Thermoplastic composition, method for producing the same, and molded article

Abstract

To provide a thermoplastic composition and a method for producing the same, and a molded article.SOLUTION: There is provided a thermoplastic composition comprising 100 pts.wt. of acrylic rubber modified resin composition (A), 0.05 pts.wt. to 10 pts.wt. of paraffin wax (B), and 0.1 pts.wt. to 2 pts.wt. of hindered amine light stabilizing composition with a dipiperidine structure (C1). The acrylic rubber modified resin composition (A) includes styrene-acrylonitrile copolymers and acrylic rubber grafted copolymers. This thermoplastic composition offers a combination of properties such as low odor, chemical resistance, mobility, and low gloss.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention provides a thermoplastic composition, and particularly provides a thermoplastic composition capable of improving the odor of a thermoplastic resin and having chemical resistance, fluidity, and low glossiness, and a molded article thereof.

Background Art

[0002] ASA (Acrylonitrile Styrene Acrylate) resin is a thermoplastic styrene resin obtained by copolymerizing an acrylic rubber, a styrene monomer, and acrylonitrile. It is used in various fields (such as automotive interior parts and building materials, etc.) and has been widely used in recent years.

[0003] When ASA resin is used in the manufacture of building materials (such as window frames), since the window frames are used in both indoor and outdoor areas, in the indoor area, in order to avoid harming the human body, it is necessary to have a low odor effect for long-term contact with the human body. On the other hand, in the outdoor area, it must have chemical resistance to withstand the erosion by chemical substances in the external environment. In addition, since window frame parts have a large volume, extremely high processability and resin fluidity are also desired. In addition, in order to avoid the influence on the line of sight due to high-light reflection, the window frame needs to have a low gloss effect. Therefore, in order to meet the requirements for low odor of building materials and automotive interior parts, there is a market need for ASA resin compositions and molded articles thereof having characteristics such as chemical resistance, fluidity, and low gloss.

[0004] However, in order for known ASA resins to reduce odor, reduce gloss, or increase fluidity, it is necessary to additionally add various functional additives such as odor suppressants, matting agents, or lubricants, but the effect is often not good, and the requirements of low odor, high chemical resistance, high fluidity, and low gloss cannot be simultaneously met.

[0005] Therefore, in order to solve the defects of known ASA resin materials, a thermoplastic composition, its manufacturing method, and a molded article are urgently needed.

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of this, according to one aspect of the present invention, it is to provide a thermoplastic composition having properties such as low odor, chemical resistance, fluidity, and low gloss, a method for producing the same, and a molded article formed of the thermoplastic composition.

Means for Solving the Problems

[0007] The thermoplastic composition of the present invention comprises 100 parts by weight of an acrylic rubber-modified resin composition (A) containing a styrene-acrylonitrile copolymer and an acrylic rubber graft copolymer, 0.05 parts by weight to 10 parts by weight of paraffin wax (B), and 0.1 parts by weight to 2 parts by weight of a hindered amine light stabilizer composition (C1) having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol.

[0008] According to some examples of the present invention, the paraffin wax (B) contains a saturated hydrocarbon compound having 17 to 50 carbon atoms and has a melting point exceeding 40°C and less than 75°C.

[0009] According to some examples of the present invention, the weight ratio of the paraffin wax (B) to the hindered amine light stabilizer composition (C1) having a dipiperidine structure is 0.025 to 100.

[0010] According to some examples of the present invention, the hindered amine light stabilizer composition (C1) having a dipiperidine structure has a structure represented by the following formula (I).

Chemical formula

[0011] According to some embodiments of the present invention, the thermoplastic composition selectively contains 0.1 to 1.6 parts by weight of a hindered amine light stabilizer composition (C2) having a molecular weight of 1000 g / mol to 5000 g / mol.

[0012] According to some embodiments of the present invention, the hindered amine light stabilizer composition (C2) contains a structure represented by the following formula (II) and / or formula (III). In formula (II), n represents an integer of 2 to 20.

Chemical formula

[0013] According to some embodiments of the present invention, the content of the hindered amine light stabilizer composition (C2) having the structure represented by formula (III) is 0.1 to 1.0 parts by weight.

[0014] According to some embodiments of the present invention, the weight ratio of the hindered amine light stabilizer composition (C1) having a dipiperidine structure to the hindered amine light stabilizer composition (C2) is 0.06 to 20.

[0015] According to some embodiments of the present invention, the thermoplastic composition selectively contains 0.1 to 1.5 parts by weight of an ultraviolet light stabilizer (D).

[0016] According to some embodiments of the present invention, the ultraviolet light stabilizer (D) contains a benzotriazole-based reactive ultraviolet light stabilizer.

[0017] According to some embodiments of the present invention, the ultraviolet light stabilizer (D) is selected from 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole or 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol].

[0018] According to some embodiments of the present invention, the weight ratio of the hindered amine light-stable composition (C1) having a dipiperidine structure to the ultraviolet light stabilizer (D) is 0.06-20.

[0019] According to some embodiments of the present invention, the thermoplastic composition optionally comprises 0.1 to 10 parts by weight of a colorant, dye and / or pigment (E) and / or 0.05 to 5 parts by weight of other additives (F).

[0020] According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic composition.

[0021] Another aspect of the present invention provides a method for producing a thermoplastic composition, comprising the steps of: providing a composition containing 100 parts by weight of an acrylic rubber-modified resin composition (A) containing a styrene-acrylonitrile copolymer and an acrylic rubber graft copolymer; 0.05 to 10 parts by weight of a paraffin wax (B); and 0.1 to 2 parts by weight of a hindered amine-based light-stabilizing composition (C1) having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol; and kneading the composition to obtain a thermoplastic composition. [Effects of the Invention]

[0022] In summary, the present invention proposes a thermoplastic composition, a method for producing the same, and a molded article. This thermoplastic composition contains 100 parts by weight of an acrylic rubber-modified resin composition (A), 0.05 to 10 parts by weight of a paraffin wax (B), and 0.1 to 2 parts by weight of a hindered amine-based light-stabilizing composition (C1) having a dipiperidine structure. The acrylic rubber-modified resin composition (A) contains a styrene-acrylonitrile copolymer and an acrylic rubber graft copolymer, and the molecular weight of the hindered amine-based light-stabilizing composition (C1) having a dipiperidine structure is 200 g / mol to 600 g / mol. The thermoplastic composition of the present invention, with the above-mentioned content ratios, combines properties such as low odor, chemical resistance, fluidity, and low gloss. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, the production and use of the embodiments of the present invention will be examined in detail. However, it is understood that the embodiments provide many applicable inventive concepts that can be implemented in various specific contents. The specific embodiments to be examined are for illustrative purposes only and are not used to limit the scope of the present invention.

[0024] In order to produce a resin composition having characteristics such as low odor, chemical resistance, fluidity, and low gloss, the present invention proposes a thermoplastic composition capable of achieving the above advantages. Hereinafter, embodiments will be given as examples that can surely implement the present invention.

[0025] The thermoplastic composition according to some embodiments of the present invention includes 100 parts by weight of an acrylic rubber-modified resin composition (A), 0.05 parts by weight to 10 parts by weight of paraffin wax (B), and 0.1 parts by weight to 2 parts by weight of a hindered amine-based light stabilizer composition (C1) having a dipiperidine structure. In some embodiments, the thermoplastic composition of the present invention selectively includes 0.1 parts by weight to 1.6 parts by weight of a hindered amine-based light stabilizer composition (C2), 0.1 parts by weight to 1.5 parts by weight of an ultraviolet light stabilizer (D), a colorant, a dye and / or a pigment (E), other additives (F), or any combination of the above components. Hereinafter, the above components will be described in detail.

[0026] Acrylic rubber-modified resin composition (A)

[0027] The acrylic rubber-modified resin composition (A) of the present invention includes a continuous phase composed of a styrene-acrylonitrile copolymer and a dispersed phase composed of an acrylic rubber graft copolymer. Specifically, the acrylic rubber-modified resin composition (A) includes 55 weight percent (wt%) to 80 wt% of a styrene-acrylonitrile copolymer and 20 wt% to 45 wt% of an acrylic rubber graft copolymer. From another perspective, the acrylic rubber-modified resin composition (A) includes 15 wt% to 25 wt% of acrylonitrile-based monomer units, 55 wt% to 65 wt% of styrene-based monomer units, and 15 wt% to 25 wt% of acrylate-based monomer units.

[0028] The styrene-acrylonitrile copolymer may be produced by polymerizing 60 wt% to 74 wt% of a styrene monomer and 26 wt% to 40 wt% of an acrylonitrile monomer. The polymerization may be carried out by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or any other suitable method, with bulk polymerization or solution polymerization being preferred. Specific examples of the styrene monomer include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene, or bromostyrene, with styrene or α-methylstyrene being preferred. Specific examples of the acrylonitrile monomer include, but are not limited to, acrylonitrile or α-methacrylonitrile, with acrylonitrile being preferred.

[0029] The acrylic acid ester-based monomer unit, styrene-based monomer unit, and acrylonitrile-based monomer unit respectively represent repeating structural units in an acrylic rubber graft copolymer or a styrene-acrylonitrile-based copolymer after polymerizing an acrylic acid ester-based monomer, a styrene-based monomer, and an acrylonitrile-based monomer, and then carrying out a graft reaction.

[0030] The method for producing a styrene-acrylonitrile copolymer preferably includes carrying out a polymerization reaction using a reactor capable of continuous bulk or solution polymerization. The reactor may include, but is not limited to, a cylindrical flow reactor, a complete mixing reactor (CSTR), or a tubular reactor containing a static mixing element. Among these, a complete mixing reactor is preferred. The number of reactors used may be one, or two or more may be used in combination.

[0031] In some embodiments, the method for producing the styrene-acrylonitrile copolymer is carried out by solution polymerization. The solvent used in the solution polymerization may be, for example, toluene, ethylbenzene, or methyl ethyl ketone. Preferably, the solution polymerization is carried out at a temperature of 70°C to 140°C, more preferably 90°C to 130°C.

[0032] In some embodiments, when producing a styrene-acrylonitrile copolymer, a thermal polymerization method may be used, or a polymerization initiator may be added to the reaction. The polymerization initiator may be, for example, a hydroperoxides-based compound [such as tert-butyl hydroperoxide, or isopropylcumyl hydroperoxide, etc.], a peroxyketal-based compound [such as 1,1-Di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, or 2,2-di-(4,4-di(tert-butylperoxy)cyclohexyl)propane, etc.], a diacyl peroxides-based compound [such as dilauroyl peroxide, didecanoyl peroxide, or dibenzoyl peroxide (BPO), etc.], a peroxyesters-based compound [such as tert-butylperoxy pivalate, or 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxy)hexane, etc.], peroxyketals [such as 4,4-di-tert-butylperoxy-valeric acid n-butyl ester (4,The polymerization initiator may be, but is not limited to, a peroxycarbonate compound (e.g., tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, etc.), azo compounds having nitro and cyclohexanes, etc. The amount of the polymerization initiator used may be 0.01 to 2.0 parts by weight, preferably 0.01 to 1.0 parts by weight, based on 100 parts by weight of the total amount of the styrene-based monomer and the acrylonitrile-based monomer.

[0033] In some embodiments, the molecular weight of the styrene-acrylonitrile copolymer produced is 60,000 to 400,000.

[0034] The acrylic rubber graft copolymer is prepared by graft polymerization of 100 parts by weight of an acrylic ester rubber latex with 50 to 100 parts by weight of a monomer mixture, the monomer mixture including 65 to 75 wt% of a styrene-based monomer and 25 to 35 wt% of an acrylonitrile-based monomer. The monomer mixture may be added all at once, in batches, continuously, or by gradually adding various monomers in the monomer mixture. The acrylic rubber graft copolymer may also include two or more acrylic rubber graft copolymers each having a different weight-average particle size. In some embodiments, the weight-average particle sizes of the acrylic rubber graft copolymers exhibit a double-peak distribution pattern of 0.12 μm and 0.45 μm.

[0035] The method for producing the acrylate ester-based rubber latex preferably includes polymerizing the main component, an acrylate ester-based monomer, by direct emulsion polymerization. The acrylate ester-based monomer may be, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, or other suitable acrylate ester-based monomer, with n-butyl acrylate being preferred. The acrylate ester-based monomers may be used alone or in combination.

[0036] The method for preparing the acrylate-based rubber latex may optionally include adding a crosslinking agent during the polymerization reaction. Examples of the crosslinking agent include, but are not limited to, ethylene diacrylate, butylene diacrylate, divinylbenzene, butenediol dimethacrylate, dimethacrylate, trimethylolpropane tri(meth)acrylate, allyl methacrylate (AMA), diallyl methacrylate, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl methacrylate, triallyl cyanurate, triallyl isocyanurate, acrylate of tricyclodecenyl alcohol, diacrylate of polyalkylene glycol, or other suitable crosslinking agents. The above crosslinking agents may be used alone or in combination. In some embodiments, the amount of the crosslinking agent is preferably 0.1 wt% to 10 wt% of the total amount of the acrylate-based monomer and crosslinking agent, which is 100 wt%.

[0037] In some embodiments, the average particle size of the acrylate latex may be controlled by adjusting the polymerization reaction conditions, such as the polymerization temperature, the amount and type of initiator, emulsifier, or activator used, and the method of monomer addition.

[0038] The initiator may be any of a variety of well-known free radical polymerization initiators, and the initiator may be added in one go, continuous, or incremental manner.Specifically, specific examples of initiators include benzoyl peroxide, layroyl peroxide, oleyl peroxide, toluyl peroxide, dicumyl peroxide, tert-butyl peroxide, di-tert-butyl diperphthalate, tert-butyl peracetate, tert-butyl perbenzoate, isoperopyl peroxy dicarbonate, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, and tert-butyl hydroperoxide. The initiators include, but are not limited to, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3-tert-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, cyclopentane hydroperoxide, diisopropylbenzene hydroperoxide, p-tert-butylcumene hydroperoxide, pinane hydroperoxide, 2,5-dimethyl-hexane-2,5-dihydroperoxide, or mixtures of the above initiators.

[0039] In some embodiments, the initiator may be used in an amount of 0.01 parts by weight to 5 parts by weight, based on 100 parts by weight of the total monomer mixture used.

[0040] Specific examples of the emulsifier may include, but are not limited to, various carboxylates such as sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and rosin acid soap, various sulfonate compounds such as sodium dihexyl sulfosuccinate, alkyl sulfate or sodium alkylbenzene sulfonate, or anionic emulsifiers such as polyethylene oxide nonylphenyl ether sodium sulfate, etc. In some embodiments, the amount of the emulsifier used may be 1 part by weight to 10 parts by weight, assuming that the total amount of the monomer mixture used is 100 parts by weight.

[0041] Specific examples of the activator may include, but are not limited to, ferrous sulfate, sodium formaldehyde sulfoxylate, disodium ethylenediaminetetraacetate, tetrasodium pyrophosphate, etc. In some embodiments, the amount of activator used is 1 part by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture used.

[0042] In some embodiments, the graft molecular weight of the acrylic rubber graft copolymer may be adjusted by changing the polymerization conditions such as the polymerization temperature, initiator, emulsifier, activator, or the type and amount of chain transfer agent, and the monomer addition method. The reaction temperature of the graft polymerization is 90 °C or lower, preferably 25 °C to 40 °C. The types and amounts of the initiator, emulsifier, and activator are as described above. Specific examples of the chain transfer agent may include n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, or tert-dodecyl mercaptan. In one embodiment, when the total amount of the monomer mixture used is 100 parts by weight, the amount of the chain transfer agent used may be 0.01 part by weight to 0.1 part by weight.

[0043] In addition, when the graft reaction is carried out to form an acrylic rubber graft copolymer, styrene polymerizes with acrylonitrile at the same time to produce a second styrene-acrylonitrile copolymer. In one embodiment, the molecular weight of the second styrene-acrylonitrile copolymer is 10,000 to 100,000.

[0044] Also, specific examples of the styrene-based monomer and acrylonitrile-based monomer contained in the monomer mixture are the same as the specific examples of the styrene-based monomer and acrylonitrile-based monomer for producing the styrene-acrylonitrile copolymer, and thus will not be described further here.

[0045] The method for producing the acrylic rubber-modified resin composition (A) is not particularly limited, and a general mixing method may be used. For example, the styrene-acrylonitrile copolymer and the acrylic rubber graft copolymer may be uniformly mixed. In some embodiments, the general mixing method may include dry mixing with a commonly used Henschel mixer and then melt mixing with a mixer such as an extrusion mixer, kneader, or Banbury mixer.

[0046] Paraffin wax (B)

[0047] The thermoplastic composition of the present invention may contain paraffin wax (B). Taking the usage amount of the acrylic rubber-modified resin composition (A) as 100 parts by weight, the usage amount of paraffin wax (B) is 0.05 to 10 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 6 parts by weight. When the usage amount of paraffin wax (B) is less than 0.05 part by weight, the manufactured molded product cannot enhance chemical resistance, fluidity, and gloss, and odor is likely to occur on the surface of the molded product of the thermoplastic composition. When the usage amount of paraffin wax (B) is more than 10 parts by weight, the manufactured molded product has low processability and the mold is likely to get dirty.

[0048] The paraffin wax (B) of the present invention may be a purified saturated hydrocarbon compound obtained by removing impurities such as aromatic hydrocarbons and sulfur compounds contained in a petroleum lubricating oil fraction using anhydrous sulfuric acid or fuming sulfuric acid.

[0049] The molecular weight of paraffin wax (B) may be defined by kinematic viscosity. The kinematic viscosity of the paraffin wax (B) of the present invention may be measured, for example, by the method specified in JIS K2283. The kinematic viscosity of paraffin wax (B) at 40°C is 0.1 mm 2 / second to 78 mm 2 / second, preferably 1 mm 2 / second to 40 mm 2It may be per second. The weight average molecular weight of the paraffin wax (B) may be 150 g / mol to 500 g / mol, preferably 180 g / mol to 450 g / mol, more preferably 200 g / mol to 350 g / mol. The weight average molecular weight may be obtained, for example, by determining the weight average value of each molecular weight component in the paraffin wax (B) by gas chromatography. When using a paraffin wax having a higher viscosity or a higher molecular weight compared to using a paraffin wax (B) having the above viscosity range or molecular weight range, the obtained thermoplastic composition can be effectively plasticized, contributing to the improvement of the processability and chemical resistance of the molded article produced from the thermoplastic composition. Preferably, the viscosity is 0.1 mm 2 / second or greater or a paraffin wax (B) having a weight average molecular weight greater than 150 g / mol, defects such as mold fouling during molding of the thermoplastic composition and leakage on the surface of the molded article can be effectively suppressed.

[0050] The paraffin wax (B) of the present invention is not particularly limited as long as its melting point is less than 75°C. In some specific examples, the paraffin wax (B) may include microcrystalline wax, petroleum waxes such as petrolatum, synthetic waxes by the Fischer-Tropsch method, or mineral waxes such as montan wax. In order to enhance the processability and chemical resistance of the molded article of the thermoplastic composition, the paraffin wax (B) is preferably a petroleum wax. Preferably, the oil content of the paraffin wax (B) of the present invention is 0.5% to 2.0%, more preferably 0.5% to 1.5%, and most optimally 0.5% to 1.0%.

[0051] The paraffin wax (B) of the present invention is not particularly limited, but may usually be obtained by separating and purifying from the distillate obtained by vacuum distillation of petroleum. The paraffin wax (B) may be used alone or in combination of multiple types.

[0052] Preferably, the paraffin wax (B) of the present invention may contain a chain saturated hydrocarbon compound having 17 to 50 carbon atoms. The chain saturated hydrocarbon compound preferably has 17 or more carbon atoms, and the number of carbon atoms in the chain saturated hydrocarbon compound is preferably 50 or less, more preferably 45 or less. The saturated chain hydrocarbon compound may be linear or branched. Preferably, the paraffin wax (B) is a branched saturated hydrocarbon compound.

[0053] The paraffin wax (B) may have a melting point exceeding 40°C, preferably 45°C or higher, more preferably 48°C or higher, or may have a melting point lower than 75°C, preferably 70°C or lower, more preferably 65°C or lower. When the melting point of the paraffin wax (B) exceeds 40°C, it is possible to avoid stickiness on the surface of molded articles of the thermoplastic composition. When the melting point of the paraffin wax (B) is lower than 75°C, it is possible to improve the molding processability of molded articles of the high thermoplastic composition, and it is possible to suppress cracking defects over time in molded articles of the thermoplastic composition. The melting point of the paraffin wax (B) may be measured based on the standard method of JIS K2235 5.3 (1991).

[0054] Hindered amine-based light-stable composition having a dipiperidine structure (C1)

[0055] The hindered amine light stabilizer composition (C1) of the present invention comprises at least one compound having a dipiperidine structure, wherein the dipiperidine structure has at least one alkyl at each of the 2- and 6-positions, and does not comprise any saturated or unsaturated ester having 12 to 21 carbon atoms at one of the 3-, 4-, or 5-positions of the piperidine structure, and the molecular weight of the at least one hindered amine light stabilizer composition (C1) having a dipiperidine structure is 200 g / mol to 600 g / mol. A preferred hindered amine light stabilizer composition (C1) having a dipiperidine structure comprises a compound having two piperidine structures, wherein the two piperidine structures are bonded via a saturated or unsaturated diester group having 3 to 11 carbon atoms bonded to one of the 3-, 4-, or 5-positions of the piperidine structure.

[0056] Preferably, the hindered amine light stabilizer composition (C1) having a dipiperidine structure contains a compound having two piperidine structures, and the two piperidine structures are bonded via a saturated diester group having 3 to 11 carbon atoms, particularly a saturated diester group having 6 to 10 carbon atoms. The saturated diester group is bonded to the 3, 4, or 5 position of the piperidine structure, and one of the 3, 4, or 5 positions of the piperidine structure does not contain any ester having 12 to 21 carbon atoms, whether saturated or unsaturated.

[0057] In some embodiments, a suitable hindered amine light stabilizer having a dipiperidine structure in the hindered amine light stabilizer composition (C1) of the present invention is preferably represented by the following formula (I).

Chemical formula

[0058] This sterically hindered amine (bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, CAS No. 52829-07-9) and its production method are well known to those skilled in the art and are disclosed in the literature (for example, US Patent US 4,396,769 and the references cited therein). The hindered amine light stabilizer having a dipiperidine structure represented by formula (I) may be, for example, a product of BASF SE, type number Tinuvin® 770 (molecular weight 481 g / mol).

[0059] In some embodiments, other suitable examples of the hindered amine light stabilizer composition (C1) having a dipiperidine structure of the present invention include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7, manufactured by BASF SE, product with model number Tinuvin® 765, molecular weight (Mw) of 509 g / mol), N,N'-diformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine (CAS No. 124172-53-8, manufactured by BASF SE, product with model number Uvinul® 4050 H, and Mw of 450 g / mol), and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) isophthalamide (CAS No. 42774-15-2, manufactured by Clariant, product with model number Ny-lostab® S-EED®, and Mw of 443 g / mol), which may be included.

[0060] Taking the usage amount of the acrylic rubber-modified resin composition (A) as 100 parts by weight, the usage amount of the hindered amine light stabilizer composition (C1) having a dipiperidine structure is 0.1 part by weight to 2 parts by weight, preferably 0.4 part by weight to 1.5 parts by weight, and more preferably 0.8 part by weight to 1.2 parts by weight.

[0061] In some embodiments, the weight ratio of the paraffin wax (B) to the hindered amine light stabilizer composition (C1) having a dipiperidine structure may be 0.025 to 100, preferably 0.1 to 80, and more preferably 1 to 50. When the weight ratio of the paraffin wax (B) to the hindered amine light stabilizer composition (C1) having a dipiperidine structure is within the above range, the odor of the thermoplastic resin can be improved, and it has the properties of chemical resistance, fluidity, and low gloss.

[0062] Hindered amine light stabilizer composition (C2)

[0063] The hindered amine light stabilizer composition (C2) of the thermoplastic composition of the present invention may be at least one compound having a polymerization structure, the polymerization structure contains a piperidine group, and there is at least one alkyl group at each of the 2- and 6-positions of the piperidine group, and does not contain any saturated ester moieties or unsaturated ester moieties having 12 to 21 carbon atoms at one of the 3-, 4-, or 5-positions of the piperidine group. The hindered amine light stabilizer composition (C2) having a polymerization structure contains at least two repeating units derived from polymerizable monomers, and is preferably defined as having at least three repeating units derived from polymerizable monomers. The molecular weight of the hindered amine light stabilizer composition (C2) having a polymerization structure may be 1000 g / mol to 5000 g / mol, preferably 1500 g / mol to 5000 g / mol, and more preferably 2000 g / mol to 5000 g / mol.

[0064] In some embodiments, a suitable hindered amine light stabilizer composition (C2) having a polymerization structure of the piperidine group of the present invention preferably contains a structure represented by the following formula (II) and / or formula (III). In formula (II), n represents an integer of 2 to 20.

Chemical formula

[0065] In some embodiments, the preferred hindered amine light-stable composition (C2) having a polymerized structure of a piperidine group of the present invention (CAS No. 71878-19-8) and its preparation are well known to those skilled in the art and are disclosed in the literature (e.g., European Patent EP-A-93693 and references cited therein). The hindered amine light-stable composition having a polymerized structure of a piperidine group represented by formula (II) may be, for example, a product manufactured by BASF SE under the model number Chimassorb® 944 (molecular weight 2100 g / mol to 3000 g / mol). The hindered amine-based light stabilizer composition having a polymerized structure of a piperidine group as shown in formula (III) may be, for example, a product manufactured by SABO SpA under the model number Sabostab® UV 119 (molecular weight 2286 g / mol, CAS number 106990-43-6) or a product manufactured by BASF SE under the model number Chimassorb® 119.

[0066] In some embodiments, the amount of the hindered amine-based light-stabilizing composition (C2) having the structure represented by formula (III) may be 0.1 to 1.0 part by weight, preferably 0.1 to 0.8 part by weight, and more preferably 0.3 to 0.6 part by weight, based on 100 parts by weight of the acrylic rubber-modified resin composition (A). When the amount of the hindered amine-based light-stabilizing composition (C2) having the structure represented by formula (III) is within this range, not only can the odor of the thermoplastic resin be improved, but also chemical resistance, fluidity, and low gloss can be achieved.

[0067] Specific examples of the hindered amine-based light stabilizer composition (C2) include a reaction product of a 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) polymer having 2,4,6-trichloro-1,3,5-triazine with N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (CAS number 192268-64-7, manufactured by BASF SE, product number Chimassorb® 2020, molecular weight may be 2600 g / mol to 3400 g / mol), a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS number 65447-77-0, manufactured by BASF SE, product number Tinuvin®), and a methyl methyl 4-piperidine-2,2,6,6-tetramethyl-1 ... 622 product, Mw may be 3100 g / mol to 4000 g / mol), reaction products of olefins, α-polymers having maleic anhydride and having 20 to 24 carbon atoms, and 2,2,6,6-tetramethyl-4-piperidinamine (CAS number 152261-33-1, manufactured by BASF SE, model number Uvinul®). 5050H product, Mw may be 3000 g / mol to 4000 g / mol), 1,3,5-triazine-2,4,6-triamine, N2,N2''-1,2-ethanediyl-bis[N2-[3-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl){1,3,5-triazine-2,4, 6-triamine,N2,N2''-1,2-ethanediylbis[N2-[3-[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-tri azin-2-yl]amino]propyl]-N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)}(CAS number is 106990-43-6 and SABO SpA product manufactured by Company A, model number Sabostab® UV 119, with a Mw of 2286 g / mol; Poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidinyl]imino]-hexa-methylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] {Poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidyl]imino]-hexa-methylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]]} (CAS number 82451-48-7 or 90751-07-8, manufactured by Solvay, model number Cyasorb®); UV-3346 product, Mw 1600 g / mol), and reaction products of polymers of 1,6-hexanediamine and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) with morpholine-2,4,6-trichloro-1,3,5-triazine (CAS numbers 193098-40-7 or 219920-30-6, manufactured by Solvay, model number Cyasorb® UV-3529).

[0068] The amount of the hindered amine light stabilizer composition (C2) used is 0.1 to 1.6 parts by weight, preferably 0.3 to 1.4 parts by weight, and more preferably 0.5 to 1.2 parts by weight, relative to 100 parts by weight of the acrylic rubber-modified resin composition (A).

[0069] The weight ratio of the hindered amine light-stable composition (C1) having a dipiperidine structure to the hindered amine light-stable composition (C2) may be 0.06 to 20, preferably 0.1 to 15, and more preferably 0.5 to 10. When the weight ratio of the hindered amine light-stable composition (C1) having a dipiperidine structure to the hindered amine light-stable composition (C2) is within this range, not only can the odor of the thermoplastic resin be improved, but also chemical resistance, fluidity, and low gloss can be achieved.

[0070] UV light stabilizer (D)

[0071] Specific examples of the UV light stabilizer (D) of the present invention may include, but are not limited to, a benzophenone compound (e.g., o-hydroxybenzophenone), a benzotriazole compound (e.g., 2-(2-hydroxyphenyl)benzotriazole), a triazine compound, a hydroxyphenyltriazine compound (e.g., 2-(2-hydroxyphenyl)-1,3,5-triazine), oxalanilide, salicylate, cinnamate, nickel chelate, a phenolic antioxidant, another hindered amine compound not belonging to the hindered amine light stable composition (C1) and the hindered amine light stable composition (C2), a hydroxyamine, a bifunctional compound, another suitable UV light stabilizer, or a mixture of the above compounds.

[0072] For example, the ultraviolet light stabilizer (D) may include, but is not limited to, compounds having CAS numbers 2440-22-4, 3147-75-9, 3896-11-5, 3846-71-7, 23328-53-2, 25973-55-1, 36437-37-3, 3864-99-1, 70321-86-7, 103597-45-1, or 84268-08-6, or mixtures of these compounds.

[0073] Preferably, the ultraviolet light stabilizer (D) may be a commercially available product having the model number Tinuvin® 329 (CAS number 3147-75-9), Tinuvin® 234 (CAS number 70321-86-7) or Tinuvin® 360 (CAS number 103597-45-1).

[0074] In one embodiment of the present invention, the UV light stabilizer (D) may be 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (Tinuvin® 329) or 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] (Tinuvin® 360).

[0075] The amount of the ultraviolet light stabilizer (D) used is 0.1 to 1.5 parts by weight, preferably 0.1 to 1.3 parts by weight, and more preferably 0.3 to 1.0 part by weight, based on 100 parts by weight of the acrylic rubber-modified resin composition (A).

[0076] The weight ratio of the hindered amine light-stable composition (C1) having a dipiperidine structure to the ultraviolet light stabilizer (D) may be 0.06 to 20, preferably 0.1 to 15, and more preferably 0.5 to 10. When the weight ratio of the hindered amine light-stable composition (C1) having a dipiperidine structure to the ultraviolet light stabilizer (D) is within this range, not only can the odor of the thermoplastic resin be improved, but also chemical resistance, fluidity, and low gloss can be achieved.

[0077] Colorants, dyes and / or pigments (E)

[0078] As described above, the thermoplastic compositions of the present invention may further comprise 0.1 to 10 parts by weight, typically 0.1 to 5 parts by weight, of a colorant, dye, and / or pigment (E), which may be added in the form of a masterbatch, which comprises a polymer matrix and the colorant, dye, and / or pigment. In some embodiments, the colorant, dye, and / or pigment is added in the form of a masterbatch, which comprises 20 to 70 wt. % of the colorant, dye, and / or pigment, or a mixture of the colorant, dye, and / or pigment, and 30 to 80 wt. % of a vinyl aromatic olefin-acrylonitrile copolymer as a polymer matrix, based on the total weight of the masterbatch. Preferably, the polymer matrix is selected from poly(styrene-acrylonitrile) (SAN), poly(α-methylstyrene / acrylonitrile) (AMSAN), and / or poly(styrene-methyl methacrylate) (SMMA).

[0079] In some specific examples, the pigments may include, but are not limited to, titanium dioxide, phthalocyanine, ultramarine, iron oxide, carbon black, and all classes of organic pigments. Specific examples of the colorants include, but are not limited to, all dyes that can be used for transparent, translucent, or opaque coloring of polymers, particularly coloring dyes suitable for styrene copolymers.

[0080] Other additives (F)

[0081] The thermoplastic composition of the present invention optionally contains one or more other additives (F), and the other additives (F) are not any of the additives described in the acrylic rubber-modified resin composition (A), paraffin wax (B), hindered amine light stabilizer composition (C1) having a dipiperidine structure, hindered amine light stabilizer composition (C2), ultraviolet light stabilizer (D), and colorant, dye and / or pigment (E). For example, the other additives (F) may be selected from plasticizers, aliphatic amide waxes, aliphatic fatty acid esters, and other ultraviolet light stabilizers that do not belong to the ultraviolet light stabilizer (D).

[0082] Optionally, various additives may be added to the thermoplastic composition as auxiliaries and / or processing additives in a dosage of 0.05 to 5 parts by weight, generally 0.1 to 5 parts by weight. Suitable other additives (F) include all substances commonly used in the processing or treatment of polymers.

[0083] The other additive (F) may be added in the form of a masterbatch, in which the other additive (F) is included in a polymer matrix. In some embodiments, the other additive (F) is added in the form of a masterbatch, which comprises 20 wt% to 70 wt%, preferably 40 wt% to 60 wt%, of the other additive (F) or a mixture thereof, based on the total weight of the masterbatch, and 30 wt% to 80 wt%, preferably 40 wt% to 60 wt% (based on the total weight of the masterbatch) of a copolymer of vinyl aromatic olefin and acrylonitrile, as the polymer matrix. Preferably, the polymer matrix is selected from poly(styrene-acrylonitrile) (SAN, Styrene Acrylonitrile), poly(α-methylstyrene / acrylonitrile) (AMSAN, Alphamethylstyrene Acrylonitrile), and / or poly(styrene-methyl methacrylate) (SMMA, Styrene Methyl Methacrylate).

[0084] Specific examples of the other additives (F) include antistatic agents, antioxidants, flame retardants, stabilizers for increasing thermal stability, stabilizers for increasing light stability, stabilizers for increasing hydrolysis resistance and chemical resistance, thermal decomposition inhibitors, and lubricants. Lubricants, in particular, contribute to the production of molded articles. These other additives (F) can be mixed at any stage of the manufacturing process, but are preferably mixed at an early stage so that the stabilizing effect (or other specific effect) of the other additives (F) can be exerted early.

[0085] Specific examples of suitable antistatic agents may include, but are not limited to, amine derivatives (e.g., N,N-bis(hydroxyalkyl)alkylamines or -alkyleneamines), polyethylene glycol, copolymers of ethylene oxide glycol and propylene oxide glycol (particularly diblock or triblock copolymers of ethylene oxide block and propylene oxide block), glycerol monostearate and distearate, and mixtures thereof.

[0086] Specific examples of suitable antioxidants include, but are not limited to, monocyclic or polycyclic sterically hindered phenolic antioxidants, which may contain various substituents or may be bridged by substituents. These antioxidants include not only monomeric compounds but also oligomeric compounds consisting of multiple phenolic units. Hydroquinone and hydroquinone analogues are also suitable antioxidants, as are substituted compounds and antioxidants based on tocopherol and its derivatives. The antioxidants used may also include mixtures of different antioxidants. In principle, any commercially available compound or compound suitable for styrene copolymers, such as antioxidants from the Irganox® series, may be used. In addition to the phenolic antioxidants listed above, further co-stabilizers, particularly those containing phosphorus or sulfur, may also be used; these phosphorus or sulfur-containing co-stabilizers are well known to those skilled in the art.

[0087] Examples of suitable flame retardants include halogen or phosphorus containing compounds, magnesium hydroxide and other commonly used flame retardant compounds or mixtures thereof known to those skilled in the art.

[0088] Specific examples of suitable light stabilizers include various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.

[0089] Suitable matting agents include inorganic substances such as talc, glass beads, or metal carbonates (e.g., MgCO3 or CaCO3), as well as polymer particles (e.g., spherical particles of methyl methacrylate, styrene compounds, acrylonitrile, or mixtures thereof, with a diameter D50 of more than 1 μm). Polymers containing copolymerized acidic and / or alkaline monomers may also be used as matting agents.

[0090] Specific examples of suitable anti-drip agents may include polytetrafluoroethylene (Teflon) polymers and ultra-high molecular weight polystyrene (weight average molecular weight (Mw) greater than 2,000,000 g / mol).

[0091] Specific examples of fibrous / powder fillers include carbon or glass fibers, which may be in the form of woven glass, glass mat or filament glass roving, chopped glass, glass beads, and wollastonite, with glass fibers being preferred. When glass fibers are used, they may be treated with sizing or coupling agents to improve compatibility with the blend components. The blended glass fibers may be in the form of short glass fibers or continuous filaments (rovings).

[0092] Specific examples of suitable particulate fillers may include amorphous silica, magnesium carbonate, sandstone powder, mica, bentonite, talc, feldspar, or calcium silicates such as wollastonite, and kaolin.

[0093] Specific examples of suitable stabilizers include hindered phenols, vitamin E and / or compounds with a similar structure, and butyl condensation products of p-cresol and dicyclopentadienyl. Other hindered amine-based light stabilizers other than the hindered amine-based light-stable compositions (C1) and (C2), such as benzophenone, resorcinol, salicylate, or benzotriazole, are also suitable stabilizers. Other suitable compounds may be, for example, thiocarboxylic acid esters, and alkyl esters of thiopropionic acid having 6 to 20 carbon atoms, particularly stearic acid esters and lauric acid esters, may also be used.

[0094] Additionally, dilauryl thiodipropionate, distearyl thiodipropionate, or mixtures of the above compounds may be used. Specific examples of other additives may include ultraviolet light absorbers (e.g., 2H-benzotriazol-2-yl-(4-methylphenol)).

[0095] Suitable lubricants and release agents include stearic acid, stearyl alcohol, stearic acid esters and / or common higher fatty acids, their derivatives and corresponding fatty acid mixtures with 1 to 45 carbon atoms. Preferably, in some embodiments, the composition contains an amide compound represented by the formula R1-CONH-R2, where R1 and R2 are each independently selected from aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 30 carbon atoms. R1 and R2 each preferably represent an aliphatic, saturated or unsaturated hydrocarbon group having 12 to 24 carbon atoms, more preferably an aliphatic, saturated or unsaturated hydrocarbon group having 16 to 20 carbon atoms. In some embodiments, the composition may further contain a fatty acid ester compound represented by the formula R3-CONH-R4, where R3 and R4 are each independently selected from aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 45 carbon atoms. R3 and R4 each preferably represent an aliphatic, saturated or unsaturated hydrocarbon group having 15 to 40 carbon atoms, more preferably an aliphatic, saturated or unsaturated hydrocarbon group having 25 to 35 carbon atoms. Ethylene bis(stearamide) is particularly suitable.

[0096] In some embodiments, the thermoplastic composition of the present invention may contain organic, inorganic or mixed phosphates, particularly alkali metal or alkaline earth metal phosphates, such as Ca3(PO4)2 and / or organic phosphates containing alkyl or aryl groups having 1 to 12 carbon atoms.

[0097] In some embodiments, the thermoplastic composition of the present invention may further contain a polyester-modified polysiloxane, particularly a polyester-polysiloxane-block copolymer, preferably a [polyester-b-polysiloxane-b-polyester] triblock copolymer. Specific examples of the polysiloxane moiety contained in the polyester-polysiloxane-block copolymer may be derived from poly(dimethylsiloxane), poly(diethylsiloxane), poly(dipropylsiloxane), poly(dibutylsiloxane) and mixtures thereof.

[0098] The method for producing the thermoplastic composition of the present invention is not particularly limited, and a general mixing method may be used. For example, an acrylic rubber-modified resin composition (A), a paraffin wax (B), and a hindered amine-based light stabilizer composition (C1) having a dipiperidine structure may be uniformly mixed, and optionally, a hindered amine-based light stabilizer composition (C2), an ultraviolet light stabilizer (D), a colorant, a dye and / or a pigment (E) and / or other additives (F) may be added. In some embodiments, the general mixing method includes dry mixing with a general Henschel mixer and then melt mixing with a mixer such as an extrusion mixer, a kneader or a Banbury mixer.

[0099] In some embodiments, the method for producing the thermoplastic composition provides 100 parts by weight of an acrylic rubber-modified resin composition (A), 0.05 to 10 parts by weight of a paraffin wax (B), and 0.1 to 2 parts by weight of a hindered amine-based light stabilizer composition (C1) having a dipiperidine structure, and is obtained by kneading at a temperature of 200°C to 230°C.

[0100] In addition, to the thermoplastic composition of the present invention, a hindered amine-based light stabilizer composition (C2), an ultraviolet light stabilizer (D), a colorant, a dye and / or a pigment (E) and / or other additives (F) may be added as necessary. For example, the other additives (F) may include, but are not limited to, antioxidants, plasticizers, processing aids, ultraviolet light stabilizers different from the ultraviolet light stabilizer (D), ultraviolet absorbers, fillers, reinforcing agents, colorants, lubricants, antistatic agents, flame retardants, flame retardant aids, heat stabilizers, coupling agents or other additives. The above additives may be added in the process of extrusion kneading.

[0101] Another embodiment of the present invention provides a molded article formed of the thermoplastic composition. Since the method for forming the molded article may use injection molding well-known to those skilled in the art, it will not be described further.

[0102] The following examples are provided to illustrate the use of the present invention, but are not intended to limit the scope of the present invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. [Example]

[0103] Example 1

[0104] Production of styrene-acrylonitrile copolymers

[0105] Raw materials such as 68 parts by weight of styrene monomer, 32 parts by weight of acrylonitrile monomer, 8 parts by weight of ethylbenzene, 0.01 parts by weight of 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and 0.15 parts by weight of tert-dodecyl mercaptan were uniformly mixed and continuously fed into two series-connected continuous complete mixing reactors, each with a volume of 40 liters. The internal temperatures of the two reactors were maintained at 110°C and 115°C, respectively, and the pressures of both reactors were 4 kg / cm. 2 The homogeneously mixed raw materials were fed into the reactor at a feed rate of 35 kg / hr to carry out the polymerization reaction. The overall conversion rate of the polymerization reaction was about 50%.

[0106] After the polymerization reaction, the resulting copolymer solution was heated in a preheater and the unreacted monomers and other volatile components were removed by evaporation in a vacuum degassing tank, and the styrene-acrylonitrile copolymer required in Example 1 was obtained by extrusion granulation.

[0107] Production of acrylic rubber graft copolymer

[0108] First, 99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 5.0 parts by weight of dioctyl sodium sulfosuccinate, 2.0 parts by weight of tert-butyl hydroperoxide solution (concentration 70 wt%), 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration 10 wt%), and 4000.0 parts by weight of distilled water were reacted at a reaction temperature of 60 °C for 7 hours to obtain an acrylic ester rubber emulsion with a weight average particle diameter of 0.1 μm.

[0109] Then, 100.0 parts by weight of the above acrylic ester rubber emulsion with a weight average particle diameter of 0.1 μm (dry weight), 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 6.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration 10 wt%), and 3000.0 parts by weight of distilled water were mixed, and a graft polymerization reaction was carried out. Styrene and acrylonitrile were added to the reaction system within 5 hours in a continuous addition method. After the graft polymerization reaction was completed, an acrylic rubber graft emulsion with a weight average particle diameter of 0.12 μm was obtained.

[0110] Also, 99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 3.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of tert-butyl hydroperoxide solution (concentration 70 wt%), 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration 10 wt%), and 4000.0 parts by weight of distilled water were uniformly mixed and reacted at a temperature of 65 °C for 7 hours to obtain an acrylic ester rubber emulsion with a weight average particle diameter of 0.4 μm.

[0111] Similarly, 100.0 parts by weight of the above acrylic ester rubber emulsion with a weight average particle diameter of 0.4 μm (dry weight), 37.6 parts by weight of styrene, 16.1 parts by weight of acrylonitrile, 4.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration 10 wt%), and 2000.0 parts by weight of distilled water were mixed, and a graft polymerization reaction was carried out. Styrene and acrylonitrile were added to the reaction system within 5 hours in a continuous addition method. After the completion of the graft polymerization reaction, an acrylic rubber graft emulsion with a weight average particle diameter of 0.45 μm was obtained.

[0112] Finally, 60 wt% (dry weight) of the above acrylic rubber graft emulsion with a weight average particle diameter of 0.12 μm and 40 wt% (dry weight) of the above acrylic rubber graft emulsion with a weight average particle diameter of 0.45 μm were mixed, coagulated and dehydrated with calcium chloride (CaCl2), and then dried until the water content was 2% or less, and the acrylic rubber graft copolymer required in Example 1 was obtained. Its weight average particle diameter had a double peak distribution pattern of 0.12 μm and 0.45 μm.

[0113] Production of Acrylic Rubber Modified Resin Composition

[0114] In a dry state, 65.1 wt% of the above styrene-acrylonitrile copolymer, 34.9 wt% of the acrylic rubber graft copolymer with a double peak distribution pattern of 0.12 μm and 0.45 μm in weight average particle diameter, and 1.04 wt% of a lubricant were kneaded at a kneading temperature of 220 °C using a twin-screw extruder (manufactured by Taiwan Zeji Industry Co., Ltd., model ZPT-25). Then, when extruded with a twin-screw extruder, the required acrylic rubber modified resin composition was obtained.

[0115] Production of Thermoplastic Composition

[0116] In the dry state, 100 parts by weight of an acrylic rubber-modified resin composition, 1.0 part by weight of Tinuvin® 770, 2 parts by weight of paraffin wax, and 1.6 parts by weight of carbon black were kneaded at a kneading temperature of 220°C using a twin-screw extruder (a device of model number ZPT-25 manufactured by Taiwan Zeji Industry Co., Ltd.). Then, when extruded with a twin-screw extruder, the thermoplastic composition of Example 1 was obtained.

[0117] Examples 2 to 6

[0118] In Examples 2 to 6, the types and / or addition amounts of the paraffin wax (B) used in the production of the thermoplastic composition were not the same, and the detailed formulations are shown in Table 1. Otherwise, it was the same as in Example 1. Note that Examples 2 to 6 have the same production method as Example 1.

[0119] Examples 7 to 9

[0120] In Examples 7 to 9, a hindered amine light stabilizer composition (C2) or an ultraviolet light stabilizer (D) with a molecular weight of 1000 g / mol to 5000 g / mol was additionally added during the production of the thermoplastic composition, and the detailed formulations are shown in Table 1. Otherwise, it was the same as in Example 1. Note that Examples 7 to 9 have the same production method as Example 1.

[0121] Example 10

[0122] In Example 10, a hindered amine light stabilizer composition (C2) and an ultraviolet light stabilizer (D) with a molecular weight of 1000 g / mol to 5000 g / mol were additionally added during the production of the thermoplastic composition, and the detailed formulations are shown in Table 1. Otherwise, it was the same as in Example 1. Note that Example 10 has the same production method as Example 1.

[0123] Comparative Example 1, Comparative Example 3, and Comparative Example 4

[0124] In Comparative Examples 1, 3, and 4, paraffin wax (B) was not used during the production of the thermoplastic composition, and the detailed formulation is shown in Table 1. Other than that, the comparative examples are the same as Example 1. Note that Comparative Examples 1, 3, and 4 have the same production method as Example 1.

[0125] Comparative Example 2

[0126] In Comparative Example 2, the hindered amine-based light stabilizer composition (C1) having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol was not used during the production of the thermoplastic composition, and the detailed formulation is shown in Table 1. Other than that, the comparative example is the same as Example 1. Note that Comparative Example 2 has the same production method as Example 1.

[0127] Comparative Example 5

[0128] In Comparative Example 5, the hindered amine-based light stabilizer composition (C1) having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol was not used during the production of the thermoplastic composition, and the detailed formulation is shown in Table 1. Other than that, the comparative example is the same as Example 1. Note that Comparative Example 5 is produced using the same method as Example 1.

[0129] Examples 11 and 14

[0130] In Examples 11 and 14, the type and / or amount of paraffin wax (B) used during the production of the thermoplastic composition is different, and an ultraviolet light stabilizer (D) is additionally added, the detailed formulation of which is shown in Table 2. Other than that, the examples are the same as Example 1. In addition, Examples 11 and 14 have the same production method as Example 1.

[0131] Examples 12 and 13

[0132] In Examples 12 and 13, the type and / or amount of paraffin wax (B) used during the production of the thermoplastic composition is not the same, but a hindered amine-based light stabilizer composition (C2) having a molecular weight of 1000 g / mol to 5000 g / mol and an ultraviolet light stabilizer (D) are additionally added, and the detailed formulation is shown in Table 2. Other than that, the composition is the same as in Example 1. Note that Examples 12 and 13 are produced using the same method as in Example 1.

[0133] Examples 15 to 17

[0134] In Examples 15 to 17, the amounts of styrene-acrylonitrile copolymer and acrylic rubber graft copolymer used during the production of the thermoplastic composition are not the same, and the type and / or amount of paraffin wax (B) used are not the same. Instead, a hindered amine light stabilizer composition (C2) having a molecular weight of 1000 g / mol to 5000 g / mol and an ultraviolet light stabilizer (D) are additionally added, and the detailed formulations are shown in Table 2. Other than that, the examples are the same as those of Example 1. Examples 15 to 17 were produced using the same method as Example 1.

[0135] Comparative Example 6

[0136] In Comparative Example 6, paraffin wax (B) was not used during the production of the thermoplastic composition, and an ultraviolet light stabilizer (D) was additionally added, the detailed formulation of which is shown in Table 2. Other than that, the comparative example is the same as Example 1. Note that Comparative Example 6 has the same production method as Example 1.

[0137] Comparative Example 7

[0138] In Comparative Example 7, the hindered amine-based light-stabilizing composition (C1) having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol was not used during the production of the thermoplastic composition, but the hindered amine-based light-stabilizing composition (C2) having a molecular weight of 1000 g / mol to 5000 g / mol and the ultraviolet light stabilizer (D) were additionally added, and the detailed formulation is shown in Table 2. Other than that, the composition is the same as in Example 1. Note that Comparative Example 7 has the same production method as in Example 1.

[0139] The principles and evaluation criteria of the physical property tests conducted on the thermoplastic compositions of Examples 1 to 17 and Comparative Examples 1 to 7 are described in detail below, and the test results of each are shown in Tables 1 and 2, respectively.

[0140] Physical Property Tests of Thermoplastic Compositions

[0141] 1. Melt Volume Flow Rate (MVR)

[0142] It is measured according to the standard method of ASTM D-1238. The test temperature is 220 °C, the load is 10 kg, and it is expressed in g / 10 min.

[0143] 2. Surface Glossiness (gloss)

[0144] The thermoplastic compositions produced in each example and comparative example are injection molded into disk test pieces with a diameter of 5.5 cm and measured according to the standard method of ASTM D-523, with % as the unit.

[0145] 3. Chemical Resistance

[0146] The chemical resistance of the thermoplastic composition is evaluated using the 1 / 4 ellipse method, and 95 unleaded gasoline and glacial acetic acid are used as reagents. To reduce the influence of the molding distortion of the test piece, the thermoplastic compositions produced in each example and comparative example are injection molded with an injection molding machine to produce elliptical test pieces for chemical resistance. The shape of the test piece is 230 mm × 30 mm × 2 mm, but the major axis radius of the ellipse is 190 mm, and the minor axis radius of the ellipse is 77 mm.

[0147] The reagent is applied to the test piece, and after leaving it at 23 °C for 48 hours, the cracks of the test piece are observed. The critical strain of the test piece is calculated by the following formula, and the chemical resistance is judged according to the following criteria. "Grade E" indicates that no cracks occur during daily use, "Grade D" indicates that cracks occur when used under large stress conditions in daily life, and "Grade C" indicates that cracks may occur during daily use.

Equation

[0148] Here, ε represents the critical strain, a represents the major radius, b represents the minor radius, X represents the crack initiation point, and t represents the thickness of the test piece. Grade E: 2.0 ≤ ε. Grade D: 0.8 ≤ ε < 2.0. Grade C: 0.5 ≤ ε < 0.8.

[0149] 4. Odor test

[0150] 10 g of the thermoplastic composition produced in each example and comparative example was added to a 500 ml glass bottle and heated in an oven at 70°C. After heating for 2 hours, it was cooled to room temperature for 0.5 to 1.5 hours, and the odor test was judged according to the following evaluation grades (grades 1 to 5). Grade 1: No odor. Grade 2: There is a slightly perceptible and acceptable odor. Grade 3: There is an odor, but it is not irritating and can be tolerated. Grade 4: There is an obvious odor and a feeling of aversion. Grade 5: There is a strong and intolerable irritating odor.

[0151] 5. Molding processability

[0152] Based on the measurement results of the melt volume flow rate, the molding processability was judged according to the following criteria. "◎" indicates excellent processability, and "○" indicates good processability. ◎: 11.5 g / 10 min ≤ MVR. ○: 9.5 g / 10 min ≤ MVR < 11.5 g / 10 min.

[0153]

Table 1

[0154] As can be seen from Table 1, in the acrylic rubber-modified resin compositions (i.e., styrene-acrylonitrile copolymer and acrylic rubber graft copolymer) in the thermoplastic compositions produced in Examples 1 to 6, paraffin wax and Tinuvin® 770 can reduce the odor of the thermoplastic composition, enhance its fluidity and chemical resistance, and reduce its gloss. Also, as the amount of paraffin wax used increases, not only does the fluidity of the thermoplastic composition increase, but its chemical resistance and low glossiness also increase. Further, compared with Examples 1 to 3, in Examples 4 to 6, the thermoplastic composition can also have characteristics such as low odor, high chemical resistance, high fluidity, and low gloss due to paraffin wax having a relatively high melting point.

[0155] In Examples 7 to 9, when a hindered amine light stabilizer composition having a molecular weight of 1000 g / mol to 5000 g / mol (for example, Chimassorb® 119 or Chimassorb® 944) or an ultraviolet light stabilizer (for example, Tinuvin® 329) is additionally added to the thermoplastic composition, the thermoplastic composition can maintain low odor and high chemical resistance, and further enhance fluidity and low glossiness.

[0156] Compared with Example 1, in Example 10, when a hindered amine light stabilizer composition having a molecular weight of 1000 g / mol to 5000 g / mol (for example, Chimassorb® 119 and Chimassorb® 944) and an ultraviolet light stabilizer (for example, Tinuvin® 329) are additionally added to the thermoplastic composition, the produced thermoplastic composition has characteristics such as low odor, high chemical resistance, high fluidity, and low glossiness.

[0157] The thermoplastic composition produced in Comparative Example 1 does not use paraffin wax and contains only a hindered amine light stabilizer composition having a molecular weight of 200 g / mol to 600 g / mol with a dipiperidine structure. Therefore, it has relatively low odor performance, chemical resistance, and fluidity, and cannot effectively reduce the gloss performance. Compared with Comparative Example 1, the thermoplastic composition of Comparative Example 2 has slightly higher odor performance, chemical resistance, fluidity, and low gloss performance, but it only uses paraffin wax and does not use a hindered amine light stabilizer composition having a molecular weight of 200 g / mol to 600 g / mol with a dipiperidine structure, so it still cannot meet the application requirements.

[0158] In Comparative Example 3, only a hindered amine light stabilizer composition having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol and an ultraviolet light stabilizer were used, and paraffin wax was not used. In Comparative Example 4, a combination of a hindered amine light stabilizer composition having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol and a hindered amine light stabilizer composition having a molecular weight of 1000 g / mol to 5000 g / mol was used, but paraffin wax was not used. In Comparative Example 3 and Comparative Example 4, since paraffin wax was not added to the thermoplastic composition in either case, its odor performance, chemical resistance, fluidity, and low gloss performance were all relatively low. Compared with Comparative Example 1, in Comparative Example 5, paraffin wax was used, but a combination of a hindered amine light stabilizer composition having a molecular weight of 1000 g / mol to 5000 g / mol and an ultraviolet light stabilizer was used. Therefore, in terms of physical properties, the odor performance, chemical resistance, fluidity, and low gloss performance can be slightly improved. However, since a hindered amine light stabilizer composition having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol was not used, it still has relatively low fluidity, low gloss, chemical resistance, odor performance, and processability, and thus cannot meet the application requirements.

[0159]

Table 2

[0160] In Table 2, the types represented by Components B-1, B-2, C1-1, C2-1, C2-2, E-1, and F-1 are the same as those described in Table 1, so no further explanation will be given here. And Component D-2 in Table 2 represents an ultraviolet light stabilizer of type Tinuvin (registered trademark) 360 manufactured by BASF SE.

[0161] In comparison with Example 1, in Examples 11 to 17, when a hindered amine-based light stabilizer (e.g., Chimassorb® 119 and Chimassorb® 944) and / or a UV light stabilizer (e.g., Tinuvin® 360) having a molecular weight of 1,000 g / mol to 5,000 g / mol was added to the thermoplastic composition, the resulting thermoplastic composition exhibited properties such as low odor, high chemical resistance, high fluidity, and low gloss. Furthermore, compared with the UV light stabilizer (D-1) used in Examples 8 and 10, the UV light stabilizer (D-2) used in Examples 11 to 17 also exhibited the same effects, resulting in the resulting thermoplastic composition exhibiting properties such as low odor, high chemical resistance, high fluidity, and low gloss.

[0162] Comparative Example 6 used only a hindered amine-based light stabilizer having a molecular weight of 200 g / mol to 600 g / mol and a UV light stabilizer, without using paraffin wax, resulting in relatively poor odor performance, chemical resistance, fluidity, and low gloss. Comparative Example 7 used paraffin wax, but combined a hindered amine-based light stabilizer having a molecular weight of 1000 g / mol to 5000 g / mol and a UV light stabilizer, which slightly improved odor performance, chemical resistance, fluidity, and low gloss. However, because it did not use a hindered amine-based light stabilizer having a molecular weight of 200 g / mol to 600 g / mol and a dipiperidine structure, the fluidity, low gloss, chemical resistance, odor performance, and processability were still relatively poor, failing to meet application needs.

[0163] As can be seen from the comparison between Examples 1 to 17 and Comparative Examples 1 to 7, when the thermoplastic composition contains only paraffin wax or only a hindered amine light stabilizer composition having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol, its fluidity, low gloss performance, chemical resistance and odor performance are all relatively low and cannot meet the application requirements. Therefore, in the present invention, by adding both paraffin wax and a hindered amine light stabilizer composition having a molecular weight of 200 g / mol to 600 g / mol in the ASA resin, due to the synergistic effect of the two, the fluidity of the thermoplastic composition can be effectively increased, and the odor performance, chemical resistance and low gloss performance can be further enhanced.

[0164] Furthermore, when the thermoplastic composition contains only paraffin wax or only a hindered amine light stabilizer composition having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol, even if at least one of a hindered amine light stabilizer composition having a molecular weight of 1000 g / mol to 5000 g / mol or an ultraviolet light stabilizer is additionally added, the fluidity, low gloss performance, chemical resistance and odor performance of the thermoplastic composition cannot meet the application requirements.

[0165] Obviously, in the present invention, by adding both paraffin wax and a hindered amine light stabilizer composition having a dipiperidine structure and a molecular weight of 200 g / mol to 600 g / mol to the acrylic rubber-modified resin composition, the fluidity, low gloss performance, chemical resistance and odor performance of the thermoplastic composition can be synergistically and significantly enhanced, and further meet the application requirements.

[0166] As described above, the present invention provides a thermoplastic composition comprising 100 parts by weight of an acrylic rubber-modified resin composition (A), 0.05 to 10 parts by weight of a paraffin wax (B), and 0.1 to 2 parts by weight of a hindered amine-based light-stabilizing composition (C1) having a dipiperidine structure, the hindered amine-based light-stabilizing composition (C1) having a molecular weight of 200 g / mol to 600 g / mol. Due to the above content, the thermoplastic composition of the present invention combines properties such as low odor, high chemical resistance, high fluidity, and low gloss.

[0167] Although the present invention has been disclosed as above in the above embodiments, it is not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is limited by the scope of the attached patent application.

Claims

1. 100 parts by weight of an acrylic rubber-modified resin composition (A) containing a styrene-acrylonitrile copolymer and an acrylic rubber graft copolymer, 0.05 parts by weight to 10 parts by weight of paraffin wax (B), 0.1 parts by weight to 2 parts by weight of a hindered amine light stabilizer composition (C1) having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol, comprising, a thermoplastic composition, wherein the weight ratio of the paraffin wax (B) to the hindered amine light stabilizer composition (C1) having a dipiperidine structure is 0.025 to 100.

2. The thermoplastic composition according to claim 1, wherein the paraffin wax (B) contains a saturated hydrocarbon compound having 17 to 50 carbon atoms and has a melting point exceeding 40°C and less than 75°C.

3. The thermoplastic composition according to claim 1, wherein the hindered amine light stabilizer composition (C1) having a dipiperidine structure has a structure represented by the following formula (I). 【Chemical 1】

4. The thermoplastic composition according to claim 1, further comprising 0.1 parts by weight to 1.6 parts by weight of a hindered amine light stabilizer composition (C2) having a molecular weight of 1000 g / mol to 5000 g / mol.

5. The hindered amine light stabilizer composition (C2) contains a structure represented by the following formula (II) and / or formula (III), [[Chemical 2]] in the formula (II), n represents an integer of 2 to 20, for the thermoplastic composition according to claim 4.

6. The thermoplastic composition according to claim 5, wherein the content of the hindered amine light stabilizer composition (C2) having a structure represented by the formula (III) is 0.1 parts by weight to 1.0 parts by weight.

7. The thermoplastic composition according to claim 4, wherein the weight ratio of the hindered amine light stabilizer composition (C1) having a dipiperidine structure to the hindered amine light stabilizer composition (C2) is 0.06 to 20.

8. The thermoplastic composition according to claim 1, further comprising 0.1 parts by weight to 1.5 parts by weight of an ultraviolet light stabilizer (D).

9. The thermoplastic composition according to claim 8, wherein the ultraviolet light stabilizer (D) contains a benzotriazole-based reactive ultraviolet light stabilizer.

10. The thermoplastic composition according to claim 8, wherein the ultraviolet light stabilizer (D) is selected from 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole or 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol].

11. The thermoplastic composition according to claim 8, wherein the weight ratio of the hindered amine light stabilizer composition (C1) having the dipiperidine structure to the ultraviolet light stabilizer (D) is 0.06 to 20.

12. The thermoplastic composition according to claim 1, further comprising 0.1 to 10 parts by weight of a colorant, a dye and / or a pigment (E), and / or 0.05 to 5 parts by weight of another additive (F).

13. A molded article comprising the thermoplastic composition according to any one of claims 1 to 12.

14. Providing a composition comprising 100 parts by weight of an acrylic rubber-modified resin composition (A) containing a styrene-acrylonitrile copolymer and an acrylic rubber graft copolymer, 0.05 to 10 parts by weight of paraffin wax (B), and 0.1 to 2 parts by weight of a hindered amine light stabilizer composition (C1) having a dipiperidine structure with a molecular weight of 200 g / mol to 600 g / mol, wherein the weight ratio of the paraffin wax (B) to the hindered amine light stabilizer composition (C1) having the dipiperidine structure is 0.025 to 100; A step of kneading the composition to obtain a thermoplastic composition; A method for producing a thermoplastic composition comprising the above steps.

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