TWI555759B - Rubber-modified styrene-based resin - Google Patents
Rubber-modified styrene-based resin Download PDFInfo
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- TWI555759B TWI555759B TW104144274A TW104144274A TWI555759B TW I555759 B TWI555759 B TW I555759B TW 104144274 A TW104144274 A TW 104144274A TW 104144274 A TW104144274 A TW 104144274A TW I555759 B TWI555759 B TW I555759B
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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Description
本揭露內容是有關於一種橡膠改質苯乙烯系樹脂,且特別是有關於一種同時具有良好流動性及耐衝擊性之橡膠改質苯乙烯系樹脂。 The present disclosure relates to a rubber-modified styrene-based resin, and more particularly to a rubber-modified styrene-based resin having both good fluidity and impact resistance.
本發明是有關於一種適用於製備電氣器材、辦公器材、汽車部件、家庭用品等塑膠成型品的材料,特別是指一種橡膠改質苯乙烯系樹脂。本發明亦提供一種製備該橡膠改質苯乙烯系樹脂的方法,及一種由該橡膠改質苯乙烯系樹脂所形成的成型品。 The invention relates to a material suitable for preparing plastic molded articles such as electrical equipment, office equipment, automobile parts and household articles, in particular to a rubber modified styrene resin. The present invention also provides a method of preparing the rubber-modified styrene-based resin, and a molded article comprising the rubber-modified styrene-based resin.
一般用於電氣器材或家庭用品等的塑膠成型品所含有的成分大都為橡膠改質苯乙烯系樹脂、聚碳酸酯樹脂(Polycarbonate Resin)等。其中,該橡膠改質苯乙烯系樹脂,如丙烯腈-丁二烯-苯乙烯樹脂(Acrylonitrile-Butadiene-Styrene Resin,簡稱ABS)之所以被廣泛使用在電器、電子及汽車零件上,主要是其加工成型性、物理性及機械性質方面皆有良好的評價。 Most of the components contained in plastic molded articles for electrical equipment, household goods, and the like are rubber-modified styrene resins, polycarbonate resins (Polycarbonate Resin), and the like. Among them, the rubber modified styrene resin, such as Acrylonitrile-Butadiene-Styrene Resin (ABS), is widely used in electrical appliances, electronic and automotive parts, mainly Good processing, physical and mechanical properties are well evaluated.
惟隨著使用者對品質要求的不斷提高,一般橡膠改質苯乙烯系樹脂在衝擊強度上仍有改良之須求。其中,將橡膠狀接枝共聚物分散於苯乙烯系共聚物中,可以製得具有耐衝撃性的 苯乙烯系樹脂組成物。此種樹脂組成物須經過各種加工、成型法(如一次加工:射出成型、押出成型等,及二次加工:真空成型等)方能製成成型商品。 However, as the quality requirements of users continue to increase, there is still a need for improvement in impact strength of rubber-modified styrene resins. Wherein, the rubbery graft copolymer is dispersed in the styrene copolymer, and the punching resistance can be obtained. A styrene resin composition. Such a resin composition can be formed into a molded product through various processing and molding methods (for example, one-time processing: injection molding, extrusion molding, and secondary processing: vacuum molding, etc.).
又目前加工成型業者為了改善射出成型品之澆口外觀,並且採用全自動化之生產,乃逐漸採用針孔式澆口(Pin gate)來射出成型,此種針孔式澆口由於孔道極小,黏度較高之樹脂熔融體不易流過孔道射出成型,因此,為提升橡膠改質苯乙烯系樹脂之流動性要求,射出成型溫度也要相對提高避免降低生產之效率;此外,由於加工廠逐漸重視成型品的加工容易度、良好物性及較佳耐衝撃強度。因此,如何使橡膠改質苯乙烯系樹脂具有良好之衝擊強度、流動性等物性平衡,乃為此領域極待改善之課題。 In order to improve the appearance of the gate of injection molded products and to adopt fully automated production, the processing and molding industry is gradually adopting a pin gate for injection molding. This pinhole gate has a very small pore size and viscosity. The higher resin melt does not easily flow through the pores to form, so in order to improve the fluidity requirements of the rubber-modified styrene resin, the injection molding temperature should be relatively increased to avoid reducing the efficiency of production; in addition, due to the increasing emphasis on molding by the processing plant The ease of processing, good physical properties and better impact resistance. Therefore, how to make the rubber-modified styrene-based resin have a good balance of physical properties such as impact strength and fluidity is an urgent problem to be solved in this field.
本揭露內容之第一目的係有關於一種橡膠改質苯乙烯系樹脂,具有同時符合高流動性及高耐衝擊性的特性,並可維持其他的物性,而能夠符合業界的需求。 The first object of the present disclosure relates to a rubber-modified styrene-based resin which has the characteristics of high fluidity and high impact resistance at the same time, and can maintain other physical properties, and can meet the needs of the industry.
根據本揭露內容之一實施例,係提出一種橡膠改質苯乙烯系樹脂,包括72重量%至88重量%的苯乙烯系共聚物以及12重量%至28重量%的橡膠粒子。苯乙烯系共聚物包括一第一苯乙烯-丙烯腈系共聚物與一第二苯乙烯-丙烯腈系共聚物,第一苯乙烯-丙烯腈系共聚物的重量平均分子量為5~10萬,第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比係為1.4~3.5。 According to an embodiment of the present disclosure, there is provided a rubber-modified styrenic resin comprising 72% by weight to 88% by weight of a styrenic copolymer and 12% by weight to 28% by weight of rubber particles. The styrene-based copolymer comprises a first styrene-acrylonitrile copolymer and a second styrene-acrylonitrile copolymer, and the first styrene-acrylonitrile copolymer has a weight average molecular weight of 50,000 to 100,000. The ratio of the weight average molecular weight of the second styrene-acrylonitrile-based copolymer to the weight average molecular weight of the first styrene-acrylonitrile-based copolymer is from 1.4 to 3.5.
本發明之第二目的,即在提供一種成型品。此成型品是由如上所述的橡膠改質苯乙烯系樹脂成型處理所製得。 A second object of the present invention is to provide a molded article. This molded article was obtained by molding a rubber-modified styrene resin as described above.
本發明之第三目的,即在提供一種橡膠改質苯乙烯系樹脂之製造方法,包含將72重量%至88重量%的苯乙烯系共聚物及12重量%至28重量%的橡膠粒子進行混煉處理,還包含一於混煉後的押出造粒處理,其中該苯乙烯系共聚物,包括一第一苯乙烯-丙烯腈系共聚物與一第二苯乙烯-丙烯腈系共聚物,該第一苯乙烯-丙烯腈系共聚物的重量平均分子量為5~10萬,該第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於該第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比係為1.4~3.5。 A third object of the present invention is to provide a method for producing a rubber-modified styrene-based resin comprising mixing 72% by weight to 88% by weight of a styrene-based copolymer and 12% by weight to 28% by weight of rubber particles. The refining treatment further comprises an extrusion granulation treatment after the kneading, wherein the styrene copolymer comprises a first styrene-acrylonitrile copolymer and a second styrene-acrylonitrile copolymer, The weight average molecular weight of the first styrene-acrylonitrile copolymer is from 50,000 to 100,000, and the weight average molecular weight of the second styrene-acrylonitrile copolymer is relative to the weight of the first styrene-acrylonitrile copolymer. The average molecular weight ratio is 1.4 to 3.5.
為了對本揭露內容之上述及其他方面有更佳的瞭解,下文特舉實施例,作詳細說明如下: In order to better understand the above and other aspects of the present disclosure, the following specific embodiments are described in detail below:
本揭露內容係有關於一種橡膠改質苯乙烯系樹脂,具有同時符合高流動性及高耐衝擊性的特性,並可維持其他的物性,而能夠符合業界的需求。 The present disclosure relates to a rubber-modified styrene-based resin which has characteristics of high fluidity and high impact resistance, and can maintain other physical properties, and can meet the needs of the industry.
以下將就本發明內容進行詳細說明: The contents of the present invention will be described in detail below:
《橡膠改質苯乙烯系樹脂》 "Rubber modified styrene resin"
根據本揭露之一實施例,一種橡膠改質苯乙烯系樹脂包括72重量%至88重量%的苯乙烯系共聚物以及12重量%至28重量%的橡膠粒子。較佳地,橡膠粒子的含量範圍為14重量%至25重量%;更佳地,橡膠粒子的含量範圍為18重量%至23重量%;最佳地,膠粒子的含量範圍為19重量%至22重量%。當苯乙烯系共聚物組分的含量小於72重量%時,會有流動性不足的缺 點;當苯乙烯系共聚物組分的含量大於88重量%時,會有衝擊強度不足的缺點。 According to an embodiment of the present disclosure, a rubber-modified styrenic resin includes 72% by weight to 88% by weight of a styrene-based copolymer and 12% by weight to 28% by weight of rubber particles. Preferably, the content of the rubber particles ranges from 14% by weight to 25% by weight; more preferably, the content of the rubber particles ranges from 18% by weight to 23% by weight; optimally, the content of the rubber particles ranges from 19% by weight to 22% by weight. When the content of the styrene-based copolymer component is less than 72% by weight, there is a lack of fluidity When the content of the styrene-based copolymer component is more than 88% by weight, there is a disadvantage that the impact strength is insufficient.
橡膠改質苯乙烯系樹脂包括由用以改質的橡膠聚合物(橡膠粒子)所形成的分散相及由苯乙烯系聚合物所形成的連續相,其中橡膠粒子分散在苯乙烯系聚合物內。所述橡膠改質苯乙烯系樹脂的製造方法例如但不限於:塊狀聚合法、溶液聚合法、塊狀懸濁聚合法等。例如橡膠改質苯乙烯系樹脂可以經由將芳族乙烯基單體(例如苯乙烯、α-甲基苯乙烯或對-甲基苯乙烯)和視需要添加之能夠與芳族乙烯基單體共聚合的共單體,使用習用方法(例如乳化聚合法)而接枝聚合在橡膠聚合物上而得到。 The rubber-modified styrene-based resin includes a dispersed phase formed of a rubber polymer (rubber particles) to be modified and a continuous phase formed of a styrene-based polymer in which rubber particles are dispersed in a styrene-based polymer. . The method for producing the rubber-modified styrene-based resin is, for example, but not limited to, a bulk polymerization method, a solution polymerization method, a bulk suspension polymerization method, or the like. For example, a rubber-modified styrenic resin can be copolymerized with an aromatic vinyl monomer via an aromatic vinyl monomer such as styrene, α -methylstyrene or p-methylstyrene, and optionally added. The polymerized comonomer is obtained by graft polymerization on a rubber polymer by a conventional method (for example, emulsion polymerization).
詳細而言,橡膠改質苯乙烯系樹脂可以由橡膠聚合物(固形份,例如是橡膠粒子)及苯乙烯系聚合物之單體組份經接枝聚合反應所製得,其中苯乙烯系聚合物之單體組份可包含苯乙烯系單體及丙烯腈系單體。接枝聚合反應中,選擇性地可添加乳化劑、聚合起始劑或鏈轉移劑等。 In detail, the rubber-modified styrene-based resin can be obtained by graft polymerization of a monomer component of a rubber polymer (solid content, for example, rubber particles) and a styrene-based polymer, wherein styrene polymerization is carried out. The monomer component of the material may comprise a styrene monomer and an acrylonitrile monomer. In the graft polymerization reaction, an emulsifier, a polymerization initiator or a chain transfer agent or the like may be optionally added.
橡膠粒子是由橡膠組份經乳化聚合法所獲得,以及選擇性於乳化聚合反應中添加其他可共聚合單體,且於乳化聚合反應後選擇地再進一步予以肥大處理。其他可共聚合單體包括但不限於苯乙烯、丙烯腈及(甲基)丙烯酸酯等。橡膠粒子包括二烯系橡膠、聚丙烯酸酯系橡膠或聚矽氧烷系橡膠。 The rubber particles are obtained by an emulsion polymerization method from the rubber component, and optionally other copolymerizable monomers are added to the emulsion polymerization reaction, and are further subjected to a hypertrophy treatment after the emulsion polymerization reaction. Other copolymerizable monomers include, but are not limited to, styrene, acrylonitrile, (meth) acrylate, and the like. The rubber particles include a diene rubber, a polyacrylate rubber, or a polyoxyalkylene rubber.
二烯系橡膠可單獨或混合使用,且二烯系橡膠包括但不限於丁二烯橡膠、異戊間二烯橡膠、氯丁二烯橡膠、苯乙烯-二烯系橡膠、丙烯腈橡膠等。 The diene rubber may be used singly or in combination, and the diene rubber includes, but not limited to, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-diene rubber, acrylonitrile rubber, and the like.
苯乙烯系單體可單獨或混合使用,且苯乙烯系單體 包括但不限於苯乙烯、α-甲基苯乙烯、α-氯苯乙烯、對-第三丁基苯乙烯、對-甲基苯乙烯、鄰-氯苯乙烯、對-氯苯乙烯、2,5-二氯苯乙烯、3,4-二氯苯乙烯、2,4,6-三氯苯乙烯或2,5-二溴苯乙烯等,其中苯乙烯系單體較佳為苯乙烯、α-甲基苯乙烯或此等一組合。 Styrene monomer can be used singly or in combination, and styrene monomer Including but not limited to styrene, α-methylstyrene, α-chlorostyrene, p-tert-butylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2, 5-Dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-trichlorostyrene or 2,5-dibromostyrene, etc., wherein the styrene monomer is preferably styrene or α. -methylstyrene or a combination of these.
丙烯腈系單體可單獨或混合使用,且丙烯腈系單體包括但不限於丙烯腈、α-甲基丙烯腈等,其中丙烯腈系單體較佳為丙烯腈。 The acrylonitrile-based monomer may be used singly or in combination, and the acrylonitrile-based monomer includes, but not limited to, acrylonitrile, α-methacrylonitrile, or the like, and the acrylonitrile-based monomer is preferably acrylonitrile.
橡膠改質苯乙烯系樹脂中的橡膠粒子的平均直徑較佳為0.1微米到2.0微米,更佳為0.1微米到1.0微米,又更佳為0.2微米到0.6微米。當橡膠粒子的平均直徑小於0.1微米時,橡膠改質苯乙烯系樹脂的耐衝擊性改良會無法令人滿意。當橡膠粒子的平均直徑超過2.0微米時,橡膠改質苯乙烯系樹脂的熔融流性和用該橡膠改質苯乙烯系樹脂製成的最終成形物件所具外觀會變得不良。 The rubber particles in the rubber-modified styrenic resin preferably have an average diameter of from 0.1 μm to 2.0 μm, more preferably from 0.1 μm to 1.0 μm, still more preferably from 0.2 μm to 0.6 μm. When the average diameter of the rubber particles is less than 0.1 μm, the improvement in impact resistance of the rubber-modified styrene-based resin may be unsatisfactory. When the average diameter of the rubber particles exceeds 2.0 μm, the melt flowability of the rubber-modified styrene-based resin and the appearance of the final molded article made of the rubber-modified styrene-based resin may become poor.
橡膠改質苯乙烯系樹脂的實例包括高耐衝擊性聚苯乙烯(High Impact Polystyrene,HIPS)樹脂、丙烯腈-丁二烯-苯乙烯共聚物(acrylonitrile-butadiene-styrene copolymer,ABS)、丙烯腈-丙烯酸系橡膠-苯乙烯共聚物(acrylonitrile-acrylate-styrene copolymer,AAS)、乳化聚合橡膠接枝共聚物(BP)、丙烯腈-乙烯-丙烯橡膠-苯乙烯共聚物(AES)或甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MS)。 Examples of the rubber-modified styrene-based resin include High Impact Polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS), and acrylonitrile. - Acrylonitrile-acrylate-styrene copolymer (AAS), emulsion polymerized rubber graft copolymer (BP), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES) or methacrylic acid Methyl ester-butadiene-styrene copolymer (MS).
在本實施方式中,橡膠改質苯乙烯系樹脂的具體實例包括丙烯腈-丁二烯-苯乙烯共聚物或乳化聚合橡膠接枝共聚物。 In the present embodiment, specific examples of the rubber-modified styrene-based resin include an acrylonitrile-butadiene-styrene copolymer or an emulsion polymerized rubber graft copolymer.
本發明橡膠改質苯乙烯系樹脂的製備可選擇性地加入添加劑或其他聚合物,即獲得本發明的橡膠改質苯乙烯系樹脂。其中,該添加劑例如但不限於抗氧化劑、可塑劑、加工助劑、紫外線安定劑、紫外線吸收劑、填充劑、強化劑、著色劑、滑劑、帶電防止劑、難燃劑、難燃助劑、熱安定劑、偶合劑等。該添加劑可分別在上述的聚合反應中、聚合反應後、凝結前,或上述添加劑可在進行押出混練處理,製備橡膠改質苯乙烯系樹脂的過程中添加。 The rubber modified styrene resin of the present invention can be selectively added with an additive or other polymer to obtain the rubber modified styrene resin of the present invention. Wherein, the additive is, for example but not limited to, an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, a UV absorber, a filler, a strengthening agent, a coloring agent, a lubricant, a charging inhibitor, a flame retardant, and a flame retardant , heat stabilizers, coupling agents, etc. The additive may be added during the above-mentioned polymerization reaction, after the polymerization reaction, before the coagulation, or during the process of preparing the rubber-modified styrene resin by performing the extrusion kneading treatment.
該抗氧化劑可單獨或混合使用,該抗氧化劑例如但不限於酚系抗氧化劑、硫醚系抗氧化劑,或磷系抗氧化劑等。較佳地,以該橡膠改質苯乙烯系樹脂的總量為100重量份計,該抗氧化劑的用量範圍為2重量份以下。 The antioxidant may be used singly or in combination, and the antioxidant is, for example but not limited to, a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based antioxidant. Preferably, the antioxidant is used in an amount of 2 parts by weight or less based on 100 parts by weight of the total of the rubber-modified styrene resin.
該酚系抗氧化劑可單獨或混合使用,該酚系抗氧化劑例如但不限於3,5-雙(1,1-二甲基乙基)-4-羥基苯基丙酸十八烷基酯(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester,型號:抗氧化劑IX-1076)、三乙二醇雙[3-(3-第三丁基-5-甲基-4-羥苯基)丙酸酯]、四[甲撐基-3-(3,5-雙第三丁基-4-羥苯基)丙酸酯]甲烷、2-第三丁基-6-(3-第三丁基-2-羥基-6-甲基苯甲基)-4-甲基苯基丙烯酸酯、2,2'-甲撐基-雙(4-甲基-6-第三丁基酚)(2,2'-methylenebis(4-methyl-6-tert-butylphenol),型號:抗氧化劑2246)、2,2'-硫雙(4-甲基-6-第三丁基酚)、2,2'-硫代-二乙撐基-雙[3-(3,5-雙第三丁基-4-羥苯基)丙酸酯],或2,2'-乙二醯胺-雙[乙基-3-(3,5-雙-第三丁基-4-羥苯基)丙酸酯]等。 The phenolic antioxidant may be used singly or in combination, and the phenolic antioxidant is, for example but not limited to, octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate ( 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, model: antioxidant IX-1076), triethylene glycol bis[3-(3-tert-butyl-5-methyl- 4-hydroxyphenyl)propionate], tetrakis[methylene-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-6 -(3-t-butyl-2-hydroxy-6-methylbenzyl)-4-methylphenyl acrylate, 2,2'-methylene-bis(4-methyl-6- Tributylphenol) (2,2'-methylenebis(4-methyl-6-tert-butylphenol), type: antioxidant 2246), 2,2'-thiobis(4-methyl-6-t-butyl Phenol), 2,2'-thio-diethylene-bis[3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate], or 2,2'-ethane Indoleamine-bis[ethyl-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate].
該硫醚系抗氧化劑可單獨或混合使用,該硫醚系抗 氧化劑例如但不限於二硬脂醯硫二丙酸酯、二棕櫚醯硫二丙酸酯、五赤蘚醇-四-(β-十二甲基-硫丙酸酯),或雙十八烷基硫醚等。 The thioether-based antioxidant may be used singly or in combination, and the thioether-based antioxidant is, for example but not limited to, distearyl thiodipropionate, dipalmitosulfur dipropionate, pentaerythritol-tetra-( β - dodecamethyl-thiopropionate), or dioctadecyl sulfide, and the like.
該磷系抗氧化劑可單獨或混合使用,該磷系抗氧化劑是擇自於含亞磷酸酯的磷系抗氧化劑、或含磷酸酯的磷系抗氧化劑或上述的一組合。該含亞磷酸酯的磷系抗氧化劑例如但不限於三(壬基苯基)亞磷酸酯、十二烷基亞磷酸酯、4,4'-亞丁基雙(3-甲基-6-第三丁基苯基-雙十三烷基亞磷酸酯)、三(2,4-第三丁基苯基)亞磷酸酯等。該含磷酸酯的磷系抗氧化劑例如但不限於四(2,4-第三丁基苯基)-4,4'-伸聯苯基磷酸酯,或9,10-二氫-9-氧-10-磷酸菲-10-氧撐等。 The phosphorus-based antioxidant may be used singly or in combination, and the phosphorus-based antioxidant is selected from a phosphite-containing phosphorus-based antioxidant or a phosphate-containing phosphorus-based antioxidant or a combination thereof. The phosphite-containing phosphorus-based antioxidants such as, but not limited to, tris(nonylphenyl) phosphite, dodecyl phosphite, 4,4'-butylene bis(3-methyl-6- Tributylphenyl-bistridecylphosphite), tris(2,4-t-butylphenyl)phosphite, and the like. The phosphate-containing phosphorus-based antioxidant such as, but not limited to, tetrakis(2,4-t-butylphenyl)-4,4'-extended biphenyl phosphate, or 9,10-dihydro-9-oxygen -10-phosphate phenoxy-10-oxygen and the like.
該滑劑可單獨或混合使用,該滑劑例如但不限於硬脂酸鈣、硬脂酸鎂、硬脂酸鋰等的金屬肥皂、乙撐二硬脂醯胺(ethylene bis-stearamide,簡稱EBA)、甲撐二硬脂醯胺、棕櫚酸醯胺、硬脂酸丁酯、硬脂酸棕櫚酯、季戊四醇四脂肪酸酯、聚丙酸醇三硬脂酸酯、正二十二烷酸、硬脂酸等的化合物、聚乙烯蠟、二十八烷酸蠟、巴西棕櫚蠟(carnuba wax)、石油蠟等。較佳地,以該橡膠改質苯乙烯系樹脂的總量為100重量份計,該滑劑的用量範圍為2重量份以下。 The slip agent may be used singly or in combination, and the slip agent is, for example, but not limited to, metal soap such as calcium stearate, magnesium stearate, lithium stearate, or ethylene bis-stearamide (EBA). ), methylene distearylamine, palmitic acid decylamine, butyl stearate, palmitate stearate, pentaerythritol tetra-fatty acid ester, polypropionic acid tristearate, n-docosanoic acid, hard A compound such as a fatty acid, a polyethylene wax, a octadecanoic acid wax, a carnuba wax, a petroleum wax or the like. Preferably, the amount of the slip agent is in the range of 2 parts by weight or less based on 100 parts by weight of the total of the rubber-modified styrene resin.
該其他聚合物例如但不限於聚碳酸酯、聚醯胺、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚伸苯基醚、聚氯乙烯、聚甲基丙烯酸甲酯、乙烯-甲基丙烯酸甲酯共聚物、聚丙烯、苯乙烯-丁二烯塊狀共聚物、氫化丙烯腈-丁二烯共聚物、氫化苯乙烯-丁二烯塊狀共聚物等。較佳地,以該橡膠改質苯乙烯系樹脂的總量為100重量份計,該聚合物的用量範圍為5重量份至200 重量份。本發明橡膠改質苯乙烯系樹脂的成型品,是由一如上所述的橡膠改質苯乙烯系樹脂經加工成型處理所製得。該加工成型處理可採用以往習知的方式,故不再贅述。 The other polymer is, for example but not limited to, polycarbonate, polyamine, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyvinyl chloride, polymethyl methacrylate , ethylene-methyl methacrylate copolymer, polypropylene, styrene-butadiene block copolymer, hydrogenated acrylonitrile-butadiene copolymer, hydrogenated styrene-butadiene block copolymer, and the like. Preferably, the polymer is used in an amount ranging from 5 parts by weight to 200 parts by weight based on 100 parts by weight of the total of the rubber-modified styrene resin. Parts by weight. The molded article of the rubber-modified styrene-based resin of the present invention is obtained by subjecting a rubber-modified styrene-based resin as described above to a processing and molding process. This processing and molding process can be carried out in a conventional manner and will not be described again.
以下分別進一步地說明本發明橡膠改質苯乙烯系樹脂中的苯乙烯系共聚物及橡膠粒子: Hereinafter, the styrene-based copolymer and the rubber particles in the rubber-modified styrene-based resin of the present invention will be further described:
<苯乙烯系共聚物> <styrene copolymer>
苯乙烯系共聚物包括一第一苯乙烯-丙烯腈系共聚物與一第二苯乙烯-丙烯腈系共聚物,第一苯乙烯-丙烯腈系共聚物的重量平均分子量為5~10萬,第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比係為1.4~3.5。 The styrene-based copolymer comprises a first styrene-acrylonitrile copolymer and a second styrene-acrylonitrile copolymer, and the first styrene-acrylonitrile copolymer has a weight average molecular weight of 50,000 to 100,000. The ratio of the weight average molecular weight of the second styrene-acrylonitrile-based copolymer to the weight average molecular weight of the first styrene-acrylonitrile-based copolymer is from 1.4 to 3.5.
該苯乙烯系共聚物的第一苯乙烯-丙烯腈系共聚物與第二苯乙烯-丙烯腈系共聚物分別包括苯乙烯系單體單元及丙烯腈系單體單元,且選擇性的添加其他可共聚合的乙烯系單體的混合物經聚合反應所形成。 The first styrene-acrylonitrile copolymer and the second styrene-acrylonitrile copolymer of the styrene copolymer each include a styrene monomer unit and an acrylonitrile monomer unit, and are selectively added to other monomers. A mixture of copolymerizable vinyl monomers is formed by polymerization.
於一實施例中,第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比例如是1.5~2.5。 In one embodiment, the ratio of the weight average molecular weight of the second styrene-acrylonitrile-based copolymer to the weight average molecular weight of the first styrene-acrylonitrile-based copolymer is, for example, 1.5 to 2.5.
於另一實施例中,第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比例如是1.5~2.0。 In another embodiment, the ratio of the weight average molecular weight of the second styrene-acrylonitrile-based copolymer to the weight average molecular weight of the first styrene-acrylonitrile-based copolymer is, for example, 1.5 to 2.0.
於一實施例中,第二苯乙烯-丙烯腈系共聚物相對於第一苯乙烯-丙烯腈系共聚物的重量比例如是10/90~17/83。 In one embodiment, the weight ratio of the second styrene-acrylonitrile-based copolymer to the first styrene-acrylonitrile-based copolymer is, for example, 10/90 to 17/83.
於另一實施例中,第二苯乙烯-丙烯腈系共聚物相對 於第一苯乙烯-丙烯腈系共聚物的重量比例如是10/90~15/85。 In another embodiment, the second styrene-acrylonitrile copolymer is relatively The weight ratio of the first styrene-acrylonitrile-based copolymer is, for example, 10/90 to 15/85.
於一實施例中,第一苯乙烯-丙烯腈系共聚物可包括例如20重量%至38重量%的丙烯腈系單體單元,第二苯乙烯-丙烯腈系共聚物可包括例如20重量%至38重量%的丙烯腈系單體單元。 In one embodiment, the first styrene-acrylonitrile-based copolymer may include, for example, 20% by weight to 38% by weight of the acrylic monomer unit, and the second styrene-acrylonitrile-based copolymer may include, for example, 20% by weight. Up to 38% by weight of an acrylic monomer unit.
於另一實施例中,第一苯乙烯-丙烯腈系共聚物可包括例如25重量%至35重量%的丙烯腈系單體單元,第二苯乙烯-丙烯腈系共聚物可包括例如25重量%至35重量%的丙烯腈系單體單元。 In another embodiment, the first styrene-acrylonitrile-based copolymer may include, for example, 25% by weight to 35% by weight of the acrylic monomer unit, and the second styrene-acrylonitrile-based copolymer may include, for example, 25 parts by weight. % to 35% by weight of an acrylic monomer unit.
<橡膠粒子> <Rubber Particles>
該種橡膠改質苯乙烯系樹脂包括72重量%至88重量%的苯乙烯系共聚物以及12重量%至28重量%的橡膠粒子;較佳地,橡膠粒子的含量範圍為14重量%至25重量%;更佳地,橡膠粒子的含量範圍為18重量%至23重量%;最佳地,膠粒子的含量範圍為19重量%至22重量%。 The rubber-modified styrenic resin comprises 72% by weight to 88% by weight of a styrene-based copolymer and 12% by weight to 28% by weight of rubber particles; preferably, the content of the rubber particles ranges from 14% by weight to 25% More preferably, the content of the rubber particles ranges from 18% by weight to 23% by weight; optimally, the content of the gel particles ranges from 19% by weight to 22% by weight.
該橡膠粒子平均直徑較佳為0.1微米到2.0微米,更佳為0.1微米到1.0微米,又更佳為0.2微米到0.6微米。 The rubber particles preferably have an average diameter of from 0.1 μm to 2.0 μm, more preferably from 0.1 μm to 1.0 μm, still more preferably from 0.2 μm to 0.6 μm.
《製備橡膠改質苯乙烯系樹脂的方法》 "Method for preparing rubber modified styrene resin"
在本實施方式中的橡膠改質苯乙烯系樹脂組成物的製備方法並無特別的限制,可採用一般的混合方法,例如將前述苯乙烯系共聚物與橡膠粒子均勻混合而得,或者是由第一苯乙烯-丙烯腈系共聚物與第二苯乙烯-丙烯腈系共聚物以及橡膠粒子均勻混合而得。所述一般的混合方法包括:以一般使用的漢歇爾混合機乾混後,再以諸如押出混合機、捏合機或班伯立混練機等的 混合機熔融混合。 The method for preparing the rubber-modified styrene resin composition in the present embodiment is not particularly limited, and a general mixing method such as uniform mixing of the styrene-based copolymer and rubber particles may be employed, or The first styrene-acrylonitrile-based copolymer is obtained by uniformly mixing the second styrene-acrylonitrile-based copolymer and the rubber particles. The general mixing method includes: dry mixing with a commonly used Hanschel mixer, and then, for example, an extrusion mixer, a kneading machine, or a Banbury mixer. The mixer melts and mixes.
以下係詳細敘述實施例中相關成份之內容及可應用之製備方法。然而需注意的是,實施例所提出的內容僅為舉例說明之用,本揭露欲保護之範圍並非僅限於所述之該些態樣。本揭露並非顯示出所有可能的實施例。可在不脫離本揭露之精神和範圍內對結構加以變化與修飾,以符合實際應用所需,所以未於本揭露提出的其他實施態樣也可能可以應用。因此,說明書內容僅作敘述實施例之用,而非作為限縮本揭露保護範圍之用。 The contents of the relevant components in the examples and the applicable preparation methods are described in detail below. However, it should be noted that the contents of the embodiments are for illustrative purposes only, and the scope of the disclosure is not limited to the described aspects. This disclosure does not show all possible embodiments. Other variations and modifications may be made to the structure without departing from the spirit and scope of the disclosure, so that other embodiments not disclosed in the present disclosure may be applied. Therefore, the description of the specification is for illustrative purposes only and is not intended to limit the scope of the disclosure.
以下係說明橡膠粒子的製備方法。 The following describes the preparation method of the rubber particles.
(1)將150.00重量份的1,3-丁二烯、15.00重量份的過硫酸鉀溶液(濃度1wt%)、2.00重量份的油酸鉀、0.13重量份的乙二醇二甲基丙烯酸酯及190.00重量份的蒸餾水在65℃的反應溫度下反應14小時,以得到重量平均粒徑為0.1微米(μm)的二烯系橡膠乳液(轉化率約94%,固體含量約36%)。 (1) 150.00 parts by weight of 1,3-butadiene, 15.00 parts by weight of potassium persulfate solution (concentration: 1% by weight), 2.00 parts by weight of potassium oleate, 0.13 parts by weight of ethylene glycol dimethacrylate And 190.00 parts by weight of distilled water was reacted at a reaction temperature of 65 ° C for 14 hours to obtain a diene rubber emulsion having a weight average particle diameter of 0.1 μm (conversion ratio of about 94%, solid content of about 36%).
(2)將90.00重量份的丙烯酸正丁酯、10.00重量份的甲基丙烯酸、0.50重量份的過硫酸鉀溶液(濃度1wt%)、0.50重量份的十二烷基硫酸鈉溶液(濃度10wt%)、1.00重量份的正-十二烷基硫醇及200.00重量份的蒸餾水在75℃反應溫度下反應5小時,得到轉化率約95%、pH值6.0的含羧酸基的高分子凝集劑乳液。 (2) 90.00 parts by weight of n-butyl acrylate, 10.00 parts by weight of methacrylic acid, 0.50 parts by weight of potassium persulfate solution (concentration: 1% by weight), 0.50 parts by weight of sodium lauryl sulfate solution (concentration: 10% by weight) 1.00 parts by weight of n-dodecyl mercaptan and 200.00 parts by weight of distilled water were reacted at a reaction temperature of 75 ° C for 5 hours to obtain a carboxylic acid group-containing polymer flocculant having a conversion of about 95% and a pH of 6.0. Emulsion.
(3)之後,利用3重量份(乾重)的含羧酸基的高分子凝集劑來肥大100重量份的二烯系橡膠膠乳,所得到的橡膠乳液的pH值為8.5,而其橡膠重量平均粒徑約為0.3微米(μm)。 (3) Thereafter, by using 3 parts by weight (dry weight) of a carboxylic acid group-containing polymer flocculant to 100 parts by weight of the diene rubber latex, the obtained rubber emulsion has a pH of 8.5 and its rubber weight The average particle size is about 0.3 micrometers (μm).
(4)再以300.0重量份的前述肥大化橡膠乳液(乾 重)、75.0重量份的苯乙烯、25.0重量份的丙烯腈、2.0重量份的第三-十二烷基硫醇、3.0重量份的異丙苯過氧化氫、3.0重量份的硫酸亞鐵溶液(濃度0.2wt%)、0.9重量份的甲醛化次硫酸鈉溶液(濃度10wt%)及3.0重量份的乙二胺四醋酸溶液(濃度0.25wt%),將前述肥大化的橡膠乳液以苯乙烯丙烯腈共聚物進行接枝聚合反應,以製造二烯系橡膠接枝共聚物。所製得的二烯系橡膠接枝共聚物乳液以氯化鈣凝結,再經脫水、乾燥至2%以下,即可製得所需的橡膠粒子(其成分為二烯系橡膠接枝共聚物),其重量平均粒徑為0.31微米(μm),橡膠含量為75重量%。 (4) further 300.0 parts by weight of the aforementioned hyperplasticized rubber emulsion (dry Heavy), 75.0 parts by weight of styrene, 25.0 parts by weight of acrylonitrile, 2.0 parts by weight of tert-dodecyl mercaptan, 3.0 parts by weight of cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration: 0.2 wt%), 0.9 parts by weight of a sodium formaldehyde sulfoxylate solution (concentration: 10% by weight), and 3.0 parts by weight of an ethylenediaminetetraacetic acid solution (concentration: 0.25 wt%), and the above-mentioned hypertrophized rubber emulsion was styrene. The acrylonitrile copolymer is subjected to graft polymerization to produce a diene rubber graft copolymer. The prepared diene rubber graft copolymer emulsion is coagulated with calcium chloride, and then dehydrated and dried to less than 2% to obtain desired rubber particles (the composition of which is a diene rubber graft copolymer) The weight average particle diameter was 0.31 micrometer (μm) and the rubber content was 75% by weight.
以下表1列出實施例與比較例所採用的苯乙烯-丙烯腈系共聚物之代號、丙烯腈系單體單元佔苯乙烯-丙烯腈系共聚物的重量百分比(AN/AS)、及重量平均分子量。 Table 1 below lists the code of the styrene-acrylonitrile-based copolymer used in the examples and the comparative examples, the weight percentage (AN/AS) of the acrylonitrile-based monomer unit to the styrene-acrylonitrile-based copolymer, and the weight. Average molecular weight.
以下係說明表1之各個苯乙烯-丙烯腈系共聚物的製備方法。 Hereinafter, the preparation method of each styrene-acrylonitrile-based copolymer of Table 1 will be described.
<PN-127-04> <PN-127-04>
將68重量份的苯乙烯、32重量份的丙烯腈、8重量份的乙苯混合後,再以0.01重量份的第三-十二烷基硫醇予以混合,並以35kg/hr的流量連續供給至完全混合連續式反應器內,其中所述反應器的容積為40公升,內溫分別保持為145℃,壓力保持為4kg/cm2,整體轉換率約為55%。在聚合終了後,將所得的共聚物溶液以預熱器加熱,並以減壓脫氣槽將未反應的單體及溶劑等的揮發性物質除去。接著,將所得的聚合熔融物押出造粒即得到代號為PN-127-04的苯乙烯-丙烯腈系共聚物,其重量平均分子量為21萬,且其中苯乙烯單體單元含量為72%、丙烯腈單體單元含量為28%。 68 parts by weight of styrene, 32 parts by weight of acrylonitrile, and 8 parts by weight of ethylbenzene were mixed, and then mixed with 0.01 part by weight of the third-dodecylmercaptan, and continuously flowed at a flow rate of 35 kg/hr. It was supplied to a fully mixed continuous reactor in which the volume of the reactor was 40 liters, the internal temperature was maintained at 145 ° C, the pressure was maintained at 4 kg/cm 2 , and the overall conversion rate was about 55%. After the completion of the polymerization, the obtained copolymer solution was heated by a preheater, and volatile substances such as unreacted monomers and solvents were removed in a vacuum degassing tank. Next, the obtained polymer melt was subjected to granulation to obtain a styrene-acrylonitrile-based copolymer code-named PN-127-04 having a weight average molecular weight of 210,000 and a styrene monomer unit content of 72%. The acrylonitrile monomer unit content was 28%.
其餘苯乙烯-丙烯腈系共聚物的製備方法同上述,其中各原料入料比與反應後單體單元含量列表入下。 The remaining styrene-acrylonitrile-based copolymer is prepared in the same manner as described above, wherein each raw material feed ratio and post-reaction monomer unit content are listed.
<製作橡膠改質苯乙烯系樹脂> <Making rubber modified styrene resin>
以下係列出本揭露其中幾組相關實驗(包括比較例和實施例)並對其進行相關之物性測試,以作說明。各組實驗之實施例和比較例的成份內容與物性測試結果一併紀錄於表1中。 The following series discloses several sets of related experiments (including comparative examples and examples) and carries out related physical property tests for illustration. The composition contents and physical property test results of the examples and comparative examples of each group of experiments are recorded in Table 1.
以實施例1-1為例作說明。 The embodiment 1-1 is taken as an example for illustration.
實施例1-1是依據表3所列各組分的用量,將橡膠粒子、第一苯乙烯-丙烯腈系共聚物和第二苯乙烯-丙烯腈系共聚物混合形成一樹脂混合物,並以該樹脂混合物的總量為100重量 份計,添加2重量份的乙烯基雙硬脂醯胺,以及1.5重量份的3,5-雙(1,1-二甲基乙基)-4-羥基苯基丙酸十八烷基酯(3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester,型號:IX-1076),形成一共聚物混合物。再以押出機(廠商型號:Werner & Pfleidrer ZSK 35)於235℃將該共聚物混合物混合押出造粒,即製得本發明橡膠改質苯乙烯系樹脂。接著,將橡膠改質苯乙烯系樹脂以射出成型機(廠商型號:震雄公司SM-90)於230℃射出試片後,即獲得本發明橡膠改質苯乙烯系樹脂的成型品,其分析及物性評價結果見表3。 In the embodiment 1-1, the rubber particles, the first styrene-acrylonitrile copolymer and the second styrene-acrylonitrile copolymer are mixed to form a resin mixture according to the amounts of the components listed in Table 3. The total amount of the resin mixture is 100 weight 2 parts by weight of vinylbisstearylamine, and 1.5 parts by weight of octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate (3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, model: IX-1076), forming a copolymer mixture. Further, the copolymer mixture was mixed and granulated at 235 ° C by an extruder (manufacturer model: Werner & Pfleidrer ZSK 35) to obtain a rubber-modified styrene-based resin of the present invention. Next, the rubber-modified styrene-based resin was extruded into a test piece at 230 ° C in an injection molding machine (manufacturer model: Zhenxiong SM-90) to obtain a molded article of the rubber-modified styrene-based resin of the present invention, and the analysis thereof was carried out. The results of the physical property evaluation are shown in Table 3.
其餘比較例和實施例請參照上述,在此不贅述。 For the rest of the comparative examples and examples, please refer to the above, and details are not described herein.
<橡膠改質苯乙烯系樹脂的物性測試> <Physical property test of rubber modified styrene resin>
實驗中係對比較例和實施例之樹脂進行多種物性測試,內容說明如下。 In the experiment, various physical properties of the resins of the comparative examples and the examples were tested, and the contents are as follows.
(1)熔融流動指數(MVR):依ASTM D-1238規定,以220℃×10kg測試(單位:cm3/10min)。 (1) Melt Flow Index (MVR): Tested at 220 ° C × 10 kg (unit: cm 3 /10 min) in accordance with ASTM D-1238.
(2)耐衝擊性強度測試(Charpy):依ISO 180法測定,在23℃下使用附有缺口(Notched,開口深度為2毫米(mm))之80mm×10mm×4mm試驗片量測(單位,kJ/m2)。在本測試中,測量值越高表示評價較好。依據應用產品之需求,耐衝擊性強度較佳為>20kJ/m2。 (2) Impact resistance test (Charpy): measured by ISO 180 method, using a notched (Notched, opening depth of 2 mm (mm)) 80 mm × 10 mm × 4 mm test piece at 23 ° C (unit , kJ/m 2 ). In this test, the higher the measured value, the better the evaluation. The impact strength is preferably >20 kJ/m 2 depending on the requirements of the application product.
(3)抗張強度(Tsy):依ASTM D-638標準方法測試,以50mm/min速度測定,單位為MPa。 (3) Tensile strength (Tsy): Tested according to ASTM D-638 standard method, measured at a speed of 50 mm/min, and the unit is MPa.
(4)斷裂拉伸強度(Tsb):依ASTM D-638標準方法測試,以50mm/min速度測定,單位為MPa。 (4) Tensile strength at break (Tsb): Tested according to ASTM D-638 standard method, measured at a speed of 50 mm/min, and the unit is MPa.
(5)伸長率(EL):依ASTM D-638規定測試,以50mm/min速度測定,單位為%。 (5) Elongation (EL): Tested in accordance with ASTM D-638, measured at a speed of 50 mm/min, in %.
(6)SP_50℃/hr10N:採用ASTM-D1525的標準手法進行量測。 (6) SP_50 ° C / hr 10 N: measured by the standard method of ASTM-D1525.
各比較例和實施例之結果,請參照表3~表8。其中,AS1表示第一苯乙烯-丙烯腈系共聚物,AS2表示第二苯乙烯-丙烯腈系共聚物,AS2/AS1表示第二苯乙烯-丙烯腈系共聚物相對於第一苯乙烯-丙烯腈系共聚物的重量比,AS2/AS1(分子量)表示第二苯乙烯-丙烯腈系共聚物的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物的重量平均分子量之比,RC表示橡膠粒子佔整體橡膠改質苯乙烯系樹脂之含量。 For the results of the respective comparative examples and examples, please refer to Tables 3 to 8. Wherein AS1 represents a first styrene-acrylonitrile copolymer, AS2 represents a second styrene-acrylonitrile copolymer, and AS2/AS1 represents a second styrene-acrylonitrile copolymer relative to the first styrene-propylene. The weight ratio of the nitrile copolymer, AS2/AS1 (molecular weight), represents the ratio of the weight average molecular weight of the second styrene-acrylonitrile copolymer to the weight average molecular weight of the first styrene-acrylonitrile copolymer, and RC represents The rubber particles account for the content of the overall rubber modified styrene resin.
如表3所示。當橡膠粒子佔橡膠改質苯乙烯系樹脂的含量為12重量%至28重量%時,則耐衝擊性指數及熔融流動指數均大於20、且兩者之總和均大於55,且其他物性均符合業界需求,顯示實施例1-1~1-5之橡膠改質苯乙烯系樹脂具有同時符合高流動性及高耐衝擊性的特性。 as shown in Table 3. When the content of the rubber-modified styrene resin is from 12% by weight to 28% by weight, the impact resistance index and the melt flow index are both greater than 20, and the sum of the two is greater than 55, and other physical properties are consistent. According to the industry demand, the rubber-modified styrene-based resins of Examples 1-1 to 1-5 have characteristics of high fluidity and high impact resistance.
如表4~5所示,相較於實施例2-1~2-5,比較例2-1~2-2之樣品中,第二苯乙烯-丙烯腈系共聚物(AS2)的重量平均分子量相對於第一苯乙烯-丙烯腈系共聚物(AS1)的重量平均分子量之比均為小於1.4或大於3.5,而比較例2-3根本不具有第二苯乙烯-丙烯腈系共聚物(AS2),比較例2-4根本不具有第一苯乙烯-丙烯腈系共聚物(AS1)。當AS2/AS1之重量平均分子量比小於1.4時,則熔融流動指數小於20,顯示其流動性不佳;而AS2/AS1之重量平均分子量比大於3.5時,耐衝擊性則不佳。當AS2/AS1之重量平均分子量比例如是1.4~3.5時,則耐衝擊性指數及熔融流動指數均大於20、且兩者之總和均大於55,且其他物性均符合業界需求,顯示實施例2-1~2-5之橡膠改質苯乙烯系樹脂具有同時符合高流動性及高耐衝擊性的特性。 As shown in Tables 4 to 5, the weight average of the second styrene-acrylonitrile copolymer (AS2) in the samples of Comparative Examples 2-1 to 2-2 compared with Examples 2-1 to 2-5. The ratio of the molecular weight to the weight average molecular weight of the first styrene-acrylonitrile-based copolymer (AS1) was less than 1.4 or more than 3.5, while Comparative Example 2-3 did not have the second styrene-acrylonitrile-based copolymer at all ( AS 2), Comparative Example 2-4 did not have the first styrene-acrylonitrile copolymer (AS1) at all. When the weight average molecular weight ratio of AS2/AS1 is less than 1.4, the melt flow index is less than 20, indicating that the fluidity is not good; and when the weight average molecular weight ratio of AS2/AS1 is more than 3.5, the impact resistance is not good. When the weight average molecular weight ratio of AS2/AS1 is, for example, 1.4 to 3.5, the impact resistance index and the melt flow index are both greater than 20, and the sum of the two is greater than 55, and other physical properties are in line with the needs of the industry. The rubber modified styrene resin of 1~2-5 has the characteristics of high fluidity and high impact resistance at the same time.
如表6所示,當AS2/AS1之含量比例如是10/90~17/83時,則耐衝擊性指數及熔融流動指數均大於20、且 兩者之總和均大於55,且其他物性均符合業界需求,顯示實施例3-1~3-4之橡膠改質苯乙烯系樹脂具有同時符合高流動性及高耐衝擊性的特性。 As shown in Table 6, when the content ratio of AS2/AS1 is, for example, 10/90 to 17/83, the impact resistance index and the melt flow index are both greater than 20, and The sum of the two is greater than 55, and other physical properties are in line with the needs of the industry. The rubber modified styrene resin of Examples 3-1 to 3-4 has the characteristics of high fluidity and high impact resistance.
如表7~8所示,當AN/AS(丙烯腈系單體單元佔苯乙烯-丙烯腈系共聚物的重量百分比)例如是26重量%至35重量%時,則耐衝擊性指數及熔融流動指數均大於20、且兩者之總和均大於55,且其他物性均符合業界需求,顯示實施例4-1~4-6之橡膠改質苯乙烯系樹脂具有同時符合高流動性及高耐衝擊性的特性。 As shown in Tables 7 to 8, when AN/AS (the weight percentage of the acrylonitrile-based monomer unit to the styrene-acrylonitrile-based copolymer) is, for example, 26% by weight to 35% by weight, the impact resistance index and melting The flow index is greater than 20, and the sum of the two is greater than 55, and other physical properties are in line with the needs of the industry. It is shown that the rubber modified styrene resin of Examples 4-1 to 4-6 has high fluidity and high resistance at the same time. Impact characteristics.
綜上所述,雖然本發明已以實施例揭露如上,然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。因此,本發明之保護範圍當視後附之申請專利範圍所界定者為準。 In conclusion, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.
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