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    • 专利摘要:
    Provided are a process for producing heat-expandable microspheres which enables constant and high-yield production of heat- expandable microspheres having a mean particle size ranging from 0.01 to 10 pm without deteriorating their expansion performance, and the application thereof.The process produces heat-expandable microspheres comprising a thermoplastic resin shell and the blowing agent encapsulated therein. The process includes the step of dispersing a polymerizable component and the blowing agent in an aqueous dispersion medium containing a polyester amide having an acid value (mgKOH/g) ranging from 95 to 140 and the step of polymerizing the polymerizable component, and produces the heat-expandable microspheres having a mean particle size ranging from 0.01 to 10 μm.
    公开号:SE1751658A1
    申请号:SE1751658
    申请日:2016-06-21
    公开日:2017-12-27
    发明作者:Hyogo Norimichi；Miki Katsushi；Sakabe Koichi
    申请人:Matsumoto Yushi Seiyaku Kk；
    IPC主号:
    专利说明:

    [3] [0003] In the above-mentioned production process for heat-expandable microspheres,constant and high yield of the intended heat-expandable microspheres is one of theimportant subjects. In the production process of small-sized heat-expandable microsphereshaving a mean particle size ranging from 0.01 to 10 um, the coalescence of oil globules andagglomeration of particles being polymerized are sometimes found and such troubles lead toscum generation in the suspension so as to inhibit constant and high-yield production ofheat-expandable microspheres. In this case, high amount of a polymeric dispersionstabilizer added to the aqueous dispersion medium is a Well-known solution for the problemto achieve constant and high-yield production of heat-expandable microspheres.
    [4] [0004] Although the solution is effective to achieve constant and high-yield production of heat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pm, the high amount of the polymeric dispersion stabilizer causes the plasticization of the 820PCT 2 WO2017002659 thermoplastic resin constituting the shell of the resultant heat-expandable microspheresand deteriorates the expansion performance of the heat-expandable microspheres.[Citation listl [Patent Literature]
    [5] [0005] [PTL 1l Japanese Patent Examination Publication 1967-26524 [Summary of Inventionl [Technical Probleml
    [6] [0006] The present invention aims to provide a process for constantly producingheat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pm withhigh yield without deteriorating their expansion performance, and the application of the[Solution to Probleml[0007] For solving the problem mentioned above, the inventors diligently studied and foundthat the problem can be solved by a process for producing heat-expandable microspheres inwhich the polymerizable component is polymerized in an aqueous dispersion mediumcontaining a polyester amide having a specific acid value, and have achieved the presentinvention.
    [8] [0008] The process of the present invention should preferably satisfy at least one of thefollowing requirements 1) to 6). 1) The polyester amide is obtained from the reaction of a carboxylic acid having at leasttwo carboxyl groups and an amino alcohol having at least one amino group and two hydroxylgroups. 2) The polyester amide has an amine value (mgKOH/g) ranging from 20 to 60. 3) The amount of the polyester amide in the aqueous dispersion medium ranges from0.0001 to 5 parts by weight to 100 parts by weight of the total of the polymerizable component and blowing agent. 820PCT 3 WO2017002659 4) The carboxylic acid having at least two carboxylic groups is adipic acid, and theamino alcohol having at least one amino group and two hydroxyl groups is diethanolamine.
    [17] [0017]The polymerizable component essentially containing a nitrile monomer as the monomer component is preferable for producing heat-expandable microspheres of high 820PCT 6 WO2017002659 expansion performance. Of those nitrile monomers, acrylonitrile (AN) andmethacrylonitrile (MAN) are preferable for their availability and high expansionperformance of the heat-expandable microspheres produced from the polymerizablecomponent containing acrylonitrile (AN) and/or methacrylonitrile (MAN).
    [18] [0018] The amount of the nitrile monomers is not specifically restricted, and shouldpreferably range from 20 to 100 Wt% of the monomer component, more preferably from 30 to100 Wt%, further more preferably from 40 to 100 Wt%, yet further more preferably from 50 to100 Wt%, and most preferably from 60 to 100 Wt%. The monomer component containingless than 20 Wt% of nitrile monomers can cause poor expansion performance of the resultantmicrospheres.
    [19] [0019] The amount of the carboxyl-group-containing monomers is not specifically restricted,and should preferably range from 10 to 70 Wt% of the monomer component, more preferablyfrom 15 to 60 Wt%, further more preferably from 20 to 50 Wt%, yet further more preferablyfrom 25 to 45 Wt%, and most preferably from 30 to 40 Wt%. The amount of thecarboxyl-group-containing monomers less than 10 Wt% can not be effective to achievesufficient heat resistance of the resultant heat-expandable microspheres. On the otherhand, the amount of the carboxyl-group-containing monomers greater than 70 Wt% cancause poor gas impermeability of the resultant microspheres Which deteriorates theirexpansion performance.
    [21] [0021] The amount of the at least one monomer selected from the group consisting ofvinylidene chloride, (meth) acrylate monomers, (meth) acrylamide monomers, maleimidemonomers and styrene monomers should preferably be less than 80 Wt% of the monomercomponent, more preferably less than 50 Wt%, and most preferably less than 30 Wt%. Themonomer component containing 80 Wt% or more of the monomer can cause poor expansionperformance of the resultant microspheres.
    [22] [0022]The cross-linking agent is not specifically restricted, and includes, for example, aromatic divinyl compounds, such as divinylbenzene; and di(meth)acrylate compounds, such 820PCT 8 WO2017002659 as allyl methacrylate, triacrylformal, triallyl isocyanate, ethylene glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate,1,9-nonanediol di(meth)acrylate,1,10-decanediol di(meth)acrylate, PEG (200) di(meth)acrylate, PEG (400) di(meth)acrylate,PEG (600) di(meth)acrylate, PPG (400) di(meth)acrylate, PPG (700) di(meth)acrylate,trimethylolpropane trimethacrylate, EO-modified trimethylolpropane trimethacrylate,glycerin dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritoltri(meth)acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,2-butyl-2-ethyl-1,3-propanediol diacrylate, tris(2-acryloyloxyethyl) isocyanurate, triallylisocyanurate, triallyl cyanurate, triglycidyl isocyanurate, polytetramethyleneglycoldimethacrylate, EO-modified bisphenol A dimethacrylate, neopentylglycol dimethacrylate,nonanediol diacrylate, trimethylol propane tri(meth)acrylate and 3-methyl-1,5 pentanedioldiacrylate. One of or a combination of at least two of those cross-linking agents can beused.
    [23] [0023] The polymerizable component should preferably be polymerized in the presence of apolymerization initiator. The polymerization initiator can be contained in the oily mixturealong With the polymerizable component and bloWing agent.
    [24] [0024] The amount of the polymerization initiator is not specifically restricted, and shouldpreferably range from 0.1 to 8 parts by Weight to 100 parts by Weight of the monomercomponent and more preferably from 0.6 to 7parts by Weight.
    [25] [0025] The aqueous dispersion medium for the polymerization step contains Water, such asdeionized Water, as the main component, and the oily mixture essentially containing thepolymerizable component and bloWing agent is dispersed therein. The aqueous dispersionmedium can further contain alcohols, such as methanol, ethanol and propanol, andhydrophilic organic solvents, such as acetone. The hydrophilic property mentioned in thepresent invention means a property of a substance optionally miscible in Water. Theamount of the aqueous dispersion medium used in the process is not specifically restricted,and should preferably range from 100 to 1000 parts by Weight to 100 parts by Weight of thepolymerizable component.
    [26] [0026] In the polymerization step, the aqueous dispersion medium contains a polyester amidehaving an acid value (mgKOH/g) ranging from 95 to 140 in order to constantly produceheat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pm Withhigh yield Without deteriorating their expansion performance.
    [27] [0027] The amine value of the polyester amide (mgKOH/g) is not specifically restricted andshould preferably range from 20 to 60, more preferably from 22 to 55, further morepreferably from 23 to 50 and most preferably from 24 to 45. The amine value (mgKOH/g) 820PCT 10 WO2017002659 mentioned herein means the number of milligrams of potassium hydroxide required toneutralize the amine in 1 g of a polyester amide, and is determined according to the methoddescribed in Example.
    [28] [0028] The amount of the polyester amide used for the polymerization is not specificallyrestricted, and should preferably range from 0.0001 to 5 parts by Weight to 100 parts byWeight of the total of the polymerizable component and bloWing agent, more preferably from0.0003 to 2.5 parts by Weight, further more preferably from 0.0004 to 1 parts by Weight, yetmore preferably from 0.0005 to 0.5 parts by Weight, and most preferably from 0.0001 to 0.3parts by Weight. The amount of the polyester amide less than 0.0001 parts by Weight candisturb the stability of the oil globules comprising the polymerizable component and bloWingagent in the aqueous dispersion medium and inhibit the constant production ofheat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pm. Onthe other hand, the amount of the polyester amide greater than 5 parts by Weight can causethe plasticization of the thermoplastic resin shell of the resultant heat-expandablemicrospheres to deteriorate their expansion performance.
    [29] [0029] The polyester amide used in the production process of the present invention exhibitsexcellent performance to stabilize the oil globules dispersed in the suspension andsufficiently prevent the coalescence of oil globules or agglomeration of particles in thepolymerization mixture to produce heat-expandable microspheres having a mean particlesize ranging from 0.01 to 10 pm even if a comparatively small amount of the polyester amideis added to the aqueous dispersion medium. Thus the amount of the polyester amide usedas the dispersion stabilizer in the present invention can be decreased from that of theconventional dispersion stabilizers. Consequently the decreased amount of the dispersionstabilizer prevents unnecessary plasticization of the thermoplastic resin constituting theshell of the heat-expandable microspheres, and enables constant and high-yield productionof heat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pmWithout deteriorating their good expansion performance.
    [30] [0030] The production process of the polyester amide having an acid value (mgKOH/g) ranging from 95 to 140 is not specifically restricted, and includes for example, the reaction of a carboxylic acid having at least two carboxyl groups and an amino alcohol having at least SZOPCT 11 WO2017002659 one amino group and two hydroxyl groups. In a preferable embodiment, dicarboxylic acid isused as the carboxylic acid having at least two carboxyl groups and dialkanolamine is usedas the amino alcohol having at least one amino group and two hydroxyl groups.
    [31] [0031] The carboxylic acid having at least two carboxyl groups includes dicarboxylic acids,tricarboxylic acids and polyfunctional carboxylic acids. The dicarboxylic acids are notspecifically restricted, and include oxalic acid, malonic acid, succinic acid, glutaric acid,adipic acid, piperic acid, suberic acid, azelaic acid, sebacic acid, undecane-onco-dicarboxylicacid, dodecane-onco-dicarboxylic acid, cis-cyclohexane-1,2-dicarboxylic acid,trans-cyclohexane-1,2-dicarboXylic acid, cis-cyclohexane-1,3-dicarboxylic acid,trans-cyclohexane-1,3-dicarboXylic acid, cis-cyclohexane-1,4-dicarboxylic acid,trans-cyclohexane-1,4-dicarboXylic acid, cis-cyclopentane-1,2-dicarboxylic acid,trans-cyclopentane-1,2-dicarboXylic acid, cis-cyclopentane-1,3-dicarboxylic acid,trans-cyclopentane-1,3-dicarboxylic acid, 2-methyl malonic acid, 2-ethyl malonic acid,2-phenyl malonic acid, 2-methyl succinic acid, 2-ethyl succinic acid, 2-phenyl succinic acid,itaconic acid, 3,3-dimethyl glutaric acid, maleic acid, fumaric acid, phthalic acid, isophthalicacid and terephthalic acid. The tricarboxylic acids and polyfunctional carboxylic acids arenot specifically restricted, and include trimesic acid, trimellitic acid, butanetricarboxylicacid, naphthalenetricarboxylic acid, and cyclohexane-1,3,5-tricarboxylic acid. One of or acombination of at least two of those carboxylic acid can be employed. Of those carboxylicacids having at least two carboxyl groups, adipic acid, itaconic acid, succinic acid, glutaricacid, phthalic acid, isophthalic acid and terephthalic acid are preferable, and adipic acid ismore preferable.
    [32] [0032] The amino alcohol (alkanolamine) having at least one amino group and two hydroxylgroups includes dialkanolamine and trialkanolamine. The dialkanolamine is notspecifically restricted and includes, for example, diethanolamine, diisopropanolamine,2-amino-1,3-propanediol, 3-amino-1,2-propanediol, diisobutanolamine,bis(2-hydroxy-1-butyl)amine, bis(2-hydroxy-1-propyl)amine, and dicyclohexanolamine.
    [33] [0033] The temperature for carrying out the reaction of the carboxylic acid and amino alcoholis not specifically restricted, and ranges, for example, from 80 to 250 °C, preferably from 90to 200 °C and more preferably from 95 to 180 °C. If a catalyst is used for the reaction, thereaction temperature is adjusted for the catalyst preferably Within the range from 90 to200 °C, more preferably from 100 to 190 °C, and further more preferably from 110 to 180 °C.[0034] The reaction of the carboxylic acid and amino alcohol should preferably be carried outbeing purged With an inert gas, such as nitrogen, or under Vacuum. A catalyst or solVentcan be optionally added. The reaction Water generated during the polymerization(polycondensation) can be removed by, for example, reducing pressure, bubbling With aninert gas, or azeotropic distillation With a proper solVent, such as toluene. The pressureapplied to the reaction is not specifically restricted and usually ranges from 0 to 10 lVIPa.The reaction time is not specifically restricted and the reaction is usually carried out for aperiod ranging from 5 minutes to 48 hours, preferably from 30 minutes to 24 hours and morepreferably from 1 to 10 hours.
    [35] [0035] The reaction of the carboxylic acid and amino alcohol should preferably be ceased by,for example, cooling, before the gelling of the resultant polymer adVances. The gellingpoint can be identified by the sudden increase of the Viscosity of the reaction mixture.[0036] In addition to the polyester amide mentioned above, the aqueous dispersion mediumcan contain, at least one dispersion stabilizer selected from the group consisting ofparticulate metal compounds, anionic surfactants, nonionic surfactants, cationic surfactants,amphoteric surfactants and polymeric dispersion stabilizers except the polyester amide.[0037] The particulate metal compound is not specifically restricted, and includes, forexample, calcium triphosphate, magnesium pyrophosphate and calcium pyrophosphate produced by double reaction, colloidal silica, alumina sol, zirconia sol, titania sol, and 820PCT 13 WO2017002659 magnesium hydroxide. One of or a combination of at least two of those dispersionstabilizers can be used. The aqueous dispersion medium should preferably contain aparticulate metal compound having a mean particle size ranging from 1.0 to 20 nm inaddition to the polyester amide mentioned above in order to achieve more constant andhigh-yield production of heat-expandable microspheres having a mean particle size rangingfrom 0.01 to 10 pm. Of those particulate metal compounds, colloidal silica is morepreferable. Colloidal silica is commercially available in a form of dispersion, in other Words,a colloidal silica dispersion, and any variants having desirable mean particle sizes of silicaand desirable properties including specific surface area are easily available among variousgrades of products, such as “Quartron” produced by Fuso Chemical Co., Ltd., “ADELITE”produced by Adeka Corporation, “SILICADOL” produced by Nippon Chemical Industrial Co.,Ltd., “SNOWTEX” produced by Nissan Chemical Industries, Ltd., “Ludox” produced byDuPont, etc.
    [39] [0039] The aqueous dispersion medium should preferably contain a particulate metal compound having a mean particle size ranging from 3.8 to 6.0 nm in addition to the polyester amide having an acid value (mgKOH/g) ranging from 95 to 140, because such 820PCT 14 WO2017002659 compound is effective to achieve constant and high-yield production of heat-expandablemicrospheres having a mean particle size ranging from 0.01 to 10 pm Without deterioratingtheir expansion performance.
    [40] [0040] The specific surface area of the particulate metal compound is not specificallyrestricted, and preferably ranges from 270 to 2720 m2/g, more preferably from 280 to 2500m2/ g, yet more preferably from 290 to 2200 m2/ g, still more preferably from 295 to 1800 m2/ g,further more preferably from 300 to 1360m2/ g, yet further more preferably from 320 to 1200m2/ g, still further more preferably from 340 to 900 m2/ g, still further more preferably from390 to 800 m2/g and most preferably from 450 to 7 00m2/g. The particulate metal compoundhaving a specific surface area ranging from 270 to 2720 m2/g contributes to more constantand high-yield production of heat-expandable microspheres having a mean particle sizeranging from 0.01 to 10 pm.
    [41] [0041] The amount of the particulate metal compound used in the polymerization step is notspecifically restricted and should preferably range from 0.15 to 20 parts by Weight to 100parts by Weight of the total amount of the polymerizable component and bloWing agent,more preferably from 0.20 to 18 parts by Weight, yet more preferably from 0.25 to 16 partsby Weight, still more preferably from 0.35 to 14 parts by Weight, further more preferablyfrom 0.40 to 12 parts by Weight, yet further more preferably from 0.50 to 11.5 parts byWeight, and most preferably from 0.55 to 11.3 parts by Weight. The amount of theparticulate metal compound Within the range of 0.15 to 20 parts by Weight to 100 parts byWeight of the total amount of the polymerizable component and bloWing agent contributes tomore constant and high-yield production of heat-expandable microspheres having a meanparticle size ranging from 0.01 to 10 pm.
    [42] [0042]The anionic surfactants are not specifically restricted and include, for example, fatty acid salts, such as potassium palmitate and triethanolamine oleate; alkyl sulfate salts, such SZOPCT 15 WO2017002659 as sodium lauryl sulfate and ammonium lauryl sulfate; alkyl benzene sulfonate salts, suchas sodium dodecyl benzene sulfonate; polyoxyalkylene alkyl ether sulfate salts; alkylphosphate salts, such as sodium monostearyl phosphate; polyoxyalkylene alkyletherphosphate salts, such as sodium polyoxyethylene oleyl ether phosphate; long-chainsulfosuccinate salts, such as sodium dioctyl sulfosuccinate; and polycarboxylate salts, suchas sodium polyacrylate.
    [43] [0043] The nonionic surfactants are not specifically restricted, and include, for example,polyoxyethylene alkyl ethers, such as polyoxyethylene cetyl ether and polyoxyethylenelauryl ether; polyoxyalkylene alkylphenyl ethers, such as polyoxyethylene nonylphenylether and polyoxyethylene octylphenyl ether; polyoxyalkylene fatty acid esters, such aspolyoxyethylene monolaurate and polyoxyethylene monooleateš sorbitan fatty acid esters,such as sorbitan monopalmitate and sorbitan monoleate; polyoxyalkylene sorbitan fatty acidesters, such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitanmonoleate; glycerin fatty acid esters, such as glycerin monostearate, glycerin monopalmitateand glycerin monolaurate; polyglycerin fatty acid esters; polyoxyalkylene alkylamines; andoxyethylene-oxypropylene block polymers.
    [44] [0044] The amphoteric surfactants are not specifically restricted, and include, for example,imidazoline-based amphoteric surfactants, such as Z-undecyl-N,N-(hydroxyethylcarboxymethyl)-Z-imidazoline sodium salt; betaine-based amphoteric surfactants, such as2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine, lauryl dimethyl aminoacetic acid betaine, alkyl betaine, amidobetaine and sulfobetaine; and amino acid-basedamphoteric surfactants, such as N-lauryl glycine, N-lauryl ß-alanine and N-stearylß-alanine.
    [45] [0045]The amount of the dispersion stabilizers used in the polymerization step other than the polyester amide and particulate metal compounds should preferably range from 0.1 to 20 820PCT 16 WO2017002659 parts by Weight to 100 parts by Weight of the total of the polymerizable component andblowing agent, and more preferably from 0.2 to 10 parts by Weight.[0046] The aqueous dispersion medium can further contain an electrolyte, such as sodiumchloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate,ammonium sulfate, and sodium hydroxide. One of or a combination of at least two of theseelectrolyte can be used.
    [47] [0047] The aqueous dispersion medium can contain at least one Water-soluble compoundselected from the group consisting of polyalkylene imines having at least 1000 l/I.W. andhaving at least one bond of nitrogen atom and alkyl group substituted With a hydrophilicfunctional group selected from the group consisting of carboxylic acid (salt) groups andphosphonic acid (salt) groups, potassium dichromate, zirconium sulfate, zirconium acetate,zirconium chloride, zirconium oxide, zirconium nitrate, titanium chloride, alkali metalnitrite salts, metal (III) halides, boric acid, Water-soluble ascorbic acids, Water-solublepolyphenols, Water-soluble vitamin Bs, Water-soluble phosphonic acids and phosphonatesalts, and Water-soluble 1,1-substitution compounds having a carbon atom bonded With ahetero atom and With a hydrophilic functional group selected from the group consisting ofhydroxyl group, carboxylic acid (salt) groups and phosphonic acid (salt) groups. The term“Water-soluble” in the present invention means that at least 1 g a substance is soluble in 100g of Water.
    [48] [0048] The aqueous dispersion medium is prepared, for example, by blending the dispersionstabilizer and optionally an electrolyte and/or Water-soluble compound With Water(deionized Water).
    [49] [0049] The polymerization of the process of the present invention can be carried out in thepresence of sodium hydroxide or a combination of sodium hydroxide and zinc chloride.
    [50] [0050] In the polymerization step, the oily mixture comprising a polymerizable componentand bloWing agent is dispersed and suspended in the aqueous dispersion medium to beformed into oil globules of a prescribed particle size. The process of the present inventionproduces heat-expandable microspheres having a mean particle size ranging from 0.01 to 10pm, and the oil globules of the oily mixture should preferably be dispersed and suspendedinto globules having a particle size ranging from 0.01 to 10 pm in the polymerization step.
    [51] [0051] Then suspension polymerization is started by heating the dispersion in Which the oilymixture is dispersed into oil globules in the aqueous dispersion medium. During thepolymerization reaction, the dispersion should preferably be agitated gently to prevent thefloating of monomers and sedimentation of polymerized heat-expandable microspheres.
    [52] [0052] The aqueous dispersion medium containing heat-expandable microspheres after thepolymerization step (hereinafter sometimes referred to as the polymerization liquid)sometimes contains, in addition to the intended heat-expandable microspheres, byproducts(scum) such as coarse microspheres formed from the coalescence of oil globules,agglomeration of microspheres and residue from polymerization generated secondarily inthe aqueous dispersion medium, and the byproducts cause decrease in the yield of theheat-expandable microspheres. Such byproducts are usually larger than the particle sizesof the heat-expandable microspheres and do not pass a sieve of a certain mesh size. Thusthe ratio of heat-expandable microspheres passing a sieve of a certain mesh size indicatesconstant and high-yield production of heat-expandable microspheres and is useful foreValuating the production stability of heat-expandable microspheres. The productionstability of heat-expandable microspheres should preferably be at least 87 Wt%, morepreferably at least 88 Wt%, further more preferably at least 90 Wt%, yet further morepreferably at least 91 Wt%, and most preferably at least 92 Wt%. The production stabilityof heat-expandable microspheres less than 87 Wt% indicates that the process has failed toproduce the heat-expandable microspheres constantly With high yield. The definition ofthe production stability of heat-expandable microspheres Will be described in detail inExamples.
    [53] [0053] The aqueous dispersion medium containing heat-expandable microspheres after thepolymerization step (hereinafter sometimes referred to as the polymerization liquid) isseparated to isolate the heat-expandable microspheres from the aqueous dispersion medium by several isolation methods, for example, suction filtration, pressure filtration or 820PCT 19 WO2017002659 centrifugal separation, and consequently a Wet cake of the heat-expandable microspheres isobtained.
    [54] [0054] Heat- expandable microspheres Then the heat-eXpandable microspheres of the present invention Will be explainedbelow. The heat-expandable microspheres, as shown in Fig. 1, have a core-shell structurecomprising the thermoplastic resin shell 11 and the core of a bloWing agent 12 encapsulatedtherein and vaporizable by heating, and the heat-expandable microspheres have thermalexpansion performance as a Whole (in other Words, Whole of a heat-expandable microsphereexpands by heating). The thermoplastic resin, the polymerizable component to bepolymerized into the thermoplastic resin, the monomer component constituting thepolymerizable component, and the bloWing agents are as those mentioned above.
    [55] [0055] The coefficient of variation, CV, of the particle size distribution of the heat-expandable microspheres is not specifically restricted, and should preferably be not greater than 35 %, more preferably not greater than 30 %, and most preferably not greater than 25 %. The CV 820PCT 20 WO2017002659 can be calculated by the following formulae (1) and (2).
    [56] [0056][Formulae 1l CV = (s / ) >< 100 (O/o) (1) s = (xi - )2 / ( n - Dll/Z (2)[0057] (Where s is a standard deviation of the particle size of the microspheres, is a meanparticle size of the microspheres, “xi” is the particle size of the i-th particle, and n representsthe number of particles) The true specific gravity of the heat-expandable microspheres at their maximumexpansion preferably ranges from 0.01 to 0.30, more preferably from 0.02 to 0.29, yet morepreferably from 0.03 to 0.25, further more preferably from 0.04 to 0.20, still further morepreferably from 0.05 to 0.15 and most preferably from 0.07 to 0.13. The heat-expandablemicrospheres having a mean particle size ranging from 0.01 to 10 pm produced in theprocess of the present invention have sufficient expansion performance, and thus exhibitsatisfactory true specific gravity at their maximum expansion as indicated by those ranges.[0058] The encapsulation ratio of the bloWing agent is defined as the percentage of thebloWing agent encapsulated in heat-expandable microspheres to the Weight of theheat-expandable microspheres. The encapsulation ratio of the bloWing agent is notspecifically restricted, and is optionally settled depending on the application of the resultantheat-expandable microspheres. The encapsulation ratio should preferably range from 1 to35 Wt%, more preferably from 2 to 30 %, and most preferably from 3 to 25 %. Anencapsulation ratio of the bloWing agent less than 1 % can lead to insufficient effect by thebloWing agent. On the other hand, an encapsulation ratio of the bloWing agent higher than35 % can excessively thin the shell of heat-expandable microspheres to make the bloWingagent escape through the shell and decrease the heat resistance and expansion performanceof the microspheres.
    [59] [0059] The expansion-initiation temperature (Ts) of the heat-expandable microspheres is notspecifically restricted, and should preferably range from 60 to 250 °C, more preferably from70 to 230 °C, further more preferably from 80 to 200 °C, yet further more preferably from 90to 180 °C, and most preferably from 100 to 160 °C. Heat-expandable microspheres having an expansion-initiation temperature lower than 60 °C can have poor storage stability and 820PCT 21 WO2017002659 can not be suitable for blending With compositions, such as paints and resins.
    [60] [0060] The amount of ash contained in the heat-expandable microspheres should preferablybe not higher than 10 Wt%, more preferably not higher than 8 wt%, yet more preferably nothigher than 5 Wt%, still more preferably not higher than 4 Wt%, further more preferably nothigher than 3 wt%, and most preferably not higher than 2.5 wt%. The heat-expandablemicrospheres containing ash in an amount higher than 10 wt% can inhibit the reduction ofthe weight of the compositions or formed products blended with the heat-expandablemicrospheres or the hollow particles mentioned below and adversely affect the physicalproperties of those compositions and products. The ash contained in heat-expandablemicrospheres is estimated to be mainly derived from the metal components in the dispersionstabilizer, and the desirable lower limit of the ash in heat-expandable microspheres is 0wt%.
    [61] [0061] Hollow particles The hollow particles of the present invention are manufactured by thermallyexpanding the heat-expandable microspheres having a mean particle size ranging from 0.01to 10 pm produced in the process mentioned above.
    [63] [0063] The amount of the ash contained in the hollow particles should preferably be nothigher than 10 wt%, more preferably not higher than 8 wt%, yet more preferably not higherthan 5 wt%, still more preferably not higher than 4 wt%, further more preferably not higherthan 3 wt%, and most preferably not higher than 2.5 wt%. The hollow particles containingash in an amount higher than 10 wt% can inhibit the reduction of the weight of thecompositions or formed products blended with the hollow particles, and can adversely affectthe physical properties of the compositions and products. The ash contained in the hollowparticles is estimated to be mainly deriVed from the metal components in the dispersionstabilizer, and the desirable lower limit of the ash in the hollow particles is 0 wt%.
    [64] [0064] The true specific graVity of the hollow particles is not specifically restricted, and shouldpreferably range from 0.01 to 0.5, more preferably from 0.02 to 0.40, yet more preferablyfrom 0.03 to 0.35, further more preferably from 0.04 to 0.30 and most preferably from 0.05 to0.20.
    [66] [0066]The hollow particles (1) can contain fine particle (4 and 5) coating the outer surface of their shell (2) as shown in Fig. 2, and such hollow particles are hereinafter sometimes 820PCT 23 WO2017002659 referred to as fine-particle-coated hollow particles (1).
    [66] [0066] The fine particle can be selected from various materials including both inorganic andorganic materials. The shape of the fine particle includes spherical, needle-like andplate-like shapes.
    [67] [0067] The fine-particle-coated hollow particles can be produced by thermally expandingfine-particle-coated heat-expandable microspheres. The preferable process formanufacturing the fine-particle-coated holloW particles includes the steps of blendingheat-expandable microspheres and a fine particle (blending step), and heating the mixtureprepared in the blending step at a temperature higher than the softening point of thethermoplastic resin constituting the shell of the heat-expandable microspheres to expandthe heat-expandable microspheres and simultaneously coat the outer surface of the shell ofthe resultant holloW particles With the fine particle (coating step).
    [68] [0068] The true specific gravity of the fine-particle-coated holloW particles is not specificallyrestricted, and should preferably range from 0.01 to 0.7, more preferably from 0.02 to 0.5,further more preferably from 0.05 to 0.3, and most preferable from 0.07 to 0.2. Theparticulate-coated hollow particles having a true specific gravity less than 0.01 can havepoor durability. On the other hand, the particulate-coated holloW particles having a truespecific gravity greater than 0.7 can be poorly effective for decreasing the specific gravity ofcompositions, because greater amount of the fine-particle-coated holloW particles is requiredfor blending With the compositions leading to poor cost performance.
    [69] [0069] Compositions and formed products The composition of the present invention contains a base component and at least oneparticulate material selected from the group consisting of the heat-expandable microspheresmentioned above, the heat-expandable microspheres producted in the process for producingheat-expandable microspheres mentioned above and the holloW particles mentioned above,and a base component. Thus the composition of the present invention has good materialproperties.
    [71] [0071] The composition of the present invention is prepared by mixing these particulatematerials and the base components.
    [72] [0072] The formed product of the present invention can be produced by forming thecomposition. The formed product of the present invention includes, for example, moldedproducts and coating films. The formed product of the present invention has improvedproperties including lightweight effect, porosity, sound absorbing performance, thermalinsulation, design potential, shock absorbing performance and strength, and low thermalconductivity and dielectric property.
    [74] [0074] Acid value and amine value of polyester amide The acid value Was determined according to JIS K2501.
    [78] [0078] True specific gravity of hollow particles The true specific gravity of the hollow particles was determined by the liquidsubstitution method (Archimedean method) with isopropyl alcohol in an atmosphere at 25°C and 50 %RH (relative humidity) as described below.
    [79] [0079] Determination of true specific gravity of microspheres at maximum expansion A 12 cm long, 13 cm wide, and 9 cm high box having a flat bottom was made ofaluminum foil, and 1.0 g of heat-expandable microspheres was filled into uniform thickness.Then the heating of the microspheres was started at the expansion initiation temperatureobtained by the measuring method mentioned above. The heating temperature wasrepeatedly raised by 5 °C and maintained for 1 minute to heat the microspheres, and at eachstep of temperature raising the true specific gravity of the expanded microspheres (hollowparticles) was determined in the same manner as in the determination method of truespecific gravity mentioned above. The lowest true specific gravity of the results wasdefined as the true specific gravity of the microspheres at their maximum expansion.
    [80] [0080] Specific surface area of colloidal silica The specific surface area of colloidal silica was measured by the Sears methoddescribed below. 1) Weigh W (g) of colloidal silica containing 1.5 g of silicon dioxide (SiOz) in a beaker. 820PCT 28 WO2017002659 After conditioning the beaker containing the silicon dioxide at 25 °C in a thermostaticChamber, add pure water to 90 mL. Then carry out the following operations in athermostatic Chamber at 25 °C. 2) Add 0.1-N hydrogen chloride solution to the sample to adjust the pH of the sample3.6. 3) Add 30 g of sodium chloride (reagent grade) to the sample, then add water to 150 mL,and agitate for 10 min. 4) Place a pH electrode in the sample, and adjust the pH of the sample at 4.0 bydropping 0.1-N sodium hydroxide aqueous solution into the sample with agitation.
    [81] [0081] ) After adjusting the pH at 4.0, titrate the sample with 0.1-N sodium hydroxideaqueous solution. Record the titer and pH at least 4 times within the pH range from 8.7 to9.3, and prepare the calibration curVe based on the titer of the 0.1-N sodium hydroxideaqueous solution, X, and the pH by the titer, Y. 6) Calculate the corrected amount, V (mL), of 0.1-N sodium hydroxide aqueous solutionrequired to change the pH of the sample containing 1.5 g of silicon dioxide from 4.0 to 9.0 bythe following formula (4), and calculate the specific surface area, SA (mZ/g), by the following formula (5).
    [82] [0082]V=<100><1.5>/ <4)sA=290V _ 28 <5) The symbols in the formulae (4) and (5) mean as follows.
    [85] [0085] Examples 2 to 8 and Comparative examples 1 to 5 Heat-expandable microspheres were produced in the same manner as that of Example1 except that the components of the aqueous dispersion medium and oily mixture werereplaced with those shown in Table 1. The properties of the resultant heat-expandablemicrospheres of each of the Examples and Comparative examples are shown in Table 1.
    [86] [0086]Table 1 Examples Comparative examples 1 2 3 4 5 6 7 8 1 2 3 4 5 Aqueous Deionized water (g) 600 680 700 740 650 400 600 650 400 400 400 600 680 dispersion Sodium chloride (g) 150 150 medlum Qdbídïflllsílíca 200 120 100 200 200 400 400 400 200dispersion A(g) Colloídal sílica dispersion B(g) ZOO Colloídal sílica dispersion C(g) 120 Colloídal sílica dispersion E(g) 40 Colloídal sílicadispersion G(g) ZOO Poiyesteramidefug) 1.0 1.0 f 0.5 1.5 Po1yesteramideB(g) 1.5 1.0 0.5 3.0Poiyesferamide C(g) 1.5 8.0 0.5 0.5 Po1yesteramideD(g) 1.5 2.5 3.0 Po1yesteramideE(g) 1.5 2.5 3.0 CMPEHg) 0.10 0.10 0.10 A1013-6H2o(g) 0.15 ššštassium dichromate 0-15 pH 3.0 2.0 3.0 2.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 4.0 Monomer AN (g) 180 180 150 135 180 180 180 90 180 180 180 180 323 820PCT 30 WO2017002659MAN (g) 105 105 130 105 105 150 90 105 105 105 105lVIlVIA(g) 15 15 30 15 15 70 15 15 15 15IBX(g) 20 Vcmg) 135 139MAA (g) 120 Cross-linking Cross-linkingagentA Lö Lö 0-5 1,5 1.5 1,5 1.5agent (g)ëišoss-linking agentB 1.0 0-5Blowing agent Isobutane (g) 30 30 70 30 40 30 Neopentane(g) 139Isopentane (g) 30 30 50 30 40 40 25 50 50 50 30 Isooctane(g) 20 25 Polymeriza-tion initiatorInitiatorA(g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0Initiawr B (g) 3.0 2.0Heat' Meanpartíclesíze 0.9 1.5 2.0 3.9 5.2 1.9 2.5 6.1 1.7 1.5 10.5 11.0expandable (pm)mlclmspheres Expansmllnltlatmn 105 103 113 35 105 112 120 162 105 104 * 103 35temp. Ts(C)Maxlmum exfansmn 126 130 147 110 132 144 150 133 131 123 135 110temp. TmaX ( C)Production Aqueous dispersionstability medium passing the 91 92 92 89 94 90 92 91 80 87 73 66sieveY(Wt%)Expansion True specific gravityperformance atmaXimum 0.28 0.15 0.07 0.05 0.04 0.18 0.05 0.02 0.25 0.56 0.02 0.02expansion * Agglomerated and solidified
    [37] [0037]Table 2 Abbreviation Description Colloidal silicadispersion A -Wt% dispersion of the colloidal silica With the mean particle size of5 nm and specific surface area of 550 mZ/g Colloidal silicadispersion B -Wt% dispersion of the colloidal silica With the mean particle size of11 nm and specific surface area of 260 mZ/g Colloidal silicadispersion C -Wt% dispersion of the colloidal silica With the mean particle size of12 nm and specific surface area of 238 mZ/g Colloidal silicadispersion E -Wt% dispersion of the colloidal silica With the mean particle size of1.3 nm and specific surface area of 2090 mZ/g Colloidal silicadispersion G -Wt% dispersion of the colloidal silica With the mean particle size of8.5 nm and specific surface area of 320 m2/g Polyester amide A Adipic acid-diethanolamine condensation product With the acid Valueof 96 mgKOH/g and amine Value of 15 mgKOH/g 820PCT 31 WO2017002659 Polyester amide B Adipic acid-diethanolamine condensation product With the acid Valueof 105 mgKOH/g and amine Value of 35 mgKOH/g Polyester amide C Adipic acid-diethanolamine condensation product With the acid valueof 118 mgKOH/g and amine value of 55 mgKOH/g Polyester amide D Adipic acid-diethanolamine condensation product With the acid valueof 85 mgKOH/g and amine value of 9.8 mgKOH/g Polyester amide E Adipic acid-diethanolamine condensation product With the acid valueof 170 mgKOH/ g and amine value of 69 mgKOH/g CMPEI Polyethylene imine derivative having 80 % of substituted alkyl groups(*CH2COONa) and M.W. of 50,000, also described ascarboxymethylated polyethylene imine sodium salt AlCls° 6H2O Aluminum chloride hexahydrate AN Acrylonitrile MAN Methacrylonitrile MMA Methyl methacrylate IBX Isobornyl methacrylate VCl2 Vinylidene chloride MAA Methacrylic acid Cross-linking agent A Trimethylolpropane trimethacrylate Cross-linking agent B Ethylene glycol dimethacrylate Isobutane 2-Methyl propane Neopentane 2,2-Dimethyl propane Isopentane 2-Methyl butane Isooctane 2,2,4-'Irimethyl pentane Initiator A 2,2'-Azobis(2,4-dimethyl valeronitrile) Initiator B Di-Z-ethylhexyl peroxy dicarbonate (70 % concentration)[ooss] In Examples 1 to 8, the heat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pm Were produced constantly With high yield oWing to the polyester amide having an acid value from 95 to 140 mgKOH/ g used as the dispersion stabilizer.
    [89] [0089] In Comparative example 2, the amount of the two polyester amides each having the acid value of 85 and 170 Was increased in the polymerization and the heat-expandable microspheres Were produced constantly With high yield, though the expansion performance of the microspheres Was deteriorated.
    In Comparative example 3, the absence of the polyester amide caused unstable oil globules of the oily mixture dispersed in the aqueous dispersion medium. Thus the flocculation and solidification of the components of the reaction mixture Were observed and 820PCT 32 WO2017002659 heat-expandable microspheres could not be produced.
    In Comparative example 4, the polyester amide used in the polymerization hadinsufficient solubility in water due to its excessively low acid value and destabilized thedispersion of the oil globules to cause inconstant and low-yield production of heat-expandable microspheres. In addition, the resultant heat-expandable microspheres had amean particle size greater than 10 pm.
    In Comparative example 5, the polyester amide used in the polymerization hadexcessively high acid value and destabilized the dispersion of the oil globules to causeinconstant and low-yield production of heat- expandable microspheres. In addition, theresultant heat-expandable microspheres had a mean particle size greater than 10 pm.Industrial Applicability[0090] The process of the present invention enables constant and high-yield production ofheat-expandable microspheres having a mean particle size ranging from 0.01 to 10 pmwithout deteriorating their expansion performance.
    The heat-expandable microspheres produced in the process of the present inventioncan be used as the lightweight additive for putties, paints, inks, sealants, mortar, paper clay,ceramic, etc., and also as the additive to matrix resins processed in injection molding,extrusion molding and pressure molding to be made into foamed products having excellentsound insulation, thermal insulation, heat-shielding property, and sound absorbency.Reference Signs List[0091] 11 Thermoplastic resin shell12 Blowing agent1 Hollow particles (fine-particle-coated hollow particles)2 Shell3 Hollow4 Fine particle (in a state of adhesion)5 Fine particle (in a state of fixation in a dent)
    权利要求:
    Claims (11)
    [1] 1. Claim 1 A process for producing heat-expandable microspheres comprising a thermoplasticresin Shell and a blowing agent encapsulated therein, the process comprising the step ofdispersing a polymerizable component and the blowing agent in an aqueous dispersionmedium containing a polyester amide having an acid value (mgKOH/g) ranging from 95 to140 and the step of polymerizing the polymerizable component, wherein the heat-expandable microspheres have a mean particle size ranging from 0.01 to 10 pm.
    [2] 2. Claim 2 The process for producing the heat-expandable microspheres according to Claim 1,wherein the polyester amide is obtained from the reaction of a carboxylic acid having atleast two carboxyl groups and an amino alcohol having at least one amino group and two hydroxyl groups.
    [3] 3. Claim 3The process for producing the heat-expandable microspheres according to Claim 1 or 2, wherein the polyester amide has an amine value (mgKOH/g) ranging from 20 to 60.
    [4] 4. Claim 4 The process for producing the heat-expandable microspheres according to any one ofClaims 1 to 3, wherein the amount of the polyester amide in the aqueous dispersion mediumranges from 0.0001 to 5 parts by weight to 100 parts by weight of the total of the polymerizable component and blowing agent.
    [5] 5. Claim 5 The process for producing the heat-expandable microspheres according to any one ofClaims 1 to 4, wherein the carboxylic acid having at least two carboxylic groups is adipicacid, and the amino alcohol having at least one amino group and two hydroxyl groups is diethanolamine.
    [6] 6. Claim 6The process for producing the heat-expandable microspheres according to any one ofClaims 1 to 5, wherein the aqueous dispersion medium further contains a particulate metal compound having a mean particle size ranging from 1.0 to 20 nm. SZOPCT 34 WO2017002659
    [7] 7. Claim 7The process for producing the heat-expandable microspheres according to Claim 6,Wherein the particulate metal compound is colloidal silica and the pH of the aqueous dispersion medium is 7 or lower.
    [8] 8. Claim 8Hollow particles manufactured by thermally expanding the heat-expandable microspheres produced in the process according to any one of Claims 1 to 7.
    [9] 9. Claim 9The holloW particles according to Claim 8, the holloW particles further of the containing fine particles coating the outer surface thereof.
    [10] 10. Claim 10 A composition containing a base component and at least one type of microspheresselected from the heat-expandable microspheres produced in the process for producing heatexpandable microspheres according to any one of Claims 1 to 7 and the holloW particles according to Claim 8 or 9.
    [11] 11. Claim 11 A formed product manufactured by forming the composition according to Claim 10.
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    法律状态:
    优先权:
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    JP2015129920|2015-06-29|
    PCT/JP2016/068335|WO2017002659A1|2015-06-29|2016-06-21|Method of manufacturing thermally-expandable microspheres and application thereof|
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