CN101522814A - Aggregate particle comprising vinyl chloride resin and process for production thereof - Google Patents
Aggregate particle comprising vinyl chloride resin and process for production thereof Download PDFInfo
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- CN101522814A CN101522814A CNA2007800372106A CN200780037210A CN101522814A CN 101522814 A CN101522814 A CN 101522814A CN A2007800372106 A CNA2007800372106 A CN A2007800372106A CN 200780037210 A CN200780037210 A CN 200780037210A CN 101522814 A CN101522814 A CN 101522814A
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Abstract
Disclosed is an aggregate particle comprising a vinyl chloride resin, which is produced by adding at least one coagulant selected from a water-soluble polymer and an inorganic salt to a vinyl chlorideresin latex having an average particle diameter of its primary particles of 0.1 to 2.0 [mu]m and then drying the resulting product. The aggregate particle is composed of an aggregate of the primary p articles and has an average particle diameter of 5 to 40 [mu]m. It becomes possible to provide a vinyl chloride resin aggregate particle for a paste, which can be used as a raw material for a plastisol having non-permeability to a fabric. Also disclosed is a process for producing the aggregate particle.
Description
Technical field
The present invention relates to contain the aggregate particle and the manufacture method thereof of vinyl chloride resin.More specifically, relate to the cloth base is had no infiltrative paste processing with the aggregate particle and the manufacture method thereof that contain vinyl chloride resin.
Background technology
The physical strength of the thin slice that covers with vinyl chloride resin, gloves, sack etc. is big, and wearability, chemical reagent resistance, oil-proofness excellence are applied to water industry, agricultural, mining industry etc. than wide-range.
All the time, the product that go up to cover vinyl chloride resin at cloth base (fabric) is made by the following method: molten mass curtain coating on the cloth base of the vinyl chloride resin that will obtain with shaping such as rolling press, forcing machine, injector perhaps will be cooperated the plastisol that obtains to spray to be coated with or to be impregnated on the cloth base and make by softening agent such as vinyl chloride resin and dioctyl phthalate (DOP)s.In order to produce the thin product that is coated with vinyl chloride resin for example gloves, sack etc. automatically, use the spraying coating or the dipping method of plastisol more favourable at economic aspect than the method for curtain coating molten mass with high production speed.
When adopting spraying coating, dipping method, because plastisol is a heavy-gravity liquid, therefore if it is coated with on the cloth base, floods, then plastisol can be penetrated in the cloth base, infiltrate into the cloth base back side, under the situation to the plastisol heat treated, the gelation molten mass also can be penetrated into the cloth base back side sometimes.If plastisol or this molten mass are penetrated into the cloth base back side, then the flexibility of product can significantly descend, and diminishes product function.During especially for gloves, even partial infiltration also can bring uncomfortable feeling to the user, value of the product descends.
As preventing the method for plastisol to cloth base infiltration, proposed to the cloth base carry out pre-treatment method, improve the method for plastisol viscosity character, but all unsatisfactory.
The water-soluble polymer of interpolation is for example arranged and carry out spray-dired method (patent documentation 1), but add water-soluble polymer the viscosity of latex is risen, obstruction etc. takes place in spray-dired nozzle.
For example also useful spontaneous heating type high speed rotating mixing machine will stick with paste with vinyl chloride resin under 60～110 ℃, heat-treat, the method (patent documentation 2) of melt bonded, cohesion, but thermal treatment is inhomogeneous, can't improve the impermeability to the cloth base.
In addition, also proposed suspension polymer with vinyl chloride resin and carried out deep cooling and pulverize, regulate the resin size distribution, make particle have the method (patent documentation 3) of intensity to a certain degree, but impermeability is insufficient.
Patent documentation 1: the Japanese Patent spy opens clear 48-16946 communique
Patent documentation 2: the special public clear 46-7177 communique of Japanese Patent
Patent documentation 3: the special fair 2-40692 communique of Japanese Patent
Summary of the invention
The present invention does not have the aggregate particle that contain vinyl chloride resin (aggregate particle) and the manufacture method thereof of infiltrative paste processing with the vinyl chloride resin particle in order to solve above-mentioned existing issue, to provide and being applicable to the cloth base.
The aggregate particle that contains vinyl chloride resin of the present invention is characterised in that, it is to be to contain at least a kind of flocculation agent that is selected from water-soluble polymer and the inorganic salt and the aggregate particle that obtains through super-dry in the vinyl chloride resin latex of scope of 0.1～2.0 μ m by the median size at primary particle, above-mentioned aggregate particle is formed by above-mentioned primary particles aggregate, and the median size of above-mentioned aggregate particle is the scope of 5 μ m～40 μ m.
The manufacture method that contains the aggregate particle of vinyl chloride resin of the present invention is characterised in that, in the median size of primary particle is in the vinyl chloride resin latex of scope of 0.1～2.0 μ m, add at least a kind of flocculation agent that is selected from water-soluble polymer and the inorganic salt, make the above-mentioned mixed aqueous solution that contains the aggregate particle of vinyl chloride resin, above-mentioned mixed aqueous solution is carried out spraying drying, and obtaining median size is the aggregate particle of 5 μ m～40 μ m.
Description of drawings
Fig. 1 is the photo of 1000 times of the scanning electron microscopes (SEM) of the aggregate particle that obtains in the embodiments of the invention 1.
Fig. 2 is 10000 times the photo of the SEM of the aggregate particle that obtains in the embodiments of the invention 1.
Fig. 3 is the diagrammatic illustration figure of the manufacturing process of the example used of the present invention.
Fig. 4 is the diagrammatic illustration figure of the atomizer (second fluid nozzle) of the example used of the present invention.
Fig. 5 is the diagrammatic illustration figure of the atomizer (rotational circle disc type spraying gun) of the example used of the present invention.
Fig. 6 is the photo of 1000 times of the scanning electron microscopes (SEM) of the aggregate particle that obtains in the embodiments of the invention 11.
Fig. 7 is 10000 times the photo of the SEM of the aggregate particle that obtains in the embodiments of the invention 11.
Embodiment
The present invention can provide following does not have the infiltrative paste processing aggregate particle that contains vinyl chloride resin to the cloth base, the vinyl chloride resin of the scope that its median size that contains primary particle is 0.1～2.0 μ m and at least a kind of flocculation agent that is selected from water-soluble polymer and the inorganic salt, above-mentioned aggregate particle is formed by above-mentioned primary particles aggregate, and the median size of above-mentioned aggregate particle is the scope of 5～40 μ m.In addition, the present invention mixes before being about to spraying with water-soluble polymer and/or water-soluble ionogen by the latex with vinyl chloride resin and carries out spraying drying immediately, thereby can make efficiently the cloth base is not had infiltrative paste processing vinyl chloride resin particle.This method is suitable especially when producing in batches.
The present invention can also provide following does not have the infiltrative paste processing aggregate particle that contains vinyl chloride resin to the cloth base, it is to be to contain in the vinyl chloride resin latex of scope of 0.1～2.0 μ m to be selected from nonionic surfactant (A) by the median size at primary particle, at least a kind of composition in the emulsion polymerization latex except that vinyl chloride-base polymer (B), with be selected from least a kind of flocculation agent in water-soluble polymer and the inorganic salt and the aggregate particle that obtains through super-dry, above-mentioned aggregate particle is formed by above-mentioned primary particles aggregate, and the median size of above-mentioned aggregate particle is the scope of 5 μ m～40 μ m.
The aggregate particle that contains vinyl chloride resin of the present invention becomes does not have infiltrative paste processing vinyl chloride resin to the cloth base.This paste processing obtains by the following method with vinyl chloride resin: specific nonionic surfactant or the polymer particle except that vinyl chloride-base polymer are existed, make the ultimate particle cohesion of the vinyl chloride resin that obtains by little suspension or letex polymerization then with specific flocculation agent, thereby obtain having mobile aggregated particle, and, obtain sticking with paste the processing vinyl chloride resin thus by it is carried out spraying drying." cloth base " is meant that fabric, cloth, non-woven fabrics etc. have used the sheet-like article of fiber in addition, in this manual.
The vinyl chloride-based resin that uses among the present invention obtains by the following method: for vinyl chloride monomer or vinyl chloride monomer and can with the monomeric mixture of this vinyl chloride monomer copolymerization, after in aqueous medium, adding dispersion auxiliary agent such as emulsifying agent, the higher alcohols that adds as required, higher fatty acid and oil-soluble polymerization initiator and carrying out homogeneity, make said mixture carry out microsuspension, or add water soluble starter and carry out letex polymerization, seeded emulsion polymerization etc., obtain the vinyl chloride-based resin that the present invention uses thus.
About the median size of the primary particle of vinyl chloride resin of the present invention, be generally the even matter dispersion liquid (latex) of water-based of the particulate of 0.1～2.0 μ m, as long as but can reach purpose of the present invention, be not limited thereto scope.From the viewpoint of polymerization stability, be preferably 0.1 μ m～1.7 μ m, more preferably 0.1～1.4 μ m.
About vinyl chloride monomer and can with the monomer of this vinyl chloride monomer copolymerization, do not have particular restriction, can use olefines such as ethene, propylene, butylene; Vinyl esters such as vinyl-acetic ester, propionate, stearic acid vinyl ester; Vinyl ethers such as methylvinylether, ethyl vinyl ether, octyl group vinyl ether, lauryl vinyl ether; Vinylidene classes such as vinylidene chloride; Unsaturated carboxylic acid and acid anhydrides thereof such as vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, maleic anhydride, itaconic anhydride; Unsaturated carboxylate types such as methyl acrylate, ethyl propenoate, toxilic acid one methyl esters, dimethyl maleate, toxilic acid butyl benzyl ester; Aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, Vinylstyrene; Unsaturated nitriles such as vinyl cyanide; Cross-linkable monomers such as Phthalic acid, diallyl ester etc. can with all known monomers of chloroethylene copolymer.These monomeric consumptions preferably with the mixture of vinylchlorid in less than 50 weight %.
The emulsifying agent that uses in the polymerization does not have particular restriction, and adopting usually with respect to monomer 100 weight parts is aniorfic surfactant about 0.1～3 weight part.As aniorfic surfactant, can enumerate sylvite, sodium salt, ammonium salt of lipid acid, alkylsurfuric acid, alkyl benzene sulphonate (ABS), alkyl sulfo-succinic acid, alpha-olefin sulfonic acid, alkyl ether phosphate etc. etc.
As the oil-soluble initiator that uses in the polymerization; can use two lauroyl peroxides; two-3; 5; diacyl peroxide classes such as 5-trimethyl acetyl superoxide; di-isopropyl peroxydicarbonate; peroxy dicarbonates such as peroxy dicarbonate two-2-ethylhexyl; the peroxidation trimethylacetic acid tert-butyl ester; organic peroxide evocating agents and 2 such as peroxyesters such as new peroxide tert-butyl caprate; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two azo series initiators such as (4-methoxyl group-2,4-methyl pentane nitriles).As the water soluble starter that uses in the letex polymerization, adopt ammonium persulphate, Potassium Persulphate, Sodium Persulfate, aqueous hydrogen peroxide solution etc., as required, can and use reductive agents such as S-WAT, Sulfothiorine, sodium sulfoxylate formaldehyde dihydrate, xitix, sodium ascorbate.They can use separately or be used in combination more than 2 kinds.
The flocculation agent that uses among the present invention is at least a kind that is selected from water-soluble polymer and the inorganic salt (ionogen).That is the combination of water-soluble polymer, inorganic salt (ionogen) or water-soluble polymer and inorganic salt (ionogen).
As water-soluble polymer, synthetic macromolecule has: monomer (being total to) polymkeric substance [poly-(methyl) acrylamide, poly-(methyl) vinylformic acid (salt) and poly-(methyl) acrylate etc.], vinyl (being total to) polymkeric substance [polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinyl methyl ether, carboxylic vinyl (being total to) polymkeric substance (polyvinyl acetate etc.) and polystyrolsulfon acid (salt) etc.], poly-amidine, polyethylene oxide and the polymine etc. that contain acryl.As natural polymer, can enumerate polyose (starch, dextrin, glucomannan, polygalactomannan, gum arabic, xanthan gum, pectin, carrageenin, locust bean gum (Locust bean gum), guar gum, tragacanth, chitin, chitosan, pulullan polysaccharide and alginate etc.) and protein (gelatin, casein and collagen protein etc.) etc.As semi-synthetic polymer, can enumerate ether of cellulose (methylcellulose gum, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanoethyl cellulose, aminoethyl-cellulose, hydroxy-methyl cellulose, hydroxy ethyl cellulose, ethyl hydroxy ethyl cellulose, methyl hydroxy propyl cellulose, carboxymethyl cellulose and carboxyethyl cellulose etc.) and starch derivative (Zulkovsky starch, methyl starch and carboxymethyl starch etc.) etc.These water-soluble polymers can add separately, also can make up interpolation more than 2 kinds.
As the addition of water-soluble polymer, with respect to vinyl chloride resin 100 weight parts, be preferably 0.01 weight part～10 weight parts, more preferably 0.1 weight part～2 weight parts.When above-mentioned scope, can obtain not having the slurry that perviousness is higher, slurry viscosity remains on suitable scope and have flowability, the trafficability characteristic of liquor charging path and nozzle is good, can also carry out spraying drying well.
About ionogen, specifically can enumerate and to be dissociated into Na
+, K
+, Mg
2+, Ca
2+, Al
3+, H
+Deng or Cl
-, Br
-, SO
4 2-, SO
3 2-, NO
2 -, NO
3 -, PO
4 3-, CO
3 2-, OH
-Isoionic compound etc.Obtain above-mentioned electrolytical inorganic salt as being used to, can enumerate NaCl, KCl, Na
2SO
4, CaCl
2, AlCl
3Deng.About addition,, be preferably 0.1～10 weight part with respect to vinyl chloride resin 100 weight parts.0.3～3 weight part more preferably.If electrolytical addition is in above-mentioned scope, the aggregated particle that then is easy to get, no perviousness more preferably can also be carried out spraying drying well.
In the ionogen,, has Na from obtaining having the viewpoint of mobile slurry
+The sodium sulfate of 1 valence metal ion like this is preferred.Also can use the metal-salt of divalent, 3 valencys, but the stability of latex descends sometimes, should be noted that.
Flocculation agent is that water-soluble polymer and the interpolation form of ionogen in vinyl chloride resin latex can from the dispersive viewpoint, be preferably the form of the aqueous solution for the arbitrary form in solid, the aqueous solution, more preferably adds in the latex that stirs.The interpolation in latex about water-soluble polymer and ionogen preferably finishes the back interpolation at the letex polymerization back segment of vinyl chloride resin or in polymerization.The temperature of the latex when adding flocculation agent is selected to get final product in the scope that the viscosity of the mixed mixture of flocculation agent does not increase.
The present invention preferably also adds nonionic surfactant before adding flocculation agent.Nonionic surfactant helps to make efficiently aggregated particle.As nonionic surfactant, can enumerate polyoxyalkylene compounds, Voranol EP 2001, polyoxyethylene alkyl phenyl ether, sorbitan-fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerol mono fatty acid ester etc.
Under the situation of adding nonionic surfactant, preferably add before at the water-soluble polymer and the inorganic salt (ionogen) that add as flocculation agent the period of its interpolation.Like this, even slurry concentration also can keep its flowability up to more than the 35 weight %, thereby can carry out pump delivery.
The addition of nonionic surfactant is, is the scope of 0.01～1 weight part with respect to vinyl chloride resin 100 weight parts.Be preferably 0.05～0.5 weight part.0.15～0.35 weight part more preferably.If in above-mentioned scope, then the productivity of aggregated particle improves.
The emulsion polymerization latex except that vinyl chloride-base polymer that the present invention uses has the function as no perviousness rising agent.As the emulsion polymerization latex except that vinyl chloride-base polymer, can enumerate the multipolymer of (methyl) acrylate homopolymer, (methyl) acrylate and (methyl) acrylate and vinyl-vinyl acetate copolymer etc.
The addition of the emulsion polymerization latex except that vinyl chloride-base polymer is that with respect to vinyl chloride resin 100 weight parts, the polymkeric substance that contains is preferably the scope of 1～10 weight part.If in above-mentioned scope, then can further improve no perviousness effect to the cloth base.
The slurry of above-mentioned cohesion is preferably heat-treated.Melt bonded securely by the particle that thermal treatment is condensed, aggregated particle forms the easier no infiltrative structure that shows.Thermal treatment temp is more than the second-order transition temperature (about 80 ℃) (with reference to Polymer Handbook, 3rd edition, V/63 page or leaf and VI/222 page or leaf) of vinyl chloride-base polymer.Be preferably 95～150 ℃.More preferably 110～145 ℃.Heat treatment time is preferably 1～120 minute scope.5～30 minutes scope more preferably.
Slurry after above-mentioned thermal treatment can directly be used the spray-drier drying, obtains sticking with paste the processing vinyl chloride resin.
About the spray-drier that uses among the present invention,, adopt the spray-drier that possesses pressurized nozzles (a fluid nozzle), second fluid nozzle, rotational circle disc type (disc type) etc. as spraying gun (atomizer).
Drying is preferably carried out warm air drying under normal pressure.The temperature of the hot blast of supplying with is for sticking with paste the ordinary temp that uses in the drying with vinyl chloride resin, i.e. 100～220 ℃ scope, and the temperature that drying machine exports is generally 50～100 ℃ scope.Be preferably 20～180 seconds time of drying (drying machine residence time).
Median size about the spray dried particle that obtains by spraying drying, if adopt the nozzle-type drying machine, then can wait and regulate with feed rate, air supply amount, the solid component concentration of nozzle footpath, latex or slurry, if adopt rotary disc dryer, then can wait and regulate with feed rate, the solid component concentration of rotating speed, latex or the slurry of rotating-disk.The median size of the vinyl chloride resin particle that obtains by spraying drying is adjusted to the scope of 5～120 μ m usually.The median size of the spray dried particle that so obtains then can be directly as product (aggregate particle) if in the scope of 5～40 μ m.
The particle that spraying drying obtains also can be pulverized the back with known method and use.As pulverizer, can use roller mill, high speed rotating pulverizer, ball mill, jet mill.
If aggregate particle (below be also referred to as " resin particle ".) median size too small, then plastisol viscosity improves.On the other hand, if median size is excessive, then the coarse grain in the plastisol increases, and is accompanied by the passing of time, and coarse grain sedimentation, mixing are necessary.From then on viewpoint is set out, and the median size of resin particle is the scope of 5 μ m～40 μ m, is preferably the scope of 5 μ m～30 μ m.Having implemented under overground situation,, there is the tendency that can not get preferred result for no perviousness.
Vinyl chloride resin particle of the present invention preferably has the space of appropriateness in particle inside, minimum plasticising dosage is preferably more than 50 weight parts.
Mix with softening agent such as dioctyl phthalate (DOP), Octyl adipates with the vinyl chloride resin particle with the paste processing that obtains after the spray-drier drying, and then use weighting agent, whipping agent, stablizer, viscosity depressant, antioxidant, UV light absorber, fire retardant, antistatic agent, lubricant, pigment, surface treatment agent, thixotropic agent, cementability imparting agents etc. such as an amount of lime carbonate as required, with they mixing, mixing, obtain sticking with paste processing vinyl chloride resin composition (plastisol).
Usually, for coating on the cloth base or dipping plastisol and the thin slice that obtains, gloves, sack etc. in order to improve the flexibility of its product, are the so a large amount of use softening agent of 80～160 weight parts with respect to vinyl chloride resin 100 weight parts.The known plasticizers amount is many more, and is easy in more the infiltration of the cloth base back side, even but paste of the present invention is processed the softening agent of admixing high umber with the vinyl chloride resin particle, and also can be to the infiltration of the back side of cloth base.
Embodiment
Below, describe the present invention in detail with embodiment, but the invention is not restricted to these embodiment.In following embodiment, comparative example, " % ", " part " of simple record are represented " weight % ", " weight part " respectively.
(1) median size of primary particle, aggregate particle, spray particle
Use Microtrac HRA MODEL9320-X100 (Nikkiso Company Limited) to measure size distribution, with the median particle diameter of volume reference as median size.As condition determination, temperature is 25 ℃, and material information is transparent and specific refractory power is 1.51, does not detect spheroidal particle, and carrier adopts water, and specific refractory power is 1.33.In addition, SET ZERO 10 seconds detects 10 seconds, does not calculate DRY CUT.
(2) no perviousness evaluation
With respect to sticking with paste processing vinyl chloride resin particle 100 weight parts, cooperate 140 weight part softening agent (dioctyl phthalate (DOP)), 3 weight part stablizers (rising sun electrification Co., Ltd. system trade(brand)name " SC73 "), at room temperature, obtain plastisol with Ishikawa formula masher mixing deaeration 10 minutes.About test, at cloth (two-sided 2 sections double rib circular knits), the 24 pin numbers of No. 29.5 (cotton numbers) that used the kapok line, 1 inch 37 hole, weight per unit area 216g/m to the infiltration of cloth base
2Cloth under room temperature, be coated with above-mentioned plastisol with about 3mm thickness curtain coating, place 180 ℃ recirculation furnace immediately, heat treated 3 minutes, carry out the gel fusion after, observe molten mass and have or not the gelation fusion permeability test that is penetrated into the cloth base back side.
Evaluation is undertaken by following Three Estate: naked eyes are not seen the be A of gel infiltration to the dorsal part of cloth, and slightly that infiltration is B, and gel infiltration is C to the dorsal part of cloth.
(3) separability evaluation
The gelation thing that obtains the sample of A evaluation in above-mentioned (2) is peeled off from cloth, judged by following benchmark.In addition, measuring area is 4cm
2(square of each 2cm of length and width).
AA: the gelation thing of residual not enough 0.03g on cloth.
A: the gelation thing more than residual 0.03g on the cloth
(4) plastisol viscosimetric analysis
Plastisol flooded 1 hour in 25 ℃ Water Tank with Temp.-controlled after, with Brookfield type viscometer (TOKIMEK system), the mensuration that reads N0.3 Rotor V 12 begins the value after 1 minute, as plastisol viscosity.
(embodiment 1)
Vinyl chloride monomer 110Kg, ion exchanged water 110Kg, ammonium persulphate 40g, copper sulfate pentahydrate 0.3g pack in 300 liters of pressure vessels of strap clamp cover, be warming up to 50 ℃, under agitation append sodium sulfite aqueous solution and the 10 weight % tetradecanoic acid aqueous ammoniums of 1 weight % continuously, carry out polymerization.Be polymerized to polymerization pressure from initial stage pressure (0.7MPa) 0.15MPa that descended, reclaim residual monomer then, obtain vinyl chloride resin latex.The latex that finally obtains is 90% with respect to initial stage charging monomer and the polymerisation conversion that appends monomeric total amount (below be designated as the total monomer amount).The median size of the primary particle of the latex that obtains in addition, is 0.35 μ m.
In polymeric latex, add ion exchanged water so that the solid component concentration of vinyl chloride resin is 30 weight %.The temperature of the mixture of this moment is 60 ℃.Then, in vinyl chloride resin, add sodium sulfate 1 weight part with the form of the 10 weight % aqueous solution, add polyvinyl alcohol (Japanese synthetic chemistry Co., Ltd. system trade(brand)name " GOHSENOL KH-17 ": saponification value is about 80mol%) 0.5 weight part with the form of the 3 weight % aqueous solution then.Obtain the aggregated particle that median size is 20 μ m (relevant) thus with the latex before flocculation agent adds back, drying, with second fluid nozzle formula spray-drier shown in Figure 3, that the latex behind this interpolation flocculation agent is dry under the condition of 180 ℃ of the warm braw temperature ins of supplying with, 71 ℃ of temperature outs.The drying machine residence time is 100 seconds.The aggregate particle that contains the vinyl chloride resin particle that obtains is (relevant with the dried resin of latex.In addition, when being defined as aggregate particle, irrelevant with drying means) median size be 6 μ m.
The photo that the scanning electron microscope of the aggregate particle that obtains (SEM) is 1000 times as shown in Figure 1.Aggregate particle is an amorphous particle.Fig. 2 is a SEM10000 photo doubly.Susceptible of proof is an aggregate particle.Primary particle (ultimate particle) is independently of one another, and is not melt bonded.
About having the evaluation of mobile latex, at room temperature measure the viscosity of latex after flocculation agent adds.Table 1 shows viscosity, the dry particle diameter of the mixture after interpolation umber, the flocculation agent of flocculation agent add, table 2 show permeability test result, viscosity through the time change.
(embodiment 2)
Except using methylcellulose gum (the Metolose SM-400 of Shin-Etsu Chemial Co., Ltd), carry out with embodiment 1 identical operations and estimate as the water-soluble polymer.
(embodiment 3)
Except not adding sodium sulfate, carry out with embodiment 1 identical operations and estimate.
(embodiment 4)
Vinyl chloride monomer 110Kg, ion exchanged water 110Kg, Sodium Lauryl Sulphate BP/USP 20g, ammonium persulphate 40g, copper sulfate pentahydrate 0.3g pack in 300 liters of pressure vessels of strap clamp cover, be warming up to 50 ℃, under agitation append the sodium sulfite aqueous solution of 1 weight % and the tetradecanoic acid aqueous ammonium of 10 weight % continuously, carry out polymerization.Be polymerized to polymerization pressure from initial stage pressure (0.7MPa) 0.15MPa that descended, reclaim residual monomer then, obtain vinyl chloride resin latex.The latex that finally obtains is 90 weight % with respect to initial stage charging monomer and the polymerisation conversion that appends monomeric total amount (below be designated as the total monomer amount).The median size of the primary particle of the latex that obtains in addition, is 0.15 μ m.
In polymeric latex, add ion exchanged water so that the solid component concentration of vinyl chloride resin is 30 weight %.The temperature of the mixture of this moment is 60 ℃.Then, in vinyl chloride resin, form with the aqueous solution of 10 weight % is added sodium sulfate 1 weight part, adds polyvinyl alcohol (Japanese synthetic chemistry Co., Ltd. system trade(brand)name " GOHSENOL KH-17 ": saponification value is about 80mol%) 0.5 weight part with the form of the aqueous solution of 3 weight % then.Obtain the aggregated particle that median size is 20 μ m thus, with second fluid nozzle formula spray-drier shown in Figure 3, that the latex behind this interpolation flocculation agent is dry under the condition of 180 ℃ of the warm braw temperature ins of supplying with, 71 ℃ of temperature outs.The median size of the aggregate particle that contains the vinyl chloride resin particle that obtains is 20 μ m.
(embodiment 5)
Except replacing second fluid nozzle, changing the spray particle diameter, carry out with embodiment 1 identical operations and estimate.
(embodiment 6)
The resin particle that obtains in the comparative example 4 is pulverized with Bantam mill.The median size of the vinyl chloride resin particle that obtains is 10 μ m.
(embodiment 7)
Except not adding the water-soluble polymer polyvinyl alcohol, carry out with embodiment 1 identical operations and estimate.
(embodiment 8)
Except spraying plant being replaced with rotating-disk, carry out with embodiment 1 identical operations and estimate.The plastisol of preparation was taken care of one day the result down at 25 ℃: in the bottom of container, coarse grain separates, sedimentation.If but it is in the rank of mixing then can re-use.
(embodiment 9)
Except spraying plant being replaced with rotating-disk, implement and embodiment 1 identical operations, obtain the drying particulate that median size is 30 μ m.It is pulverized with MicoBantam mill AP-B, and obtaining median size is the vinyl chloride resin particle of 15 μ m, and it is estimated.
(embodiment 10)
Except the rotating speed that changes rotating-disk, implement and embodiment 9 identical operations, obtain the drying particulate that median size is 100 μ m.It is pulverized with MicroBantam mill AP-B, and obtaining median size is the vinyl chloride resin particle of 25 μ m, and it is estimated.
(comparative example 1)
Except the polyvinyl alcohol that do not add water-soluble polymer, as the electrolytical saltcake, carry out with embodiment 1 identical operations and estimate.
(comparative example 2)
The resin particle that obtains among the embodiment 6 is pulverized with airflow milling.But the particle that obtains is meticulous, and no perviousness evaluation is poor.
(comparative example 3)
In the latex of the vinyl chloride resin that polymerization in embodiment 1 obtains, add Tai-Ace S 150 1 weight part, add 0.5 weight account polyethylene alcohol then.Latex integral body is solidified, and can't offer spray-drier, can't obtain sample by spraying drying.
(comparative example 4)
Except the rotating speed that reduces spraying plant, carry out with embodiment 8 identical operations and estimate.The plastisol of preparation was taken care of one day the result down at 25 ℃: in the bottom of container, a large amount of coarse grain separate sedimentation.In addition, it is as shown in the table is the C level for no perviousness.
Table 1
Remarks 1:PVA is the abbreviation of polyvinyl alcohol.
Table 2
As show shown in the 1-2, for embodiments of the invention 1～10, its no perviousness is estimated high, and the plastisol viscosity characteristics is also high.
(embodiment 11)
Vinyl chloride monomer 110Kg, ion exchanged water 110Kg, ammonium persulphate 40g, copper sulfate pentahydrate 0.3g pack in 300 liters of pressure vessels of strap clamp cover, be warming up to 50 ℃, under agitation append 1wt% sodium sulfite aqueous solution and 10wt% tetradecanoic acid aqueous ammonium continuously, carry out polymerization.Be polymerized to polymerization pressure from initial stage pressure (0.7MPa) 0.15MPa that descended, reclaim residual monomer then, obtain vinyl chloride resin latex.The latex that finally obtains is 90wt% with respect to initial stage charging monomer and the polymerisation conversion that appends monomeric total amount (below be designated as the total monomer amount).The median size of the primary particle of the latex that obtains in addition, is 0.35 μ m.The solid component concentration of latex is 46wt%.
Then, in this latex,, the sodium sulfate of 1 weight part is added with the form of the 10wt% aqueous solution with respect to vinyl chloride resin 100 weight parts.
Then, the 3wt% aqueous solution of preparation polyvinyl alcohol (Japanese synthetic chemistry Co., Ltd. system: GOHSENOL KH-17: saponification value is about 80mol%).
To the spray-drier of the two fluid-type spray nozzles that two-pack mixed type shown in Figure 4 has been installed (ASTMAX of Co., Ltd. system, CNW200) (the warm braw temperature in of supply is that 180 ℃, temperature out are 71 ℃ condition), feed speed with 54kg/ hour (47 liters/hour) provides fluid (latex and aqueous electrolyte liquid) 31, supply with the water-soluble polymer aqueous solution 33 with 3.6kg/ hour feed speed, making the residence time in the second fluid nozzle is below 0.15 second.Particle spray-drier drying from the ejection of two fluid-type spray nozzles.The median size of the vinyl chloride resin particle that obtains is 65 μ m.
Primary particle is illustrated in figure 6 as amorphous.The figure that Fig. 7 improves for multiple, ultimate particle is independently of one another, and is not melt bonded.Fig. 6 is the photo of 1000 times of the scanning electron microscopes (SEM) of the aggregate particle that obtains of present embodiment, and Fig. 7 is 10000 times the photo of the SEM of the aggregate particle that obtains of present embodiment.
The resin particle that obtains is pulverized with the ホ ソ カ ワ シ Network ロ Application system MicroBantam millAP-B of Co., Ltd. type pulverizer.The median size of the resin particle that obtains is 10 μ m.
Dry particle diameter, powder particle diameter, no perviousness evaluation result are shown in Table 3.
(embodiment 12)
Except using methylcellulose gum (the Metolose SM-400 of Shin-Etsu Chemial Co., Ltd), carry out with embodiment 11 identical operations and estimate as the water-soluble polymer.
(embodiment 13)
Except not adding sodium sulfate, carry out with embodiment 11 identical operations and estimate.
(embodiment 14)
Except spraying gun is replaced with rotational circle disc type shown in Figure 4, use the method identical to obtain the dry resin particle with embodiment 11.Disk diameter is 84mm, and rotating speed is 15000rpm, and the feed speed of fluid (latex and aqueous electrolyte liquid) 31 is 54kg/ hour (47 liters/hour), and the feed speed of the water-soluble polymer aqueous solution 33 is 3.6kg/ hour.Two liquid are below 1 second in the residence time on the rotating-disk.The median size of the vinyl chloride resin particle that obtains is 60 μ m.It is pulverized with the ホ ソ カ ワ シ Network ロ Application system MicroBantam mill AP-B of Co., Ltd. type pulverizer.The median size of the resin particle that obtains is 8 μ m.
(comparative example 5)
Add 1 part of sodium sulfate, 0.5 part of PVA in latex, adding each aqueous solution, to make mixed resin solid constituent concentration be 40wt%, and mix, and becomes " bean dregs " shape (difficult mobile state) rapidly, can not deliver to spraying gun.Can confirm: when producing in batches, must be before being about to spraying with the aqueous solution of above-mentioned each composition.
(reference example 1)
Add 1 part of sodium sulfate, 0.5 part of PVA in latex, adding each aqueous solution, to make mixed resin solid constituent concentration be 20wt%, and mix, and obtains having mobile slurry.Its drying machine with embodiment 14 is handled, pulverized, obtain the resin particle that median size is 7 μ m.This particle demonstrates good no perviousness.
As mentioned above; according to embodiments of the invention; latex by the vinyl chloride resin that will be obtained by letex polymerization etc. or the solution that has dissolved inorganic salt in advance therein mix continuously with the water-soluble polymer aqueous solution; before losing flowability, mixture carries out micronize with spraying gun; spraying drying, pulverizing can obtain embodying the cloth base not had infiltrative plastisol.
(embodiment 15)
Vinyl chloride monomer 110Kg, ion exchanged water 110Kg, ammonium persulphate 40g, copper sulfate pentahydrate 0.3g pack in 300 liters of pressure vessels of strap clamp cover, be warming up to 50 ℃, under agitation append the sodium sulfite aqueous solution of 1 weight % and the tetradecanoic acid aqueous ammonium of 10 weight % continuously, carry out polymerization.Be polymerized to polymerization pressure from initial stage pressure (0.7MPa) 0.15MPa that descended, reclaim residual monomer then, obtain vinyl chloride resin latex.The latex that finally obtains is 90% with respect to initial stage charging monomer and the polymerisation conversion that appends monomeric total amount (below be designated as the total monomer amount).The median size of the primary particle of the latex that obtains in addition, is 0.35 μ m.The solid component concentration of latex is 46.4wt%.
In the 3L stainless steel vessel, gather the above-mentioned latex that obtains of 1077.6g (counting 500g) with solids component.Under agitation, add 1g (is 0.2 weight part with respect to vinyl chloride resin) nonionic surfactant (NOF Corp's system trade(brand)name " プ ロ ノ Application 102 ").Further add the 46.6g ion exchanged water.The temperature of the mixture of this moment is 30 ℃.Then, with respect to vinyl chloride resin, the sodium sulfate of 1 weight part is added 50g with the form of the 10 weight % aqueous solution, then with the form interpolation 83.3g of 0.5 weight account polyethylene alcohol (Japanese synthetic chemistry Co., Ltd. system trade(brand)name " GOHSENOL KH-17 ": saponification value be about 80mol%) with the 3 weight % aqueous solution.Then, continue to stir 5 minutes, obtain slurry.The solid component concentration that obtains vinyl chloride resin thus is that 40 weight %, median size are the aggregated particle (relevant with the latex before flocculation agent adds back, drying) of 20 μ m, with second fluid nozzle formula spray-drier, that the latex behind this interpolation flocculation agent is dry under the condition of 180 ℃ of the warm braw temperature ins of supplying with, 81 ℃ of temperature outs.The drying machine residence time is 100 seconds.The aggregate particle that contains the vinyl chloride resin particle that obtains is (relevant with the dried resin of latex.In addition, when being defined as aggregate particle, irrelevant with drying means) median size be 6 μ m.
(embodiment 16)
Except adding 1.5g (is 0.3 weight part with respect to vinyl chloride resin) nonionic surfactant (NOF Corp's system trade(brand)name " プ ロ ノ Application 102 "), carry out with embodiment 15 identical operations and estimate.
(embodiment 17)
In the 3L stainless steel vessel, gather the polyvinylchloride latex that obtains among the embodiment 15 of 1077.6g (counting 500g) with solids component.Under agitation, add the acrylic acid series latex (JSR Corp.'s system trade(brand)name " AE945H " solid component concentration 51.75%) of 29.0g (counting 3 weight parts by solids component) with respect to vinyl chloride resin.Further add the 435.3g ion exchanged water.The temperature of the mixture of this moment is 30 ℃.Then, with respect to vinyl chloride resin, the sodium sulfate of 1 weight part is added 50g with the form of the 10 weight % aqueous solution, with the form interpolation 83.3g of the polyvinyl alcohol of 0.5 weight part (Japanese synthetic chemistry Co., Ltd. system trade(brand)name " GOHSENOL KH-17 ": saponification value be about 80mol%) with the 3 weight % aqueous solution.Then, continue to stir 5 minutes, obtain slurry.The solid component concentration that obtains vinyl chloride resin thus is that 30 weight %, median size are the aggregated particle (relevant with the latex before flocculation agent adds back, drying) of 25 μ m.Estimate similarly to Example 15.
(embodiment 18)
Add 14.5g (counting 1.5 weight parts by solids component) acrylic acid series latex (JSR Corp.'s system trade(brand)name " AE945H " solid component concentration 51.75%) with respect to vinyl chloride resin.Add the 456.3g ion exchanged water, carry out operation similarly to Example 17 in addition and estimate.
(embodiment 19)
Add 58g (counting 6 weight parts by solids component) acrylic acid series latex (JSR Corp.'s system trade(brand)name " AE945H " solid component concentration 51.75%) with respect to vinyl chloride resin.Add the 435.3g ion exchanged water, carry out operation similarly to Example 17 in addition and estimate.
(embodiment 20)
Except adding 26.5g (counting 3 weight parts by solids component) vinyl-vinyl acetate copolymer latex (Showa Highpolymer Co., Ltd's system trade(brand)name " AD-10 " solid component concentration 56.52%), 451.7g ion exchanged water, carry out operation similarly to Example 17 and estimate with respect to vinyl chloride resin.
(embodiment 21)
Add 29.4g (counting 3 weight parts by solids component) acrylic acid series latex (JSR Corp.'s system trade(brand)name " 0568 " solid component concentration 51.0%) with respect to vinyl chloride resin.Add the 448.8g ion exchanged water, carry out operation similarly to Example 17 in addition and estimate.
(embodiment 22)
(1) the latex Production Example 1
The 2500g ion exchanged water of in the detachable flask of 8L, packing into.Gas phase portion is stirred with beginning after the nitrogen displacement, add 20g Sodium dodecylbenzene sulfonate, 200g methyl methacrylate, temperature is 70 ℃ in making.Append 2% persulfate aqueous solution 500g, the beginning polymerization.After 5 minutes, spend 3 hours and add vinylbenzene 1800g, repolymerization 1 hour.The transformation efficiency of the latex that obtains is 99%.The solid component concentration of latex is 39.4wt%.
(2) manufacturing of aggregated particle and evaluation
Latex 37.7g (counting 3 weight parts by solids component), the ion exchanged water 440.6g that in adding latex Production Example 1, obtains, carry out operation similarly to Example 17 and estimate with respect to vinyl chloride resin.
(embodiment 23)
(1) the latex Production Example 2
Carry out polymerization with the methyl methacrylate in the latex Production Example 1 of butyl acrylate replacement embodiment 22.The transformation efficiency of the latex that obtains is 99.5%.The solid component concentration of latex is 39.8wt%.
(2) manufacturing of aggregated particle and evaluation
Latex 37.9g (counting 3 weight parts by solids component), the ion exchanged water 440.4g that in adding latex Production Example 2, obtains, carry out operation similarly to Example 17 and estimate with respect to vinyl chloride resin.
(embodiment 24)
The cohesion latex of the concentration 40% that obtains among the embodiment 15 is packed in the 3L pressure vessel of being with stirrer, under agitation, is blown into steam and is warming up to 120 ℃, keep 120 ℃ 5 minutes.After the cooling, take out latex, carry out drying, evaluation similarly to Example 15.Confirm with scanning electron microscope (SEM, 1000 times): resulting aggregated particle is melt bonded.
(embodiment 25)
Except the temperature among the embodiment 24 is set at 140 ℃, carry out operation similarly to Example 24, and estimate.Confirm with SEM (1000 times): resulting aggregated particle is melt bonded.
(embodiment 26)
Second fluid nozzle among the embodiment 15 is changed into rotating-disk and changes spray particle diameter, obtain the drying particulate that median size is 60 μ m.Pulverize with the system MicroBantammill AP-B of ホ ソ カ ワ シ Network ロ Application Co., Ltd. type pulverizer, obtain the resin that median size is 40 μ m.In addition, carry out operation similarly to Example 15, and estimate.
(comparative example 6)
Except do not add nonionic surfactant, as the polyvinyl alcohol of water-soluble polymer, as the electrolytical saltcake, carry out operation similarly to Example 15, and estimate.
(comparative example 7)
In the latex of the vinyl chloride resin that polymerization in embodiment 15 obtains, add Tai-Ace S 150 1 weight part, add polyvinyl alcohol 0.5 weight part then.Latex integral body is solidified, and can't offer spray-drier, can't obtain sample by spraying drying.
(comparative example 8)
Replace the acrylic acid series latex of embodiment 17 and add the 449.1g ion exchanged water except adding 29.2g (counting 3 weight parts by solids component) poly latex (Showa Highpolymer Co., Ltd's system trade(brand)name " SH-502 " solid component concentration 51.45%), carry out operation similarly to Example 17 and estimate with respect to vinyl chloride resin.
(comparative example 9)
(1) the latex Production Example 3
Carry out polymerization with the methyl methacrylate in the latex Production Example 1 of vinylbenzene replacement embodiment 22.The transformation efficiency of the latex that obtains is 99%.The solid component concentration of latex is 39.6wt%.
(2) manufacturing of aggregated particle and evaluation
Replace acrylic acid series latex among the embodiment 17 except adding the polystyrene latex 38.1g (counting 3 weight parts by solids component) that obtains in the latex Production Example 3 with respect to vinyl chloride resin, and add beyond the ion exchanged water 440.2g, carry out operation similarly to Example 17 and estimate.
Above condition and the results are shown in table 4.
As shown in table 4, according to embodiments of the invention,, then can improve concentration of treatment if add nonionic surfactant, no perviousness evaluation is good, and plastisol viscosity is also excellent.Promptly, when interpolation is selected from the multipolymer of (methyl) acrylate homopolymer except that vinyl chloride-base polymer, (methyl) acrylate and (methyl) acrylate and the vinyl-vinyl acetate copolymer at least a kind emulsion polymerization latex, except that no perviousness, separability is also good, and plastisol viscosity is also excellent.
Claims (20)
1, a kind of aggregate particle that contains vinyl chloride resin, it is characterized in that, it is to be to contain at least a kind of flocculation agent that is selected from water-soluble polymer and the inorganic salt and the aggregate particle that obtains through super-dry in the vinyl chloride resin latex of scope of 0.1～2.0 μ m by the median size at primary particle
Described aggregate particle is formed by described primary particles aggregate, and the median size of described aggregate particle is the scope of 5 μ m～40 μ m.
2, the aggregate particle that contains vinyl chloride resin as claimed in claim 1; wherein, described water-soluble polymer is to be selected from least a kind that contains in acryl monomer (being total to) polymkeric substance, vinyl (being total to) polymkeric substance, poly-amidine, polyethylene oxide and polymine, polyose, protein, ether of cellulose and the starch derivative.
3, the aggregate particle that contains vinyl chloride resin as claimed in claim 1 or 2, wherein, the content of described water-soluble polymer is: with respect to vinyl chloride resin 100 weight parts is the scope of 0.01～10 weight part.
4, the aggregate particle that contains vinyl chloride resin as claimed in claim 1, wherein, described inorganic salt are ionogen.
5, as claim 1 or the 4 described aggregate particles that contain vinyl chloride resin, wherein, described inorganic salt are to be selected from NaCl, KCl, Na
2SO
4, CaCl
2And AlCl
3In at least a kind.
6, as claim 1, the 4 or 5 described aggregate particles that contain vinyl chloride resin, wherein, the addition of described inorganic salt is: with respect to vinyl chloride resin 100 weight parts is the scope of 0.1～10 weight part.
7, as each described aggregate particle that contains vinyl chloride resin in the claim 1～6, wherein, in described aggregate particle, also add at least a kind that is selected from nonionic surfactant (A) and the emulsion polymerization latex except that vinyl chloride-base polymer (B).
8, the aggregate particle that contains vinyl chloride resin as claimed in claim 7, wherein, described nonionic surfactant (A) is at least a kind that is selected from polyoxyalkylene compounds, Voranol EP 2001, polyoxyethylene alkyl phenyl ether, sorbitan-fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester and the glycerol mono fatty acid ester.
9, as claim 7 or the 8 described aggregate particles that contain vinyl chloride resin, the content of described nonionic surfactant (A) is: with respect to vinyl chloride resin 100 weight parts is the scope of 0.05～1 weight part.
10, the aggregate particle that contains vinyl chloride resin as claimed in claim 7, wherein, described emulsion polymerization latex (B) except that vinyl chloride-base polymer is at least a kind that is selected from the multipolymer of (methyl) acrylate homopolymer, (methyl) acrylate and (methyl) acrylate and the vinyl-vinyl acetate copolymer.
11, as claim 7 or the 10 described aggregate particles that contain vinyl chloride resin, wherein, the content of described emulsion polymerization latex (B) is: with respect to vinyl chloride resin 100 weight parts is the scope of 1～10 weight part.
12, as each described aggregate particle that contains vinyl chloride resin in the claim 1～11, wherein, described aggregate particle takes place melt bonded.
13, a kind of manufacture method that contains the aggregate particle of vinyl chloride resin, it is characterized in that, in the median size of primary particle is in the vinyl chloride resin latex of scope of 0.1～2.0 μ m, add at least a kind of flocculation agent that is selected from water-soluble polymer and the inorganic salt, make the described mixed aqueous solution that contains the aggregate particle of vinyl chloride resin, by described mixed aqueous solution is carried out spraying drying, obtaining median size is the aggregate particle of 5 μ m～40 μ m.
14, the manufacture method that contains the aggregate particle of vinyl chloride resin as claimed in claim 13, wherein, before adding described flocculation agent, also add at least a kind that is selected from nonionic surfactant (A) and the emulsion polymerization latex except that vinyl chloride-base polymer (B).
15, the manufacture method of vinyl chloride resin particle as claimed in claim 13; wherein; described mixing, spray-dired method are with vinyl chloride resin latex and the aqueous solution that contains water-soluble polymer before mixture loses flowability; carry out micronize with spraying gun, and carry out spray-dired method.
16, the manufacture method of vinyl chloride resin particle as claimed in claim 15, wherein, described spraying gun is mixture to be sprayed carry out micronized device from rotator or injection nozzle.
17, the manufacture method of vinyl chloride resin particle as claimed in claim 13, wherein, with described vinyl chloride resin latex with contain the aqueous solution of water-soluble polymer before, in advance with the aqueous solution of vinyl chloride resin latex and inorganic salt.
18, the manufacture method that contains the aggregate particle of vinyl chloride resin as claimed in claim 13, wherein, by more than the second-order transition temperature of vinyl chloride-base polymer, the described mixed aqueous solution that contains the aggregate particle of vinyl chloride resin being heat-treated, make described aggregate particle melt bonded.
19, as the manufacture method of each described vinyl chloride resin particle in the claim 13～18, wherein, the vinyl chloride resin particle after the described spraying drying is pulverized.
20, the manufacture method of vinyl chloride resin particle as claimed in claim 19, wherein, the median size of the resin particle after the described pulverizing is 5～30 μ m.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP272174/2006 | 2006-10-03 | ||
| JP2006272174 | 2006-10-03 | ||
| JP082650/2007 | 2007-03-27 | ||
| JP245428/2007 | 2007-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101522814A true CN101522814A (en) | 2009-09-02 |
Family
ID=41082408
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800372106A Pending CN101522814A (en) | 2006-10-03 | 2007-10-02 | Aggregate particle comprising vinyl chloride resin and process for production thereof |
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| CN (1) | CN101522814A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103119089A (en) * | 2010-09-17 | 2013-05-22 | 株式会社钟化 | Vinyl chloride resin aggregate particles, process for producing same, and glove obtained using same |
| CN103562232A (en) * | 2011-05-31 | 2014-02-05 | 株式会社钟化 | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| CN111741984A (en) * | 2018-02-16 | 2020-10-02 | 株式会社钟化 | Vinyl chloride resin aggregate particles, method for producing same, composition for metal can coating, composition for marking film, and coating film |
-
2007
- 2007-10-02 CN CNA2007800372106A patent/CN101522814A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103119089A (en) * | 2010-09-17 | 2013-05-22 | 株式会社钟化 | Vinyl chloride resin aggregate particles, process for producing same, and glove obtained using same |
| CN103119089B (en) * | 2010-09-17 | 2014-07-23 | 株式会社钟化 | Vinyl chloride resin aggregate particles, process for producing same, and glove obtained using same |
| CN103562232A (en) * | 2011-05-31 | 2014-02-05 | 株式会社钟化 | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| TWI464185B (en) * | 2011-05-31 | 2014-12-11 | Kaneka Corp | Vinyl chloride resin agglomerated particles, a method for producing the same, and a glove using the same |
| CN104277143A (en) * | 2011-05-31 | 2015-01-14 | 株式会社钟化 | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| CN103562232B (en) * | 2011-05-31 | 2015-04-01 | 株式会社钟化 | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| CN104277143B (en) * | 2011-05-31 | 2017-04-12 | 株式会社钟化 | Vinyl chloride resin aggregate particle, method for producing same, and gloves comprising same |
| CN111741984A (en) * | 2018-02-16 | 2020-10-02 | 株式会社钟化 | Vinyl chloride resin aggregate particles, method for producing same, composition for metal can coating, composition for marking film, and coating film |
| CN111741984B (en) * | 2018-02-16 | 2022-12-27 | 株式会社钟化 | Vinyl chloride resin aggregate particles, method for producing same, composition for metal can coating, composition for marking film, and coating film |
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