GB2175591A - Fine powder of an acrylonitrile-type polymer and method for its production - Google Patents
Fine powder of an acrylonitrile-type polymer and method for its production Download PDFInfo
- Publication number
- GB2175591A GB2175591A GB8610974A GB8610974A GB2175591A GB 2175591 A GB2175591 A GB 2175591A GB 8610974 A GB8610974 A GB 8610974A GB 8610974 A GB8610974 A GB 8610974A GB 2175591 A GB2175591 A GB 2175591A
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- acrylonitrile
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- particle size
- polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 116
- 239000000843 powder Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 154
- 238000010298 pulverizing process Methods 0.000 claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 14
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- 239000011802 pulverized particle Substances 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000011256 inorganic filler Substances 0.000 abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000000945 filler Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
- B29K2033/20—PAN, i.e. polyacrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Abstract
A fine powder of an acrylonitrile-type polymer having a copolymerized acrylonitrile content of at least 95% by weight, containing substantially no sulfonic acid groups and having a reduced viscosity of from 1.0 to 8.0, a volume average particle size of from 1 to 5 mu m and a content of particles having a size exceeding 8 mu m being at most 0.05% by number, may be produced by aqueous suspension polymerisation followed by pulverisation e.g. using an air jet current. The powder is useful as a substitute for inorganic fillers, e.g. in electrostatic recording media or in coating materials.
Description
SPECIFICATION
Fine powder of an acrylonitriSe-type polymer and method for its production
The present invention relates to a uniform fine powder of a polymer composed mainly of acrylonitrile, which is useful as a substitute for an inorganic filler such as titanium oxide, silica gel, kaolin or clay, and a method for its production.
Inorganic fillers such as titanium oxide, silica gel and kaolin have excellent chemical resistance and weather resistance, and they are used in various fields of application coupled with the advanced technology for their pulverization into fine powders. However, these inorganic fillers are strongly acidic because of the process for their preparation. Accordingly, when used as fillers for paper, they are iikely to lead to yellowing of the paper or to a deterioration of the paper quality during the storage of the paper for a long period of time, which has become a serious social problem.Further, coupled with the increase in the volume of the paper used in the information-oriented society, the weight of paper attributable to the weight of the incorporated inorganic fillers has now become a serious problem also in the field of the printing process and in the transportation fieid. Under the circumstances, some attempts are being made to overcome the above-mentioned various problems by using organic fillers instead of the inorganic fillers.
Inorganic fillers are incorporated also in dielectric recording layers of electrostatic recording papers to provide surface roughness to the layers. However, it is known that since the inorganic fillers are hydrophilic, they tend to impair the insulating properties of the dielectric layers and thus lead to a deterioration of the electrostatic recording properties. Therefore, it is desired to develop a filler which does not bring about such drawbacks.
Japanese Examined Patent Publication No. 31753/1974 discloses a method for obtaining a uniform fine particulate polymer which comprises polymerizing acrylonitrile in a solvent which does not dissolve polyacrylonitrile, such as methanol, ethanol, butanol, cyclohexane, toluene, xylene or water, and subjecting the resulting polymer to dispersing treatment by means of a physical dispersing means such as a ball mill or a roller mill. The acrylonitrile-type polymer particles obtained by this method usually have irregular shapes with an average particle size of from about 10 to about 40 pom, as shown in Figure 1 (a).Such polymer particles can be pulverized in a solvent into particles having an average particle size of from about 6 to about 20 vim by physical dispersing treatment by means of e.g. a ball mill or a roller mill. However, they can hardly be pulverized into polymer particles having an average particle size of at most 5 pom, which is required for a fine powder of an organic polymer. Further, their particle size distribution is as wide as from 1 to 20 pm, and by the nature of the organic fillers, it is extremely difficult to narrow down the particle size distribution of such organic polymers adequately by classification.
Japanese Examined Patent Publication No. 31732/1982 discloses a method for producing a fine particulate polymer of acrylonitrile-type, which comprises polymerizing an unsaturated compound composed essentially of acrylonitrile under stirring in water having a cation concentration of from 0.03 to 3 g ions/liter (H2O) at a temperature of at least 120"C to create a spontaneous pressure, and introducing sulfonic acid groups into the resulting acrylonitrile-type polymer in an amount of at least 2 x 10-5 mol/g(polymer) and at the same time, forming an aqueous dispersion of polymer drops substantially in a molten state with a particle size of from 1 to 2000 pom, followed by cooling.
According to this method, a fine powder of acrylonitrile-type polymer having a uniform particle size is obtainable. However, the copolymerized acrylonitrile content in the acrylonitrile-type polymer is required to be at most 93% by weight, since it is necessary to form molten drops of the acrylonitrile-type polymer in the aqueous medium. Accordingly, it has been pointed out as difficulties that the heat resistance of the resulting acrylonitrile-type polymer particles is inadequate, and the whiteness required for a filler is inadequate.
Further, the acrylonitrile-type polymer particles obtained by this method, contain sulfonic acid groups or their salts in an amount of at least 2 x 10-5 mol/g(polymer), and thus have a relatively high hydrophilic nature, such being undesirable for an organic filler for an electrostatic recording medium. Therefore, it has been desired to develop a fine powder of an acrylonitrile-type polymer having a low hydrophilic nature.
According to the technology so far developed for organic fillers useful as a substitute for the inorganic fillers, it is extremely difficult to prepare fine particles of organic resins having an average particle size of at most 5pm and containing no coarse particles, or it is at best possible to prepare a fine powder from a particular resin containing a substantial amount of hydrophilic groups or polar groups.
The present inventors have conducted extensive researches on superfine pulverization of various acrylonitrile-type polymers, and have found that a specific fine powder obtained by the pulverization and classification of an acrylonitrile4ype polymer having a specific composition, exhibits excellent effects as a filler for e.g. an electrostatic recording medium.
The present invention provides a fine powder of an acrylonitrile-type polymer having a copolymerized acrylonitrile content of at least 95% by weight, containing substantially no sulfonic acid groups and having a reduced viscosity of from 1.0 to 8.0, a volume average particle size of from 1 to 5 pom and a content of particles having a size exceeding 8 pm being at most 0.05% by number.
Further, the present invention provides a method for producing such a fine powder of an acrylonitrile-type polymer.
Now, the present invention will be described in detail with reference to the preferred embodiments.
In the accompanying drawings, Figure 1(a) is an enlarged microscopic photograph of acrylonitrile-type polymer particles obtained by suspension polymerization to be used in the present invention.
Figure 1(b) is an enlarged microscopic photograph of a fine powder of an acrylonitrile-type polymer according to the present invention.
Figure 2 is an enlarged microscopic photograph of polymer particles of a Comparative Example.
Figure 3(a) is a plan view of the pulverization zone of a disintegration-type pulverizer to be used for the operation of the present invention.
Figure 3(b) is a cross-sectional view along line Y-Y of the supply portion of the disintegration-type pulverizer.
Figure 4(a) is a plan view of the pulverization zone of an impact-type pulverizer.
Figure 4(b) is a cross-sectional view along line X-X of the impact-type pulverizer.
The monomer for the acrylonitrile-type polymer of the present invention is the one containing at least 95% by weight of acrylonitrile, and a reduced viscosity (a viscosity measured at 250C by using a dimethylformamide solution having a polymer concentration of 0.5%) indicating the molecular weight of the resulting polymer, is within a range of from 1.0 to 8.0.
If the copolymerized acrylonitrile content in the polymer constituting the fine powder of the present invention is less than 95% by weight, the polymer shows thermoplasticity and exhibits inadequate hardness and chemical resistance as compared with the acrylonitrile-type polymer used in the present invention, and the polymer will be inferior in the whiteness and the weather resistance and photo resistance which are essential requirementsforfillers. If the reduced viscosity is less than 1.0, the acrylonitrile-type polymer tends to be brittle. On the other hand, it is difficult to obtain a uniform fine powder having a particle size of at most 5 calm from a polymer having a reduced viscosity exceeding 8.0.
The acrylonitrile-type polymer according to the present invention, contains substantially no sulfonic acid groups, particularly less than 5 x 10-5 mol/g (polymer), more preferably 2 x 10-5 mol/g(polymer). An acrylonitrile-type polymer powder prepared from a polymer containing more than 5 x 10-5 mol/g(polymer) of sulfonic acid groups in the acrylonitrile-type polymer, tends to be rich in the hydrophilic nature, and when used as an additive for a coating material, the coating layer tends to have a hydrophilic nature, thus leading to a deterioration of the coating layer. When it is used as an additive for paper, the paper itself tends to be acidic, thus leading to a deterioration of the paper quality during the storage for a long period of time.
Further, when it is used as a filler for an electrostatic recording paper, it is hardly possible to obtain an electrostatic recording paper having excellent resolution and image density. For these reasons, the acrylonitrile-type polymer to be used in the present invention is desired to contain substantially no sulfonic acid groups. More particularly, the sulfonic acid groups content is preferably less than 5 x 10-5 mol/g(polymer), more preferably less than 2 x 10-5 mol/g(polymer).
Other vinyl monomers copolymerizable in an amount of not higher than 5% by weight with acrylonitrile, include methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl chloride, vinyl acetate, styrene, a-methylstyrene, maleic acid, maleic acid amide and N-phenyl substituted maleimide.
The fine powder of an acrylonitrile-type polymer obtained by the present invention is required to have a volume average particle size of from 1 to 5pm and a content of particles having a size exceeding 811m being at most 0.05% by number. Preferably, the volume average particle size is within a range of from 1.5 to 4 pom, and the content of particles having a size exceeding 8pm is at most 0.02% by number.If a fine powder having an average particle size of less than 1 pm is used as a delustering filler for a coating material or for a paper coating agent, it is hardly possible to obtain the desired delustering effects, and when it is used as a paper coating agent, it tends to be difficult to obtain a paper surface having good writability or printabiiity.
On the other hand, the acrylonitrile-type polymer particles having an average particle size exceeding 5 pom, are so coarse by themselves that it is hardly possible to obtain a coating layer having a good outer appearance because when such particles are used as a filler, the coating layer will have a rough surface.
Likewise, when such acrylonitrile-type polymer particles are used as a paper coating filler, it is difficult to obtain a coating paper having good writability or printability.
Such undesirable tendency becomes distinct when the content of particles having a size exceeding 8 lim, exceeds 0.05% by number. Namely, when it is assumed that acrylonitrile-type polymer particles are spherical, the maximum cross sectional surface area of a particle having a size of 2.5 pm is 4.9 pm2, whereas the maximum cross sectional surface area of a particle having a size of 8 Cam is 50.2 pom2, and likewise the maximum cross sectional surface area of a particle having a size of 10 cm is 78.5 pom2. Thus, as the particle size increases by 2.4 times or 4 times, the cross sectional surface area rapidly increases by 10.3 times or 16 times, respectively.Thus, the properties as the filler will be impaired if the fine powder of an acrylonitrile-type polymer having an average particle size of from 1 to 5 pm contains more than 0.05% of particles having a size exceeding 8 pom.
As described above, it is possible to substantially improve the properties of the fine powder of an acrylonitrile-type polymer containing a certain amount of particles having a large size, by bringing the content of particles having a size exceeding 8 pom to a level of not more than 0.05% by number, peferably not more than 0.02% by number. Particularly when the polymer particles are used as a filler for the production of an electrostatic recording medium which is required to have a resolution with a recording density of more than 8 lines/mm, it is further desired that the content of particles having a size exceeding 10 pom is at most 30 particles per 500,000 particles counted by a fine powder particle size distribution measuring apparatus (Coulter Counter, manufactured by Coulter Counter Electronics, Inc.).An electrostatic recording medium prepared by using the fine powder of an acrylonitrile-type polymer having such properties, may have a recording density as high as 16 lines/mm.
By using the fine powder of an acrylonitrile-type polymer of the present invention having the above-mentioned properties as a filler for a coating material, it is possible to form a coating layer having excellent weather resistance without any coating defects such as hard spots or fish eyes.
As a polymerization method for the acrylonitrile-type polymer of the present invention, there may be employed an aqeuous suspension polymerization in which an oxidation-reduction polymerization catalyst is used or a method as disclosed in Japanese Patent Applications No. 133552/1984 and No. 133553/1984 wherein acrylonitrile is polymerized in the presence of a peroxide catalyst in an aqueous solvent prepared by mixing an aqueous organic solvent and water in a specific ratio, to obtain a polymer comprising from 95 to 100% by weight of acrylonitrile and not higher than 5% by weight of other vinyl monomers copolymerizable therewith, containing substantially no sulfonic acid groups and having a reduced viscosity of from 1.0 to 8.0.
The polymer obtained by the above polymerization methods is in the form of agglomerated porous polymer particles having a volume average particle size of from about 20 to about 40 pm formed during the polymerization process by agglomeration of fine primary polymer particles having a size of from 0.1 to 2 pm.
Such agglomerated polymer particles can hardly be pulverized into a fine powder having a particle size of at most 5 pom by a conventional means for producing a fine powder such as a ball mill or a hammer mill.
As shown in Figure 3(a), air jet currents are blown from air jet current inlets 11 into a pulverization zone 13 having no impact pulverization means to form a circulating air jet current, and the agglomerated polymer particles are supplied from an particle supply inlet to the pulverization zone so that a circulating force is given to the particles and the particles are pulverized by collision of the particles themselves, whereby it is possible to efficiently prevent the exothermic phenomenon of the polymer during the pulverization and to efficiently pulverize the agglomerated polymer particles by the circulating force of the particles and by the collision of the particles themselves, and it is possible to obtain a fine powder of an acrylonitrile-type polymer having a volume average particle size of from 1 to 5 pm, preferably from 1.5 to 4 pom, and a content of particles having a size exceeding 8 pm being at most 0.05% by number, preferably at most 0.02% by number.
Figure 3(a) is a plan view of the pulverization zone of a disintegration-type pulverizer to be used in the present invention, and Figure 3(b) is a cross sectional view taken along line Y-Y of Figure 3(a). In these
Figures, reference numeral 11 designates an inlet for compressed air to accelerate the circulating movement of the particles, to create a turbulence in the air flow and thus to increase the frequency of collision of the particles themselves, numeral 14 indicates an inlet for compressed air to drive the particles into the pulverization zone, numeral 15 is a particle supply inlet, numeral 16 is a Venturi tube to accelerate the particles by compressed air, and numeral 17 is a discharge outlet for the pulverized fine powder.
In the present invention, it is also possible to obtain a fine powder of an acrylonitrile-type polymer having the desired properties by using a combination of an impact-type pulverizer and a cyclone-system classifier as shown in Figures 4(a) and (b) under certain specific conditions so that the above-mentioned agglomerated particles of an acrylonitrile-type polymer are forcibly pulverized.
Figure 4(a) is a plan view of the pulverization zone of the impact-type pulverizer to be used in the present invention, and Figure 4(b) is a cross sectional view taken along line ) of Figure 4(a). In these Figures, 21 designates an inlet for an air jet current, numeral 22 designates an air jet nozzle, numeral 23 designates a supply inlet for the starting material particles, numeral 24 is a particle flow rate acceleration portion, numeral 25 is an impact wall for pulverizing the particles, and numeral 26 is a classification chamberforthe pulverized particles. The impact wall 25 is preferably a rotary ring adapted to rotate in a direction opposite to the direction of the air jet current in the pulverization chamber.When a pulverizer of this type is employed, it is preferred that acrylonitrile-type polymer particles are accelerated and bombarded against the impactpulverization wall by an air jet current having a high velocity of at least 200 m/sec, whereby the acrylonitrile-type polymer particles in an agglomerated state are forcibly pulverized. If the flow rate of the high velocity air jet current is less than 200 m/sec, the agglomerated acrylonitrile-type polymer particles tend to be hardy pulvrized, whereby the resulting powder will contain at least 30% of particles having a particle size of at least 5 cam, and the content of particles having a particle size or at least 8 pm will be at least 10%, thus leading to an extremely wide particle size distribution.Whereas, when a high velocity air jet current having a flow rate of at least 200 m/sec is employed, it is possible to obtain a fine powder having a content of particles having a particle size of at least 5 pm being from 10 to 15%, a content of particles having a particle size of at least 8 pm being from 1 to 5%, and a volume average particle size being from 3 to 5 pm.
The fine powder thus obtained is treated by a classifier to obtain a desired powder having the desired volume average particle size and a content of particles having a particle size exceeding, 8 pm being at most 0.05% by number.
The classifier may be of a cyclone type, or of a type wherein a pulverizer and a classifier are combined.
Namely, it is possible to employ a method wherein the acrylonitrile-type polymer particles are pulverized by collision of the particles themselves by an air jet current, and at the same time the pulverized particles in the pulverization chamber are classified by the centrifugal force of the circulation.
Further, in the classifier of a cyclone system, the flow rate in the classification chamber, i.e. the velocity of the fine powder, is preferably at least 80 m/sec per 0.1 m of the radius.
The acrylonitrile-type polymer particles obtained by the present invention have a volume average particle size of from 1 to 5 m, preferably from 1.5 to 4 pm, a content of particles having a size exceeding 8 pom being at most 0.05% by number, preferably at most 0.02% by number, and particularly a content of particles having a size exceeding 10 corm being at most 50 particles, preferably at most 30 particles, per 500,000 particles measured, and thus they can be effectively used as fillers, particularly as fillers for electrostatic recording media where the property requirements are strict.Further, the acrylonitrile-type polymer to be used has a copolymerized acrylonitrile content of at least 95% by weight and a sulfonic acid group content of at most 5.0 x 10-5 mol/g(polymer), preferably at most 2 x 10-5 mol/g(polymer), and it has excellent chemical resistance, water resistance and weather resistance, a high level of whiteness, a low specific gravity and excellent adhesive properties with binders. Thus, when used as a substitute for inorganic fillers commonly employed as fillers for coating materials or as delustering agents, various advantages may be obtained.
Now, the present invention will be described in detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by these specific Examples.
Examples 1 to 6 and Comparative Examples 1 to 3
Preparation of acrylonitrile-type polymer powders
By an aqueous suspension polymerization method, a polyacrylonitrile polymer having a reduced viscosity of 2.3 was obtained. The sulfonic acid group content was 1.8 x 10-5 mol/g(polymer), and the average particle size was 25 m. Figure 1 (a) shows an enlarged microscopic photograph of the polymer particles thus obtained. The acrylonitrile-type polymer particles were pulverized and classified by using a pulverizer of a type wherein the particles were bombarded against an impact wall for the pulverization of particles, as shown in Figure 4 and a cyclone-system classifier at the respective air flow rates as shown in Table 1. Thus, acrylonitrile-type polymer powders having an average particle size of from 2.0 to 3.5 m were prepared and designated as acrylonitrile polymer powders 1 to 9.Figure 1 (b) shows an enlarged electroscopic photograph of the fine powder thus obtained.
The powder properties were measured, and the results are shown in Table 1.
TABLE 1
Acrylonitrile-type polymer powder
Experi- Type Sulfonic acid Volume Particle size distribution (% by number) ment group content average
No. (mol/g.polymer) particle
size
( m) # 1 m 1 to 5 m 5 to 8 m 8 m < 1 [1] 1.8 x 10-5 2.0 23.712 76.090 0.197 0.001 2 [2] 1.8 x 10-5 2.3 22.239 76.865 0.894 0.002 3 [3] 1.8 x 10-5 2.5 28.519 70.942 0.531 0.008 4 [4] 1.8 x 10-5 2.6 17.441 82.171 0.836 0.012 5 [5] 1.8 x 10-5 2.7 26.194 72.839 0.949 0.018 6 [6] 1.8 x 10-5 2.9 23.046 74.604 7.318 0.032 7 [7] 1.8 x 10-5 3.2 21.031 74.942 3.955 0.072 8 [8] 1.8 x 10-5 3.4 10.429 79.990 9.475 0.106 9 [9] 1.8 x 10-5 3.5 19.346 75.694 4.623 0.167 *1) Air flow rate to the pulverizer *2) AirflowrateperO.1 m of the radius Table 1 continued
Air flow rates (m/sec)
Number of *1 *2 particles Pulveriza- Classificaexceeding 10pm tion zone tion zone (particles/ 500,000 particles) 0 250 140 10 250 130 15 250 120 20 230 130 25 230 120 42 230 90 71 230 70 32 180 120 150 230
Application to electrostatic recording media
50 parts of each of acrylonitrile-type polymer powders 1 to 9 was introduced into 200 parts of methyl ethyl ketone, and dispersed by a stirrer, whereby each acrylonitrile-type polymer powder was dispersed in methyl ethyl ketone satisfactorily. No coagulation due to agglomeration of the powder particles was observed by inspection with naked eyes. A 30% toluene solution of an acrylic resin comprising 40 parts of methyl methacrylate and 60 parts of butyl methacrylate as comonomers, was prepared.The above-mentioned methyl ethyl ketone dispersions of various acrylonitrile polymer powders, were added thereto, respectively, to obtain solutions for forming dielectric recording media.
The above-mentioned solutions for forming various dielectric recording media, were applied on base sheets treated with high molecular cations, followed by drying to obtain electrostatic recording media. The surface resistivity of these electrostatic recording media was measured at 20"C under a relative humidity of 60% at 100V DC, and the results are shown in Table 2.
Further, negative signal electric charges with line densities of 8 lines/mm and 16 lines/mm were applied to these electrostatic recording media by a fixed multihead, and the development was conducted with a developing powder with a positive electric charge to conduct a test for the formation of static images. The results are shown in Table 2.
Comparative Example 4
By an aqueous suspension polymerization method, a monomer mixture comprising 93% by weight of acrylonitrile and 7% by weight of vinyl acetate was polymerized to obtain acrylonitrile-type polymer particles having a reduced viscosity of 2.5, a sulfonic acid group content of 2.2 x 10-5 mol/g(polymer) and an average particle size of 30 pm. The acrylonitrile-type polymer particles were supplied by a high velocity air jet current at a flow rate of 230 m/sec into a pulverizer of a type where the particles were bombarded against the impact wall for pulverization of the particles, as shown in Figure 3, whereby the particles were pulverized to obtain a powder 10 having an average particle size of 6.5 pom. However, it was impossible to pulverize the particles into a fine powder having a smaller average particle size. Further, the surface of the powder 10 was fused as shown in Figure 2. For the purpose of comparison, an electrostatic recording medium was prepared in the same manner as in "Application to electrostatic recording media" of Example 1 by using the powder 10, and the properties were measured. The results are shown in Table 2.
The evaluation standards for the recording properties in Tables 2 and 4were as follows: (p): No breakage of the image was observed.
0: No substantial breakage of the image which may impair the recording properties, was observed.
A: Breakage of the image was distinctly observed.
X: A number of breakage of the image was observed.
TABLE 1
Image properties
Type of Recording properties
acrylonitrile- Surface Writability Fogging Image
type polymer resistivity density
powder 8 lines/mm 16 lines/mm
Example 1 [1] 1013 # # # Excellent Nil High
Example 2 [2] 1013 # # # Excellent Nil High
Example 3 [3] 1013 # # # Excellent Nil High
Example 4 [4] 1013 # # # Excellent Nil High
Example 5 [5] 1013 # # # to # Excellent Nil High
Example 6 [6] 1013 # # # Excellent Nil High
Comparative
Example 1 [7] 1013 # # to X X Excellent Nil High
Comparative
Example 2 [8] 1013 # X X Excellent Nil High
Comparative
Example 3 [9] 1013 # X X Excellent Nil High
Comparative
Example 4 [10] < 1011 # X X Poor Observed Low
Examples 7 to 12
Acrylonitrile-type polymer powders 11 to 16 were obtained by supplying the same polymer particles as used in "Preparation of acrylonitrile-type polymer powders" of Example 1 into a pulverizer of a type where the polymer particles were pulverized by collission of the particles themselves by means of an air jet current as shown in Figure 3. The powder properties were measured, and the results are shown in Table 3.
Further, electrostatic recording media were prepared in the same manner as in "Application to electrostatic recording medla" of Example 1 by using powders 11 to 16, and their properties were measured.
The results are shown in Table 4.
TABLE 3
Experiment Sulfonic acid Acrylonitrile-type polymer powder
No. Type group content Volume Particle size distribution (% by number) Number of particles
(mol/g. polymer) average # 1 m 1 to 4 m 4 to 8 m 8 m < exceeding 10 m
particle (particles/500,000
size ( m) particles) 11 [11] 1.8 X 10-5 2.1 23.542 75.940 0.517 0.001 0 12 [12] 1.8 X 10-5 2.4 27.513 71.353 1.132 0.002 10 13 [13] 1.8 X 10-5 2.5 18.554 80.827 1.111 0.008 15 14 [14] 1.8 X 10-5 2.6 26.097 71.993 1.900 0.012 20 15 [15] 1.8 X 10-5 2.7 31.635 66.662 1.685 0.018 25 16 [16] 1.8 X 10-5 2.8 21.804 75.648 2.534 0.014 25
TABLE 4
Image Properties
Type of Recording properties
acrylonitrile- Surface Writability Fogging Image
type polymer resistivity
powder Blines/mm 16 lines/mm
Example 7 [11] 1013# # # Excellent Nil High
Example 8 [12] 1013# # # Excellent Nil High
Example 9 [13] 1013# # # Excellent Nil High
Example 10 [14] 1013# # # Excellent Nil High
Example 11 [15] 1013# # # to # Excellent Nil High
Example 12 [16] 1013# # # Excellent Nil High Examples 13to 16
A 2 liter polymerization reactor equipped with a stirrer and a thermometer was purged with nitrogen, and a feed composition as identified in Table 5 was introduced, and the polymerization was initiated. When white turbidity was observed in the polymerization system, an additional solvent as identified in Table 5 was added. After the addition of the additional solvent, the polymerization was further continued for 70 minutes, whereupon the polymerization was terminated. The acrylonitrile-type polymer thus obtained, was separated, washed and dried to obtain white polymer particles having an average particle size of from 20 to 30 pm.
The acrylonitrile-type polymer particles Ato D obtained as described above, were pulverized in the same manner as in "Preparation of acrylonitrile-type polymer powders" of Example 1, whereby fine powders of acrylonitrile-type polymers having an average particle size of from 2.0 to 3.0 were obtained. The powder
properties were measured, and the results are shown in Table 6.
TABLE 5
Acrylonitrile Solvents AIBN * 1) Polymeri- Additional solvent Polymeriza- Reduced polymer fine Acrylonitrille (% relative zation tion degree viscosity powder DMF Water to monomer) temp. ( C) (%)
+2)
A 300 g 450 g 450 g 1.0 55 DMF 450 g 72 2.05
(25 %) (37.5 %) (37.5 %) (relative to monomer :
1.5 parts)
B 240 g 480 g 480 g 2.0 60 Distilled water 480 g 75 3.25
(20 %) (40 %) (40 %) (relative to monomer :
2 parts)
C 300 g 450 g 450 g 1.0 55 DMF 450 g 69 4.30
(25 %) (37.5 %) (36.5 %) Distilled water 450 g
(relative to monomer :
3 parts)
D 240 g 480 g 480 g 2.0 50 Distilled water 480 g 68 5.25
(20 %) (40 %) (40 %) (relative to monomer :
2 parts) * 1) AIBN : Azobisisobutyronitrile * 2) DMF :Dimethylformamide TABLE 6
Volume Particle size distribution Number of Air flow rate (misec)
Acrylonitrila- Sulfonic average particles type polymer acid group particle # 1 m 1 to 5 m 5 to 8 m 8 m < exceeding 10 m Pulveriza- Classificla
content size lparticles/ tion zone tion zone
(mol/g. ( m) 500,000 particles)
polymer)
Example A 0 2.0 22.800 77.083 0.116 0.001 2 250 140 13
Example B 0 2.3 18.548 78.528 0.912 0.012 13 250 130 14
Example C 0 2.7 23.614 76.204 0.173 0.009 22 230 120 15
Example D 0 3.0 18.182 80.815 0.211 0.017 27 220 120 16
Examples 17 to 20
White polymer particles having a volume average particle size offrom 20 to 30 m obtained in the same polymerization method as in Example 3, was pulverized in the same manner as in Example 7 to obtain fine powders of acrylonitrile-type polymers having a volume aver age particle size offrom 2 to 3 m. The powder porperties were measured, and the results are shown in Table 7.
TABLE 7
Acrylonitrille- Sulfonic acid Volume
type polymer group content average Particle size distribution (% by number) Number of particles
(mol/g. polymer) particle exceeding 10 m
size # 1 m 1 to 4 m 4 to 8 m 8 m < (particles/
( m) 500,000 particles)
Example 17 A 0 2.1 24.152 76.094 0.218 0.001 3
Example 18 B 0 2.3 18.548 80.167 1.274 0.011 15
Example 19 C 0 2.5 26.783 73.023 0.186 0.008 13
Example 20 D 0 2.8 19.241 78.634 2.098 0.018 28
Claims (8)
1. A fine powder of an acrylonitrile-type polymer having a copolymerized acrylonitrile content of at least 95% by weight, containing substantially no sulfonic acid groups and having a reduced viscosity of from 1.0 to 8.0, a volume average particle size of from 1 to 5 pom and a content of particles having a size exceeding 8 pm being at most 0.05% by number.
2. The fine powder according to Claim 1, wherein the volume average particle size is from 1.5 to 4 pm, and the content of particle having a size exceeding 8 pm is at most 0.02% by number.
3. A method for producing a fine powder of an acrylonitrile-type polymer, which comprises pulverizing acrylonitrile-type polymer particles obtained by aqueous suspension polymerization, having a copolymerized acrylonitrile content of at least 95% by weight, containing substantially no sulfonic acid groups, having a reduced viscosity of from 1.0 to 8.0 and a volume average particle size of at least 10 pom, and formed by agglomeration of primary polymer particles having a particle size of from 0.1 to 2 pom and classifying the pulverized particles to obtain a fine powder having a volume average particle size of from 1 to 5 pm and a content of particles having a size exceeding 8 pom being at most 0.05% by number.
4. The method according to Claim 3, wherein the pulverization is conducted by accelerating the acrylonitrile-type polymer particles by an air jet current at a velocity of at least 200 m/sec and bombarding the accelerated particles against a collision wall in a pulverization chamber.
5. The method according to Claim 3, wherein the pulverization is conducted by permitting the
acrylonitrile-type polymer particles to collide themselves by means of an air jest current.
6. The method according to Claim 3, wherein the acrylonitrile-type polymer particles are accelerated and
circulated in a pulverization chamber, by an air jet current, so that the polymer particles are pulverized by
collision with themselves, and at the same time, the pulverized particles are classified by the centrifugal
force of the circulation.
7. An acrylonitrile-type polymer powder as claimed in claim 1, substantially as described.
8. A method according to claim 3, substantially as described.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9871785 | 1985-05-09 | ||
| JP13151185 | 1985-06-17 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8610974D0 GB8610974D0 (en) | 1986-06-11 |
| GB2175591A true GB2175591A (en) | 1986-12-03 |
| GB2175591B GB2175591B (en) | 1989-01-25 |
Family
ID=26439843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8610974A Expired GB2175591B (en) | 1985-05-09 | 1986-05-06 | Fine powder of an acrylonitrile-type polymer and method for its production |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6289711A (en) |
| AU (1) | AU583918B2 (en) |
| CA (1) | CA1293235C (en) |
| DE (1) | DE3615155A1 (en) |
| GB (1) | GB2175591B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272659A2 (en) * | 1986-12-22 | 1988-06-29 | Daikin Industries, Limited | Powders of tetrafluoroethylene copolymer and process for preparing the same |
| WO2001000713A1 (en) * | 1999-06-24 | 2001-01-04 | Dynea Chemicals Oy | Polymer pigment applicable in dry form |
| WO2007028748A1 (en) * | 2005-09-07 | 2007-03-15 | Basf Se | Polymerization method |
| CN104761671A (en) * | 2015-03-31 | 2015-07-08 | 东华大学 | Preparation method of polyacrylonitrile nano latex particles |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPN388195A0 (en) * | 1995-06-29 | 1995-07-20 | Glover, Mark Richard | Water grinding of particulate material using high and ultra high pressure water processing |
| AUPN829796A0 (en) * | 1996-02-23 | 1996-03-21 | Bengold Holdings Pty Ltd | Improved grinding method and apparatus for performing same |
| DE19851676A1 (en) * | 1998-11-10 | 2000-05-11 | Bayer Ag | Thermoplastic molding compounds with improved mechanical properties |
| JP5773234B2 (en) * | 2009-06-23 | 2015-09-02 | 東洋紡株式会社 | Organic matte |
| JP6115588B2 (en) * | 2015-06-15 | 2017-04-19 | 東洋紡株式会社 | Organic matte |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6026099A (en) * | 1983-07-25 | 1985-02-08 | 株式会社リンレイ | Bleaching agent |
| JPS6114201A (en) * | 1984-06-29 | 1986-01-22 | Soken Kagaku Kk | Production of fine polymer powder |
-
1986
- 1986-04-24 JP JP9563686A patent/JPS6289711A/en active Granted
- 1986-04-28 CA CA000507789A patent/CA1293235C/en not_active Expired - Fee Related
- 1986-05-01 AU AU57077/86A patent/AU583918B2/en not_active Ceased
- 1986-05-05 DE DE19863615155 patent/DE3615155A1/en not_active Withdrawn
- 1986-05-06 GB GB8610974A patent/GB2175591B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272659A2 (en) * | 1986-12-22 | 1988-06-29 | Daikin Industries, Limited | Powders of tetrafluoroethylene copolymer and process for preparing the same |
| EP0272659A3 (en) * | 1986-12-22 | 1989-10-25 | Daikin Industries, Limited | Powders of tetrafluoroethylene copolymer and process for preparing the same |
| US4898779A (en) * | 1986-12-22 | 1990-02-06 | Daikin Industries Ltd. | Powders of tetrafluoroethylene copolymer and process for preparing the same |
| US4977221A (en) * | 1986-12-22 | 1990-12-11 | Daikin Industries, Ltd. | Powders of tetrafluoroethylene copolymer and process for preparing the same |
| WO2001000713A1 (en) * | 1999-06-24 | 2001-01-04 | Dynea Chemicals Oy | Polymer pigment applicable in dry form |
| WO2007028748A1 (en) * | 2005-09-07 | 2007-03-15 | Basf Se | Polymerization method |
| CN104761671A (en) * | 2015-03-31 | 2015-07-08 | 东华大学 | Preparation method of polyacrylonitrile nano latex particles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3615155A1 (en) | 1986-11-13 |
| AU583918B2 (en) | 1989-05-11 |
| CA1293235C (en) | 1991-12-17 |
| GB2175591B (en) | 1989-01-25 |
| GB8610974D0 (en) | 1986-06-11 |
| JPS6289711A (en) | 1987-04-24 |
| JPH0556762B2 (en) | 1993-08-20 |
| AU5707786A (en) | 1986-11-13 |
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| PCNP | Patent ceased through non-payment of renewal fee |
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