JPH0511142B2 - - Google Patents
Info
- Publication number
- JPH0511142B2 JPH0511142B2 JP60023529A JP2352985A JPH0511142B2 JP H0511142 B2 JPH0511142 B2 JP H0511142B2 JP 60023529 A JP60023529 A JP 60023529A JP 2352985 A JP2352985 A JP 2352985A JP H0511142 B2 JPH0511142 B2 JP H0511142B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- modified polystyrene
- polydimethylsiloxane
- higher fatty
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004793 Polystyrene Substances 0.000 claims description 32
- 229920002223 polystyrene Polymers 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 29
- -1 Polydimethylsiloxane Polymers 0.000 claims description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 description 15
- 230000007423 decrease Effects 0.000 description 9
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000005060 rubber Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- MWKGOHCHXBLCSH-UHFFFAOYSA-L [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O MWKGOHCHXBLCSH-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- VMPHSYLJUKZBJJ-UHFFFAOYSA-N lauric acid triglyceride Natural products CCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC VMPHSYLJUKZBJJ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Description
（産業上の利用分野）
本発明は、優れた品質総合バランスを有する改
良されたゴム変性ポリスチレン組成物に関するも
のである。
例えば、ゴム変性ポリスチレンは、家庭電機製
品の部品などに多く用いられているが、従来
ABS樹脂に比して、衝撃強度に劣り、成形品表
面の光沢も低いという欠点を有していた。最近、
ABS樹脂の特性に近づいた改良されたゴム変性
ポリスチレンの出現の要望が、コストダウン、薄
肉化志向により、市場から強まつてきている。
本発明の樹脂組成物は、衝撃強度、光沢、引張
強度及び耐熱の優れた品質総合バランスが、射出
成形品、押出シート、押出真空成形品等にて発現
される。高価なABS樹脂からの代替、製品薄肉
化が可能となり、コストダウンを計れる経済的な
樹脂としての価値は大である。
（従来の技術）
ゴム変性ポリスチレンは、従来から工業的に多
く用いられているが、その分散ゴム粒子径は、一
般に1.0〜5.0ミクロン（μ）程度であり、1.0μ以
下の小さいゴム粒子径の場合には、好ましい樹脂
が得られていない。また、ゴム変性スチレン系樹
脂と、有機ポリシロキサンからなる樹脂組成物
は、Modern Plastics 1972年11月号114〜116ペ
ージ、プラスチツクス・エージ1974年20巻５月号
107ページ、特開昭55−3494号公報、特開昭53−
124561号公報、特開昭57−187345号公報、特開昭
57−187346号公報などの先行文献に述べられてい
るが、ゴム粒子径の小さいゴム変性ポリスチレン
を用いた場合には好ましい樹脂組成物が得られて
いない。また、ゴム変性スチレン系樹脂に高級脂
肪酸の亜鉛塩を多量に添加し、離型性を高めるこ
とは一般によく知られているが、衝撃強度を高め
る発現はなされていない。
（発明が解決しようとする問題点）
先に述べた、優れた品質総合バランスを有する
改良されたゴム変性ポリスチレンに対する市場の
要望に合致するには、衝撃強度、光沢、引張強度
及び耐熱の品質バランスの優れた改良されたゴム
変性ポリスチレンが必要となる。上記する衝撃強
度、光沢、引張強度、耐熱の品質バランスの優れ
た安価な改良されたゴム変性ポリスチレンを得る
ことが本発明の目的である。
（問題点を解決するための手段）
本発明は、従来技術では一般的でない特定のミ
クロ構造を有するゴム変性ポリスチレンと、有機
ポリシロキサンの中でも特定のポリジメチルシロ
キサン及び高級脂肪酸金属塩の中でもステアリン
酸亜鉛に代表される特定の高級脂肪酸亜鉛塩より
なる。
即ち、本発明は、ゴム重合体が粒子状に分散し
ているゴム変性ポリスチレン組成物において
(A) 分散粒子の平均粒子が0.20〜1.00ミクロンの
範囲にあり
(B) 該組成物中にポリジメチルシロキサンが
0.005〜0.8重量％と
(C) 高級脂肪酸の亜鉛塩が0.01〜１重量％含有さ
れているゴム変性ポリスチレンである。要件(A)
(B)(C)の全てを組み合せることによつてはじめ
て、驚くべきことに、非常に品質総合バランス
が優れた改良されたゴム変性ポリスチレン組成
物を得ることに成功したものである。
本発明に用いるゴム変性ポリスチレンは、ゴム
状重合体の存在下に芳香族モノビニル単量体を重
合せしめる塊状重合法又は塊状懸濁重合法にて製
造することができる。本発明に特定された特殊な
ミクロ構造を有するゴム変性ポリスチレンは、重
合工程における撹拌の状態、ゴム粒子生成時の混
合状態などをコントロールすることにより製造す
ることができる。芳香族モノビニル単量体として
は、スチレン及びｏ−メチルスチレン、ｐ−メチ
ルスチレン、ｍ−メチルスチレン、２，４−ジメ
チルスチレン、エチルスチレン、ｐ−tert−ブチ
ルスチレン等の核アルキル置換スチレン、α−メ
チルスチレン、α−メチル−ｐ−メチルスチレン
等のα−アルキル置換スチレンなどが用いられ
る。また、ゴム状重合体としては、ポリブタジエ
ン、スチレン−ブタジエン共重合体等であり、ポ
リブタジエンとしてはシス含有量の高いハイシス
ポリブタジエン、シス含有量の低いローシスポリ
ブタジエンともに用いることができる。
製造されたゴム変性ポリスチレンは、特定のミ
クロ構造を有していることが必要であり、ゴム状
重合体が粒子状に分散しており、その平均粒子径
が0.20〜1.00ミクロン、好ましくは0.20〜0.70ミ
クロンの範囲に、最も好ましくは0.20〜0.50ミク
ロンの範囲にあることが必要である。平均粒子径
が0.20ミクロンより小さくなると衝撃強度が低下
し、また1.00ミクロンより大きくなると、光沢、
引張強度が低下して品質総合バランスが優れた樹
脂が得られない。
ここで云う平均粒子径とはゴム変性ポリスチレ
ンの超薄切片法による透過型電子顕微鏡写真を撮
影し、写真中のゴム状重合体粒子1000個の粒子径
を測定して次式により算出したものである。
平均粒子径＝ΣniDi2／ΣniDi
（ここにniは粒子径Diのゴム状重合体粒子の個数
である。）
ゴム状重合体粒子の平均粒子径は、重合時の撹
拌強度、用いるゴム状重合体の溶液粘度などによ
り左右され、これらを変更することにより調節す
ることができる。
本発明で用いるポリジメチルシロキサンは
(Industrial Application Field) The present invention relates to an improved rubber-modified polystyrene composition having an excellent overall quality balance. For example, rubber-modified polystyrene is often used in parts of home appliances, but
Compared to ABS resin, it had the disadvantages of inferior impact strength and low gloss on the surface of the molded product. recently,
Demand for improved rubber-modified polystyrene that approaches the properties of ABS resin is increasing in the market due to the desire for cost reduction and thinner walls. The resin composition of the present invention exhibits an excellent overall quality balance of impact strength, gloss, tensile strength, and heat resistance in injection molded products, extruded sheets, extruded vacuum molded products, and the like. It has great value as an economical resin that can replace expensive ABS resin, make products thinner, and reduce costs. (Prior art) Rubber-modified polystyrene has been widely used industrially, but the dispersed rubber particle size is generally about 1.0 to 5.0 microns (μ), and it is difficult to find small rubber particle sizes of 1.0 μ or less. In some cases, preferred resins have not been obtained. In addition, resin compositions consisting of rubber-modified styrene resin and organic polysiloxane are published in Modern Plastics, November 1972 issue, pages 114-116, and Plastics Age, Volume 20, May 1974 issue.
107 pages, JP-A-55-3494, JP-A-53-
124561, JP 57-187345, JP
Although described in prior literature such as Japanese Patent No. 57-187346, a preferable resin composition has not been obtained when rubber-modified polystyrene having a small rubber particle size is used. Furthermore, it is generally well known that adding a large amount of zinc salt of a higher fatty acid to a rubber-modified styrenic resin improves mold releasability, but it has not been demonstrated to increase impact strength. (Problems to be Solved by the Invention) In order to meet the market demand for an improved rubber-modified polystyrene having an excellent overall quality balance as described above, it is necessary to have a quality balance of impact strength, gloss, tensile strength, and heat resistance. There is a need for an improved rubber-modified polystyrene with superior properties. It is an object of the present invention to obtain an inexpensive and improved rubber-modified polystyrene having an excellent quality balance of impact strength, gloss, tensile strength, and heat resistance. (Means for Solving the Problems) The present invention utilizes rubber-modified polystyrene having a specific microstructure that is not common in the prior art, a specific polydimethylsiloxane among organic polysiloxanes, and stearic acid among higher fatty acid metal salts. Consists of specific higher fatty acid zinc salts typified by zinc. That is, the present invention provides a rubber-modified polystyrene composition in which a rubber polymer is dispersed in the form of particles, (A) the average particle size of the dispersed particles is in the range of 0.20 to 1.00 microns, and (B) polydimethyl is present in the composition. Siloxane
It is a rubber-modified polystyrene containing 0.005 to 0.8% by weight and (C) 0.01 to 1% by weight of zinc salt of higher fatty acid. Requirement(A)
By combining all of (B) and (C), it was surprisingly possible to obtain an improved rubber-modified polystyrene composition with an excellent overall quality balance. The rubber-modified polystyrene used in the present invention can be produced by a bulk polymerization method or a bulk suspension polymerization method in which an aromatic monovinyl monomer is polymerized in the presence of a rubbery polymer. The rubber-modified polystyrene having the special microstructure specified in the present invention can be produced by controlling the stirring state during the polymerization process, the mixing state during rubber particle production, and the like. Examples of aromatic monovinyl monomers include styrene and nuclear alkyl-substituted styrenes such as o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert-butylstyrene; -methylstyrene, α-alkyl-substituted styrene such as α-methyl-p-methylstyrene, etc. are used. Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, and the like. As the polybutadiene, both high-cis polybutadiene with a high cis content and low-cis polybutadiene with a low cis content can be used. The produced rubber-modified polystyrene must have a specific microstructure, in which the rubbery polymer is dispersed in particles, and the average particle size is 0.20 to 1.00 microns, preferably 0.20 to 1.00 microns. It should be in the 0.70 micron range, most preferably in the 0.20-0.50 micron range. When the average particle size is smaller than 0.20 microns, impact strength decreases, and when it is larger than 1.00 microns, gloss,
The tensile strength decreases, making it impossible to obtain a resin with an excellent overall balance of quality. The average particle diameter referred to here is calculated by taking a transmission electron micrograph of rubber-modified polystyrene using an ultra-thin section method, measuring the particle diameter of 1000 rubber-like polymer particles in the photograph, and using the following formula. be. Average particle size = ΣniDi 2 /ΣniDi (where ni is the number of rubbery polymer particles with particle size Di.) The average particle size of rubbery polymer particles is determined by the stirring intensity during polymerization, the rubbery polymer used It depends on the viscosity of the solution, etc., and can be adjusted by changing these. The polydimethylsiloxane used in the present invention is
【式】で表わされる構造単位を有してい
ることが必要である。本発明のような小さなゴム
粒子径を有するゴム変性ポリスチレンの場合に
は、ポリジメチルシロキサン以外の先行技術文献
に述べられているような有機ポリシロキサンでは
好ましい樹脂組成物が得られない。更に好ましく
は、ポリジメチルシロキサンの粘度も25℃で、10
〜10000センチストークスと比較的分子量の低い
範囲にあることである。
更に樹脂組成物中のポリジメチルシロキサンの
含有量は、0.005〜0.8重量％の範囲にあることで
ある。含有量が0.005重量％未満となると衝撃強
度の低下が見られ、0.8重量％を超えると、樹脂
成形品の二次加工性（化学接着性、印刷性、塗装
性等）に好ましくない。添加量が多くなつた場
合、二次加工性が悪化する理由は定かでないがゴ
ム変性ポリスチレン中へのポリジメチルシロキサ
ンの相溶性が低下する為ではないかと考えられ
る。このような点から、ポリジメチルシロキサン
の含有量が好ましい樹脂組成物を得るために重要
である。また、本発明で用いる高級脂肪酸亜鉛塩
とは、高級脂肪酸であるC12〜C32なる直鎖飽和モ
ノカルボン酸と亜鉛との塩類を総称するものであ
り、代表的な例を挙げれば、ラウリン酸亜鉛、ミ
リスチン酸亜鉛、パルミチン酸亜鉛、ステアリン
酸亜鉛、ベヘン酸亜鉛またはモンタン酸亜鉛など
である。これらは単独でも、二種以上の混合物で
も用いることができる。高級脂肪酸亜鉛塩以外
の、金属塩、例えばリチウム、ナトリウム、カリ
ウム、マグネシウム、カルシウムまたはアルミニ
ウムなどの高級脂肪酸金属塩では、衝撃強度に好
ましい効果を示さない。樹脂組成物中の高級脂肪
酸の亜鉛塩の含有量は、0.01〜１重量％の範囲に
あることである。含有量が、0.01重量％未満で
は、衝撃強度の低下が見られ、１重量％を越える
と、成形金型の腐蝕がみられ好ましくない。特に
好ましい範囲は、0.01〜0.1重量％である。0.1重
量％を越えるとビカツト軟化点の低下がみられ、
耐熱性を要する成形品に好ましくない。
樹脂組成物中には、ポリジメチルシロキサン及
び高級脂肪酸の亜鉛塩が含有されていることが必
要であり、ポリジメチルシロキサン単独でも、ま
た高級脂肪酸の亜鉛塩が単独でも、衝撃強度、光
沢に好ましい効果を示さない。すなわち、特定の
ミクロン構造を有するゴム変性ポリスチレンと、
ポリジメチルシロキサンと高級脂肪酸と亜鉛塩と
を組み合わせることによつてはじめて、驚くべき
衝撃強度、光沢の向上が発現されることを見出す
に及んで本発明を完成させるに到つた。
本発明の樹脂組成物を製造する方法は、特に限
定されることはなく、例えばスチレンモノマーに
ポリジメチルシロキサン及び高級脂肪酸の亜鉛塩
を添加して重合を行なつてもよいし、ゴム変性ポ
リスチレンとポリジメチルシロキサン及び高級脂
肪酸の亜鉛塩を押出機等を用いて溶融混合を行な
つてもよい。高級脂肪酸の亜鉛塩は熱変色し易い
ので、押出機等を用いて短時間で溶融混合を行な
う方が好ましい。更にはポリジメチルシロキサン
とポリスチレンからポリジメチルシロキサン濃度
の高いマスターペレツトを製造し、そのマスター
ペレツトとゴム変性ポリスチレンを混合し成形物
を得てもよい。同様に高級脂肪酸の亜鉛塩濃度の
高いマスターペレツトとゴム変性ポリスチレンを
混合し、成形物を得てもよい。
更に本発明の樹脂組成物に染顔料、滑剤、充填
剤、離型剤、可塑剤、帯電防止剤等の添加剤を必
要に応じて添加することができる。
（効果）
本発明の樹脂組成物は衝撃強度、光沢、引張強
度及び耐熱の物性面での品質総合バランスに優れ
る。これらの点は、ABS樹脂の特性に近づいた
ものであり、ABS樹脂にかわるものとしての経
済的効果は大であり、また、薄肉化志向の市場の
要望に充分、答えることができるものである。
本発明の樹脂組成物は、弱電機器、雑貨、玩具
等の分野において成形品として使用できる。
（実施例）
以下に実施例を示す。実施例に示されたデータ
ーは次の方法に基いて測定されたものである。
アイゾツト衝撃強度；ASTM D256
引張強度；ASTM D638；ビカツト軟化点；
ASTM D1525
光沢；ASTM D638のダンベル試験片のゲー
ト部と流動末端部の光沢度（入射角60゜）を測定
し平均した。
参考例
ゴム変性ポリスチレンの製造：
第一の流れとして２／時間の供給速度にて、
ポリブタジエン９重量％、スチレン77重量％、エ
チルベンゼン14重量％からなる溶液100重量部、
１，１ビス（オーブチルパーオキシ）シクロヘキ
サン0.075重量部からなる混合物を2.4の第一重
合機に連続的に送入する。第一重合機は温度100
℃である。第二の流れとして１／時間の供給速
度にて、スチレン86重量％とエチルベンゼン14重
量％の混合溶液を容量6.2、温度130〜145℃の
第二重合機に送入する。これらの第一の流れと第
二の流れは1.5のダブルヘリカルリボン状翼の
装着された混合機内に導入され、100〜300回／分
の範囲の回転で混合される。更に容量6.2、温
度115゜〜140℃の第三重合機、容量6.2、温度
145〜170℃の第四重合機に送入し重合を進めた後
に、未反応モノマー及び溶媒を減圧下に除去して
ペレツト状のゴム変性ポリスチレンを得る。
上記の方法にて、ポリブタジエン含有量が7.5
重量％であり、分散ゴム粒子の平均粒子径が、
0.17μ、0.32μ、0.48μ、0.80μ、0.93μ、1.20μであ
る
ゴム変性ポリスチレンを得た。
実施例１〜４及び比較例１〜２
参考例で得た平均粒子径が0.17μ、0.32μ、
0.48μ、0.80μ、0.93μ、1.20μのゴム変性ポリスチ
レンにポリジメチルシロキサン0.2重量％及びス
テアリン酸亜鉛0.07重量％を添加し、押出機にて
混練して樹脂組成物を得て、アイゾツト衝撃強
度、引張強度、光沢及びビカツト軟化点を評価し
た。その結果を表−１に示す。平均粒子径が
0.20μ未満では、アイゾツト衝撃強度が低下し、
また1.00μを越えると光沢及び引張強度が大巾に
低下することがわかる。平均粒子径が、0.20〜
1.00μの範囲にある時が好ましいことがわかる。
実施例５〜10及び比較例３〜６
参考例で得た平均粒子径が0.48μのゴム変性ポ
リスチレンにポリジメチルシロキサンを表−２に
示した添加量で、実施例１と同様な方法にて、樹
脂組成物を得て、物性を評価した。その結果を表
−２に示した。ポリジメチルシロキサンの添加量
が0.002重量％と少なくなるとアイゾツト衝撃強
度が低下する。ポリジメチルシロキサンの添加量
が0.8重量％を越えて多い場合は、樹脂成形品の
二次加工性し化学接着性、印刷性、塗装性等）に
好ましくない。
実施例11〜14及び比較例５〜８
参考例で得た平均粒子径が0.48μのゴム変性ポ
リスチレンにポリジメチルシロキサン0.2重量％
及びステアリン酸亜鉛を表−３に示した添加量で
実施例１と同様な方法にて樹脂組成物を得て、物
性を評価した。ステアリン酸亜鉛の添加量が
0.005重量％と少ないと、アイゾツト衝撃強度が
低下することがわかる。また２重量％と多すぎる
とビカツト軟化点が低下する。ステアリン酸亜鉛
の添加量が0.01〜１重量％の範囲にある時が品質
総合バランスにおいて特に好ましいことがわか
る。
比較例５及び７に示すように、ポリジメチルシ
ロキサン単独、あるいはステアリン酸亜鉛単独で
は、アイゾツト衝撃強度が低く、ポリジメチルシ
ロキサンとステアリン酸亜鉛の組み合わせによつ
てはじめてアイゾツト衝撃強度が大巾に向上し、
更に光沢も向上し、品質バランスがよくなる。
実施例14〜15及び比較例９〜12
比較例９〜12では、実施例14、15のステアリン
酸亜鉛の代わりにステアリン酸マグネシウム、ま
たはステアリン酸カルシウムを用いて同様の試験
を行なつた。その結果を表−４に示す。It is necessary to have a structural unit represented by the formula: In the case of rubber-modified polystyrene having a small rubber particle size as in the present invention, preferred resin compositions cannot be obtained with organopolysiloxanes such as those described in prior art documents other than polydimethylsiloxane. More preferably, the viscosity of the polydimethylsiloxane is also 10 at 25°C.
It has a relatively low molecular weight of ~10,000 centistokes. Furthermore, the content of polydimethylsiloxane in the resin composition is in the range of 0.005 to 0.8% by weight. When the content is less than 0.005% by weight, a decrease in impact strength is observed, and when it exceeds 0.8% by weight, it is unfavorable for the secondary processability (chemical adhesion, printability, paintability, etc.) of the resin molded product. The reason why secondary processability deteriorates when the amount added is not clear is clear, but it is thought to be because the compatibility of polydimethylsiloxane in rubber-modified polystyrene decreases. From this point of view, the content of polydimethylsiloxane is important in order to obtain a preferable resin composition. Further, the higher fatty acid zinc salt used in the present invention is a general term for salts of higher fatty acids, C12 to C32 linear saturated monocarboxylic acids, and zinc.A typical example is laurin. zinc acid, zinc myristate, zinc palmitate, zinc stearate, zinc behenate or zinc montanate. These can be used alone or in a mixture of two or more. Metal salts other than higher fatty acid zinc salts, such as higher fatty acid metal salts such as lithium, sodium, potassium, magnesium, calcium, or aluminum, do not have a favorable effect on impact strength. The content of the zinc salt of higher fatty acid in the resin composition is in the range of 0.01 to 1% by weight. If the content is less than 0.01% by weight, a decrease in impact strength is observed, and if it exceeds 1% by weight, corrosion of the molding die is observed, which is not preferable. A particularly preferred range is 0.01 to 0.1% by weight. When it exceeds 0.1% by weight, a decrease in the Vikatsu softening point is observed,
Not suitable for molded products requiring heat resistance. It is necessary that the resin composition contains polydimethylsiloxane and a zinc salt of a higher fatty acid, and even if polydimethylsiloxane alone or a zinc salt of a higher fatty acid alone has a favorable effect on impact strength and gloss. does not indicate. That is, rubber-modified polystyrene having a specific micron structure,
The present invention was completed by discovering that surprising improvements in impact strength and gloss can be achieved only by combining polydimethylsiloxane, higher fatty acids, and zinc salts. The method for producing the resin composition of the present invention is not particularly limited, and for example, polydimethylsiloxane and a zinc salt of higher fatty acid may be added to styrene monomer for polymerization, or rubber-modified polystyrene may be polymerized. The polydimethylsiloxane and the zinc salt of higher fatty acid may be melt-mixed using an extruder or the like. Since zinc salts of higher fatty acids are easily discolored by heat, it is preferable to perform melt mixing in a short time using an extruder or the like. Furthermore, master pellets with a high polydimethylsiloxane concentration may be produced from polydimethylsiloxane and polystyrene, and the master pellets may be mixed with rubber-modified polystyrene to obtain a molded product. Similarly, a molded product may be obtained by mixing master pellets with a high concentration of zinc salts of higher fatty acids and rubber-modified polystyrene. Furthermore, additives such as dyes and pigments, lubricants, fillers, mold release agents, plasticizers, and antistatic agents can be added to the resin composition of the present invention, if necessary. (Effects) The resin composition of the present invention has an excellent overall quality balance in terms of physical properties such as impact strength, gloss, tensile strength, and heat resistance. These points are close to the characteristics of ABS resin, and it has a great economic effect as an alternative to ABS resin, and can fully meet the demands of the market for thinner walls. . The resin composition of the present invention can be used as a molded article in fields such as light electrical equipment, miscellaneous goods, and toys. (Example) Examples are shown below. The data shown in the examples were measured based on the following method. Izot impact strength; ASTM D256 tensile strength; ASTM D638; Vikatsu softening point;
ASTM D1525 Gloss: The gloss of the gate part and flow end part of the ASTM D638 dumbbell test piece was measured (at an incident angle of 60°) and averaged. Reference example Production of rubber-modified polystyrene: At a feed rate of 2/hour as the first stream,
100 parts by weight of a solution consisting of 9% by weight of polybutadiene, 77% by weight of styrene, and 14% by weight of ethylbenzene;
A mixture consisting of 0.075 parts by weight of 1,1 bis(obutylperoxy)cyclohexane is continuously fed into the first polymerizer of 2.4. The temperature of the first polymerization machine is 100
It is ℃. As a second stream, a mixed solution of 86% by weight styrene and 14% by weight ethylbenzene is fed into a second polymerizer with a volume of 6.2 and a temperature of 130-145°C at a feed rate of 1/hour. These first and second streams are introduced into a mixer equipped with 1.5 double helical ribbon blades and mixed at a rotation rate ranging from 100 to 300 revolutions per minute. In addition, a third polymerization machine with a capacity of 6.2 and a temperature of 115° to 140°C, a capacity of 6.2 and a temperature of 115° to 140°C.
After the polymerization is carried out in a fourth polymerizer at 145 to 170°C, unreacted monomers and solvent are removed under reduced pressure to obtain rubber-modified polystyrene in the form of pellets. By the above method, the polybutadiene content was 7.5
% by weight, and the average particle diameter of the dispersed rubber particles is
Rubber-modified polystyrene with sizes of 0.17μ, 0.32μ, 0.48μ, 0.80μ, 0.93μ, and 1.20μ was obtained. Examples 1 to 4 and Comparative Examples 1 to 2 The average particle diameter obtained in the reference example was 0.17μ, 0.32μ,
Add 0.2% by weight of polydimethylsiloxane and 0.07% by weight of zinc stearate to 0.48μ, 0.80μ, 0.93μ, and 1.20μ rubber-modified polystyrene, knead in an extruder to obtain a resin composition, and obtain Izot impact strength. , tensile strength, gloss and Vikato softening point were evaluated. The results are shown in Table-1. The average particle size is
If it is less than 0.20μ, the Izotsu impact strength decreases,
It is also seen that when the thickness exceeds 1.00μ, the gloss and tensile strength are significantly reduced. Average particle size is 0.20~
It can be seen that a value in the range of 1.00μ is preferable. Examples 5 to 10 and Comparative Examples 3 to 6 Polydimethylsiloxane was added to the rubber-modified polystyrene having an average particle diameter of 0.48μ obtained in the reference example in the amounts shown in Table 2, and in the same manner as in Example 1. A resin composition was obtained and its physical properties were evaluated. The results are shown in Table-2. When the amount of polydimethylsiloxane added is as small as 0.002% by weight, the Izot impact strength decreases. If the amount of polydimethylsiloxane added exceeds 0.8% by weight, it is unfavorable for the secondary processability, chemical adhesion, printability, paintability, etc. of the resin molded product. Examples 11 to 14 and Comparative Examples 5 to 8 0.2% by weight of polydimethylsiloxane was added to the rubber-modified polystyrene with an average particle size of 0.48μ obtained in the reference example.
A resin composition was obtained in the same manner as in Example 1 using the addition amounts of zinc stearate and zinc stearate shown in Table 3, and the physical properties were evaluated. The amount of zinc stearate added is
It can be seen that when the content is as low as 0.005% by weight, the Izot impact strength decreases. On the other hand, if the amount is too large (2% by weight), the Vicatto softening point will be lowered. It can be seen that it is particularly preferable in terms of overall quality balance when the amount of zinc stearate added is in the range of 0.01 to 1% by weight. As shown in Comparative Examples 5 and 7, polydimethylsiloxane alone or zinc stearate alone had low izod impact strength, and it was not until the combination of polydimethylsiloxane and zinc stearate that the izod impact strength was significantly improved. ,
Furthermore, the gloss is improved and the quality balance is improved. Examples 14-15 and Comparative Examples 9-12 In Comparative Examples 9-12, similar tests were conducted using magnesium stearate or calcium stearate instead of zinc stearate in Examples 14 and 15. The results are shown in Table-4.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
性ポリスチレン組成物において (A) 分散粒子の平均粒子径が0.20〜1.00ミクロン
の範囲にあり、 (B) 該組成物中にポリジメチルシロキサンが
0.005〜0.8重量％と、 (C) 高級脂肪酸の亜鉛塩が0.01〜１重量％ 含有されていることを特徴とする改良されたゴム
変性ポリスチレン組成物。 ２ 高級脂肪酸の亜鉛塩の含有量が0.01〜0.1重
量％である特許請求の範囲第１項記載の改良され
たゴム変性ポリスチレン組成物。[Scope of Claims] 1. A rubber-modified polystyrene composition in which a rubbery polymer is dispersed in the form of particles, wherein (A) the average particle diameter of the dispersed particles is in the range of 0.20 to 1.00 microns, and (B) the composition Polydimethylsiloxane inside
An improved rubber-modified polystyrene composition characterized in that it contains 0.005 to 0.8% by weight and (C) 0.01 to 1% by weight of a zinc salt of a higher fatty acid. 2. The improved rubber-modified polystyrene composition according to claim 1, wherein the content of zinc salt of higher fatty acid is 0.01 to 0.1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2352985A JPS61183339A (en) | 1985-02-12 | 1985-02-12 | Improved rubber-modified polystyrene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2352985A JPS61183339A (en) | 1985-02-12 | 1985-02-12 | Improved rubber-modified polystyrene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61183339A JPS61183339A (en) | 1986-08-16 |
| JPH0511142B2 true JPH0511142B2 (en) | 1993-02-12 |
Family
ID=12112973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2352985A Granted JPS61183339A (en) | 1985-02-12 | 1985-02-12 | Improved rubber-modified polystyrene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61183339A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63113073A (en) * | 1986-05-19 | 1988-05-18 | Harima Chem Inc | Electrically conductive polymer composition |
| JPH01275649A (en) * | 1988-04-27 | 1989-11-06 | Asahi Chem Ind Co Ltd | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| CA1335524C (en) * | 1988-04-11 | 1995-05-09 | Hideo Kasahara | Rubber-modified polystyrene resin composition |
| KR100385722B1 (en) * | 1999-10-11 | 2003-05-27 | 주식회사 엘지화학 | Transparent thermoplastic resin composition having superior parting properties and method for preparing the same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929947A (en) * | 1972-07-17 | 1974-03-16 | ||
| JPS51100145A (en) * | 1975-03-01 | 1976-09-03 | Japan Synthetic Rubber Co Ltd | NETSUKASOSEIJUSHISOSEIBUTSU |
| JPS54127454A (en) * | 1978-03-27 | 1979-10-03 | Asahi Chem Ind Co Ltd | Styrene resin composition |
| JPS5534203A (en) * | 1978-08-30 | 1980-03-10 | Asahi Chem Ind Co Ltd | Readily releasable styrene resin composition |
| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPS57172948A (en) * | 1981-04-17 | 1982-10-25 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57187346A (en) * | 1981-05-14 | 1982-11-18 | Mitsui Toatsu Chem Inc | Improved rubber-modified styrene resin composition |
| JPS59196349A (en) * | 1983-04-05 | 1984-11-07 | Dainippon Ink & Chem Inc | Styrene resin composition |
-
1985
- 1985-02-12 JP JP2352985A patent/JPS61183339A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929947A (en) * | 1972-07-17 | 1974-03-16 | ||
| JPS51100145A (en) * | 1975-03-01 | 1976-09-03 | Japan Synthetic Rubber Co Ltd | NETSUKASOSEIJUSHISOSEIBUTSU |
| JPS54127454A (en) * | 1978-03-27 | 1979-10-03 | Asahi Chem Ind Co Ltd | Styrene resin composition |
| JPS5534203A (en) * | 1978-08-30 | 1980-03-10 | Asahi Chem Ind Co Ltd | Readily releasable styrene resin composition |
| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPS57172948A (en) * | 1981-04-17 | 1982-10-25 | Mitsui Toatsu Chem Inc | Rubber-modified styrene resin composition |
| JPS57187346A (en) * | 1981-05-14 | 1982-11-18 | Mitsui Toatsu Chem Inc | Improved rubber-modified styrene resin composition |
| JPS59196349A (en) * | 1983-04-05 | 1984-11-07 | Dainippon Ink & Chem Inc | Styrene resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61183339A (en) | 1986-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2157129B1 (en) | Thermoplastic acrylonitrile-butadiene-styrene resin composition with excellent releasability and colorability | |
| EP0337569B2 (en) | Rubber-modified polystyrene resin composition | |
| JPH0456061B2 (en) | ||
| JPH0463099B2 (en) | ||
| US4496690A (en) | Alloys of styrenic resins and polyamides | |
| JPH0511142B2 (en) | ||
| JPH0525897B2 (en) | ||
| KR100297071B1 (en) | Rubber-Modified Polystyrene Resin Compositions and Injection Molded Parts | |
| JPS6351460B2 (en) | ||
| KR101594648B1 (en) | Thermoplastic ABS resin composition with improved mold shrinkage for blow molding | |
| JPH0511143B2 (en) | ||
| JPH0376338B2 (en) | ||
| JPH0545624B2 (en) | ||
| JPS60130614A (en) | Rubber-modified aromatic monovinyl polymer resin composition | |
| JPS61123660A (en) | Thermoplastic resin composition | |
| KR920001046B1 (en) | Rubber-modified polystyrene resin composition | |
| JPS6326774B2 (en) | ||
| KR101174939B1 (en) | Thermoplastic resin composition having excellent ejectability | |
| JPH0518348B2 (en) | ||
| US4518742A (en) | Thermoplastic resin composition having toughness and high heat distortion resistance | |
| JPS6333461A (en) | High-gloss rubber-reinforced polystyrene composition | |
| EP4101895A1 (en) | Thermoplastic resin composition, preparation method therefor, and molded article comprising same | |
| JPH03163163A (en) | Impact-resistant thermoplastic resin composition | |
| EP1123347A1 (en) | Monovinylidene aromatic resins | |
| JPH0753816B2 (en) | High gloss rubber modified polystyrene composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |