examples of the polyamide elastomer include a polyamide elastomer which is a copolymer of nylon and polyester or a copolymer of nylon and polyalkylene ether glycol. Examples of the polyalkylene ether glycol include polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol, polyhexamethylene oxide glycol and the like. Examples of the polyester include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene naphthalate, and polybutylene naphthalate.
ポリアミドは、1種又は2種以上を組み合わせて用いることができる。なお、ポリアミドエラストマーは、特に限定されるものではないが、ポリアミドブロック及びポリエーテルブロックを含んでなるブロック共重合体が好ましい。特に、ポリアミド及びポリエーテルが共重合した構造を有するブロック共重合体が好ましく、なかでもポリアミド及びポリエーテルが共重合した構造からなるブロック共重合体が好ましい。ポリエーテルブロックの構成成分としては、例えば、ポリエチレンオキシドグリコール、ポリプロピレンオキシドグリコール、ポリテトラメチレンオキシドグリコール、ポリヘキサメチレンオキシドグリコール等のグリコール化合物並びにポリエーテルジアミン等のジアミン化合物等を挙げることができる。これらの構成成分は、2種以上のものが用いられてもよい。このようなポリアミドエラストマーとしては、ポリアミドブロックとポリエーテルブロックとの結合部の分子構造、すなわち結合形態が異なる数種類のもの、例えば、「(ポリアミドブロック)-CO-NH-(ポリエーテルブロック)」の結合形態を有するポリエーテルブロックアミド共重合体、「(ポリアミドブロック)-CO-O-(ポリエーテルブロック)」の結合形態を有するポリエーテルエステルブロックアミド共重合体等を挙げることができる。
Polyamide can be used alone or in combination of two or more. The polyamide elastomer is not particularly limited, but a block copolymer containing a polyamide block and a polyether block is preferable. In particular, a block copolymer having a structure in which a polyamide and a polyether are copolymerized is preferable, and a block copolymer having a structure in which a polyamide and a polyether are copolymerized is particularly preferable. Examples of the constituent components of the polyether block include glycol compounds such as polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol and polyhexamethylene oxide glycol, and diamine compounds such as polyether diamine. Two or more kinds of these constituents may be used. As such a polyamide elastomer, several types having different molecular structures of the bonding portion between the polyamide block and the polyether block, that is, the bonding morphology, for example, "(polyamide block) -CO-NH- (polyamide block)" Examples thereof include a polyether block amide copolymer having a bonded form, a polyether ester block amide copolymer having a bonded form of "(polyamide block) -CO-O- (polyamide block)", and the like.
ポリアルキレンポリアミンアルキレンオキシド付加物としては、例えばアミノ化合物中の1~3個の活性水素に酸化アルキレンを付加させた構造を有するものが好ましい。 具体的には、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ポリエチレンイミンなどのアミンに、アルキレンオキシドを付加重合した構造を有するものが好ましく、特に酸化エチレン/酸化プロピレンをブロック又はランダムで付加重合させたものがより好ましい。なお、ポリエチレンイミンは、直鎖状又は分岐鎖状のいずれであってもよい。
As the polyalkylene polyamine alkylene oxide adduct, for example, one having a structure in which an alkylene oxide is added to 1 to 3 active hydrogens in an amino compound is preferable. Specifically, for example, those having a structure in which alkylene oxide is addition-polymerized with amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine are preferable, and ethylene oxide / propylene oxide is particularly preferable. Is more preferably blocked or randomly subjected to addition polymerization. The polyethyleneimine may be either linear or branched.
かかるポリアルキレンポリアミンアルキレンオキシド付加物としては、特に限定はされないが、特にポリエチレンイミンにアルキレンオキシド成分として、ポリプロピレンオキサイドとポリエチレンオキサイドをブロックで付加した構造を有するポリエチレンイミンアルキレンオキシド付加物が好適に用いられる。
The polyalkylene polyamine alkylene oxide adduct is not particularly limited, but a polyethyleneimine alkylene oxide adduct having a structure in which polypropylene oxide and polyethylene oxide are added as alkylene oxide components to polyethyleneimine in a block is particularly preferably used. ..
また、ポリエチレンイミンアルキレンオキシド付加物としては、下記式(1):
As a polyethyleneimine alkylene oxide adduct, the following formula (1):
(式中、AOはアルキレンオキシドを示し、nは整数を示す。)で表される繰り返し単位を含むものも好ましく挙げられる。ここでのAO(アルキレンオキシド)は、例えば-CH2CH2O-、-CH2CH(CH3)O-、あるいはこれらのブロック又はランダム共重合体が好ましく挙げられる。
(In the formula, AO represents an alkylene oxide and n represents an integer), and those containing a repeating unit represented by the above are also preferably mentioned. As the AO (alkylene oxide) here, for example, -CH 2 CH 2 O-, -CH 2 CH (CH 3 ) O-, or a block or a random copolymer thereof is preferably mentioned.
本開示のポリアミド水性分散液に用いるポリアルキレンポリアミンアルキレンオキシド付加物は、融点が25℃以上であり、好ましくは25~100℃である。当該範囲の上限又は下限は例えば26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、51、52、53、54、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、74、75、76、77、78、79、80、81、82、83、84、85、86、87、88、89、90、91、92、93、94、95、96、97、98、又は99℃であってもよい。当該範囲は、例えば、より好ましくは30~80℃、さらに好ましくは60~80℃である。
The polyalkylene polyamine alkylene oxide adduct used in the aqueous polyamide dispersion of the present disclosure has a melting point of 25 ° C. or higher, preferably 25 to 100 ° C. The upper or lower limit of the range is, for example, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, It may be 97, 98, or 99 ° C. The range is, for example, more preferably 30 to 80 ° C, still more preferably 60 to 80 ° C.
ポリアルキレンポリアミンアルキレンオキシド付加物の数平均分子量は、好ましくは 5000~25000である。当該範囲の上限又は下限は、例えば6000、7000、8000、9000、10000、11000、12000、13000、14000、15000、16000、17000、18000、19000、20000、21000、22000、23000、又は24000であってもよい。当該範囲は、例えば、より好ましくは10000~20000である。数平均分子量が5000以上であることにより、高分子型非イオン性界面活性剤として粒子の周囲で保護コロイド的により好ましく働き、水性分散体の安定化に好ましく寄与し得る。また、数平均分子量が25000以下であることにより、粒子の安定化に寄与するだけでなく、水性分散体の粘度が高くなりすぎることがなく、より実用的な好ましい粘度となり得る。
The number average molecular weight of the polyalkylene polyamine alkylene oxide adduct is preferably 5000 to 25000. The upper or lower limit of the range is, for example, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, or 24000. May be good. The range is, for example, more preferably 10,000 to 20,000. When the number average molecular weight is 5000 or more, it works more preferably as a protective colloid around the particles as a polymer-type nonionic surfactant, and can preferably contribute to the stabilization of the aqueous dispersion. Further, when the number average molecular weight is 25,000 or less, not only contributes to the stabilization of the particles, but also the viscosity of the aqueous dispersion does not become too high, which can be a more practical and preferable viscosity.
なお、ここでの数平均分子量の値は、次の記載の測定方法により求められる値である。数平均分子量測定方法:ポリアルキレンポリアミンアルキレンオキシド付加物を濃度0.2質量%で含むテトラヒドロフラン液を調整し、高速液体クロマトグラフを用いて測定する。そして、分子量が既知の分子量マーカー(ポリスチレン)を同一条件で測定し、較正曲線を作成して、数平均分子量(Mn)を算出する。なお測定条件は以下の通りとする。
The value of the number average molecular weight here is a value obtained by the measurement method described below. Number average molecular weight measurement method: A tetrahydrofuran solution containing a polyalkylene polyamine alkylene oxide adduct at a concentration of 0.2% by mass is prepared, and measurement is performed using a high performance liquid chromatograph. Then, a molecular weight marker (polystyrene) having a known molecular weight is measured under the same conditions, a calibration curve is created, and the number average molecular weight (Mn) is calculated. The measurement conditions are as follows.
測定機 :GPC-101(Shodex)
カラム :東ソー株式会社製 TSK GEL Multipore HZ-N
カラム温度:40℃
流出液 :テトラヒドロフラン
流速 :0.25ml/min Measuring machine: GPC-101 (Shodex)
Column: TSK GEL Multipore HZ-N manufactured by Tosoh Corporation
Column temperature: 40 ° C
Outflow: tetrahydrofuran Flow rate: 0.25 ml / min
カラム :東ソー株式会社製 TSK GEL Multipore HZ-N
カラム温度:40℃
流出液 :テトラヒドロフラン
流速 :0.25ml/min Measuring machine: GPC-101 (Shodex)
Column: TSK GEL Multipore HZ-N manufactured by Tosoh Corporation
Column temperature: 40 ° C
Outflow: tetrahydrofuran Flow rate: 0.25 ml / min
また、ポリアルキレンポリアミンアルキレンオキシド付加物の水への溶解性は、好ましくは25質量%以上であり、より好ましくは26、27、28、又は29質量%以上であり、さらに好ましくは30質量%以上である。なお、ここでの水への溶解性は、25℃の水を用いて検討した場合に次のようにして求められる値である。
The solubility of the polyalkylene polyamine alkylene oxide adduct in water is preferably 25% by mass or more, more preferably 26, 27, 28, or 29% by mass or more, and further preferably 30% by mass or more. Is. The solubility in water here is a value obtained as follows when examined using water at 25 ° C.
溶解性(質量%)=A/(A+B)×100
但し、A:ポリアルキレンポリアミンアルキレンオキシド付加物の質量
B:ポリアルキレンポリアミンアルキレンオキシド付加物を溶解した水の質量 Solubility (% by mass) = A / (A + B) x 100
However, A: mass of polyalkylene polyamine alkylene oxide adduct B: mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
但し、A:ポリアルキレンポリアミンアルキレンオキシド付加物の質量
B:ポリアルキレンポリアミンアルキレンオキシド付加物を溶解した水の質量 Solubility (% by mass) = A / (A + B) x 100
However, A: mass of polyalkylene polyamine alkylene oxide adduct B: mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
このようなポリアルキレンポリアミンアルキレンオキシド付加物は、高分子型非イオン性界面活性剤として市販されており、例えば、第一工業製薬株式会社製のポリアルキレンポリアミンアルキレンオキシド付加物である「ディスコールN-518」を使用することができる。
Such a polyalkylene polyamine alkylene oxide adduct is commercially available as a polymer type nonionic surfactant, and for example, "Discol N" which is a polyalkylene polyamine alkylene oxide adduct manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. -518 ”can be used.
ポリアルキレンポリアミンアルキレンオキシド付加物は一種単独で、あるいは二種以上を組み合わせて用いることができる。
The polyalkylene polyamine alkylene oxide adduct can be used alone or in combination of two or more.
本開示のポリアミド水性分散液におけるポリアルキレンポリアミンアルキレンオキシド付加物の使用量は、ポリアミド100質量部に対して、好ましくは1~20質量部である。当該範囲の上限又は下限は例えば2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、又は19質量部であってもよい。当該範囲は、例えばより好ましくは3~17質量部であり、さらに好ましくは5~15質量部である。
The amount of the polyalkylene polyamine alkylene oxide adduct used in the aqueous polyamide dispersion of the present disclosure is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide. The upper or lower limit of the range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 parts by mass. Good. The range is, for example, more preferably 3 to 17 parts by mass, still more preferably 5 to 15 parts by mass.
ポリアルキレンポリアミンアルキレンオキシド付加物を含まないポリアミド水性分散液は、通常、アニオン性(例えばpH9~10程度)である。当該ポリアミド水性分散液に酸性物質を添加するとポリアミド凝集物が生成しやすいのに対して、ポリアルキレンポリアミンアルキレンオキシド付加物をも含むポリアミド水性分散液は、中性領域(例えばpH7程度又はさらに酸性よりのpH)まで安定な状態を維持できる。このためポリアミド水性分散液の使用範囲が広がるだけでなく、酸性添加剤等との混合も可能になり、各種の性能改良等を容易に行うことができる。
The aqueous polyamide dispersion containing no polyalkylene polyamine alkylene oxide adduct is usually anionic (for example, pH 9 to 10). When an acidic substance is added to the polyamide aqueous dispersion, polyamide agglomerates are likely to be formed, whereas the polyamide aqueous dispersion also containing a polyalkylene polyamine alkylene oxide adduct has a neutral region (for example, about pH 7 or more acidic). It can maintain a stable state up to pH). Therefore, not only the range of use of the aqueous polyamide dispersion can be expanded, but also it can be mixed with an acidic additive or the like, and various performance improvements and the like can be easily performed.
理論的な制限を望むものではないが、ポリアルキレンポリアミンアルキレンオキシド付加物をポリアミド水性分散液に添加することで、中性領域まで安定な状態を維持できる理由として、一般的な高分子型非イオン性界面活性剤を使用する場合、これらの高分子鎖は粒子周辺に自由に存在するだけで、化学的な安定化効果は弱いのに対し、窒素原子を持つポリアルキレンポリアミンアルキレンオキシド付加物を使用する場合、ポリアミド粒子の表面にあるカルボニル基に、窒素原子が引き寄せられ、ポリアルキレンポリアミンアルキレンオキシド付加物が、比較的粒子表面に近くに存在することで、より大きな安定化効果に寄与するものと推測される。
Although we do not want a theoretical limitation, the reason why the stable state can be maintained up to the neutral region by adding the polyalkylene polyamine alkylene oxide adduct to the aqueous polyamide dispersion is that it is a general polymer type non-ion. When using a sex surfactant, these polymer chains are only freely present around the particles and have a weak chemical stabilizing effect, whereas a polyalkylene polyamine alkylene oxide adduct having a nitrogen atom is used. In this case, nitrogen atoms are attracted to the carbonyl group on the surface of the polyamide particles, and the polyalkylene polyamine alkylene oxide adduct is present relatively close to the particle surface, which contributes to a greater stabilizing effect. Guess.
本開示のポリアミド水性分散液を製造する方法としては、特に限定されない。例えば、ポリアミドが分散されている水性分散液(以下、ポリアミド水性分散液前駆体ともいう)とポリアルキレンポリアミンアルキレンオキシド付加物とを混合する工程を含む方法により製造することができる。また、ポリアルキレンポリアミンアルキレンオキシド付加物の水溶液を用いてポリアミドを分散して水性分散液を得る工程を含む方法により製造することもできる。
The method for producing the aqueous polyamide dispersion liquid of the present disclosure is not particularly limited. For example, it can be produced by a method including a step of mixing an aqueous dispersion in which polyamide is dispersed (hereinafter, also referred to as a polyamide aqueous dispersion precursor) and a polyalkylene polyamine alkylene oxide adduct. It can also be produced by a method including a step of dispersing polyamide using an aqueous solution of a polyalkylene polyamine alkylene oxide adduct to obtain an aqueous dispersion.
ポリアミド水性分散液前駆体を製造する方法については、特に限定はなく、水性媒体中にポリアミドを均一に分散できる方法であればよい。
The method for producing the polyamide aqueous dispersion precursor is not particularly limited, and any method may be used as long as the polyamide can be uniformly dispersed in the aqueous medium.
例えば、ポリアミドを、機械粉砕法、冷凍粉砕法、湿式粉砕法等の粉砕法により粉砕して得られるポリアミド粉体を水性媒体中に分散させる方法、ポリアミドと塩基性物質を用いて乳化させて、水性分散液を製造する方法、界面活性剤を用いてポリアミドを乳化し水性分散液を製造する方法、等が挙げられる。
For example, a method of dispersing polyamide powder obtained by pulverizing polyamide by a pulverization method such as a mechanical pulverization method, a freezing pulverization method, or a wet pulverization method in an aqueous medium, or emulsifying using polyamide and a basic substance. Examples thereof include a method of producing an aqueous dispersion, a method of emulsifying polyamide using a surfactant, and producing an aqueous dispersion.
以下に、代表的な製造例として、ポリアミドと塩基性物質を用いて乳化し、水性分散液を製造する方法について示す。
Below, as a typical production example, a method of emulsifying using polyamide and a basic substance to produce an aqueous dispersion is shown.
この製造方法では、例えば、容器内にポリアミド、塩基性物質および水性媒体を投入し、これらの混合液を調製する。
In this production method, for example, a polyamide, a basic substance, and an aqueous medium are put into a container to prepare a mixed solution thereof.
混合液の調製に用いる容器としては、ポリアミドが水性媒体中で軟化する温度以上の温度に加熱するための加熱手段と、内容物にせん断力を与えることのできる攪拌手段とを備えた、耐圧容器が好ましい。例えば、攪拌機付きの耐圧オートクレーブ等が好ましい。
The container used for preparing the mixture is a pressure-resistant container provided with a heating means for heating the polyamide to a temperature higher than the temperature at which it softens in an aqueous medium and a stirring means capable of applying a shearing force to the contents. Is preferable. For example, a pressure resistant autoclave with a stirrer is preferable.
次に、この容器内でポリアミド、塩基性物質および水性媒体を混合して混合液を得る。そして、当該混合液をポリアミドの軟化温度以上に加熱し攪拌して、乳化させ、乳濁液を得る。当該乳濁液を室温まで冷却すると、ポリアミド水性分散液前駆体が得られる。
Next, the polyamide, basic substance and aqueous medium are mixed in this container to obtain a mixed solution. Then, the mixed solution is heated to a temperature equal to or higher than the softening temperature of the polyamide and stirred to emulsify the mixture to obtain an emulsion. Cooling the emulsion to room temperature gives a polyamide aqueous dispersion precursor.
塩基性物質としては、特に限定されないが、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物やアンモニア、アミン化合物等が挙げられる。塩基性物質は1種単独又は2種以上を組み合わせて用いることができる。なお、これらの中でも、分散液の静置安定性が優れる観点から特に水酸化ナトリウムおよび/または水酸化カリウムが好適に用いられる。
The basic substance is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and amine compounds. The basic substance may be used alone or in combination of two or more. Of these, sodium hydroxide and / or potassium hydroxide are particularly preferably used from the viewpoint of excellent static stability of the dispersion.
塩基性物質の使用量は、得られる水性分散液の粘度の経時変化が少ない等、静置安定性に優れるという観点から、ポリアミドの末端カルボキシル基1モルあたり0.1~2モルであることが好ましく、0.4~1モルであることがより好ましい。
The amount of the basic substance used is 0.1 to 2 mol per 1 mol of the terminal carboxyl group of the polyamide from the viewpoint of excellent static stability such as little change in the viscosity of the obtained aqueous dispersion with time. It is preferably 0.4 to 1 mol, more preferably 0.4 to 1 mol.
ポリアミドの使用量は、特に限定されるものではないが、得られるポリアミド水性分散液前駆体100質量部に対して0.1~80質量部に設定するのが好ましく、20~60質量部に設定するのがより好ましい。
The amount of the polyamide used is not particularly limited, but is preferably set to 0.1 to 80 parts by mass, and set to 20 to 60 parts by mass with respect to 100 parts by mass of the obtained polyamide aqueous dispersion precursor. It is more preferable to do so.
また、本願発明の効果を損なわない限り、塩基性物質と界面活性剤(分散安定剤)を併用してポリアミド水性分散液前駆体を得ることもできる。
Further, as long as the effect of the present invention is not impaired, a polyamide aqueous dispersion precursor can be obtained by using a basic substance and a surfactant (dispersion stabilizer) in combination.
ポリアミド水性分散液前駆体を得るために(つまり、ポリアミドを水性媒体へ分散させるために)使用用される界面活性剤(分散安定剤)としては、得られる本開示のポリアミド水性分散液の効果を損なわない範囲において、アニオン性界面活性剤、ノニオン性界面活性剤、高分子系分散剤等の添加剤を用いることもできる。
As a surfactant (dispersion stabilizer) used to obtain a polyamide aqueous dispersion precursor (that is, to disperse polyamide in an aqueous medium), the effect of the obtained polyamide aqueous dispersion of the present disclosure can be used. Additives such as anionic surfactants, nonionic surfactants, and polymer-based dispersants can also be used as long as they are not impaired.
アニオン性界面活性剤としては、例えば、脂肪族系ポリオキシアルキレンアルキルエーテル硫酸塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルジフェニルスルホン酸塩、α-オレフィンスルホン酸塩、アルキル硫酸エステル塩、ナフタレンスルホン酸塩ホルマリン縮合物、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、ロジン酸塩および脂肪酸塩等が挙げられる。
Examples of the anionic surfactant include aliphatic polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkylphenyl ether sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyldiphenyl sulfonates, and α-olefins. Examples thereof include sulfonates, alkyl sulfates, naphthalene sulfonate formalin condensates, dialkyl sulfosuccinates, polyoxyethylene alkyl ether acetates, rosin salts and fatty acid salts.
ノニオン性界面活性剤としては、例えば、ポリエチレングリコール、エチレンオキシド/プロピレンオキシド共重合体、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルチオエーテル、ポリオキシエチレンソルビタン脂肪酸モノエステル、ポリオキシエチレンアルキルアミド、ポリグリセリンエステル等を挙げることができる。
Examples of the nonionic surfactant include polyethylene glycol, ethylene oxide / propylene oxide copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl thioether, polyoxyethylene sorbitan fatty acid monoester, and polyoxy. Examples thereof include ethylene alkyl amide and polyglycerin ester.
高分子系分散安定剤としては、例えば、ポリビニルアルコール、ヒドロキシエチルセルロース、メチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドンや、ポリアクリル酸塩、ポリアクリル酸エステル塩、アルギン酸塩、エチレン/アクリル酸共重合体の塩(特にアンモニウム塩)、スチレン/無水マレイン酸共重合体の塩、スチレン-マレイン酸モノエステル共重合体の塩、イソブチレン/無水マレイン酸共重合体の塩、カルボキシメチルセルロースの塩 等が挙げられる。
Examples of the polymer-based dispersion stabilizer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyacrylic acid salt, polyacrylic acid ester salt, alginate, and salts of ethylene / acrylic acid copolymers. (Especially ammonium salt), styrene / maleic anhydride copolymer salt, styrene-maleic acid monoester copolymer salt, isobutylene / maleic anhydride copolymer salt, carboxymethyl cellulose salt and the like can be mentioned.
これらの添加剤の中で、得られる本開示の水性分散液の安定性を高めるという観点から、ノニオン系界面活性剤や高分子系分散安定剤が好適に用いられる。中でも、得られる本開示の水性分散液が耐熱性に優れ、高温で長時間加工しても分解しにくく、当該水性分散液で処理した積層体とマトリックス樹脂との接着性が良好という点において、エチレンオキシド/プロピレンオキシド共重合体、ポリオキシエチレンアルキルエーテル(例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンミリステルエーテル、ポリオキシエチレンオクチルドデシルエーテル、等)、エチレン/アクリル酸共重合体アンモニウム塩、スチレン/無水マレイン酸共重合体アンモニウム塩、スチレン-マレイン酸モノエステル共重合体アンモニウム塩、イソブチレン/マレイン酸エステル共重合体のアンモニウム塩が好適に用いられる。
Among these additives, a nonionic surfactant and a polymer-based dispersion stabilizer are preferably used from the viewpoint of enhancing the stability of the obtained aqueous dispersion liquid of the present disclosure. Above all, the obtained aqueous dispersion of the present disclosure has excellent heat resistance, is not easily decomposed even when processed at a high temperature for a long time, and has good adhesion between the laminate treated with the aqueous dispersion and the matrix resin. Ethylene oxide / propylene oxide copolymer, polyoxyethylene alkyl ether (eg polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene mi Listel ether, polyoxyethylene octyldodecyl ether, etc.), ethylene / acrylic acid copolymer ammonium salt, styrene / maleic anhydride copolymer ammonium salt, styrene-maleic acid monoester copolymer ammonium salt, isobutylene / maleic acid The ammonium salt of the ester copolymer is preferably used.
これらの添加剤は、1種又は2種以上を組み合わせて用いることができる。
These additives can be used alone or in combination of two or more.
添加剤の使用量は、ポリアミド100質量部に対して、好ましくは10質量部未満、より好ましくは0.1~8質量部が例示される。但し、これらの添加剤の使用は、得られる分散液で処理した積層体とマトリックス樹脂との接着性に悪影響を及ぼすおそれもあるため、前記量を参考として、比較的多く使用することを避けつつ適宜設定することが望ましい。
The amount of the additive used is preferably less than 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyamide. However, since the use of these additives may adversely affect the adhesiveness between the laminate treated with the obtained dispersion and the matrix resin, refer to the above amount and avoid using a relatively large amount. It is desirable to set it appropriately.
なお、これらの添加剤は、製造過程において、ポリアミド水性分散液前駆体が得られた後に、さらに添加してもよい。
Note that these additives may be further added after the polyamide aqueous dispersion precursor is obtained in the manufacturing process.
上記のようにして調製されたポリアミド水性分散液前駆体に、ポリアルキレンポリアミンアルキレンオキシド付加物を混合することにより、本開示のポリアミド水性分散液が得られる。ポリアミド水性分散液前駆体とポリアルキレンポリアミンアルキレンオキシド付加物を混合する方法として特に限定されず、例えば、ポリアミド水性分散液前駆体とポリアルキレンポリアミンアルキレンオキシド付加物を同一容器内に投入して、撹拌し、混合する方法などが挙げられる。
The polyamide aqueous dispersion of the present disclosure can be obtained by mixing the polyalkylene polyamine alkylene oxide adduct with the polyamide aqueous dispersion precursor prepared as described above. The method for mixing the polyamide aqueous dispersion precursor and the polyalkylene polyamine alkylene oxide adduct is not particularly limited. For example, the polyamide aqueous dispersion precursor and the polyalkylene polyamine alkylene oxide adduct are put into the same container and stirred. Then, a method of mixing and the like can be mentioned.
本開示のポリアミド水性分散液中のポリアミドの濃度(w/w%)は、0.1~80質量%であることが好ましく、より好ましくは1~60質量%であり、さらに好ましくは5~50質量%である。ポリアミドの濃度が80質量%以下であれば、ポリアミド水性分散液の安定性がより向上し得る。また、当該濃度が0.1質量%以上であれば、積層体の被着体へポリアミドをより付着させやすくなる。
The concentration (w / w%) of the polyamide in the aqueous polyamide dispersion of the present disclosure is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, and further preferably 5 to 50% by mass. It is mass%. When the concentration of polyamide is 80% by mass or less, the stability of the aqueous polyamide dispersion can be further improved. Further, when the concentration is 0.1% by mass or more, the polyamide can be more easily adhered to the adherend of the laminated body.
本開示のポリアミド水性分散液において、分散されたポリアミド(粒子)の平均粒子径は、例えば好ましくは2μm未満である。また、当該平均粒子径の下限は、特に制限はされないが、例えば0.05μm以上である。例えば2μm未満0.05μm以上であることがさらに好ましい。当該範囲の上限又は下限は、例えば1.9、1.8、1.7、1.6、1.5、1.4、1.3、1.2、1.1、1.0、0.9、0.8、0.7、0.6、0.5、0.4、0.3、0.2、又は0.1μmであってもよい。また、上記の通り、下限は設定されなくてもよい。例えば、さらに好ましくは、1.5μm以下、1.0μm以下、又は0.8μm以下であり得る。なお、本明細書において、ポリアミドの平均粒子径は、レーザー回折式粒度分布測定法による体積平均粒子径である。すなわち、ポリアミド水性分散液をレーザー回折式粒度分布測定装置にて測定した際に得られる体積平均粒子径値である。
In the aqueous polyamide dispersion of the present disclosure, the average particle size of the dispersed polyamide (particles) is, for example, preferably less than 2 μm. The lower limit of the average particle size is not particularly limited, but is, for example, 0.05 μm or more. For example, it is more preferably less than 2 μm and 0.05 μm or more. The upper or lower limit of the range is, for example, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0. It may be 9.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 μm. Further, as described above, the lower limit does not have to be set. For example, it can be more preferably 1.5 μm or less, 1.0 μm or less, or 0.8 μm or less. In the present specification, the average particle size of the polyamide is the volume average particle size measured by the laser diffraction type particle size distribution measurement method. That is, it is a volume average particle diameter value obtained when the polyamide aqueous dispersion is measured by a laser diffraction type particle size distribution measuring device.
また、本開示のポリアミド水性分散液は、酸性物質を用いてpHを低下させた際に、ポリアミドの凝集物が生成し難いものが好ましい。ポリアミドの凝集程度は、例えば、粒子径が2μm以上のポリアミド量(体積)が全ポリアミド量(体積)のどの程度の割合(体積%)であるかで示すことができる。当該値は、レーザー回折・散乱法による粒度分布測定で求められる。例えば、pHを6.5まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下であることが好ましく、14、13、12、11、又は10体積%以下であることがより好ましく、9、8、7、6、5、4、又は3体積%以下であることがさらに好ましい。また例えば、pHを6.4まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下であることが好ましく、14、13、12、11、又は10体積%以下であることがより好ましく、9、8、7、6、5、4、又は3体積%以下であることがさらに好ましい。また例えば、pHを6.2まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下であることが好ましく、14、13、12、11、又は10体積%以下であることがより好ましく、9、8、7、6、5、4、又は3体積%以下であることがさらに好ましい。
Further, the aqueous polyamide dispersion liquid of the present disclosure is preferably one in which agglomerates of polyamide are unlikely to be formed when the pH is lowered by using an acidic substance. The degree of aggregation of polyamide can be indicated by, for example, the ratio (volume%) of the total polyamide amount (volume) to the polyamide amount (volume) having a particle size of 2 μm or more. The value is obtained by measuring the particle size distribution by the laser diffraction / scattering method. For example, when the pH is lowered to 6.5, the amount of polyamide having a particle size of 2 μm or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume or less. Is more preferable, and 9, 8, 7, 6, 5, 4, or 3% by volume or less is further preferable. Further, for example, when the pH is lowered to 6.4, the amount of polyamide having a particle size of 2 μm or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume. It is more preferably 9, 8, 7, 6, 5, 4, or 3% by volume or less. Further, for example, when the pH is lowered to 6.2, the amount of polyamide having a particle size of 2 μm or more is preferably 15% by volume or less of the total amount of polyamide, and is 14, 13, 12, 11, or 10% by volume. It is more preferably 9, 8, 7, 6, 5, 4, or 3% by volume or less.
なお、ポリアミド水性分散液のpHを低下させるために用いる酸性物質としては、ポリアミドの凝集に影響を与えない酸性物質が好ましく、より具体的には例えば硫酸アンモニウム等が好ましく挙げられる。
As the acidic substance used to lower the pH of the aqueous polyamide dispersion, an acidic substance that does not affect the aggregation of the polyamide is preferable, and more specifically, for example, ammonium sulfate and the like are preferably mentioned.
本開示のポリアミド水性分散液は、例えば、pHが6.7未満であって、且つポリアミドの平均粒子径が上記好ましい範囲を満たすものも、好ましく包含する。当該pH範囲は、6.65以下、6.6以下、6.55以下、6.5以下、6.45以下、6.4以下、6.35以下、6.3以下、6.25以下、6.2以下、6.15以下、又は6.1以下であってもよい。また、ポリアミドの平均粒子径が上記好ましい範囲を満たす限り、当該pH下限は特に制限されない。例えば、5、5.1、5.2、5.3、5.4、5.5、5.6、5.7、5.8、5.9、又は6が挙げられる。
The aqueous polyamide dispersion liquid of the present disclosure preferably includes, for example, one having a pH of less than 6.7 and an average particle size of polyamide satisfying the above preferable range. The pH range is 6.65 or less, 6.6 or less, 6.55 or less, 6.5 or less, 6.45 or less, 6.4 or less, 6.35 or less, 6.3 or less, 6.25 or less, It may be 6.2 or less, 6.15 or less, or 6.1 or less. Further, as long as the average particle size of the polyamide satisfies the above preferable range, the lower limit of pH is not particularly limited. For example, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.
また、本開示のポリアミド水性分散液は、例えば、pHが6.7未満であって、且つ平均粒子径2μm以上のポリアミド粒子を含まないものも、好ましく包含する。当該pH範囲は、6.65以下、6.6以下、6.55以下、6.5以下、6.45以下、6.4以下、6.35以下、6.3以下、6.25以下、6.2以下、6.15以下、又は6.1以下であってもよい。また、平均粒子径2μm以上のポリアミド粒子を含まない限り、当該pH下限は特に制限されない。例えば、5、5.1、5.2、5.3、5.4、5.5、5.6、5.7、5.8、5.9、又は6が挙げられる。
Further, the aqueous polyamide dispersion liquid of the present disclosure preferably includes, for example, one having a pH of less than 6.7 and containing no polyamide particles having an average particle diameter of 2 μm or more. The pH range is 6.65 or less, 6.6 or less, 6.55 or less, 6.5 or less, 6.45 or less, 6.4 or less, 6.35 or less, 6.3 or less, 6.25 or less, It may be 6.2 or less, 6.15 or less, or 6.1 or less. Further, the lower limit of pH is not particularly limited as long as it does not contain polyamide particles having an average particle diameter of 2 μm or more. For example, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, or 6.
なお、本明細書において、ポリアミド水性分散液のpHは、25℃においてpHメータを用いて測定した値である。
In the present specification, the pH of the aqueous polyamide dispersion is a value measured at 25 ° C. using a pH meter.
本開示のポリアミド水性分散液を含む塗工剤を用いて、各種の成形体を加工することができる。当該塗工剤は、各種の成形体を製造するための材料として有用である。
Various molded products can be processed by using the coating agent containing the aqueous polyamide dispersion liquid of the present disclosure. The coating agent is useful as a material for producing various molded products.
成形体の製造方法は、特に限定されないが、基材に本開示のポリアミド水性分散液を塗布又は、型枠内へ流し込む工程、及び塗布した又は流し込んだポリアミド水性分散液の水性分散体を乾燥させる(すなわち、水分を除去する)工程を含む。このような工程を含む成形体の製造方法により、ポリアミド水性分散液を含む皮膜、フィルム若しくはシート状等の各種の形態の成形体を得ることができる。
The method for producing the molded product is not particularly limited, but the step of applying the aqueous polyamide dispersion liquid of the present disclosure to the base material or pouring it into a mold, and drying the aqueous dispersion of the coated or poured polyamide aqueous dispersion. It involves a step (ie, removing water). By a method for producing a molded product including such a step, it is possible to obtain a molded product having various forms such as a film, a film or a sheet containing an aqueous polyamide dispersion.
本開示のポリアミド水性分散液を基材に塗布する方法は、特に限定されないが、例えば、はけ、ヘラ、ローラー、コーキングガン、シルクスクリーン、エア・スプレー、ノズルスプレー、ロールコーター等を用いる塗布方法が挙げられる。
The method for applying the aqueous polyamide dispersion liquid of the present disclosure to the substrate is not particularly limited, and for example, a coating method using a brush, a spatula, a roller, a caulking gun, a silk screen, an air spray, a nozzle spray, a roll coater, or the like. Can be mentioned.
基材へのポリアミド水性分散液の塗布量は、目的に応じて適宜設定され、例えば、本開示のポリアミド水性分散液から得られる膜の厚みが0.001mm~5mmとなるように塗布される。
The amount of the polyamide aqueous dispersion applied to the base material is appropriately set according to the purpose, and for example, the film is applied so that the thickness of the film obtained from the polyamide aqueous dispersion of the present disclosure is 0.001 mm to 5 mm.
型枠内へポリアミド水性分散液を流し込む方法は、特に限定されない。
The method of pouring the aqueous polyamide dispersion into the mold is not particularly limited.
例えば、ポリアミド水性分散液を基材へ塗布するか、型枠内へ流し込んだ後、水分を除去する方法が挙げられる。水分を除去する工程における乾燥温度は、特に限定されないが、通常、40~300℃に設定される。
For example, a method of applying a polyamide aqueous dispersion to a substrate or pouring it into a mold and then removing water can be mentioned. The drying temperature in the step of removing water is not particularly limited, but is usually set to 40 to 300 ° C.
乾燥時間は特に限定されず、例えば、100℃にて乾燥を行う場合、0.2~2時間である。
The drying time is not particularly limited, and for example, when drying at 100 ° C., it is 0.2 to 2 hours.
成形体の製造に用いる基材は、特に限定されないが、例えば、アルミや銅などの金属、ガラス、木質、ゴム、熱可塑性樹脂、熱硬化性樹脂、さらにそれらを強化繊維やフィラーなどで強化した樹脂などから製造される。基材の厚みおよび形状などは特に限定されない。
The base material used for manufacturing the molded product is not particularly limited, but is, for example, metal such as aluminum or copper, glass, wood, rubber, thermoplastic resin, thermosetting resin, and further reinforced with reinforcing fibers or fillers. Manufactured from resin or the like. The thickness and shape of the base material are not particularly limited.
このようにして得られた成形体(例えば、基材に塗布し、乾燥させて得られた積層体)におけるポリアミド水性分散液の塗布側と、更なる基材とを合わせて、例えば、ホットプレスを用いて120~300℃にて、必要により0.1~100MPaに加圧し、1~500秒間加熱することにより、基材を層状に接合させた複合材料を製造できる。接合させる基材は異なる種類の基材であっても、同種の基材であってもよい。
The coating side of the aqueous polyamide dispersion in the molded product thus obtained (for example, a laminate obtained by coating on a base material and drying) and a further base material are combined, for example, hot pressing. A composite material in which base materials are bonded in layers can be produced by pressurizing the mixture at 120 to 300 ° C., if necessary, to 0.1 to 100 MPa and heating for 1 to 500 seconds. The base material to be bonded may be a different type of base material or the same type of base material.
本開示のポリアミド水性分散液は、自動車部品、スポーツ関連製品及び医療器具等を製造するための材料、紙及びフィルム等のコーティング剤、接着剤、表面改質剤、フォームラバー用原料、コーティング剤、あるいはホース、チューブ、ベルト、ガスケット及びパッキング等の製造用材料、コネクター、センサー類のシール剤、熱接着剤、コード被覆、アンテナカバー等の電気・電子部品を製造するための材料等の広い用途において活用することができる。
The polyamide aqueous dispersion of the present disclosure includes materials for manufacturing automobile parts, sports-related products, medical instruments, etc., coating agents for paper and films, adhesives, surface modifiers, raw materials for foam rubber, coating agents, etc. Alternatively, in a wide range of applications such as manufacturing materials such as hoses, tubes, belts, gaskets and packings, sealants for connectors and sensors, thermal adhesives, cord coatings, materials for manufacturing electrical and electronic parts such as antenna covers, etc. It can be utilized.
本開示のポリアミド水性分散液は、マトリックス樹脂との接着性に優れる皮膜を基材上に形成させることができる。マトリックス樹脂の中でも好ましい物はポリアミド樹脂であり、良好な複合材料が得られる。
The aqueous polyamide dispersion liquid of the present disclosure can form a film having excellent adhesiveness to the matrix resin on the substrate. Among the matrix resins, a polyamide resin is preferable, and a good composite material can be obtained.
なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する(The term "comprising" includes "consisting essentially of” and "consisting of.")。
In this specification, "including" also includes "consisting of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of.").
また、上述した各実施形態について説明した各種特性(性質、構造、機能等)は、本開示に包含される主題を特定するにあたり、どのように組み合わせられてもよい。
Further, the various characteristics (property, structure, function, etc.) described for each of the above-described embodiments may be combined in any way in specifying the subject matter included in the present disclosure.
以下、本開示に包含される主題をより具体的に説明するが、当該主題は下記の例に限定されるものではない。
Hereinafter, the subject matter included in the present disclosure will be described in more detail, but the subject matter is not limited to the following examples.
水性ポリアミド水性分散液の製造
実施例1
直径50mmのタービン型撹拌羽根を備えた内容積1リットルの耐圧オートクレーブ中に、ポリアミドとして6/66/12共重合ナイロン(融点120℃)240g、脱イオン水150gおよび10%水酸化ナトリウム水溶液10gを仕込み密閉した。次に、撹拌機を始動し、500rpmの回転数で撹拌しながらオートクレーブ内部を160℃まで昇温した。内温を160℃に保ちながらさらに30分間撹拌した後、冷却し、エチレン-アクリル酸共重合体アンモニウム塩の水性分散液(固形分濃度29重量%)24.5gおよび脱イオン水198gを加えた。さらに、室温まで冷却後、第一工業製薬株式会社製のポリアルキレンポリアミンアルキレンオキシド付加物の水溶液である「ディスコールN-518」120g(数平均分子量:16000、融点64.5℃、水への溶解性は30質量%以上35質量%未満、固形分濃度:20質量%)および脱イオン水33.5gを加えて、よく混合してポリアミド水性分散液を得た。 Production of aqueous polyamide aqueous dispersion
Example 1
240 g of 6/66/12 copolymerized nylon (melting point 120 ° C.), 150 g of deionized water and 10 g of 10% sodium hydroxide aqueous solution as polyamide in a pressure resistant autoclave having an internal volume of 1 liter equipped with a turbine-type stirring blade having a diameter of 50 mm. It was prepared and sealed. Next, the stirrer was started, and the temperature inside the autoclave was raised to 160 ° C. while stirring at a rotation speed of 500 rpm. After stirring for another 30 minutes while maintaining the internal temperature at 160 ° C., the mixture was cooled, and 24.5 g of an aqueous dispersion (solid content concentration 29% by weight) of an ammonium salt of an ethylene-acrylic acid copolymer and 198 g of deionized water were added. .. Further, after cooling to room temperature, 120 g of "Discol N-518", which is an aqueous solution of a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (number average molecular weight: 16000, melting point 64.5 ° C., in water). Solubility was 30% by mass or more and less than 35% by mass, solid content concentration: 20% by mass) and 33.5 g of deionized water were added and mixed well to obtain a polyamide aqueous dispersion.
実施例1
直径50mmのタービン型撹拌羽根を備えた内容積1リットルの耐圧オートクレーブ中に、ポリアミドとして6/66/12共重合ナイロン(融点120℃)240g、脱イオン水150gおよび10%水酸化ナトリウム水溶液10gを仕込み密閉した。次に、撹拌機を始動し、500rpmの回転数で撹拌しながらオートクレーブ内部を160℃まで昇温した。内温を160℃に保ちながらさらに30分間撹拌した後、冷却し、エチレン-アクリル酸共重合体アンモニウム塩の水性分散液(固形分濃度29重量%)24.5gおよび脱イオン水198gを加えた。さらに、室温まで冷却後、第一工業製薬株式会社製のポリアルキレンポリアミンアルキレンオキシド付加物の水溶液である「ディスコールN-518」120g(数平均分子量:16000、融点64.5℃、水への溶解性は30質量%以上35質量%未満、固形分濃度:20質量%)および脱イオン水33.5gを加えて、よく混合してポリアミド水性分散液を得た。 Production of aqueous polyamide aqueous dispersion
Example 1
240 g of 6/66/12 copolymerized nylon (melting point 120 ° C.), 150 g of deionized water and 10 g of 10% sodium hydroxide aqueous solution as polyamide in a pressure resistant autoclave having an internal volume of 1 liter equipped with a turbine-type stirring blade having a diameter of 50 mm. It was prepared and sealed. Next, the stirrer was started, and the temperature inside the autoclave was raised to 160 ° C. while stirring at a rotation speed of 500 rpm. After stirring for another 30 minutes while maintaining the internal temperature at 160 ° C., the mixture was cooled, and 24.5 g of an aqueous dispersion (solid content concentration 29% by weight) of an ammonium salt of an ethylene-acrylic acid copolymer and 198 g of deionized water were added. .. Further, after cooling to room temperature, 120 g of "Discol N-518", which is an aqueous solution of a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (number average molecular weight: 16000, melting point 64.5 ° C., in water). Solubility was 30% by mass or more and less than 35% by mass, solid content concentration: 20% by mass) and 33.5 g of deionized water were added and mixed well to obtain a polyamide aqueous dispersion.
なお、ポリアルキレンポリアミンアルキレンオキシド付加物(ディスコールN-518)の水への溶解性は、ディスコールN-518を乾固後、水に所定量添加し、25℃下、5時間撹拌後、溶解するかを検討して、以下の式で算出した。
The solubility of the polyalkylene polyamine alkylene oxide adduct (Discol N-518) in water was determined by drying Discol N-518, adding a predetermined amount to water, stirring at 25 ° C. for 5 hours, and then stirring the mixture. It was examined whether it would dissolve and calculated by the following formula.
溶解性(質量%)=A/(A+B)×100
但し、A:ポリアルキレンポリアミンアルキレンオキシド付加物の質量
B:ポリアルキレンポリアミンアルキレンオキシド付加物を溶解した水の質量 Solubility (% by mass) = A / (A + B) x 100
However, A: mass of polyalkylene polyamine alkylene oxide adduct B: mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
但し、A:ポリアルキレンポリアミンアルキレンオキシド付加物の質量
B:ポリアルキレンポリアミンアルキレンオキシド付加物を溶解した水の質量 Solubility (% by mass) = A / (A + B) x 100
However, A: mass of polyalkylene polyamine alkylene oxide adduct B: mass of water in which the polyalkylene polyamine alkylene oxide adduct is dissolved.
30質量%では、流動性ある溶液である一方で、35質量%ではゲル状物生成、また溶け残りがある状態であったため、水への溶解性は30質量%以上35質量%未満と判断した。
At 30% by mass, the solution was fluid, while at 35% by mass, a gel-like substance was formed and there was undissolved residue. Therefore, the solubility in water was judged to be 30% by mass or more and less than 35% by mass. ..
また、このポリアミド水性分散液中のポリアミドの体積平均粒子径を回折式粒度分布測定装置(株式会社島津製作所、商品名“SALD-2300”)を用いて測定したところ、0.53μmであった。
Further, the volume average particle size of the polyamide in the polyamide aqueous dispersion was measured using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name "SALD-2300") and found to be 0.53 μm.
実施例2
「ディスコールN-518」の使用量を90gとし、脱イオン水使用量を47.8gとした以外は、実施例1と同様にしてポリアミド水性分散液を得た。 Example 2
An aqueous polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of "Discol N-518" used was 90 g and the amount of deionized water used was 47.8 g.
「ディスコールN-518」の使用量を90gとし、脱イオン水使用量を47.8gとした以外は、実施例1と同様にしてポリアミド水性分散液を得た。 Example 2
An aqueous polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of "Discol N-518" used was 90 g and the amount of deionized water used was 47.8 g.
この水性分散液中のポリアミドの体積平均粒子径を回折式粒度分布測定装置(株式会社島津製作所、商品名“SALD-2300”)を用いて測定したところ、0.53μmであった。
The volume average particle size of polyamide in this aqueous dispersion was measured using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name "SALD-2300") and found to be 0.53 μm.
比較例1
「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、脱イオン水53gを添加した以外は、実施例1と同様にして、ポリアミド分散液を得た。 Comparative Example 1
A polyamide dispersion was obtained in the same manner as in Example 1 except that 53 g of deionized water was added instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass).
「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、脱イオン水53gを添加した以外は、実施例1と同様にして、ポリアミド分散液を得た。 Comparative Example 1
A polyamide dispersion was obtained in the same manner as in Example 1 except that 53 g of deionized water was added instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass).
比較例2
「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、第一工業製薬株式会社製のポリアルキレンポリアミンアルキレンオキシド付加物である「ディスコールN-206」24g(数平均分子量33,000、融点25℃未満、水への溶解性20質量%以上25質量%未満)を用い、また脱イオン水使用量を96gとした以外は、実施例1と同様にして、ポリアミド分散液を得た。 Comparative Example 2
Instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass), 24 g (number average molecular weight) of "Discol N-206" which is a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 33,000, melting point less than 25 ° C, solubility in water 20% by mass or more and less than 25% by mass), and the amount of deionized water used was 96 g. Got
「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、第一工業製薬株式会社製のポリアルキレンポリアミンアルキレンオキシド付加物である「ディスコールN-206」24g(数平均分子量33,000、融点25℃未満、水への溶解性20質量%以上25質量%未満)を用い、また脱イオン水使用量を96gとした以外は、実施例1と同様にして、ポリアミド分散液を得た。 Comparative Example 2
Instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass), 24 g (number average molecular weight) of "Discol N-206" which is a polyalkylene polyamine alkylene oxide adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 33,000, melting point less than 25 ° C, solubility in water 20% by mass or more and less than 25% by mass), and the amount of deionized water used was 96 g. Got
なお、ディスコールN-206の水への溶解性は、上記ディスコールN-518の水への溶解性の検討方法と同様にして検討した値である。
The solubility of Discol N-206 in water is a value examined in the same manner as the method for examining the solubility of Discol N-518 in water.
比較例3
実施例1において、「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、ノニオン系界面活性剤としてエチレンオキシド/プロピレンオキシド共重合体(プルロニックF108 株式会社ADEKA)24gを用い、また脱イオン水使用量を96gにした以外は、実施例1と同様にしてポリアミド分散液を得た。 Comparative Example 3
In Example 1, 24 g of an ethylene oxide / propylene oxide copolymer (Pluronic F108 ADEKA Corporation) was used as a nonionic surfactant instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass). A polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of deionized water used was 96 g.
実施例1において、「ディスコールN-518」120g(固形分濃度:20質量%)の代わりに、ノニオン系界面活性剤としてエチレンオキシド/プロピレンオキシド共重合体(プルロニックF108 株式会社ADEKA)24gを用い、また脱イオン水使用量を96gにした以外は、実施例1と同様にしてポリアミド分散液を得た。 Comparative Example 3
In Example 1, 24 g of an ethylene oxide / propylene oxide copolymer (Pluronic F108 ADEKA Corporation) was used as a nonionic surfactant instead of 120 g of "Discol N-518" (solid content concentration: 20% by mass). A polyamide dispersion was obtained in the same manner as in Example 1 except that the amount of deionized water used was 96 g.
なお、上記の例でポリアルキレンポリアミンアルキレンオキシド付加物として用いた「ディスコールN-518」及び「「ディスコールN-206」は、第一工業製薬株式会社カタログによれば、いずれも下記式(1):
According to the catalog of Dai-ichi Kogyo Seiyaku Co., Ltd., both "Discol N-518" and "Discol N-206" used as the polyalkylene polyamine alkylene oxide adduct in the above example have the following formulas ( 1):
(式中、AOはアルキレンオキシドを示し、nは整数を示す。)で表される繰り返し単位からなるポリアルキレンポリアミンアルキレンオキシド付加物と説明されている。
(In the formula, AO represents an alkylene oxide and n represents an integer.) It is described as a polyalkylene polyamine alkylene oxide adduct consisting of repeating units represented by.
ポリアミド水性分散液の安定性評価
上記のようにして得られた各ポリアミド水性分散液(実施例1~2及び比較例1~3)を、脱イオン水でポリアミド濃度が1(w/w)%となるように希釈し、希釈したポリアミド水性分散液を50ml量りとり、酸成分として、1mol/L硫酸アンモニウム水溶液を徐々に添加し、粒子の凝集が開始する添加量を検討した。粒子の凝集については、回折式粒度分布測定装置(株式会社島津製作所、商品名“SALD-2300”)を用いて粒度分布測定より凝集状態を確認した。 Evaluation of Stability of Aqueous Polyamide Dispersion The aqueous polyamide dispersions (Examples 1 and 2 and Comparative Examples 1 to 3) obtained as described above were mixed with deionized water to have a polyamide concentration of 1 (w / w)%. 50 ml of the diluted polyamide aqueous dispersion was weighed out, and a 1 mol / L ammonium sulfate aqueous solution was gradually added as an acid component, and the amount of addition at which particle aggregation started was examined. Regarding the agglutination of particles, the agglutination state was confirmed by particle size distribution measurement using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name “SALD-2300”).
上記のようにして得られた各ポリアミド水性分散液(実施例1~2及び比較例1~3)を、脱イオン水でポリアミド濃度が1(w/w)%となるように希釈し、希釈したポリアミド水性分散液を50ml量りとり、酸成分として、1mol/L硫酸アンモニウム水溶液を徐々に添加し、粒子の凝集が開始する添加量を検討した。粒子の凝集については、回折式粒度分布測定装置(株式会社島津製作所、商品名“SALD-2300”)を用いて粒度分布測定より凝集状態を確認した。 Evaluation of Stability of Aqueous Polyamide Dispersion The aqueous polyamide dispersions (Examples 1 and 2 and Comparative Examples 1 to 3) obtained as described above were mixed with deionized water to have a polyamide concentration of 1 (w / w)%. 50 ml of the diluted polyamide aqueous dispersion was weighed out, and a 1 mol / L ammonium sulfate aqueous solution was gradually added as an acid component, and the amount of addition at which particle aggregation started was examined. Regarding the agglutination of particles, the agglutination state was confirmed by particle size distribution measurement using a diffraction type particle size distribution measuring device (Shimadzu Corporation, trade name “SALD-2300”).
ポリアミド分散液のpHが6.4まで低下しても、凝集物(2μm以上の粒子)の生成がないものを○、6.4までに凝集物が生成するものを×と評価した。
Even if the pH of the polyamide dispersion was lowered to 6.4, those in which no agglomerates (particles of 2 μm or more) were not formed were evaluated as ◯, and those in which agglomerates were formed by 6.4 were evaluated as ×.
ポリアミド分散液に酸性成分である硫酸アンモニウムを添加してpHを小さくしていくと、比較例1ではpHが7.2で凝集物が生成し、比較例2ではpHが7.2で凝集物が生成し、比較例3ではpHが6.7で凝集物が生成するのに対し、実施例1ではpH6.2まで分散状態を維持でき、すなわち、pHが6.4においても、分散状態を維持でき、2μm以上の粒子の含有率が0体積%であり、実施例2ではpH6.4まで分散状態を維持でき、2μm以上の粒子の含有率が0体積%となることが分かった。
When ammonium sulfate, which is an acidic component, is added to the polyamide dispersion to reduce the pH, agglomerates are formed at a pH of 7.2 in Comparative Example 1 and agglomerates are formed at a pH of 7.2 in Comparative Example 2. In Comparative Example 3, agglomerates were formed at a pH of 6.7, whereas in Example 1, the dispersed state could be maintained up to pH 6.2, that is, the dispersed state was maintained even at a pH of 6.4. It was found that the content of particles of 2 μm or more was 0% by volume, and in Example 2, the dispersed state could be maintained up to pH 6.4, and the content of particles of 2 μm or more was 0% by volume.
また、比較例1では、ポリアミド分散液に酸性成分である硫酸アンモニウムを3mmol添加すると凝集物が生成し、比較例2では、ポリアミド分散液に酸性成分である硫酸アンモニウムを3mmol添加すると凝集物が生成し、比較例3では、ポリアミド分散液に酸性成分である硫酸アンモニウムを9mmol添加するとpHが6.7で凝集物が生成するのに対し、実施例1では、ポリアミド分散液に酸性成分である硫酸アンモニウムを50mmolまで添加しても分散状態を維持でき、実施例2では、ポリアミド分散液に酸性成分である硫酸アンモニウムを30mmolまで添加しても分散状態を維持できることが分かる。
Further, in Comparative Example 1, when 3 mmol of ammonium sulfate, which is an acidic component, was added to the polyamide dispersion, aggregates were formed, and in Comparative Example 2, when 3 mmol of ammonium sulfate, which was an acidic component, was added to the polyamide dispersion, aggregates were formed. In Comparative Example 3, when 9 mmol of ammonium sulfate, which is an acidic component, was added to the polyamide dispersion, aggregates were formed at a pH of 6.7, whereas in Example 1, ammonium sulfate, which is an acidic component, was added to the polyamide dispersion up to 50 mmol. It can be seen that the dispersed state can be maintained even if it is added, and in Example 2, the dispersed state can be maintained even if ammonium sulfate, which is an acidic component, is added to the polyamide dispersion liquid up to 30 mmol.
なお、表1の「2μm以上の粒子の含有量(%)」は、分散液に含まれる全ポリアミド量に対する体積%を表している。
The "content (%) of particles of 2 μm or more" in Table 1 represents the volume% with respect to the total amount of polyamide contained in the dispersion liquid.
以上の結果から、ポリアルキレンポリアミンアルキレンオキシド付加物を含むポリアミド水性分散体は、pHが低い領域(pH7程度又はそれよりも低い領域)でも分散状態を維持できることがわかった。
From the above results, it was found that the aqueous polyamide dispersion containing the polyalkylene polyamine alkylene oxide adduct can maintain the dispersed state even in a low pH region (a region having a pH of about 7 or lower).
Claims (9)
- 水性媒体と、前記水性媒体中に分散したポリアミドと、融点が25℃以上であるポリアルキレンポリアミンアルキレンオキシド付加物とを含む、ポリアミド水性分散液。 A polyamide aqueous dispersion containing an aqueous medium, a polyamide dispersed in the aqueous medium, and a polyalkylene polyamine alkylene oxide adduct having a melting point of 25 ° C. or higher.
- ポリアミドが、6-ナイロン、66-ナイロン、610-ナイロン、11-ナイロン、12-ナイロン、6/66共重合ナイロン、6/610共重合ナイロン、6/11共重合ナイロン、6/12共重合ナイロン、6/66/11共重合ナイロン、6/66/12共重合ナイロン、6/66/11/12共重合ナイロン、6/66/610/11/12共重合ナイロン、ダイマー酸系ポリアミド、ナイロン系エラストマーからなる群より選ばれる少なくとも1種である請求項1に記載のポリアミド水性分散液。 Polyamides are 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, 6/66 copolymerized nylon, 6/610 copolymerized nylon, 6/11 copolymerized nylon, 6/12 copolymerized nylon. , 6/66/11 copolymerized nylon, 6/66/12 copolymerized nylon, 6/66/11/12 copolymerized nylon, 6/66/610/11/12 copolymerized nylon, dimer acid-based polyamide, nylon-based The aqueous polyamide dispersion according to claim 1, which is at least one selected from the group consisting of elastomers.
- ポリアルキレンポリアミンアルキレンオキシド付加物が、数平均分子量が5000~25000で、25℃における水への溶解性が25質量%以上のポリアルキレンポリアミンアルキレンオキシド付加物である、請求項1又は2に記載のポリアミド水性分散液。 The polyalkylene polyamine alkylene oxide adduct according to claim 1 or 2, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a number average molecular weight of 5000 to 25000 and a solubility in water at 25 ° C. of 25% by mass or more. Polyamide aqueous dispersion.
- ポリアミド100質量部に対して、ポリアルキレンポリアミンアルキレンオキシド付加物が1~20質量部含まれる、請求項1~3のいずれかに記載のポリアミド水性分散液。 The aqueous polyamide dispersion according to any one of claims 1 to 3, wherein 1 to 20 parts by mass of a polyalkylene polyamine alkylene oxide adduct is contained with respect to 100 parts by mass of the polyamide.
- ポリアルキレンポリアミンアルキレンオキシド付加物が、ポリエチレンイミンにアルキレンオキシドを付加重合した構造を有するポリアルキレンポリアミンアルキレンオキシド付加物である、請求項1~4のいずれかに記載のポリアミド水性分散液。 The aqueous polyamide dispersion according to any one of claims 1 to 4, wherein the polyalkylene polyamine alkylene oxide adduct is a polyalkylene polyamine alkylene oxide adduct having a structure in which alkylene oxide is addition-polymerized to polyethyleneimine.
- ポリアミドの平均粒子径が、1.0μm以下である、請求項1~5のいずれかに記載のポリアミド水性分散液。 The aqueous polyamide dispersion according to any one of claims 1 to 5, wherein the average particle size of the polyamide is 1.0 μm or less.
- pHを6.5まで低下させたときに、粒子径が2μm以上のポリアミド量が全ポリアミド量の15体積%以下である、請求項1~6のいずれかに記載のポリアミド水性分散液。 The aqueous polyamide dispersion according to any one of claims 1 to 6, wherein the amount of polyamide having a particle size of 2 μm or more is 15% by volume or less of the total amount of polyamide when the pH is lowered to 6.5.
- 請求項1~7のいずれかに記載のポリアミド水性分散液を含む塗工剤。 A coating agent containing the polyamide aqueous dispersion according to any one of claims 1 to 7.
- 請求項8に記載の塗工剤を用いて加工された成型体。 A molded body processed by using the coating agent according to claim 8.
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JPH02144141A (en) * | 1988-11-24 | 1990-06-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for stabilizing dispersion of fine powder in aqueous system and dispersion liquid |
JP2012233082A (en) * | 2011-04-28 | 2012-11-29 | Unitika Ltd | Aqueous dispersion, and method for producing the same |
JP2017114942A (en) * | 2015-12-21 | 2017-06-29 | 住友精化株式会社 | Polyamide aqueous dispersion |
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JPH02144141A (en) * | 1988-11-24 | 1990-06-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for stabilizing dispersion of fine powder in aqueous system and dispersion liquid |
JP2012233082A (en) * | 2011-04-28 | 2012-11-29 | Unitika Ltd | Aqueous dispersion, and method for producing the same |
JP2017114942A (en) * | 2015-12-21 | 2017-06-29 | 住友精化株式会社 | Polyamide aqueous dispersion |
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