WO2008041697A1 - Aggregate particle comprising vinyl chloride resin and process for production thereof - Google Patents

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 chloride resin latex having an average particle diameter of its primary particles of 0.1 to 2.0 μm and then drying the resulting product. The aggregate particle is composed of an aggregate of the primary particles and has an average particle diameter of 5 to 40 μm. 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

 Specification

 Aggregate particles containing chlorinated resin and method for producing the same

 Technical field

 TECHNICAL FIELD [0001] 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.

 Background art

 [0002] 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.

 [0003] Conventionally, products in which a cloth is coated with a chlorinated resin are cast on a cloth with a molten chlorinated resin molded by a calendar, an extruder, an injection machine, or the like, or the chlorinated resin is dioctylphthalate. It is manufactured by dipping a plastisol blended with a plasticizer such as an acid into a fabric by spray coating. In order to automatically produce products coated with thin-walled chlorinated resin, such as gloves, bags, etc., at a high production rate, spray coating using plastisol or dipping method is more effective than casting melt. Economically advantageous.

 [0004] In the case of spray coating and dipping methods, 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.

 [0005] As a method for preventing the penetration of plastisol into the fabric, a method of pretreating the fabric and a method of improving the viscosity property of the plastisol have been proposed, but both are insufficient.

[0006] 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.

 [0007] 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.

[0008] Further, a method (Patent Document 3) has been proposed 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

 Disclosure of the invention

 [0009] In order to solve the above-mentioned conventional problems, 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. .

 [0010] 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.

 [0011] 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. By adding at least one aggregating agent selected from the group consisting of force and agglomerated particles of the above-mentioned chlorinated vinyl resin, 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.

 Brief Description of Drawings

 FIG. 1 is a scanning electron microscope (SEM) 1000 × photograph of the aggregate particles obtained in Example 1 of the present invention.

[Figure 2] 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] 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.

M) The picture is 1000 times larger.

 [Fig. 7] Fig. 7 is a photograph 10,000 times larger than the SEM.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0013] 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 μm to 40 μm. 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.

 [0014] Further, 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.

[0015] Aggregate particles containing the butyl chloride resin of the present invention become a chlorinated resin for paste processing that is impermeable to the fabric. In addition, 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. Exist and Is then agglomerated with a specific aggregating agent to obtain fluidized agglomerated particles, which are obtained by spray drying. In this specification, “fabric” refers to a sheet-like material using fibers such as woven fabric, knitted fabric, and non-woven fabric.

 [0016] 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. By adding a dispersion aid such as higher alcohol and higher fatty acid, and further adding 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.

 [0017] 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. Μm, 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.

 [0018] 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, α-methylstyrene All known monomers that can be copolymerized with butyl chloride, such as aromatic bur compounds such as ethylene and dibutene benzene, unsaturated nitriles such as acrylonitrile, and crosslinkable monomers such as diaryl phthalate Can be used. The amount of these monomers used is preferably less than 50% by weight in the mixture with butyl chloride.

[0019] 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. Examples of 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.

[0020] 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. As the water-soluble initiator used in the emulsion polymerization, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide water, etc. are used. If necessary, 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.

 [0021] 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).

 [0022] As the water-soluble polymer, the synthetic polymer is an alitaroyl group-containing monomer (co) polymer.

[Poly (meth) acrylamide, poly (meth) acrylic acid (salt), poly (meth) acrylate, etc.], vinyl (co) polymers [polybulal alcohol, polybulurpyrrolidone, polybulumethyl ether, carboxyl group Containing bur (co) polymer (polyacetate butyl, etc.) and polystyrene sulfonic acid (salt), etc.], polyamidine, polyethylene oxide and polyethyleneimine. 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) and starch derivatives (soluble starch, methyl starch, carboxymethyl starch, etc.). These water-soluble polymers may be added alone or in combination of two or more.

[0023] 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.

[0024] Specifically, 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.

[0025] Among electrolytes, 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.

 [0026] 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!

[0027] In the present invention, it is preferable to add a nonionic surfactant before adding the flocculant. 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.

 [0028] When the nonionic surfactant is 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.

 [0029] 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.

 [0030] The emulsion polymerized latex other than the chlorinated chloride polymer used in the present invention has a function as an impermeable improving agent. Examples of 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.

 [0031] 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.

 [0032] 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.

 [0033] The slurry heat-treated as described above can be directly dried in a spray dryer to obtain a chlorinated resin for paste processing.

 As the spray dryer used in the present invention, an atomizer (a sprayer), a pressure nozzle

 Spray dryers equipped with (one-fluid nozzle), two-fluid nozzle, rotary disk type (disk type), etc. are used.

[0035] It is preferable to dry with hot air at normal pressure! /. 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.

 [0036] 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.

 [0037] The particles obtained by spray drying can be used after being pulverized by a known method. As the pulverizer, a roller mill, a high-speed rotary pulverizer, a ball mill, and an airflow-type pulverizer can be used.

 [0038] If 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 μm to 30 μm. When pulverizing excessively, favorable results tend not to be obtained with respect to impermeability.

 [0039] 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.

 [0040] 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. Thus, a butyl resin composition (plastisol) for paste processing is obtained.

[0041] In general, plastisol is applied to a fabric, there is! /, A sheet obtained by dipping, a glove, a bag, etc. In order to improve the flexibility of the product, 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 ,.

 Example

 Next, the power to explain the present invention in detail by way of examples The present invention is not limited to these examples. In the following examples and comparative examples, “%” and “parts” are simply “wt%” and “parts by weight”, respectively.

 [0043] (1) Average particle diameter of primary particles, aggregate particles, and spray particles

 Using 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.

 [0044] (2) Impermeability evaluation

Compounding 140 parts by weight of plasticizer (dioctyl phthalate) and 3 parts by weight of stabilizer (trade name "SC73" manufactured by Asahi Denka Co., Ltd.) with 100 parts by weight of chlorinated resin particles for paste processing. The plastisol was obtained by mixing and defoaming for 10 minutes with a type crusher. 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.

 [0045] 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.

 [0046] (3) Evaluation of peelability

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: More than 0.03 g of gelled product remained on the cloth.

 [0047] (4) Measurement of plastisol viscosity

 After soaking the plastisol in a constant-temperature water bath at 25 ° C for 1 hour, a Brookfield viscometer (manufactured by TOKIMEK) was used to read the value 1 minute after the start of No. 3 spindle V12 measurement to obtain the plastisol viscosity.

 [0048] (Example 1)

 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.

 [0049] 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. As a result, 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 μm.

 [0050] 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.

 [0051] As an evaluation of latex having fluidity, the latex viscosity after addition of the flocculant was measured at room temperature. Table 1 shows the number of parts added to the flocculant, the viscosity of the mixture after the addition, the dry particle size, and Table 2 shows the results of the penetration test and changes with time in viscosity.

 [0052] (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.

 [0053] (Example 3)

 Evaluation was carried out in the same manner as in Example 1 except that sodium sulfate was not added.

 [Example 4]

 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.

[0055] 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. As a result, 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.

 [Example 5]

 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.

[0057] (Example 6)

 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 7]

 Evaluation was carried out in the same manner as in Example 1, except that the water-soluble polymer polybulal alcohol was not added.

[Example 8]

 The same operation as in Example 1 was performed except that the spraying device was replaced with a rotating disk. When 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 9]

 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 10]

 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.

[0062] (Comparative Example 1)

 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!

[0063] (Comparative Example 2)

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)

 1 part by weight of a sulfuric acid band was added to the latex of the chlorinated resin obtained by polymerization in Example 1, and then 0.5 part by weight of polybule alcohol was added. The whole latex coagulated and could not be supplied to the spray dryer, and a sample by spray drying could not be obtained.

[0065] (Comparative Example 4)

 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.

[0066] [Table 1]

 Remarks 1: Ρ V 一 stands for polyvinyl alcohol.

[0067] [Table 2]

Solid female peelable plastisol ffiJS

 Evaluation Evaluation Adjustment 1 hour later Adjustment 1 day later

 mPa ■ s mPa · s Viscosity after 1 day ® Viscosity after hour 錢 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 8 B ― 1 350 1 60 1.08

¾¾6 Example 9 A A 1 600 1 550 0. 97 Difficult example 1 0 A A 1 600 1 500 0. 94

J: translation 1 C-700 750 1. 07

1: Translation 2 C-900 850 0. 94

J: 醜 3 Evaluation not possible-Measurement not possible-― t Translator 4 C-1 300 1 400 1. 08

[0068] As shown in Table 12, the Examples of the present invention;! To 10 had high plastizonole viscosity characteristics with high impermeability evaluation.

 [0069] (Example 11)

 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. Under stirring, 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 (hereinafter referred to as total monomer amount) 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%.

 [0070] Next, to this latex, 1 part by weight of sodium sulfate was added as a 1 Owt% aqueous solution with respect to 100 parts by weight of butyl chloride resin.

[0071] Next, a 3 wt% aqueous solution of polybulualcohol (manufactured by Nippon Synthetic Chemical Co., Ltd .: Gohsenol KH-17: Ken value of about 80 mol%) was prepared.

[0072] A two-fluid mixing type two-fluid spray nozzle shown in Fig. 4 (manufactured by Atmax Co., Ltd., C

NW200) spray dryer (supplied hot air inlet temperature 180 ° C, outlet temperature 71 ° C 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.

 [0073] The primary particles were indefinite as shown in FIG. Figure 7 shows the force increased in magnification. The basic particles were independent of each other, and the force was not fused. 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.

 [0074] 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.

[0075] Table 3 shows the dry particle size, pulverized particle size, and impermeability evaluation results.

[Example 12]

 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.

[0077] (Example 13)

 The same operation as in Example 11 was carried out except that sodium sulfate was not added! /, And evaluation was performed.

[0078] (Example 14)

 Other than changing the atomizer to the rotating disk type shown in Fig. 4. Dry resin particles were obtained in the same manner as in Example 11. The diameter of the disk was 84 mm, the rotation speed was 15000 rpm, fluid (latex and aqueous electrolyte solution) 31 was supplied at 54 kg / hr (47 liter / hr), and the aqueous polymer solution 33 was supplied at a feed rate of 3.6 kg / hr. The residence time of both liquids on the rotating disk was less than lsec. The average particle diameter of the resulting chlorinated resin resin particles was 60 m. This was pulverized by a micro bantam mill AP-B type pulverizer manufactured by Hosokawa Mikulon Co., Ltd. The average particle diameter of the obtained resin particles was 8 am.

[0079] (Comparative Example 5)

1 part of sodium sulfate and 0.5 part of PVA were added to the latex, and each aqueous solution was added and mixed so that the resin solids concentration after mixing was 40 wt%. The power was not able to be delivered to the atomizer. For this reason, in mass production, it was confirmed that it was necessary to mix the aqueous solutions of the aforementioned components immediately before spraying.

 [0080] (Reference Example 1)

 When 1 part of sodium sulfate and 0.5 part of PVA were added to the latex and each aqueous solution was added and mixed so that the resin solid content concentration after mixing was 20 wt%, a fluid slurry was obtained. When this was treated with the dryer of Example 14 and pulverized, resin particles having an average particle diameter of 7 m were obtained. The particles showed good impermeability.

[0081] [Table 3]

[0082] As described above, according to the examples of the present invention, 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.

 [0083] (Example 15)

 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%.

[0084] 1077. 6 g (500 g in solid content) of the latex obtained above was collected in a 3 L stainless steel container. Under stirring, 1 g of a nonionic surfactant (Nippon Yushi Co., Ltd., trade name “Pronon 102”) (0.2 parts by weight with respect to butyl resin) was added. Further, 46.6 g of ion-exchanged water was added. The temperature of the mixture at this time was 30 ° C. Next, 50 g of 1 part by weight of sodium sulfate as a 10% by weight aqueous solution was added to the chlorinated resin. Next, 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. This gives agglomerated particles with a solid content concentration of 40% by weight and an average particle size of 20 11 m (related to latex after addition of coagulant and before drying). 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.

 [0085] (Example 16)

 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.

 [0086] (Example 17)

 10777.6 g (500 g in solid content) of the polychlorinated butyl latex obtained in Example 15 was collected in a 3 L stainless steel container. Under stirring, acrylic latex (trade name “AE9 45H” manufactured by JSR Corporation, solid content concentration 51.75%) 29. Og (3 parts by weight in solid content with respect to chlorinated resin) was added. Furthermore, 435.3 g of ion-exchanged water was added. The temperature of the mixture at this time was 30 ° C. Next, 50 g of 1 part by weight of sodium sulfate as a 10% by weight aqueous solution is added to the chlorinated resin. Next, polybulal alcohol (trade name “GOHSENOL KH-17” manufactured by Nippon Synthetic Chemical Co., Ltd. (About 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. As a result, aggregated particles (with regard to latex after adding the coagulant and before drying) having a solid content concentration of butyl chloride resin of 30% by weight and an average particle size of 25, im were obtained. Evaluation was performed in the same manner as in Example 15.

 [Example 18]

 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.

 [0088] (Example 19)

 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 20]

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.

 [0091] (Example 22)

 (1) Latex production example 1

 2500 g of ion-exchanged water was charged into an 8 L separable flask. After replacing the gas phase with nitrogen, stirring was started, 20 g of sodium dodecylbenzenesulfonate and 200 g of methyl methacrylate were added, and the internal temperature was adjusted to 70 ° C. Polymerization was started by adding 500 g of 2% aqueous potassium persulfate solution. After 5 minutes, 1800 g of styrene was added over 3 hours and polymerized for another 1 hour. The conversion rate of the obtained latex was 99%. The latex solids concentration was 39.4 wt%.

 (2) Production and evaluation of aggregated particles

 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.

[0092] (Example 23)

 (1) Latex production example 2

 In 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%.

 (2) Production and evaluation of aggregated particles

 37.9 g of the latex obtained in Latex Production Example 2 (3 parts by weight in solid content with respect to chlorinated resin) was added. Evaluation was performed by the same operation as in Example 17 except that 40.4 g of ion-exchanged water was added.

[Example 24]

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.

[Example 25]

 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!

[0095] (Example 26)

 In 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.

[0096] (Comparative Example 6)

 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.

[0097] (Comparative Example 7)

 1 part by weight of a sulfuric acid band was added to the latex of the chlorinated resin obtained by polymerization in Example 15, and then 0.5 part by weight of polybutyl alcohol was added. The whole latex was solidified and could not be supplied to the spray dryer, and a sample by spray drying could not be obtained.

[0098] (Comparative Example 8)

 In 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.

[0099] (Comparative Example 9)

 (1) Latex production example 3

In 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%.

 (2) Production and evaluation of aggregated particles

 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.

[0100] The above conditions and results are summarized in Table 4.

[0101] [Table 4]

 'i: PVA stands for polyvinyl alcohol D

 麟 3: AE945 H ”S R ^ St ¾ ^ Product name“ AE945 H ”. ΐΙ # 4: AD1 otias Japanese Product name "AD — 1 0".

"0568" CDB§.5: 0568 is JS

"0568" CDB§.

 # 6: PMM A stands for polymethylmethacrylate.

 'i: P B A stands for Polyacryno UK Petit.

： SH502 is an abbreviation of Showa High School trade name “SH-502”. fl 9: PST stands for polystyrene.

As shown in Table 4, according to the examples of the present invention, 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.

Claims

The scope of the claims  [1] Aggregated particles in which primary particles are dried and contain at least one aggregating agent selected from water-soluble polymer and inorganic salt power in a chlorinated bull resin latex having an average particle size of 0 · ;! to 2 · 0 m. And  The aggregate particles are formed by agglomeration of the primary particles, and the aggregate particles have an average particle diameter in the range of 5,1 m to 40,1 m. Aggregated particles.  [2] The water-soluble polymer is selected from a monomer (co) polymer containing allyloyl group, a bull (co) polymer, polyamidine, polyethylene oxide and polyethyleneimine, polysaccharide, protein, cellulose ether, and starch derivative. 2. Aggregate particles comprising a chlorinated bull resin according to claim 1 which is at least one of the above. [3] The agglomerated particles containing a chlorinated resin of claim 1 or 2, wherein the water-soluble polymer is in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the chlorinated resin. [4] The aggregate particle containing a chlorinated bull resin according to claim 1, wherein the inorganic salt is an electrolyte. Yes  [5] The inorganic salt is at least selected from NaCl, KC1, Na SO, CaCl, and A1C1.  2 4 2 3  The aggregate particle | grains containing the chlorinated bull resin of Claim 1 or 4 which is one. [6] The aggregate containing the bull chloride resin according to claim 1, 4 or 5, wherein the addition amount of the inorganic salt is in the range of 0.;! To 10 parts by weight with respect to 100 parts by weight of the bull chloride resin. particle. [7] The aggregate particles according to any one of claims 1 to 6, wherein at least one selected from an emulsion surfactant latex (B) other than a noionic surfactant (A) and a chlorinated bull polymer is further added to the aggregate particles. Agglomerated particles containing the chlorinated bur resin according to any one of the above. [8] The nonionic surfactant (A) is a polyoxyalkylene compound, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester. And an agglomerated particle comprising a chlorinated bull resin according to claim 7, which is at least one selected from glycerin monofatty acid esters. [9] The nonionic surfactant (A) is used in an amount of 0.05 to 9. Aggregate particles containing a chlorinated bulu resin according to claim 7 or 8 in a range of 1 part by weight. [10] The emulsion polymerization latex (B) other than the above-mentioned butyl chloride polymer is a (meth) acrylic acid ester homopolymer, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid ester. 8. Aggregate particles comprising a chlorinated bur resin according to claim 7, which is at least one selected from ethylene acetate butyl copolymer. [11] The aggregate particles containing a chlorinated bull resin according to claim 7 or 10, wherein the emulsion polymerization latex (B) is in a range of from! To 10 parts by weight with respect to 100 parts by weight of the chlorinated bull resin. [12] The aggregate particles comprising a bull chloride resin according to any one of claims 1 to 11 above, wherein the aggregate particles are fused! /.  [13] At least one flocculant selected from a water-soluble polymer and an inorganic salt is added to a chlorinated bull resin latex having an average particle diameter of 0 .; A mixed aqueous solution containing resin aggregate particles,  A method for producing aggregate particles containing a chlorinated resin, characterized in that aggregate particles having an average particle diameter of 5 m to 40 m are obtained by spray drying the mixed aqueous solution. [14] The butyl chloride according to claim 13, wherein at least one selected from the emulsion surfactant latex (B) other than the noionic surfactant (A) and the chlorinated polymer is further added before adding the flocculant. A method for producing aggregate particles containing a resin. [15] The method of mixing and spray drying is a method in which an aqueous solution containing a chlorinated resin resin latex and a water-soluble polymer is mixed, atomized by an atomizer and spray-dried before the fluidity of the mixture is lost. The method for producing bull chloride resin particles according to claim 13. 16. The method for producing butyl resin particles according to claim 15, wherein the atomizer is a device that sprays the mixture from a rotating body or a spray nozzle to atomize the mixture. [17] The chlorinated resin particles of claim 13, wherein the chlorinated resin resin latex and the aqueous solution of an inorganic salt are mixed in advance before mixing the chlorinated resin resin latex and the aqueous solution containing a water-soluble polymer. Production method. [18] The bull chloride resin according to claim 13, wherein the aggregated particles are fused by heat-treating a mixed aqueous solution containing the agglomerate particles of the bull chloride resin at a temperature equal to or higher than a glass transition temperature of the bull chloride polymer. A method for producing aggregate particles. The method for producing bull chloride resin particles according to any one of claims 13 to 18, wherein the sprayed vinyl chloride resin particles are pulverized.  20. The method for producing chlorinated bull resin particles according to claim 19, wherein the pulverized resin particles have an average particle diameter of 5 to 30 m.