KR20090072946A - Low Gloss Rubber Modified Aromatic Vinyl-Vinyl Cyanide Copolymer and Method for Continuously Preparing the Same - Google Patents

Abstract

A rubber modified aromatic vinyl-vinyl cyanide copolymer is provided to ensure uniform anti-glare property, excellent chemical resistance, and good outer appearance and color characteristic. A method for continuously preparing a low gloss rubber modified aromatic vinyl-vinyl cyanide copolymer comprises the steps of: mixing a mixed solution, a polymerization initiator and a molecular weight controlling agent to prepare the reaction solution, wherein the mixed solution comprises an aromatic vinyl compound, a vinyl cyanide compound, a diene-based rubber and solvent; injecting the reaction solution in a first reactor and polymerizing the solution to conversion ratio of 30-40 %; and injecting the material polymerized in the first reactor in the second reactor to conversion ratio of 70-80 %.

Description

Low Gloss Rubber Modified Aromatic Vinyl-Vinyl Cyanide Copolymer and Method for Continuously Preparing the Same}

1 is an electron micrograph (TEM) of the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer prepared in Example 1. FIG.

2 is an electron micrograph of the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer prepared in Example 2. FIG.

3 is an electron micrograph of the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer prepared in Example 3. FIG.

Field of invention

The present invention relates to a matte rubber-modified aromatic vinyl-vinyl cyanide copolymer and a process for the continuous production thereof. More specifically, the present invention relates to a rubber-modified aromatic vinyl-vinyl cyanide copolymer and its continuous polymerization method capable of expressing excellent matte by controlling the particle size of the rubber phase in a specific range.

Background of the Invention

In general, acrylonitrile-butadiene-styrene copolymer (ABS) resins are used in a wide range of parts from daily necessities to automobile interior materials, office equipment, and building materials.

Recently, with increasing interest in sensitizing resins, the demand for matting resins is increasing. Particularly, matte resins are actively employed in automobile interior materials and exterior materials for electronic products. In addition, as environmental problems are on the rise, there is an increasing tendency to use matte resins directly by omitting the painting process.

Methods for producing such matte resins, in particular matte ABS resins, are largely divided into three categories. The most widely used method is to apply a matte additive-quenching agent using inorganic fillers or acrylic resins or crosslinked styrene resins. The second method is a method of forming a rough surface by adjusting the size of rubber particles, which are dispersed phases of ABS resin. The surface thus formed scatters incident light to lower gloss. The third method is to remove gloss in the post-processing process. Such methods include a method of producing a matt effect in an injection or painting process using a corrosion mold.

The method of implementing the matte effect through the additive is convenient in many aspects, but the quality of the gloss is limited because the uniformity of the gloss is not constant according to the dispersion state of the additive. In addition, the method of using a corrosion mold or the painting process increases the cost with the introduction of additional processes and disadvantages in terms of environment. On the other hand, the method of controlling the gloss by adjusting the particle diameter of the rubber has an advantage in that it is possible to realize high-quality matt characteristics without requiring any additional process in the continuous bulk polymerization process.

In order to lower the gloss by adjusting the particle diameter of the rubber, various conditions must be properly adjusted in the polymerization process. In order to control the rubber particle size, bulk polymerization or solution polymerization is advantageous to polymerization rather than emulsion polymerization. ABS resin produced through emulsion polymerization is usually almost impossible to control the rubber particle size to 1 ㎛ or more. On the other hand, when used in the bulk polymerization process, particularly in the case of HIPS it is also easy to form a particle size of 2 to 3 ㎛ level. In the case of ABS resin, in the case of bulk polymerization or solution polymerization, a particle diameter of 1 µm or less is usually achieved.

It is known that three factors play an important role in controlling the rubber particle diameter in the production of ABS resin in a continuous process using bulk polymerization or solution polymerization (Rubber-Toughened Plastics, C. Keith Riew, Advances in chemistry series 222, 1987.). The size of the rubber particles can be controlled by the shear force generated by the stirring force of the reactor, the viscosity ratio between the dispersed phase and the continuous phase, and the interface force between the two phases. In general, the faster the stirring speed of the reactor, the stronger the shear force tends to be smaller particles. However, if the stirring speed is too high, the dispersed particles recombine, and the particle size increases. In the viscosity ratio of the dispersed phase (rubber) and the continuous phase (SAN), it is known that the size of the rubber particles increases as the viscosity ratio, that is, (viscosity of the dispersed phase) / (viscosity of the continuous phase) increases. It is also common for the particle size to decrease as the interfacial force between the dispersed and continuous phases increases.

European Patent Publication No. 0412801 discloses an ABS resin having a small particle size of 0.5 μm or less and a large particle rubber particle having a level of 1 to 2 μm. In European Patent Publication No. 0277687, branch type rubber is used to reduce the viscosity of a solution. Examples of use are disclosed.

In addition, Japanese Patent Laid-Open No. Hei 8-120032 discloses that the surface gloss is improved in a process in which an ABS resin having similar rubber particles includes an extruder. This method aims at improving surface gloss and physical properties.

U.S. Patent No. 5,250,611 discloses a method of applying a tubular reactor and using a low temperature initiator to produce good ABS products, and U.S. Patent No. 5,223,577 continuously produces ABS resin using SBR rubber. A method is disclosed. However, all of these methods are limited to methods for producing products having an average rubber particle diameter of 1 m or less.

US Patent No. 4,277,574 discloses a bimodal type ABS product having a small particle rubber of 0.01 to 0.5 μm and a large particle rubber of 0.7 to 10 μm. However, the size of the large-diameter rubber actually used in the patent is limited to the level of 0.8 ~ 3 ㎛, and for the purpose of excellent balance of physical properties irrespective of matte ABS.

As such, the existing patents on most continuous ABS polymerization processes have focused on improving the physical properties by introducing a rubber particle size of 1 μm or less, or by introducing some large particle size rubber (1 to 3 μm level). Such ABS products have advantages in color, purity, manufacturing cost, etc., compared to ABS products manufactured by conventional emulsion polymerization, but most of them have some limitations in physical properties.

Therefore, the present inventors, in order to solve the above problems, by adjusting the type of rubber, the stirring speed of the reactor, the conversion rate of the reactants, etc., the rubber particles in the dispersed phase has a size of about 6 to 20 ㎛ matte rubber modified aromatic vinyl- It has begun to develop a vinyl cyanide copolymer and a continuous production method thereof. In addition, the present inventors provide a new method for producing a matte rubber-modified aromatic vinyl-vinyl cyanide copolymer product, which is difficult to manufacture by an existing emulsion polymerization process or a continuous polymerization process, using a general continuous polymerization facility.

An object of the present invention is to provide a rubber-modified aromatic vinyl-vinyl cyanide copolymer having an average rubber particle diameter of 6 to 20 µm and a span of 1.2 to 2.8 as a dispersed phase.

Another object of the present invention is to provide a rubber-modified aromatic vinyl-vinyl cyanide copolymer having a gloss of 1 to 10 degrees of 60 degrees using a BYK-Gardner Gloss Meter.

Another object of the present invention is to provide a rubber-modified aromatic vinyl-vinyl cyanide copolymer having uniform matte properties.

Still another object of the present invention is to provide a rubber-modified aromatic vinyl-vinyl cyanide copolymer having excellent chemical resistance.

Another object of the present invention is to provide a rubber-modified aromatic vinyl-vinyl cyanide copolymer having excellent appearance and color characteristics.

Still another object of the present invention is to provide a new method for preparing the rubber-modified aromatic vinyl-vinyl cyanide copolymer using a continuous polymerization method.

It is another object of the present invention to provide a continuous production method of a rubber-modified aromatic vinyl-vinyl cyanide copolymer that can be prepared using a general continuous polymerization equipment.

Still another object of the present invention is to provide a production method capable of stably preparing a rubber-modified aromatic vinyl-vinyl cyanide copolymer.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

The present invention provides a matt rubber modified aromatic vinyl-vinyl cyanide copolymer. The copolymer is grafted 80 to 93% by weight of the aromatic vinyl-vinyl cyanide copolymer to 7 to 20% by weight of the diene rubber, the average rubber particle diameter of the dispersed phase is 6 to 20 ㎛, characterized in that 1.2 to 2.8 do.

The aromatic vinyl-vinyl cyanide copolymer of the present invention comprises 60 to 90 wt% of the aromatic vinyl compound component and 10 to 40 wt% of the vinyl cyanide compound component.

The matte rubber-modified aromatic vinyl-vinyl cyanide copolymer has a 60-degree glossiness of 1 to 10 using a BYK-Gardner Gloss Meter for a specimen having a thickness of 2 mm, and a BYK-Gardner for a specimen having a thickness of 0.02 mm. 60 degree glossiness using a gloss meter (Gardner Gloss Meter) is characterized in that 1 to 5.5.

In another aspect of the present invention, there is provided a method for producing the above-mentioned glossy rubber-modified aromatic vinyl-vinyl cyanide copolymer. The preparation method is prepared by mixing a polymerization initiator and a molecular weight regulator in a mixed solution of an aromatic vinyl compound, a vinyl cyanide compound, a diene rubber and a solvent to prepare a reaction solution; Adding the reaction solution into a first reactor to polymerize conversion to 30-40%; Then, the polymerized product polymerized in the first reactor is added to the second reactor, and the polymerization is carried out to the step of polymerization up to 70-80%.

The solvent may be an aromatic organic solvent. In embodiments, one or more may be selected from the group consisting of ethylbenzene, xylene, toluene.

In embodiments, the diene rubber may have a viscosity of 5 wt% styrene solution of 150 to 300 cps.

In an embodiment, the mixed solution may be composed of 40 to 60% by weight of aromatic vinyl compound, 10 to 25% by weight of vinyl cyanide compound, 7 to 20% by weight of diene rubber, and 5 to 30% by weight of solvent.

In an embodiment, the stirring speed is 60 to 150 rpm in the first reactor and the stirring speed is 50 to 100 rpm in the second reactor.

The polymerization initiator may have a half life of 10 minutes or less at the polymerization temperature.

In another embodiment of the present invention may further comprise devolatilizing the polymerized polymer in the second reactor. The devolatilization process may be performed using a devolatilization tank. In embodiments, the devolatilization process may remove residual unreacted material from the first and second devolatilization tanks connected vertically.

The first devolatilization tank may be operated at a pressure of 100 to 600 torr and a temperature of 160 to 240 ° C., and the second devolatilization tank may be operated at a pressure of 1 to 50 torr and a temperature of 210 to 250 ° C.

The rubber-modified aromatic vinyl-vinyl cyanide copolymer prepared by the above production method is characterized in that the specimen having a thickness of 2 mm is 60 degrees glossiness of 1 to 10 using a BYK-Gardner Gloss Meter.

Hereinafter, with reference to the accompanying drawings will be described in detail the specific content of the present invention.

Detailed Description of the Invention

The present invention provides a matt rubber modified aromatic vinyl-vinyl cyanide copolymer. The copolymer is characterized in that 80 to 93% by weight of the aromatic vinyl-vinyl cyanide copolymer is grafted to 7 to 20% by weight of the diene rubber, and the average rubber particle diameter of the dispersed phase is 6 to 20 μm. In one embodiment, the average rubber particle diameter of the dispersed phase may be 6.5 to 15 ㎛. In other embodiments, the average rubber particle diameter of the dispersed phase may be 10 to 20 μm. The average rubber particle size mentioned below refers to volume average particle size and span measured using Malvern's Mastersizer S Ver.2.14.

The dispersed phase is characterized in that the average rubber particle diameter is 6 to 20 ㎛ and the span is 1.2 to 2.8, this rubber particle diameter characteristics are very large compared to the rubber particle diameter of the conventional rubber-modified aromatic vinyl-vinyl cyanide copolymer and due to these characteristics It is characterized by expressing excellent matt characteristics.

The diene rubber constitutes a dispersed phase, and polybutadiene, butadiene-styrene copolymer or a mixture thereof may be used. The diene rubber is included 7 to 20% by weight of the total copolymer, preferably 10 to 17% by weight . In one embodiment, the particles in which the aromatic vinyl compound and the vinyl cyanide compound are grafted to the diene rubber may form a dispersed phase.

The aromatic vinyl-vinyl cyanide copolymer constitutes a continuous phase. In an embodiment the aromatic vinyl-vinyl cyanide copolymer comprises from 60 to 90% by weight of an aromatic vinyl compound component and from 10 to 40% by weight of a vinyl cyanide compound component. In another embodiment of the present invention, the aromatic vinyl-vinyl cyanide copolymer comprises 65 to 85 wt% of the aromatic vinyl compound component and 15 to 35 wt% of the vinyl cyanide compound component. In another embodiment, the aromatic vinyl-vinyl cyanide copolymer comprises 70 to 83 wt% of the aromatic vinyl compound component and 17 to 30 wt% of the vinyl cyanide compound component.

As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, or the like may be used, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The vinyl cyanide compound may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The present invention provides a new continuous production method of the matt rubber modified aromatic vinyl-vinyl cyanide copolymer. The matte rubber-modified aromatic vinyl-vinyl cyanide copolymer is preferably prepared by continuous solution polymerization.

In one embodiment, the production method is a mixture of an aromatic vinyl compound, a vinyl cyanide compound, a diene rubber and a solvent mixed with a polymerization initiator and a molecular weight regulator to prepare a reaction solution; Adding the reaction solution into a first reactor to polymerize conversion to 30-40%; Then, the polymerized product polymerized in the first reactor is added to the second reactor, and the polymerization is carried out to the step of polymerization up to 70-80%.

In an embodiment of the present invention, the mixed solution is composed of 40 to 60% by weight of an aromatic vinyl compound, 10 to 25% by weight of a vinyl cyanide compound, 7 to 20% by weight of a diene rubber, and 5 to 30% by weight of a solvent.

As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, or the like may be used, and these may be used alone or in combination of two or more thereof.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, and these may be used alone or in combination of two or more thereof.

The diene rubber may be polybutadiene, butadiene-styrene copolymer or a mixture thereof.

In the present invention, the diene rubber has a viscosity of 5 wt% styrene solution of 150 cps or more, preferably 150 to 300 cps, more preferably 160 to 200 cps. If the styrene solution viscosity is too high or low, it may be difficult to control the rubber particle diameter. In one embodiment, the 5 wt% styrene solution viscosity of the diene rubber may be 165 to 250 cps. In another embodiment, the 5 wt% styrene solution viscosity of the diene rubber may be 170 to 280 cps.

An aromatic organic solvent may be used as the reaction solvent. In embodiments, ethylbenzene, xylene, toluene and the like may be used, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The polymerization initiator preferably has a half life of 10 minutes or less at the reactor polymerization temperature. A radical initiator may be used as the polymerization initiator. The content of the polymerization initiator may be used in 0.007 to 0.07 parts by weight based on 100 parts by weight of the mixed solution, preferably 0.01 to 0.05 parts by weight. When the polymerization initiator used has a half-life at the polymerization temperature of more than 10 minutes or exceeds 0.07 parts by weight, it may remain until the devolatilization process to cause various problems in appearance.

Examples of the polymerization initiator include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane and 2-bis (4,4-di-t -Butyl peroxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxylau Late, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxy Benzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, One type or two types or more can be selected and used from the category which consists of n-butyl-4, 4-bis (t-butyl peroxy) valerate, etc.

Molecular weight regulators used in the present invention include alkyl mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and preferably t-dodecyl mercaptan. In the present invention, the molecular weight modifier is used in an amount of 0.02 to 1 part by weight, more preferably 0.03 to 0.5 part by weight, based on 100 parts by weight of the mixed solution.

The reaction apparatus used in the present invention is not particularly limited. However, since there is an exothermic phenomenon due to a polymerization reaction in the reactor, it is preferable to control the reaction apparatus by circulating a refrigerant through a jacket or a coil.

The polymerization The reaction solution to which the initiator and the molecular weight regulator are added is added to the first reactor and polymerized to a conversion rate of 30-40%. In an embodiment it can be polymerized up to 32-38% conversion in the first reactor. If it is less than 30%, the glossiness increases, so that the matte of the present invention cannot be obtained, and if it exceeds 40%, an excessive load is applied to the stirrer and it cannot be manufactured stably.

The reaction temperature in the first reactor proceeds to 60 to 150 ℃, preferably 70 to 130 ℃, the reaction temperature may be changed depending on the reactor, stirring speed, initiator type and the like.

In an embodiment of the present invention, the stirring speed in the first reactor is adjusted to 60 to 150 rpm, preferably 80 to 120 rpm, and when it is out of the above range, rubber particles may be difficult to form. The stirring speed may vary depending on reactor size, initiator type, and reaction temperature. In a specific embodiment, the stirring speed in the first reactor can be adjusted to 90 to 130 rpm, or 100 to 140 rpm.

The polymerized product polymerized in the first reactor is introduced into the second reactor and polymerized to a conversion rate of 70-80%. Uniform matte can be obtained within the above range. The reaction temperature in the second reactor proceeds to 80 to 170 ℃, preferably 120 to 160 ℃, the reaction temperature may be changed depending on the reactor, the stirring speed, the initiator type and the like.

In an embodiment of the present invention, the stirring speed in the second reactor is controlled to 50 to 100 rpm, preferably 60 to 80 rpm, and the stirring speed may be changed depending on the reactor size, initiator type, and reaction temperature. In a specific embodiment, the stirring speed in the second reactor can be adjusted to 65 to 90 rpm, or 67 to 85 rpm. Within this range, the matteness of the present invention can be obtained.

In another embodiment of the present invention may further comprise devolatilizing the polymerized polymer in the second reactor. The devolatilization process may be performed using a devolatilization tank. In embodiments, the devolatilization process may use a single devolatilization tank. In a preferred embodiment, the devolatilization process can remove residual unreacted material in the first and second devolatilization tanks connected vertically. When the devolatilization step is carried out, the residual monomer content is 1500 ppm or less, preferably 1000 ppm or less, more preferably 700 ppm or less, and most preferably 500 ppm or less.

In one embodiment, the polymerized polymer in the second reactor is introduced into a devolatilization apparatus to remove unreacted monomer and residual solvent. The devolatilization device is not particularly limited, but it is important to shorten the residence time in the devolatilization device. Such a devolatilization device is a fall-stranding devolatilization (DEVO) type. The pole-stranding type devolatilizer is designed so that the angle of the cone minimizes the residence time and should be able to be effectively transmitted to the lower gear pump.

In one embodiment of the present invention, the first devolatilization tank and the second devolatilization tank are connected and used. Preferably it is connected vertically up and down to minimize the connection line between these DEVOs. In addition, in the first devolatilization tank DV-1, it is preferable that a control valve or a regulator is provided to enable pressure adjustment.

In an embodiment of the present invention, the first devolatilization tank is preferably operated at a residence time of 10 minutes or less in a pressure range of 100 to 600 torr and a temperature of 160 to 240 ° C. The pressure is more preferably in the range of 200 to 500 torr and a temperature of 180 to 220 ° C. If it is operated below 100 torr, there is a possibility that the productivity is lowered, and if it exceeds 600 torr, the amount of residual monomers increases. If the temperature is less than 160 ℃ may cause problems during the transport of the reactants, the residual monomers increase, if the temperature exceeds 240 ℃ YI of the product may increase.

Further, the second devolatilization tank is preferably operated at a residence time of 10 minutes or less, preferably 5 minutes or less in a pressure range of 1 to 50 torr and a temperature of 210 to 250 ° C. If the residence time exceeds 10 minutes, color history may occur due to thermal history.

The rubber-modified aromatic vinyl-vinyl cyanide copolymer prepared by the method of the present invention has a dispersed average rubber particle diameter in the range of 6-20 μm, and a specimen having a thickness of 2 mm is 60 degrees using a BYK-Gardner Gloss Meter. Surface glossiness exhibits an excellent matt effect of 10 or less and maintains uniform gloss over a large area. In an embodiment, the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer has a 60-degree glossiness of 1-10 using a BYK-Gardner Gloss Meter for a specimen having a thickness of 2 mm and a specimen having a thickness of 0.02 mm. The 60 degree glossiness using the BYK-Gardner Gloss Meter is 1-5.5. In another embodiment, a 60-degree glossiness using a BYK-Gardner Gloss Meter for a 2 mm thick specimen is 4 to 8.5 and a BYK-Gardner Gloss Meter for a 0.02 mm thick specimen. The 60 degree glossiness used may be 1-5. The standard deviation of glossiness was 0.3 or less, preferably 0.25 or less, and 1 m in width, for a sheet fabricated using the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer having a width of 0.05 m, a length of 1 m, and a thickness of 0.02 mm. The standard deviation of glossiness is 0.4 or less, preferably 0.35 or less, for sheets fabricated with a length of 1 m and a thickness of 2 mm.

The matte rubber-modified aromatic vinyl-vinyl cyanide copolymer of the present invention can be used for molding various products. In particular, since the matte characteristics can produce a luxurious appearance atmosphere, it can be applied to products where exterior characteristics are important, such as automotive interior parts, architectural interior materials, or exterior materials of electronic products. In addition, since the matte can be obtained without adding an inorganic additive, the weight of the product can be reduced, and uniform gloss can be obtained without deteriorating the physical properties of the resin.

The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

Butadiene rubber having a solution viscosity of 170 cps in a 5 wt% styrene solution in a mixed solution consisting of 53.4 parts by weight of styrene monomer, 17.8 parts by weight of acrylonitrile monomer and 20 parts by weight of ethylbenzene as a reaction solvent (BR-1: ASADENE 55AE) After dissolving 8.8 parts by weight, 0.015 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane as a polymerization initiator and t-dodecyl mercaptan as a molecular weight regulator 0.07 parts by weight of (t-dodecyl mercaptan) was added to prepare a mixed solution. The prepared solution was introduced into the reactor at a rate of 25 kg / hr. The first reactor had a stirring speed of 120 rpm and a conversion rate of 35%. In the second reactor, the stirring rate was controlled at 70 rpm, and the conversion rate was polymerized to a 75% level. Then, the remaining unreacted material was removed through a devolatilization tank to prepare ABS resin in pellet form. The average rubber particle diameter of the produced ABS resin was 6.16 mu m. An electron micrograph of the rubber particles is shown in FIG. 1.

In addition, the produced ABS resin was manufactured with a sheet of 0.05 m in width, 1 m in length and 0.02 mm in thickness, and a sheet-2 in 1 m in width, 1 m in length and 2 mm in thickness, respectively. The degree was measured. The properties of the ABS thus prepared are shown in Table 1.

Example 2

The same process as in Example 1 was carried out except that the stirring speed of the first reactor was 100 rpm. The average rubber particle diameter of the produced ABS resin was 8.58 μm. An electron micrograph of the rubber particles is shown in FIG. 2.

Example 3

The same process as in Example 1 was carried out except that the stirring speed of the first reactor was 80 rpm. The average rubber particle diameter of the produced ABS resin was 14.11 μm. An electron micrograph of the rubber particles is shown in FIG. 3.

Comparative Example 1

The same procedure as in Example 1 was carried out except that butadiene rubber (BR-2: ASAPRENE 700A) having a solution viscosity of 45 cps in a 5 wt% styrene solution was used. The average rubber particle diameter of the produced ABS resin was 1.37 μm.

Comparative Example 2

The same process as in Example 1 was carried out except that the conversion rate of the first reactor was 25%. The average rubber particle diameter of the produced ABS resin was 3.02 μm.

Comparative Example 3

The same process as in Example 1 was carried out except that the conversion rate of the first reactor was 45%. In this case, excessive load was applied to the stirrer of the first reactor, so that ABS resin could not be stably produced.

Comparative Example 4

The same process as in Example 1 was carried out except that the stirring speed of the first reactor was 50 rpm. In this case, since the particle formation of the rubber is not properly made in the first reactor, ABS resin could not be stably produced.

Comparative Example 5

5 parts by weight of an organic matting agent (BMAT, GE specialty chemical) and 5 parts by weight of talc, an inorganic filler, were mixed with 100 parts by weight of the ABS resin prepared by emulsion polymerization, and then extruded to prepare an ABS pellet. The sheet was prepared in the same manner as in Example 1.

Property evaluation method

(1) Average rubber particle size (µm) and span: The volume average particle size was measured using Malvern's Mastersizer S Ver.2.14.

(2) Evaluation of chemical resistance: After contacting cyclopentane with urethane foaming for 3 hours, break strain (%) was measured by tensioning under 0.6% strain and 60 mm / min.

(3) Glossiness: 60 degree glossiness was measured using a BYK-Gardner Gloss Meter.

(4) Standard deviation of glossiness: Sheets produced with 0.05 m width, 1 m length, and 0.02 mm width, and Sheet-2 with width 1 m, length 1 m, and 2 mm thickness were respectively fabricated from the ABS resin. The standard deviation was calculated by measuring the glossiness of 10 spots with different values.

Span: {D [V, 0.9] -D [V, 0.1]} / D [V, 0.5]

          (※ D [V, 0.1]: means diameter at volume fraction 0.1)

* Sheet-1: 0.05 m X 1 m, thickness 0.02 mm, no roller contact.

* Sheet-2: 1 m X 1 m, thickness 2 mm, Roller temperature 80 ℃.

As shown in Table 1, the ABS resin prepared according to Examples 1 to 3 according to the present invention was observed to exhibit an excellent matt effect of surface gloss of 10 or less. In addition, when the matt effect was expressed through continuous solution polymerization, it was possible to maintain uniform gloss over a large area. On the other hand, as in Comparative Example 5, the matt effect through the additive was observed to show a limit in terms of uniformity of gloss. In addition, it was observed that the ABS resin prepared according to the present invention can express excellent chemical resistance compared to general ABS resin. This excellent chemical resistance means that it can be effectively applied to various applications.

The present invention provides a rubber-modified aromatic vinyl having a substantially low surface gloss and uniform gloss by controlling the type of rubber, the stirring speed of the reactor, the conversion rate of the reactants, and the like so that the rubber particles in the dispersed phase have a size of about 6 to 20 μm. It has the effect of providing a vinyl cyanide copolymer.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (14)

80 to 93% by weight of the aromatic vinyl-vinyl cyanide copolymer is grafted to 7 to 20% by weight of the diene rubber, and the average rubber particle size of the dispersed phase is 6 to 20 µm, and the span is 1.2 to 2.8. Rubber modified aromatic vinyl-vinyl cyanide copolymer. The matte rubber-modified aromatic vinyl-vinyl cyanide copolymer according to claim 1, wherein the aromatic vinyl-vinyl cyanide copolymer comprises 60 to 90 wt% of the aromatic vinyl compound component and 10 to 40 wt% of the vinyl cyanide compound component. coalescence. The method of claim 1, wherein the diene rubber is a polybutadiene, butadiene-styrene copolymer or a mixture thereof; The aromatic vinyl compound is styrene, α-methylstyrene, p-methylstyrene or mixtures thereof; The vinyl cyanide compound is acrylonitrile, methacrylonitrile, ethacrylonitrile or a mixture thereof. The method of claim 1, wherein the matte rubber-modified aromatic vinyl-vinyl cyanide copolymer has a 60 degree glossiness of 1 to 10 using a BYK-Gardner Gloss Meter on a specimen having a thickness of 2 mm, and has a thickness of 0.02 mm. A matte rubber-modified aromatic vinyl-vinyl cyanide copolymer, characterized in that 60 degree glossiness of 1 to 5.5 using a BYK-Gardner Gloss Meter on a specimen. Preparing a reaction solution by mixing a polymerization initiator and a molecular weight regulator with a mixed solution containing an aromatic vinyl compound, a vinyl cyanide compound, a diene rubber, and a solvent; Adding the reaction solution into a first reactor to polymerize conversion to 30-40%; And Injecting the polymerized polymer in the first reactor into a second reactor to polymerize to a conversion rate of 70-80%; A continuous production method of a matte rubber-modified aromatic vinyl-vinyl cyanide copolymer, characterized in that it comprises a step. The method of claim 5, wherein the solvent is at least one selected from the group consisting of ethylbenzene, xylene, toluene. The method of claim 5, wherein the diene rubber is characterized in that the 5 wt% styrene solution viscosity of 150 to 300 cps. The method of claim 5, wherein the mixed solution comprises 40 to 60 wt% of an aromatic vinyl compound, 10 to 25 wt% of a vinyl cyanide compound, 7 to 20 wt% of a diene rubber, and 5 to 30 wt% of a solvent. . The method of claim 5, wherein the stirring speed is 60 to 150 rpm in the first reactor, and the stirring speed is 50 to 100 rpm in the second reactor. The method of claim 5 wherein the polymerization initiator has a half-life of 10 minutes or less at the polymerization temperature. The method of claim 10, wherein the polymerization initiator is 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2-bis (4, 4-di-t-butylperoxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate , t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t- Butyl peroxybenzoate, n-butyl-4,4-bis (t-butyl peroxy) valerate and mixtures thereof. 6. The process of claim 5 further comprising devolatilizing the polymerized polymer in said second reactor. 13. The method of claim 12 wherein the devolatilization process removes residual unreacted material in the first and second devolatilization tanks connected vertically. 15. The method of claim 13 wherein the first devolatilizer operates at a pressure of 100 to 600 torr and a temperature of 160 to 240 ° C., and the second devolatilizer operates at a pressure of 1 to 50 torr and a temperature of 210 to 250 ° C. How to feature.

Images