JPH08199021A - Rubber-modified styrene resin composition excellent in moldability - Google Patents
Rubber-modified styrene resin composition excellent in moldabilityInfo
- Publication number
- JPH08199021A JPH08199021A JP7010424A JP1042495A JPH08199021A JP H08199021 A JPH08199021 A JP H08199021A JP 7010424 A JP7010424 A JP 7010424A JP 1042495 A JP1042495 A JP 1042495A JP H08199021 A JPH08199021 A JP H08199021A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- resin composition
- modified styrene
- styrene
- polymer
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title abstract description 57
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- 239000002245 particle Substances 0.000 abstract description 77
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 36
- 229920000642 polymer Polymers 0.000 abstract description 29
- 150000003440 styrenes Chemical class 0.000 abstract description 27
- 229920001971 elastomer Polymers 0.000 abstract description 19
- 238000000465 moulding Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 41
- 239000004797 high-impact polystyrene Substances 0.000 description 41
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920001890 Novodur Polymers 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 239000005064 Low cis polybutadiene Substances 0.000 description 5
- 230000002902 bimodal effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- -1 t-butylperoxy Chemical group 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- UJNVTDGCOKFBKM-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)hexane Chemical compound CCCCCC(OOC(C)(C)C)OOC(C)(C)C UJNVTDGCOKFBKM-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- 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
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐衝撃性、耐熱変形
性、および成形加工性に優れ、かつ、射出成形により成
形品を得る場合、ウェルドラインやフローマーク等の成
形品の表面外観不良が目立たないゴム変性スチレン系樹
脂組成物に関するものである。FIELD OF THE INVENTION The present invention is excellent in impact resistance, heat distortion resistance and molding processability, and when a molded product is obtained by injection molding, the surface appearance of the molded product such as weld lines and flow marks is poor. Relates to a rubber-modified styrene-based resin composition that is inconspicuous.
【０００２】[0002]
【従来の技術】一般に、ゴム変性スチレン系樹脂は耐衝
撃性、耐熱性、および成形加工性に優れ、かつ良好な表
面光沢を有することから、各種成形品の成形材料として
幅広く利用されている。特にテレビ、ビデオデッキ、コ
ンピューター等の家電用品、ＯＡ機器のハウジングに利
用される場合、成形品の表面外観の良好なものが要求さ
れる。2. Description of the Related Art Generally, a rubber-modified styrene resin is widely used as a molding material for various molded products because it is excellent in impact resistance, heat resistance and molding processability and has a good surface gloss. In particular, when it is used for a home electric appliance such as a television, a VCR, a computer, or a housing for OA equipment, a molded product having a good surface appearance is required.
【０００３】表面外観不良の例としては、射出成形した
場合、金型内で溶融した樹脂同士が衝突する箇所に生じ
るウェルドラインや、樹脂の流れ方向と直角に発生す
る、縞模様を呈したフローマーク等を挙げることができ
る。このような表面外観不良を防ぐ手段として、射出
成形の際、樹脂温度や金型温度を上げることにより、樹
脂の流動性を改善したり、射出速度を速くなりすぎない
ように調整する、成形品表面に塗装を施す、樹脂に
滑剤や可塑剤を添加することにより、樹脂の流動性を改
善する、といった方法を挙げることができる。しかしな
がら、の方法は最適な成形条件を設定することで、あ
る程度の外観不良改善は達成できるものの、温度を上げ
ることにより、樹脂物性の低下や金型の早期劣化を引き
起こしたり、冷却期間が長いために成形に要する時間が
長くなりコストアップとなる。また、の方法では、成
形品表面に塗装を施すことで外観不良を消すことができ
るが、塗装によるコストアップは否めず、また塗料中に
含まれる有機溶剤等が作業環境に悪影響を及ぼすという
重大な問題点がある。の方法では、エステル類（特開
平４−348152号公報）やワックス（特公平２−41541 号
公報）を添加することで樹脂の流動性を向上させる方法
も公知だが、満足な外観不良の改善効果は得られず、し
かも樹脂の耐熱性が低下するという問題点がある。ま
た、低分子量のポリマー、例えばスチレンオリゴマーを
配合してマトリックス樹脂の分子量を下げる方法（特開
平１−256550号公報）では樹脂の流動性が向上すること
により、ウェルドライン、フローマークはある程度まで
は改善されているが、粒子径についての規定がなされて
いないために耐衝撃性が著しく低下し、実用に耐えうる
ものではない。As an example of a surface appearance defect, in injection molding, a weld line generated at a position where molten resins collide with each other in a mold, or a flow having a striped pattern which is generated at a right angle to a resin flowing direction. Marks etc. can be mentioned. As a means to prevent such a poor surface appearance, during injection molding, the resin temperature and mold temperature are raised to improve the fluidity of the resin and to adjust the injection speed not to become too fast. Examples thereof include a method of coating the surface and a method of improving fluidity of the resin by adding a lubricant or a plasticizer to the resin. However, although the method of (1) can achieve some degree of improvement in appearance defects by setting the optimum molding conditions, increasing the temperature causes deterioration of resin physical properties, early deterioration of the mold, and a long cooling period. In addition, the time required for molding becomes long and the cost increases. In addition, with the method of (1), it is possible to eliminate the appearance defect by painting the surface of the molded product, but it is unavoidable that the cost will increase due to painting, and that the organic solvent contained in the paint adversely affects the working environment. There is a problem. The method of improving the fluidity of the resin by adding an ester (Japanese Patent Application Laid-Open No. 4-348152) or a wax (Japanese Patent Publication No. 2-41541) is also known, but the effect of improving the satisfactory appearance defect is known. However, there is a problem that the heat resistance of the resin is lowered. Further, in a method of lowering the molecular weight of a matrix resin by blending a low molecular weight polymer, for example, a styrene oligomer (JP-A-1-256550), the fluidity of the resin is improved, and thus the weld line and the flow mark are to some extent. Although it has been improved, the impact resistance is remarkably lowered because the particle size is not specified, and it is not practical.
【０００４】また、耐衝撃性を改善する方法として、ゴ
ム変性スチレン系樹脂中に含まれるゴム状重合体粒子
に、小粒子部分と大粒子部分とからなる二峰性の粒子径
分布を持たせる技術（特公平５−25897 号公報）がある
が、樹脂の流動性についての規定がなされていないた
め、満足な成形品外観が得られていない。As a method for improving impact resistance, the rubber-like polymer particles contained in the rubber-modified styrene resin are made to have a bimodal particle size distribution consisting of small particle portions and large particle portions. Although there is a technology (Japanese Patent Publication No. 5-25897), a satisfactory molded product appearance cannot be obtained because the fluidity of the resin is not specified.
【０００５】[0005]
【本発明が解決しようとする課題】本発明の目的は、金
型温度などの成形条件を変えたり、成形品表面に塗装を
施すことなくウェルドラインやフローマーク等の表面外
観不良の見られないゴム変性スチレン系樹脂組成物を提
供することにある。DISCLOSURE OF THE INVENTION The object of the present invention is to prevent the appearance of poor surface appearance such as weld lines and flow marks without changing the molding conditions such as the mold temperature or coating the surface of the molded product. It is to provide a rubber-modified styrene resin composition.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記ゴム
変性スチレン系樹脂組成物を開発すべく鋭意検討を重ね
た結果、小粒子と大粒子、それぞれの平均粒子径を特定
領域に制御し、かつ小粒子部分の重量割合を特定し、特
定のメルトフローレートに制御することで、ウェルドラ
インやフローマーク等の表面外観不良の見られないゴム
変性スチレン系樹脂組成物を完成するに至った。Means for Solving the Problems As a result of intensive studies to develop the rubber-modified styrenic resin composition, the inventors of the present invention have controlled the average particle diameter of each of small particles and large particles in a specific region. In addition, by specifying the weight ratio of the small particle portion and controlling it to a specific melt flow rate, it was possible to complete a rubber-modified styrenic resin composition that does not show surface defects such as weld lines and flow marks. It was
【０００７】すなわち、本発明は、ゴム変性スチレン系
樹脂組成物において、 (A) スチレン系重合体からなるマトリックス中に、粒子
状のゴム状重合体が分散しており、かつ (B) 前記ゴム状重合体粒子が、（イ）平均粒子径 0.1〜
0.5 μm の小粒子部分と、（ロ）平均粒子径 0.6〜4.0
μm の大粒子部分とからなる二峰性の粒子径分布を有
し、 (C) 前記ゴム状重合体粒子の総重量に占める小粒子部分
の比率が60〜95重量％であり、 (D) 該ゴム変性スチレン系樹脂組成物の 200℃、５kg荷
重におけるメルトフローレートが５ｇ／10min 以上であ
る、成形性に優れたゴム変性スチレン系樹脂組成物を提
供するものである。That is, the present invention provides a rubber-modified styrenic resin composition in which a particulate rubbery polymer is dispersed in a matrix composed of (A) a styrene polymer, and (B) the rubber. Polymer particles have an average particle diameter of 0.1-
0.5 μm small particle part and (b) average particle size 0.6 to 4.0
having a bimodal particle size distribution consisting of large particles of (μm), (C) the proportion of small particles in the total weight of the rubber-like polymer particles is 60 to 95% by weight, (D) The rubber-modified styrene-based resin composition has a melt flow rate of 5 g / 10 min or more at 200 ° C. under a load of 5 kg, and is excellent in moldability.
【０００８】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【０００９】本発明のゴム変性スチレン系樹脂組成物
は、ゴム状重合体をスチレン系単量体に溶解した後、一
般的な重合方法を用いて製造することができる。一般的
な重合方法の例としては、塊状重合法、溶液重合法、ま
たは塊状重合後、さらに懸濁重合を行う塊状−懸濁重合
法を挙げることができる。中でも塊状重合法が好まし
い。The rubber-modified styrenic resin composition of the present invention can be produced by dissolving a rubbery polymer in a styrenic monomer and then using a general polymerization method. Examples of general polymerization methods include a bulk polymerization method, a solution polymerization method, and a bulk-suspension polymerization method in which suspension polymerization is performed after bulk polymerization. Of these, the bulk polymerization method is preferable.
【００１０】スチレン系単量体としては、例えばスチレ
ン、アルキル置換スチレン（例えば、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、ｐ−エチルスチレン、ｐ−ｔ−ブチ
ルスチレンなど）、α−アルキル置換スチレン（例え
ば、α−メチルスチレン、α−メチル−ｐ−メチルスチ
レンなど）、ハロゲン化スチレン（例えば、ｏ−クロロ
スチレン、ｐ−クロロスチレンなど）などが挙げられ
る。これらの中でも、スチレン系単量体としては、スチ
レン、ｏ−メチルスチレン、ｐ−メチルスチレンが好ま
しく、特にスチレンが好ましい。これらのスチレン系単
量体は、一種で使用してもよいし、または二種以上混合
して使用してもよい。Examples of the styrene-based monomer include styrene, alkyl-substituted styrene (for example, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-
Dimethyl styrene, p-ethyl styrene, pt-butyl styrene, etc.), α-alkyl substituted styrene (eg, α-methyl styrene, α-methyl-p-methyl styrene, etc.), halogenated styrene (eg, o-chloro). Styrene, p-chlorostyrene, etc.) and the like. Among these, styrene, o-methylstyrene, and p-methylstyrene are preferable as the styrene-based monomer, and styrene is particularly preferable. These styrenic monomers may be used alone or in combination of two or more.
【００１１】スチレン系単量体には、必要に応じて、例
えばアクリル酸、メタクリル酸等の（メタ）アクリル
酸、メタクリル酸メチル、アクリル酸エチル、アクリル
酸ブチル等の（メタ）アクリル酸エステル、無水マレイ
ン酸、アクリロニトリルなどの共重合可能な単量体を、
経済性が劣らない範囲で添加してもよい。The styrenic monomer may be, for example, (meth) acrylic acid such as acrylic acid or methacrylic acid, or (meth) acrylic acid ester such as methyl methacrylate, ethyl acrylate or butyl acrylate, if necessary. Maleic anhydride, a copolymerizable monomer such as acrylonitrile,
You may add in the range which is not inferior to economy.
【００１２】また、ゴム状重合体としては、ポリブタジ
エンやスチレン・ブタジエン共重合体等、特に限定され
るものではなく、一般的なゴム状重合体は全て使用する
ことができる。ポリブタジエンとしては、 1,4−シス結
合の含有量が高いハイシスポリブタジエン、1,4 −シス
結合の含有量が低いローシスポリブタジエン、さらにス
チレン・ブタジエン共重合体等のいずれを用いてもよ
い。ゴム状重合体は、前記スチレン系単量体をグラフト
重合させることが可能なゴム状物質であり、不飽和二重
結合を含む必要がある。好ましいゴム状重合体には、ロ
ーシスポリブタジエンやスチレン・ブタジエンブロック
共重合体などが含まれる。これらのゴム状重合体は、一
種でまたは二種以上混合して使用できる。また、ゴム変
性スチレン系樹脂組成物中のゴム成分含有量は 0.1〜30
重量％、好ましくは３〜20重量％である。ゴム成分含有
量が 0.1重量％未満では充分な衝撃強度が得られず、30
重量％を超えると外観不良が目立つ。The rubber-like polymer is not particularly limited, such as polybutadiene and styrene-butadiene copolymer, and any general rubber-like polymer can be used. As the polybutadiene, any of high cis polybutadiene having a high content of 1,4-cis bonds, low cis polybutadiene having a low content of 1,4-cis bonds, and a styrene-butadiene copolymer may be used. The rubber-like polymer is a rubber-like substance that can be graft-polymerized with the styrene-based monomer, and needs to contain an unsaturated double bond. Preferred rubbery polymers include low cis polybutadiene and styrene-butadiene block copolymers. These rubber-like polymers can be used alone or in combination of two or more. Further, the rubber component content in the rubber-modified styrene resin composition is 0.1 to 30.
%, Preferably 3 to 20% by weight. If the rubber component content is less than 0.1% by weight, sufficient impact strength cannot be obtained.
If it exceeds the weight%, the appearance is noticeable.
【００１３】本発明において、重合開始剤を用いない場
合は90〜200 ℃の温度範囲で、有機過酸化物などの重合
開始剤存在下では50〜180 ℃の温度範囲で重合を行うこ
とができる。In the present invention, the polymerization can be carried out in the temperature range of 90 to 200 ° C. when no polymerization initiator is used, and in the temperature range of 50 to 180 ° C. in the presence of the polymerization initiator such as organic peroxide. .
【００１４】必要に応じて用いられる重合開始剤として
は、例えば 1,1−ビス（ｔ−ブチルパーオキシ）シクロ
ヘキサン、 1,1−ビス（ｔ−ブチルパーオキシ)3,3,5−
トリメチルシクロヘキサン等のパーオキシケタール類、
ジ−ｔ−ブチルパーオキサイド、 2,5−ジメチル− 2,5
−ジ（ｔ−ブチルパーオキシ）ヘキサン等のジアルキル
パーオキサイド類、ベンゾイルパーオキサイド、ｍ−ト
ルオイルパーオキサイド等のジアシルパーオキサイド
類、その他、パーオキシジカーボネート類、パーオキシ
エステル類、ケトンパーオキサイド類、ハイドロパーオ
キサイド類を挙げることができる。また、重合開始剤の
添加量としては、スチレン系単量体に対して10重量％以
下が好ましい。重合開始剤の添加量が10重量％を超える
と重合速度の制御が困難となる。Examples of the polymerization initiator used as necessary include 1,1-bis (t-butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) 3,3,5-
Peroxyketals such as trimethylcyclohexane,
Di-t-butyl peroxide, 2,5-dimethyl-2,5
-Dialkyl peroxides such as di (t-butylperoxy) hexane, benzoyl peroxide, diacyl peroxides such as m-toluoyl peroxide, and others, peroxydicarbonates, peroxyesters, ketone peroxides And hydroperoxides. The addition amount of the polymerization initiator is preferably 10% by weight or less with respect to the styrene-based monomer. When the amount of the polymerization initiator added exceeds 10% by weight, it becomes difficult to control the polymerization rate.
【００１５】また、重合時に溶剤を存在させることもで
きる。溶剤としては、芳香族炭化水素類、例えば、トル
エン、キシレン、エチルベンゼン等の一種または二種以
上の混合物を挙げることができる。溶剤の使用量として
は、重合溶液中０〜50重量％の範囲が望ましい。溶剤の
使用量が50重量％を超えると重合速度が著しく低下し、
また溶剤の回収に大きなエネルギーを要するため経済性
が劣ってくる。A solvent may be present during the polymerization. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, or a mixture of two or more thereof. The amount of the solvent used is preferably in the range of 0 to 50% by weight in the polymerization solution. If the amount of solvent used exceeds 50% by weight, the polymerization rate will decrease significantly,
In addition, the recovery of the solvent requires a large amount of energy, resulting in poor economic efficiency.
【００１６】また、本発明においては、必要に応じて連
鎖移動剤、例えばα−メチルスチレンリニアダイマー、
ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタ
ン、１−フェニルブテン−２−フルオレン、ターピノー
レン、ジペンテン、クロロホルムなどを用いることがで
きる。連鎖移動剤の添加量としては、スチレン系単量体
に対して10重量％以下が好ましい。連鎖移動剤の添加量
が10重量％を超えると分子量低下が著しく、充分な衝撃
強度が得られない。In the present invention, if necessary, a chain transfer agent such as α-methylstyrene linear dimer,
It is possible to use n-dodecyl mercaptan, t-dodecyl mercaptan, 1-phenylbutene-2-fluorene, terpinolene, dipentene, chloroform and the like. The addition amount of the chain transfer agent is preferably 10% by weight or less with respect to the styrene-based monomer. If the amount of the chain transfer agent added exceeds 10% by weight, the molecular weight is remarkably reduced and sufficient impact strength cannot be obtained.
【００１７】本発明のゴム変性スチレン系樹脂組成物に
おいて、前記ゴム状重合体は、（イ）平均粒子径 0.1〜
0.5 μm 、好ましくは0.15〜0.45μm の小粒子部分と、
（ロ）平均粒子径 0.6〜4.0 μm 、好ましくは 0.8〜2.
0 μm の大粒子部分とに分散されており、二峰性の粒子
径分布を有する必要がある。小粒子部分の平均粒子径が
0.1μm 未満では衝撃強度が低下し、 0.5μm を超える
と外観不良が目立つ。また、大粒子部分の平均粒子径が
0.6μm 未満では衝撃強度が低下し、 4.0μmを超える
と外観特性が低下する。なお、前記ゴム状重合体の粒子
径分布が単一のピークしか有さない場合には、耐衝撃
性、剛性および外観特性のいずれかが劣る。In the rubber-modified styrenic resin composition of the present invention, the rubber-like polymer has (a) an average particle diameter of 0.1 to
0.5 μm, preferably 0.15-0.45 μm small particle portion,
(B) Average particle size 0.6 to 4.0 μm, preferably 0.8 to 2.
It should be dispersed in a large particle size of 0 μm and have a bimodal particle size distribution. The average particle size of the small particles is
If it is less than 0.1 μm, the impact strength will decrease, and if it exceeds 0.5 μm, the appearance will be poor. Also, the average particle size of the large particles is
If it is less than 0.6 μm, the impact strength will decrease, and if it exceeds 4.0 μm, the appearance characteristics will deteriorate. When the particle size distribution of the rubber-like polymer has only a single peak, any of impact resistance, rigidity and appearance characteristics is poor.
【００１８】本発明において、二峰性の粒子径分布を有
するゴム変性スチレン系樹脂組成物は種々の方法、例え
ば小粒子径のゴム粒子を含有するゴム変性スチレン系
樹脂組成物と大粒子径のゴム粒子を含有するゴム変性ス
チレン系樹脂組成物とを個別に製造し、混合機や押出機
などでブレンドする方法、二つの重合反応器を用い、
小粒子のゴム状重合体を含む重合液と大粒子のゴム状重
合体を含む重合液とをそれぞれ別に調製し、両者を混合
して重合を完結させる方法、粒子分散機をインターバ
ル運転する等の方法を用い、重合過程で小粒子と大粒子
のゴム状重合体を同時に形成させる方法、などにより製
造できる。In the present invention, the rubber-modified styrene resin composition having a bimodal particle size distribution can be prepared by various methods, for example, a rubber-modified styrene resin composition containing rubber particles having a small particle size and a large particle size. A rubber-modified styrenic resin composition containing rubber particles is separately produced, and a method of blending with a mixer or an extruder, using two polymerization reactors,
A polymerization solution containing a small particle rubber-like polymer and a polymerization solution containing a large particle rubber-like polymer are separately prepared, and the two are mixed to complete the polymerization, and a particle disperser is operated at intervals. It can be produced by a method such that a small particle and a large particle rubber-like polymer are simultaneously formed in the polymerization process.
【００１９】なお、ゴム状重合体の小粒子と大粒子の粒
子径の制御は、粘度の異なるゴム状重合体を使用する方
法、スチレン・ブタジエン共重合体を添加する方法、ス
チレン系単量体とゴム状重合体との混合液を重合する過
程で、重合温度、攪拌速度、ゴム粒子生成時の攪拌状態
を変化させる方法、などの方法によって可能である。The particle size of the small particles and large particles of the rubber-like polymer can be controlled by using a rubber-like polymer having different viscosities, adding a styrene-butadiene copolymer, or a styrene-based monomer. In the process of polymerizing the mixed liquid of the rubbery polymer and the rubber-like polymer, a method such as changing the polymerization temperature, the stirring speed, and the stirring state at the time of producing the rubber particles can be used.
【００２０】本発明において、ゴム状重合体粒子の総重
量に占める小粒子部分の比率は60〜95重量％である必要
がある。好ましくは75〜95重量％、さらに好ましくは80
〜95重量％である。小粒子部分の比率が95重量％を超え
ると耐衝撃性が急激に低下し、60重量％未満であると外
観不良が目立つ。In the present invention, the proportion of the small particle portion in the total weight of the rubber-like polymer particles needs to be 60 to 95% by weight. Preferably 75-95% by weight, more preferably 80
~ 95% by weight. If the proportion of small particles exceeds 95% by weight, the impact resistance sharply deteriorates, and if it is less than 60% by weight, poor appearance is noticeable.
【００２１】本発明のゴム変性スチレン系樹脂組成物の
200℃、５kg荷重におけるメルトフローレートは５ｇ／
10min 以上、好ましくは18〜30ｇ／10min である必要が
ある。200 ℃、５kg荷重におけるメルトフローレートが
５ｇ／10min 未満では良好な表面外観が得られない。Rubber-modified styrenic resin composition of the present invention
Melt flow rate at 200 ℃, 5kg load is 5g /
It should be 10 min or more, preferably 18 to 30 g / 10 min. If the melt flow rate at 200 ° C. under a load of 5 kg is less than 5 g / 10 min, a good surface appearance cannot be obtained.
【００２２】ゴム変性スチレン系樹脂組成物のメルトフ
ローレートを制御する方法には、例えばミネラルオイ
ルのような可塑剤を添加したり、ゴム状重合体とスチレ
ン系単量体との重合時に連鎖移動剤を添加してマトリッ
クス分子量を下げる方法、高級脂肪酸の金属塩や高級
脂肪酸アミドのような滑剤を添加する方法などがある。To control the melt flow rate of the rubber-modified styrene resin composition, a plasticizer such as mineral oil may be added, or chain transfer may occur during the polymerization of the rubbery polymer and the styrene monomer. There are a method of adding a lubricant to lower the molecular weight of the matrix, a method of adding a lubricant such as a metal salt of a higher fatty acid or a higher fatty acid amide, and the like.
【００２３】本発明において、ゴム状重合体のトルエン
中の膨潤指数は特に限定されるものではないが、好まし
くは５〜10、さらに好ましくは５〜７である。トルエン
中の膨潤指数が５未満では衝撃強度が低下し、10を超え
ると外観不良が目立つ。In the present invention, the swelling index of the rubbery polymer in toluene is not particularly limited, but it is preferably 5 to 10, and more preferably 5 to 7. If the swelling index in toluene is less than 5, the impact strength will decrease, and if it exceeds 10, poor appearance will be noticeable.
【００２４】本発明において、前記ゴム状重合体の総重
量に対するゴム変性スチレン系樹脂組成物の不溶分重量
の比率は特に限定されるものではないが、好ましくは
4.1以上である。ここでいうゴム変性スチレン系樹脂組
成物の不溶分重量とは、ゴム変性スチレン系樹脂組成物
をトルエン中に溶解させた際に得られる不溶分の重量で
ある。ゴム状重合体の総重量に対するゴム変性スチレン
系樹脂組成物の不溶分重量の比率が 4.1未満であると耐
衝撃性が低下する。In the present invention, the ratio of the insoluble content of the rubber-modified styrenic resin composition to the total weight of the rubber-like polymer is not particularly limited, but is preferably.
4.1 or higher. The insoluble content weight of the rubber-modified styrene-based resin composition as used herein is the weight of the insoluble content obtained when the rubber-modified styrene-based resin composition is dissolved in toluene. If the ratio of the insoluble content weight of the rubber-modified styrene-based resin composition to the total weight of the rubber-like polymer is less than 4.1, the impact resistance decreases.
【００２５】また、不溶分重量および膨潤指数は、粘度
の異なるゴム状重合体を使用したり、重合温度、重合時
間、重合した樹脂組成物の脱揮条件を変化させる、開始
剤を使用するなどの方法によってコントロールできる。The weight of the insoluble matter and the swelling index are determined by using rubbery polymers having different viscosities, changing the polymerization temperature, the polymerization time, the devolatilization conditions of the polymerized resin composition, and the use of an initiator. Can be controlled by.
【００２６】本発明のゴム変性スチレン系樹脂組成物に
は、必要に応じて、滑剤、可塑剤、離型剤、難燃剤、酸
化防止剤、紫外線吸収剤、帯電防止剤、着色剤、充填剤
等の添加剤を配合することができる。The rubber-modified styrene resin composition of the present invention contains, if necessary, a lubricant, a plasticizer, a release agent, a flame retardant, an antioxidant, an ultraviolet absorber, an antistatic agent, a colorant, and a filler. Additives such as
【００２７】このようにして得られた本発明のゴム変性
スチレン系樹脂組成物は、耐衝撃性、耐熱変形性、およ
び成形加工性に優れ、かつ、その成形品はウェルドライ
ンやフローマーク等の表面外観不良が目立たないため、
例えばテレビ、クーラー、冷蔵庫などの家電製品、コン
ピューター、複写機などのＯＡ機器のハウジング、自動
車用内装部品、日用品など広範囲にわたって利用でき
る。The rubber-modified styrenic resin composition of the present invention thus obtained is excellent in impact resistance, heat distortion resistance and molding processability, and the molded product has a weld line, a flow mark and the like. Since the surface appearance defect is not noticeable,
For example, it can be used in a wide range of home appliances such as televisions, coolers, refrigerators, housings of office automation equipment such as computers and copiers, interior parts for automobiles, and daily necessities.
【００２８】[0028]
【実施例】以下に、実施例に基づいて本発明をさらに詳
細に説明するが、本発明はこれらの実施例によって何ら
限定されるものではない。なお、実施例、比較例におけ
る物性等の測定は、以下の方法を用いた。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. The following methods were used to measure the physical properties and the like in Examples and Comparative Examples.
【００２９】(1) ゴム粒子の体積平均粒子径は、超薄切
片法によるゴム変性スチレン系樹脂組成物の切片を透過
型電子顕微鏡で写真撮影し、ゴム状重合体粒子1000個の
粒子径を測定して、次式に従って算出した。 Dv＝（Σni・Di4)／（Σni・Di3) ここで、Dvは平均粒子径、niは粒子径Diのゴム状重合体
粒子の個数を示す。(1) The volume average particle size of the rubber particles is determined by taking a photograph of a section of the rubber-modified styrenic resin composition by the ultrathin section method with a transmission electron microscope, and measuring the particle size of 1000 rubber-like polymer particles. It was measured and calculated according to the following formula. Dv = (Σni · Di 4 ) / (Σni · Di 3 ), where Dv is the average particle diameter, and ni is the number of rubber-like polymer particles having the particle diameter Di.
【００３０】(2) メルトフローレート(MFR) はASTM-D12
38に準拠して 200℃、５kg荷重で測定した。(2) Melt flow rate (MFR) is ASTM-D12
According to 38, it was measured at 200 ° C. and a load of 5 kg.
【００３１】(3) ゴム変性スチレン系樹脂組成物の不溶
分重量（以下、不溶分重量と称す）、およびゴム状重合
体のトルエン中における膨潤指数は、ゴム変性スチレン
系樹脂組成物のをトルエン中に完全に溶解し、24時間暗
所に静置した後、遠心分離器にて不溶分を沈降させ、デ
カンテーションで沈降した不溶分を分離し、その重量(W
s)(g) を秤量する。得られたトルエンで膨潤した不溶分
を60℃、減圧下で24時間真空乾燥し、デシケータ中で放
冷した後の乾燥した重量（不溶分重量、Wd）(g)を秤量
する。これらの値を用い、次式に従って膨潤指数を算出
した。 膨潤指数＝Ws／Wd (4) ノッチ付アイゾット衝撃強度は、JIS-K6871 に準拠
して測定した。(3) The insoluble content weight of the rubber-modified styrene resin composition (hereinafter referred to as "insoluble content weight") and the swelling index of the rubber-like polymer in toluene are as follows: After completely dissolving in the solution and leaving it in the dark for 24 hours, the insoluble matter was settled by a centrifuge and the insoluble matter was separated by decantation, and the weight (W
s) Weigh (g). The obtained insoluble matter swollen with toluene is vacuum-dried at 60 ° C. under reduced pressure for 24 hours, and the dried weight (insoluble matter weight, Wd) (g) after cooling in a desiccator is weighed. Using these values, the swelling index was calculated according to the following formula. Swelling index = Ws / Wd (4) Notched Izod impact strength was measured according to JIS-K6871.
【００３２】(5) 成形品の表面外観は、シリンダー温度
220℃、金型温度50℃で、射出成形を行い平板状の成形
品を作成し、得られた成形品のウェルドライン、フロー
マークを下記の基準で目視による観察で評価した。 ◎：全く目立たない ○：目立たない △：目立つ ×：大変目立つ。(5) The surface appearance of the molded product is the cylinder temperature.
Injection molding was performed at 220 ° C. and a mold temperature of 50 ° C. to prepare a flat plate-shaped molded product, and the weld line and flow mark of the molded product obtained were visually evaluated according to the following criteria. ⊚: Not noticeable ○: Not noticeable Δ: Conspicuous ×: Very noticeable
【００３３】実施例１、比較例１，２ 内容積30リットルの重合反応器に、スチレンモノマー80
重量％と、スチレン・ブタジエンブロック共重合体（旭
化成工業（株）製：アサプレン670A）20重量％との混合
溶液20kgを仕込み、連鎖移動剤としてターピノーレン10
ｇを添加する。これを攪拌回転数60rpm で攪拌しなが
ら、 130℃の重合温度で３時間、続いて 150℃の重合温
度で４時間熱重合させた後、 220℃、20分間の脱揮過程
を経て、小粒子ゴムが分散したゴム変性ポリスチレンHI
PS(A−1)を得た。以後、ゴム変性ポリスチレンをHIPSと
略す。一方、スチレンモノマー95重量％と、ローシスポ
リブタジエン（シス− 1,4構造含有率35％）（旭化成工
業（株）製：ジエン55AS）３重量％、およびスチレン・
ブタジエンブロック共重合体（旭化成工業（株）製：ア
サプレン670A）２重量％との混合溶液20kgを仕込む以外
は、前記と同様にして大粒子ゴムが分散したHIPS(B−1)
を得た。次いで、前記HIPS(A−1)とHIPS(B−1)とを表１
に示す割合で配合し、押出機にて溶融混練してゴム変性
スチレン系樹脂組成物を得た。表１に該樹脂組成物の各
特性を示す。Example 1, Comparative Examples 1 and 2 A styrene monomer 80 was placed in a polymerization reactor having an internal volume of 30 liters.
20 kg of a mixed solution of 20% by weight of styrene / butadiene block copolymer (Asaprene 670A manufactured by Asahi Chemical Industry Co., Ltd.) was charged, and terpinolene 10 was used as a chain transfer agent.
g is added. While stirring at a rotation speed of 60 rpm, this was thermally polymerized at a polymerization temperature of 130 ° C. for 3 hours and then at a polymerization temperature of 150 ° C. for 4 hours, and then subjected to a devolatilization process at 220 ° C. for 20 minutes to obtain small particles. Rubber-modified polystyrene HI with rubber dispersed
PS (A-1) was obtained. Hereinafter, rubber-modified polystyrene is abbreviated as HIPS. On the other hand, 95% by weight of styrene monomer, 3% by weight of low cis polybutadiene (cis-1,4 structure content 35%) (Asahi Kasei Co., Ltd .: Diene 55AS), and styrene
HIPS (B-1) in which large particle rubber was dispersed in the same manner as above except that 20 kg of a mixed solution with 2% by weight of a butadiene block copolymer (Asaprene 670A manufactured by Asahi Kasei Kogyo Co., Ltd.) was charged.
I got Then, the HIPS (A-1) and HIPS (B-1) are shown in Table 1.
Were blended in the proportions shown in and melt-kneaded with an extruder to obtain a rubber-modified styrene resin composition. Table 1 shows each characteristic of the resin composition.
【００３４】表１から明らかなように、実施例１は、本
発明のゴム変性スチレン系樹脂組成物であり、本発明の
目的とする物性および表面外観が得られている。しかし
ながら、比較例１は、ゴム状重合体粒子の総重量に占め
る小粒子部分の比率が60重量％未満であるため、外観不
良が目立っている。比較例２は、ゴム状重合体粒子の総
重量に占める小粒子部分の比率が95重量％を超えるた
め、衝撃強度が劣り好ましくない。As is clear from Table 1, Example 1 is the rubber-modified styrene resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention are obtained. However, in Comparative Example 1, since the proportion of the small particle portion in the total weight of the rubber-like polymer particles is less than 60% by weight, the appearance defect is remarkable. In Comparative Example 2, the proportion of the small particle portion in the total weight of the rubber-like polymer particles is more than 95% by weight, and therefore the impact strength is poor, which is not preferable.
【００３５】比較例３ 前記HIPS(A−1)の調製において、攪拌回転数を100rpmに
上げて重合を行う以外は実施例１と同様にして、HIPS(A
−2)を得た。HIPS(A−2)とHIPS(B−1)とを表１に示す割
合で配合し、押出機にて溶融混練して樹脂組成物を得
た。表１に該樹脂組成物の各特性を示す。Comparative Example 3 HIPS (A-1) was prepared in the same manner as in Example 1 except that the stirring rotation speed was increased to 100 rpm to carry out the polymerization.
-2) was obtained. HIPS (A-2) and HIPS (B-1) were blended in a ratio shown in Table 1 and melt-kneaded with an extruder to obtain a resin composition. Table 1 shows each characteristic of the resin composition.
【００３６】表１から明らかなように、比較例３は、ゴ
ム状重合体の小粒子部分の平均粒子径が 0.1μm 未満で
あるため、耐衝撃性は極端に劣っている。As is clear from Table 1, in Comparative Example 3, the impact resistance is extremely poor because the average particle diameter of the small particle portion of the rubber-like polymer is less than 0.1 μm.
【００３７】比較例４ 前記HIPS(A−1)の調製において、スチレンモノマー90重
量％と、ローシスポリブタジエン（シス−1,4 構造含有
率35％）10重量％との混合溶液20kgを仕込み、攪拌回転
数を80rpm に下げて重合を行う以外は実施例１と同様に
して、HIPS(A−3)を得た。HIPS(A−3)とHIPS(B−1)とを
表１に示す割合で配合し、押出機にて溶融混練して樹脂
組成物を得た。表１に該樹脂組成物の各特性を示す。Comparative Example 4 In the preparation of the HIPS (A-1), 20 kg of a mixed solution of 90% by weight of a styrene monomer and 10% by weight of low cis polybutadiene (cis-1,4 structure content 35%) was charged, HIPS (A-3) was obtained in the same manner as in Example 1 except that the stirring rotation speed was lowered to 80 rpm to carry out the polymerization. HIPS (A-3) and HIPS (B-1) were blended in a ratio shown in Table 1 and melt-kneaded with an extruder to obtain a resin composition. Table 1 shows each characteristic of the resin composition.
【００３８】表１に示すように、比較例４は、ゴム状重
合体の小粒子部分の平均粒子径が 0.5μm を超えている
ため、外観不良が目立っている。As shown in Table 1, in Comparative Example 4, the average particle diameter of the small particle portion of the rubber-like polymer exceeds 0.5 μm, so that the appearance defect is remarkable.
【００３９】比較例５ 前記HIPS(B−1)の調製において、攪拌回転数を100rpmに
上げて重合を行う以外は実施例１と同様にして、HIPS(B
−2)を得た。次いで、前記HIPS(A−1)とHIPS(B−2)とを
表１に示す割合で配合し、押出機にて溶融混練して樹脂
組成物を得た。表１に該樹脂組成物の各特性を示す。Comparative Example 5 In the preparation of HIPS (B-1), HIPS (B-1) was prepared in the same manner as in Example 1 except that the stirring rotation speed was increased to 100 rpm to carry out the polymerization.
-2) was obtained. Then, the HIPS (A-1) and HIPS (B-2) were blended in the proportions shown in Table 1 and melt-kneaded with an extruder to obtain a resin composition. Table 1 shows each characteristic of the resin composition.
【００４０】表１から、比較例５は、大粒子部分の平均
粒子径が 0.6μm 未満であるため、衝撃強度が十分でな
いことが分かる。From Table 1, it can be seen that Comparative Example 5 has an insufficient impact strength because the average particle size of the large particles is less than 0.6 μm.
【００４１】比較例６ 前記HIPS(B−1)の調製において、攪拌回転数を 30rpmに
下げて重合を行う以外は実施例１と同様にして、HIPS(B
−3)を得た。次いで、前記HIPS(A−1)とHIPS(B−3)とを
表１に示す割合で配合し、押出機にて溶融混練して樹脂
組成物を得た。表１に該樹脂組成物の各特性を示す。Comparative Example 6 In the preparation of HIPS (B-1), HIPS (B-1) was prepared in the same manner as in Example 1 except that the stirring rotation speed was lowered to 30 rpm to carry out the polymerization.
-3) was obtained. Then, the HIPS (A-1) and HIPS (B-3) were blended in the proportions shown in Table 1 and melt-kneaded with an extruder to obtain a resin composition. Table 1 shows each characteristic of the resin composition.
【００４２】表１に示すように、比較例６は、大粒子部
分の平均粒子径が 4.0μm を超えているため、外観不良
が非常に目立っている。As shown in Table 1, in Comparative Example 6, the average particle size of the large particles exceeds 4.0 μm, so that the defective appearance is very noticeable.
【００４３】[0043]
【表１】 [Table 1]
【００４４】実施例２ 前記HIPS(A−1)の調製において、連鎖移動剤ターピノー
レンの添加量を30ｇに増やして重合を行う以外は実施例
１と同様にして、HIPS(A−4)を得た。前記HIPS(A−4)と
HIPS(B−1)とを表２に示す割合で配合し、押出機にて溶
融混練して樹脂組成物を得た。表２に該樹脂組成物の各
特性を示す。Example 2 HIPS (A-4) was obtained in the same manner as in Example 1 except that the amount of the chain transfer agent terpinolene added was increased to 30 g in the preparation of HIPS (A-1). It was HIPS (A-4) and
HIPS (B-1) was blended in a ratio shown in Table 2 and melt-kneaded with an extruder to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００４５】表２から明らかなように、実施例２は、本
発明のゴム変性スチレン系樹脂組成物であり、本発明の
目的とする物性および表面外観が得られている。As is clear from Table 2, Example 2 is the rubber-modified styrene resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention are obtained.
【００４６】実施例３、４ 前記HIPS(A−4)とHIPS(B−1)、およびミネラルオイル
（Witco co. 製：PL−380)とを表２に示す割合で配合
し、押出機にて溶融混練して樹脂組成物を得た。表２に
該樹脂組成物の各特性を示す。Examples 3 and 4 The above HIPS (A-4) and HIPS (B-1) and mineral oil (PL-380 manufactured by Witco co.) Were mixed in the proportions shown in Table 2, and the mixture was put into an extruder. And melt-kneaded to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００４７】表２から明らかなように、実施例３は、本
発明のゴム変性スチレン系樹脂組成物であり、本発明の
目的とする物性および表面外観が得られている。また、
実施例４は、本発明のゴム変性スチレン系樹脂組成物で
あり、本発明の目的とする表面外観が得られているが、
200℃、５kg荷重におけるメルトフローレートが30ｇ／
10min を超えているため、衝撃強度がわずかに低い値を
示した。As is clear from Table 2, Example 3 is the rubber-modified styrene resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention were obtained. Also,
Example 4 is the rubber-modified styrenic resin composition of the present invention, and the surface appearance targeted by the present invention was obtained.
Melt flow rate at 200 ℃, 5kg load is 30g /
Since it exceeded 10 min, the impact strength showed a slightly low value.
【００４８】比較例７ 前記HIPS(A−1)の調製において、連鎖移動剤を添加せ
ず、重合温度 110℃で３時間、続いて重合温度 140℃で
４時間熱重合を行う以外は実施例１と同様にして、HIPS
(A−5)を得た。前記HIPS(A−5)とHIPS(B−1)とを表２に
示す割合で配合し、押出機に溶融混練して樹脂組成物を
得た。表２に該樹脂組成物の各特性を示す。Comparative Example 7 In the preparation of HIPS (A-1) above, a chain transfer agent was not added and thermal polymerization was carried out at a polymerization temperature of 110 ° C. for 3 hours and then at a polymerization temperature of 140 ° C. for 4 hours. HIPS as in 1
(A-5) was obtained. HIPS (A-5) and HIPS (B-1) were blended in the proportions shown in Table 2 and melt-kneaded in an extruder to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００４９】表２から明らかなように、比較例７は、 2
00℃、５kg荷重におけるメルトフローレートが５ｇ／10
min 未満であるため流動性に劣り、十分な表面外観が得
られない。As is clear from Table 2, Comparative Example 7
Melt flow rate at 5 ℃ load of 5 ℃ at 00 ℃
Since it is less than min, the fluidity is poor and sufficient surface appearance cannot be obtained.
【００５０】実施例５ 前記HIPS(B−1)の調製において、スチレンモノマー95重
量％と、ローシスポリブタジエン（シス−1,4 構造含有
率35％）５重量％との混合溶液20kgを仕込む以外は実施
例１と同様にして、HIPS(B−4)を得た。前記HIPS(A−1)
とHIPS(B−4)とを表２に示す割合で配合し、押出機にて
溶融混練して樹脂組成物を得た。表２に該樹脂組成物の
各特性を示す。Example 5 In preparation of the HIPS (B-1), 20 kg of a mixed solution of 95% by weight of styrene monomer and 5% by weight of low cis polybutadiene (cis-1,4 structure content 35%) was charged. In the same manner as in Example 1, HIPS (B-4) was obtained. HIPS (A-1)
And HIPS (B-4) were blended in a ratio shown in Table 2 and melt-kneaded with an extruder to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００５１】表２から、実施例５は、本発明のゴム変性
スチレン系樹脂組成物であり、本発明の目的とする物性
および表面外観が得られていることがわかる。From Table 2, it can be seen that Example 5 is the rubber-modified styrenic resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention are obtained.
【００５２】実施例６ 前記HIPS(A−1)の調製において、重合後の脱揮時間を５
分間にすること以外は実施例１と同様にして、HIPS(A−
6)を得た。前記HIPS(A−6)とHIPS(B−1)とを表２に示す
割合で配合し、押出機にて溶融混練して樹脂組成物を得
た。表２に該樹脂組成物の各特性を示す。Example 6 In the preparation of HIPS (A-1), the devolatilization time after polymerization was 5
HIPS (A-
Got 6). HIPS (A-6) and HIPS (B-1) were blended in the proportions shown in Table 2 and melt-kneaded in an extruder to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００５３】表２から、実施例６は、本発明のゴム変性
スチレン系樹脂組成物であり、本発明の目的とする物性
および表面外観が得られていることがわかる。From Table 2, it can be seen that Example 6 is the rubber-modified styrene resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention are obtained.
【００５４】実施例７ 前記HIPS(A−1)の調製において、重合後の脱揮時間を40
分間にすること以外は実施例１と同様にして、HIPS(A−
7)を得た。前記HIPS(A−7)とHIPS(B−1)とを表２に示す
割合で配合し、押出機にて溶融混練して樹脂組成物を得
た。表２に該樹脂組成物の各特性を示す。Example 7 In the preparation of HIPS (A-1), the devolatilization time after polymerization was 40
HIPS (A-
7) got. HIPS (A-7) and HIPS (B-1) were blended in the proportions shown in Table 2 and melt-kneaded with an extruder to obtain a resin composition. Table 2 shows each characteristic of the resin composition.
【００５５】表２から明らかなように、実施例７は、本
発明のゴム変性スチレン系樹脂組成物であり、本発明の
目的とする物性および表面外観が得られていることがわ
かる。As is clear from Table 2, Example 7 is the rubber-modified styrene resin composition of the present invention, and the physical properties and surface appearance targeted by the present invention are obtained.
【００５６】[0056]
【表２】 [Table 2]
【００５７】[0057]
【本発明の効果】本発明のゴム変性スチレン系樹脂組成
物は、ゴム状重合体が、それぞれ特定の平均粒子径を有
する小粒子部分と大粒子部分の二峰からなる粒子径分布
を持ち、特定のメルトフローレートを持つために、耐衝
撃性や耐熱性を保持したまま十分な成形性を示し、金型
温度などの成形条件を変えたり、成形品表面に塗装を施
すことなくウェルドラインやフローマーク等の表面外観
不良の見られない成形品を得ることができる。In the rubber-modified styrene resin composition of the present invention, the rubber-like polymer has a bimodal particle size distribution of a small particle portion and a large particle portion each having a specific average particle diameter. Since it has a specific melt flow rate, it exhibits sufficient moldability while maintaining impact resistance and heat resistance, and does not need to change molding conditions such as mold temperature or to apply weld lines or weld lines without coating the molded product surface. It is possible to obtain a molded product that does not show a surface appearance defect such as a flow mark.
Claims (5)
て、 (A) スチレン系重合体からなるマトリックス中に、粒子
状のゴム状重合体が分散しており、かつ (B) 前記ゴム状重合体粒子が、（イ）平均粒子径 0.1〜
0.5 μm の小粒子部分と、（ロ）平均粒子径 0.6〜4.0
μm の大粒子部分とからなる二峰性の粒子径分布を有
し、 (C) 前記ゴム状重合体粒子の総重量に占める小粒子部分
の比率が60〜95重量％であり、 (D) 該ゴム変性スチレン系樹脂組成物の 200℃、５kg荷
重におけるメルトフローレートが５ｇ／10min 以上であ
る、成形性に優れたゴム変性スチレン系樹脂組成物。1. A rubber-modified styrene-based resin composition, wherein a particulate rubber-like polymer is dispersed in a matrix composed of (A) a styrene-based polymer, and (B) the rubber-like polymer particles. However, (a) average particle size 0.1-
0.5 μm small particle part and (b) average particle size 0.6 to 4.0
having a bimodal particle size distribution consisting of large particles of (μm), (C) the proportion of small particles in the total weight of the rubber-like polymer particles is 60 to 95% by weight, (D) A rubber-modified styrene-based resin composition excellent in moldability, wherein the rubber-modified styrene-based resin composition has a melt flow rate of 5 g / 10 min or more at 200 ° C. under a load of 5 kg.
指数が５〜10の範囲である請求項１記載のゴム変性スチ
レン系樹脂組成物。2. The rubber-modified styrenic resin composition according to claim 1, wherein the swelling index of the rubber-like polymer particles in toluene is in the range of 5 to 10.
指数が５〜７の範囲である請求項２記載のゴム変性スチ
レン系樹脂組成物。3. The rubber-modified styrene resin composition according to claim 2, wherein the swelling index of the rubber-like polymer particles in toluene is in the range of 5 to 7.
スチレン系樹脂組成物の不溶分重量の比率が 4.1以上で
ある請求項２又は３記載のゴム変性スチレン系樹脂組成
物。4. The rubber-modified styrene-based resin composition according to claim 2, wherein the ratio of the insoluble content weight of the rubber-modified styrene-based resin composition to the total weight of the rubber-like polymer is 4.1 or more.
℃、５kg荷重におけるメルトフローレートが18〜30ｇ／
10min である請求項２〜４の何れか１項に記載のゴム変
性スチレン系樹脂組成物。5. A rubber-modified styrene resin composition of 200
Melt flow rate at ℃, 5kg load 18-30g /
The rubber-modified styrene resin composition according to any one of claims 2 to 4, which has a duration of 10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7010424A JPH08199021A (en) | 1995-01-26 | 1995-01-26 | Rubber-modified styrene resin composition excellent in moldability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7010424A JPH08199021A (en) | 1995-01-26 | 1995-01-26 | Rubber-modified styrene resin composition excellent in moldability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08199021A true JPH08199021A (en) | 1996-08-06 |
Family
ID=11749779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7010424A Pending JPH08199021A (en) | 1995-01-26 | 1995-01-26 | Rubber-modified styrene resin composition excellent in moldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08199021A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244022A (en) * | 1988-08-03 | 1990-02-14 | Matsushita Electric Ind Co Ltd | Production of polycrystalline silicon |
| KR100411088B1 (en) * | 2001-08-17 | 2003-12-18 | 제일모직주식회사 | Styrenic Resin Composition with Excellent Heat Resistance and Surface Gloss |
| JP2019073577A (en) * | 2017-10-12 | 2019-05-16 | 東洋スチレン株式会社 | Styrene resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63230754A (en) * | 1987-03-19 | 1988-09-27 | Asahi Chem Ind Co Ltd | Impact-resistant polystyrene resin composition having excellent gloss |
| JPH0425555A (en) * | 1990-05-22 | 1992-01-29 | Asahi Chem Ind Co Ltd | Resin composition having improved resistance to blistering |
| JPH05132605A (en) * | 1991-11-06 | 1993-05-28 | Nippon Steel Chem Co Ltd | Rubber modified polystyrene composition |
| JPH06287248A (en) * | 1993-04-06 | 1994-10-11 | Mitsubishi Kasei Corp | Method for producing rubber-modified styrene resin composition |
-
1995
- 1995-01-26 JP JP7010424A patent/JPH08199021A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63230754A (en) * | 1987-03-19 | 1988-09-27 | Asahi Chem Ind Co Ltd | Impact-resistant polystyrene resin composition having excellent gloss |
| JPH0425555A (en) * | 1990-05-22 | 1992-01-29 | Asahi Chem Ind Co Ltd | Resin composition having improved resistance to blistering |
| JPH05132605A (en) * | 1991-11-06 | 1993-05-28 | Nippon Steel Chem Co Ltd | Rubber modified polystyrene composition |
| JPH06287248A (en) * | 1993-04-06 | 1994-10-11 | Mitsubishi Kasei Corp | Method for producing rubber-modified styrene resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244022A (en) * | 1988-08-03 | 1990-02-14 | Matsushita Electric Ind Co Ltd | Production of polycrystalline silicon |
| KR100411088B1 (en) * | 2001-08-17 | 2003-12-18 | 제일모직주식회사 | Styrenic Resin Composition with Excellent Heat Resistance and Surface Gloss |
| JP2019073577A (en) * | 2017-10-12 | 2019-05-16 | 東洋スチレン株式会社 | Styrene resin composition |
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