[Cross Citation with Application(s)]
[2]
This application has the benefit of priority based on Korean Patent Application No. 10-2019-0120583 dated September 30, 2019 and Korean Patent Application No. 10-2020-0113904, which was re-applied on September 07, 2020 based thereon. All contents disclosed in the document of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to an acrylic graft copolymer, a method for preparing the same, and a thermoplastic resin composition comprising the same, and more particularly, UV reactive ultraviolet rays to the graft shell of the acrylic graft copolymer including a seed, a core and a graft shell. The present invention relates to an acrylic graft copolymer having excellent mechanical properties by introducing a stabilizer, excellent weather resistance and surface glossiness, and reduced mold deposit, a method for preparing the same, and a thermoplastic resin composition comprising the same.
background
[4]
Acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS resin') based on conjugated diene rubber has excellent processability, mechanical properties and appearance characteristics, so parts of electrical and electronic products, automobiles, small toys, and furniture , and is widely used as a building material. However, since the ABS resin is based on butadiene rubber containing chemically unstable unsaturated bonds, the rubber polymer is easily aged by ultraviolet rays, and the weather resistance is very weak, so it is not suitable as an outdoor material.
[5]
In order to overcome the problems of the ABS resin as described above, an acrylic copolymer represented by an acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as 'ASA resin') without an ethylenically unsaturated bond is used. , This ASA resin has excellent weather resistance and aging resistance, and is used in various fields such as automobiles, ships, leisure products, construction materials, and horticulture.
[6]
Recently, the level of weather resistance for ASA resins required in the market is increasing. To meet this, rubber with a small particle size is used, or an acrylate monomer containing methyl methacrylate (hereinafter referred to as 'MMA') is shell polymerized. A method of copolymerizing with styrene and acrylonitrile, or adding a matrix resin containing MMA during compounding is used.
[7]
However, when a rubber with a small particle diameter is used for the ASA resin, mechanical properties such as impact resistance are deteriorated. There is a problem of lowering
[8]
In addition, when a UV stabilizer is added when compounding a thermoplastic resin composition containing an ASA resin to improve weather resistance, decomposition products due to volatilization of the UV stabilizer during long-term injection molding are attached to the mold due to the mold deposit. It not only causes problems such as poor molding and poor gloss, but is often not easily removed. In order to solve this problem, a UV stabilizer with a large molecular weight can be introduced to suppress volatilization of the UV stabilizer during injection processing, but as the molecular weight increases, the input amount must be increased to maintain the weather resistance, which leads to a decrease in physical properties and an increase in production cost. there is a problem.
[9]
Therefore, there is a need for the development of a resin capable of reducing the mold deposit by suppressing volatilization of the UV stabilizer while improving the weather resistance of the ASA resin.
[10]
[Prior art literature]
[11]
[Patent Document] Korean Patent Publication No. 2001-0066310
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
In order to solve the problems of the prior art as described above, an object of the present invention is to provide an acrylic graft copolymer having excellent mechanical properties, excellent weather resistance and surface glossiness, and reduced mold deposit.
[13]
In addition, an object of the present disclosure is to provide a method for preparing the acrylic graft copolymer.
[14]
In addition, an object of the present disclosure is to provide a thermoplastic resin composition including the acrylic graft copolymer.
[15]
The above and other objects of the present disclosure can all be achieved by the present disclosure described below.
means of solving the problem
[16]
In order to achieve the above object, the present substrate is based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer, (A) one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound. seeds polymerized including 4 to 25 wt % of at least one compound; (B) a rubber core wrapped around the seed and polymerized including 25 to 55 wt% of an alkyl acrylate compound; and (C) a graft shell wrapped around the rubber core and polymerized including 40 to 70% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound; The graft shell contains 0.05 to 2 parts by weight of a reactive UV stabilizer based on 100 parts by weight of the acrylic graft copolymer, and the graft shell has an average particle diameter of 80 to 140 nm (greater than the core average particle diameter), characterized in that It provides an acrylic graft copolymer.
[17]
In addition, the present substrate is based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer, (A) at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound 4 to 25 A seed preparation step of preparing a seed by polymerizing 1.4 to 2.4 parts by weight of an emulsifier and weight %; (B) a core preparation step of preparing a core by adding 25 to 55% by weight of an alkyl acrylate compound in the presence of the prepared seed, and polymerization; and (C) 40 to 70% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinylcyanide compound and 0.05 to 2 parts by weight of a reactive UV stabilizer in the presence of the prepared core, and graft polymerization to prepare a shell It provides a method for producing an acrylic graft copolymer, including a; but, the shell has an average particle diameter of 80 to 140 nm (greater than the core average particle diameter).
[18]
In addition, the present substrate includes 20 to 50 parts by weight of the acrylic graft copolymer, 1 to 15 parts by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer having an average particle diameter of 0.2 to 0.7 μm of the rubber polymer, and 45 parts by weight of a hard matrix resin. To provide a thermoplastic resin composition comprising 70 parts by weight.
Effects of the Invention
[19]
According to the present invention, the acrylic graft copolymer includes a reactive UV stabilizer in the graft shell of the acrylic graft copolymer and has excellent mechanical properties, excellent weather resistance and surface glossiness, and reduced mold deposits to improve the appearance and productivity of the molded product. There is an effect of providing a copolymer, a method for preparing the same, and a thermoplastic resin composition comprising the same.
Best mode for carrying out the invention
[20]
Hereinafter, the acrylic graft copolymer of the present substrate will be described in detail.
[21]
The present inventors have found that in the case of bonding the reactive UV stabilizer to the backbone of the polymer constituting the shell in an acrylic graft copolymer including a seed, a core and a shell, volatilization of the UV stabilizer during injection molding is suppressed to form a mold deposit. To confirm the effect of reducing and greatly improving weather resistance, based on this, further research was devoted to complete the present invention.
[22]
A detailed look at the acrylic graft copolymer according to the present disclosure is as follows.
[23]
The acrylic graft copolymer of the present disclosure is based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer, (A) at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound. seeds polymerized comprising 4 to 25 wt % of a compound; (B) a rubber core wrapped around the seed and polymerized including 25 to 55 wt% of an alkyl acrylate compound; and (C) a graft shell wrapped around the rubber core and polymerized including 40 to 70% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound; The graft shell contains 0.05 to 2 parts by weight of a reactive UV stabilizer based on 100 parts by weight of the acrylic graft copolymer, and the graft shell has an average particle diameter of 80 to 140 nm (greater than the core average particle diameter), characterized in that In this case, there is an effect of excellent mechanical properties, excellent weather resistance and surface glossiness, and reduction of mold deposits.
[24]
In the present description, the monomer refers to an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound included in the polymerization of the acrylic graft copolymer.
[25]
In the present description, a mold deposit refers to a deposit formed by attaching decomposition products due to volatile substances to a mold during long-term injection molding of a resin 100 times or more under the same injection conditions. When the mold deposit is attached to the mold, phenomena such as unmolding, poor gloss, underweight, poor appearance, and mold release may occur, and the attached mold deposit is often not easily removed.
[26]
Each component constituting the acrylic graft copolymer of the present disclosure will be described in detail as follows.
[27]
(A) Seed
[28]
The seed is, for example, 4 to 25% by weight, preferably 10 to 20% by weight, more preferably 13 to 17% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound. It can be polymerized including, and within this range, there is an excellent effect in impact strength, tensile strength, weather resistance and surface glossiness.
[29]
The seed, for example, may have an average particle diameter of 42 to 82 nm, preferably 45 to 80 nm, and more preferably 50 to 75 nm, and within this range, the effect of excellent impact strength, tensile strength, weather resistance and surface glossiness there is
[30]
In the present description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, it can be measured as an intensity value in Gaussian mode using Nicomp 380 equipment (product name, manufacturer: PSS).
[31]
In addition, the average particle diameter of the present invention may mean an arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of scattering intensity (Intensity Distribution).
[32]
The seed may be, for example, a polymerized rubber polymer including 1.4 to 2.4 parts by weight, preferably 1.7 to 2.2 parts by weight of an emulsifier, based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer. It has excellent effects in impact strength, tensile strength, weather resistance and surface gloss.
[33]
(B) core
[34]
The core may be, for example, a polymerized rubber core surrounding the seed and comprising 25 to 55% by weight, preferably 30 to 45% by weight, more preferably 33 to 40% by weight of an alkyl acrylate compound, in this case It has excellent impact strength, tensile strength, weather resistance and surface gloss.
[35]
The core may have, for example, an average particle diameter including seeds of 62 to 110 nm, preferably 70 to 105 nm (greater than the average particle size of seeds), and within this range, impact strength, tensile strength, weather resistance and surface gloss. It has an excellent performance.
[36]
The core may be, for example, a rubber polymer polymerized including at least one selected from the group consisting of a crosslinking agent, an initiator, and an emulsifier, and in this case, there is an effect excellent in impact strength, tensile strength, weather resistance and surface glossiness.
[37]
(C) graft shell
[38]
The graft shell, for example, surrounds the rubber core and includes 40 to 70% by weight, preferably 45 to 60% by weight, more preferably 45 to 54% by weight of one or more compounds selected from the group consisting of aromatic vinyl compounds and vinyl cyan compounds. It may be a polymer that is polymerized including weight %, and in this case, there is an excellent effect in impact strength, tensile strength, weather resistance and surface glossiness.
[39]
The graft shell, for example, may have an average particle diameter including seeds and cores of 80 to 140 nm, preferably 88 to 135 nm, and within this range, the effect of excellent impact strength, tensile strength, weather resistance and surface glossiness is achieved. have.
[40]
The graft shell is, for example, 0.05 to 2 parts by weight of the reactive ultraviolet stabilizer, preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1.3 parts by weight, even more preferably based on 100 parts by weight of the acrylic graft copolymer. may include 0.3 to 1 part by weight, and within this range, impact strength, tensile strength, weather resistance and surface gloss are excellent, and mold deposits are reduced.
[41]
The reactive UV stabilizer is bonded to the backbone of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound included in the graft shell, for example, to suppress volatilization of the UV stabilizer during injection processing, thereby preventing long-term injection. It is excellent in preventing mold deposits in the mold during molding and improving weather resistance and reducing mold deposits compared to compounding UV stabilizers as additives.
[42]
The reactive ultraviolet stabilizer may be, for example, a benzotriazole reactive ultraviolet stabilizer, a benzophenone reactive ultraviolet stabilizer, or a mixture thereof. In this case, the volatilization of the ultraviolet stabilizer during long-term injection molding is suppressed to reduce mold deposit and has excellent weather resistance and surface glossiness.
[43]
The benzotriazole-based reactive ultraviolet stabilizer may be specifically a compound represented by the following Chemical Formula 1, and the benzophenone-based reactive ultraviolet stabilizer may be specifically a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or It may be a mixture thereof, and in this case, volatilization of the UV stabilizer is suppressed during long-term injection molding, thereby reducing mold deposits and having excellent weather resistance and surface glossiness.
[44]
[Formula 1]
[45]

[46]
[Formula 2]
[47]

[48]
[Formula 3]
[49]

[50]
The graft shell may be a polymer polymerized including, for example, a reactive emulsifier, and the reactive emulsifier is 0.1 to 3 parts by weight, preferably based on 100 parts by weight of the total monomers used in the preparation of the acrylic graft copolymer. may contain 0.5 to 2.5 parts by weight, more preferably 1 to 2.5 parts by weight, within this range, there is an excellent effect in impact strength, tensile strength, weather resistance and surface glossiness.
[51]
The reactive emulsifier may be, for example, an emulsifier containing at least one functional group selected from the group consisting of carbonate, sulfonate and sulfate, and in this case, it has excellent impact strength, tensile strength, weather resistance and surface glossiness. .
[52]
Specific examples of the reactive emulsifier include sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, Sodium dodecyl allyl sulfosuccinate, styrene and sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkylphenyl ether ammonium sulfate, alkenyl C16-18 It may be at least one selected from the group consisting of succinic acid di-potassium salt (alkenyl C16-18 succinic acid, di-potassium salt) and sodium methallyl sulfonate, and in this case, impact strength, tensile strength, and weather resistance and excellent surface glossiness.
[53]
The alkyl acrylate compound may be, for example, at least one selected from the group consisting of an alkyl acrylate having 2 to 8 carbon atoms, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acryl lactate or ethylhexyl acrylate.
[54]
The aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
[55]
The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, preferably acrylonitrile.
[56]
The acrylic graft copolymer may have, for example, a graft rate of 20 to 33%, preferably 21 to 32%, and more preferably 26 to 32%, and within this range, impact strength, tensile strength, weather resistance and There is an effect of reducing mold deposits while having excellent surface glossiness.
[57]
In the present description, the graft rate is obtained by coagulating, washing and drying the graft polymer latex to obtain a powder form, and after adding 30 ml of acetone to 1 g of the graft polymer dry powder, stirring for 24 hours, and centrifuging it to obtain a powder form that does not dissolve in acetone. After collecting the insoluble fraction, it is dried and then the weight is measured and calculated according to Equation 1 below.
[58]
[Equation 1]
[59]
Graft rate (%) = (weight of grafted monomer (g) / rubber weight (g)) *100
[60]
[61]
In addition, the method for preparing the acrylic graft copolymer of the present disclosure is, for example, based on 100 parts by weight of the total monomers used in the preparation of the acrylic graft copolymer, (A) an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound. a seed preparation step of preparing a seed by polymerizing 4 to 25% by weight of at least one compound selected from the group consisting of; (B) a core preparation step of preparing a core by adding 25 to 55% by weight of an alkyl acrylate compound in the presence of the prepared seed, and polymerization; and (C) 40 to 70% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinylcyanic compound and 0.05 to 2 parts by weight of a reactive UV stabilizer in the presence of the prepared core, and graft polymerization to prepare a shell Including; but, the shell is characterized in that the average particle diameter is 80 to 140 nm (greater than the core average particle diameter), and in this case, the impact strength, tensile strength, weather resistance and surface gloss are excellent while There is an effect that the mold deposit is reduced.
[62]
The reactive ultraviolet stabilizer may be, for example, a benzotriazole reactive ultraviolet stabilizer, a benzophenone reactive ultraviolet stabilizer, or a mixture thereof. In this case, the volatilization of the ultraviolet stabilizer during long-term injection molding is suppressed to reduce mold deposit and has excellent weather resistance and surface glossiness.
[63]
As a specific example, the benzotriazole-based reactive ultraviolet stabilizer may be a compound represented by the following Chemical Formula 1, and the benzophenone-based reactive ultraviolet stabilizer may be a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or these may be a mixture of, and in this case, the volatilization of the UV stabilizer is suppressed during long-term injection molding, thereby reducing mold deposits and having excellent weather resistance and surface glossiness.
[64]
[Formula 1]
[65]

[66]
[Formula 2]
[67]

[68]
[Formula 3]
[69]

[70]
The graft shell manufacturing step may include, for example, a reactive emulsifier, and 0.1 to 3 parts by weight, preferably 0.5 to 2.5 parts by weight, based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer; More preferably, it may contain 1 to 2.5 parts by weight, and within this range, there is an effect excellent in impact strength, tensile strength, weather resistance and surface glossiness.
[71]
The reactive emulsifier may be, for example, an emulsifier containing at least one functional group selected from the group consisting of carbonate, sulfonate and sulfate, and in this case, it has excellent impact strength, tensile strength, weather resistance and surface glossiness. .
[72]
The seed preparation step may include, for example, an emulsifier, preferably in an amount of 1.4 to 2.4 parts by weight, more preferably 1.7 to 2.2 parts by weight, based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer. Within this range, impact strength, tensile strength, weather resistance and surface gloss are excellent.
[73]
The seed preparation step may be prepared, for example, by including at least one selected from the group consisting of an electrolyte, a crosslinking agent, a grafting agent, an initiator and an emulsifier, and in this case, the effect of excellent impact strength, tensile strength, weather resistance and surface glossiness there is
[74]
Specifically, in the seed preparation step, 0.001 to 1 parts by weight of an electrolyte, 0.01 to 1 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of a grafting agent, and 0.01 to 3 parts by weight of an initiator based on 100 parts by weight of the total monomers used in the preparation of the acrylic graft copolymer. It can be prepared including parts by weight, and within this range, there is an excellent effect in impact strength, tensile strength, weather resistance and surface glossiness.
[75]
The core manufacturing step may include, for example, at least one selected from the group consisting of a crosslinking agent, an initiator, and an emulsifier.
[76]
Specifically, the core manufacturing step may include 0.01 to 1 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier based on 100 parts by weight of the total monomers used in the preparation of the acrylic graft copolymer.
[77]
The graft shell manufacturing step may include, for example, a crosslinking agent, an initiator, or a mixture thereof.
[78]
Specifically, the graft shell manufacturing step may include 0.01 to 3 parts by weight of a crosslinking agent and 0.01 to 3 parts by weight of an initiator based on 100 parts by weight of the total monomers used to prepare the acrylic graft copolymer.
[79]
The electrolyte included in the seed preparation step is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 4 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , Na 2 HPO 4 It may be at least one selected from the group consisting of KOH and NaOH.
[80]
The crosslinking agent included in the seed, core and shell manufacturing step is, for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, ethylene glycol diacrylate, Hexanediol ethoxylate diacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxy Late diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropanepropoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythro It may be at least one member from the group consisting of tolpropoxylate triacrylate and vinyl trimethoxyl.
[81]
The grafting agent included in the seed preparation step is, for example, one selected from the group consisting of allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallyl amine (TAA) and diallyl amine (DAA). may be more than
[82]
The initiator included in the seed and core preparation step is not particularly limited, but a radical initiator may be preferably used.
[83]
The radical initiator may include, for example, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide and t-butyl peroxy isobutylate; and azo compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyronitrile (butyric acid) methyl; may be at least one selected from the group consisting of have.
[84]
An activator may be used together with the initiator to promote the initiation reaction of the peroxide. Examples of the activator include sodium formaldehyde, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, dextrose, pyrrole. At least one selected from the group consisting of sodium phosphate and sodium sulfite may be used.
[85]
The emulsifier included in the seed and core preparation step is, for example, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, potassium dodecyl benzene sulfate, sodium dodecyl benzene sulfo. nate, sodium lauryl sulfate, sodium oleate, potassium dodecyl benzene sulfonate, potassium octadecyl sulfate, and potassium oleate may be at least one selected from the group consisting of.
[86]
The emulsifier included in the seed and core production step is not the same as the reactive emulsifier included in the graft shell production step.
[87]
The acrylic graft copolymer latex produced after the graft shell manufacturing step may be prepared as a powder, for example, after agglomeration, aging, dehydration, washing and drying.
[88]
The aggregation, for example, may be carried out with at least one selected from the group consisting of sulfuric acid, MgSO 4 , CaCl 2 and Al 2 (SO 4 ) 3 , preferably CaCl 2 .
[89]
The acrylic graft copolymer latex is specifically coagulated under atmospheric pressure at 65 to 80° C. using an aqueous calcium chloride solution, aged at 90 to 95° C., dehydrated and washed, and 20 to 40 minutes with hot air at 85 to 95° C. During drying, powder particles of the copolymer can be obtained.
[90]
In the present description, atmospheric pressure means atmospheric pressure, specifically, 1 atmosphere.
[91]
The acrylic graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in impact strength, tensile strength, weather resistance and surface glossiness.
[92]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[93]
The alkyl acrylate compound, aromatic vinyl compound, and vinyl cyan compound included in the method for preparing the acrylic graft copolymer may be those used in the acrylic graft copolymer.
[94]
In addition, the thermoplastic resin composition of the present disclosure may include (A) 20 to 50 parts by weight of the acrylic graft copolymer; (B) 1 to 15 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core; and (C) 45 to 70 parts by weight of the hard matrix resin, preferably (A) 35 to 45 parts by weight of the acrylic graft copolymer; (B) 5 to 10 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.25 to 0.45 μm as a core; And (C) 50 to 60 parts by weight of the hard matrix resin; in this case, there is an excellent effect in impact strength, tensile strength, weather resistance and surface glossiness.
[95]
The (B) graft copolymer may be, for example, a polymer polymerized including 40 to 60% by weight of acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound, within this range It has excellent effects in impact strength, tensile strength, weather resistance and surface gloss.
[96]
As a preferred example, the (B) graft copolymer may be a copolymer polymerized including 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, Within the range, it has excellent impact strength, tensile strength, weather resistance and surface gloss.
[97]
The (B) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in impact strength, tensile strength, weather resistance and surface glossiness.
[98]
The emulsion polymerization is not particularly limited if the emulsion graft polymerization method commonly carried out in the art to which the present invention belongs.
[99]
The acrylate rubber in the (B) graft copolymer preferably has an average particle diameter of 0.2 to 0.5 μm, more preferably 0.25 to 0.45 μm, and within this range, impact strength, tensile strength, weather resistance and surface gloss It has an excellent performance.
[100]
The rigid matrix resin may be, for example, a vinyl cyanide compound-aromatic vinyl compound copolymer, preferably a styrene-acrylonitrile copolymer (SAN resin), α-methyl styrene-acrylonitrile copolymer (heat-resistant SAN resin) Or it may be a mixture thereof, and more preferably an α-methyl styrene compound-acrylonitrile copolymer, and in this case, there is an effect of imparting appropriate processability and excellent heat resistance.
[101]
The α-methyl styrene-acrylonitrile copolymer may be a copolymer polymerized including 70 to 85% by weight of α-methylstyrene and 15 to 30% by weight of acrylonitrile, and has excellent heat resistance within this range. It works.
[102]
The α-methyl styrene-acrylonitrile copolymer may have, for example, a weight average molecular weight of 80,000 to 120,000 g/mol, preferably 90,000 to 110,000 g/mol, and has excellent processability and heat resistance within this range.
[103]
In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent ) can be measured as a relative value for a standard PS (standard polystyrene) sample.
[104]
The vinyl cyanide compound-aromatic vinyl compound copolymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, preferably bulk polymerization, and in this case, there is an excellent effect of heat resistance and fluidity, etc. .
[105]
The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.
[106]
The thermoplastic resin composition is, for example, an accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner) / S. Boro (outer) filter, irradiance 0.55 W / m 2 at 340 nm) using Thus, ΔE calculated by the following Equation 2 after 6000 hours of measurement by the SAE J1960 method may be 1.9 or less, preferably 1 to 1.8, more preferably 1.2 to 1.6, within this range, the physical property balance is excellent and the automobile It has the effect of having suitable weather resistance as an exterior material for construction.
[107]
[Equation 2]
[108]

[109]
The thermoplastic resin composition is, for example, continuously injected into a removable mold core under the conditions of 200 to 260° C. and 30 to 100 bar pressure by an injection machine (LS Corporation, clamping force: 220 tons), and then volatile gas is added to the mold core. The mold deposit calculated by Equation 3 by measuring the content of the deposited weight is 6.2 mg or less, preferably 3.5 to 6.2 mg, more preferably 4 to 5.5 mg, more Preferably, it may be 4.5 to 5.3 mg, and while the physical property balance is excellent within this range, the appearance quality is improved and the productivity is increased.
[110]
[Equation 3]
[111]
Mold Deposit (mg) = Weight of mold core after 100 shots - Weight of initial mold core
[112]
The thermoplastic resin composition is, for example, maintained at 230° C. for 10 minutes using a purge & trap-gas chromatography/mass spectrometry method, and then the amount of the measured volatile organic compound (TVOC) is 2700 ppm or less, preferably Preferably, it may be 1500 to 2700 ppm, more preferably 2000 to 2600 ppm, more preferably 2100 to 2500 ppm, and within this range, the mold deposit is reduced while the physical property balance is excellent, and there is an effect of excellent weather resistance.
[113]
In this description, Total Volatiile Organic Compounds (TVOC) are liquid or gaseous organic compounds that are easily evaporated into the atmosphere due to their low boiling point. It is very diverse from the organic gas emitted from the process, and there are liquid fuels with low boiling points, paraffins, olefins, and aromatic compounds.
[114]
The thermoplastic resin composition has an Izod impact strength of 10 kgf·cm/cm or more, preferably 10 to 15 kgf·cm/cm, more preferably, measured according to ASTM D256 using a specimen thickness of 1/4″, for example. may be 11 to 14.5 kgf·cm/cm, and within this range, the physical property balance has an excellent effect.
[115]
The thermoplastic resin composition has, for example, a tensile strength of 470 kg/cm 2 or more, preferably 470 to 550 kg/cm 2 , more preferably 480 to 520 kg/cm 2 , as measured according to ASTM D638 , even more preferably It may be 500 to 515 kg/cm 2 , and there is an excellent effect of the physical property balance within this range.
[116]
The thermoplastic resin composition has, for example, a fluidity of 7.5 g/10 min or more, preferably 7.5 to 10 g/10 min, more preferably 8 to 9.5 g/10 min, measured according to ASTM D1238 under a condition of 220° C. and 10 kg. In this range, the physical property balance is excellent and the fluidity is excellent, and there is an advantage that molding into various shapes is easy.
[117]
The thermoplastic resin composition may have, for example, a thermal deformation temperature of 89.5° C. or higher, preferably 89.5 to 95° C., more preferably 90 to 92° C., measured according to ASTM D648, and has excellent physical property balance within this range. It works.
[118]
The thermoplastic resin composition is optionally made of a lubricant, an antioxidant, a dye, a pigment, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame retardant, an anti-drip agent, an anti-friction agent and a wear-resisting agent, if necessary. 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and still more preferably 0.5 to 1 parts by weight of at least one selected from the group may be further included in this range There is an effect that the necessary physical properties are well implemented without reducing the original properties of the thermoplastic resin composition of the present invention.
[119]
The method for preparing the thermoplastic resin composition of the present invention may include (A) 20 to 50 parts by weight of the acrylic graft copolymer; (B) 1 to 15 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core; And (C) 45 to 70 parts by weight of the hard matrix resin; characterized in that it comprises a step of preparing pellets using an extrusion kneader under 200 to 250 ° C. conditions after mixing, in this case the conventional ASA-based resin There is an advantage of providing a thermoplastic resin composition having excellent weather resistance and surface glossiness and reducing mold deposits during long-term injection molding while maintaining the same or higher mechanical properties and processability.
[120]
The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
[121]
The step of preparing the pellets using the extrusion kneader may be preferably carried out under 200 to 250 ° C., more preferably under 210 to 230 ° C., wherein the temperature means the temperature set in the cylinder.
[122]
[123]
The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
[124]
The molded article of the present substrate is characterized in that it contains the thermoplastic resin composition of the present substrate, and in this case, the mechanical properties and processability are maintained at the same or higher than that of the conventional molded article, but the weather resistance and surface glossiness are excellent, and the mold deposit is reduced has the effect of being
[125]
The molded article may be, for example, an extrusion-molded article or an injection-molded article, preferably an injection-molded article, and more preferably a radiator grille or a side mirror as an automobile molded article.
[126]
In describing the thermoplastic resin composition of the present invention, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. do.
[127]
Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present disclosure, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[128]
[Example]
[129]
Materials used in the following Examples and Comparative Examples are as follows.
[130]
* Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core: SA927 (LG Chem, Core: 50 wt% of an acrylate polymer having an average particle diameter of 0.3 μm, Shell: styrene 38% by weight and acrylonitrile 12% by weight)
[131]
* Rigid matrix resin: 100UH (LG Chemical, 69% by weight of α-methyl styrene and 31% by weight of acrylonitrile)
[132]
* Benzotriazole reactive UV stabilizer: RUV-1 (2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate)
[133]
* Benzophenone reactive UV stabilizer: RUV-2 (2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate)
[134]
* Benzophenone reactive UV stabilizer: RUV-3 (2-(4-benzoyl-3-hydroxyphenoxy)amidoethyl methacrylate; 2-(4-benzoyl-3-hydroxyphenoxy)carbonyl]amino}ethyl 2-methylprop-2-enoate )
[135]
* UV Stabilizer: Tinuvin P (BASF)
[136]
* Lubricant: EBS10 (LG Household & Health Care)
[137]
* Antioxidant: Songnox1076 (Songwon)
[138]
Example 1
[139]
< Seed manufacturing step >
[140]
Batch administration of 15 parts by weight of butyl acrylate, 2.0 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.03 parts by weight of allyl methacrylate, 0.1 parts by weight of potassium hydroxide and 80 parts by weight of distilled water to a nitrogen-substituted reactor and, after raising the temperature to 70° C., 0.04 parts by weight of potassium persulfate was added to initiate the reaction. After that, polymerization was carried out for 1 hour.
[141]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 50 nm.
[142]
< Core manufacturing stage >
[143]
35 parts by weight of butyl acrylate, 0.3 parts by weight of sodium dodecyl sulfate, 0.25 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate, 35 parts by weight of distilled water and 0.03 parts by weight of potassium persulfate were mixed with the polymer seed The mixture was continuously added at 70° C. for 1 hour, and polymerization was further carried out for 0.5 hour after the addition was completed.
[144]
It was confirmed that the average particle diameter of the rubber polymer obtained after the completion of the reaction was 70 nm.
[145]
< Graft shell manufacturing step >
[146]
23 parts by weight of distilled water, 38 parts by weight of styrene, 12 parts by weight of acrylonitrile and 1.0 parts by weight of RUV-1 as a reactive UV stabilizer, 1.8 parts by weight of potassium rosinate, 0.1 parts by weight of TDDM and cumene hydroper in the presence of the polymer core A polymerization reaction was carried out while continuously introducing 0.05 parts by weight of an emulsion of oxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of textrose, and 0.002 parts by weight of ferrous sulfide at 75° C. for 2.5 hours. In addition, in order to increase the polymerization conversion rate, after the addition of the mixture was completed, the mixture was further reacted at 75° C. for 0.5 hours and cooled to 60° C. to terminate the polymerization reaction to prepare an acrylic graft copolymer latex.
[147]
The polymerization conversion rate of the prepared acrylic graft copolymer latex was 99.0%, and it was confirmed that the final average particle diameter was 90 nm.
[148]
< Preparation of acrylic graft copolymer powder >
[149]
After applying 0.8 parts by weight of an aqueous calcium chloride solution to the prepared acrylic graft copolymer latex, atmospheric pressure aggregation at 70° C., aging at 93° C., dehydration and washing, and drying at 90° C. for 30 minutes with hot air. Coalesced powder was prepared.
[150]

[151]
36 parts by weight of the acrylic graft copolymer powder, 8 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core, and 56 parts by weight of a hard matrix resin , 0.5 parts by weight of a lubricant and 0.5 parts by weight of an antioxidant were added and mixed. This was prepared in the form of pellets using a 36-pi extrusion kneader at a cylinder temperature of 220 ° C., and then injected into the pellets to prepare a physical property specimen.
[152]
Example 2
[153]
< Graft shell manufacturing step >
[154]
Example 1 was carried out in the same manner as in Example 1, except that the reactive UV stabilizer was changed to 1 part by weight of RUV-2.
[155]
The polymerization conversion rate of the prepared acrylic graft copolymer latex was 99.2%, and it was confirmed that the final average particle diameter was 88 nm.
[156]
Example 3
[157]
< Seed manufacturing step >
[158]
It was carried out in the same manner as in the seed preparation step of Example 1, except that 15 parts by weight of butyl acrylate and 1.5 parts by weight of sodium dodecyl sulfate were added to the nitrogen-substituted reactor in Example 1.
[159]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 75 nm.
[160]
< Core manufacturing stage >
[161]
It was carried out in the same manner as in the core manufacturing step of Example 1.
[162]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 105 nm.
[163]
< Graft shell manufacturing step >
[164]
It was carried out in the same manner as in the graft shell manufacturing step of Example 1.
[165]
The polymerization conversion rate of the acrylic graft copolymer obtained after completion of the reaction was 99.0%, and it was confirmed that the final average particle diameter was 135 nm.
[166]
Example 4
[167]
< Graft shell manufacturing step >
[168]
Example 3 was carried out in the same manner as in Example 3, except that the reactive UV stabilizer was changed to 1 part by weight of RUV-2.
[169]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.0%, and it was confirmed that the final average particle diameter was 130 nm.
[170]
Example 5
[171]
Example 1 was carried out in the same manner as in Example 1, except that 0.3 parts by weight of the reactive UV stabilizer RUV-1, which was added during the manufacture of the graft shell, was added.
[172]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.2%, and it was confirmed that the final average particle diameter was 92 nm.
[173]
Example 6
[174]
Example 1 was carried out in the same manner as in Example 1, except that 2.0 parts by weight of the reactive UV stabilizer RUV-1, which was added during the manufacture of the graft shell, was added.
[175]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.4%, and it was confirmed that the final average particle diameter was 91 nm.
[176]
Example 7
[177]
Example 1 was carried out in the same manner as in Example 1, except that 1.0 parts by weight of RUV-3 was added as a reactive UV stabilizer to be added during the manufacture of the graft shell.
[178]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.3%, and it was confirmed that the final average particle diameter was 91 nm.
[179]
Example 8
[180]
Example 3 was carried out in the same manner as in Example 1, except that 1.0 parts by weight of RUV-3 was added as a reactive UV stabilizer to be added during the manufacture of the graft shell.
[181]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.0%, and it was confirmed that the final average particle diameter was 136 nm.
[182]
Example 9
[183]
Example 5 was carried out in the same manner as in Example 1, except that 1.0 parts by weight of the reactive UV stabilizer RUV-3, which was added during the manufacture of the graft shell, was added.
[184]
The polymerization conversion rate of the acrylic graft copolymer latex obtained after the completion of the reaction was 99.4%, and it was confirmed that the final average particle diameter was 90 nm.
[185]
Comparative Example 1
[186]
< Graft shell manufacturing step >
[187]
Example 1 was carried out in the same manner as in Example 1, except that the reactive UV stabilizer was not added.
[188]
After completion of the reaction, the obtained acrylic graft copolymer polymerization conversion rate was 99.3%, and it was confirmed that the final average particle diameter was 86 nm.
[189]

[190]
38 parts by weight of the acrylic graft copolymer powder, 8 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core, 56 parts by weight of a hard matrix resin, 0.5 parts by weight of lubricant, 0.5 parts by weight of antioxidant and 0.4 parts by weight of Tinuvin P as UV stabilizer were added and mixed. This was prepared in the form of pellets using a 36-pi extrusion kneader at a cylinder temperature of 220 ° C., and then injected into the pellets to prepare a physical property specimen.
[191]
Comparative Example 2
[192]
< Seed manufacturing step >
[193]
It was carried out in the same manner as in the seed preparation step of Example 1, except that 15 parts by weight of butyl acrylate and 3.0 parts by weight of sodium dodecyl sulfate were added to the nitrogen-substituted reactor in Example 1.
[194]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 33 nm.
[195]
< Core manufacturing stage >
[196]
It was carried out in the same manner as in the core manufacturing step of Example 1.
[197]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 53 nm.
[198]
Comparative Example 3
[199]
< Seed manufacturing step >
[200]
It was carried out in the same manner as in the seed preparation step of Example 1, except that 15 parts by weight of butyl acrylate and 1.2 parts by weight of sodium dodecyl sulfate were added to the nitrogen-substituted reactor in Example 1.
[201]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 90 nm.
[202]
< Core manufacturing stage >
[203]
It was carried out in the same manner as in the core manufacturing step of Example 1.
[204]
It was confirmed that the average particle diameter of the rubber polymer obtained after completion of the reaction was 125 nm.
[205]
[206]
< Graft shell manufacturing step >
[207]
It was carried out in the same manner as in the shell polymerization step of Example 1.
[208]
After completion of the reaction, the polymerization conversion rate of the obtained acrylic graft copolymer was 98.5%, and it was confirmed that the final average particle diameter was 155 nm.
[209]
Comparative Example 4
[210]
< Graft shell manufacturing step >
[211]
In Example 1, the same procedure as in Example 1 was carried out, except that 2.5 parts by weight of RUV-1 was added as a reactive UV stabilizer when preparing the graft shell.
[212]
Reference Example 1
[213]
It was carried out in the same manner as in Example 1, except that 2.0 parts by weight of potassium rosinate was used instead of the reactive emulsifier in the .
[214]
Reference Example 2
[215]
It was carried out in the same manner as in Example 1, except that the reactive emulsifier was changed to 4 parts by weight in .
[216]
[Test Example]
[217]
The properties of the specimens prepared in Examples 1 to 9, Comparative Examples 1 to 4, and Reference Examples 1 to 2 were measured in the following manner, and the results are shown in Tables 1 to 3 below.
[218]
How to measure
[219]
* Graft rate (%): The graft polymer latex is coagulated, washed and dried to obtain a powder form, and 30 ml of acetone is added to 1 g of the graft polymer dry powder, stirred for 24 hours, and then centrifuged to dissolve in acetone. After the insoluble fraction was collected and dried, the weight was measured and calculated according to Equation 1 below.
[220]
[Equation 1]
[221]
Graft rate (%) = (weight of grafted monomer (g) / rubber weight (g)) *100
[222]
* Izod impact strength (kgf·cm/cm): It was measured in accordance with ASTM D256 using a specimen thickness of 1/4”.
[223]
* Polymerization conversion: After drying 1.5 g of the prepared latex in a hot air dryer at 150 ° C. for 15 minutes, the weight is measured to obtain the total solid content (TSC) by the following Equation 4, and with this, the following Equation 5 was calculated using
[224]
Equation 4 was based on the total weight of the added monomer being 100 parts by weight.
[225]
[Equation 4]
[226]

[227]
[Equation 5]
[228]
Polymerization conversion (%) = [total solid content (TSC) X (total weight of the added monomer, ion-exchanged water, and auxiliary materials) / 100] - (weight of added additives other than monomer and ion-exchanged water)
[229]
In Equation 4, the auxiliary material refers to an initiator, an emulsifier, an electrolyte, and a molecular weight regulator.
[230]
The input monomer refers to an acrylate, an aromatic vinyl compound, and a vinyl cyan compound.
[231]
* Average particle diameter (nm): measured using Nicomp 380 equipment (product name, manufacturer: PSS).
[232]
* Weight average molecular weight (g/mol): Standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40 ° C through gel chromatography (GPC) filled with porous silica as a column packing material. Relative values ​​were measured.
[233]
* Melt flow index (MI): The prepared pellets were measured according to ASTM D1238 under conditions of 220° C. and 10 kg. Here, the unit of the flow index is g/10min.
[234]
* Tensile strength (kg/cm 2 ): Measured according to ASTM D638.
[235]
* Thermal deformation temperature (℃, measured according to ASTM D648.
[236]
* Weather resistance (ΔE): using accelerated weather resistance test device (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiance 0.55W/m 2 at 340nm) After 6000 hours of measurement by the SAE J1960 method, it was evaluated as ΔE calculated by Equation 2 below. The closer the ΔE value is to 0, the better the weather resistance is.
[237]
[Equation 2]
[238]

[239]
* TVOC analysis (JTD-GC/MS-02): Purge & Trap-gas chromatography/mass spectrometry was used to perform purge and trap at 230°C for 10 minutes, followed by GC-MS was used to measure the total volatilization amount. The measured volatilization amount was quantified using toluene as a standard reagent.
[240]
* Mold deposit (mg): A removable mold core is applied to the injection machine (LS company, clamping force: 220 tons), the injection machine temperature is 260℃-260℃-255℃-245℃, and the injection pressure is 70 bar/ After continuous injection of 100 shots under the same injection condition of 100 bar of injection back pressure, the weight of the mold core on which the volatilized material was deposited was measured to calculate the mold deposit by Equation 3 below.
[241]
[Equation 3]
[242]
Mold Deposit (after 100 shots, mg) = mold core weight after 100 shots - initial mold core weight
[243]
[244]
[Table 1]
division Example 1 Example 2 Example 3 Example 4 Example 5
Acrylic-based graft copolymer polymerization conversion rate 99.0 99.2 99.0 99.0 99.2
final entrance 90 88 135 130 92
weight average molecular weight 120,000 121,000 120,000 120,000 110,000
Graft rate 26 26 31 30 26.5
Thermoplastic resin composition impact strength 12.0 12.8 14.2 14.0 11.0
liquidity 8.5 8.4 9.0 9.0 9.0
tensile strength 510 507 500 505 505
heat deflection temperature 90.5 91.0 90.0 90.0 90.0
△E 1.4 1.6 1.4 1.6 1.3
TVOC 2600 2500 2400 2200 2500
mold deposit 5.5 5.4 5.2 5.3 5.1
[245]
[Table 2]
division Example 6 Example 7 Example 8 Example 9
Acrylic-based graft copolymer polymerization conversion rate 99.4 99.3 99.0 99.4
final entrance 91 91 136 90
weight average molecular weight 170,000 160,000 150,000 140,000
Graft rate 28.0 21.0 22.0 25.0
Thermoplastic resin composition impact strength 10.5 12.5 14.0 13.5
liquidity 7.5 8.0 8.3 8.5
tensile strength 480 520 515 510
heat deflection temperature 91.2 91.0 90.5 91.0
△E 1.6 1.5 1.7 1.8
TVOC 2550 2600 2500 2550
mold deposit 6.0 5.6 5.2 5.2
[246]
[Table 3]
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Reference Example 1 Reference Example 2
Acrylic graft copolymer polymerization conversion rate 99.3 99.5 99.5 99.5 99.0 99.5
final entrance 86 69 155 91 90 91
Molecular Weight 130,000 135,000 115,000 200,000 115,000 140,000
Graft rate 26 20 35 30.3 26.5.5 25.5
Thermoplastic resin composition impact strength 10.0 7.0 15 8.0 11.5 12.5
liquidity 7.0 6.0 10.0 6.0 9.0 7.0
tensile strength 520 525 480 450 505 520
heat deflection temperature 91.0 91.5 89.5 90.5 90.1 91.0
△E 2.0 1.4 3.5 2.5 2.0 2.5
TVOC 4100 3100 2500 3000 3200 4000
mold deposit 15.5 6.5 5.5 7.0 6.0 9.0
[247]
As shown in Tables 1 to 3, in Examples 1 to 9 prepared according to the present invention, Comparative Example 1 without a reactive UV stabilizer in the shell of the acrylic graft copolymer, the average particle diameter of the graft shell was Compared to Comparative Examples 2 and 3, which is out of 80 to 140 nm, and Comparative Example 4 containing an excessive amount of reactive ultraviolet stabilizer in the shell of the acrylic graft copolymer, the impact strength, fluidity, tensile strength and thermal deformation temperature are excellent, but the weather resistance is excellent and TVOC generation was suppressed, confirming the effect of reducing mold deposits.
[248]
In particular, it was confirmed that Comparative Example 1, in which a UV stabilizer was added as an additive during the production of the thermoplastic resin composition, lowered impact strength and fluidity, deteriorated weather resistance, and rapidly increased TVOC generation and mold deposits.
[249]
In addition, in Reference Example 1 containing potassium rosinate instead of a reactive emulsifier in the graft shell manufacturing step, the weather resistance was lowered compared to Examples 1 to 6, the amount of TVOC generation was greatly increased, and the mold deposit was at a similar level.
[250]
In addition, in Reference Example 2 including an excessive amount of the reactive emulsifier in the graft shell manufacturing step, the weather resistance and mold deposit were poor compared to Examples 1 to 9, and the amount of TVOC generation was greatly increased.
Claims
[Claim 1]
Based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer, (A) 4 to 25% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound. polymerized seeds; (B) a rubber core wrapped around the seed and polymerized including 25 to 55 wt% of an alkyl acrylate compound; and (C) a graft shell wrapped around the rubber core and polymerized including 40 to 70% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound; The graft shell contains 0.05 to 2 parts by weight of a reactive UV stabilizer based on 100 parts by weight of the acrylic graft copolymer, and the graft shell has an average particle diameter of 80 to 140 nm (greater than the core average particle diameter), characterized in that acrylic graft copolymer.
[Claim 2]
The acrylic graft copolymer according to claim 1, wherein the reactive ultraviolet stabilizer is a benzotriazole reactive ultraviolet stabilizer, a benzophenone reactive ultraviolet stabilizer, or a mixture thereof.
[Claim 3]
The method according to claim 2, wherein the benzotriazole-based reactive ultraviolet stabilizer is a compound represented by the following formula (1), and the benzophenone-based reactive ultraviolet stabilizer is a compound represented by the following formula (2), a compound represented by the following formula (3), or An acrylic graft copolymer, characterized in that it is a mixture thereof. [Formula 1] [Formula 2] [Formula 3]
[Claim 4]
The acrylic graft copolymer according to claim 1, wherein the graft shell is a polymer polymerized including 0.1 to 3 parts by weight of a reactive emulsifier based on 100 parts by weight of the acrylic graft copolymer.
[Claim 5]
The acrylic graft copolymer according to claim 4, wherein the reactive emulsifier is an emulsifier containing at least one functional group selected from the group consisting of carbonate, sulfonate and sulfate.
[Claim 6]
The acrylic graft copolymer according to claim 1, wherein the seed has an average particle diameter of 42 to 82 nm.
[Claim 7]
The acrylic graft copolymer according to claim 1, wherein the core including the seed has an average particle diameter of 62 to 110 nm (greater than the average particle diameter of the seed).
[Claim 8]
Based on 100 parts by weight of the total monomer used in the preparation of the acrylic graft copolymer, (A) 4 to 25% by weight of at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate compound, a seed preparation step of preparing a seed; (B) a core preparation step of preparing a core by adding 25 to 55% by weight of an alkyl acrylate compound in the presence of the prepared seed, and polymerization; and (C) 40 to 70 wt% of at least one compound selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and 0.05 to 2 parts by weight of a reactive UV stabilizer in the presence of the prepared core, and graft polymerization to prepare a shell A method for producing an acrylic graft copolymer, comprising: a graft shell manufacturing step; wherein the graft shell has an average particle diameter of 80 to 140 nm (greater than the core average particle diameter).
[Claim 9]
The method according to claim 8, wherein the reactive ultraviolet stabilizer is a benzotriazole reactive ultraviolet stabilizer, a benzophenone reactive ultraviolet stabilizer, or a mixture thereof.
[Claim 10]
The method of claim 8, wherein the graft shell manufacturing step comprises 0.1 to 3 parts by weight of a reactive emulsifier.
[Claim 11]
(A) 20 to 50 parts by weight of the acrylic graft copolymer of any one of claims 1 to 7; (B) 1 to 15 parts by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.2 to 0.6 μm as a core; And (C) 45 to 70 parts by weight of the hard matrix resin; Thermoplastic resin composition comprising a.
[Claim 12]
12. The method of claim 11, wherein the thermoplastic resin composition is an accelerated weather resistance test device (weather-o-meter, ATLAS Corporation Ci4000, xenon arc lamp, Quartz (inner) / S. Boro (outer) filter, irradiance 0.55 W / m 2 at 340 nm) using the SAE J1960 method, and after 6000 hours of measurement, ΔE calculated by the following Equation 2 is 1.9 or less. [Equation 2]
[Claim 13]
The method of claim 11, wherein the thermoplastic resin composition is an injection molding machine (LS Corporation, clamping force: 220 tons) on a removable mold core under injection molding conditions 200 to 260 ℃, pressure 30 to 100 bar (shot) 100 shots (shot) A thermoplastic resin composition, characterized in that the mold deposit calculated by Equation 3 below by measuring the content of the weight of the gas deposited on the mold core after continuous injection is 6.2 mg or less. [Equation 3] Mold deposit (mg) = Weight of mold core after 100 shots - Weight of initial mold core
[Claim 14]
The method according to claim 11, wherein the thermoplastic resin composition is maintained at 230°C for 10 minutes using Purge & Trap-gas chromatography/mass spectrometry, and then the amount of the measured volatile organic compound (TVOC) is 2700 The thermoplastic resin composition, characterized in that ppm or less.