JPS62220538A - High-gloss rubber modified polystyrene composition - Google Patents
High-gloss rubber modified polystyrene compositionInfo
- Publication number
- JPS62220538A JPS62220538A JP6416386A JP6416386A JPS62220538A JP S62220538 A JPS62220538 A JP S62220538A JP 6416386 A JP6416386 A JP 6416386A JP 6416386 A JP6416386 A JP 6416386A JP S62220538 A JPS62220538 A JP S62220538A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- modified polystyrene
- gloss
- composition
- polydimethylsiloxane
- 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.)
- Granted
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 45
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 45
- 229920001971 elastomer Polymers 0.000 title claims abstract description 36
- 239000005060 rubber Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 29
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-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
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 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
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-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
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（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高光沢ゴム
変性ポリスチレン組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a high-gloss rubber-modified polystyrene composition having an excellent overall quality balance.
例えば、ゴム変性ポリスチレンは、家庭室ａｌ製品の部
品などに多く用いられているが、従来ＡＢ８閘脂Ｃ二比
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、ＡＢ８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、市場から強まってきてい
る。For example, rubber-modified polystyrene is often used for parts of household aluminum products, but it has the drawbacks of inferior impact strength and lower gloss on the surface of molded products than conventional AB8 resin C2. Ta. Recently, there has been a growing demand in the market for improved rubber-modified polystyrene that approaches the properties of AB8 resin due to the desire for cost reduction and thinner walls.
本発明の樹脂組成物は、衝撃強度、光沢、引張強間及び
耐熱の優れた品質総合バランスが、射出成形品、押出ン
ート、押出真空成形品等にて発現される。高価なＡＢ８
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。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, extrusion pieces, extrusion vacuum molded products, and the like. expensive AB8
It has great value as an economical resin that can be used as a substitute for resins, make products thinner, and reduce costs.
（従来の技術及びその問題点）
ゴム変性ポリスチレンは、従来から工業的（二多く用い
られているが、その分散ゴム粒子径は、一般に１．θ〜
！、θミクロン（μ）程度であり、１．θμ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、ゴム変性ポリスチレンζ二おいてゲル成分と
゛ゴム成分の比率は普通３．ｊ以上である。（Ｅｎｃｙ
ｃｌｏｐｅｄｉａ ｏｆ Ｐｏｌｙｍｅｒ ｓｃｉｅｎ
ｃｅａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｖｏｌ ／ ３の
グθ／ページにもゴム変性ポリスチレンのゴム成分３〜
／θ係に対して、ゲル成分は７０〜＜１０％であること
が述べられている。）また市販されているゴム変性ポリ
スチレンのゲル成分とゴム成分の比率は、Ｊｏｕｒｎａ
ｌ ｏｆＡｐｐ目ｅｄ Ｐｏｌｙｍｅｒ ５ｃｉｅｎｃ
ｅ ＶＯＩ ／Ｊ”、３夕３ページと３５グページに示
されており、り、１．３．６、１．乙、３．５とほとん
どが３．！以上である。(Prior art and its problems) Rubber-modified polystyrene has traditionally been used industrially, but its dispersed rubber particle diameter is generally 1.θ to
! , θ microns (μ), and 1. In the case of a small rubber particle diameter of θμ or less, a desirable resin cannot be obtained. In addition, in rubber-modified polystyrene ζ2, the ratio of gel component to rubber component is usually 3. j or more. (Ency
clopedia of polymer science
The rubber component 3 of rubber-modified polystyrene is also shown on the page θ/page of ceand Technology Vol/3.
/θ ratio, the gel component is stated to be 70 to <10%. ) Also, the ratio of gel component to rubber component of commercially available rubber-modified polystyrene is determined by Journa
l ofApp ed Polymer 5cienc
e VOI /J'', 3rd page 3rd page and 35th page, most of them are above 3.!, 1.3.6, 1.otsu, 3.5.
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
／り７２年／／月号／／４ｔ〜ｌ／゛６ページ、プラス
チックス・エージ／９７４を年、２０巻！月号１０７ベ
ージ、特開昭ｊｊ−３４ｔ９’１号公報、特開紹ｊ３−
／コ４ｔ！乙／号公報、特開昭５７−／♂７３グ！号公
報、特開昭！７−／ざ７３４ｔ≦号公報などの先行文献
に述べられているが、ゴム粒子径め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。In addition, a resin composition consisting of a rubber-modified styrenic resin and an organic polysiloxane is manufactured by Modern Plastics.
/1972//Month issue//4t~l/゛6 pages, Plastics Age/974, 20 volumes! Monthly issue 107 pages, JP-A-Shojj-34t9'1, JP-A-J3-
/ko4t! Otsu/No. Publication, JP-A-57-/♂73g! Publication, Tokukaisho! Although it is stated in prior literature such as Publication No. 7-/ZA734t≦, a preferable resin composition cannot be obtained when rubber-modified polystyrene having a smaller rubber particle size is used.
先（；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高光沢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。In order to meet the market demand for an improved rubber-modified polystyrene with an excellent overall quality balance as mentioned earlier, an improved rubber-modified polystyrene with an excellent quality balance of impact strength, gloss, tensile strength and heat resistance is required. An object of the present invention is to obtain an inexpensive high-gloss rubber-modified polystyrene having an excellent quality balance of impact strength, gloss, tensile strength, and heat resistance.
′ （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、有機ポリシロキチン
の中でも特定のポリジメチルシロキサンよりなる。(Means for Solving the Problems) The present invention comprises rubber-modified polystyrene having a specific microstructure that is not common in the prior art, and a specific polydimethylsiloxane among organic polysiloxitins.
即ち、本発明は、ゴム重合体が粒子状（二分散している
ゴム変性ポリスチレン組成物Ｃ二おいて（５） 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） Ｕ組成物中に含有されているゲル成分とゴム
成分との比率が２．０〜３．３の範囲にあり、（Ｃ）
該組成物中にポリジメチルシロキサンがｏ、ｏｏｓ〜
θ、♂重ｉｔ％含有されているゴム変性ポリスチレン組
成物である。That is, the present invention provides a rubber modified polystyrene composition C2 in which the rubber polymer is in the form of particles (bidispersed) (5) The average particle size of the dispersed particles is in the range of 0.20 to 1.00 microns, [B) The ratio of the gel component to the rubber component contained in the U composition is in the range of 2.0 to 3.3, and (C)
Polydimethylsiloxane in the composition is o, oos~
It is a rubber-modified polystyrene composition containing θ, ♂% by weight.
本発明は、要件囚、（Ｂｌ、（Ｃ）の全てを組み合わせ
ることによって、非常Ｃ：品質総合バランスが優れた高
光沢ゴム変性ポリスチレン組成物を得ることに成功し声
ものである。The present invention has succeeded in obtaining a high-gloss rubber-modified polystyrene composition with an excellent overall balance of quality and quality by combining all of the requirements (Bl and (C)).
本発明（二相いるゴム変性ポリスチレンは、ゴム状重合
体の存在下１＝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。また、該ゴム変性ポリスチレンは、重合工程におけ
る攪拌の状態、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。−メチルスチ
レン、ｐ−メチルスチレン、ｍ−メチルスチレン、 Ｊ
、４を一ジメチルスチレン、エチルスチレン、ｐ−ｔａ
ｒｔ−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、ポリブタジェン、スチレン−ブ
タジェン共重合体等であり、ポリブタジェンとしてはシ
ス含有址の高いハイシスポリブタジェン、シス含有量の
低いローシスポリブタジェンともに用いることができる
。The rubber-modified polystyrene of the present invention (two-phase) can be produced by a bulk polymerization method or a bulk suspension polymerization method in which 1=aromatic monovinyl monomer is polymerized in the presence of a rubbery polymer. Modified polystyrene can be produced by controlling the stirring state during the polymerization process, the mixing state during rubber particle production, etc. Examples of aromatic monovinyl monomers include styrene, -methylstyrene, and p-methylstyrene. , m-methylstyrene, J
, 4 is monodimethylstyrene, ethylstyrene, p-ta
Nuclear alkyl-substituted styrene such as rt-butylstyrene, α
α-alkyl substituted styrenes such as -methylstyrene and α-methyl-p-methylstyrene are used. Also,
Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, etc. As the polybutadiene, both high-cis polybutadiene with a high cis content and low-cis polybutadiene with a low cis content can be used.
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０．２θ〜７．００
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０．３０〜０．６０ミクロンの範
囲にあることが必要である。The produced rubber-modified polystyrene must have a specific microstructure, in which the rubber-like polymer is dispersed in particles with an average particle size of 0.2θ to 7.00.
microns, preferably in the range of 0.20 to 0.70 microns, most preferably in the range of 0.30 to 0.60 microns.
平均粒子径が０．２９ミクロンより小さくなると面撃強
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。When the average particle size is smaller than 0.29 microns, the surface impact strength decreases, and when it is larger than 1.00 microns,
The gloss and tensile strength decrease, making it impossible to obtain a resin with an excellent overall balance of quality.
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。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.
（ここにｎｉは粒子径Ｄｉのゴム状重合体粒子の個数モ
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。(Here, ni is the number of rubbery polymer particles with a particle size Di.) The average particle size of the rubbery polymer particles is the stirring intensity during polymerization,
It depends on the solution viscosity of the rubbery polymer used, and can be adjusted by changing these.
本発明に用いるゴム変性ポリスチレンに含有されている
ゲル成分とゴム成分との比率はユθ〜３．３、好ましく
は２．３〜３．θの範囲にあることが必要である。ゲル
成分とゴム成分との比率が２．θより小さくなると衝撃
強度が低下し、また比率が３．３より大きくなると光沢
、着色性および剛性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。The ratio of the gel component to the rubber component contained in the rubber-modified polystyrene used in the present invention is θ~3.3, preferably 2.3-3. It is necessary that it be within the range of θ. The ratio of gel component to rubber component is 2. If the ratio is smaller than θ, the impact strength will be reduced, and if the ratio is larger than 3.3, the gloss, colorability and rigidity will be reduced, making it impossible to obtain a resin with an excellent overall quality balance.
ここで云うゲル成分の量はゴム変性ポリスチレンをトル
エンに溶解分散させた後、遠心分離とデカンテーション
で不溶分を分離し、トルエンを除去した後に重址を測定
することによって求められたものである。またゴム成分
は重合時に使用するゴムと七ツマ−の比率から算出する
ことが出来るし、また赤外スペクトル分析のような方法
にて分析することも出来る。The amount of gel component mentioned here was determined by dissolving and dispersing rubber-modified polystyrene in toluene, separating the insoluble matter by centrifugation and decantation, and measuring the weight after removing the toluene. . Further, the rubber component can be calculated from the ratio of the rubber used during polymerization and the rubber, and can also be analyzed by a method such as infrared spectrum analysis.
ゲル成分とゴム成分との比率は、ゴム状重合体を芳香族
モノビニル単量体（：溶解した溶液の重合開始前又は重
合途中にポリスチレンを添加する方法などによってコン
トロールすることが出来る。The ratio of the gel component to the rubber component can be controlled by adding polystyrene to the rubber-like polymer before or during the polymerization of the dissolved solution of the aromatic monovinyl monomer.
本発明に用いるゴム変性ポリスチレンを製造する為の好
ましい方法としては、ゴム状重合体と芳香族モノビニル
単量体からなる溶液を重合させて得た重合溶液と芳香族
モノビニル単量体を重合させて得た重合溶液とを高ぜん
断力下に混合し、更に重合を進行させること（二よる方
法がある。A preferred method for producing the rubber-modified polystyrene used in the present invention is to polymerize a polymer solution obtained by polymerizing a solution consisting of a rubbery polymer and an aromatic monovinyl monomer and an aromatic monovinyl monomer. The obtained polymerization solution is mixed under high shear force to further advance the polymerization (there are two methods).
本発明で用いるポリジメチルシロキサンはることが必要
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；二は、ポリ９メチルシロキチ
ン以外の先行技術木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２Ｊ″℃
で、１０〜／ ０．０００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。It is necessary to use the polydimethylsiloxane used in the present invention. In the case of rubber-modified polystyrene having a small rubber particle size as in the present invention; second, a preferable resin composition cannot be obtained with organic polysiloxanes other than poly9-methylsiloxane such as those described in the prior art Mokuken; . More preferably, the viscosity of the polydimethylsiloxane is also 2J″°C.
It has a relatively low molecular weight of 10 to 0.000 centistokes.
更にゴム変性ポリスチレン組成物中のポリ９メチルシロ
キチンの含有量は、ｏ、ｏ ｏ ｓ〜０．♂重量％の範
囲にあることである。含有量がθ、θＯ！重量係未満と
なると衝撃強度の低下が見られ、０．８重量％を越える
と、着色性および樹脂成形品の二次加工性（化学接着性
、印刷性、壁装性等）の点で好ましくない。添加量が多
くなった場合、着色性及び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
量が好ましいゴム変性ポリスチレン組成物を得るために
重要である。Furthermore, the content of poly9-methylsiloxitin in the rubber-modified polystyrene composition ranges from o, o o s to 0. It should be within the range of ♂% by weight. The content is θ, θO! If it is less than 0.8% by weight, the impact strength will decrease, and if it exceeds 0.8% by weight, it is preferable in terms of colorability and secondary processability of resin molded products (chemical adhesion, printability, wall mountability, etc.). do not have. It is not clear why the colorability and secondary processability deteriorate when the amount added is large, but it is thought that it is because the compatibility of polydimethylsiloxane in rubber-modified polystyrene decreases. From this point of view, the content of polydimethylsiloxane is important for obtaining a preferable rubber-modified polystyrene composition.
本発明のゴム変性ポリスチレン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
；；ポリジメチルシロキサンを添加して重合を行なって
もよいし、ゴム変性ポリスチレンとポリジメチルシロキ
サンを押出機等を用いて溶融混合を行なってもよい。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
メチルシロキチン濃度の高いマスターペレットを製造し
、そのマスターペレッ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。The method for producing the rubber-modified polystyrene composition of the present invention is not particularly limited, and for example, polymerization may be carried out by adding a styrene monomer; Melt mixing may be performed using an extruder or the like. Furthermore, a master pellet with a high concentration of polydimethylsiloxitin may be produced from polydimethylsiloxane and polystyrene, and the master pellet and rubber-modified polystyrene may be mixed to obtain a molded product.
本発明のゴム変性ポリスチレン組成物には高級脂肪酸の
金属塩、たとえばステアリン酸鈍鉛、ステアリン酸カル
ンウムなど 島級脂肪酸のアミド類、たとえばエチレン
ビスステアロアミドなど、の滑剤を組み合せて用いるこ
と１：より、衝撃強度及び光沢の点で好ましい結果が得
られる。用いる滑剤の量はθ、０７〜７．０重ｉｌ係、
好ましくはθ、θ／〜０．二重を優である。In the rubber-modified polystyrene composition of the present invention, a lubricant such as metal salts of higher fatty acids, such as blunt lead stearate and carunium stearate, and amides of island-class fatty acids, such as ethylene bisstearamide, is used in combination.1: Therefore, favorable results can be obtained in terms of impact strength and gloss. The amount of lubricant used is θ, 07 to 7.0 weight,
Preferably θ, θ/~0. Double is better.
また、本発明のゴム変性ポリスチレン組成物には染顔料
、滑剤、充填剤、離型剤、可塑剤、帯砥防止剤等の添加
剤を必要に応じて添加することができる。Furthermore, additives such as dyes and pigments, lubricants, fillers, mold release agents, plasticizers, anti-sanding agents, etc. can be added to the rubber-modified polystyrene composition of the present invention, if necessary.
（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、ＡＢＳＩ
Ｉ脂（：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艷に充分、答えることができ
るものである。(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 ABSI
It has a great economic effect as an alternative to I fat, and can fully meet the demands of the market, which is oriented toward thinner walls.
本発明の１脂組成物は、弱′ゼ機器、雑貨、玩具等の分
野において成形品として使用できる。The single-fat composition of the present invention can be used as molded articles in the fields of low-temperature appliances, miscellaneous goods, toys, and the like.
（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（二基いて測定されたものである。(Example) Examples are shown below. The data shown in the examples were measured using the following methods (two methods).
アイゾツト南撃強度： ＡＳＴＭ Ｄ ２ｊｔｌ二よっ
た。Izot south attack strength: According to ASTM D 2jtl2.
引張強度： ＡＳＴＭ Ｄ ６３♂
光沢： ＡＳＴＭ Ｄ ６３♂のダンベル試験片のゲー
ト部とエンドゲート部の光沢度（入射角６００）を測定
し平均した。Tensile strength: ASTM D 63♂ Gloss: The glossiness (incident angle 600) of the gate part and end gate part of the ASTM D 63♂ dumbbell test piece was measured and averaged.
着色性；樹脂７００重を部に黒糸の染顔料の一定量を瘉
加して、黒着色品として、成形片（たて７９ｍ、よこ！
Ｏｔｍ、厚み、２．５＋ｗ）をつくる。対照サンプルと
して、９恵量憾のポリブタジェンゴムを含有するハイイ
ンパクトポリスチレンに染顔料を添加してつくった黒色
成形片をつくっておき、色調、風合いを比較してランク
付けする。Coloring properties: A certain amount of black thread dye and pigment is added to 700 weight parts of the resin, and a black colored product is made into a molded piece (height 79 m, width!
Otm, thickness, 2.5+w). As a control sample, black molded pieces made by adding dyes and pigments to high-impact polystyrene containing 90% polybutadiene rubber were prepared and ranked by comparing the color tone and texture.
自然色のハイインパクトポリスチレン（二／Ｖ４アたり
１．２５円、２０円、／５円相当の染顔料を添加して作
成した黒着色成形片をそれぞれ対照サンプル入、Ｂ、Ｃ
とする。Contains control samples of natural-colored high-impact polystyrene (black colored molded pieces made by adding dye and pigment equivalent to 1.25 yen, 20 yen, and 5 yen per 2/V4), B and C.
shall be.
参考例／
ゴム変性ポリスチレンの製造
第一の流れとして２２７時間の供給速度【二で、ポリブ
タジェン７０重量％、スチレン♂θ重ｔ％、エチルベン
ゼン／θ゛重ｉｉ係からなる溶液１０ｏｓ黴部、汽／ビ
ス（ｔ−ブチルパーオキシ） ３，３．ｊ−トリメチル
シクロへキナンＯ０θ４ｔＪ−重量部からなる混合物を
第−重合機に連続的に送入する。第−重合機は温度１０
ｊ℃である。第二の流れとして／ １７時間の供給速度
にて、メチレフ９０重！俤とエチルベンゼン７０重ｔＳ
の混合溶液を、温度／２０〜／ダ０℃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せん断速度
２００ｓｅｃ−’のせん断力下に混合機内で混合される
。Reference example/Production of rubber-modified polystyrene As the first flow, a supply rate of 227 hours [2, 10 os mold part, steam/ Bis(t-butylperoxy) 3,3. A mixture consisting of parts by weight of j-trimethylcyclohequinane O0θ4tJ is continuously fed into the first polymerization machine. - The temperature of the polymerization machine is 10
It is j℃. As the second flow / At a feed rate of 17 hours, Metilev 90 weight! Ethylbenzene 70 weight tS
The mixed solution is fed into a second polymerization machine at a temperature of /20 to /0°C. These first and second streams are mixed in a mixer under shear force at a shear rate of 200 sec-'.
更：：、温度／／θ〜／３θ℃の第三重合機、温度／３
３〜／６０℃の第四重合機に送入し重合を進めた後（二
、未反応上ツマ−及び溶媒を減圧下に除去してペレット
状のゴム変性ポリスチレンを得る。Further::, third polymerization machine with temperature //θ ~ /3θ℃, temperature /3
After feeding into a fourth polymerizer at 3 to 60°C and proceeding with polymerization (2. Unreacted upper polymer and solvent are removed under reduced pressure to obtain pellet-shaped rubber-modified polystyrene.
上記の方法にて、ポリブタジェン含有量が２重ｔ４ｊで
あり、分散ゴム粒子の平均粒子径が、θ、７７μ〜八２
θμの範囲で、ゲル成分とゴム成分との比率゛が１．♂
〜３．コの範囲である７種類のゴム変性ポリスチレンを
得た。In the above method, the polybutadiene content is double t4j, and the average particle diameter of the dispersed rubber particles is θ, 77μ to 82μ.
Within the range of θμ, the ratio of gel component to rubber component is 1. ♂
~3. Seven types of rubber-modified polystyrene were obtained.
参考例コ
−ｒム変性ポリスチレンの製造
ポリブタジェン７重量係、スチレン／３重ｔチ、エチル
４７４７７０重を憾からなる溶液／θ０惠量部と、１．
／ビス（ｔ−ブチルパーオキシ） ３．３゜！−計りメ
チルシクロヘキナンＯ，Ｏ４ｔ！重量部とからなる混合
物を第−重合機に連続的（−送入し、攪拌下（二重合を
進め、その後第二重合機、第三重゛合機にて更に重合を
進行させた後（二、未反応モノマー及び溶媒を減圧下（
：除去してベレット状のゴム変性ポリスチレンを得る。Reference Example Production of comb-modified polystyrene A solution consisting of 7 parts by weight of polybutadiene, 3 parts by weight of styrene, 474,770 parts by weight of ethyl/θ0 parts by weight, 1.
/bis(t-butylperoxy) 3.3°! -Weigh methylcyclohexane O, O4t! The mixture consisting of parts by weight is continuously fed into the first polymerization machine and polymerization is proceeded under stirring. 2. Remove unreacted monomers and solvent under reduced pressure (
: Removal to obtain pellet-shaped rubber-modified polystyrene.
上記の方法（二て、ポリブタジェン含ａｍが９恵量憾で
あり、分散ゴム粒子の平均粒径が０．３２μと０．５夕
μでゲル成分とゴム成分との比率が０．３５と０．４ｔ
θの２種類のゴム変性ポリスチレンを得た。The above method (second, the polybutadiene content is 9%, the average particle size of the dispersed rubber particles is 0.32μ and 0.5μ, and the ratio of gel component to rubber component is 0.35 and 0. .4t
Two types of rubber-modified polystyrene with θ were obtained.
実施例７〜グ及び比較例／〜ｊ
参考例／及び参考例コで得た各種のゴム変性ポリスチレ
ン（二粘度がｊＯＯセンチストークスのポリジメチルシ
ロキサン０．／重ｉｔ係を両顎し、押出機（二て混練し
て樹脂組成物を得て、アイゾツト＝撃強度、引張強度、
光沢及び着色性を評価した。Examples 7-g and Comparative Examples/-j Reference Examples/and Various rubber-modified polystyrenes (polydimethylsiloxane with a biviscosity of (Second kneading to obtain a resin composition, Izot = impact strength, tensile strength,
The gloss and colorability were evaluated.
その結果を表−／：二示す。平均粒子径がθ、２０μ未
満では、アイゾツト衝撃強度が低下し、また１．θ０μ
を越えると光沢及び引張強度が低下することがわかる。The results are shown in Table 2. If the average particle diameter is less than θ or 20μ, the Izot impact strength will decrease, and 1. θ0μ
It can be seen that the gloss and tensile strength decrease when the amount is exceeded.
またゲル成分とゴム成分との比率が０．２０未満である
とアイゾツト衝撃強度が低下し、０．３３を越えると、
光沢、着色性及び引張強度が低下することがわかる。平
均粒子径が０．２０〜１．θθμの範囲にあり、かつゲ
ル成分とゴム成分との比率が０．２θ〜θ、３３の範囲
にある時が好ましいことがわかる。Also, if the ratio of gel component to rubber component is less than 0.20, the Izot impact strength will decrease, and if it exceeds 0.33,
It can be seen that the gloss, colorability and tensile strength are reduced. The average particle diameter is 0.20 to 1. It can be seen that it is preferable that θθμ is in the range and the ratio of the gel component to the rubber component is in the range of 0.2θ to θ,33.
実施例ｊ〜７及び比較例６〜７
参考例／で得た平均粒子径が０．！θμ、ゲル成分とゴ
ム成分との比率が２．♂であるゴム変性ポリスチレンに
実施例／で用いたポリジメチルシロキサン及びステアリ
ン酸炬鉛を表−コに示した添加量で、実施例／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（：示した。Examples j to 7 and Comparative Examples 6 to 7 The average particle diameter obtained in Reference Example/ is 0. ! θμ, the ratio of gel component to rubber component is 2. A resin composition was obtained in the same manner as in Example 1 by adding the polydimethylsiloxane and lead stearate used in Example 1 to the male rubber-modified polystyrene in the amounts shown in Table C, and the physical properties were evaluated. did. The results are shown in Table 2.
ポリジメチルシロキチンの添加量がθ、００．２重量悌
と少なくなるとアイゾツト衝撃強度が低下する。When the amount of polydimethylsiloxitin added is as small as θ, 00.2% by weight, the Izot impact strength decreases.
ポリジメチルシロキチンの添加量が０．♂重ｉｌ係を越
えて多い場合は着色性が低下し好ましくない。The amount of polydimethylsilochitin added is 0. If the amount exceeds ♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♂♡♂♂♂♂♂♂♂”
Claims (1)
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）該組成物中に含有されているゲル成分とゴム成分
の比率が２．０〜３．３の範囲にあり、（Ｃ）該組成物
中にポリジメチルシロキサンが０．００５〜０．８重量
％含有されていることを特徴とする高光沢ゴム変性ポリ
スチレン組成物[Claims] In a rubber-modified polystyrene composition in which a rubbery polymer is dispersed in the form of particles, (A) the average particle diameter of the dispersed particles is in the range of 0.20 to 1.00 microns, and (B) The ratio of the gel component to the rubber component contained in the composition is in the range of 2.0 to 3.3, and (C) the composition contains 0.005 to 0.8% by weight of polydimethylsiloxane. A high-gloss rubber-modified polystyrene composition characterized by containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6416386A JPH0753816B2 (en) | 1986-03-24 | 1986-03-24 | High gloss rubber modified polystyrene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6416386A JPH0753816B2 (en) | 1986-03-24 | 1986-03-24 | High gloss rubber modified polystyrene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62220538A true JPS62220538A (en) | 1987-09-28 |
| JPH0753816B2 JPH0753816B2 (en) | 1995-06-07 |
Family
ID=13250122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6416386A Expired - Lifetime JPH0753816B2 (en) | 1986-03-24 | 1986-03-24 | High gloss rubber modified polystyrene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753816B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310886A (en) * | 1989-12-29 | 1994-05-10 | Hoechst Aktiengesellschaft | Azo compounds which contain a 1-sulfo-6-carboxy-2-aminonaphthalene diazo component radical and use thereof as dyes |
| WO1997016489A1 (en) * | 1995-10-31 | 1997-05-09 | Nippon Steel Chemical Co., Ltd. | Rubber-modified aromatic vinyl resin composition and process for the production thereof |
-
1986
- 1986-03-24 JP JP6416386A patent/JPH0753816B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310886A (en) * | 1989-12-29 | 1994-05-10 | Hoechst Aktiengesellschaft | Azo compounds which contain a 1-sulfo-6-carboxy-2-aminonaphthalene diazo component radical and use thereof as dyes |
| WO1997016489A1 (en) * | 1995-10-31 | 1997-05-09 | Nippon Steel Chemical Co., Ltd. | Rubber-modified aromatic vinyl resin composition and process for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753816B2 (en) | 1995-06-07 |
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