KR101181674B1 - Method for making uniformly particle sized Acrylic polymer with impact resistance using emulsion latex - Google Patents

Abstract

The present invention relates to a method for producing acrylic resin particles having excellent impact resistance, wherein the suspension latex is mixed with an acrylic latex prepared by emulsion polymerization to provide excellent impact resistance. It relates to a method for producing acrylic resin particles.

According to the present invention, when the suspension polymerization is carried out using a heterogeneous suspension dispersant when producing one type of suspension dispersant, acrylic resin particles having a uniform shape and size can be produced. At the same time, it reduces the content, improves yield, prevents process problems caused by particle aggregation, and reduces dusting during extrusion.

Polymethyl methacrylate resin, acrylic latex, polyvinyl alcohol, hydroxyethyl cellulose, impact resistance

Description

Method for making uniformly particle sized Acrylic polymer with impact resistance using emulsion latex}

The present invention relates to a method for producing an acrylic resin particle of uniform size having excellent impact resistance, and, in suspension polymerization by mixing an acrylic latex prepared by emulsion polymerization with an acrylic monomer, polyvinyl alcohol and hydroxyethyl cellulose as a suspension dispersant. It relates to a method for producing acrylic resin particles characterized in that the use of.

Polymethyl methacrylate (hereinafter referred to as 'PMMA') resin is a polymer of methyl methacrylate (hereinafter referred to as 'MMA'), which polymerizes MMA alone or bulk polymerization, suspension polymerization, solution of a small amount of other acrylate monomers. It is resin manufactured by copolymerization by superposition | polymerization etc .. However, the PMMA resin produced in this way has a weaker impact strength than other plastic materials, so it has a defect that is easily broken by external impact. Therefore, techniques for impact resistance reinforcement using impact modifiers have been studied.

Conventional impact-resistant acrylic resin is obtained through the process of melting and extruding the powder or flake-shaped impact modifier obtained in the step of flocculating, dehydrating and drying the elastomer latex at a high temperature with the acrylic resin.

However, it is difficult to say that the latex produced by emulsion polymerization in powder form is satisfactory in terms of economics and energy saving. In addition, the possibility of alien substances in the latex dehydration and drying process may increase, which may impair optical properties.

In order to overcome this disadvantage, in case of suspension polymerization by dispersing acrylic latex in acrylic monomer without going through the dehydration / drying step, the process step is reduced and it is attractive in terms of economics or optical properties, but it remains due to the emulsifier remaining during suspension polymerization. Compared to the suspension polymerization of the particle size distribution is wider, it will contain a large amount of fine particles (fine powder). Although this lowers the polymerization yield, it causes process problems such as microparticles sticking to the surface of the polymerized particles and causing agglomeration of the polymerized particles, or hindering the work environment and processability due to flying of the microparticles during processing.

The present invention is to solve the problems of the prior art as described above, it is an object of the present invention to provide impact-resistant acrylic resin particles having a uniform particle size and less fine powder and improved yield and extrusion processability.

More specifically, in the step of converting from emulsion polymerization to suspension polymerization using a heterogeneous suspension dispersant during suspension polymerization, the stability of the acrylic latex is improved, and the acrylic latex is stably dispersed in the acrylic matrix resin stably by suspension polymerization. It is an object of the present invention to provide a method for producing acrylic resin particles of uniform size having excellent impact resistance.

The present invention has been made in order to achieve the above object, the inventors of the present invention by using a mixture of different polyvinyl alcohol and hydroxyethyl cellulose as a suspension dispersant during suspension polymerization, in the conventional emulsion-suspension using one type of suspension dispersant The present invention has been completed by discovering that acrylic resin particles having a more uniform shape and size than the sum can be reproducibly produced and having excellent impact resistance.

Hereinafter, the present invention will be described in more detail.

At this time, if there is no other definition in the technical terms used in the present invention, it has a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs, and in the following description unnecessary the gist of the present invention Descriptions of well-known functions and configurations that may be blurred are omitted.

The present invention comprises the steps of (A) mixing polyvinyl alcohol and hydroxyethyl cellulose with an acrylic monomer, a flocculant and a suspension dispersant in ion-exchanged water; (B) adding an acrylic latex prepared by emulsion polymerization to the mixture of step (A) to disperse the acrylic latex onto an acrylic monomer; (C) suspending polymerization by adding a chain transfer agent and an initiator on the acrylic monomer in which the acrylic latex of step (B) is dispersed.

Hereinafter will be described in detail with respect to the configuration of the present invention.

In the present invention, the acrylic latex of the impact modifier used in the step (B) has a seed / core / shell (seed / core / shell) structure by emulsion polymerization of two to three stages to reinforce hard acrylic resin It is manufactured to have.

The method for preparing the acrylic latex is divided into the first aspect and the second aspect, the method of manufacturing the first aspect is a glass transition temperature of 20 ℃ by adding an acrylic monomer, an emulsifier, a graft agent and an initiator to ion-exchanged water First stage polymerization to produce seed particles above; A second stage polymerization in which an acrylic monomer, a comonomer, a crosslinking agent, an emulsifier, an initiator, and a graft agent are added to the polymer by the first stage polymerization to graf the rubbery core having a glass transition temperature of 0 ° C. or lower to the seed particles; And a third step of preparing an acrylic latex by adding an acrylic monomer and an initiator to the polymer by the second step of polymerization to graf the glassy shell having a glass ion degree of 20 ° C. or higher to the core.

In the first step of the first aspect, when the ion-exchanged water temperature in the reactor reaches 70-90 ° C. under a nitrogen stream, acryl-based monomers, emulsifiers, graft agents and initiators are added to obtain glass seed particles.

The ion-exchanged water is preferably used 100 to 500 parts by weight based on 100 parts by weight of the total monomer used in the production of acrylic latex.

In order to control the size of the innermost glass-like seed particles, it is possible to control the content of an emulsifier, and the acrylic monomer used in the first step of the first aspect is 1 to 40% by weight based on the total monomer weight used in preparing the acrylic latex. It is preferable to use as.

In the second step of the first aspect, an acrylic monomer capable of forming a rubber phase in the polymer by the first step polymerization, styrene or halogen having a high refractive index to adjust the refractive index, or an alkyl or aryl having 1 to 20 carbon atoms. It is preferable to polymerize using a small amount of a styrene derivative substituted with a group as a comonomer.

Also in the second step. The content of the acrylic monomer and the comonomer for grafting the rubbery core to the seed particles is preferably 40 to 80% by weight, more preferably 50 to 70% by weight relative to the total monomer weight used in the production of the acrylic latex. If the content is less than 40% by weight, the impact resistance is lowered. If the content is more than 80% by weight, the impact resistance is improved, but the hardness and the heat resistance may be reduced. desirable.

The acrylic monomer and the comonomer used in the second step of the first aspect are preferably used by mixing in a weight ratio of 4-9: 1.

Thereafter, a crosslinking agent, an emulsifier, an initiator and a graft agent are gradually added dropwise to the polymer obtained by the first step polymerization to prepare a polymer obtained by grafting a rubbery core to the seed particles. If the dropping time and polymerization time of the monomers used in the second step of the first aspect is not sufficient or no emulsifier is used, the monomers may agglomerate with each other. Therefore, the particle size of the polymer in which the rubber core is grafted to the seed particles is preferably very uniform.

Next, the 3rd stage polymerization of 1st aspect is demonstrated.

In the third step, the content of the acrylic monomer for grafting the glass shell on the core is preferably used in 10 to 40% by weight based on the total monomer weight used in the production of acrylic latex. In addition, the particle size of the polymer (acrylic latex) grafted the shell of the final glass is preferably uniform.

If the glass-like shell is not coated on the rubbery core, when the acrylic latex particles are transferred from the emulsion system to the suspension system and polymerized, the stability is lowered and suspension polymerization is not possible. Since the glass transition temperature of the free-form core rises, desirable impact strength cannot be obtained.

As the acrylic monomer used in the present invention, any one or a mixture of two or more selected from an aromatic vinyl monomer, an alkyl (meth) acrylate monomer having 1 to 15 carbon atoms, and a (meth) acrylic acid monomer having 1 to 15 carbon atoms is preferably used. Can be. For example, styrene may be used as an aromatic vinyl monomer, and an alkyl (meth) acrylate monomer having 1 to 15 carbon atoms may be ethyl acrylate, ethyl methacrylate, methyl acrylate, methyl methacrylate, or butyl. Acrylate, butyl methacrylate, and the like can be used, but is not limited thereto.

As the emulsifier used in the present invention, an anionic emulsifier such as an alkyl alkyl salt having 4 to 30 carbon atoms and an alkyl sulfate salt such as sodium dodecyl sulfate and sodium dodecylbenzene sulfate may be used, but is not limited thereto. It is preferable to use 0.02 to 4 parts by weight based on 100 parts by weight of the total monomers used in the production of the silver acrylic latex.

Examples of the crosslinking agent used in the present invention include 1,2-ethanedioldi (meth) acrylate, 1,3-propanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,5- Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, divinylbenzene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, allyl (meth) acrylate Although it may be used, but is not limited thereto, the amount thereof is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total monomers used in preparing the acrylic latex.

As the graft agent used in the present invention, one or more monomers having a double bond having different reactivity, such as allyl (meth) acrylate or diallyl maleate, may be used, but the present invention is not limited thereto. It is preferable to use 0.1 to 10 parts by weight based on 100 parts by weight of the total monomers used in the preparation.

In the present invention, the initiator used in the production of the acryl-based latex is cumene hydroperoxide, tertiary butyl peroxide, 2,2'- in the presence of ferrous sulfate, sodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate. Azobisisobutyronitrile and the like can be used, but is not limited thereto, and the amount thereof is preferably used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomers used in preparing the acrylic latex.

In the second aspect of the process for producing the acrylic latex, the acrylic monomer, comonomer, crosslinking agent, emulsifier, initiator and graft agent are added to ion-exchanged water to prepare a rubbery core having a glass transition temperature of 0 ° C. or less. Step polymerization; A second stage polymerization is performed by adding an acrylic monomer and an initiator to the polymer by the first stage polymerization to graf the glassy shell having a glass transition temperature of 20 ° C. or higher to the core to produce an acrylic latex.

The manufacturing method of the second aspect omits the first step polymerization of the manufacturing method of the first aspect, and the following steps are the same as the manufacturing method of the first aspect.

In general, in the case of an acrylic impact modifier, it is known that including hard seed particles is advantageous in reinforcing impact resistance. However, the first stage polymerization of the first aspect is optionally omitted since the hard acrylic resin serves to keep the acrylic impact modifier from being deformed during processing or when absorbing the impact.

Next, suspension polymerization for manufacture of the acrylic resin particle excellent in the impact resistance of this invention is demonstrated.

The method for preparing acrylic resin particles of the present invention comprises the steps of: (A) mixing polyvinyl alcohol and hydroxyethyl cellulose with ion-exchanged water as an acrylic monomer, a flocculant and a suspension dispersant; (B) adding an acrylic latex prepared by emulsion polymerization to the mixture of step (A) to disperse the acrylic latex onto an acrylic monomer; (C) suspending polymerization by adding a chain transfer agent and an initiator on the acrylic monomer in which the acrylic latex of step (B) is dispersed.

First, the acrylic monomer, flocculant, and suspension dispersant are added to ion-exchanged water and stirred through step (A). Next, the step (B) is performed by adding and stirring the acrylic latex prepared by emulsion polymerization to the step (A) mixture.

The acrylic monomers usable in the step (A) may use the acrylic monomers used to prepare the acrylic latex for the impact modifier described above, more preferably methyl acrylate, ethyl (meth) compared to methyl methacrylate. ) A comonomer selected from acrylate, butyl (meth) acrylate and styrene is preferably used by polymerization in a weight ratio of 80 to 99:20 to 1. More preferably, the use of the comonomer in the weight ratio of methylmethacrylate to 85 to 97:15 to 3 does not lose the hardness and heat resistance of the acrylic matrix resin.

Step (A) is characterized in that the acrylic monomer is added in a weight ratio of 10 to 65: 90 to 35 compared to the acrylic latex.

In addition, the ion-exchanged water of step (A) may be used in an amount of 100 to 500 parts by weight based on 100 parts by weight of the acrylic monomer used in step (A).

The coagulant of step (A) is used to reduce the activity of the emulsifier in the acryl-based latex added in step (B), in the present invention may be used an aqueous organic acid solution such as sodium acetate, calcium acetate, sodium formate, calcium formate, It is not limited to this. In the present invention, when the coagulant is added in an excessive amount, excessive coagulation of the acrylic latex occurs, thereby lowering the dispersibility in the acrylic matrix resin after suspension polymerization, and polymerization stability is inhibited so that the suspension polymerization particles are reacted with the reactor wall and agitator. Clumping in baffles, etc., causes excessive scale in the reactor. In addition, when the flocculant is not added, the contact between the acryl-based latex and the acryl-based monomer is insufficient, and thus the shape and quality of the suspended particles are reduced. Therefore, the amount of the flocculant used in the step (A) is 100 parts by weight It is recommended to use 0.02 to 2.5 parts by weight.

The suspension dispersant is used to control the shape and distribution of the suspension polymerized particles, and in the present invention, the suspension dispersant is characterized by using polyvinyl alcohol and hydroxyethyl cellulose together. Among them, hydroxyethyl cellulose, a cellulose-based dispersant, improves the stability of the acrylic latex and serves to help distribute the acrylic latex evenly in the acrylic monomer.

In the step (A), it is preferable to add hydroxyethyl cellulose to the polyvinyl alcohol in a weight ratio of 3 to 9: 7 to 1 as a suspension dispersant. When the suspension dispersant used in the present invention is outside the range of the weight ratio, that is, when hydroxyethyl cellulose is used in a small amount compared to polyvinyl alcohol, the content of fine particles (powder) exceeds 3%, and the fine particles are suspended. If a phenomenon occurs that adheres to the surface of the polymerized particles, and hydroxyethyl cellulose is used in excess of polyvinyl alcohol, an oversize particle of more than 1 mm in size of the acrylic resin particles is generated, which causes difficulties in the process.

The suspension dispersant of step (A) is preferably used in an amount of 0.04 to 2 parts by weight based on 100 parts by weight of the acrylic monomer used in step (A), and the size of the particles is excessively large or the microparticles are increased within the above range. The phenomenon can be minimized.

The production method according to the present invention can produce the acrylic resin particles in a uniform and reproducible shape of the particles compared to the usual suspension polymerization, the yield is improved, preventing the problems in the polymerization process caused by the particles sticking together, acrylic-based The latex is uniformly dispersed in the acrylic matrix resin, thereby producing an acrylic resin particle having excellent impact resistance. In addition, when hydroxyethyl cellulose is used in combination with suspension polymerization using a polyvinyl alcohol single dispersant, it is possible to improve the processability by reducing the distribution of fine particles and reducing the blowing of fine particles during processing.

Step (C) in the present invention is a step of carrying out suspension polymerization by adding a chain transfer agent and an initiator on the acrylic monomer in which the acrylic latex of step (B) is dispersed.

The chain transfer agent used in the step (C) can be used to control the molecular weight of the acrylic resin, mercaptan series such as dodecyl mercaptan, normal octin mercaptan can be used, but is not limited thereto. The content of the chain transfer agent can be adjusted according to the purpose of use of the impact-resistant acrylic resin, it is preferable to use 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic monomer used in step (A), the range of the present invention It may not impair physical properties.

In addition, as the initiator used in step (C), a peroxide initiator such as t-amylperoxy 2-ethylhexanoite, 2,2'-azobisisobutyronitrile, or an azo-based initiator may be used. It is not limited to this. The initiator used in step (C) is preferably used 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic monomer used in step (A), it may not inhibit the physical properties of the present invention in the above range.

Suspension polymerization for producing the acrylic resin particles is polymerized by heating the reaction product obtained as a result of step (B) for a sufficient time at a temperature between 60 ~ 110 ℃ at a stirring speed of 500 ~ 700 rpm in a nitrogen atmosphere. Upon completion of the reaction, the particles are washed and dried to obtain bead-shaped acrylic resin particles having impact resistance.

Acrylic resin beads according to the present invention may include common thermoplastic additives such as fillers, reinforcing agents, colorants, lubricants, stabilizers, antioxidants, heat resistant agents, ultraviolet stabilizers, and other compound components as desired.

Based on the above description, those skilled in the art will be able to easily understand the essential features of the present invention, and changes and modifications suitable for various uses, conditions, and specific examples can be made without departing from the spirit and scope of the present invention. Can be applied.

The composition according to the present invention can be produced as a molded article by a method such as injection and extrusion, it can be seen that it is specifically applicable to products that require impact resistance without harming the surface hardness and optical properties.

Acrylic resin particles of uniform size having excellent impact resistance according to the present invention has an effect that the acrylic latex is evenly distributed in the acrylic resin particles to improve the impact resistance of the resin. In addition, the present invention is to significantly improve the fine powder content of the suspension-polymerized acrylic resin particles it is possible to produce acrylic resin particles of uniform and reproducible shape of the particles. The present invention can also control the physical properties according to the content of the acrylic latex, because the particles are produced through suspension polymerization, the application range of the resin is wide.

Hereinafter, the present invention will be better understood by reference to the following examples, and the following examples are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

[Test Example] Measurement of Properties

1) impact strength

Notched Izod impact strength (kg.cm/cm) was measured at room temperature according to ASTM D256 method.

2) Acrylic resin particle size distribution and fine particle measurement

The particle size distribution and the fine particle content of the acrylic resin were measured using a light scattering measurement method, in which light was scattered due to the solute in the solution.

3) light transmittance

It was measured by Hazemeter according to ASTM D1003 method.

4) Particle shape

It was visually observed to show that the particles were uniformly dispersed, uniformly dispersed, entangled with each other, and the particles were uneven.

Example 1

This embodiment relates to the production of impact resistant PMMA resin containing 10% by weight of emulsion-polymerized acrylic latex and having a weight ratio of polyvinyl alcohol and hydroxyethyl cellulose 1: 1.

? Preparation of Acrylic Latex by Emulsion Polymerization (First Embodiment)

In the first step, 250 parts by weight of ion-exchanged water, 0.002 parts by weight of ferrous sulfate, 0.008 parts by weight of EDTA 2 Na salt, 0.2 parts by weight of sodium formaldehyde sulfoxylate, and 0.05 parts by weight of sodium dodecyl sulfate were added to the reactor with a stirrer, and then nitrogen replacement. Then, it heated up to 80 degreeC. A mixed solution of 14% by weight of methyl methacrylate, 6% by weight of ethyl acrylate, 0.1 part by weight of allyl methacrylate, and 0.05 part by weight of cumene hydroperoxide was added dropwise for 2 hours, followed by 1 hour at 80 ° C. And emulsion polymerization while stirring at 400 rpm. The average particle size of the glassy seed particles obtained at this time was 130 nm.

In step 2, 0.002 parts by weight of ferrous sulfate, 0.004 parts by weight of EDTA 2 Na salt, 0.1 part by weight of sodium formaldehyde sulfoxylate, and 1.8 parts by weight of sodium dodecyl sulfate were added, followed by the glassy seed particles prepared in the first step. . A mixed solution of 53.6% by weight of butyl acrylate, 11.4% by weight of styrene, 1.2 parts by weight of allyl methacrylate, 0.2 parts by weight of 1,4-butanediol dimethacrylate, and 0.2 parts by weight of cumene hydroperoxide was mixed for 3 hours. After dropping over, it was polymerized at 80 ° C for 2 hours. The average particle size of the polymer obtained at this time was 250 nm.

Finally, in step 3, after adding 0.1 part by weight of sodium formaldehyde sulfoxylate while keeping the temperature at 80 ° C., 14.25% by weight of methyl methacrylate, 0.75% by weight of methyl acrylate, 0.05 part by weight of dodecyl mercaptan and cumene A mixed solution containing 0.02 parts by weight of hydroperoxide was added dropwise over 1 hour, and then polymerized at 80 ° C. for 1 hour. The average particle size of the acrylic latex, the final polymer obtained at this time, was 280 nm.

? Preparation of impact resistant acrylic resin through suspension polymerization

(A) step: 90% by weight of methyl methacrylate, 10% by weight of methyl acrylate, 0.1 parts by weight of 4% polyvinyl alcohol solution, 0.4 parts by weight of 1% hydroxyethylcellulose solution, and 0.05 parts by weight of calcium acetate After adding to 250 parts by weight of water and stirred.

(B) step: dispersing the acrylic latex prepared by emulsion polymerization onto an acrylic monomer to disperse, the acrylic monomer compared to the acrylic latex to the mixture of step (A) in a weight ratio of 15: 85, obtained The mixture was stirred.

(C) step: suspension polymerization of the acrylic monomer phase in which the acrylic latex of step (B) is dispersed, 0.3 part by weight of dodecyl mercaptan and 0.15 part by weight of azobisisobutyronitrile are added to the solution of step (B) After the temperature was raised to 80 ° C., polymerization was performed for 120 minutes while stirring at 600 rpm to complete suspension polymerization. The average particle size of the beads obtained after polymerization was 277 μm, and the physical properties thereof are shown in Table 1 below.

[Example 2]

In the present embodiment, in the production of impact-resistant acrylic resin through suspension polymerization, except that the acrylic monomer compared to the acrylic latex to the mixture of the step (A) in the step (B) in a weight ratio of 35: 65 It carried out similarly to Example 1. The average particle size of the beads obtained after polymerization was 294 μm, and the physical properties thereof are shown in Table 1 below.

[Example 3]

In the present embodiment, in the production of impact-resistant acrylic resin through suspension polymerization, in the step (A), 90% by weight of methyl methacrylate, 10% by weight of methyl acrylate, 0.2% by weight of polyvinyl alcohol aqueous solution, 0.2 weight part of 1% hydroxyethyl cellulose aqueous solution and 0.05 weight part of calcium acetate were added to 250 weight part of ion-exchanged water, and it carried out similarly to Example 1 except for stirring. The average particle size of the beads obtained after the polymerization is 316 ㎛, the physical properties are shown in Table 1 below.

Comparative Example 1

In the present Comparative Example, in the production of impact-resistant acrylic resin through suspension polymerization, in the step (A), 90% by weight of methyl methacrylate, 10% by weight of methyl acrylate, 0.2% by weight of polyvinyl alcohol aqueous solution, acetic acid Except for adding 0.05 parts by weight of calcium to 250 parts by weight of ion-exchanged water and was stirred in the same manner as in Example 2. The average particle size of the beads obtained after polymerization was 285 μm, and the physical properties thereof are shown in Table 1 below.

Comparative Example 2

In the present Comparative Example, in the preparation of impact-resistant acrylic resin through suspension polymerization, in the step (A), 90% by weight of methyl methacrylate, 10% by weight of methyl acrylate, 0.8% by weight of a 1% hydroxyethyl cellulose aqueous solution, The same procedure as in Example 2 was carried out except that 0.05 parts by weight of calcium acetate was added to 250 parts by weight of ion-exchanged water and then stirred. The average particle size of the beads obtained after polymerization was 2763 μm, and the physical properties thereof are shown in Table 1 below.

Table 1 shows the results of the basic physical properties of the Examples and Comparative Examples according to the present invention, the sample was prepared by using an injection molding machine (LG wire, 170 tons), the injection molding at room temperature for the evaluation of physical properties 48 Measurement was made after time retention.

[Table 1]

As shown in Table 1, in the production of impact-resistant acrylic resin through suspension polymerization, in the case of Examples 1 to 3 using polyvinyl alcohol and hydroxyethyl cellulose as a suspension dispersant, comparison using a single dispersant Compared with Example 1 and Comparative Example 2, the fine powder content was greatly reduced and the shape and size of the prepared acrylic resin particles were uniform and reproducible. In addition, the acrylic latex during suspension polymerization was uniformly dispersed in the acrylic matrix resin was confirmed that the impact resistance is improved.

On the other hand, in Comparative Example 1 using polyvinyl alcohol alone as a suspension dispersant, the particles were uneven, and the particles were stuck together. In Comparative Example 2 using hydroxyethyl cellulose alone, the particle size was 1 mm. Oversize particles are produced which present difficulties in the manufacturing process.

Claims (9)

(A) preparing a mixture by mixing polyvinyl alcohol and hydroxyethyl cellulose in a weight ratio of 3 to 9: 7 to 1 with an acrylic monomer, a flocculant and a suspension dispersant in ion-exchanged water; (B) adding an acrylic latex prepared by emulsion polymerization to the mixture of step (A) to disperse the acrylic latex onto an acrylic monomer; (C) suspending and polymerizing a chain transfer agent and an initiator on an acrylic monomer in which the acrylic latex of step (B) is dispersed; Method of producing an acrylic resin particles of uniform size excellent impact resistance comprising a. The method of claim 1, The suspension dispersant of step (A) is used in the production of acrylic resin particles of uniform size, excellent impact resistance, characterized in that the use of 0.04 ~ 2 parts by weight with respect to 100 parts by weight of the acrylic monomer. delete The method of claim 1, The coagulant of step (A) is used in the production of acrylic resin particles of uniform size, excellent impact resistance, characterized in that the use of 0.02 to 2.5 parts by weight with respect to 100 parts by weight of the acrylic monomer. The method of claim 1, The step (A) is a method for producing acrylic resin particles having a uniform impact resistance, characterized in that the acrylic monomer is added in a weight ratio of 10 to 65: 90 to 35 compared to the acrylic latex. The method of claim 1, The emulsion polymerization of the acrylic latex, A first step of polymerizing a seed particle having a glass transition temperature of 20 ° C. or more by adding an acrylic monomer, an emulsifier, a graft agent, and an initiator to ion-exchanged water; A second stage polymerization in which an acrylic monomer, a comonomer, a crosslinking agent, an emulsifier, an initiator, and a graft agent are added to the polymer by the first stage polymerization to graf the rubbery core having a glass transition temperature of 0 ° C. or lower to the seed particles; A third step of preparing an acrylic latex by adding an acrylic monomer and an initiator to the polymer by the second step of polymerization and grafting a glass-like shell having a glass transition temperature of 20 ° C. or higher to the core; Method of producing an acrylic resin particles of uniform size excellent impact resistance comprising a. The method of claim 1, The emulsion polymerization of the acrylic latex, A first stage polymerization for producing a rubbery core having a glass transition temperature of 0 ° C. or less by adding an acrylic monomer, a comonomer, a crosslinking agent, an emulsifier, an initiator and a graft agent to ion-exchanged water; A second stage polymerization for producing an acrylic latex by adding an acrylic monomer and an initiator to the polymer by the first stage polymerization and grafting a glass-shaped shell having a glass transition temperature of 20 ° C. or higher to the core; Method of producing an acrylic resin particles of uniform size excellent impact resistance comprising a. The method according to any one of claims 1 to 2 and 4 to 7, wherein The acrylic monomer is any one or a mixture of two or more selected from an aromatic vinyl monomer, an alkyl (meth) acrylate monomer having 1 to 15 carbon atoms and a (meth) acrylic acid monomer having 1 to 15 carbon atoms, and the comonomer is a styrene or a halogen. A method for producing acrylic resin particles having a uniform impact resistance, characterized in that styrene derivatives substituted with C1-C20 alkyl or C6-C20 aryl groups are used. Acrylic beads prepared by the manufacturing method according to any one of claims 1 to 2 and 4 to 7.