KR20210144026A - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising: a rubbery polymer comprising a first styrene-based monomer unit and a diene-based monomer unit and having an average particle diameter of 250 to 450 nm; a (meth)acrylate-based monomer unit; and a second styrene-based monomer unit, wherein the weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and to a thermoplastic resin composition in which the composition and average particle diameter of a rubbery polymer are adjusted, and the weight ratio of (meth)acrylate monomer units to styrenic monomer units is adjusted.

Recently, as industries are advanced and people's lives are diversified, many studies have been conducted to provide high functionality to materials for product differentiation. For example, research on transparent materials such as a washing machine cover that can see the contents of laundry, a vacuum cleaner that can check how much dust has been collected, a game machine housing, a transparent window for home appliances, and a transparent window for office equipment is being intensively studied.

However, the diene-based graft copolymer prepared by graft polymerization of a styrene-based monomer and an acrylonitrile-based monomer to the diene-based rubber polymer used for these parts has excellent impact resistance, chemical resistance, processability and surface gloss. , the transparency is not excellent.

Meanwhile, polycarbonate, polymethyl methacrylate, polystyrene, and polyacrylonitrile-styrene are generally used as transparent materials. However, although polycarbonate has excellent impact strength and transparency, it is difficult to make complex products due to poor processability and has poor chemical resistance. Polymethyl methacrylate has excellent optical properties, but is not excellent in impact resistance and chemical resistance. Also, polystyrene and polyacrylonitrile-styrene are not excellent in impact resistance and chemical resistance. In addition, the diene-based graft polymer is excellent while balancing impact resistance and processability, but is not excellent in transparency.

Therefore, there is a demand for the development of materials excellent in transparency, impact resistance, chemical resistance and processability.

KR2003-0034998A

The problem to be solved by the present invention is to provide a thermoplastic resin composition that balances transparency, impact resistance and processability, and can improve chemical resistance by reducing the amount of (meth)acrylate-based monomer, while reducing manufacturing costs will do

In order to solve the above problems, the present invention is a rubbery polymer comprising a first styrene-based monomer unit and a diene-based monomer unit and having an average particle diameter of 250 to 450 nm; (meth)acrylate-based monomer units; and a second styrene-based monomer unit, wherein a weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less.

The thermoplastic resin composition of the present invention has excellent transparency, impact resistance, processability and chemical resistance, and can reduce the amount of (meth)acrylate-based monomer used, thereby reducing manufacturing costs.

Hereinafter, the present invention will be described in detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In the present invention, the average particle diameter may be measured using a dynamic light scattering method, and in detail, may be measured using a Nicomp 380 equipment manufactured by Particle Sizing Systems. In the present invention, the average particle diameter may mean an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the scattering intensity average particle diameter.

In the present invention, the average particle diameter may be measured with a transmission electron microscope (TEM).

In the present invention, the refractive index refers to the absolute refractive index of a material, and the refractive index can be recognized as a ratio of the speed of electromagnetic radiation in free space to the speed of radiation in the material. In this case, the radiation may be visible light having a wavelength of 450 nm to 680 nm, specifically, visible light having a wavelength of 589.3 nm. The refractive index can be measured by a known method, that is, an Abbe refractometer.

In the present invention, the graft copolymer and the non-graft copolymer are stretched to a thickness of 0.2 mm, and then measured with an Abbe refractometer at 25° C. using visible light having a wavelength of 589.3 nm.

In the present invention, the weight of the rubber polymer, the diene-based monomer unit, the (meth)acrylate-based monomer unit, the first styrene-based monomer unit, and the second styrene-based monomer unit included in the thermoplastic resin composition is measured by infrared spectroscopy (Infrared Spectroscopy). can do.

In the present invention, the impact reinforcing region of the thermoplastic resin composition may mean a region composed of a rubber polymer and the rubber polymer and the grafted monomer unit, and the matrix region is a region excluding the impact reinforcing region, the rubber polymer in the graft copolymer and It may mean a region composed of a non-grafted monomer unit and a monomer unit included in the non-grafted copolymer.

In the present invention, the first styrenic monomer unit may mean a styrenic monomer unit included in the rubbery polymer, and the second styrenic monomer unit is included in the thermoplastic resin composition, but is not included in the rubbery polymer. can mean

In the present invention, the first and second styrenic monomer units may be units derived from styrenic monomers, respectively. The styrene-based monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferable.

In the present invention, the (meth)acrylonitrile-based monomer unit may be a unit derived from a (meth)acrylonitrile-based monomer. The (meth) acrylonitrile-based monomer may be a C ₁ to C ₁₀ alkyl (meth) acrylate-based monomer, and the C ₁ to C ₁₀ alkyl (meth) acrylate-based monomer is methyl (meth) acrylate, Ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and decyl (meth)acrylic It may be at least one member selected from the group consisting of methyl methacrylate, among which methyl methacrylate is preferable.

In the present invention, the acrylonitrile-based monomer unit may be a unit derived from an acrylonitrile-based monomer. The acrylonitrile-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, among which acrylonitrile is preferable.

In the present invention, the diene-based monomer unit may be a unit derived from the diene-based monomer. The diene-based monomer unit may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene is preferable.

Thermoplastic resin composition

A thermoplastic resin composition according to an embodiment of the present invention includes: a rubbery polymer including a first styrene-based monomer unit and a diene-based monomer unit and having an average particle diameter of 250 to 450 nm; (meth)acrylate-based monomer units; and a second styrene-based monomer unit, wherein a weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less.

The present inventors control the composition and average particle diameter of the rubber polymer, and if the weight ratio of the second styrene-based monomer unit and the (meth)acrylate-based monomer unit included in the thermoplastic resin composition is adjusted, transparency, impact resistance, processability and chemical resistance It was found that this excellent thermoplastic resin composition was prepared, and thus the present invention was completed.

Hereinafter, the present invention will be described in detail.

Since the rubbery polymer included in the thermoplastic resin composition according to an embodiment of the present invention includes the first styrene-based monomer unit as well as the diene-based monomer unit, the refractive index of the rubbery polymer may be increased. Due to this, even if there is no or minimal difference in refractive index between the impact reinforcing region and the matrix region of the thermoplastic resin composition, the matrix region may include a (meth)acrylate-based monomer unit in a small amount. Accordingly, a decrease in chemical resistance and an increase in manufacturing cost caused by the (meth)acrylate-based monomer unit can be minimized.

However, if the rubbery polymer contains only the diene-based monomer unit, the refractive index of the rubbery polymer is lowered. Therefore, in order for the thermoplastic resin composition to implement transparency, the matrix region must contain an excessive amount of the (meth)acrylate-based monomer unit. Chemical resistance may be lowered due to an excess of (meth)acrylate-based monomer units, and manufacturing costs may increase. In addition, the rubbery polymer cannot be prepared by the styrenic monomer alone.

Meanwhile, since the rubbery polymer includes both the diene-based monomer unit and the first styrene-based monomer, the refractive index may be higher than that of the rubbery polymer made of only the diene-based monomer. In addition, the rubber polymer may have a refractive index of 1.523 to 1.542, preferably 1.53 to 1.54.

In addition, the rubbery polymer included in the thermoplastic resin composition according to an embodiment of the present invention has an average particle diameter of 250 to 450 nm, preferably 300 to 350 nm. If the thermoplastic resin composition according to an embodiment of the present invention includes a rubbery polymer that is less than the above-described range, processability and impact resistance may be significantly reduced. In addition, if the average particle diameter includes the rubbery polymer exceeding the above-mentioned range, the surface gloss properties may be deteriorated. In addition, when the rubbery polymer is prepared by emulsion polymerization, it is not preferable because the latex stability of the rubbery polymer is significantly lowered.

In the thermoplastic resin composition according to an embodiment of the present invention, a weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit may be 2 or less, preferably 0.8 to 2. If the weight ratio of the (meth) acrylate-based monomer unit to the second styrene-based monomer unit exceeds 2, the (meth) acrylate-based monomer unit must be included in excess, so that the chemical resistance is significantly reduced, ( The manufacturing cost may increase due to the meth)acrylate monomer unit.

On the other hand, the thermoplastic resin composition according to an embodiment of the present invention is 10 to 35% by weight of the rubbery polymer; 24 to 60 wt% of the (meth)acrylate-based monomer unit; and 19 to 47 wt% of the second styrenic monomer unit. Preferably, 15 to 30% by weight of the rubbery polymer; 30 to 55 wt% of the (meth)acrylate-based monomer unit; and 25 to 42 wt% of the second styrenic monomer unit. When the above-described conditions are satisfied, a thermoplastic resin composition having improved impact resistance, chemical resistance and processability may be prepared.

The thermoplastic resin composition according to an embodiment of the present invention may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit may be included in an amount of 10 wt% or less, preferably 1 to 10 wt%, more preferably 5 to 9 wt%, in order to minimize yellowing while improving chemical resistance. .

Meanwhile, the thermoplastic resin composition according to an embodiment of the present invention may include a graft copolymer and a non-graft copolymer.

The graft copolymer may have a refractive index of 1.523 to 1.542, preferably 1.53 to 1.54. When the above-described range is satisfied, the refractive index of the above-described rubbery polymer is identical to or similar to that of the above-described rubbery polymer, so that the transparency of the graft copolymer can be further improved.

The difference in refractive index between the graft copolymer and the non-graft copolymer may be 0.01 or less, preferably 0. When the above conditions are satisfied, the thermoplastic resin composition may become more transparent.

The weight ratio of the graft copolymer to the non-graft copolymer may be 25:75 to 70:30, preferably 30:70 to 60:40. When the above-described range is satisfied, workability may be further improved without lowering impact resistance.

The graft copolymer includes a first styrene-based monomer unit and a diene-based monomer unit and has an average particle diameter of 250 to 450 nm, a rubbery polymer, a (meth)acrylate-based monomer unit grafted onto the rubbery polymer, and the rubbery polymer A second styrenic monomer unit grafted to the polymer may be included.

The rubbery polymer included in the thermoplastic resin composition according to an embodiment of the present invention and the rubbery polymer included in the graft copolymer are the same.

The graft copolymer may also include a (meth)acrylate-based monomer unit and a second styrene-based monomer unit that are not grafted to the rubbery polymer.

Meanwhile, the transparency of the graft copolymer may be determined by the refractive index of the rubbery polymer and the shell including the monomer units grafted to the rubbery polymer. And, the refractive index of the shell can be adjusted by the mixing ratio of the monomer units. That is, the refractive indices of the rubbery polymer and the shell should be similar and preferably match. Accordingly, the difference between the refractive index of the rubber polymer included in the graft copolymer and the refractive index of the monomer unit grafted to the rubber polymer may be 0.01 or less, preferably 0. When the above conditions are satisfied, the thermoplastic resin composition may become more transparent.

The graft copolymer may include 30 to 65 weight % of the rubbery polymer, preferably 35 to 60 weight %. When the above-described range is satisfied, the impact resistance is excellent, and grafting occurs sufficiently during the preparation of the graft copolymer, so that the graft copolymer can realize excellent transparency.

The rubbery polymer may include the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65, preferably 15:85 to 30:70. If the above conditions are satisfied, the impact resistance can be improved and the refractive index can be increased, so that the amount of the (meth)acrylate-based monomer unit used can be reduced, and the chemical resistance due to the (meth)acrylate-based monomer unit is reduced and The increase in manufacturing cost can be minimized.

The graft copolymer may include 14 to 47 wt% of the (meth)acrylate-based monomer unit, preferably 20 to 40 wt%. When the above-described range is satisfied, the graft copolymer may realize excellent transparency.

The graft copolymer may include the second styrenic monomer unit in an amount of 12 to 36 wt%, preferably 17 to 30 wt%. When the above-described range is satisfied, the graft copolymer can implement excellent processability.

The graft copolymer may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit is preferably included in an amount of 7 wt% or less in order to minimize yellowing while improving chemical resistance.

The graft copolymer is preferably used by emulsion polymerization in order to prepare a rubbery polymer under the above-mentioned conditions.

The non-graft copolymer may include a non-graft copolymer including a (meth)acrylate-based monomer unit and a second styrene-based monomer unit.

The non-graft copolymer may include 39 to 66% by weight of the (meth)acrylate-based monomer unit, preferably 45 to 60% by weight. When the above-described range is satisfied, a thermoplastic resin composition having improved transparency can be prepared.

The non-graft copolymer may include the second styrenic monomer unit in an amount of 34 to 61 wt%, preferably 40 to 55 wt%. When the above-described conditions are satisfied, a thermoplastic resin composition having improved processability can be manufactured.

The non-graft copolymer may further include an acrylonitrile-based monomer unit to further improve chemical resistance. The acrylonitrile-based monomer unit is preferably included in an amount of 12 wt % or less in order to minimize yellowing while improving chemical resistance.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

manufacturing example One: graft Preparation of copolymer powder A-1

A styrene/butadiene rubbery polymer latex (SBR 1) having an average particle diameter of 300 nm and a refractive index of 1.5315 was prepared by emulsion polymerization of a monomer mixture composed of 21 wt% of styrene and 79 wt% of 1,3-butadiene.

27.1 parts by weight of methyl methacrylate, 19.9 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.3 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After heating the reactor in which 50 parts by weight (based on solid content) of the styrene/butadiene rubbery polymer latex (SBR 1) is present to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-1 having a refractive index of 1.5315.

manufacturing example 2: graft Preparation of copolymer powder A-2

1,3-butadiene was emulsion-polymerized to prepare butadiene rubbery polymer latex (BR 1) having an average particle diameter of 300 nm and a refractive index of 1.516.

27.1 parts by weight of methyl methacrylate, 19.9 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.3 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After the temperature of the reactor in which 50 parts by weight of the butadiene rubbery polymer latex (BR 1) was present (based on solid content) was raised to 75° C., the mixed solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-2. The graft copolymer powder A-2 became opaque due to the difference in refractive index between the butadiene rubbery polymer (BR 1) and the hard polymer grafted thereto, and the refractive index was not measured.

manufacturing example 3: graft Preparation of copolymer powder A-3

A styrene/butadiene rubbery polymer latex (SBR 2) having an average particle diameter of 100 nm and a refractive index of 1.5315 was prepared by emulsion polymerization of a monomer mixture composed of 21 wt% of styrene and 79 wt% of 1,3-butadiene.

27.1 parts by weight of methyl methacrylate, 19.9 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.3 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After heating the reactor in which 50 parts by weight (based on solid content) of the styrene/butadiene rubbery polymer latex (SBR 2) is present to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-3 having a refractive index of 1.5315.

manufacturing example 4: graft Preparation of copolymer powder A-4

A styrene/butadiene rubbery polymer latex (SBR 3) having an average particle diameter of 350 nm and a refractive index of 1.538 was prepared by emulsion polymerization of a monomer mixture composed of 30% by weight of styrene and 70% by weight of 1,3-butadiene.

21.2 parts by weight of methyl methacrylate, 20.8 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.2 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After heating the reactor in which 55 parts by weight (based on solid content) of the styrene/butadiene rubbery polymer latex (SBR 3) exists to 75° C., the mixture solution was continuously introduced for 5 hours and polymerization was performed. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-4 having a refractive index of 1.538.

manufacturing example 5: graft Preparation of copolymer powder A-5

1,3-butadiene was emulsion-polymerized to prepare butadiene rubbery polymer latex (BR 1) having an average particle diameter of 300 nm and a refractive index of 1.516.

21.2 parts by weight of methyl methacrylate, 20.8 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.2 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After the temperature of the reactor in which 55 parts by weight of the butadiene rubbery polymer latex (BR 1) is present was raised to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-5 having a refractive index of 1.516.

manufacturing example 6: graft Preparation of copolymer powder A-6

A styrene/butadiene rubbery polymer latex (SBR 4) having an average particle diameter of 300 nm and a refractive index of 1.5212 was prepared by emulsion polymerization of a monomer mixture composed of 7 wt% of styrene and 93 wt% of 1,3-butadiene.

32.97 parts by weight of methyl methacrylate, 15.03 parts by weight of styrene, 2 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.2 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After heating the reactor in which 50 parts by weight of the styrene/butadiene rubbery polymer latex (SBR 4) exists to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with calcium chloride, washed, dehydrated and dried to obtain a graft copolymer powder A-6 having a refractive index of 1.5212.

manufacturing example 7: graft Preparation of copolymer powder A-7

1,3-butadiene was emulsion-polymerized to prepare butadiene rubbery polymer latex (BR 1) having an average particle diameter of 300 nm and a refractive index of 1.516.

35 parts by weight of methyl methacrylate, 12 parts by weight of styrene, 3 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 1.0 parts by weight of sodium oleate, 0.5 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight of ethylenediaminetetraacetic acid Part, sodium formaldehyde sulfoxylate 0.1 parts by weight, ferrous sulfate 0.001 parts by weight, and cumene hydroperoxide 0.2 parts by weight were uniformly mixed to prepare a mixed solution.

After the temperature of the reactor in which 50 parts by weight of the butadiene rubbery polymer latex (BR 1) was present (based on solid content) was raised to 75° C., the mixture solution was continuously introduced for 5 hours to perform polymerization. After the continuous input was completed, the reactor was heated to 80 °C, aged for 1 hour, and then polymerization was terminated to obtain a graft copolymer latex.

The graft copolymer latex was aggregated with acetic acid, washed, dehydrated and dried to obtain a graft copolymer powder A-7 having a refractive index of 1.516.

manufacturing example 8: non-graft copolymer pellet Preparation of B-1

A mixed solution containing 52 parts by weight of methyl methacrylate, 39 parts by weight of styrene, 9 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.3 parts by weight of t-dodecyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. was put in. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5315 Phosphorus non-graft copolymer pellets B-1 were prepared.

manufacturing example 9: non-graft copolymer pellet Preparation of B-2

A mixed solution containing 45.3 parts by weight of methyl methacrylate, 45.7 parts by weight of styrene, 9 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.3 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.538 Phosphorus non-graft copolymer pellets B-2 were prepared.

manufacturing example 10: non-graft copolymer pellet Preparation of B-3

A mixed solution containing 70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.3 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.516 Phosphorus non-graft copolymer pellets B-3 were prepared.

manufacturing example 11: non-graft copolymer pellet Preparation of B-4

A mixed solution containing 65.2 parts by weight of methyl methacrylate, 29.8 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene, and 0.3 parts by weight of n-octyl mercaptan was continuously added to the reactor so that the average polymerization time was 3 hours. did. At this time, the polymerization temperature was maintained at 148 ℃. The polymerization solution continuously discharged from the reactor is heated in a preheating tank, the unreacted monomer and solvent are volatilized in the volatilization tank, and the temperature of the polymer is maintained at 210 ° C. Using a polymer transfer pump extrusion processor, the refractive index is 1.5212 Phosphorus non-graft copolymer pellets B-4 were prepared.

Example and comparative example

A thermoplastic resin composition was prepared by uniformly mixing the graft copolymer powder and the non-graft copolymer pellet at the content shown in Tables 1 to 3 below.

Experimental example One

The physical properties of the thermoplastic resin compositions of Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1 to 3.

1) Methyl methacrylate unit/second styrene unit (MMA unit/ST unit): After deriving the weight of the methyl methacrylate unit in the thermoplastic resin composition and the styrene unit not included in the rubbery polymer by infrared spectroscopy, the styrene unit The weight ratio of the methyl methacrylate unit was calculated.

Experimental example 2

After uniformly mixing 100 parts by weight of the thermoplastic resin composition of Examples and Comparative Examples, 0.3 parts by weight of lubricant, and 0.2 parts by weight of antioxidant, pellets were prepared using a twin-screw extrusion kneader having a cylinder temperature of 220 °C. The physical properties of the pellets were measured by the following method, and the results are shown in Tables 1 to 3.

1) Melt flow index (g/10 min): It was measured under the conditions of 220 °C and 10 kg according to ASTM D1238.

Experimental example 3

Specimens were prepared by injecting the pellets prepared in Experimental Example 2, and physical properties were measured by the following method, and the results are shown in Tables 1 to 3 below.

1) Haze (Haze value, %): Measured according to ASTM D1003.

2) Notched Izod impact strength (kgf·cm/cm, 1/4 inch): It was measured at 23° C. according to ASTM D256.

3) Chemical resistance: Ethanol was applied to the specimen fixed on a jig with a jig strain of 0.5% and examined for 10 minutes. If there was no change, OK, and if cracks occurred, it was recorded as NG.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 graft
copolymer powder Content (parts by weight) 35 35 35 40 Kinds A-1 A-2 A-3 A-3 refractive index 1.5315 not measurable 1.5315 1.5315 monomer mixture
(weight%) SBR 1 50 0 0 0 SBR 2 0 0 50 50 SBR 3 0 0 0 0 BR 1 0 50 0 0 MMA 27.1 27.1 27.1 27.1 ST 19.9 19.9 19.9 19.9 AN 3 3 3 3 non-graft
copolymer Content (parts by weight) 65 65 65 60 Kinds B-1 B-1 B-1 B-1 refractive index 1.5315 1.5315 1.5315 1.5315 monomer mixture
(weight%) MMA 52 52 52 52 ST 39 39 39 39 AN 9 9 9 9 Thermoplastic resin composition MMA unit/ST unit about 1.34 about 1.34 about 1.34 about 1.34 flow index 28 28 13 12 haze 1.9 >90 1.4 1.5 impact strength 10 13 2 3 chemical resistance OK OK NG OK SBR 1: rubbery polymer prepared from a monomer mixture consisting of 21 wt% of styrene and 79 wt% of 1,3-butadiene, average particle diameter 300 nm, refractive index 1.5315
SBR 2: A rubbery polymer prepared from a monomer mixture consisting of 21% by weight of styrene and 79% by weight of 1,3-butadiene, average particle diameter of 100 nm, refractive index of 1.5315
SBR 3: rubbery polymer prepared from a monomer mixture consisting of 30% by weight of styrene and 70% by weight of 1,3-butadiene, average particle diameter 350 nm, refractive index: 1.538
BR 1: Rubber polymer made of 100% 1,3-butadiene, average particle diameter 300 nm, refractive index: 1.516
MMA: methyl methacrylate
ST: Styrene
AN: acrylonitrile

division Example 2 Comparative Example 4 Comparative Example 5 graft
copolymer powder Content (parts by weight) 40 40 40 Kinds A-4 A-5 A-4 refractive index 1.538 1.516 1.538 monomer mixture
(weight%) SBR 1 0 0 0 SBR 2 0 0 0 SBR 3 55 0 55 BR 1 0 55 0 MMA 21.2 21.2 21.2 ST 20.8 20.8 20.8 AN 3 3 3 non-graft
copolymer Content (parts by weight) 60 60 60 Kinds B-2 B-2 B-3 refractive index 1.538 1.538 1.516 monomer mixture
(weight%) MMA 45.3 45.3 70.4 ST 45.7 45.7 24.6 AN 9 9 5 Thermoplastic resin composition MMA unit/ST unit about 1.00 about 1.00 about 2.20 flow index 30 31 26 haze 2.1 >90 >50 impact strength 11 15 10 chemical resistance OK OK NG SBR 1: rubbery polymer prepared from a monomer mixture consisting of 21 wt% of styrene and 79 wt% of 1,3-butadiene, average particle diameter 300 nm, refractive index 1.5315
SBR 2: A rubbery polymer prepared from a monomer mixture consisting of 21% by weight of styrene and 79% by weight of 1,3-butadiene, average particle diameter of 100 nm, refractive index of 1.5315
SBR 3: rubbery polymer prepared from a monomer mixture consisting of 30% by weight of styrene and 70% by weight of 1,3-butadiene, average particle diameter 350 nm, refractive index: 1.538
BR 1: Rubber polymer made of 100% 1,3-butadiene, average particle diameter 300 nm, refractive index: 1.516
MMA: methyl methacrylate
ST: Styrene
AN: acrylonitrile

division Comparative Example 6 Comparative Example 7 Comparative Example 8 graft
copolymer powder Content (parts by weight) 35 35 40 Kinds A-6 A-7 A-7 refractive index 1.5212 1.516 1.516 monomer mixture
(weight%) SBR 1 0 0 0 SBR 2 0 0 0 SBR 3 0 0 0 SBR 4 50 0 0 BR 1 0 50 50 MMA 32.97 35 35 ST 15.03 12 12 AN 2 3 3 non-graft
copolymer Content (parts by weight) 65 65 60 Kinds B-4 B-3 B-2 refractive index 1.5212 1.516 1.538 monomer mixture
(weight%) MMA 65.2 70.4 45.3 ST 29.8 24.6 45.7 AN 5 5 9 Thermoplastic resin composition MMA unit/ST unit about 2.20 about 2.87 about 1.28 flow index 29 24 27 haze 1.9 1.7 >50 impact strength 11 13 14 chemical resistance NG NG OK SBR 1: rubbery polymer prepared from a monomer mixture consisting of 21 wt% of styrene and 79 wt% of 1,3-butadiene, average particle diameter 300 nm, refractive index 1.5315
SBR 2: A rubbery polymer prepared from a monomer mixture consisting of 21% by weight of styrene and 79% by weight of 1,3-butadiene, average particle diameter of 100 nm, refractive index of 1.5315
SBR 3: rubbery polymer prepared from a monomer mixture consisting of 30% by weight of styrene and 70% by weight of 1,3-butadiene, average particle diameter 350 nm, refractive index: 1.538
SBR 4: rubbery polymer prepared from a monomer mixture consisting of 7% by weight of styrene and 93% by weight of 1,3-butadiene, average particle diameter of 300 nm, refractive index: 1.5219
BR 1: Rubber polymer made of 100% 1,3-butadiene, average particle diameter 300 nm, refractive index: 1.516
MMA: methyl methacrylate
ST: Styrene
AN: acrylonitrile

Referring to Table 1, the thermoplastic resin composition of Example 1 comprising a styrene/butadiene rubber polymer having an average particle diameter of 300 nm and having a weight ratio of (meth)acrylate units to styrene units of about 1.34 has a flow index, Haze, impact strength and chemical resistance were all excellent.

However, the thermoplastic resin composition of Comparative Example 1 containing a butadiene rubber polymer having an average particle diameter of 300 nm and having a weight ratio of (meth)acrylate-based monomer units to styrene-based monomer units of about 1.34 has a haze value too high and thus is transparent The material was difficult to use.

In addition, the thermoplastic resin compositions of Comparative Examples 2 and 3 containing a styrene/butadiene rubber polymer having an average particle diameter of 100 nm and a weight ratio of (meth)acrylate-based monomer units to styrene-based monomer units of about 1.34, the flow index is too low, the workability was deteriorated, and the impact strength was also significantly reduced. In the case of Comparative Example 3, since it contains a styrene/butadiene rubber polymer having a small average particle diameter, not only impact strength but also chemical resistance should be reduced, but chemical resistance was not reduced because the graft copolymer was included in a relatively excessive amount.

Referring to Table 2, the thermoplastic resin composition of Example 2, including a styrene/butadiene rubber polymer having an average particle diameter of 350 nm, and having a weight ratio of (meth)acrylate units to styrene units of about 1, has a flow index, Haze, impact strength and chemical resistance were all excellent.

However, the thermoplastic resin composition of Comparative Example 4, which includes a butadiene rubber polymer having an average particle diameter of 300 nm and a weight ratio of (meth)acrylate-based monomer units to styrene-based monomer units of about 1, has a haze value too high to be transparent The material was difficult to use.

In addition, the thermoplastic resin composition of Comparative Example 5, including a styrene/butadiene rubber polymer having an average particle diameter of 350 nm, and having a weight ratio of (meth)acrylate units to styrene units of about 2.20, has a haze value too high to be used as a transparent material. It was difficult to use, and since it contained an excessive amount of methyl methacrylate units, chemical resistance was deteriorated, and since methyl methacrylate, an expensive raw material, was used in excess, the manufacturing cost increased.

Referring to Table 3, the thermoplastic resin composition of Comparative Example 6 including a styrene/butadiene rubber polymer having an average particle diameter of 300 nm and a weight ratio of (meth)acrylate units to styrene units of about 2.20 is methyl methacrylate Since the unit is included in excess, chemical resistance is lowered, and since methyl methacrylate, an expensive raw material, is used in excess, the manufacturing cost is increased.

In addition, the thermoplastic resin composition of Comparative Example 7, which includes a butadiene rubber polymer having an average particle diameter of 300 nm and a weight ratio of (meth)acrylate units to styrene units of about 2.87, contains an excess of methyl methacrylate units, The chemical resistance was lowered, and the manufacturing cost increased because the expensive raw material, methyl methacrylate, was used in excess.

In addition, the thermoplastic resin composition of Comparative Example 8 containing a butadiene rubber polymer having an average particle diameter of 300 nm and having a weight ratio of (meth)acrylate units to styrene units of about 1.28 had a haze value too high, making it difficult to use as a transparent material. .

Claims (8)

a rubbery polymer including a first styrene-based monomer unit and a diene-based monomer unit and having an average particle diameter of 250 to 450 nm;
(meth)acrylate-based monomer units; and
a second styrenic monomer unit;
A weight ratio of the (meth)acrylate-based monomer unit to the second styrene-based monomer unit is 2 or less.
The method according to claim 1,
The weight ratio of the (meth) acrylate-based monomer unit to the second styrene-based monomer unit is 0.8 to 2 of the thermoplastic resin composition.
The method according to claim 1,
The thermoplastic resin composition is
10 to 35% by weight of the rubbery polymer;
24 to 60 wt% of the (meth)acrylate-based monomer unit; and
The thermoplastic resin composition comprising 19 to 47% by weight of the second styrenic monomer unit.
The method according to claim 1,
The thermoplastic resin composition further comprises an acrylonitrile-based monomer unit.
5. The method according to claim 4,
The thermoplastic resin composition is a thermoplastic resin composition comprising the acrylonitrile-based monomer unit in an amount of 10 wt% or less.
The method according to claim 1,
The rubbery polymer is a thermoplastic resin composition comprising the first styrene-based monomer unit and the diene-based monomer unit in a weight ratio of 10:90 to 35:65.
The method according to claim 1,
The thermoplastic resin composition is
A rubbery polymer comprising a first styrene-based monomer unit and a diene-based monomer unit and having an average particle diameter of 250 to 450 nm, a (meth)acrylate-based monomer unit grafted to the rubbery polymer, and a product grafted to the rubbery polymer 2 graft copolymers containing styrenic monomer units; and
A thermoplastic resin composition comprising a (meth) acrylate-based monomer unit and a non-grafted copolymer including a second styrene-based monomer unit.
8. The method of claim 7,
The refractive index of the graft copolymer is 1.523 to 1.542 of the thermoplastic resin composition.