WO2008041697A1 - Particules agrégées contenant de la résine de chlorure de vinyle et procédé de production desdites particules agrégées - Google Patents

Particules agrégées contenant de la résine de chlorure de vinyle et procédé de production desdites particules agrégées Download PDF

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WO2008041697A1
WO2008041697A1 PCT/JP2007/069275 JP2007069275W WO2008041697A1 WO 2008041697 A1 WO2008041697 A1 WO 2008041697A1 JP 2007069275 W JP2007069275 W JP 2007069275W WO 2008041697 A1 WO2008041697 A1 WO 2008041697A1
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Prior art keywords
resin
chlorinated
particles
latex
bull
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PCT/JP2007/069275
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English (en)
Japanese (ja)
Inventor
Kyoji Uku
Keizo Hayashi
Hideo Yamada
Shinobu Ochikoshi
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Kaneka Corporation
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Priority to JP2008537531A priority Critical patent/JPWO2008041697A1/ja
Publication of WO2008041697A1 publication Critical patent/WO2008041697A1/fr

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    • 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
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2327/00—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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to an aggregate particle containing a chlorinated resin and a method for producing the same. More particularly, the present invention relates to an aggregate particle containing a chlorinated resin for paste processing that is impervious to fabric and a method for producing the same.
  • Sheets, gloves, bags, etc. coated with chlorinated resin are excellent in wear resistance, chemical resistance, and oil resistance with high mechanical strength, and are used in a wide range of fields such as fisheries, agriculture, and mining. Yes.
  • plastisol is a viscous liquid. When this is applied and dipped in the fabric, the plastisol penetrates into the fabric and penetrates to the back of the fabric. Even when heat-treated, the gelled melt can penetrate into the back of the fabric. If plastisol or this melt penetrates into the back of the fabric, the flexibility of the product is remarkably inferior and the product function is impaired. In particular, when used for gloves, even local penetration may cause discomfort to the user and reduce the product value.
  • Patent Document 1 There is a method of adding a water-soluble polymer and spray drying (Patent Document 1), but adding a water-soluble polymer increases the viscosity of the latex and clogs the spray drying nozzle. Etc. occur.
  • Patent Document 2 There is a method (Patent Document 2) in which a chlorinated resin for paste is heat-treated at 60 to 110 ° C with a self-heating high-speed rotary mixer, but it is heat-treated non-uniformly. Improves the non-penetration of rea, nare.
  • Patent Document 3 a method in which a suspension polymer of a chlorinated vinyl resin is deeply pulverized to adjust the resin particle size distribution to give the particles some strength (Patent Document 3). Not enough for sex.
  • Patent Document 1 Japanese Patent Laid-Open No. 48-16946
  • Patent Document 2 Japanese Patent Publication No.46-7177
  • Patent Document 3 Japanese Patent Publication No. 2-40692
  • the present invention provides an aggregate particle containing a chlorinated resin suitable for a vulcanized resin particle for paste caloe that is impermeable to a fabric, and a method for producing the same. .
  • the aggregate particles containing the chlorinated resin of the present invention are selected from a water-soluble polymer and an inorganic salt as a chlorinated chloric resin latex whose primary particles have an average particle size in the range of 0.00; Agglomerated particles containing at least one aggregating agent and dried, wherein the agglomerated particles are formed by aggregating the primary particles, and the agglomerated particles have an average particle size of 5 m to 40,1 m. It is a range.
  • the method for producing aggregate particles containing a chlorinated resin of the present invention includes a chlorinated butyl resin latex in which the primary particles have an average particle diameter in the range of 0.;! To 2.0 m, a water-soluble polymer and an inorganic salt.
  • the agglomerated particles having an average particle diameter of 5 m to 4011 m are obtained by spray drying the mixed aqueous solution. It is characterized by obtaining.
  • FIG. 1 is a scanning electron microscope (SEM) 1000 ⁇ photograph of the aggregate particles obtained in Example 1 of the present invention.
  • Figure 2 is a photograph 10,000 times larger than the SEM.
  • FIG. 3 is a schematic explanatory diagram of an example manufacturing process used in the present invention.
  • FIG. 4 is a schematic explanatory view of an example sprayer (two-fluid nozzle) used in the present invention.
  • FIG. 5 is a schematic explanatory view of an example of a sprayer (rotating disk type atomizer) used in the present invention.
  • FIG. 6 shows a scanning electron microscope (SE) of aggregate particles obtained in Example 11 of the present invention.
  • Fig. 7 is a photograph 10,000 times larger than the SEM.
  • the present invention provides the coagulant, wherein the primary particles contain an average particle size of 0. Aggregate particles are formed by agglomeration of the primary particles, and the average particle diameter of the aggregate particles is in the range of 5 ⁇ m to 40 ⁇ m.
  • the aggregate particle containing a chlorinated resin can be provided.
  • the present invention also provides a chlorinated resin for paste processing that is impermeable to fabric by mixing latex of chlorinated resin with water-soluble polymer and / or water-soluble electrolyte immediately before spraying and immediately spray-drying. Resin particles can be produced efficiently. This method is particularly suitable for mass production.
  • the present invention relates to emulsion polymerization other than the nonionic surfactant (A) and the butyl chloride polymer in the chlorinated chloric resin latex in which the primary particles have an average particle diameter of 0.;! To 2.0 m.
  • Agglomerated particles containing at least one component selected from latex (B) and at least one aggregating agent selected from a water-soluble polymer and an inorganic salt, and the aggregated particles are aggregated with the primary particles.
  • the average particle diameter of the aggregate particles is in the range of 5 m to 40,1 m, so that the aggregate particles containing vinyl chloride resin for paste processing that is impervious to the fabric can be obtained. Can be provided.
  • Aggregate particles containing the butyl chloride resin of the present invention become a chlorinated resin for paste processing that is impermeable to the fabric.
  • this chlorinated resin for paste processing is a polymer particle other than a specific nonionic surfactant or a chlorinated polymer in latex in the form of a fine particle of chlorinated resin obtained by fine suspension or emulsion polymerization.
  • agglomerated with a specific aggregating agent to obtain fluidized agglomerated particles, which are obtained by spray drying.
  • fabric refers to a sheet-like material using fibers such as woven fabric, knitted fabric, and non-woven fabric.
  • the chlorinated resin used in the present invention includes a chlorinated monomer or a mixture of a chlorinated monomer and a monomer copolymerizable therewith in an aqueous medium, an emulsifier, and if necessary.
  • a dispersion aid such as higher alcohol and higher fatty acid
  • an oil-soluble polymerization initiator and homogenizing it, followed by fine suspension polymerization or emulsion polymerization and seeding emulsion polymerization by adding a water-soluble initiator, etc. can get.
  • the average particle diameter of the primary particles of the chlorinated resin in the present invention is usually an aqueous homogenous dispersion (latex) of fine particles of 0.;! ⁇ 2. ⁇ m, and has the object of the present invention. If it is, it is not limited to this range. From the viewpoint of the stability of the polymerization, it is preferably 0.1 l rn or more; 1.7 ⁇ 111 force, and more preferably 0.;! To 1 ⁇ 4 111.
  • the butyl chloride monomer and the monomer copolymerizable therewith are not particularly limited, but olefins such as ethylene, propylene and butene, butyl acetate, butyl propionate, vinoleate stearate, etc.
  • Vinino estenoles methino levinino reetenore, ethyl vinino ree tenole, otachinole vinino ree tenole, vinino ree tenores such as laurino levino ree tenole, vinylidenes such as vinylidene chloride, acrylic acid, methacrylic acid , Fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride and other unsaturated carboxylic acids and their anhydrides, methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, butyl maleate Unsaturated carboxylic acid esters such as benzyl, styrene, ⁇ -methylstyrene All known monomers that can be copolymerized with butyl chloride, such as aromatic bur compounds such as ethylene and dibutene benzene, unsaturated nitrile
  • the emulsifier used for the polymerization is not particularly limited, but an anionic surfactant is usually used in an amount of about 0.;! To about 3 parts by weight per 100 parts by weight of the monomer.
  • the anionic surfactant include fatty acids, alkyl sulfates, alkylbenzene sulfonic acids, alkyl sulphosuccinic acids, ⁇ -olefin sulfonic acids, alkyl ether phosphates and other potassium ethers. Um, sodium, ammonium salt and the like.
  • Oil-soluble initiators used in the polymerization include disilver oxides such as dilauroyl peroxide, di-3, 5, 5, trimethylhexanoyl peroxide, diisopropyl peroxydicarbonate, G 2 —Peroxydicarbonates such as ethylhexenoreperoxydicarbonate, organic peroxide initiators such as peroxyesters such as t-butyl peroxybivalate, t-butyl peroxynedecanoate, and 2, Use azo initiators such as 2, -azobisisobutyronitrile, 2,2'-azobis (2,4 dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4 dimethylvaleronitrile) Ability to do S.
  • disilver oxides such as dilauroyl peroxide, di-3, 5, 5, trimethylhexanoyl peroxide, diisopropyl peroxydicarbonate
  • G 2 Peroxydicarbonates such
  • ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide water, etc. are used as the water-soluble initiator used in the emulsion polymerization.
  • sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate 2 A reducing agent such as hydrate, ascorbic acid or sodium ascorbate can be used in combination. These can be used alone or in combination of two or more.
  • the flocculant used in the present invention is at least one selected from a water-soluble polymer and an inorganic salt (electrolyte). That is, a water-soluble polymer, an inorganic salt (electrolyte), or a combination of a water-soluble polymer and an inorganic salt (electrolyte).
  • the synthetic polymer is an alitaroyl group-containing monomer (co) polymer.
  • Natural polymers include polysaccharides (such as starch, dextrin, dalcomannan, galactomannan, gum arabic, xanthan gum, pectin, carrageenan, locust bean gum, guar gum, tragacanth, chitin, chitosan, pullulan and alginate), and proteins. White matter (gelatin, casein, collagen, etc.).
  • Semi-synthetic polymers include cellulose etherenoles (methinoresenorelose, ethinoresenorelose, benzenoresenorelose, tritinolecellulose, cyanethylcellulose, aminoethylcellulose, hydroxymethylcellulose.
  • Ethinorehydroxyethinorescenellose methinorehydro And xylpropyl cellulose, carboxymethyl cellulose and carboxyethyl cellulose
  • starch derivatives soluble starch, methyl starch, carboxymethyl starch, etc.
  • the addition amount of the water-soluble polymer is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 2 parts by weight with respect to 100 parts by weight of the chlorinated resin. preferable. Within the above range, slurry viscosity with higher impermeability can be maintained within a suitable range, and a slurry with fluidity can be obtained. Can be good.
  • the electrolyte includes Na + , K +, Mg 2+ , Ca 2+ , Al 3+ , H + , CI—, Br—, SO 2 —, S
  • Examples include compounds that dissociate into ions such as O 2 —, NO—, NO—, PO 3 —, CO 2 —, and OH—.
  • examples of inorganic salts for obtaining the electrolyte include NaCl, KC1, Na 2 SO, and CaCK A1C 1.
  • the addition amount is preferably 0.;! To 10 parts by weight with respect to 100 parts by weight of butyl chloride resin. Furthermore, 0.3 to 3 parts by weight are preferable. If the amount of electrolyte added is in the above range, it is possible to obtain agglomerated particles and to achieve good spray drying, which is immediately more preferable for impermeability.
  • sodium sulfate having a monovalent metal ion such as Na + is preferable in terms of obtaining a fluid slurry.
  • Divalent and trivalent metal salts can be used. S, Latex stability may be reduced, so be careful.
  • the form of addition of the water-soluble polymer and electrolyte as the flocculant to the chlorinated butyl resin latex may be either a solid or an aqueous solution, but in terms of dispersion, the aqueous solution form is preferred. It is preferable to add into the stirring latex.
  • the addition of the water-soluble polymer and the electrolyte to the latex is preferably added in the latter half of the emulsion polymerization of the butyl chloride resin or after the completion of the polymerization.
  • the temperature of the latex when adding the flocculant should be selected in a range that does not increase the viscosity of the mixture after the flocculant is mixed!
  • Nonionic surfactants contribute to efficient production of aggregated particles.
  • Nonionic surfactants include polyoxyalkylene compounds and polyoxyethylenes. Examples include lenalkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerin monofatty acid ester and the like.
  • the nonionic surfactant When added, it is preferably added before the addition of the water-soluble polymer and inorganic salt (electrolyte) as the flocculant. By doing this, even if the slurry concentration is as high as 35% by weight or more, the fluidity is maintained and pumping becomes possible.
  • the addition amount of the nonionic surfactant is in the range of 0.01 to! Parts by weight with respect to 100 parts by weight of the chlorinated resin. Preferably, it is 0.05 to 0.5 part by weight. More preferably, it is 0.15 to 0.35 parts by weight. If it is the said range, productivity of an aggregated particle will improve.
  • the emulsion polymerized latex other than the chlorinated chloride polymer used in the present invention has a function as an impermeable improving agent.
  • emulsion polymerization latexes other than chlorinated butyl polymers include (meth) acrylic acid ester homopolymers, copolymers of (meth) acrylic acid esters and (meth) acrylic acid esters, and ethylene Examples include coalescence.
  • the addition amount of the emulsion polymerization latex other than the chlorinated chloride polymer is preferably in the range of 1 to 10 parts by weight of the polymer contained with respect to 100 parts by weight of the chlorinated resin. If it is the said range, the impervious effect with respect to a fabric can be made still higher.
  • the agglomerated slurry is preferably heat-treated.
  • the aggregated particles are firmly fused by the heat treatment, and the aggregated particles have a structure that is more easily impervious.
  • the heat treatment temperature is equal to or higher than the glass transition temperature (about 80 ° C) of the chlorinated polymer (see Polymer Handbook, 3rd edition, pages V / 63 and VI / 222). Preferably, it is 95 to 150 ° C. More preferably, the temperature is 110 to 145 ° C.
  • the heat treatment time is preferably in the range of 1 to 120 minutes. More preferably, it is in the range of 5 to 30 minutes.
  • the slurry heat-treated as described above can be directly dried in a spray dryer to obtain a chlorinated resin for paste processing.
  • an atomizer a sprayer
  • a pressure nozzle a pressure nozzle
  • Spray dryers equipped with (one-fluid nozzle), two-fluid nozzle, rotary disk type (disk type), etc. are used.
  • the temperature of the hot air supplied is the salt for paste Typical temperatures used for drying vulcanized resin are in the range of 100-220 ° C, and the temperature at the outlet of the dryer is usually in the range of 50-100 ° C.
  • the drying time (dryer residence time) is preferably 20 to 180 seconds.
  • the average particle diameter of the spray-dried particles obtained by spray drying is adjusted by the nozzle diameter, the amount of latex or slurry supplied, the amount of air supplied, the solid content concentration, etc. in a nozzle-type dryer. In this dryer, the number of revolutions of the rotating disk, the amount of latex or slurry supplied, and the solid content concentration are adjusted.
  • the average particle diameter of the chlorinated resin particles obtained by spray drying is generally adjusted in the range of 5 to 120 m.
  • the spray-dried particles obtained in this way can be used as products (aggregate particles) as long as the average particle size is in the range of 5-40111.
  • the particles obtained by spray drying can be used after being pulverized by a known method.
  • a roller mill, a high-speed rotary pulverizer, a ball mill, and an airflow-type pulverizer can be used.
  • the average particle size of the aggregate particles (hereinafter also referred to as "resin particles”) is too small, the viscosity of the plastisol increases. On the other hand, if the average particle size is too large, the coarse particles in the plastisol will increase, they will settle over time, and mixing will be necessary. From this viewpoint, the average particle diameter of the resin particles is in the range of 5 am to 40 am, and preferably in the range of 5 ⁇ m to 30 ⁇ m. When pulverizing excessively, favorable results tend not to be obtained with respect to impermeability.
  • the minimum amount of plasticizer in which the chlorinated resin particles of the present invention preferably have an appropriate space inside the particles is preferably 50 parts by weight or more.
  • the chlorinated resin particles for paste processing dried with a spray dryer are mixed with a plasticizer such as dioctyl phthalate and dioctyl adipate, and further, a filler such as calcium carbonate, a foaming agent, and a stabilizer. , Thickeners, antioxidants, UV absorbers, flame retardants, antistatic agents, lubricants, pigments, surface treatment agents, thixotropic agents, adhesion-imparting agents, etc.
  • a butyl resin composition (plastisol) for paste processing is obtained.
  • plastisol is applied to a fabric, there is! /, A sheet obtained by dipping, a glove, a bag, etc.
  • the plasticizer is used in a large amount of 80 to 160 parts by weight with respect to 100 parts by weight of the chlorinated resin. It is clear that the greater the amount of plasticizer, the more likely the penetration of the back side of the fabric occurs.
  • the chlorinated resin resin paste for paste processing of the present invention does not penetrate into the back side of the fabric even with a high proportion of plasticizer. Nare ,.
  • Microtrac HRA MODEL9320-X100 (Nikkiso Co., Ltd.) the particle size distribution was measured, and the median diameter based on volume was used as the average particle size.
  • the measurement conditions were a temperature of 25 ° C., the substance information was transparent and the refractive index was 1.51, the spherical particles were not checked, the carrier was water, and the refractive index was 1.33. Also, SET ZERO 10 seconds, measurement 10 seconds, and no DRY CUT calculation.
  • the penetration test on the fabric was carried out on a fabric with cotton yarn 29.5 (cotton count) (double-sided, 2-stage smooth circular knitting), 24 gauge, 1 inch 37 stitches, basis weight 216 g / m 2 Cast plastisol at a thickness of about 3 mm at room temperature, immediately place it in a circulating hot air oven at 180 ° C, heat-treat for 3 minutes to melt the gel, and then check whether the melt penetrates into the back of the fabric. A melt penetration test was performed.
  • the evaluation is that the gel penetrates the back side of the fabric visually! /, If not, A, slightly penetrates! /, If B, the gel penetrates to the back of the fabric! /, If C A three-step evaluation was made.
  • the gelled product of the sample obtained with the evaluation of A in (2) was peeled off from the cloth, and judged according to the following criteria. Note that the measurement area was 4 cm 2 (2 cm in length and width each). AA: Less than 0.03 g of gelled material remained on the cloth.
  • a 300-liter pressure vessel with a jacket was charged with 1 lOKg of chlorinated monomer, 110 Kg of ion-exchanged water, 40 g of ammonium persulfate, 40 g of copper sulfate pentahydrate, and heated to 50 ° C.
  • Polymerization was carried out by continuously adding a 1% by weight aqueous sodium sulfite solution and a 10% by weight aqueous ammonium myristate solution. After polymerization until the polymerization pressure decreased by 0.15 MPa from the initial pressure (0.7 MPa), the residual monomer was recovered to obtain a chlorinated butyl resin latex.
  • the polymerization conversion rate of the finally obtained latex with respect to the total amount of initially charged monomer and additional monomer (hereinafter referred to as total monomer amount) was 90%.
  • the average particle diameter of the resulting primary particles of Lattus was 0.35 m.
  • Ion-exchanged water was added to the polymerized latex so that the solid content concentration of the chlorinated resin was 30% by weight.
  • the temperature of the mixture at this time was 60 ° C.
  • 1 part by weight of sodium sulfate is added to the chlorinated resin as a 10% by weight aqueous solution.
  • polybulal alcohol (trade name "GOHSENOL KH-17" manufactured by Nippon Synthetic Chemical Co., Ltd.): Ken value of about 80m ol%) 0.5 part by weight was added as a 3% by weight aqueous solution.
  • aggregated particles having an average particle size of 20 m (related to latex after adding the flocculant and before drying) were obtained, and the latex after adding the flocculant was sprayed using a two-fluid nozzle spray dryer as shown in FIG.
  • the supplied hot air was dried under the conditions of an inlet temperature of 180 ° C and an outlet temperature of 71 ° C.
  • the drier residence time was 100 seconds.
  • the average particle size of the obtained aggregate particles containing the chlorinated resin particles (related to the resin after latex drying. When defined as aggregate particles, any drying method) was 6 ⁇ m.
  • Fig. 1 shows a scanning electron microscope (SEM) 1000 times photograph of the obtained aggregate particles.
  • Aggregate particles were amorphous.
  • Figure 2 is a photograph of SEM 10,000 times. With aggregate particles You can confirm that there is power S.
  • the primary particles (basic particles) were independent of each other and were not fused.
  • Example 2 The same operations as in Example 1 were carried out and evaluated except that methylcellulose (Shin-Etsu Chemical Co., Ltd. Metroles SM-400) was used as the water-soluble polymer.
  • methylcellulose Shin-Etsu Chemical Co., Ltd. Metroles SM-400
  • a 300-liter pressure vessel with a jacket is charged with 1 lOKg of chlorinated monomer, 110 Kg of ion-exchanged water, 20 g of sodium lauryl sulfate, 40 g of ammonium persulfate, 40 g of copper sulfate pentahydrate, and heated to 50 ° C. While stirring, the polymerization was carried out by continuously adding a 1% by weight sodium sulfite aqueous solution and a 10% by weight ammonium myristate aqueous solution. Polymerization was carried out until the polymerization pressure was reduced by 0.15 MPa from the initial pressure (0.7 MPa), and then the remaining monomer was recovered to obtain a chlorinated bule resin latex.
  • the polymerization conversion rate of the finally obtained latex with respect to the total amount of initial charged monomer and additional monomer (hereinafter referred to as total monomer amount) was 90% by weight.
  • the average particle size of the primary particles of the obtained latex was 0 ⁇ 15 m.
  • Ion-exchanged water was added to the polymerized latex so that the solid content concentration of the chlorinated resin was 30% by weight. The temperature of the mixture at this time was 60 ° C. Next, 1 part by weight of sodium sulfate is added to the chlorinated resin as a 10% by weight aqueous solution. Next, polybulal alcohol (trade name "GOHSENOL KH-17" manufactured by Nippon Synthetic Chemical Co., Ltd.): Ken value of about 80m ol%) 0.5 part by weight was added as a 3% by weight aqueous solution.
  • polybulal alcohol trade name "GOHSENOL KH-17" manufactured by Nippon Synthetic Chemical Co., Ltd.
  • agglomerated particles with an average particle diameter of 20 m were obtained, and the latex after the addition of the aggregating agent was supplied using the two-fluid nozzle type spray dryer shown in Fig. 3, hot air inlet temperature 180 ° C, outlet temperature Dried at 71 ° C.
  • the average particle diameter of the aggregate particles containing the resulting chlorinated resin particles is 20 111. I got it.
  • Evaluation was performed by performing the same operation as in Example 1 except that the two-fluid nozzle was replaced and the spray particle size was changed.
  • the resin particles obtained in Comparative Example 4 were pulverized with a bantam mill.
  • the average particle size of the obtained chlorinated butyl resin particles was 10 m.
  • Example 2 The same operation as in Example 1 was performed except that the spraying device was replaced with a rotating disk.
  • the adjusted plastisol was stored at 25 ° C for one day, coarse particles separated and settled at the bottom of the container. However, it was at a level that could be reused if mixed.
  • Example 2 Except that the atomizer was replaced with a rotating disk, the same operation as in Example 1 was performed to obtain dry particles having an average particle size of 30 and 1 m. This was pulverized using a micro bantam mill AP-B to obtain a chlorinated resin resin particle having an average particle diameter of 15 m, which was evaluated.
  • Example 9 Except for changing the rotational speed of the rotating disk, the same operation as in Example 9 was performed to obtain dry particles having an average particle diameter of 100 m. This was pulverized using a micro bantam mill AP-B to obtain chlorinated butyl resin particles having an average particle size of 25 am, and this was evaluated.
  • Example 2 The same operations as in Example 1 were performed and evaluated, except that the water-soluble polymer polybulal alcohol and the electrolyte bow glass were not added!
  • Example 6 The resin particles obtained in Example 6 were pulverized with a jet mill. However, the obtained particles were too fine and the impermeability evaluation was poor. [0064] (Comparative Example 3)
  • Example 8 The same operation as in Example 8 was performed except that the number of revolutions of the spraying device was lowered! When the prepared plastisol was stored at 25 ° C for one day, a large amount of coarse particles separated and settled at the bottom of the container. The impermeability was C rank as shown in the table.
  • Example 1 AA 1 640 1 590 0.97 Male 2 AA 1 700 1 670 0.98 Difficult 3 AA 251 0 1 460 0.58 Difficult 4 AA 1 660 1 680 0.99 Example 5 AA 1 300 1 450 1. 1 2 Example 6 AA 1 500 1 480 0.99 Example 7 B-850 890 1. 05
  • Example 9 A A 1 600 1 550 0. 97 Difficult example 1 0 A A 1 600 1 500 0. 94
  • a 300-liter pressure vessel with a jacket was charged with 110 kg of butyl chloride monomer, 110 kg of ion-exchanged water, 40 g of ammonium persulfate, and 0.3 g of copper sulfate pentahydrate, and the temperature was raised to 50 ° C.
  • lwt Polymerization was carried out by continuously adding an aqueous sodium sulfite solution and an aqueous 10 wt% ammonium myristate solution. Polymerization was carried out until the polymerization pressure decreased by 0.15 MPa from the initial pressure (0.7 MPa), and then the residual monomer was recovered to obtain a chlorinated butyl resin latex.
  • the polymerization conversion rate of the finally obtained latex with respect to the total amount of initially charged monomer and additional monomer was 90 wt%.
  • the average particle diameter of the obtained primary particles of the latex was 0 ⁇ 35 111.
  • the latex solids concentration was 46 wt%.
  • the fluid (latex and electrolyte aqueous solution) 31 is supplied at a supply rate of 54 kg / hr (47 liters / hr), and the water-soluble polymer aqueous solution 33 is supplied at a supply rate of 3.6 kg / hr, and the residence time in the two-fluid nozzle is Was set to 0.15 sec or less.
  • the particles sprayed from the two-fluid spray nozzle were dried with a spray dryer.
  • the average particle size of the resulting chlorinated resin resin particles was 65 111.
  • FIG. 6 is a photograph of the aggregate particles obtained in this example at 1000 times magnification with a scanning electron microscope (SEM), and FIG. 7 is a photograph at 10 000 times magnification of the SEM.
  • SEM scanning electron microscope
  • the obtained resin particles were pulverized with a micro bantam mill AP-B type crusher manufactured by Hosokawa Micron Corporation.
  • the average particle diameter of the obtained resin particles was 10 11 m.
  • Table 3 shows the dry particle size, pulverized particle size, and impermeability evaluation results.
  • Example 11 The same operations as in Example 11 were performed and evaluated except that methylcellulose (Shin-Etsu Chemical Co., Ltd., Metrology SM-400) was used as the water-soluble polymer.
  • methylcellulose Shin-Etsu Chemical Co., Ltd., Metrology SM-400
  • Example 11 The same operation as in Example 11 was carried out except that sodium sulfate was not added! /, And evaluation was performed.
  • latex of a chlorinated resin obtained by emulsion polymerization or the like, or a solution in which an inorganic salt is dissolved in advance and a water-soluble polymer aqueous solution are continuously added. It was confirmed that by mixing, atomizing with an atomizer before the fluidity of the mixture was lost, spray drying and pulverizing, a plastisol that exhibited impermeability to the fabric was obtained.
  • a 300-liter pressure vessel with a jacket was charged with 1 lOKg of chlorinated monomer, 110 Kg of ion-exchanged water, 40 g of ammonium persulfate, 40 g of copper sulfate pentahydrate, and heated to 50 ° C.
  • Polymerization was carried out by continuously adding a 1% by weight aqueous sodium sulfite solution and a 10% by weight aqueous ammonium myristate solution. After polymerization until the polymerization pressure decreased by 0.15 MPa from the initial pressure (0.7 MPa), the residual monomer was recovered to obtain a chlorinated butyl resin latex.
  • the polymerization conversion rate of the finally obtained latex with respect to the total amount of initially charged monomer and additional monomer (hereinafter referred to as total monomer amount) was 90%.
  • the average particle diameter of the primary particles of the obtained latex was 0 ⁇ 35 m.
  • the solid content concentration of the latex was 46.4 wt%.
  • polybutyl alcohol (trade name “GOHSENOL KH-17” manufactured by Nippon Synthetic Chemical Co., Ltd.) 80 mol%) 0.5 part by weight was added as a 3% by weight aqueous solution to 83.3 g. Thereafter, stirring was continued for 5 minutes to obtain a slurry.
  • Using a fluid nozzle spray dryer drying was performed under the conditions of the supplied hot air inlet temperature of 180 ° C and outlet temperature of 81 ° C.
  • the drier residence time was 100 seconds. Average particle size of aggregate particles containing the resulting chlorinated resin resin particles (related to the resin after latex drying. When defined as aggregate particles, any drying method may be used) was 6 m.
  • Nonionic surfactant (Nippon Yushi Co., Ltd., trade name “Pronon 102”) 1.5 g (0.3 parts by weight based on chlorinated chlor resin) was added, and the same procedure as in Example 15 was performed. did.
  • Acrylic latex (trade name “AE945H” manufactured by JSR Corporation, solid content concentration 51 ⁇ 75%) 14.5 g (1.5 parts by weight in solid content with respect to chlorinated resin) was added. Evaluation was performed in the same manner as in Example 171 except that 45 6.3 g of ion-exchanged water was added.
  • Acrylic latex (trade name “AE945H” manufactured by JSR Corporation, solid content concentration 51 ⁇ 75%) 5 8 g (6 parts by weight in solid content with respect to bull chloride resin) was added. Evaluation was carried out in the same manner as in Example 17, except that 435.3 g of ion-exchanged water was added.
  • Example 21 Ethylene acetate butyl copolymer latex (trade name "AD-10", solid product concentration 56. 52%, manufactured by Showa Polymer Co., Ltd.) 26.5 g (3 parts by weight solids with respect to chlorinated resin), ion exchange The same operation as in Example 17 was performed, except that 451.7 g of water was added, and evaluated. [0090] (Example 21)
  • Acrylic latex (trade name “0568” manufactured by JSR Corporation, solid content concentration 51.0%) 29.4 g (3 parts by weight in solid content with respect to butyl chloride resin) was added. Evaluation was carried out in the same manner as in Example 17 except that 448.8 g of ion-exchanged water was added.
  • Example 17 Evaluation was performed in the same manner as in Example 17 except that 37.7 g of the latex obtained in Latex Production Example 1 (3 parts by weight in solids with respect to chlorinated resin) and 44.6 g of ion-exchanged water were added. did.
  • Example 1 of latex production in Example 22 polymerization was performed using butyl acrylate instead of methyl methacrylate.
  • the conversion rate of the obtained latex was 99.5%.
  • the latex solids concentration was 39.8 wt%.
  • Example 15 The agglomerated latex having a concentration of 40% obtained in Example 15 was charged into a 3 L pressure vessel equipped with a stirrer. Under stirring, the temperature was raised to 120 ° C with steam blowing and maintained at 120 ° C for 15 minutes. After cooling, the latus status was taken out, dried and evaluated in the same manner as in Example 15. It was confirmed with a scanning electron microscope (SEM, 1000 times) that the obtained aggregated particles were fused to form V.
  • SEM scanning electron microscope
  • Example 24 Evaluations were made in the same manner as in Example 24 except that the temperature in Example 24 was changed to 140 ° C. It was confirmed by SEM (1000 times) that the obtained aggregated particles were fused!
  • Example 15 the two-fluid nozzle was changed to a rotating disk to change the spray particle size, and dry particles having an average particle size of 60 m were obtained.
  • the resin was pulverized with a micro bantam mill AP-B type pulverizer manufactured by Hosokawa Micron Co., Ltd. to obtain a resin having an average particle size of 4 ( ⁇ 111.
  • Example 15 Evaluation was carried out in the same manner as in Example 15 except that a nonionic surfactant, a water-soluble polymer polybulal alcohol, and electrolyte electrolyte were not added.
  • Example 17 instead of acrylic latex, polyacetic acid latex (trade name “SH-502”, solid product concentration 51.45%, manufactured by Showa Polymer Co., Ltd.) 29.2 g (3% solid content relative to chlorinated resin) Parts by weight) and ion-exchanged water 449. lg were added, and the same operations as in Example 17 were performed and evaluated.
  • polyacetic acid latex trade name “SH-502”, solid product concentration 51.45%, manufactured by Showa Polymer Co., Ltd. 29.2 g (3% solid content relative to chlorinated resin) Parts by weight
  • ion-exchanged water 449. lg were added, and the same operations as in Example 17 were performed and evaluated.
  • Example 1 of Latex Production Example 22 polymerization was performed using styrene instead of methyl methacrylate. The conversion rate of the obtained latex was 99%. Latex solids The concentration was 39.6 wt%.
  • Example 17 Except for the addition of 38. lg of polystyrene latex obtained in Latex Production Example 3 instead of acrylic latex in Example 17 (3 parts by weight in solid content with respect to butyl chloride resin) and 440.2 g of ion-exchanged water. Were evaluated in the same manner as in Example 17.
  • PVA polyvinyl alcohol
  • 5: 0568 is JS "0568" CDB ⁇ .
  • PMM A stands for polymethylmethacrylate.
  • P B A stands for Polyacryno UK Petit.
  • SH502 is an abbreviation of Showa High School trade name “SH-502”.
  • the treatment concentration could be increased by adding a noionic surfactant, the impermeability evaluation was good, and the plastisol viscosity was excellent. That is, from the group consisting of (meth) acrylic acid ester homopolymers other than butyl chloride polymer, copolymers of (meth) acrylic acid ester and (meth) acrylic acid ester, and ethylene-butyl acetate copolymer When at least one selected emulsion polymerization latex was added, in addition to impermeability, the peelability was good and the plastisol viscosity was excellent.

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Abstract

L'invention concerne des particules agrégées contenant une résine de chlorure de vinyle, qui sont produites en ajoutant au moins un coagulant choisi parmi un polymère hydrosoluble et un sel inorganique, à un latex de résine de chlorure de vinyle présentant un diamètre particulaire moyen de ses particules primaires compris entre 0,1 et 2,0 μm, puis en faisant sécher le produit résultant. Les particules agrégées sont composées d'un agrégat des particules primaires, et présentent un diamètre particulaire moyen compris entre 5 et 40 μm. Il devient possible de fournir des particules agrégées de résine de chlorure de vinyle pour une pâte qui peut être utilisée en tant que matière première de plastisol non perméable par rapport à un tissu. L'invention concerne également un procédé destiné à produire les particules agrégées.
PCT/JP2007/069275 2006-10-03 2007-10-02 Particules agrégées contenant de la résine de chlorure de vinyle et procédé de production desdites particules agrégées WO2008041697A1 (fr)

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WO2012165021A1 (fr) * 2011-05-31 2012-12-06 株式会社カネカ Particules d'agrégats de résine de chlorure de vinyle, procédé pour leur préparation et gants les comprenant
US8895657B2 (en) 2010-09-17 2014-11-25 Kaneka Corporation Vinyl chloride resin aggregate particles, process for producing same, and glove obtained using same
JP2015108122A (ja) * 2013-10-25 2015-06-11 東ソー株式会社 塩化ビニルポリマーラテックス、ポリオール組成物及びその製造方法
KR20170032279A (ko) * 2014-07-18 2017-03-22 도소 가부시키가이샤 염화비닐 폴리머 라텍스, 폴리올 조성물 및 그 제조 방법
WO2019159896A1 (fr) * 2018-02-16 2019-08-22 株式会社カネカ Particules d'agrégat de résine de chlorure de vinyle, procédé de production associé, composition de revêtement pour boîte métallique, composition pour marquer un film, et film de revêtement
WO2023189509A1 (fr) * 2022-03-31 2023-10-05 日本ゼオン株式会社 Composition de résine de chlorure de vinyle, corps moulé en résine de chlorure de vinyle, et stratifié
WO2024204711A1 (fr) * 2023-03-30 2024-10-03 積水化成品工業株式会社 Particules de résine, procédé de production de particules de résine, matière thermofusible, matière de revêtement et composition de résine

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JPH1135873A (ja) * 1997-07-23 1999-02-09 Shindaiichi Enbi Kk ペースト加工用塩化ビニル系樹脂顆粒およびその製造方法
JP2004035850A (ja) * 2002-07-08 2004-02-05 Tosoh Corp 塩化ビニル系樹脂ラテックス用粒径制御剤、それを用いた塩化ビニル系樹脂ラテックスとペースト加工用塩化ビニル系樹脂の製造方法
WO2006092897A1 (fr) * 2005-02-28 2006-09-08 Kaneka Corporation Procédé de fabrication de particules de latex agrégées

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JPH1135873A (ja) * 1997-07-23 1999-02-09 Shindaiichi Enbi Kk ペースト加工用塩化ビニル系樹脂顆粒およびその製造方法
JP2004035850A (ja) * 2002-07-08 2004-02-05 Tosoh Corp 塩化ビニル系樹脂ラテックス用粒径制御剤、それを用いた塩化ビニル系樹脂ラテックスとペースト加工用塩化ビニル系樹脂の製造方法
WO2006092897A1 (fr) * 2005-02-28 2006-09-08 Kaneka Corporation Procédé de fabrication de particules de latex agrégées

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8895657B2 (en) 2010-09-17 2014-11-25 Kaneka Corporation Vinyl chloride resin aggregate particles, process for producing same, and glove obtained using same
JP5383952B2 (ja) * 2011-05-31 2014-01-08 株式会社カネカ 塩化ビニル系樹脂凝集体粒子、及びその製造方法とそれを用いた手袋
US8937113B2 (en) 2011-05-31 2015-01-20 Kaneka Corporation Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same
WO2012165021A1 (fr) * 2011-05-31 2012-12-06 株式会社カネカ Particules d'agrégats de résine de chlorure de vinyle, procédé pour leur préparation et gants les comprenant
JP2015108122A (ja) * 2013-10-25 2015-06-11 東ソー株式会社 塩化ビニルポリマーラテックス、ポリオール組成物及びその製造方法
KR102340165B1 (ko) * 2014-07-18 2021-12-15 도소 가부시키가이샤 염화비닐 폴리머 라텍스, 폴리올 조성물 및 그 제조 방법
KR20170032279A (ko) * 2014-07-18 2017-03-22 도소 가부시키가이샤 염화비닐 폴리머 라텍스, 폴리올 조성물 및 그 제조 방법
WO2019159896A1 (fr) * 2018-02-16 2019-08-22 株式会社カネカ Particules d'agrégat de résine de chlorure de vinyle, procédé de production associé, composition de revêtement pour boîte métallique, composition pour marquer un film, et film de revêtement
JPWO2019159896A1 (ja) * 2018-02-16 2021-02-12 株式会社カネカ 塩化ビニル系樹脂凝集体粒子、その製造方法、金属缶塗料用組成物、マーキングフィルム用組成物及び塗膜
JP7231604B2 (ja) 2018-02-16 2023-03-01 株式会社カネカ 塩化ビニル系樹脂凝集体粒子、その製造方法、金属缶塗料用組成物、マーキングフィルム用組成物及び塗膜
US11746249B2 (en) 2018-02-16 2023-09-05 Kaneka Corporation Polyvinyl chloride aggregate particles, method for producing the same, composition for metal can coating material, composition for marking film, and coating film
WO2023189509A1 (fr) * 2022-03-31 2023-10-05 日本ゼオン株式会社 Composition de résine de chlorure de vinyle, corps moulé en résine de chlorure de vinyle, et stratifié
WO2024204711A1 (fr) * 2023-03-30 2024-10-03 積水化成品工業株式会社 Particules de résine, procédé de production de particules de résine, matière thermofusible, matière de revêtement et composition de résine

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