WO2021054652A1 - Method for preparing graft polymer - Google Patents

Abstract

The present invention relates to a method for preparing a graft polymer, the method comprising the steps of: preparing a composite rubber-like polymer by adding, into a reactor, a diene-based rubber-like polymer, a first monomer mixture comprising a (meth)acrylate-based monomer and an aromatic vinyl-based monomer, and a reactive UV stabilizer and polymerizing same; and graft-polymerizing, onto the composite rubber-like polymer, a second monomer mixture comprising a (meth)acrylate-based monomer, an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to prepare a graft polymer, wherein 0.1-2 parts by weight of the reactive UV stabilizer is added with respect to 100 parts by weight of the total of the diene-based rubber-like polymer, the first monomer mixture, and the second monomer mixture.

Description

Method for producing graft polymer

[Mutual citation with related application]

The present invention claims the benefit of priority based on Korean Patent Application No. 10-2019-0114888 filed on September 18, 2019 and Korean Patent Application No. 10-2020-0110944 filed on September 01, 2020, All contents disclosed in the document of the Korean patent application are included as part of this specification.

[Technical field]

The present invention relates to a method for producing a graft polymer, and more particularly, to a method for producing a graft polymer using a reactive UV stabilizer.

A diene-based graft polymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer on a diene-based rubber polymer has a good balance of physical properties such as impact strength and processability. Accordingly, diene-based graft polymers are variously used in automobile products, home appliances, and OA products. In recent years, development of transparent materials is underway due to diversification of designs, and technologies for imparting transparency by introducing alkyl (meth)acrylate-based monomers to diene-based graft polymers are being developed.

The transparent diene-based graft polymer produced by these techniques has excellent impact strength and workability, but it cannot be used outdoors because of poor weather resistance, and even when used indoors, discoloration occurs during long-term use, which is a problem. In order to improve the weather resistance, a method of introducing an additive such as a UV stabilizer has been proposed when preparing a thermoplastic resin composition, but there is a limitation.

The problem to be solved by the present invention is to provide a graft polymer having excellent transparency, impact strength, and weather resistance.

In order to solve the above-described problems, the present invention is a composite rubber polymer by introducing and polymerizing a first monomer mixture and a reactive UV stabilizer including a diene-based rubber polymer, a (meth)acrylate-based monomer and an aromatic vinyl-based monomer into a reactor. Manufacturing a; And graft polymerization of a second monomer mixture comprising a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer to the composite rubbery polymer to prepare a graft polymer, wherein the reactive UV It provides a method for producing a graft polymer in which a stabilizer is added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total of the diene-based rubber polymer, the first monomer mixture, and the second monomer mixture.

According to the method for producing a graft polymer of the present invention, a graft polymer having excellent transparency, impact strength, and weather resistance can be prepared.

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

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

In the present invention, the refractive index means 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. At this time, the radiation may be visible light having a wavelength of 450 to 680 nm, and specifically, may be visible light having a wavelength of 589.3 nm. The refractive index can be measured using a known method, that is, an Abbe refractometer.

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

In the present invention, the diene-based rubber polymer may mean a polymer prepared by crosslinking a diene-based monomer alone or a diene-based monomer and a comonomer copolymerizable therewith. The diene-based monomer 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. The comonomer may include an aromatic vinyl monomer, a vinyl cyanide monomer, and an olefin monomer. The diene-based rubber polymer may include a butadiene rubber polymer, a butadiene-styrene rubber polymer, and a butadiene-acrylonitrile rubber polymer. The diene rubber polymer is preferably a butadiene rubber polymer having excellent impact strength and chemical resistance.

In the present invention, the (meth) acrylate monomer may be a C ₁ to C ₁₀ alkyl (meth) acrylate monomer, and the C ₁ to C ₁₀ alkyl (meth) acrylate 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) It may be one or more selected from the group consisting of acrylate, of which one or more selected from the group consisting of methyl methacrylate and butyl acrylate is preferred.

In the present invention, the aromatic vinyl-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 vinyl cyanide monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is preferable.

In the present invention, the C ₁ to C ₁₀ linear alkyl group may be a C ₁ to C ₁₀ linear or branched alkyl group, and preferably a C ₁ to C ₃ linear or branched alkyl group. The C ₁ to C ₁₀ linear alkyl group may be a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, heptyl group, isoheptyl group, hexyl group or isohexyl group, of which methyl group is preferable. Do.

In the present invention, the C ₁ to C ₁₀ linear _{alkylene group may be a C 1} to C ₁₀ linear or branched alkylene group, and preferably a C ₁ to C ₃ linear or branched alkylene group. The C ₁ to C ₁₀ linear alkylene group may mean a divalent group having two bonding positions in _{the C 1} to C _{10 linear alkyl group.}

1. Method for producing graft polymer

The method for preparing a graft polymer according to an embodiment of the present invention includes 1) a first monomer mixture including a diene-based rubber polymer, a (meth)acrylate-based monomer, and an aromatic vinyl-based monomer and a reactive UV stabilizer into the reactor. And polymerizing to prepare a composite rubbery polymer; And 2) graft polymerization of a second monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer to the composite rubbery polymer to prepare a graft polymer, wherein the reaction The type UV stabilizer is added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total of the diene-based rubber polymer, the first monomer mixture, and the second monomer mixture.

Hereinafter, a method for producing a graft polymer according to an embodiment of the present invention will be described in detail.

1) Preparation of composite rubbery polymer

First, a first monomer mixture including a diene-based rubber polymer, a (meth)acrylate-based monomer, and an aromatic vinyl-based monomer, and a reactive UV stabilizer are added to the reactor and polymerized to prepare a composite rubbery polymer.

The reactive UV stabilizer is a UV stabilizer having a double bond capable of participating in the polymerization, and if it is added in an appropriate amount in the step of preparing the composite rubbery polymer, it can be directly bonded to the chain of the composite rubbery polymer, thereby remarkably improving the weather resistance. I can. In addition, since the reactive UV stabilizer is added in the step of preparing the composite rubbery polymer, the diene-based rubbery polymer and the shell may have no or only minimal effect. Accordingly, the impact strength and transparency of the graft polymer may not be affected or may be minimally affected.

The reactive UV stabilizer is added in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 1.2 parts by weight, based on 100 parts by weight of the diene-based rubbery polymer, the first monomer mixture, and the second monomer mixture. can do. If the above-described range is satisfied, weather resistance can be remarkably improved while minimizing influence on transparency and impact strength. If it is added in less than the above-described range, the weather resistance improvement effect is insufficient, and if it is added in excess of the above-described range, transparency and impact strength are lowered, making it unsuitable for use as a transparent material.

The reactive UV stabilizer may be a compound represented by the following Formula 1:

<Formula 1>

In Formula 1,

R ₁ is hydrogen or a C ₁ to C ₁₀ alkyl group,

L ₁ is a direct bond or a C ₁ to C ₁₀ alkylene group.

The reactive UV stabilizer is 2-[2'-hydroxy-5'-[2-(acryloxy)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-( Methacryloxy)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)methyl]phenyl]-2H-benzotriazole, 2-[2'-hydro Roxy-5'-[2-(methacryloxy)methyl]phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)ethyl]phenyl]-2H- Benzotriazole, 2-[2'-hydroxy-5'-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2- (Acrylooxy)propyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(methacrylooxy)propyl)phenyl]-2H-benzotriazole, 2- [2'-hydroxy-5'-[2-(acrylooxy)butyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(methacrylooxy) Butyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)hexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy- 5'-[2-(methacryloxy)hexyl)phenyl]-2H-benzotriazole may be one or more selected from the group consisting of, among which 2-[2'-hydroxy-5'-[2-( Methacryloxy)ethyl)phenyl]-2H-benzotriazole is preferred.

The diene-based rubber polymer may have an average particle diameter of 200 to 400 nm, and preferably 250 to 450 nm. If the above-described conditions are satisfied, a graft polymer having excellent impact strength can be prepared.

The diene-based rubber polymer is added to the reactor in a total of 100 parts by weight of the diene-based rubber polymer, the first monomer mixture and the second monomer mixture, 7 to 30 parts by weight, preferably 10 to 30 parts by weight, more preferably May be added in an amount of 15 to 25 parts by weight. If the above-described conditions are satisfied, a graft polymer having excellent impact strength and chemical resistance can be prepared. If added in less than the above-described range, the impact strength at room temperature and low temperature may be reduced. If the above-described range is exceeded, since a relatively small amount of the (meth)acrylate-based monomer is added in the manufacturing process of the composite rubbery polymer, the weather resistance of the graft polymer may be deteriorated.

The first monomer mixture in the reactor is 10 to 50 parts by weight, preferably 30 to 50 parts by weight, more preferably based on 100 parts by weight of the sum of the diene-based rubbery polymer, the first monomer mixture, and the second monomer mixture. Can be added in 35 to 45 parts by weight. If the above-described conditions are satisfied, a graft polymer having excellent weather resistance can be produced. If the amount is less than the above-described range, the content of the composite rubbery polymer in the graft polymer increases, so that mechanical properties such as tensile strength and flexural strength may decrease, and transparency may decrease.

The first monomer mixture may include a (meth)acrylate-based monomer and an aromatic vinyl-based monomer in a weight ratio of 70:30 to 50:50, preferably 65:35 to 55:45. If the above-described range is satisfied, a graft polymer having excellent weather resistance can be prepared.

In order to further improve the weather resistance, the first monomer mixture preferably includes an acrylate-based monomer and an aromatic vinyl-based monomer, and more preferably includes butyl acrylate and styrene.

Meanwhile, in the preparation of the composite rubbery polymer, polymerization may be emulsion polymerization, and at least one selected from the group consisting of an initiator, an emulsifier, a crosslinking agent, a grafting agent, and an electrolyte may be additionally added to the reactor.

The initiator may be at least one selected from the group consisting of t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, potassium persulfate, sodium persulfate and ammonium persulfate, of which cumene hydroperoxide is desirable.

The emulsifier is fatty acid soap, potassium oleate, sodium oleate, sodium dicyclohexyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexyl Sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, sodium dodecyl sulfate, potassium octadecyl sulfate, potassium loginate and sodium lodge It may be one or more selected from the group consisting of nate, of which sodium dioctyl sulfosuccinate is preferred.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol It may be one or more selected from the group consisting of dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolmethane tetraacrylate, of which ethylene glycol dimethacrylate is preferred.

The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanonate, triallylamine, and diallylamine, among which allyl methacrylate is preferred.

The electrolyte is KCl, NaCl, KOH, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K4P2O7, Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , It _{may be one or more selected from the group consisting of K 2} HPO ₄ and Na ₂ HPO ₄ , of which at least one selected from the group consisting of KOH and K ₂ CO ₃ is preferred.

On the other hand, the composite rubbery polymer may have an average particle diameter of 250 to 500 ㎚, preferably 280 to 450 ㎚. If the above-described conditions are satisfied, transparency and mechanical properties of the graft polymer may be improved.

2) Preparation of graft polymer

A graft polymer is prepared by graft polymerization of a second monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer in the composite rubbery polymer.

In the reactor, the second monomer mixture is added in an amount of 20 to 70 parts by weight, preferably 30 to 50 parts by weight, more preferably, based on 100 parts by weight of the total of the diene-based rubbery polymer, the first monomer mixture, and the second monomer mixture. May be added in an amount of 35 to 45 parts by weight. If the above-described range is satisfied, a graft polymer having excellent transparency, appearance characteristics, and impact strength can be prepared. If it is put in less than the above-described range, the appearance characteristics deteriorate, and in particular, a flow mark or the like may be generated. If it is added in excess of the above-described range, the impact strength may be significantly lowered.

The second monomer mixture may include 60 to 80% by weight of a (meth)acrylate monomer, 15 to 35% by weight of an aromatic vinyl monomer, and 1 to 7% by weight of a vinyl cyanide monomer, preferably 65 to 75% by weight of a (meth)acrylate-based monomer, 20 to 30% by weight of an aromatic vinyl-based monomer, and 3 to 7% by weight of a vinyl cyanide-based monomer may be included. If the above-described range is satisfied, processability and chemical resistance may be improved while maintaining transparency.

In order to further improve the weather resistance, the second monomer mixture preferably includes a methacrylate-based monomer and an aromatic vinyl-based monomer, and more preferably includes methyl methacrylate, styrene, and acrylonitrile.

Meanwhile, in the preparation of the graft polymer, polymerization may be emulsion polymerization, and at least one selected from the group consisting of an initiator, an emulsifier, a redox catalyst, and a molecular weight regulator may be additionally added to the reactor.

Kinds of the initiator and emulsifier are as described above.

The oxidation-reduction catalyst may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate, and sodium sulfate. And, it is preferable that it is at least one selected from the group consisting of ferrous sulfate, dextrose, and sodium pyrophosphate.

The molecular weight modifier is α-methyl styrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetra ethyl thiuram disulfide, dipentamethylene thiuram disulfide. , Diisopropylxanthogen may be one or more selected from the group consisting of disulfide, of which t-dodecyl mercaptan is preferred.

On the other hand, in order for the graft polymer to have transparency, it is preferable that the difference in refractive index between the diene-based rubber polymer, the composite rubber polymer, and the shell is 0.01 or less, and there is no difference in the refractive index thereof.

In addition, the graft polymer may have a refractive index of 1.51 to 1.52, preferably 1.515 to 1.517. If the above-described conditions are satisfied, a graft polymer having excellent transparency can be prepared.

2. Thermoplastic resin composition

The thermoplastic resin composition according to another embodiment of the present invention is a graft polymer prepared by the manufacturing method according to an embodiment of the present invention; And a matrix polymer that is a polymer of a third monomer mixture including a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer.

The difference in refractive index between the graft polymer and the matrix polymer may be 0.01 or less, and it is preferable that there is no difference in refractive index. If the above-described conditions are satisfied, a thermoplastic resin molded article having excellent transparency can be manufactured.

The third monomer mixture may include 40 to 75 parts by weight of a (meth)acrylate-based monomer, 15 to 40 parts by weight of an aromatic vinyl-based monomer, and 1 to 20 parts by weight of a vinyl cyanide-based monomer, preferably (meth)acrylic It may include 55 to 70 parts by weight of an ite-based monomer, 20 to 30 parts by weight of an aromatic vinyl-based monomer, and 5 to 15 parts by weight of a vinyl cyanide-based monomer. If the above-described conditions are satisfied, a matrix polymer having excellent transparency, chemical resistance, scratch resistance, and processability can be prepared.

The thermoplastic resin composition may include a graft polymer and a matrix polymer in a weight ratio of 25:75 to 75:25, preferably 50:50 to 25:75.

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

Manufacturing Example 1

A polymerization solution in which 63.36 parts by weight of methyl methacrylate, 24.64 parts by weight of styrene, 12 parts by weight of acrylonitrile, 30 parts by weight of toluene and 0.15 parts by weight of t-dodecyl mercaptan were mixed in a reactor was prepared so that the average polymerization time was 3 hours. Polymerization was carried out while continuously adding at a rate, and the polymerization temperature was maintained at 148°C. The polymer discharged from the reactor was heated in a preheating bath, and unreacted monomers were volatilized in the volatilization bath. Then, it was extruded in an extruder at 210° C. to prepare a pellet-shaped MSAN polymer (refractive index: 1.516).

Example 1

<Production of Graft Polymer Powder>

In the reactor, butadiene rubber polymer latex (PBL, gel content: 70%, average particle diameter: 300 nm) 20 parts by weight (based on solid content), butyl acrylate (BA) 24 parts by weight, styrene (S) 16 parts by weight, ion-exchanged water 100 parts by weight, reactive UV stabilizer (RUVA93 of Otsuka Chemical), cumene hydroperoxide 0.1 parts by weight, sodium ethylenediaminetetraacetate 0.01 parts by weight, sodium formaldehyde sulfoxylate 0.04 parts by weight, sulfuric acid Ferrous 0.0001 parts by weight, sodium dioctyl sulfosuccinate 0.7 parts by weight, ethylene glycol dimethacrylate 0.4 parts by weight, allyl methacrylate 0.1 parts by weight, NaHCO ₃ 0.1 parts by weight at a constant rate for 3 hours at 70° C. Polymerization was carried out while continuously adding. Thereafter, the temperature of the reactor was raised to 80° C. and polymerized for 1 hour to prepare a composite rubbery polymer latex.

To the composite rubbery polymer latex, 28 parts by weight of methyl methacrylate (MMA), 10 parts by weight of styrene (S), 2 parts by weight of acrylonitrile (AN), 0.1 parts by weight of cumene hydroperoxide, 0.01 parts by weight of sodium ethylenediaminetetraacetate Parts, sodium formaldehyde sulfoxylate 0.04 parts by weight, ferrous sulfate 0.001 parts by weight, sodium oleate 0.5 parts by weight, and t-dodecyl mercaptan 0.4 parts by weight were continuously added at 75° C. for 5 hours at a constant rate while polymerization was carried out. . Thereafter, the temperature of the reactor was raised to 80° C., aged for 1 hour, and polymerization was terminated, and a graft polymer latex was obtained.

The graft polymer latex was aggregated with an aqueous calcium chloride solution, and then aged, washed, dehydrated and dried to obtain a graft polymer powder.

<Production of thermoplastic resin composition>

35 parts by weight of the graft polymer powder and 65 parts by weight of the MSAN polymer of Preparation Example 1 were uniformly mixed to prepare a thermoplastic resin composition.

Examples 2 to 4

A graft polymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that a reactive UV stabilizer (RUVA93 of Otsuka Chemical Co., Ltd.) was added to the reactor at the contents shown in the following table.

Example 5

<Production of Graft Polymer Powder>

Graft polymer powder was prepared in the same manner as in Example 1.

<Production of thermoplastic resin composition>

45 parts by weight of the graft polymer powder and 55 parts by weight of the MSAN polymer of Preparation Example 1 were uniformly mixed to prepare a thermoplastic resin composition.

Comparative Example 1 and Comparative Example 2

A graft polymer powder and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that a reactive UV stabilizer (RUVA93 of Otsuka Chemical Co., Ltd.) was added to the reactor at the contents shown in the following table.

Comparative Example 3

<Production of Graft Polymer Powder>

In the reactor, butadiene rubber polymer latex (PBL, gel content: 70%, average particle diameter: 300 nm) 20 parts by weight (based on solid content), butyl acrylate (BA) 17.5 parts by weight, styrene (S) 12.5 parts by weight, ion-exchanged water 100 parts by weight, potassium persulfate 0.06 parts by weight, sodium dioctyl sulfosuccinate 0.5 parts by weight, ethylene glycol dimethacrylate 0.28 parts by weight, allyl methacrylate 0.1 parts by weight, NaHCO ₃ 0.1 parts by weight at 70° C. for 3 hours During the polymerization was carried out while continuously added at a constant rate. Thereafter, the temperature of the reactor was raised to 80° C. and polymerized for 1 hour to prepare a composite rubbery polymer latex.

To the composite rubbery polymer latex, methyl methacrylate (MMA) 34.56 parts by weight, styrene (S) 13.44 parts by weight, acrylonitrile (AN) 2 parts by weight, cumene hydroperoxide 0.1 parts by weight, sodium ethylenediaminetetraacetate 0.01 parts by weight Parts, sodium formaldehyde sulfoxylate 0.04 parts by weight, ferrous sulfate 0.001 parts by weight, sodium oleate 0.5 parts by weight, t-dodecyl mercaptan 0.5 parts by weight, polymerization was carried out at a constant rate at 75° C. for 5 hours. . Thereafter, the temperature of the reactor was raised to 80° C., aged for 1 hour, and polymerization was terminated, and a graft polymer latex was obtained.

The graft polymer latex was aggregated with an aqueous calcium chloride solution, and then aged, washed, dehydrated and dried to obtain a graft polymer powder.

<Production of thermoplastic resin composition>

40 parts by weight of the graft polymer powder and 60 parts by weight of the MSAN polymer of Preparation Example 1 were uniformly mixed to prepare a thermoplastic resin composition.

Comparative Example 4

<Production of Graft Polymer Powder>

In the reactor, butadiene rubbery polymer latex (PBL, gel content: 70%, average particle diameter: 300 nm) 20 parts by weight (based on solid content) 50 parts by weight, methyl methacrylic acid 35.5 parts by weight, styrene 12.5 parts by weight, acrylonitrile 2 parts by weight Parts, cumene hydroperoxide 0.1 parts by weight, sodium oleate 0.5 parts by weight, sodium ethylenediaminetetraacetate 0.1 parts by weight, sodium formaldehyde sulfoxylate 0.04 parts by weight, ferrous sulfate 0.001 parts by weight at 75° C. for 5 hours Polymerization was carried out while continuously charged at a rate. Thereafter, the temperature of the reactor was raised to 80° C., aged for 1 hour, and polymerization was terminated, and a graft polymer latex was obtained.

The graft polymer latex was aggregated with an aqueous calcium chloride solution, and then aged, washed, dehydrated and dried to obtain a graft polymer powder.

<Production of thermoplastic resin composition>

40 parts by weight of the graft polymer powder and 60 parts by weight of the MSAN polymer of Preparation Example 1 were uniformly mixed to prepare a thermoplastic resin composition.

Comparative Example 5

<Preparation of diene rubber polymer>

In a nitrogen-substituted polymerization reactor, 90 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene (BD), 3.5 parts by weight of reactive UV stabilizer (RUVA93 of Otsuka Chemical Co., Ltd.), 1.2 parts by weight of rosinate potassium salt, potassium oleate Salt 0.8 parts by weight, K ₂ CO ₃ 1.0 parts by weight, t-dodecyl mercaptan 0.4 parts by weight, potassium persulfate 0.5 parts by weight were put in a batch. After raising the temperature of the reactor to 70° C., polymerization was initiated.

Subsequently, when the polymerization conversion rate was about 35%, 25 parts by weight of 1,3-butadiene (BD) and 0.15 parts by weight of potassium persulfate were collectively added to the reactor to continue polymerization.

When the polymerization conversion rate was about 60%, the reactor was polymerized while heating the reactor to 80°C, and the polymerization was terminated at the time when the polymerization conversion rate was 90%, and the butadiene rubbery polymer latex (gel content: 70%, average particle diameter: 300 nm) Was prepared.

<Production of Graft Polymer Powder>

In the reactor, butadiene rubbery polymer latex 20 parts by weight (based on solid content), butyl acrylate (BA) 24 parts by weight, styrene (S) 16 parts by weight, ion-exchanged water 100 parts by weight, cumene hydroperoxide 0.1 parts by weight, sodium ethylenediamine Tetraacetate 0.01 parts by weight, sodium formaldehyde sulfoxylate 0.04 parts by weight, ferrous sulfate 0.0001 parts by weight, sodium dioctyl sulfosuccinate 0.7 parts by weight, ethylene glycol dimethacrylate 0.4 parts by weight, allyl methacrylate 0.1 Polymerization was carried out while continuously adding 0.1 parts by weight of NaHCO _{3 at 70° C. for 3 hours at a constant rate.} Thereafter, the temperature of the reactor was raised to 80° C. and polymerized for 1 hour to prepare a composite rubbery polymer latex.

To the composite rubbery polymer latex, methyl methacrylate (MMA) 28 parts by weight, styrene (S) 10 parts by weight, acrylonitrile (AN) 2 parts by weight, cumene hydroperoxide 0.1 parts by weight, sodium ethylenediaminetetraacetate 0.01 parts by weight Parts, sodium formaldehyde sulfoxylate 0.04 parts by weight, ferrous sulfate 0.001 parts by weight, sodium oleate 0.5 parts by weight, t-dodecyl mercaptan 0.4 parts by weight, polymerization was carried out at 75° C. for 5 hours at a constant rate for 5 hours. . Thereafter, the temperature of the reactor was raised to 80° C., aged for 1 hour, and polymerization was terminated, thereby obtaining a graft polymer latex.

The graft polymer latex was aggregated with an aqueous calcium chloride solution, and then aged, washed, dehydrated and dried to obtain a graft polymer powder.

<Production of thermoplastic resin composition>

35 parts by weight of the graft polymer powder and 65 parts by weight of the MSAN polymer of Preparation Example 1 were uniformly mixed to prepare a thermoplastic resin composition.

Experimental Example 1

The physical properties of the composite rubbery polymers of Examples and Comparative Examples were measured by the method described below, and the results are shown in the following table.

① Average particle diameter (nm): Measured by dynamic light scattering using Nicomp 380 manufactured by Particle Sizing Systems.

Experimental Example 2

The physical properties of the graft polymer powders of Examples and Comparative Examples were measured by the method described below, and the results are shown in Tables 1 and 2 below.

② Refractive index: The graft polymer powder was irradiated with visible light of 589.3 nm and measured with an Abbe refractometer.

Experimental Example 3

100 parts by weight of the thermoplastic resin compositions of Examples and Comparative Examples, 0.2 parts by weight of ethylene bis stearate, 0.2 parts by weight of IR1076, and 0.1 parts by weight of BASF's Tinuvin 770 were uniformly mixed, and then extruded and injected to prepare a specimen. The physical properties of the specimen were measured by the method described below, and the results are shown in Tables 1 and 2 below.

③ Haze (Haze value, %): It was measured according to ASTM1003.

④ Notched Izod impact strength (kgf·cm/cm, 1/4 inch): Measured at 25°C according to ASTM D256.

⑤ Weather resistance: The weather resistance was evaluated by calculating the color difference between the specimens stored for 500 hours and before storage using UV2000 (ATLAS) by the following equation.

On the other hand, the weather resistance evaluation conditions were as follows.

Light Source: Fluorescent UV lamps (40W, UVA 340 lamp)

Irradiance: 0.55 W/㎡ (340 nm)

The temperature of the black panel: 60 ℃

In the above formula, L', a', b'are L, a, and b values measured by the CIE LAB color coordinate system after storage for 500 hours in the specimen, and L ₀ , a _{0, and} b ₀ are the CIE LAB colors before storage. These are L, a, and b values measured with a coordinate system.

division		Comparative example	Example				Comparative example
		One	One	2	3	4	2
Composite rubbery polymer latex (parts by weight)	PBL	20	20	20	20	20	20
	BA	24	24	24	24	24	24
	S	16	16	16	16	16	16
	Reactive UV Stabilizer	0.05	0.3	0.7	1.5	2	3
	Average particle diameter (nm)	410	410	410	410	410	410
Graft polymer powder (parts by weight)	MMA	28	28	28	28	28	28
	S	10	10	10	10	10	10
	AN	2	2	2	2	2	2
	Refractive index	1.516	1.516	1.516	1.516	1.516	1.516
Thermoplastic resin composition	Graft polymer powder (parts by weight)	35	35	35	35	35	35
	MSAN polymer of Preparation Example 1 (parts by weight)	65	65	65	65	65	65
	Haze	1.8	1.8	1.9	2.1	2.2	2.5
	Impact strength	9.0	8.8	8.9	8.7	8.7	8.6
	Weather resistance	4.2	1.5	0.9	0.8	0.6	0.6

division		Example 5	Comparative Example 3	Comparative Example 4	Comparative Example 5
Preparation of diene rubber polymer latex (parts by weight)	BD	-	-	-	100
	Reactive UV Stabilizer	-	-	-	3.5
	Average particle diameter (nm)	-	-	-	300
Composite rubbery polymer latex (parts by weight)	PBL	20	20	50	20
	BA	24	17.5	0	24
	S	16	12.5	0	16
	Reactive UV Stabilizer	0.7	0	0	0
	Average particle diameter (nm)	410	390	300	410
Graft polymer powder (parts by weight)	MMA	28	34.56	35.5	28
	S	10	13.44	12.5	10
	AN	12	2	2	12
	Refractive index	1.516	1.518	1.516	1.516
Thermoplastic resin composition	Graft polymer powder (parts by weight)	45	40	40	35
	MSAN polymer (parts by weight)	55	60	60	65
	Haze	2.1	2.1	1.9	2.5
	Impact strength	12.3	8.3	18.1	8.5
	Weather resistance	1.0	3.9	7.2	2.1

Referring to Tables 1 and 2, it was confirmed that Examples 1 to 5 using a reactive UV stabilizer in an appropriate amount were excellent in all of transparency, impact strength, and weather resistance. On the other hand, in Comparative Example 1 using a reactive UV stabilizer in a small amount, the weather resistance was markedly lowered. Comparative Example 2 using a reactive UV stabilizer in an excessive amount was inappropriate as a transparent material due to decreased transparency. In Comparative Example 3 without using a reactive UV stabilizer, it was confirmed that the weather resistance was significantly lowered. Comparative Example 4 prepared with a diene-based rubbery polymer rather than a composite rubbery polymer without using a reactive UV stabilizer was found to significantly lower the weather resistance. In Comparative Example 5, in which the reactive UV stabilizer was used in the manufacture of a diene-based rubbery polymer latex, it was confirmed that transparency, impact resistance, and weather resistance were deteriorated. In Comparative Example 5, the content of the reactive UV stabilizer included in the graft copolymer was the same, but it was confirmed that transparency, impact resistance, impact resistance, and weather resistance were deteriorated even when compared with Example 2, which differed only in the timing of addition.

Claims (8)

1. Adding a first monomer mixture including a diene-based rubber polymer, a (meth)acrylate-based monomer, and an aromatic vinyl-based monomer and a reactive UV stabilizer to a reactor and polymerizing to prepare a composite rubbery polymer; And

   Graft polymerization of a second monomer mixture comprising a (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer to the composite rubbery polymer to prepare a graft polymer,

   The method for producing a graft polymer in which the reactive UV stabilizer is added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total of the diene-based rubbery polymer, the first monomer mixture, and the second monomer mixture.
2. The method according to claim 1,

   The method for producing a graft polymer in which the reactive UV stabilizer is added in an amount of 0.5 to 1.2 parts by weight based on 100 parts by weight of the total of the diene-based rubber polymer, the first monomer mixture, and the second monomer mixture.
3. The method according to claim 1,

   The reactive UV stabilizer is a method for producing a graft polymer that is a compound represented by the following formula (1):

   <Formula 1>

   

   In Formula 1,

   R ₁ is hydrogen or a C ₁ to C ₁₀ linear alkyl group,

   L ₁ is a direct bond or a C ₁ to C ₁₀ linear alkylene group.
4. The method according to claim 1,

   The reactive UV stabilizer is 2-[2'-hydroxy-5'-[2-(acryloxy)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-( Methacryloxy)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)methyl]phenyl]-2H-benzotriazole, 2-[2'-hydro Roxy-5'-[2-(methacryloxy)methyl]phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)ethyl]phenyl]-2H- Benzotriazole, 2-[2'-hydroxy-5'-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2- (Acrylooxy)propyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(methacrylooxy)propyl)phenyl]-2H-benzotriazole, 2- [2'-hydroxy-5'-[2-(acrylooxy)butyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(methacrylooxy) Butyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-[2-(acryloxy)hexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy- 5′-[2-(methacryloxy)hexyl)phenyl]-2H-benzotriazole.
5. The method according to claim 1,

   Based on 100 parts by weight of the total of the diene-based rubber polymer, the first monomer mixture, and the second monomer mixture,

   7 to 30 parts by weight of the diene rubber polymer;

   10 to 50 parts by weight of the first monomer mixture; And

   The method for producing a graft polymer is added in an amount of 20 to 70 parts by weight of the second monomer mixture.
6. The method according to claim 1,

   The diene-based rubber polymer is a method for producing a graft polymer having an average particle diameter of 200 to 400 nm.
7. The method according to claim 1,

   The method for producing a graft polymer wherein the composite rubbery polymer has an average particle diameter of 250 to 450 nm.
8. The method according to claim 1,

   The graft polymer is a method of producing a graft polymer having a refractive index of 1.51 to 1.52.