TW476772B - Acrylic copolymer, process for producing same and vinyl chloride resin composition containing same - Google Patents

Abstract

An acrylic copolymer suitable as a processability-modifier for vinyl chloride resin is obtained by polymerizing 10-30 wt. parts of a second monomer mixture comprising 20-70 wt.% of methyl methacrylate, 0-60 wt.% of an alkyl methacrylate having an alkyl group of 2-8 carbon atoms, 0-70 wt.% of an alkyl acrylate having an alkyl group of 1-8 carbon atoms and 0-10 wt.% of another copolymerizable vinyl monomer in the presence of 70-90 wt. parts of a copolymer obtained by polymerizing a first monomer mixture comprising 60-95 wt.% of methyl methacrylate, 5-40 wt.% of at least one monomer selected from the group consisting of alkyl methacrylates having an alkyl group of 2-8 carbon atoms and alkyl acrylates having an alkyl group of 1-8 carbon atoms, and 0-10 wt.% of another copolymerizable vinyl monomer. The second monomer mixture, when polymerized alone, provides a glass transition temperature of at most 50 DEG C. Through moderate coagulation, the acrylic copolymer is recovered as a powdery product containing little fine powder, showing good flowability and providing a vinyl chloride resin composition having improved gelation characteristic and processability when blended with vinyl chloride resin.

Description

476772 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______ _B7_ V. Description of the invention (!) The scope of the invention and related arts The present invention relates to an acrylic copolymer and its manufacturing method and chlorine containing the acrylic copolymer Ethylene resin composition, and more specifically, the present invention relates to a powdery acrylic copolymer having porosity and excellent powder characteristics, a method for producing the same, and a vinyl chloride resin having excellent processability containing the acrylic copolymer. combination. Vinyl chloride resin is widely used in the manufacture of plastic products due to its excellent physical and chemical properties. However, the processing and molding temperature of vinyl chloride resin is close to its decomposition temperature, and it takes a long time to melt, making the processing of vinyl chloride resin difficult. In order to eliminate such difficulties, in practice, stabilizers and plasticizers are added, and an acrylic polymer processing aid mainly containing methyl methacrylate is added to promote gelation and increase melt elasticity, thereby expanding Processing range. This acrylic processing aid added to improve processing and forming characteristics is a polymer with a high degree of polymerization, which cannot be formed by bulk polymerization or suspension polymerization, so it is easy to use polymers The latex form is produced by providing a high degree of polymerization by emulsion polymerization, whereby the polymer latex recovers a powdered polymer product. In order to recover a powdery product from a polymer latex, a method of mixing the polymer latex with an aqueous electrolyte solution to aggregate the resin part and a method of spraying the polymer latex into a stream of hot air for drying are generally used. However, this acrylic polymer has a high glass transition temperature, and the powdery product obtained by mixing the latex of this high acrylic polymer with an aqueous electrolyte solution will contain many fine-grained parts because the fusion does not Adequate size of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) -4 476772

A7 B7 V. Description of the invention (2), which causes poor processability, and is easy to dust (d u s t i n g) during subsequent processing (such as filtration, dewatering, drying, conveying, metering and feeding). The difficulty faced by the powdery product obtained by the spray-drying method is that the polymer latex is not easy to dry due to the characteristics of the drying method, unless it is sprayed into a fine particle form, which is liable to cause the phenomenon of dust. Acrylic polymer processing aids mainly containing methyl methacrylate have excellent effects in promoting gelation, inhibiting drawdown, and improving high-temperature tensile elongation, but they are also accompanied by chlorine The problem of insufficient dispersibility in vinyl resins is prone to produce unmelted or ungelatinized parts (called fish eyes), making the appearance of the molded product poor or generating a light scattering source, thereby reducing transparency. Furthermore, If such an acrylic polymer is incorporated into a soft vinyl chloride resin composition together with a large amount of plasticizer, the power of dispersing the acrylate polymer processing aid is insufficient compared with the rigid vinyl chloride resin composition, resulting in The undispersed spots of the polymer processing aid result in poor transparency and appearance. Many techniques have been proposed to overcome the above-mentioned difficulties by improving the dispersibility of such acrylate polymer processing aids. For example, Japanese Patent Publication No. (JP-B) 5 3 — 2 8 9 8 discloses: (1) a two-step polymerization reaction product obtained by the following method: adding a methyl methacrylate containing a small amount of methyl methacrylate And a monomer mixture of a large amount of acrylate and / or methacrylate, and the monomer is polymerized in the presence of an acrylic copolymer (containing a large amount of methyl methacrylate) latex; or the paper size Applicable to China National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back first

(This page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics ~ 5-476772 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (3) (2) — A polymer mixture made by the following methods: Obtain: blending a latex containing an acrylic copolymer with a large amount of methyl methacrylate and a latex containing a copolymer with a small amount of methyl methacrylate and a large amount of acrylate and / or methacrylate in a latex form, It is then aggregated, and it is a resin additive for vinyl chloride resin, which has an excellent gelation promotion effect. This Japanese bulletin proposes some implementation systems and effects of incorporating hard vinyl chloride resin composition, but does not propose implementation bodies incorporating soft vinyl chloride resin composition, and also does not disclose suitable for providing granular morphology A latex agglomeration method for acrylic copolymers (which can reduce the non-gelling part and have excellent dispersibility). JP — B — 52-1745 reveals (1) a two-step polymerization reaction product, including (A) 99-5 1% copolymer component, containing 9 0-5 5% methyl methacrylate, 10-4 5% Acrylate and 0—20% of another copolymerizable monomer, and (B) —49% of polymethyl methacrylate, polymerize the monomer component of (A) and then in the polymerization system Obtained by adding and polymerizing the monomer component of (B) or polymerizing the monomer component of (B) followed by adding and polymerizing the monomer component of (A); or (2) a polymer mixture, Including (A) 99-51% copolymer content, containing 90-50% methyl methacrylate, 104-55% acrylate and 0-20% of another copolymerizable monomer, and (B) 1 to 49% of polymethyl methacrylate is obtained by polymerizing (A) and (B) respectively in the form of latex and agglomerating them. (Please read the precautions on the back before filling this page. ) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 476772 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7 _V. Description of the invention (4) Used as a processing aid, it has good dispersibility in both rigid vinyl chloride resin and soft vinyl chloride resin. Similarly, JP-B 52-1746 discloses (1) a two-step polymerization reaction product, including (A) a copolymer component of 99 -51%, containing 90-5 5% methyl methacrylate, 10-45% Acrylate, 10-45% acrylate and 0-20% another copolymerizable monomer, and (B) 1-49% copolymer, containing at least 90% of methyl methacrylate and up to 10%. % Of another copolymerizable monomer, which is obtained by polymerizing the monomer component of (A), and then adding and polymerizing the monomer component of (B) in the polymerization system, or the monomer component of (B) It is obtained by polymerizing and then adding (A) the monomer component; or (2) a polymer mixture, including (A) 9 9-5 1% copolymer component, containing 90-5 5% methyl Methyl acrylate, 10-45% acrylate and 0-20% another copolymerizable monomer, and (B) 1-49% copolymer, containing at least 90% methyl methacrylate and up to Another 10% of another copolymerizable monomer is obtained by polymerizing (A) and (B) in the form of latex after polymerization, and used as a processing aid. Vinyl chloride resin also has excellent dispersibility. However, the particle shape of acrylic copolymers disclosed in these Japanese Patent Publications JP-B 5 2-1 7 4 5 and JP — B 5 2 — 1 7 4 6 is irregular. , And contains a considerable amount of fine powder, so that the handling characteristics or processability is poor. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) 1 1 1 476772 A7

V. Description of the invention (5) Summary of inventions printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs In order to develop a polymer processing aid that is mainly used to improve the processability of vinyl chloride resins, the inventors have conducted extensive research. This processing aid The agent includes an acrylic copolymer, which is excellent in handling characteristics, powder properties, and effects of improving processability. The research items include composition, polymerization method and polymerization conditions, and other process conditions such as agglomeration methods. As a result, it was found that the monomer composition that contributes to excellent powder properties and the monomer composition that contributes to improvement in processability, melt viscoelasticity, and transparency may not necessarily be the same as each other, but have both cohesive properties or powder properties and improved processability The combination of performance characteristics can be obtained by polymerizing a monomer composition that contributes to the improvement of the properties of vinyl chloride resin, and then polymerizing a monomer composition that contributes to cohesiveness to the aforementioned polymer product particles. Deposition. In addition, a moderate agglomeration method has also been found suitable for graft copolymers containing rubber-like elastomers (provided by our research and development group, see Japanese Patent Early Publication j P — A 60 — 2 1 7224) For coagulation, first polymer latex is moderately coagulated with a dilute coagulant aqueous solution to precipitate out as spherical particles, and then a higher concentration of coagulant aqueous solution is added. This method can also be used as a coacervation method for recovering a powdery acrylic copolymer having excellent powder properties from a latex containing latex particles (the core and the outermost layer of which have different compositions and properties). Furthermore, it was found that the acrylic copolymer particles obtained in the above manner are porous, have micropores inside the particles, and have excellent melt dispersibility during processing and molding, so that almost no residues remain in the molded product. The size of the unfused paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ~ " '— 8 8 (please read the precautions on the back first)

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Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The part of the invention description (6). The present invention has been completed based on the above findings. Therefore, the main object of the present invention is to provide an acrylic copolymer, which contains very few fine particles, is not easy to generate dusting or dust explosion, has good operation characteristics, and has an improved effect on the molding and processing characteristics of vinyl chloride resin. The trapped fruit is also excellent. Another object of the present invention is to provide a method for producing the above-mentioned acrylic copolymer and a resin composition containing such an acrylic copolymer and a vinyl chloride resin. -The acrylic copolymer provided according to the present invention is prepared in the following manner: 70 to 90 parts by weight of 60 to 9 5 weight percent methyl methacrylate and 5 to 40 weight percent at least One monomer selected from alkyl methacrylate (alkyl having 2 to 8 carbon atoms) and alkyl acrylate (alkyl having 1 to 8 carbon atoms) and 0 to 10% by weight of another monomer In the case of a copolymer obtained by polymerizing a first monomer mixture of a copolymerizable vinyl monomer, 10 to 30 parts by weight contains Wi% by weight of methyl methacrylate and W2% by weight of alkyl methacrylate (the alkyl group is Those having 2 to 8 carbon atoms), W3% by weight alkyl acrylates (alkyl groups are from .1 to 8 carbon atoms), and 4% by weight of a second monomer mixture of another copolymerizable vinyl monomer It is polymerized, and the second monomer mixture meets the following composition requirements: 2 0 S w 1 € 7 0, 〇 $ W 2 $ 6 0, go ^ Wa + Ws + weioo, and W4 = 1 〇0 — Wi -W2 — w3; and (Please read the notes on the back first

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This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 476772

5. Description of the invention (7) If this second monomer mixture is polymerized alone, the glass transition temperature obtained is at most 50 ° C. The method package for manufacturing an acrylic copolymer provided by another aspect of the present invention (please read the notes on the reverse side and write this page) includes: (1) Polymerization step, when there are 7 0-90 0 parts by weight containing 60- 95% by weight of alkyl methacrylate, 5 to 40% by weight of at least one selected from alkyl methacrylate (alkyl having 2 to 8 carbon atoms) and alkyl acrylate (alkyl having 1 to 8 In the case of a monomer obtained by polymerizing a monomer of 0-10% by weight and a copolymer of a first monomer mixture of another copolymerizable vinyl monomer, 10-30% by weight contains Wi% by weight Methyl acrylate, W2% by weight methacrylic acid ester (alkyl having 2-8 carbon atoms), 3% by weight alkyl acrylate (alkyl having 1-8 carbon atoms), and 4 A second monomer mixture of another copolymerizable vinyl monomer by weight is polymerized to form an acrylic copolymer latex, wherein the second monomer mixture meets the following composition requirements: 2 0 ^ W α ^ 7 0 »Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 0 SW 2 S 6 0, 9〇 $ Ψι + Ψ2 + Ψ3 $ 100, and 'W4 = 10-O—Wi—Wz—W3; and if this second monomer mixture is polymerized separately, the resulting glass transition temperature is at most 50 ° C; and (2) follow-up Coagulation step, in which the acrylic copolymer latex is mixed with a dilute coagulant aqueous solution (i) under agitation, so that the acrylic paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm)-476772

V. Description of the invention (8) Copolymer latex first undergoes proper agglomeration, and then agglomerates under stronger agglomeration conditions than the appropriate agglomerate, to complete the agglomeration of the acrylic copolymer latex. In the manufacturing method, 'the coagulant aqueous solution (i) for moderate coagulation is preferably an aqueous solution of an organic acid or an inorganic acid', and is added to the latex so that the P Η value of the latex in the coagulation after adding the solution is · 2. 4.5; or the flocculant aqueous solution (i) is preferably an aqueous solution of an inorganic acid or a mixture of an organic acid and an organic salt or an inorganic salt, < and added to the latex so that the latex pH in the coagulation is 3 · 0-6 · 0. Furthermore, if the aqueous solution of the coagulant used for moderate coagulation is an aqueous solution of an inorganic salt or an organic salt, the aqueous solution of the coagulant (i) preferably has an inorganic or organic salt solution of a monovalent, divalent, or trivalent cation, and the latex is added The concentration of salts contained in the latex in the intermediate coagulation is 0 · 08 — 0 · when monovalent cations, 0 · 05-0 · 05 mo when divalent cations, and 0 · 0008 when trivalent cations. — 0 · 00 5ποΡ / 5. The present invention further provides a vinyl chloride resin composition containing 100 parts by weight of a vinyl chloride resin and 0 · 1-2 5 parts by weight of the aforementioned acrylic copolymer. The above and other objects, features, and advantages of the present invention will be more obvious and easy to see after referring to the following preferred implementation system and the accompanying drawings. Brief description of the drawings Figures 1 to 4 are magnified photos of the powdery acrylic copolymer particles obtained in Examples 1 and Comparative Examples 2 to 4 using an optical microscope, respectively. The paper dimensions apply the Chinese National Standard (CNS) Α4 size (210 × 297 mm) (please read the precautions on the back first-horse page)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -11-476772

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) (magnification: 35 times). Detailed description of the invention [acrylic copolymer] The acrylic copolymer used in the vinyl chloride resin composition of the present invention is prepared by: containing 60 to 9 5% methyl methacrylate, 5 to 40 weight % At least one monomer selected from alkyl methacrylate (alkyl having 2 to 8 carbon atoms) and alkyl acrylate (alkyl having 1 to 8 carbon atoms) and 0 to 10% by weight In the case of another copolymer (1) obtained by polymerizing another monomer composition (first monomer mixture) of a vinyl monomer copolymerizable with the above monomer, an acrylic monomer mixture (2) (second monomer) is added Mixture) obtained by polymerizing the acrylic monomer mixture (2). If the content of methyl methacrylate in the first monomer mixture used for the copolymer (1) is less than 60% by weight, the mutual solubility between the obtained acrylic copolymer and the vinyl chloride resin is poor, so that the vinyl chloride resin The molded article obtained from the composition has poor transparency; if it is higher than 95% by weight, the dispersibility of the obtained acrylic copolymer in the vinyl chloride resin is insufficient, and an unfused portion is generated in the molded article of the composition. Or spots. In addition, unless the slurry is heated to a temperature of 100 ° C or above in the step of heat-treating the slurry after the following agglomeration process (the size is enlarged), the agglomerated particles will disintegrate into fine particles, and the operating characteristics cannot be obtained. Good powdery product. The latex of the copolymer (1) can be prepared through a one-step emulsion polymerization reaction method, but in order to reduce the degree of polymer adhesion to the reactor, it is better to use a two-step or multi-step emulsion polymerization reaction method. Or more (Please read the notes on the back before this page)

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This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -12-476772 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 The composition used in each step may be changed to obtain a final composition within the above range. More specifically, the acrylic copolymer obtained by using the copolymer (1) prepared by the one-step polymerization reaction requires a high agglomeration temperature when moderately agglomerated, and it is still difficult to obtain powder particles having excellent spherical shape. In order to improve the coacervation characteristics, an acrylic monomer mixture (2) containing methyl methacrylate, alkyl methacrylate (having a c2-8 alkyl group), and alkyl acrylate (having a <1-8 alkyl group) (No. Dimonomer mixture) (the composition of which is in accordance with the following relationship) is added to the latex of the copolymer (1) and the acrylic monomer mixture (2) is subjected to the emulsion polymerization reaction in the presence of the copolymer (1) latex Polymerization is a polymer having a glass transition temperature of at most 50 ° &lt;: The glass transition temperature is preferably from 20 ° C to 50 ° C, and more preferably from 10 ° C to 40 ° C. Specifically, the acrylic monomer mixture (2) contains Wi% by weight of methyl methacrylate, W2% by weight of alkyl methacrylate (having a C2-8 alkyl group), and W3% by weight of alkyl acrylate (having a Chs alkyl group) ) And W4% by weight of another vinyl monomer that can be copolymerized with the above monomers. This acrylic monomer mixture (2) meets the following composition requirements: 2 0 ^ W! ^ 7 0 * 〇 $ W 6 0, gosWi + Wz + w ^ ioo, and W4 = 100-Wi-W2-W3. Acrylic monomer copolymers that can be used with copolymer (1) and monomer mixture (2) Another suitable example of the above-mentioned vinyl monomer may include (please read the precautions on the back before filling this page) This paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 476772 No. 86100777 Patent Application Chinese Manual Amendment Page A7 B7 Fine April 1989 Amendment Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs ) Don't have methacrylonitrile, methacrylonitrile and styrene with C 9-12 alkyl group (but more appropriate in (2)). If the monomer mixture used (with no copolymer (150 ° C), the monomer mixture (2 polymerization process will inevitably be reduced at an inappropriate high temperature, which can reduce the temperature characteristics of moderate agglomeration, but The tendency of the resulting acrylic copolymer to decrease. Therefore, in order to influence the effect of moderate coagulation characteristics such as ethyl chloride, the glass transition temperature range to 40 ° C should be lower than the glass transition of the copolymer (1) to at least 10 ° C is better. The polymer that forms the outer shell of latex particles and is polymerized by its latex has a vinyl chloride resin with good processability (such as pectin and transparency and appearance, but if the excess is sufficient (and only using copolymers (1 The substance (2) is added to the copolymer (1) and is used for emulsification polymerization reaction at a degree of polymerization of 70 to 90 parts by weight of the copolymer (acid alkyl styrene 2))), The addition of a single-component coagulated property with a vinyl chloride resin at a special temperature will cause the amount of monomers to be mixed in the case. 1) It is formed by mixing glass with alkyl acrylate and propylene using only the monomer mixture. If it can be changed The ene resin composition is balanced and good. This at least 5 polymer-transition-temperature latex's glass transitions are moderately interpenetrating to reach glass transition ° C, and the solubility of coagulation at a temperature above the moderate condensation temperature alone is clear and The temperature change is 10 to 100 parts by weight.) For monomer mixtures, the effect of improving the coacervation characteristics is insufficient, and the bulk mixture (after measurement and melt viscoelastic processability change) must be set. Compound (2) 10-30 (2) if it is low and vice versa if it is higher than 2) and does not harm the sex) the effect is not determined by mixing the monomers, so that the amount is relative to the weight part (10 weight 3) 0 weight ^ -------------------- Order · -------- (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 Specification (210 X 297 mm) -14-476772 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs __5. Invention Description (12), the improvement of processability will be adversely affected The amount of the monomer mixture (2) is used in an amount of 12 to 75-88 parts by weight of the copolymer (1). 55 parts by weight is preferred. The acrylic copolymer of the present invention having excellent agglomeration characteristics is not particularly limited in its average degree of polymerization or average molecular weight, but it has a weight average molecular weight in the range of 104-1 (corresponding to a coacervation chromatography method) (Measured by polystyrene) is preferred. The average molecular weight of this acrylic copolymer can be set according to its purpose, for example, an acrylic copolymer manufactured to provide improved melt elasticity or improved foamability. It should preferably have a high molecular weight; conversely, the acrylic copolymer used to improve the gelation characteristics of vinyl chloride resin and to provide molded products with improved surface properties and transparency should preferably have a low molecular weight. The agglomeration method used in the present invention can be applied to the production of any type of acrylic copolymer. The acrylic copolymer having excellent cohesive properties can be prepared by a general emulsion polymerization reaction method. As the emulsifier, known anionic surfactants and non-anionic surfactants can be used. In addition, general water-soluble or oil-soluble polymerization initiators can be used alone or a redox catalyst system can be formed. The latex particle size of the acrylic copolymer is preferably in the range of 80 to 500 nm, and more preferably 100 to 250 nm. If it is lower than 80 nm, the outermost layer which has a favorable influence on the agglomeration characteristics will be too thin to provide a sufficient effect of improving the agglomeration characteristics, resulting in insufficient polymerization stability. Conversely, if the particle size of the latex is greater than 500 nm, the number of particles used as a polymerization site is insufficient, and the amount of polymer attached to the reactor is increased, so that the thermal conductivity is reduced and the reactor is not easily cooled. In addition, China National Standard (CNS) A4 specifications (210X29? Mm) are applicable to the paper size of the finished paper. ~ -15-(Please read the precautions on the back before filling this page) 476772 Employees of the Central Bureau of Standards, Ministry of Economic Affairs Printed by consumer cooperatives A7 B7_V. Description of the invention (13) The particles that are not gelled at the time of 13 tend to make the molded product of vinyl chloride resin poor in transparency. The acrylic copolymer latex usually has a solid content of 2-6 0. Range of weight%. [Cohesion of Acrylic Copolymers] If the acrylic copolymer latex with improved cohesive properties made by the above method and a dilute coagulant aqueous solution are blended under appropriate stirring conditions, spherical particles will begin to form over time. And increase the viscosity of the coagulation system. The state of increasing the viscosity of the agglomeration system will continue for a while, and then when most of the resin components are converted into spherical particles to form a so-called resin particle slurry, the viscosity of the agglomeration system will decrease. In order to form such resin particles, it is necessary to have a condition suitable for establishing an appropriate moderate aggregation state which can provide a moderate aggregation speed. For this reason, it is preferable to determine a dilute coagulant aqueous solution which satisfies the following conditions for blending. 1) When the aqueous solution of the coagulant is an aqueous solution of an inorganic acid or an organic acid, the mixture produced with the acrylic copolymer latex during the coagulation period has a p 2 value of 2 · 0-4 · 5 and a value of 2 · 5-4 · P 0 value of 0 is better. 2) When the aqueous solution of the coagulant is an aqueous solution of an inorganic acid or a mixture of an organic acid and an inorganic salt or an organic salt, the ρ Η value required for the coagulation time is higher, that is, 3.0-6.0, and 3.5-5.5 is preferred. 3) When the aqueous solution of the coagulant has a unit price, a divalent or a trivalent positive ion, the paper standard is applicable to China National Standards (CNS) A4 specifications (210 × 297 mm) &quot; &quot; (Please read the precautions on the back before filling (This page) 476772 When the A7 __B7_ printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People ’s Republic of China (14) of the inorganic electrolyte or organic electrolyte aqueous solution, the electrolyte contained in the mixture produced with the latex during the coagulation period. For the case of monovalent cations, the concentration is 0 · 08 — 0 · 5mo, preferably 0 · Ιο. For the case of divalent cations, it is 0 · 005 — 0 · 0 5moj2 / 5, where 0 · 006 — 0. 02moj? / 5 is preferred; in the case of trivalent cations, it is 0. 0008 — 0 • 005moJ? / 芡, and 0. 00 1-0.00. 3mo3 / 芡 is more preferred. As for the flocculant, it should be an inorganic acid or an organic acid, or an inorganic salt or an organic salt, mainly depending on the type of emulsifier used in the production of the acrylic copolymer latex. More specifically, if a carboxylic acid is used in the production of latex, Acidic emulsifiers, preferably with inorganic acids or Organic acids are used as coagulants; if a sulfonic or non-ionic emulsifier is used in the manufacture of latex, inorganic salts or organic salts should be used as coagulants. Preferred examples of coagulants include inorganic acids such as hydrochloric acid, Sulfuric acid and phosphoric acid; organic acids such as acetic acid, oxalic acid, and tartaric acid. Examples of electrolytes used as coagulants include: (1) those with monovalent cations, including inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, and sodium carbonate Organic acid salts such as sodium acetate, potassium acetate, sodium oxalate and sodium tartrate; (2) those with divalent cations, including inorganic salts such as calcium chloride, magnesium chloride and magnesium sulfate; organic acid salts such as calcium acetate and acetic acid Magnesium; and (3) those with trivalent cations, such as aluminum sulfate. The blending ratio of the acrylic copolymer latex and the coagulant aqueous solution should be such that the concentration of the coagulated slurry is 5-20% for coagulation (for granulation ) This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the notes on the back before filling this page) -17-476772 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____B7 V. Description of the invention (15) The process is smooth. When the slurry concentration is less than 5% by weight, the formation of spherical particles is insufficient to provide a powdery product with a wide particle size distribution and it is easy to cause dusting. If the concentration exceeds 2 0% by weight, it is prone to excessively increase the viscosity of the agglomeration system, which makes it difficult to obtain a uniform stirring state and produce an undesired wide range particle size distribution. The agglomeration temperature should be 20-70 ° C to make the agglomeration smooth, If it is lower than 20 ° C, it is difficult to cool the general industrial water and special cooling equipment is required. When the condensation temperature exceeds 70 ° C, the condensation speed will become too fast, which makes it suitable for obtaining moderate aggregation of spherical particles. Since it is extremely narrow, it is difficult to obtain an acrylic copolymer suitable for the purpose of the present invention. The coagulation temperature may also depend on the concentration of the coagulant and the stirring conditions, but it is significantly affected by the properties of the acrylic copolymer latex particles. Particles containing a copolymer with a low glass transition temperature as the outermost shell (easy to agglomerate) require a lower aggregation temperature, while particles containing a copolymer with a high glass transition temperature as the outermost shell require a higher aggregation temperature. Therefore, in order to perform the granulation smoothly by the moderate agglomeration method of the present invention, the copolymer constituting the outermost layer of the particles (the polymerization product of the above-mentioned monomer mixture (2)) has a glass transition temperature within the above-mentioned appropriate range (ie, at most 50) ° C, preferably between 10 and 40 ° C) becomes very important. The acrylic copolymer of the present invention used in a vinyl chloride resin composition can be obtained in the state of particles having a substantially spherical shape using only the above-mentioned moderate agglomeration method, but in some cases, only a small amount of non-agglomerated particles remain when the above-mentioned moderate agglomeration method is used. Latex, uncondensed latex is not from the viewpoint of producing fine powder and environmental sanitation (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (21〇 × 297 mm) ) -18-476772 Yin Sang A7 B7, Consumer Cooperative of Employees of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (16) What we want, in this case, it is best to use a coagulant for the second stage of coagulation to complete the coagulation. This second stage The coagulation process should be performed under strong coagulation conditions (for example, the concentration of the aqueous solution of the coagulant used is higher than that during a moderate coagulation process), so that a small amount of residual uncoagulated thin latex can be coagulated completely. More specifically, if only acid or When a mixed solution of an acid and a salt is used, the P Η value of the coagulation system should be suppressed to less than 2.0 after adding the acid or the mixed solution with the salt. If a monovalent cation salt is used, the concentration of the salt in the agglomeration system should be set to at least 0. If a divalent or trivalent cation salt is used, the concentration of the two in the agglomeration system should be set to at least 0 respectively. · 08moj? / 5 or at least 0 · Olmoj? / Again. In the second-stage agglomeration method used for agglomerating latexes, it is not necessary to use the same type of agglomerating agent as used in the moderate agglomeration method. The effect and economic factors of the obtained acrylic copolymer are appropriately selected. The detailed mechanism of the porous acryl-based acrylic copolymer obtained through the appropriate agglomeration method is not clear, but it may be related to the copolymer latex particles. A method of performing coagulation at a moderate speed using a dilute coagulant aqueous solution is related. Under the condition of rapid agglomeration of the acrylic copolymer latex, a granular product with a wide particle size distribution and irregularly shaped particles is produced. The combination of the copolymer composition with a particle structure, a method of agglomeration for moderate agglomeration, and the like may have resulted in porous particles suitable for use in a vinyl chloride resin composition. After the granulation is completed and the uncondensed latex disappears, if the slurry is alkaline, the system should be neutralized with hydrochloric acid; otherwise, if the slurry is acidic, it should be hydroxideed with paper. The Chinese National Standard (CNS) A4 specification is applicable. (210X297mm) ~ _ (Please read the notes on the back before filling out this page) 476772 A7 ______B7 V. Description of the invention (17) The system is neutralized by sodium, and then heat treated at a temperature of 50-100 ° C . The heat treatment temperature is related to the porosity of the granular product finally obtained. If the polymer has only a low glass transition temperature obtained by polymerizing the monomer mixture (2), a lower heat treatment temperature can be selected, otherwise the glass transition temperature can be used. Choose a higher heat treatment temperature. When the heat treatment temperature is too low, the granular product is liable to disintegrate, and when the heat treatment temperature is too high, the granular product is liable to have insufficient porosity, and the acrylic copolymer having excellent dispersibility and melting properties applicable to the vinyl chloride resin composition of the present invention cannot be obtained. . The heat-treated slurry can be dehydrated and dried in a general manner to obtain porosity-rich acrylic copolymer powder particles with high water washing efficiency and low polymerization component residues during dehydration, which are suitable for the vinyl chloride resin composition of the present invention, but Reduce its thermal stability. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The above-mentioned moderate agglomeration method for providing the acrylic copolymer of the present invention can be performed in batch operation or continuous operation. In batch operation mode, all operations can be performed in a single coagulation tank or the slurry after the coagulation is completely transferred to another stirring tank for subsequent neutralization or heat treatment operations. Conversely, if continuous operation is used, several stirring tanks can be set in series so that the condensation process can be performed in the first stirring tank, the condensation process can be completely performed in the second stirring tank, and processes such as neutralization and heat treatment can be performed. In the third and subsequent mixing tanks. Blending 0. 1-2 5 parts by weight of the acrylic copolymer thus obtained with 100 parts by weight of a vinyl chloride resin can obtain a vinyl chloride resin composition which can achieve another object of the present invention. If the blending amount is less than 0.1 parts by weight, sufficient improvement in processability cannot be achieved. Conversely, if the blending amount exceeds 25 weights, the Chinese paper standard (CNS) A4 size (210X 297 mm) is applicable to this paper size. -476772 A 7 B7 5. Description of the invention (18) Quantities, in some cases will significantly damage the performance of the vinyl chloride resin itself. The vinyl chloride resin used in the present invention described in the article may include vinyl chloride homopolymer ; Copolymers of vinyl chloride with other ingredients such as vinyl acetate, vinylidene chloride, alkane (such as ethylene and propylene), acrylates, long-chain alkyl vinyl esters or ethers, and acrylonitrile; and chlorinated vinyl chloride Resin. The degree of polymerization of vinyl chloride resin may be 400 to 3000, and 700 to 1 700 is preferred. Other additives commonly used in vinyl chloride resin compositions may be incorporated into the vinyl chloride resin composition of the present invention as needed. Examples thereof include stabilizers, lubricants, plasticizers, impact strength modifiers, colorants, Fillers, foaming agents, ultraviolet absorbers and infrared absorbers. As for the manner of incorporation of these additives, it can be carried out in a general manner and is not limited to any particular manner. [Example] Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The following will further explain the technical content of the present invention through the examples and comparative examples. However, the scope of the present invention is not It is not limited to the contents disclosed in the embodiments. The values described herein are determined or measured in accordance with the following methods. (1) Glass transition temperature (Tg) of the outermost copolymer of latex particles The glass transition temperature Tg (K) of the copolymer that constitutes the outermost layer of latex particles is based on the composition of the copolymer according to the following Fox's calculation formula (such as MD Baijal "Plastics Polymer Science of Technology" page 205 (1982), John Wiley &amp; Sons) This paper size applies to China National Standard (CNS) A4 (210X 297 mm)-21-476772 A7 B7 V. Description of the invention (19) 1 \ T g = Wi / T gi + W2 / T g2 + W3 / T g3 + ......

Wi: weight fraction of monomer component 1 W2: weight fraction of monomer component 2 W 3: weight fraction of monomer component 3

Tgi: polymer glass transition temperature of monomer component 1 (K) Tg2: polymer glass transition temperature of monomer component 2 (K) Tg3: polymer glass transition temperature of monomer component 3 (K) (2) latex particles The average particle diameter (diameter) of the particle diameter was measured with a sub-micron particle size analyzer ("Coulter Counter N4SD" by Coulter Electronics Inc.). (3) The average particle size of powdered acrylic polymer is cracked by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). It contains 0 · 2g of carbon black (for preventing static electricity) 20g powder samples are placed on the standard sieve stack series according to ASTM-EH11. The stacking order of these standard sieves is 20 mesh (mesh opening = 850 / zm), 35 mesh (500 // m), 45 mesh (355 μm), 50 mesh (300em), 60 @ (250 gm), 70 mesh (212 // m), 100 mesh (150em), 140 mesh (106em), and 325 mesh (45 // m), the size of this paper applies Chinese National Standards (CNS) A4 specifications (210X297 mm)-11-476772 Printed by A7 __B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) Use external electromagnetic vibration for 10 minutes to measure the amount of powder on each sieve ^ Draw the cumulative particle size distribution curve from the amount of powder on each sieve (cumulative amount to the opening of the mesh), and then use the cumulative amount of 50% by weight particles on the curve The diameter is regarded as the average particle diameter. (4) The fluidity and the slag characteristics of the powdery acrylic copolymer are measured by a specific gravity meter (1 2 Omj?) According to JIS-K-6 7 2 1 for the time that the sample powder naturally falls due to its gravity. This time was used as an index of the fluidity of the sample powder. During the powder fall, observe the situation of powder spreading at the same time and divide it into the following grades A: No flying dust B: Slight flying dust C: Clear flying dust (5) The transparency of the vinyl chloride resin composition is on a kneading roller with a surface temperature of 180 ° C The vinyl chloride resin composition containing the acrylic copolymer and having the following formula was kneaded for 3 minutes, and the sheet-shaped kneaded product was preheated on a press having a surface temperature of a pressure plate of 200 ° C for 2 minutes, and then A load of 150 kg / cm2 was applied for 1 minute to form a 3 mm thick sheet-like product. A piece was cut out from the sheet product, and the parallel light transmittance (parallel 1 i g h t t r a n s m i 11 a n c e, T p) and haze (Η) were measured according to J I S — K-7 105. • li m 1— —LI Ism I i I (Please read the precautions on the back before filling in this page) The paper size of the book is applicable to Chinese national standards (_Α · (210χ · Thin) _ _ 476772 A7 __B7_ V. Description of the invention 21) Vinyl chloride resin composition Vinyl chloride resin (degree of polymerization K = 5 7) 100 parts by weight of acrylic copolymer 2.0 dioctyltinyl type stabilizer 2.5 stearic acid monoglyceride 1.0 stearic acid G.3 ( 6) Anti-drawdown properties of vinyl chloride resin composition The vinyl chloride resin composition containing the composition described in (5) above is passed through a diameter of 20 mm and a ring mold with an outer diameter of 10 mm facing downward. The single-screw extruder with a die and a die temperature of 1 8 — 19 ° C is used to extrude into a rod-like product. Measure the time that the molded product is extruded to a length of 60 cm. A longer time indicates better anti-draft properties. It is helpful for the manufacture of uniform thickness molded products during molding and processing by suction molding. (7) Gelation properties of vinyl chloride resin composition Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) Fill out this page again) Let vinyl chloride have the composition described in (5) above The fat composition is passed through "plasti-corder" (available from BRABENDER OHG DUISBUG). Knead under the following conditions to measure the gel time from the beginning of kneading to the time when the maximum force is exhibited. Kneader type: Type 50 Sleeve temperature: 1 3 5 ° C Rotor speed: 35rpm This paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) -24-476772

V. Description of the invention (22) w-Sample weight: 5 2 g (8) Fisheye phenomenon of vinyl chloride resin composition (i) Hard resin composition The vinyl chloride resin composition having the composition described in (5) above is passed through A 3 mm single-screw extruder equipped with a T die was extruded at a die temperature of 18 to 190 ° C to produce a 1 mm thick sheet-like product. From this sheet-shaped product, a strip of 2 3 mmx was taken out. For a 100 mm test piece, count the number of ungelated spots on the test piece with a size of 0.1 mm or more. (ii) Soft resin composition: 5 1 g of a vinyl chloride resin composition having the composition described below was fed into a "plasticorder" (kneader type: 50, as used in (7) above) at 1 5 ° C Kneading temperature and 50 r pm rotor several degrees, kneading for 10 minutes, and pressing at 180 ° C press temperature to form a sheet sample with a thickness of 100mm × 100mm and a thickness of 0.1mm. (Please read the note on the back first matter

(This page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs and counting the number of transparent spots. Vinyl chloride resin (k = 71) 100 parts by weight of acrylic copolymer 5.0 dioctyl tin fluorene-based stabilizer 3.0 plasticizer (dioctyl phthalate) 6.0 carbon black 0.5 This paper applies Chinese national standards (CNS) A4 specifications (210X297 mm) _ 2 5 476772 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____B7___ V. Description of the invention (23) Example 1 [Manufacture of acrylic copolymer latex] Ionized water was added to a reaction tank equipped with a stirrer, and then the system was heated to 50 ° C with nitrogen. Tetrasodium pyrophosphate 0.1 parts by weight Ferrous sulfate 0.0 Q 2 Disodium ethylenediamine tetraacetate 0.003 Potassium oleate (15.5%) aqueous solution 10.9 Deionized water 200 Then add the following monomers while stirring Mixture (1). (Monomer mixture (1)) Methyl methacrylate 32.0 parts by weight butyl methacrylate 4.0 butyl acrylate 4.0 Subsequently, 0.004 parts by weight of third butyl hydrogen peroxide and 0 · 0 0 8 Part by weight of sodium formaldehyde sulfoxylate was added to the reaction tank at 50. (: Acrylic copolymer latex (A) is obtained by emulsion polymerization for 3 hours. 〇Add the above monomer mixture (1) with the same amount of the third butyl hydrogen peroxide and sodium formate sulfoxylate to the latex ( In step A), a second-stage emulsion polymerization reaction was performed at 50 ° C for 3 hours to obtain an acrylic copolymer (B). The following monomer mixture (2) and a polymerization assistant were added to the copolymer latex (B) Medium 'The third-stage emulsification polymerization is carried out at 50 ° C. The paper size applies Chinese National Standard (CNS) A4 specification (210X 297)' ~ ~ -26-(Please read the notes on the back before filling (This page) 476772 A7 B7 V. Description of the invention (24) It takes 4 hours to obtain the acrylic copolymer latex (C). The polymerization reaction yield is calculated by the amount of residual monomer in the latex (measured through analysis): and 99.8%, with an average latex particle size of 118 nm. (Monomer mixture (2)) 10. 0 parts by weight 4. 0 6.0 0. 02 0. 04 (Please read the precautions on the back before filling in this Page) Methyl methacrylate, Butyl methacrylate, Butyl acrylate The monomer composition added at each stage of hydrogen oxide, formaldehyde and sodium bisulfite is shown in Table 1, and the monomer composition used in other examples is also included. [Cohesion of acrylic copolymer latex (C)] Central of the Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau. Add 600 parts by weight of 0.0 1111 05 / $ hydrochloric acid aqueous solution to a condensing tank equipped with a stirrer and heat to 5 5 ° C. Then 301.4 parts by weight (containing 100 parts by weight of solids) of the above-mentioned acrylic copolymer latex (C) was added, and the pΗ value in the agglomeration tank was 3.5 at this time. After ten seconds, the viscosity in the agglomeration tank increased to the beginning of the formation of spherical particles. Part of the latex will turn into spherical particles when the viscosity of the system drops to the end of moderate aggregation. A small amount of unaggregated latex remains in the agglomeration tank, and 100 parts by weight of 0 · 40m οί / j? Hydrochloric acid aqueous solution is added to the agglomerate. After the coalescence is completed, the system is neutralized with an aqueous solution of sodium hydroxide. The paper size applies the Chinese National Standard (CNS) A4 (210X 297 mm) -27-476772 A7 B7 Central Standard of the Ministry of Economic Affairs Bureau staff Printed by Fei Cooperative 5. Description of the invention (25) The produced slurry is heated to 90 ° C for heat treatment, and the resulting slurry is filtered, washed, dehydrated and dried to obtain a powder sample of an acrylic copolymer (a) The powder sample (a) has a narrow particle size distribution (sharp), contains very few fine powders, and consists of spherical particles with excellent fluidity. Optical micrographs (magnification) of this powder sample 3 5 times) is shown in Figure 1. The properties of the powdery sample (a) and the performance of the vinyl chloride resin composition obtained from the sample are shown in Table 1. Example 2 and Comparative Examples 1 to 3 The emulsification polymerization was carried out in the same manner as in Example 1, but the monomer composition at each stage was changed as shown in Table 1. Next, it was agglomerated in the same manner as in Example 1 except that the temperature at a moderate agglomeration was changed as shown in Table 2 to obtain powder samples of acrylic copolymers (b)-(e). Their properties and evaluation efficiency Shown in Table 2. The optical micrographs of the powdery tests (c) and (d) (magnification of 35 times) are shown in Figures 2 and 3. More specifically, in Comparative Example 1, only methyl methacrylate was used as the monomer component of the first and second stages of the emulsion polymerization reaction, and in the third stage, the same composition as in Example 1 was used. The powdery test (b) of Comparative Example 1 contains less fine powder and has excellent fluidity similar to the powdery test (a) of Example 1. From these results, it can be confirmed that the copolymer having a low glass transition temperature is the outermost layer. The structure of latex particles can effectively achieve good moderate agglomeration characteristics. However, when the first stage and the second stage polymerization are only the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~~ &quot;-28-(Please read the precautions on the back before filling in this Page) 476772 A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (26) During the homopolymerization of methyl methacrylate, the acrylic copolymer produced cannot be adequately represented in the vinyl chloride resin composition The dispersibility of the copolymer caused a lot of fish eyes, so that the copolymer could not achieve the effect of improving the workability of vinyl chloride resin. The copolymer of Comparative Example 2 did not have the outermost layer of the composition required to improve cohesiveness, so its powdery test (c) had a small average particle size and contained a large amount of fine powder that caused dust (see Figure 2). The powder obviously has poor flowability. The composition of Comparative Example 3 was prepared by adding 80 parts by weight of a monomer mixture having the same composition as the monomer mixture (2) of Example 1 and emulsifying the acrylic copolymer emulsion (B) of Example 1 The polymerization reaction caused 100 parts by weight of the obtained latex to contain 50 parts by weight of the inner layer polymer and 50 parts by weight of the outermost polymer, that is, the two are equal, as shown in Table 2. The agglomeration temperature of Example 3 is lower than that of Example 1. Therefore, the characteristic showing moderate agglomeration is related to the amount of the polymer constituting the outermost shell layer. In addition, the vinyl chloride resin composition obtained from the powdery sample (d) of Comparative Example 3 had poor penetration so that it could not show a good balance with the powder properties. (By the way, the agglomeration temperature is constant. In order to facilitate the operation, a temperature range of about 1 0 0-2 0 0 // m average particle size (room temperature to about 7 5 ° C) is generated.) In the second embodiment, the third-stage emulsion polymerization reaction was changed. The monomer composition obtained when polymerized alone results in a polymer with a glass transition temperature (T g) of less than 0 ° C. and thus latex particles with a soft outermost layer. The resulting latex is used to provide a moderate particle size distribution of powdery products with an appropriate particle size distribution. This paper is based on China National Standard (CNS) A4 specifications (210 '乂 297 Kg ^ 1 ~ (Please read the precautions on the back before filling in (This page) 476772 A7 ____B7 __V. Description of the invention (27) 4 5 ° C, and the moderate condensation temperature changes with the change of the outermost polymer glass transition temperature. Example 3 [Manufacture of acrylic copolymer latex] An acrylic copolymer latex (A) was prepared in the same manner as in Example 1, and the following monomer mixture (3) and a polymerization assistant were added to a reaction tank containing the latex (A) to perform at 50 ° C. Acrylic copolymer latex (B) was obtained in the second stage of emulsion polymerization reaction for 3 hours. (Monomer mixture (3)) (Please read the precautions on the back before filling this page) Butyl methacrylate The third butyl hydroperoxyformaldehyde sodium bisulfite 25.5 parts by weight 4. 5 0. 004 0. 008 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The following monomer mixture (4) and polymerization reaction aid Agent In the latex (D), an acrylic copolymer latex (E) was obtained by performing a third-stage emulsification polymerization reaction at 50 ° C for 4 hours. (Monomer mixture (4)) Methyl methacrylate acrylate acrylic acid Ester ethyl ester third butyl hydroperoxyformaldehyde and sodium bisulfite 12. 0 parts by weight 6. 0 12. 0 0. 02 0. 04 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -30-476772 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) [Cohesion of acrylic copolymer latex (E)] Let acrylic copolymer latex (E) be the same as in Example 1. Coagulation was performed in the same manner, and the obtained slurry was filtered, washed, dehydrated, and dried to obtain a powdery sample (f) of an acrylic copolymer. From the results shown in Table 3, it can be seen that the powdery sample (f) is the powder of Example 1. Samples generally have good powder properties, and can provide a vinyl chloride resin composition with similarly excellent performance. Examples 4 to 6 Let the part of the acrylic copolymer latex (E) prepared in Example 3 be similarly implemented. Example 3 way cohesion However, the species and concentration of the coagulant aqueous solution were changed to those shown in Table 3, and the powdered samples of the acrylic copolymer were obtained without neutralization (g) — (i), The evaluation results are shown in Table 3. Comparative Example 4 600 parts by weight of 0.006 moj2 / calcium chloride aqueous solution was added as a coagulant aqueous solution to a coagulant tank equipped with a stirrer and heated to 5 6 ° C. Part of the acrylic copolymer latex (E) 301 · 4 parts by weight (containing 100 parts by weight of solids) prepared in Example 3 was added to the coagulation tank for coagulation. At this stage, 90% or more of the coagulation tank was coagulated. The latex is in an unagglomerate state. Then add 100 parts by weight of 0.5m05 / i2 sodium chloride aqueous solution to the system to complete the coagulation, and then filter, wash, dehydrate and dry the paper. The size of the paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) &Quot; -31-(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative Department of the Central Bureau of Standards of the Ministry of Economic Affairs 476772 A7 _______B7 __ V. Description of the Invention (29) Acrylic copolymer powder was obtained after drying Test sample (j). As shown in the optical micrograph in Fig. 4 (magnification of 35 times), the ‘powder sample (j) contains many fine powders, which is likely to cause yang 麈’, and contains particles with irregular shapes, which results in poor fluidity. Comparative Example 5 Moderate coagulation was performed in a similar manner as in Example 4, but the concentration of the aqueous solution of calcium chloride added to the coagulation tank was changed to 0.1 lmoi / j ?, as a result, the solids in the latex adhered to the agitator and these solids were unable to The product was recovered as a powder.賨 Example 7 [Production of acrylic copolymer latex (F)] An acrylic copolymer latex (F) was prepared in the same manner as in Example 1. However, when the first-stage emulsion polymerization reaction was carried out, the polymer used in Example 1 was prepared. The monomer mixture (1) and the polymerization assistant were changed to the monomer mixture (5) and the polymerization assistant shown below. (Monomer mixture (5)) 18.0 parts by weight of methyl methacrylate, butyl acrylate 2.0, tertiary butyl hydroperoxide 0.02, sodium ammonium formate sulfoxylate 0.04, and the following monomer mixture (6) and polymerized The reaction auxiliary is added to the copolymer latex (F) and the second-stage polymerization reaction is performed at 50 ° C for 3 hours. The paper size is applicable to the Chinese National Standard (CNS) Ai see grid (210X 297 male 4) ---:- (Please read the notes on the back before filling this page)

476772 A7 B7 5. Description of the invention (30), and then further adding the following monomer mixture (6) and polymerization assistant to carry out the third-stage emulsification polymerization reaction to obtain acrylic copolymer latex (G). (Monomer mixture (6)) Methyl methacrylate, butyl acrylate, tert-butyl hydroperoxide, and formaldehyde sodium sulfoxylate 2 4. G parts by weight 6. 0 0. 03 0. 04 The following monomer mixture ( 7) Add the latex (G) and a polymerization assistant to the latex (G) to perform the fourth-stage emulsification polymerization reaction at 50 ° C for 4 hours to obtain an acrylic copolymer latex (Η). (Monomer mixture (7)) Methyl methacrylate, butyl methacrylate, acrylonitrile, third butyl hydroperoxide, formaldehyde and sodium bisulfite 0.0 3 0. 04 (Please read the precautions on the back before filling in this page ) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs [Condensation of acrylic copolymer latex (Η)] Let the acrylic copolymer latex (Η) condense in the same manner as in Example 1, but the temperature of the hydrochloric acid aqueous solution is The temperature was changed to 60 ° C. The resulting slurry was filtered, washed with water, dehydrated, and dried to obtain a powdery sample (¢) of an acrylic copolymer. The results of evaluating the powder properties and performance are shown in Table 4. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 476772 A7 B7__V. Description of the invention (31) Comparative Example F; The monomer mixture used in Example 7 (5)-(7) is different The acrylic copolymer latex (I) was prepared in the following order. The preparation order was based on the first stage of the emulsion polymerization reaction using the monomer mixture (7) provided as the outermost layer of Example 7. The second stage of the emulsion polymerization reaction used the monomer mixture ( 5), and the third and fourth stages of the emulsification polymerization use the monomer mixture (6), and the other aspects are in the same manner as in Example 7. Therefore, the particles of the acrylic copolymer latex (I) contain the innermost layer of the polymer constituting the outermost layer of Example 7 and the outermost layer of the polymer constituting the intermediate layer of Example 1. The latex (I) was treated in the same manner as in Example 1, except that the moderate condensation temperature was changed to 68 ° C to obtain a powdery sample (m). The properties and performance are shown in Table 4. As shown in Table 4, the powdery sample (m) contains many fine powders, which is liable to cause dust and has poor fluidity, and the obtained vinyl chloride resin composition has a slow gelation speed, more fish eyes, and a hard resin composition. Shi Ran (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Comparative Example 7 All monomers used in each polymerization reaction stage of Example 7 are blended to form a monomer Mixture, this monomer mixture is divided into four parts of 20, 30, 30 and 20 parts by weight, and the four parts are used for the four-stage emulsion polymerization reaction in order, and the other aspects are performed under similar conditions of Example 7 to form Acrylic copolymer latex (J). The latex (J) was treated in the same manner as in Example 1, but the moderate condensation temperature was changed to 65 ° C to obtain a powdery sample (η). Its properties and efficiency are in accordance with Chinese national standards (CNS). Α4 specifications (210 × 297 mm) \ -34-476772 A7 B7 V. Description of the invention (32) I ~ ~ M are shown in Table 4 1 and Table 4 '__ (11) and powder sample (m) — both sample It is easy to cause dust, and the gelled green resin composition has poor gelation properties and a large number of fish eyes (in the case of a hard resin composition). (Please read the notes on the back _ IV Pack-, the book is printed on the paper printed by the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives. The paper size applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -35 476772 A7 B7 V. Description of the invention (33) Table 1: Composition of monomers used to make acrylic copolymers (* 1) 'The first stage of MMA / ΜΒΑ / ΒΑ / ΑΝ The second stage of MMA / ΒΜΑ / ΒΑ The third stage of MMA / ΒΜΑ / BA Ε Fourth stage ΜΜΑ / ΒΜΑ / BA / AN Example 1 32 4 4-32 4 4 10 4 6-Comparative Example 1 40-1-40--10 4 6 2 32 4 4-32 4 4 3 32 4 4-32 4 4 40 16 24 Example 2 32 4 4-32 4 4 6 4-----3 32 4 4-25.5-4.5 12 6-12----4 32 4 4-25.5 -4.5 12 6-12----5 32 4 4-25.5-4.5 12 6-12----6 32 4 4-25.5-4.5 12 6-12----Comparative Example 4 32 4 4-25.5 — 4.5 12 6-12 One-on-one 5 32 4 4-25.5-4.5 12 6-12----Example 7 18-2 • 24-6 24 -6-9 5 5 1 Comparative example 6 9 5 5 1 18 — 2 24 -6-24-6- 7 (Μ7): &quot; 2Χ〇.2 (Μ7 ) * 2 × 〇 · 2 (M7Γ 2 × 〇 · 2 (Μ7) * 2 × 〇 · 2 * 1: MMA: methyl methacrylate, BMA: butyl methacrylate, BA: butyl acrylate, EA: ethyl acrylate , AN: acrylic eyes * 2: ΜΜΑ / ΜΒΑ / ΒΑ / ΑΝ = 75/5/19/1 (same as all monomers in Example 7). — Rj --- ^ ------ (please first Read the notes on the back and fill in this page.) Order the paper printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) -36-476772 A7 B7 V. Description of the invention ( 34) Table 2: Powder properties and performance of acrylic copolymers Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 2 Particle size (nm) of the latex 118 120 119 139 119 Coagulation temperature (° c) 55 57 79 29 45 Powder sample (a) (b) (c) (d) (e) Outer layer Tg (° C) 23 23 m 23 -7 Average particle size (from) 145 170 82 288 180 Flowability (sec.) 10 12 25 12 20 Dust performance of ABCAA PVC composition Draft (sec.) 121 120 122 112 120 Gelation time (min.) 1.7 3.6 2.0 1.2 2.1 Parallel light transmission (Tp%) 85.6 80.1 85.7 79.1 77.3 Haze (Η%) 2.1 3.6 2.0 4.0 5.1 Fisheye (number) (i) 25 Uncountable 250 6 7 (ii) 2 51 13 1 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -37-476772 A7 B7 V. Description of the invention (35) Table ^ Properties and performance of acrylic copolymer powder Example 3 Example 4 Example 5 Example 6 Comparative Example 4 Comparative Example 5 Latex particle size (lira) 120 120 120 120 120 120 Moderate coagulant HC1 CaCl2 CaCl2 AlCla CaCl2 CaCl2 Concentration (πι5 / 3Π 0.01 0. 009 0. 009 0. 0025 0.006 0.01 Extra Coagulant HC1 CaCl2 CaCl2 CaCl2 CaCl2-Concentration (raoi / iH 0.4 0.4 0.4 0.4 0.5 0.5-Coagulation temperature (° C) 57 56 56 56 56 56 Powder sample (f) (g) (h) (i) Cj) (k ) Outer layer Tg (° C) 26 26 26 26 26 26 26 Average particle size (in) 155 175 150 140 92-Flowability (sec.) 7 8 6 11 21 Yangyao AAAAC-Performance Draft of PVC Composition (sec .) 119 121 120 120 119 Gel time (rain.) 1.6 1.8 1.6 1.5 1.2-Parallel light transmission (Tp%) 85.2 85.1 85 · 3 85.0 85.0-Haze (Η%) 2.1 2.1 2.0 2.2 2.1-Fish Eyes (number) (i) 28 27 32 21 20-(ii) 3 4 2 1 0-(Please read the notes on the back before filling this page) The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -38-476772 A7 B7 V. Description of the invention (36) Printed by the Consumer ’s Cooperatives of the Central Standards Bureau of the Ministry of Economics Table 4: Acrylic acid Powder properties and performance of the copolymers Example 3 Example 4 Example 5 Latex particle size (nra) 115 109 131 Coagulation temperature (° c) 60 68 65 Powder sample (1) (m) (η) outermost 最Tg (° C) &lt; 28 &lt; 57 &lt; 55 Average particle size U) 148 91 88 Flowability (sec.) 9 16 18 Dust ACC Performance of PVC composition Draft (sec ·) 121 120 119 Gelation time (min.) 1.7 3.6 3.4 Parallel light transmittance (Tp%) 85.6 85.2 85.3 Haze ⑽) 2.0 2.2 2.2 Fisheye (number) (i) 36 112 96 (ii) 5 3 2 (Please read the note on the back first Please fill in this page again for the items) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) -39-476772 A7 __B7_ V. Description of the invention (37) As mentioned above, the acrylic copolymer of the present invention Has a composite structure, including mainly containing methyl methacrylate and Effectively improve performance of various vinyl chloride resin and a layer of polymer particles on the polymer glass transition temperature of the particles formed of the acrylic copolymer of at most 5 0 ° C the. As a result, through moderate coagulation, this acrylic copolymer provides a powdery product containing a very small amount of fine powder, which is not easy to cause danger (such as dust explosion), and is also excellent in handling characteristics. In addition, the powdery acrylic copolymer particles of the present invention are porous and contain many micropores. Therefore, the acrylic copolymer has excellent melt dispersibility during the manufacturing process or when blended with a vinyl chloride resin to form a composition. There is almost no unfused material in the resulting product. These effects are also exhibited when a vinyl chloride resin composition product containing a soft resin composition containing a large amount of plasticizer is formed. Therefore, the acrylic copolymer of the present invention has excellent performance when used as a processability improver of a vinyl chloride resin composition suitable for general use. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for China National Standards (CNS) Α4 (21 × 297 mm) 1 40 1

Claims (1)

7 ^ 6 7 Public I • Employment is a wooden complaint 8888 ABCD V / X VI. Applying for a patent i .. (Please read the precautions on the back before filling this page) Patent Application No. 861GG777 Chinese Patent Application Scope Amendments in October 1990, Amendment 1 · A powdery acrylic copolymer was prepared by a method including the following steps: (1) Polymerization reaction steps printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 90 parts by weight is composed of 60 to 95% by weight of methyl methacrylate, and 5 to 40% by weight of at least one selected from the group consisting of alkyl methacrylates (alkyl groups having 2 to 8 carbon atoms) and alkyl acrylates (alkanes In the case of a copolymer obtained by polymerizing a monomer having a group consisting of 1 to 8 carbon atoms) and a first monomer mixture of 0 to 10% by weight of another copolymerizable vinyl monomer, 10 -3 0 parts by weight containing Wi% by weight of methyl methacrylate, W2% by weight of alkyl methacrylate (alkyl having 2 to 8 carbon atoms), and W3% by weight of alkyl acrylate (alkyl having 1-1 8 carbon atoms) and ~ 4% by weight A second monomer mixture of another copolymerizable vinyl monomer is polymerized to form an acrylic copolymer latex, wherein the second monomer mixture meets the following composition requirements: 2 0 ^ W α ^ 7 0 »〇 $ W 2 S 6 0, 〇 $ W 7 0, 9 0SWi 10 W2 + W3S100, and W4 = 1 00—Wi—W2—w3; and if this second monomer mixture is polymerized alone, the glass transition of the resulting copolymer · This paper uses China National Standard (CNS) A4 (210X297 mm) -1 476772 A8 B8 C8 D8 6. The temperature range of patent application is at most 50 ° C; and (Please read the precautions on the back first (Fill in this page again) (2) A subsequent coagulation step, in which the acrylic copolymer latex is mixed with a dilute coagulant aqueous solution (i) under agitation, so that the acrylic copolymer latex is first moderately coagulated, and then The modest agglomeration is performed under strong agglomeration conditions to complete the agglomeration of the acrylic copolymer latex, wherein the modest agglomeration is performed in any one of the following modes (A), (B), and (C): (A ) The coagulant The solution (i) is an aqueous solution of an organic acid or an inorganic acid and is added to the latex to make the latex in the agglomerate have a pH value of 2.0 to 4.5 after adding the solution; (B) the aqueous solution of the coagulant (i) is an inorganic acid or An aqueous solution of a mixture of an organic acid and an organic salt or an inorganic salt, and is added to the latex to make the latex pH in the agglomeration pH 3.0-6.0; and (C) the coagulant aqueous solution (i) has a monovalent, An aqueous solution of an inorganic or organic salt of a divalent or trivalent cation, and added to the latex so that the concentration of the salt contained in the latex in the agglomeration is printed for the monovalent cation for the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 08 — 0.5m0P / $, in the case of divalent cations, 0. 005 — 0. 05mo $ /, and in the case of trivalent cations, 0.0008 — O.OOSmo ^ / ^. 2. The acrylic copolymer according to item 1 of the patent application range, wherein the moderate agglomeration is performed in (A) mode. 3. The acrylic copolymer according to item 1 of the patent application range, wherein the moderate agglomeration is performed in (B) mode. 4. If the acrylic copolymer of item 1 in the scope of patent application 'wherein the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) — 2-476772 A8 B8 C8 D8 6. The scope of patent application should be moderate Coacervation is performed in (C) mode. 5. A vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin and 0.1-25 parts by weight of an acrylic copolymer according to any one of claims 1 to 4 of the scope of patent application. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is based on China National Standard (CNS) A4 (210X297 mm)-3-