WO1994007923A1 - Latex of diene polymer particles, process for producing the latex, and process for producing rubber-containing thermoplastic resin from said polymer particles - Google Patents

Abstract

A latex of diene polymer particles wherein the mean particle diameter is 0.1 to 0.5 νm, the monodispersity ratio is 15 % or less and the content of the particles having diameters 0.85-1.15 times as large as the mean particle diameter is 85 % or above. The latex is produced by polymerizing a monomer composition containing a conjugated diene monomer in the presence of a seed latex having the emulsifier coverage of 85 % or less. A rubber-containing thermoplastic resin is produced by grafting a mixture of an ethylenically unsaturated nitrile monomer with an aromatic vinyl monomer onto the diene polymer particles, preferably a mixture thereof with second diene polymer particles having mean particle diameters smaller than those of the first diene polymer particles by at least 0.05 νm.

Description

 Description Latex of gen-based polymer particles and method for producing the same

 And rubber containing the gen-based polymer particles

 Manufacturing method of thermoplastic resin

 The present invention relates to a latex of gen-based polymer particles and a method for producing the same, and more particularly to a latex of gen-based polymer particles having a large average particle size and a narrow particle size distribution, and a method for producing the same.

 The present invention also relates to a method for producing a rubber-containing thermoplastic resin using the above-mentioned gen-based polymer particles. More specifically, the present invention relates to a rubber-containing thermoplastic resin having both high surface gloss and high impact strength and excellent in its balance. Related to the production method.

 Background art

 Large particle size gen-based polymer latex has been used in the manufacture of rubber-containing thermoplastic resins such as ABS resins, for example.

 Conventionally, as a method of producing a polymer latex having a large particle size by emulsion polymerization, for example, a method of adding an inorganic electrolyte to a polymerization system. A method of lowering the pH of emulsion in polymerization is known.

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In the case of latex of non-gen polymer particles such as acrylic polymer latex, the average particle diameter of non-gen polymer particles is 0.2 μm or more and 0.85 to 1.15 Twice as large Particles having a ratio of particles of 85% or more can be easily obtained by the above method.

 However, in the case of the latex of the gen-based polymer particles, the average particle size of the polymer particles constituting the polymer particles is 0.2 m or more and 0.7 to 1.3 times the average particle size. Particles with a particle size of only about 90% can be obtained, and those with a particle size in the narrow range of 0.85-1.15 times exceed 80%. Could not be obtained.

 Further, as another method, a method is known in which an emulsifier and 1,3-butadiene are charged in the presence of Sea Doratex and polymerized without using an inorganic electrolyte. However, in this method, a large amount of agglomerates were generated, and only a material having a wide particle size distribution was obtained.

 On the other hand, rubber-containing thermoplastic resins such as ABS resins generally have excellent characteristics such as excellent mechanical strength and moldability, and are used in a wide range of fields such as home appliances and automobiles. In particular, in consumer electronics applications, demand for rubber-containing thermoplastic resins that provide molded articles with extremely high surface gloss is increasing in order to increase commercial value.

 In order to meet this demand, the average particle size is 0.1 l / z m or more,

The proportion of particles having a particle size of less than 0. IB m and 0.7 to 1.3 times the average particle size is about 90%, or 0.85 to 1.15 There has been proposed a method in which vinyl aromatic and vinyl cyanide compounds are emulsified and graft-polymerized on gen-based polymer particles in which the ratio of particles having a particle diameter within the double range is less than 8.0%. However, in the rubber-containing thermoplastic resin obtained by this method, either the surface gloss or the impact resistance was low, and the balance between them was insufficient.

 Disclosure of the invention

 A first object of the present invention is to provide a latex of gen-based polymer particles having a large average particle size and an extremely narrow particle size distribution, and a method for producing the same.

 A second object of the present invention is to provide a method for producing a rubber-containing thermoplastic resin which has both high surface gloss and high shochu impact strength, and has an excellent balance between them.

 The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a monomer composition containing a conjugated diene monomer in the presence of a seed latex having an emulsifier coverage of a specific value or less. It has been found that the first object can be achieved by polymerization.

 In addition, the present inventors have found that gen-based polymer particles having an average particle size and a particle size distribution defined in a specific range contain an ethylenically unsaturated nitrile 1} monomer and an aromatic vinyl monomer. It has been found that the second object can be achieved by performing a graft polymerization of the resulting monomer mixture. The present invention has been completed based on these findings.

Thus, according to the present invention, on one side, the average particle diameter is 0.1 to 0.5 m, the monodispersity ratio is 15% or less, and the average particle diameter is 0.85 to 1 Provided is a latex of gen-based polymer particles, wherein the ratio of particles having a particle diameter in the range of 15 times is 85% or more. According to the present invention, in another aspect, a conjugated diene monomer is contained in the presence of 0.2 to 30 parts by weight (solid conversion) of a seed latex having an emulsifier coverage of 85% or less. 100 parts by weight of the monomer composition to be produced is provided, and a method for producing a latex of the gen-based polymer particles is provided.

 According to the present invention, in another aspect, the gen-based polymer particles constituting the latex are mixed with a monomer mixture containing an ethylenically unsaturated nitrile monomer and an aromatic vinyl monomer. The present invention provides a method for producing a rubber-containing thermoplastic resin, which comprises subjecting a product to graft polymerization.

 In the latex of the gen-based polymer particles of the present invention, the gen-based polymer particles constituting the latex have an average particle diameter of 0.1 to 0.5 m, preferably 0.15 to 0.5. m, more preferably from 0.23 to 0.5 m. If the average particle diameter of the gen-based polymer particles is smaller than 0.1 μm, the impact resistance of the rubber-containing thermoplastic resin obtained by graph-polymerizing the gen-based polymer particles is reduced, and conversely, 0.1. If it is larger than 5 m, the surface gloss of the rubber-containing thermoplastic resin decreases.

 BRIEF DESCRIPTION OF THE FIGURES

 Figure 1 is a graph showing the relationship between the amount of emulsifier added and the surface tension.

BEST MODE FOR CARRYING OUT THE INVENTION The particle size distribution of the gen-based polymer particles is such that particles having a particle size in the range of 0.85 to 1.15 times the average particle size have a harmful ij ratio of 8 5. % Or more, and preferably 90% or more. If it is less than 85%, the balance between the surface gloss of the rubber-containing thermoplastic resin and the impact resistance becomes poor. In addition, when the particle size distribution is expressed by a monodispersity ratio, it is necessary that it be 15% or less, and preferably 10% or less. If the content exceeds 15%, the balance between the surface gloss and the impact strength of the rubber-containing thermoplastic resin becomes poor.o

 In order to produce a latex of the gen-based polymer particles of the present invention, a monomer mixture containing a conjugated diene monomer is polymerized in the presence of a silica latex.

 The latex used in the production of the gen-based polymer particle latex is a latex of a polymer in which the polymer constituting the latex has an emulsifier coverage of 85% or less, preferably 60% or less. is there. The emulsifier coverage refers to the ratio of the amount of the emulsifier contained in the Sea Dratex to the amount of the emulsifier capable of covering the particle surface of the polymer constituting the Sea Dra Tex. The evaluation method will be described later.

Non-ionic emulsifiers such as polyoxyethylene alkylene ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester and polyoxyethylene sorbin alkyl ester; emulsifier; myristiminic acid And fatty acids such as palmitic acid, oleic acid, and linolenic acid, and salts thereof, anionic emulsifiers such as alkylarylsulfonates, higher alcohol esters, and alkylsulfosuccinic acids. . Also, S—Sulfoester of unsaturated carboxylic acid, H—Sulfate of unsaturated carboxylic acid Copolymerizable emulsifiers containing a double bond such as stell and sulfoalkylaryl ether can also be used. These emulsifiers can be used alone or in combination of two or more. When an alkali metal salt of a higher fatty acid such as rosin acid, oleic acid, or stearic acid is used among these emulsifiers, it is easy to obtain gen-based polymer particles having a narrow particle size distribution, which is the object of the present invention. I like it.

 As the seed latex, those having an average particle diameter of the polymer particles constituting it of usually 0.03 to 2 m, preferably 0.04 to 0.12 m are used. If it is less than 0.03 m, the reaction time becomes longer. Conversely, if it exceeds 0.2 / m, the particle size distribution of the gen-based polymer particles becomes wide.

 The monomer used in the production of seed latex is not particularly limited, and for example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; styrene, and -Aromatic vinyl quasimers such as methylstyrene; (meth) ethylenically unsaturated monocarboxylic acids such as acrylic acid; ethylenically unsaturated polycarboxylic acids such as maleic acid and itaconic acid; Ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl maleate and monoethyl itaconate; (meth) methyl acrylate,

(META) Ethylenically unsaturated carboxylic acid esters such as ethyl acrylate; single ethylenically unsaturated carboxylic acid esters such as acrylonitrile and methacrylonitrile Fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; Vinyl pyridine; Vinyl norbornene, dicyclopentene, 1, 4-hydroxy Non-conjugated diene monomers such as sagen; monoolefins such as ethylene and propylene; and ethylenically unsaturated carboxylic acid amides such as (meta) acrylamide. These can be used alone or in combination of two or more. Among these monomers, conjugated diene monomers such as 1,3-butadiene are preferred.

 The method for producing seed latex is not particularly limited. Usually, it can be produced by an emulsion polymerization method, but can also be produced by a phase inversion method.

 The monomer composition containing a conjugated gen monomer used in the method for producing a latex of gen-based polymer particles according to the present invention may be a conjugated gen monomer alone or in combination with a conjugated gen monomer. It is a mixture of body and body.

 Examples of conjugated diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentene,口 口 プ レ 等。 An example of this is a mouthpiece. Of these monomers, 1, 3 — butylbenzene is preferred. The conjugated diene monomer is used in an amount of at least 50% by weight, preferably at least 70% by weight, more preferably at least 100% by weight, of the monomer composition containing the co-active diene monomer. It is.

Examples of the ethylenically unsaturated monomers include, for example, aromatic vinyl monomers such as styrene, dimethylstyrene, and divinylbenzene; and ethylenic monomers such as (meth) acrylic acid. Unsaturated monocarboxylic acid; ethylenic unsaturated polycarboxylic acid such as maleic acid and itaconic acid; ethylenically unsaturated polycarboxylic acid such as monoethyl maleate Polyvalent carboxylic acid partial ester; (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, 2-hydroxyhydryl acrylate, glycidyl methacrylate Ethylenically unsaturated carboxylic acid esters such as acrylates; ethylenically unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; dicyclopentene, vinyl Non-cogenerating gen monomers such as norbornene; olefins such as ethylene and propylene; and ethylenically unsaturated carboxylic acid amides such as (meth) acrylamide. Can be

 The ratio of the amount of the Sea Doratex to the monomer composition containing the conjugated gen monomer is 100 parts by weight of the monomer composition containing the conjugated gen monomer, and The amount is 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight. When the amount is less than 0.2 parts by weight, the polymerization stability of the gen-based polymer particles is poor. When the amount exceeds 30 parts by weight, the particle distribution of the gen-based polymer particles becomes wide. During the polymerization of the monomer composition containing the conjugated diene monomer, an emulsifier is added in order to improve the polymerization stability of the latex of the diene polymer particles of the present invention. It can be added in a range where the emulsifier coverage of the latex of the body particles is 85% or less, preferably 60% or less. Addition of an emulsifier in an amount exceeding 85% broadens the particle size distribution of the gen-based polymer particles of the present invention.

The method for producing the rubber-containing thermoplastic resin of the present invention is characterized in that the gen-based ffi-combined particles constituting the latex of the gen-polymer particles are added to an ethylenically unsaturated nitrile monomer and an aromatic vinyl monomer. To It is to polymerize the contained monomer mixture.

 In the production method of the present invention, as the gen-based polymer particles, (1) an average particle diameter of 0.15 to 0.5 μm, preferably 0.23 to 0.5 μm, more preferably (2) the monodispersity ratio is 15% or less, preferably 10% or less, and (3) the average particle diameter is 0.85.

~ 1.15 Gen-based polymer particles (A) having a particle size in the range of 15 times or more, preferably 85% or more, preferably 90% or more, and an average particle size of 0.0 8 to 0.22 m, preferably 0.1 to 0.2 m, which is composed of the gen-based polymer particles (B) and from the average particle diameter of the gen-based polymer particles (A). When a mixed particle having a value obtained by subtracting the average particle size of the polymer particles (B) from 0.05 // m or more, preferably 0.1 / m or more is used, the rubber-containing thermoplastic resin can be used. It is preferable to use the mixed particles because the balance between the impact resistance and the surface gloss increases.

 In the mixed particles, the weight ratio between the gen-based polymer particles (A) and the gen-based polymer particles (B) is usually 5Z95 to 85/15, preferably 10/90. ~ 70/30.

 Examples of the ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile, and two or more kinds may be used as a mixture. Of these ethylenically unsaturated nitrile monomers, acrylonitrile is preferred. The amount of the ethylenically unsaturated ditolyl monomer is usually from 2 to 50% by weight of the monomer mixture used in the graft polymerization to improve the solvent resistance of the rubber-containing thermoplastic resin. %.

Examples of the aromatic vinyl monomer include styrene and permethylstyrene. Examples thereof include len, vinyltoluene, and styrogenated styrene, and these may be used in combination of two or more. These aromatic vinyls! Of the Ji-mers, styrene is preferred. The amount of the aromatic vinyl monomer is usually 10 to 90% by weight of the monomer mixture used for the graft polymerization in order to improve the hardness of the rubber-containing thermoplastic resin.

 If necessary, other monomers copolymerizable with the ethylenically unsaturated nitrile monomer and the aromatic vinyl monomer can be used. Specifically, (meth) acrylic acid ester monomers such as (meth) methyl acrylate, (meth) ethyl acrylate, and (meth) butyl acrylate; vinyl chloride; Halogenated vinyl such as vinyl acetate; vinyl carboxylate monomer such as vinyl acetate; and ethylenically unsaturated carboxylic acid monomer such as methyl acrylate and acrylate. Can be. The amount of these monomers is usually not more than 70% by weight of the monomer mixture used for the graft polymerization.

 In the present invention, the weight ratio between the gen-based polymer particles (or mixed particles) and the monomer mixture to be subjected to the graft polymerization is usually 5Z95 to 75/25, preferably 30/70. ~ 65/35. If the ratio of the gen-based polymer particles is less than 5% by weight, the gloss and impact strength of the rubber-containing thermoplastic resin become insufficient. Conversely, if it exceeds 75% by weight, the gloss of the rubber-containing thermoplastic resin is significantly reduced.

The graft polymerization is performed using a known polymerization technique. Usually, the latex of the ene-based polymer particles is charged into a reactor, and the mixture contains an ethylenically unsaturated monomer and an aromatic vinyl monomer. The resulting monomer mixture is added for polymerization.

 After the polymerization, a coagulant is added to the polymerization reaction system, and the coagulated material is filtered, dehydrated and dried to obtain a rubber-containing thermoplastic resin.

 A coloring agent, a stabilizer, an antistatic agent, a plasticizer, and the like may be appropriately added to the rubber-containing thermoplastic resin obtained by the present invention.

 The rubber-containing thermoplastic resin obtained by the present invention can be used alone as a material or the like for producing a molded article. In addition, if necessary, heat treatment such as polyvinyl chloride, polyvinyl acetate, polyamide, polyacryl, polyolefin, polyester, acrylonitrile-relu-styrene copolymer (AS resin), and polycarbonate Can be used in combination with a plastic resin.

 Hereinafter, the present invention will be described more specifically with reference to examples. The parts and percentages in these examples are on a weight basis.

 The evaluation method performed in this example will be described below.

 [Emulsifier coverage of Sea Doratex]

A suitable amount of emulsifier (0.2 m 0 \ / II aqueous solution, approx. 2 m) was added to 0.00.0 g of Sea Doratex with a solid content of 25% ?) Drops were added, stirred, and the surface tension was measured with a Duney-type surface tensiometer, and plotted on a square graph. This operation was repeated until the measured value of the surface tension did not change even if the emulsifier was further added dropwise. Next, as shown in FIG. 1, the minimum addition amount S2 of the emulsifier at which the surface tension became a constant value was determined from this grid graph. Emulsifier coating The rate is given by Equation 1. Note that S 0 represents the amount of emulsifier contained in 40.0 g of Cydratex with a solid concentration of 25%.

 S 0

 Emulsifier coverage (: = 100 (Equation 1)

 (S 0 + S 2)

 (Average particle size and monodispersity ratio)

 Gen-based polymer particles were stained with osmic acid, photographed with a transmission electron microscope, and 350 particles were randomly selected from the photograph to measure the particle diameter.

 The average particle diameter is represented by the value (m) obtained by dividing the sum of the measured values by the number of measured particles, and the monodispersity ratio is the value (%) obtained by dividing the standard deviation of the measured values by the average particle diameter and multiplying by 100. Represent.

 (Evaluation of rubber-containing thermoplastic resin)

 (1) Graph rate

 A certain amount (w.) Of the rubber-containing thermoplastic resin is poured into acetonitrile, stirred for 2 hours with a stirrer, and then the solution is centrifuged at 23,000 rpm using a centrifuge. Centrifuged for minutes. The separated insolubles were dried for 1 D at 120 ° C using a vacuum dryer and weighed.

 (w,) was measured, and the graft ratio was determined by the following equation.

W! -ΛΥ 2 X (content of gen-based polymer particles in rubber-containing thermoplastic resin) w ₂ X (content of gen-based polymer particles in rubber-containing thermoplastic resin)

 1 0 0

(2) Surface gloss and impact strength

 100 parts of rubber-containing thermoplastic resin is AS resin (acrylonitrile content: 30%, intrinsic viscosity of methyl ethyl ketone at 30 ° C)

0.4 d / g) to obtain a rubber-containing thermoplastic resin. The ratio of the gen-based polymer particles used in the above was adjusted to 15% of the total amount of the rubber-containing thermoplastic resin and the AS resin.

 Further, after adding and mixing 0.8 parts of ethylene bis stearyl amide, the mixture was pelletized at 200 ° C. using a 4 O mZm extruder. Next, a 90 mm × 50 mm × 3 mm plate was produced at a mold temperature of 40 ° C. using an injection molding machine (Nissei Resin Industry Co., Ltd., NC—800 PZ).

 (A) Surface gloss

 The plate was measured using a GROSS meter (manufactured by MURAKAMI COLOR RESERCH LABORATORY, GIVI-26D) at an incident angle of 60 degrees.

 (Mouth) Impact strength

 The above plate was measured under the conditions of 14 inches, notched, 50% R.II. and 23 ° C. according to ASTM D-256.

 (Example of Sea Doratex production)

Reference example 1

 In a nitrogen-purged autoclave equipped with a stirrer, add 1,3-butene 100 parts, soft water 200 parts, □ potassium dicate 2.0 parts, potassium carbonate 0.3 parts, 0.3 parts of potassium persulfate and 0.5 part of t-dedecylmer force plate were charged, and the mixture was kept at 60 for 15 hours with stirring and mixing to obtain Seedratex A. Table 1 shows the physical properties of Cydratex A.

Reference example 2

Except for following the polymerization formula shown in Table 1, the same method as in Reference Example 1 was used. Obtained Sea Dratex B and C. Table 2 shows the physical properties of Seedratex B and Table 1 shows the physical properties of Seedratex C.

Reference example 3

 To 100 parts of Sea Dratex A obtained in Reference Example 1 (in terms of solid content) was added 10.0 parts of a 20% aqueous solution of rosin acid potassium, and the mixture was stirred to obtain Sea Dratex D. Was. Table 2 shows the physical properties of SEEDRATEX D.

Reference example 4

 To 100 parts of citratex A obtained in Reference Example 1 (in terms of solid content), 30.0 parts of a 20% aqueous solution of rosin acid potassium was added, and stirred, to thereby obtain sea doratex E. Obtained. Table 2 shows the physical properties of SEEDRATEX E.

 (Production example of gen-based polymer particles)-Example 1

 Sea Dratex A 7.5 parts in autoclaved with nitrogen

(In terms of solid content), 100 parts of butadiene, 100 parts of soft water, 0.3 parts of t-dodecylmer, 0.3 parts of lithium persulfate, and 0.3 parts of calcium carbonate It was charged, kept at 70 and stirred. When the polymerization conversion reached 7096, 1.0 part of a 20% aqueous solution of potassium rosinate was added (the emulsifier coverage after adding the emulsifier was 85%).

% Or less. ). After 30 hours from the start of stirring, the mixture was cooled to 25 ° C to obtain a latex of gen-based polymer particles. Table 1 shows the physical properties of the latex of this gen-based polymer.

Examples 2 to 9 and Comparative Examples 1 to 2

Same as Example 1 except that the polymerization recipe shown in Table 1 or Table 2 was followed. A latex of gen-based polymer particles was obtained by the same method. Tables 1 and 2 show the physical properties of the latex of these gen-based polymer particles.

Comparative Example 3

 Nitrogen-purged autoclaved 3-butadiene 100 parts, soft water 100 parts, 25% potassium rosinate 8 parts, t-dedecylmer force 0.5 parts, persulfuric acid 0.3 parts of lithium and 0.5 parts of carbon dioxide were charged, and the mixture was stirred at 55 ° C. When the polymerization conversion reached 70%, 4.0 parts of a 25% aqueous solution of potassium rosinate was added. After about 40 hours from the start of stirring, the mixture was cooled to 25 ° C to obtain a latex of gen-based polymer particles. Table 2 shows the physical properties of the latex of the gen-based polymer particles.

Comparative Example 4

A latex of gen-based polymer particles was obtained in the same manner as in Reference Example 5, except that the charged amount of soft water was changed to 75 parts. Table 2 shows the physical properties of the latex of the gen-based polymer particles.

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m example

 1 2 3 4 5 6 7 Seed latex A A A A A A c Monomer

! , ₃ —butadiene 100 100 100 100 100 100 100 Potassium rosinate 2.0 2.0 2.0 2.0 2.0 2.0 1.0 Polymer conversion (9 98 98 98 98 98 98 98 Properties

 H 10.5 10.5 10.5 10.5 10.5 10.5 10.6 Average particle size (zm) 0.08 0.08 0.08 0.08 0.08 0.08 0.14 Emulsifier coverage () 33 33 33 33 33 33 36 Used amount Converted to dry matter (parts) 7.5 4.0 1.5 1.5 0.4 20.0 25.0 Monomer (parts)

 1,3-butadiene 100 100 100 75 75 100 100 Styrene--25---Acrylonitrile----25 1-Addition rate (%) 98 99 98 99 98 99 99 Evaluation of gen-based polymer particles ffi

 Average particle size 0.19 0.24 0.32 0.31 0.45 0.14 0.13 Monodispersity ratio 4.2 4.8 3.1 5.1 7.5 8.5 12.0 0.7 to 1.3 times the average particle size

 Proportion of particles within the range (¾) 99.5 99.3 99.9 99.0 98.5 98.3 88.4 0.85 to 1.15 times the average particle size

Proportion of particles in the recitation (¾) 98.9 98.4 99.5 98.2 97.2 96.3 90.5 07923

17 Table 2

 Example Example Comparative Example

 8 9 1 3 4 Seedratex B D A E ― ― Monomer (%)

 80 100 100 100 ― ― Styrene 20 ― ― ― ― ― Potassium rosinate 5.0 2.0 2.0 2.0 ― ― Polymer conversion () 97 98 98 98 I ― Characteristics

 PH 10.5 10.6 10.5 10.7 ― ― Average particle diameter (m) 0.05 0.08 0.08 0.08 ― ― Emulsifier coverage (%) 29 67 33 100 ― Amount (converted into fractions) (parts) 15.0 7.5 35.0 7.5 ― ― Single Quantity (parts)

 100 100 100 100 100 100 Polymer addition ratio (%) 99 98 99 98 98 99 Evaluation of gen-based polymer particles

 Average particle size 0.12 0.14 0.09 0.17 0.08 0.30 Monodispersity ratio 5.5 10.1 17.6 20.3 20.2 28.0 0.7 to 1.3 times the average particle size

 99.0 98.3 94.9 91.6 90.5 88.3 0.85 to 1.15 times the average particle size

Range Proportion of particles in BH 0) 98.1 91.9 69.1 57.4 56.5 56.0 From Tables 1 and 2, according to the present invention, when a seed latex having an emulsifier coverage of 85% or less is used, the latex of the obtained gen-based polymer particles has an average particle size of 0. It can be seen that the ratio of particles having a particle diameter of 1 to 0.5 m and within a range of 0.85 to 1.15 times the average particle diameter is 85% or more. Example 10

 Average particle size 0.19 m, latex of polybutadiene particles having a ratio of 98.9% of particles within the range of 0.85 to 1.15 times the average particle size 45 parts ( 20 parts of styrene, 7.5 parts of acrylonitrile, 0.8 part of potassium rosinate, 0.2 parts of t-dodecylmercaptan and 130 parts of ion-exchanged water The mixture was charged into a jacket and a reactor equipped with a stirrer. After replacing the air inside with nitrogen, the internal temperature was raised to 60 ° C, and 10 parts of water and sodium pyrophosphate were added. A mixture of 0.4 part of chromium, 0.5 part of dextros, 0.01 part of ferrous sulfate and 0.05 part of peroxide at the mouth of a cumenehydride was added and reacted (first stage).

 After 1 hour, styrene 20 parts, acrylonitrile 7.5 parts, t-dodecylmer force plate 0.2 parts, potassium rosinate 0.5 parts, Kumenhai dropper oxide A mixture of 0.1 part and 10 parts of ion-exchanged water was added over 3 hours, and the reaction was continued for another hour after the addition was completed (second stage). The total polymerization conversion of the monomers polymerized in the first and second stages was 96% or more.

To the resulting rubber-containing thermoplastic resin emulsion was added 0.5 part of 2,2'-methylenebis (4-methyl-16-butylphenol) as an anti-aging agent and coagulated. Separation of coagulated material from water After releasing, washing with water, dehydrating and drying, a rubber-containing thermoplastic resin was obtained.

Examples 11 to 14 and Comparative Examples 5 to 7

 A rubber-containing thermoplastic resin was obtained in the same manner as in Example 10, except that the latex of the gen-based polymer particles and the composition of the monomer to be polymerized were changed to the formulations shown in Table 3.

Table 3 shows the evaluation results of the rubber-containing thermoplastic resins obtained in Examples 10 to 14 and Comparative Examples 5 to 7.

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 Note) PBD: polybutadiene

SBR: Styrene-butadiene copolymer (monomer MJ seven 25/75) From Table 3, it can be seen that the rubber-containing thermoplastic resin obtained using a latex of a gen-based polymer with a particle ratio of 0.85 to 1.15 times the average particle size and less than 85% In Comparative Examples 5 to 7, it can be seen that characteristics satisfying both the surface gloss and the impact resistance cannot be obtained.

 On the other hand, according to the present invention, the ratio of particles having an average particle diameter of 0.1 to 0.5 m and within a range of 0.85 to 1.1 times the average particle diameter is 85% or more. It can be seen that the rubber-containing thermoplastic resin obtained by graft polymerization of the gen-based polymer particles has a good balance between the surface gloss and the impact resistance.

Example 15

 In Example 10, in place of the latex of polybutadiene particles, the ratio of particles having an average particle diameter of 0.32 m and within a range of 0.85 to 1.15 times the average particle diameter was 99%. 13.5 parts (solid content conversion) of 3% of boribenien particles with an average particle diameter of 0.13〃m and 0.85-1.15 times the average particle diameter The rubber-containing heat was the same as in Example 10 except that the polybutene particles in the range of 96.3% were replaced with 31.5 parts (converted to solid content) of latex particles. A plastic resin was obtained.

Examples 16 to 18

A rubber-containing thermoplastic resin was obtained in the same manner as in Example 15 except that the latex of the gen-based polymer particles and the formulation of the monomer to be polymerized were changed to the formulation shown in Table 4. Three

22 Table 4

 Note) PBD: polybutadiene

SBR: Styrene-butadiene copolymer (monomer ffiftLt25 / 75) Table 4 shows that the rubber-containing thermoplastic resin obtained by the production method of the present invention has both high surface gloss and high impact resistance and good balance.

 Industrial applicability

 According to the present invention, a latex of gen-based polymer particles having a large average particle size and a narrow particle size distribution is provided, and a rubber-containing thermoplastic resin obtained from the gen-based polymer particles constituting the latex is provided. Has both high and balanced surface gloss and impact resistance.

 This rubber-containing thermoplastic resin is used in applications such as home appliances and vehicles.

Claims

Scope of claim  1. Particles having an average particle diameter of 0.1 to 0.5 m, a monodispersity ratio of 15% or less, and a particle diameter within the ifi range of 0.85 to 1.15 times the average particle diameter. The ratio of the gen-based polymer particles is 85% or more.  2. The latex of the gen-based polymer particles according to claim 1, wherein the average particle diameter is 0.15 to 0.5 m.  3. Make sure that the ratio of particles having an i | i dispersibility ratio of 10% or less and having a particle diameter in the range of 0.85 to 1.15 times the average abductor diameter is 90% or more. The latex of the gen-based polymer particles according to claim 1, wherein:  4. Sea Doratex with emulsifier coverage of 85% or less 2. The method according to claim 1, wherein 100 parts by weight of the monomer composition containing the conjugated gen monomer is polymerized in the presence of 0.2 to 30 parts by weight (in terms of solid content). A method for producing a latex of gen-based polymer particles.  5. The production method according to claim 4, wherein the average particle diameter of the seed particles is from 0.03 to 0.2 im.  6. The method according to claim 4, wherein the emulsifier coverage of Sea Doratex is 60% or less.  7. The method according to claim 4, wherein the emulsifier for coating Sea Doratex is an alkali metal salt of a higher fatty acid. 8. The method according to claim 4, wherein the polymer constituting the sea dex is a 1,3-butene-gene polymer. Law.  9. The method according to claim 4, wherein the monomer composition containing a conjugated diene monomer is composed of 1,3-butadiene.  10. The gen-based polymer particles constituting the latex of the gen-based polymer particles according to claim 1 contain an ethylenically unsaturated ditolyl monomer and an aromatic vinyl monomer. Production of rubber-containing thermoplastic resin characterized by subjecting a mixture of substances to a graph polymerization ii o  11. The weight ratio of the gen-based polymer particles to the monomer mixture containing the ethylenically unsaturated ditolyl monomer and the aromatic vinyl monomer is 5Z95 to 75/2. The method according to claim 10, wherein the method is 5.  12. The process according to claim 10, wherein the ethylenically unsaturated ditolyl monomer is acrylonitrile.  13. The process according to claim 10, wherein the aromatic vinyl monomer is styrene. 1 4. The gen-based polymer particles (A) constituting the latex of the gen-based polymer particles according to claim 2, and the gen-based polymer particles having an average particle diameter of 0.08 to 0.22 m. (B) and the value obtained by subtracting the average particle diameter of the gen-based polymer particles (B) from the average particle diameter of the gen-based polymer particles (A) is 0.05 m or more. 10. The process according to claim 10, wherein a monomer mixture containing an ethylenically unsaturated ditolyl monomer and an aromatic vinyl monomer is subjected to graph polymerization. 15. The method according to claim 14, wherein the weight ratio of the gen-based polymer particles (A) to the gen-based polymer particles (B) is 5Z95 to 85Z15. .