JP3325399B2 - Method for producing ABS resin having various surface morphologies - Google Patents
Method for producing ABS resin having various surface morphologiesInfo
- Publication number
- JP3325399B2 JP3325399B2 JP21852694A JP21852694A JP3325399B2 JP 3325399 B2 JP3325399 B2 JP 3325399B2 JP 21852694 A JP21852694 A JP 21852694A JP 21852694 A JP21852694 A JP 21852694A JP 3325399 B2 JP3325399 B2 JP 3325399B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- particles
- extruder
- molded product
- screw
- 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 - Fee Related
Links
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002245 particle Substances 0.000 claims description 125
- 229920005989 resin Polymers 0.000 claims description 89
- 239000011347 resin Substances 0.000 claims description 89
- 229920001971 elastomer Polymers 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 54
- 239000005060 rubber Substances 0.000 claims description 54
- 238000004898 kneading Methods 0.000 claims description 46
- 238000011084 recovery Methods 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 238000000635 electron micrograph Methods 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000010008 shearing Methods 0.000 claims description 13
- 238000001746 injection moulding Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 74
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- YJCVRMIJBXTMNR-UHFFFAOYSA-N 1,3-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=CC(Cl)=C1C=C YJCVRMIJBXTMNR-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-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
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-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
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SZSWKGVWJBZNIH-UHFFFAOYSA-N 2-chloro-1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C(Cl)=C1 SZSWKGVWJBZNIH-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- VUKHQPGJNTXTPY-UHFFFAOYSA-N but-2-enylbenzene Chemical compound CC=CCC1=CC=CC=C1 VUKHQPGJNTXTPY-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009863 impact test Methods 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
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は成形物のモルフォロジ
ー、更に詳しくは成形物表面のモルフォロジーをコント
ロールするＡＢＳ系樹脂成形物の製造方法に関するもの
である。本発明によって成形物の表面におけるゴム粒子
モルフォロジーが自由に変えられるのでＡＢＳ樹脂の表
面の特徴を極めて容易に発現させることができ、例えば
光沢・艶消しを任意にコントロールできるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a morphology of a molded article, and more particularly to a method for producing an ABS resin molded article which controls the morphology of the surface of the molded article. According to the present invention, the rubber particle morphology on the surface of the molded product can be freely changed, so that the characteristics of the surface of the ABS resin can be extremely easily expressed, and for example, gloss / mat can be arbitrarily controlled.
【０００２】[0002]
【従来の技術】従来ＡＢＳ系樹脂において表面の特性を
コントロールするために様々な方法が用いられてきた。
例えばゴム粒子径の大きいゴム粒子を用いることにより
表面のゴム粒子（もちろん内部の粒子も同様であるが）
形状を大きくしたり、あるいは逆にゴム粒子径の小さい
ゴム粒子を用いて表面及び内部のゴム粒子の形状を小さ
くすることにより表面の特性をコントロールしていた。
即ち従来技術においてはＡＢＳ樹脂の製造工程からゴム
粒子径をコントロールする事が一般的であり、そのため
表面のみならず、成形物の衝撃や剛性等にまでゴム粒子
径のコントロールの影響が現れ、物性バランスの面で大
きな問題であった。例えば艶消し性を持たせるため、粒
子径の大きなゴム粒子を用いると表面の艶消し性は優れ
るが、一方で衝撃強度が低下するという問題があった。
また表面に光沢性を付与するためにゴム粒子径を小さく
すると光沢性は優れるが衝撃強度が低下するためゴム成
分を多量に必要とした。その他にＡＢＳ樹脂の表面モル
フォロジーをコントロールする方法としては成形段階で
成形条件を特定する方法がある。例えば光沢を高く保持
するために射出成形時、高温の金型温度を用いるという
ことが行われてきた。この場合は成形条件が限定され、
成形射出サイクルが長くなり、生産性に重要な問題が残
る。2. Description of the Related Art Conventionally, various methods have been used to control surface properties of ABS resins.
For example, by using rubber particles having a large rubber particle diameter, rubber particles on the surface (of course, the same applies to particles inside)
The characteristics of the surface have been controlled by enlarging the shape, or conversely, reducing the shape of the surface and internal rubber particles by using rubber particles having a small rubber particle diameter.
That is, in the prior art, it is common to control the rubber particle diameter from the ABS resin manufacturing process. Therefore, the influence of the control of the rubber particle diameter appears not only on the surface but also on the impact and rigidity of the molded product. It was a big problem in terms of balance. For example, when rubber particles having a large particle diameter are used to impart a matting property, the matting property of the surface is excellent, but on the other hand, there is a problem that the impact strength is reduced.
In addition, when the rubber particle diameter is reduced to impart gloss to the surface, the gloss is excellent, but the impact strength is reduced, so that a large amount of the rubber component is required. As another method for controlling the surface morphology of the ABS resin, there is a method of specifying molding conditions at the molding stage. For example, it has been practiced to use a high mold temperature during injection molding to maintain high gloss. In this case, the molding conditions are limited,
The molding injection cycle lengthens, leaving significant productivity issues.
【０００３】また、従来表面光沢を特定の値に保持する
ためには重合工程で厳密に管理しなければならなかっ
た。本発明においては原料樹脂の製造でのコントールだ
けでなく押出工程で表面特性が厳密にコントロールでき
る。[0003] Conventionally, in order to maintain the surface gloss at a specific value, it was necessary to strictly control in the polymerization step. In the present invention, not only the control in the production of the raw material resin but also the surface characteristics can be strictly controlled in the extrusion step.
【０００４】[0004]
【本発明が解決しようとする課題】従ってＡＢＳ系樹脂
の成形物表面モルフォロジーを、衝撃強度等を維持しな
がら任意にコントロールする方法を提供する事にある。Accordingly, an object of the present invention is to provide a method for arbitrarily controlling the surface morphology of a molded article of an ABS resin while maintaining impact strength and the like.
【０００５】[0005]
【課題を解決するための手段】本発明においては、従来
とは全く異なる技術手段を用いて成形物表面で観察され
るゴム粒子の形態（ゴム粒子のモルフォロジー）のコン
トロールを行う。即ち本発明では少なくともスチレン系
単量体及びアクリロニトリル系単量体、及びゴム状重合
体を含む原料を重合工程に供給し、該単量体の一部もし
くは全量を重合させてゴム状重合体粒子（ゴム粒子）形
成を含む重合体を重合する工程の後、重合体、未反応単
量体および／または溶剤を含む混合液を加熱し、同時に
または加熱後減圧室に導入して単量体および／または溶
剤を樹脂成分と分離する分離回収工程を持ち、その分離
回収工程を出た樹脂を射出成形して得られた成形物（成
形物１）は、成形物表面で観察されるゴム粒子のうち、
長径ａと短径ｂの比率ａ／ｂが１．５以下の粒子Ａ、及
び、長径ａと短径ｂの比率ａ／ｂが５以上である粒子Ｂ
を有している。（本発明において成形物１を得る方法と
しては、重合で得られた樹脂のモルフォロジーを測定す
るので、分離回収工程出口にサンプル弁を設け、そこか
らひも状に樹脂をを取り出し、水槽中で冷却してストラ
ンドを得、これを切断してペレットを作成し、これから
射出成形によって成形物１を得る。） かかる樹脂を分離回収工程後、剪断効果のある２軸押出
機で押し出すことによりこれら粒子Ａ・粒子Ｂの量がコ
ントロールできることは全く知られていなかった。本発
明者らは成形物表面付近で観察されるゴム粒子、粒子Ａ
と粒子Ｂという異なる形態のゴム粒子の割合を押出機に
より調整するという従来にない方法によって成形物表面
の光沢を任意にコントロールできることを見いだし本発
明に至った。In the present invention, the morphology (rubber particle morphology) of the rubber particles observed on the surface of the molded product is controlled by using a technical means completely different from the conventional one. That is, in the present invention, at least a styrene-based monomer and an acrylonitrile-based monomer, and a raw material containing a rubber-like polymer are supplied to the polymerization step, and a part or all of the monomer is polymerized to produce rubber-like polymer particles. After the step of polymerizing the polymer including (rubber particle) formation, the mixed solution containing the polymer, the unreacted monomer and / or the solvent is heated and introduced into the reduced pressure chamber simultaneously or after the heating, and the monomer and And / or a separation / recovery step of separating the solvent from the resin component, and a molded product (molded product 1) obtained by injection-molding the resin that has gone through the separation / recovery process is formed of rubber particles observed on the surface of the molded product. home,
Particle A having a ratio a / b of major axis a to minor axis b of 1.5 or less and particle B having a ratio a / b of major axis a to minor axis b of 5 or greater
have. (As a method for obtaining the molded article 1 in the present invention, the morphology of the resin obtained by polymerization is measured. Therefore, a sample valve is provided at the outlet of the separation / recovery step, the resin is taken out in a string form, and cooled in a water bath. To obtain a molded product 1 by injection molding.) After the resin is separated and recovered, the particles A are extruded by a twin-screw extruder having a shearing effect. -It was not known at all that the amount of the particles B could be controlled. The present inventors have found that rubber particles, particle A, observed near the surface of a molded product
It has been found that the gloss of the surface of a molded product can be arbitrarily controlled by an unconventional method of adjusting the ratio of rubber particles having different forms, ie, particles B and particles B, by an extruder, and have reached the present invention.
【０００６】即ち［I］少なくともスチレン系単量体及
びアクリロニトリル系単量体、及びゴム状重合体を含む
原料を重合工程に供給し、該単量体の一部もしくは全量
を重合させてゴム粒子形成を含む重合体を重合する工程
の後、重合体、未反応単量体および／または溶剤を含む
混合液を加熱し、同時にまたは加熱後減圧室に導入して
単量体および／または溶剤を樹脂成分と分離する分離回
収工程を持ち、この分離回収工程を出る樹脂を射出成形
して得られた成形物（成形物１）の表面から０．５〜
１．５μｍの深さに存在するゴム粒子が、成形物表面と
の平行面を超薄切片法による電子顕微鏡写真で観察する
時、 長径ａと短径ｂの比率ａ／ｂが１．５以下の粒子Ａ、
及び 長径ａと短径ｂの比率ａ／ｂが５以上である粒子Ｂ の少なくとも２種類の形態を有し、且つ超薄切片法によ
る電子顕微鏡写真で観察されるゴム粒子の全面積を１０
０％とした時に粒子Ａの面積が少なくとも１０％以上、
粒子Ｂの面積が０．０１〜９０％であるＡＢＳ樹脂を、
［II］分離回収工程を出た後、ニーディングディスクま
たはローターを有する２軸押出機により剪断を与えるこ
とによって、得られた成形物（成形物２）の表面を上記
と同じ方法で、 即ち成形物表面から０．５〜１．５μ
ｍの深さの平行面を超薄切片法による電子顕微鏡写真で
観察し、粒子Ｂの面積を上記成形物１で観察された粒子
Ｂの割合を１００％とするとき０〜９５％となる様コン
トロールする方法である。本発明では分離回収工程を出
た樹脂を射出成形して得られた成形物（成形物１）の表
面には粒子Ａと粒子Ｂが存在する事が特徴である。即ち
成形物１の表面から０．５〜１．５μｍの深さに存在す
るゴム粒子のうち、観察されるゴム粒子の全面積を１０
０％とすると、１０％以上が粒子Ａの面積、好ましくは
１０〜５０％、さらに好ましくは１０〜４０％であり、
且つ０．０１〜９０％が粒子Ｂの面積、好ましくは０．
０５〜５０％、より好ましくは０．１〜３０％を占めて
いることが特徴である。本発明において、粒子Ａの面積
が１０％未満、または粒子Ｂの面積が０．０１％未満で
あれば本発明の目的である表面のゴム粒子のモルフォロ
ジーがコントロールできなくなり、局所的に光沢が低い
部分が生じる。また、粒子Ｂが９０％を越えると押出機
による処理を行っても成形物表面にすじ模様が発生し好
ましくない。That is, [I] a raw material containing at least a styrene monomer, an acrylonitrile monomer, and a rubbery polymer is supplied to a polymerization step, and a part or all of the monomer is polymerized to obtain rubber particles. After the step of polymerizing the polymer including formation, the mixture containing the polymer, the unreacted monomer and / or the solvent is heated, and simultaneously or after heating, introduced into a vacuum chamber to remove the monomer and / or the solvent. It has a separation / recovery step of separating from the resin component, and the resin exiting the separation / recovery step is injected from the surface of the molded product (molded product 1) by injection molding at 0.5 to
When the rubber particles existing at a depth of 1.5 μm and the parallel plane with the surface of the molded article are observed with an electron micrograph by an ultra-thin section method, the ratio a / b of the major axis a to the minor axis b is 1.5 or less. Particles A of
And at least two types of particles B having a ratio a / b of the major axis a to the minor axis b of 5 or more, and the total area of the rubber particles observed in the electron micrograph by the ultra-thin section method is 10%.
0%, the area of the particles A is at least 10% or more,
ABS resin having an area of particles B of 0.01 to 90%,
[II] After exiting the separation / recovery step, the surface of the obtained molded product (molded product 2) is subjected to shearing by a twin-screw extruder having a kneading disk or a rotor in the same manner as described above, ie, molding. 0.5-1.5μ from object surface
The parallel plane having a depth of m is observed with an electron micrograph by an ultra-thin section method, and the area of the particles B is 0 to 95% when the percentage of the particles B observed in the molded article 1 is 100%. How to control. The present invention is characterized in that particles A and B are present on the surface of a molded product (molded product 1) obtained by injection-molding a resin that has gone through the separation and recovery step. That is, among the rubber particles present at a depth of 0.5 to 1.5 μm from the surface of the molded article 1, the total area of the observed rubber particles is 10
If 0%, 10% or more is the area of the particles A, preferably 10 to 50%, more preferably 10 to 40%,
And 0.01 to 90% is the area of the particles B, preferably 0.1%.
It is characterized in that it accounts for 0.5 to 50%, more preferably 0.1 to 30%. In the present invention, if the area of the particles A is less than 10% or the area of the particles B is less than 0.01%, the morphology of the rubber particles on the surface, which is the object of the present invention, cannot be controlled, and the gloss is locally low. Parts arise. On the other hand, if the content of the particles B exceeds 90%, a streak pattern is formed on the surface of the molded product even if the treatment is performed by an extruder, which is not preferable.
【０００７】また本発明において［I］少なくともスチ
レン系単量体及びアクリロニトリル系単量体、及びゴム
状重合体を含む原料を重合工程に供給し、該単量体の一
部もしくは全量を重合させてゴム粒子形成を含む重合体
を重合する工程の後、重合体、未反応単量体および／ま
たは溶剤を含む混合液を加熱し、同時にまたは加熱後減
圧室に導入して単量体および／または溶剤を樹脂成分と
分離する分離回収工程を持ち、この分離回収工程を出る
樹脂を射出成形して得られた成形物（成形物１）の表面
から０．５〜１．５μｍの深さに存在するゴム粒子が、
成形物表面との平行面を超薄切片法による電子顕微鏡写
真で観察する時、粒子Ａ、及び粒子Ｂの少なくとも２種
類の形態を有し、且つ超薄切片法による電子顕微鏡写真
で観察されるゴム粒子の全面積を１００％とした時に粒
子Ａの面積が少なくとも１０％以上、粒子Ｂの面積が
０．０１〜９０％であるＡＢＳ樹脂を、［II］分離回収
工程を出た後、ニーディングディスクまたはローターを
有する２軸押出機で、分離回収出口とニーディングディ
スクまたはローターが設置されている部分（ニーディン
グゾーン）との間に樹脂に水を添加する部分と添加した
水を蒸発させる部分を有し、且つ添加した水を蒸発させ
る部分はニーディングゾーン入り口と同時またはその直
前部に設けられた押出機を用いて剪断を与えることによ
って得られた成形物（成形物２）の表面を上記と同じ方
法で、即ち成形物表面から０．５〜１．５μｍの深さの
平行面を超薄切片法による電子顕微鏡写真で観察し、粒
子Ｂの面積を上記成形物１で観察された粒子Ｂの割合を
１００％とするとき０〜９５％となる様コントロールす
る方法である。この時添加する水の割合は単位時間当た
りの樹脂の押出量１００重量部に対して０〜１５重量
部、好ましくは０．１〜１０重量部、より好ましくは
０．５〜７重量部である。水の添加量が１５重量部を越
えると押出機の処理能力が低下して生産性に影響が出て
好ましくない。また、ニーディングゾーン直前で水を添
加・蒸発させニーディングゾーン直前部で回収工程出口
の樹脂温の０〜６０％低下させることによりニーディン
グゾーンで十分な剪断力が与えられる。水を添加しない
場合は押出機中でニーディングディスクが設置されてい
る部分またはその直前部で押出機シリンダーの温度を回
収工程出口の樹脂温の０〜６０％低下させた温度とする
ことにより水を添加した場合と同様、十分な剪断力が樹
脂に与えられる。ただしシリンダーの温度によって樹脂
温を低下させる場合は、押出機の大きさが制限され、大
型押出機の装置になるとシリンダー温度によって樹脂温
を制御できなくなる。In the present invention, [I] a raw material containing at least a styrene monomer, an acrylonitrile monomer, and a rubbery polymer is supplied to a polymerization step, and a part or all of the monomer is polymerized. After the step of polymerizing the polymer including the formation of rubber particles by heating, the mixed solution containing the polymer, the unreacted monomer and / or the solvent is heated, and simultaneously or after heating, introduced into a reduced pressure chamber and the monomer and / or Alternatively, it has a separation / recovery step of separating the solvent from the resin component, and has a depth of 0.5 to 1.5 μm from the surface of a molded product (molded product 1) obtained by injection-molding the resin exiting the separation / recovery process. The rubber particles that exist
When observing the plane parallel to the surface of the molded article with an electron micrograph by an ultra-thin section method, it has at least two types of particles A and B, and is observed by an electron micrograph by an ultra-thin section method. An ABS resin in which the area of the particles A is at least 10% or more and the area of the particles B is 0.01 to 90% when the total area of the rubber particles is 100%, after leaving the [II] separation and recovery step, In a twin-screw extruder having a loading disk or a rotor, a portion where water is added to the resin between a separation and recovery outlet and a portion (kneading zone) where the kneading disk or the rotor is installed, and the added water is evaporated. A molded product obtained by applying a shear using an extruder provided at the same time as or immediately before the entrance of the kneading zone, and a portion for evaporating the added water. The surface of the molded product 2) was observed in the same manner as described above, that is, a parallel plane having a depth of 0.5 to 1.5 μm from the surface of the molded product was observed with an electron micrograph by an ultra-thin section method, and the area of the particles B was determined as described above. In this method, the ratio of particles B observed in the molded product 1 is controlled to be 0 to 95% when the ratio is 100%. The proportion of water added at this time is 0 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the resin extruded per unit time. . If the amount of water exceeds 15 parts by weight, the processing capacity of the extruder is reduced, and the productivity is undesirably affected. Further, by adding and evaporating water immediately before the kneading zone and lowering the resin temperature at the outlet of the recovery step by 0 to 60% immediately before the kneading zone, a sufficient shearing force is given in the kneading zone. When water is not added, the temperature of the extruder cylinder is reduced by 0 to 60% of the resin temperature at the outlet of the recovery step at the portion where the kneading disk is installed or immediately before the portion where the kneading disk is installed. As in the case where is added, a sufficient shearing force is applied to the resin. However, when the resin temperature is reduced by the temperature of the cylinder, the size of the extruder is limited, and in the case of a large extruder, the resin temperature cannot be controlled by the cylinder temperature.
【０００８】また本発明において押出機のスクリュー長
さ（Ｌ）とシリンダー径（Ｄ）の比Ｌ／Ｄが１０〜５０
であるものが好ましい。より好ましくは１５〜３５、更
に好ましくは２５〜３０である。またニーディングゾー
ンがシリンダー有効長の５〜６０％、好ましくは１０〜
５０％となるようニーディングディスクを備えた２軸押
出機を用いる。ニーディングゾーンがシリンダー有効長
の５％未満では十分な剪断がかからず、また６０％を越
えると剪断がかかりすぎ、剪断発熱作用により、樹脂の
劣化が進む。In the present invention, the ratio L / D of the screw length (L) of the extruder to the cylinder diameter (D) is 10 to 50.
Is preferred. More preferably, it is 15 to 35, and still more preferably 25 to 30. In addition, the kneading zone has a cylinder effective length of 5 to 60%, preferably 10 to 60%.
A twin-screw extruder equipped with a kneading disc to be 50% is used. If the kneading zone is less than 5% of the effective cylinder length, sufficient shear will not be applied, and if it exceeds 60%, excessive shear will be applied, and the deterioration of the resin will proceed due to the heat generated by shearing.
【０００９】本発明におけるスクリュー有効長とはスク
リューの根元のグランド部や先端の円錐形の部分を除い
たスクリューの長さを表し、通常前述のＬ／Ｄ、または
Ｄの何倍という表示をする。The effective length of the screw in the present invention means the length of the screw excluding the gland part at the root of the screw and the conical part at the tip, and is usually expressed as L / D or a multiple of D mentioned above. .
【００１０】また本発明において押出機としてシリンダ
ー径（Ｄ）と、スクリューエレメントの溝深さ（ｄ）の
比Ｄ／ｄが３〜１２、好ましくは３〜１０、さらに好ま
しくは３〜８である。スクリューエレメントがスクリュ
ーの有効長の４０〜９５％、好ましくは５０〜９０％、
より好ましくは５０〜８０％である。In the present invention, the ratio D / d of the cylinder diameter (D) to the groove depth (d) of the screw element as the extruder is 3 to 12, preferably 3 to 10, and more preferably 3 to 8. . The screw element is 40-95% of the effective length of the screw, preferably 50-90%,
More preferably, it is 50 to 80%.
【００１１】ここでスクリューエレメントの溝深さ
（ｄ）とはスクリューエレメントの底部から頂部までの
距離を表す。これはニーディングゾーン以外での不必要
な剪断をかけないためであり、上記のスクリューエレメ
ントを用いることにより樹脂の劣化が抑制され、色相等
の低下が抑えられる。この様なスクリューエレメントが
スクリュー有効長の５０％より少ないと樹脂の推進力が
低下し、押出機内での樹脂の滞留時間分布が広がった
り、滞留時間が長くなり樹脂の劣化をまねく。またスク
リューエレメントがスクリュー有効長の９５％を越える
と剪断力がかからなくなる。Here, the groove depth (d) of the screw element represents the distance from the bottom to the top of the screw element. This is because unnecessary shearing is not applied to portions other than the kneading zone. By using the above screw element, deterioration of the resin is suppressed, and reduction in hue and the like is suppressed. If such a screw element is less than 50% of the effective screw length, the propulsion force of the resin will decrease, and the residence time distribution of the resin in the extruder will be widened and the residence time will be prolonged, leading to deterioration of the resin. When the screw element exceeds 95% of the effective screw length, no shearing force is applied.
【００１２】また本発明における押出機とは押し出し成
形やコンパウンディングするために用いられる機器の一
つで、材料をシリンダーと呼ばれる部分と、回転スクリ
ューとの間で連続的に加熱、溶融、混練し、それをダイ
から押し出し、成形あるいはペレット状にするものであ
り、回転スクリューの形状等により剪断量が異なる。本
発明では特に２軸押出機を用いる。２軸押出機とは回転
スクリューが平行に２本設置されているもので２本のス
クリューの回転方向が同じである同方向回転型と、２本
のスクリューが異なる方向に回転する異方向回転型があ
り、それぞれ目的・性能が異なる。The extruder according to the present invention is one of the devices used for extrusion molding and compounding. The extruder continuously heats, melts and kneads a material between a portion called a cylinder and a rotary screw. It is extruded from a die to form or pellet, and the amount of shear varies depending on the shape of the rotary screw. In the present invention, a twin-screw extruder is particularly used. A twin-screw extruder is a two-screw extruder in which two rotating screws are installed in parallel, the same-direction rotating type in which the two screws rotate in the same direction, and the other direction rotating type in which the two screws rotate in different directions. And each has different purpose and performance.
【００１３】また本発明におけるスクリューエレメント
とは２軸押出機のスクリューを構成する一部であり、順
ねじ・逆ねじタイプがある。スクリューエレメントは樹
脂を流れ方向に推し進める能力、或いは逆流させて圧力
をかける能力をもつ。また本発明におけるニーディング
ディスクとはスクリューエレメントと同様２軸押出機の
スクリューを構成する一部であり、混練を目的とするミ
キシング部である。ニーディングディスクは２条ディス
ク、３条ディスク等様々なタイプがある。ローターとは
その断面形状はオーバル型であり、フライトは順ねじと
逆ねじから成っている。即ち、順ねじと逆ねじ部から成
る２条のニーディングディスクの組み合わせを連続・固
定化したようなものである。これらスクリューエレメン
トとニーディングディスク・ローターの組み合わせによ
り、目的に応じた性能を押出機にもたせることができ
る。The screw element in the present invention is a part of a screw of a twin screw extruder, and includes a forward screw type and a reverse screw type. The screw element has the ability to push the resin in the flow direction or the ability to apply pressure by flowing backward. The kneading disk in the present invention is a part of the screw of the twin-screw extruder similar to the screw element, and is a mixing unit for kneading. There are various types of kneading discs such as a two-way disc and a three-way disc. The rotor has an oval cross section, and the flight consists of forward and reverse threads. That is, the combination of two kneading disks consisting of a forward thread and a reverse thread is continuous and fixed. The combination of the screw element and the kneading disk / rotor makes it possible to provide the extruder with the desired performance.
【００１４】成形物表面のモルフォロジーは、成形物表
面特性に影響を与え、重合工程から生成したゴム粒子平
均径が同じでも上記粒子Ｂの面積の割合が少なければ成
形物表面の光沢は向上し、逆に粒子Ｂの面積の割合が多
くなると成形物表面は艶消しされる。本発明は重合工程
からのゴム粒子径の調整だけでなく、粒子Ｂの面積の割
合を押出機によりコントロールすることにより同一の原
料ＡＢＳ樹脂から成形物表面の特性を任意に調整する事
ができるので工業的利益は極めて大きい。従来の方法で
原料のゴム粒子を調整して光沢を制御する方法では製造
工程が非常に長く、特に艶消し樹脂から高光沢樹脂にグ
レードを変更する場合には、製造の最初の工程からＡＢ
Ｓ樹脂の性質を変更させるために長時間にわたって光沢
の異なる製品が必然的に生成する。通常の工業プラント
では、全工程の滞留時間が４時間とすると上記の正規品
でない製品が約４〜１２時間生成するこになる。この間
の製品は光沢が中途半端なだけでなく変化しており用途
としては極めて制限される。工業的には一つのプラント
で多種多様のグレードを生産するためにグレード交換に
際して正規でない製品が発生することはプラントの生産
性にとって極めて重要である。The morphology of the surface of the molded product affects the surface characteristics of the molded product. Even if the average particle diameter of the rubber particles produced from the polymerization step is the same, if the area ratio of the particles B is small, the gloss of the surface of the molded product is improved, Conversely, when the area ratio of the particles B increases, the surface of the molded product is matted. In the present invention, not only the adjustment of the rubber particle diameter from the polymerization step, but also the characteristics of the molded product surface can be arbitrarily adjusted from the same raw material ABS resin by controlling the ratio of the area of the particles B by an extruder. The industrial benefits are huge. In the conventional method of controlling the gloss by adjusting the rubber particles of the raw material, the production process is very long. Particularly, when changing the grade from a matting resin to a high gloss resin, the AB process is performed from the first step of the production.
Over time, products with different glosses are inevitably produced to alter the properties of the S-resin. In a normal industrial plant, if the residence time of all processes is 4 hours, the above non-genuine product will be produced for about 4 to 12 hours. During this period, the products are not only half-finished but also vary in gloss, and are extremely limited in use. Industrially, in order to produce a wide variety of grades in one plant, it is extremely important for the productivity of the plant that irregular products are generated at the time of grade exchange.
【００１５】これに対して、本発明の方法では工程の最
後の段階であり、工程の時間が短く、容易な調整で希望
する光沢を有する樹脂が得られる。On the other hand, in the method of the present invention, which is the last step of the process, the time of the process is short, and a resin having a desired gloss can be obtained by easy adjustment.
【００１６】本発明でいうＡＢＳ樹脂は、ゴム状重合体
とスチレン系単量体、アクリロニトリル系単量体及び、
必要であれば他の単量体の共重合体からなる樹脂であ
る。ここでスチレン系単量体としては、スチレン，α−
アルキルモノビニリデン芳香族単量体（例えばα−メチ
ルスチレン；α−エチルスチレン；α−メチルビニルト
ルエン；α−メチルジアルキルスチレン；など），環置
換アルキルスチレン（例えばｏ−ｍ−及びｐ−ビニルト
ルエン；ｏ−エチルスチレン；ｐ−エチルスチレン；
２，４−ジメチルスチレン；ｐ−第三級ブチルスチレ
ン；など），環置換ハロスチレン（例えばｏ−クロロス
チレン；ｐ−クロロスチレン；ｏ−ブロモスチレン；
２，４−ジクロロスチレン；など），環−アルキル，環
−ハロ置換スチレン（例えば２−クロロ−４−メチルス
チレン；２，６−ジクロロスチレン；など）ビニルナフ
タレン，ビニルアントラセンの一種又は混合物が用いら
れる。一般にアルキル置換基は１〜４個の炭素原子を有
し、そしてイソプロピル及びイソブチル基を含む。この
モノビニリデン芳香族単量体の一種もしくは混合物が用
いられる。また、アクリロニトリル系単量体としては、
アクリロニトリル、メタクリロニトリル、エタクリロニ
トリル、フマロニトリル及びこれらの混合物等があげら
れる。The ABS resin referred to in the present invention comprises a rubbery polymer, a styrene monomer, an acrylonitrile monomer and
If necessary, it is a resin comprising a copolymer of another monomer. Here, styrene, α-
Alkylmonovinylidene aromatic monomers (eg, α-methylstyrene; α-ethylstyrene; α-methylvinyltoluene; α-methyldialkylstyrene; etc.), ring-substituted alkylstyrenes (eg, om- and p-vinyltoluene) O-ethylstyrene; p-ethylstyrene;
2,4-dimethylstyrene; p-tert-butylstyrene; etc.), ring-substituted halostyrenes (eg, o-chlorostyrene; p-chlorostyrene; o-bromostyrene;
2,4-dichlorostyrene; etc.), ring-alkyl, ring-halo-substituted styrenes (eg, 2-chloro-4-methylstyrene; 2,6-dichlorostyrene; etc.) One or a mixture of vinylnaphthalene and vinylanthracene is used. Can be Generally, alkyl substituents will have from 1 to 4 carbon atoms and include isopropyl and isobutyl groups. One or a mixture of the monovinylidene aromatic monomers is used. Also, as the acrylonitrile monomer,
Examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and mixtures thereof.
【００１７】またゴム状重合体は常温でゴム状を示すも
のであれば良く特に限定を要しないが、好ましくは、共
役１，３−ジエン（例えばブタジエン；イソプレン；な
ど）などのポリブタジエン類やスチレン−ブタジエン共
重合体又はＥＰＤＭ（エチレン−プロピレン−ジエンメ
チレンリンケ−ジ）等があげられる。The rubbery polymer is not particularly limited as long as it shows a rubbery state at room temperature, but is preferably a polybutadiene such as conjugated 1,3-diene (eg, butadiene; isoprene; etc.) or styrene. -Butadiene copolymer or EPDM (ethylene-propylene-dienemethylene linker).
【００１８】本発明でいう他の単量体とは、スチレン、
アクリロニトリルと共重合可能な単量体であれば特に限
定しないが、メチルメタクリレ−ト等のアクリレ−ト類
や、Ｎ−フェニルマレイミド、シクロヘキシルマレイミ
ド等のマレイミド類があげられる。The other monomers referred to in the present invention include styrene,
The monomer is not particularly limited as long as it is a monomer copolymerizable with acrylonitrile, and examples thereof include acrylates such as methyl methacrylate and maleimides such as N-phenylmaleimide and cyclohexylmaleimide.
【００１９】ＡＢＳ樹脂の組成は樹脂中で、スチレン５
０〜９５重量部、アクリロニトリル５〜５０重量部、ブ
タジエン重合体、あるいはスチレン−ブタジエンブロッ
ク共重合体３〜３０重量部が好ましい。これらの組成の
樹脂を得るために好ましい方法としては、ゴム状重合体
存在下で、スチレン、アクリロニトリルを有機過酸化物
を開始剤として重合することにより得られる。重合方法
は連続塊状重合及び溶液重合法が好ましく用いられる。The composition of the ABS resin is as follows.
It is preferably 0 to 95 parts by weight, 5 to 50 parts by weight of acrylonitrile, 3 to 30 parts by weight of a butadiene polymer or a styrene-butadiene block copolymer. A preferable method for obtaining a resin having such a composition is obtained by polymerizing styrene and acrylonitrile using an organic peroxide as an initiator in the presence of a rubbery polymer. As the polymerization method, continuous bulk polymerization and solution polymerization are preferably used.
【００２０】本発明の中で用いるＡＢＳ系樹脂とは、上
記のＡＢＳ樹脂及びＡＢＳ樹脂を成分とする樹脂であ
り、ＡＢＳ樹脂を成分とする樹脂とは、ＡＢＳ樹脂と他
の樹脂、例えば、ポリカーボネート、ポリフェニレンエ
ーテル、ポリプロピレン、ポリスチレン、アクリロニト
リル−スチレン共重合樹脂等の混合物や、ＡＢＳ樹脂と
難燃剤等の混合物、またガラスフィラー、タルク等の混
合物等、ＡＢＳ樹脂を成分とする樹脂であれば特に限定
するものではない。The ABS resin used in the present invention is the above-mentioned ABS resin and a resin containing the ABS resin as a component. The resin containing the ABS resin as a component is an ABS resin and another resin such as polycarbonate. Any resin containing an ABS resin, such as a mixture of polyphenylene ether, polypropylene, polystyrene, an acrylonitrile-styrene copolymer resin, a mixture of an ABS resin and a flame retardant, or a mixture of a glass filler and talc is particularly limited. It does not do.
【００２１】本発明の中で用いるＡＢＳ系樹脂の成形物
とはＡＢＳ系樹脂を成形加工した成形物であり、ＡＢＳ
系樹脂の機械的、化学的特徴を利用して、機械部品とし
て、或いは文房具用品、玩具等それ自体が最終製品とし
て用いられるものである。成形加工はこれまで知られて
いる通常の樹脂の成形方法が用いられ、例えば射出成
形、押出成形などがあげられる。好ましくは射出成形法
である。好ましい射出成形条件としては、成形機のシリ
ンダー温度が１７０℃〜２８０℃、好ましくは１８０℃
〜２６０℃、更に好ましくは２００℃〜２５０℃とし、
金型温度３０〜９０℃の条件によって行われる。The molded article of the ABS resin used in the present invention is a molded article obtained by molding the ABS resin.
Utilizing the mechanical and chemical characteristics of the system resin, it is used as a mechanical part or as a final product such as stationery supplies and toys. For the molding process, a conventionally known ordinary resin molding method is used, and examples thereof include injection molding and extrusion molding. Preferably, it is an injection molding method. As preferable injection molding conditions, the cylinder temperature of the molding machine is 170 ° C to 280 ° C, preferably 180 ° C.
To 260 ° C, more preferably 200 ° C to 250 ° C,
This is performed under the condition of a mold temperature of 30 to 90 ° C.
【００２２】本発明で問題とするモルフォロジーを定め
る領域を表面から０．５〜１．５μｍの深さとするの
は、この範囲の深さに存在するゴム粒子を従来にない特
定のモルフォロジーにすることにより、成形物の表面特
性をコントロールできることを見い出したことに基づ
く。表面付近の０．５〜１．５μというのは、この深さ
の間ではゴム粒子の存在状態が、深さに対して依存性が
なく略一定であることを発見したことにも基づいてい
る。即ち、深さが０．５μｍより浅い場合は、ゴム粒子
の形態のばらつきが多くまた、１．５μｍを越えると、
深さにより存在状態が変化するため、表面特性と相関の
あるゴム粒子の形態を特定するのに向いていない。The region defining the morphology of interest in the present invention is defined as having a depth of 0.5 to 1.5 μm from the surface because the rubber particles existing in this range have a specific morphology which has not been achieved before. Based on the fact that it is possible to control the surface properties of the molded article. The value of 0.5 to 1.5 μ near the surface is based on the finding that the state of existence of the rubber particles is substantially constant without being dependent on the depth during this depth. . That is, when the depth is shallower than 0.5 μm, the morphology of the rubber particles varies greatly, and when the depth exceeds 1.5 μm,
Since the state of existence changes depending on the depth, it is not suitable for specifying the morphology of the rubber particles correlated with the surface characteristics.
【００２３】本発明において、ゴム粒子の形態は成形物
表面の平行面において測定する。この平行な断面は、成
形物表面に平行にミクロト−ムを用いて超薄切片に成形
物を切り出して得られる。この時、ミクロト−ムによっ
て切り出す１枚あたりの試料の厚みは、０．０５μｍと
して表面から順に切り出し、１１枚目以降３０枚目まで
の試料を用いて形態を測定する。In the present invention, the form of the rubber particles is measured on a plane parallel to the surface of the molded product. This parallel cross section is obtained by cutting a molded product into an ultrathin section using a microtome parallel to the surface of the molded product. At this time, the thickness of each sample cut out by the microtome is set to 0.05 μm, and the sample is cut out sequentially from the surface, and the morphology is measured using the 11th to 30th samples.
【００２４】本発明における粒子Ａとは、かかる試料の
電子顕微鏡写真において、ゴム粒子の長径をａμｍ、短
径をｂμｍとする時、ａとｂの比であるａ／ｂが１．５
以下のものを粒子Ａと定める。Ｂはａ／ｂが５以上であ
る粒子である。The particle A in the present invention means that the ratio of a to b, a / b, is 1.5 when the major axis of the rubber particles is a μm and the minor axis is b μm in an electron micrograph of such a sample.
The following are defined as particles A. B is a particle having a / b of 5 or more.
【００２５】本発明で言う長径ａとは超薄切片法による
電子顕微鏡写真で観察されるゴム粒子の周上の２点間の
距離の最大の長さを表し、短径ｂとは、長径ａにおいて
ａ／２の点における、長径ａに垂直なゴム粒子の長さを
示す。かかる制約条件において、粒子Ａ、Ｂの面積を算
出する際、全面積は１０００μｍ2 以上とれる様に電子
顕微鏡で観察する視野の大きさを定める。この数は特に
限定はしないが、前記の電子顕微鏡の視野はゴム粒子の
数として１０００個以上含まれる視野の大きさである。The major axis a referred to in the present invention represents the maximum length of the distance between two points on the circumference of the rubber particle observed in an electron micrograph by an ultra-thin section method, and the minor axis b refers to the major axis a Indicates the length of rubber particles perpendicular to the major axis a at the point a / 2. When calculating the areas of the particles A and B under such constraints, the size of the visual field to be observed with an electron microscope is determined so that the total area can be 1000 μm 2 or more. Although the number is not particularly limited, the field of view of the above-mentioned electron microscope is the size of the field of view containing 1000 or more rubber particles.
【００２６】本発明においては上記成形物１の表面から
０．５〜１．５μｍの深さの平行面を超薄切片法による
電子顕微鏡で観察したとき、粒子Ａと粒子Ｂを有するよ
うな樹脂を分離回収工程を出た溶融状態で２軸押出機に
より剪断を与える。こうして得られた樹脂を成形し（成
形物２）、成形物表面を成形物１と同様にして電子顕微
鏡写真で観察したとき、成形物１で観察された粒子Ｂの
面積の割合を１００％とすると成形物２での粒子Ｂの面
積の割合が０〜９５％とすることで成形物の表面特性を
任意にコントロールすることができる。In the present invention, when a parallel plane having a depth of 0.5 to 1.5 μm from the surface of the molded article 1 is observed by an electron microscope using an ultra-thin section method, a resin having particles A and B is obtained. Is subjected to shearing by a twin-screw extruder in a molten state after the separation and recovery step. The resin thus obtained was molded (molded product 2), and when the surface of the molded product was observed with an electron micrograph in the same manner as in molded product 1, the area ratio of particles B observed in molded product 1 was 100%. Then, by setting the area ratio of the particles B in the molded product 2 to 0 to 95%, the surface characteristics of the molded product can be arbitrarily controlled.
【００２７】例えば成形物２のモルフォロジーは、成形
物１での粒子Ｂの面積の割合（Ｂ1）と押出機の剪断の
程度により、成形物２での粒子Ｂの面積の割合（Ｂ2）
への粒子Ｂの面積の割合の変化の程度（粒子Ｂの変化
率）で決められる。つまり押出機の剪断の程度とＢ1と
の組み合わせにより粒子Ｂの変化率は調整することがで
きる。For example, the morphology of the molded article 2 depends on the ratio of the area of the particles B in the molded article 1 (B 1 ) and the degree of shearing of the extruder, and the proportion of the area of the particles B in the molded article 2 (B 2 ).
Is determined by the degree of change in the ratio of the area of the particles B to the particles (change rate of the particles B). It can change rate of the particles B is adjusted that is the combination of the degree and B 1 shear extruder.
【００２８】例えば成形物１で観察される粒子Ｂの面積
の割合は、溶液又は塊状重合法によるＡＢＳ樹脂製造工
程の分離回収工程での回収温度の変動により生成する。
例えば前記塊状重合法によるＡＢＳ樹脂製造工程で溶剤
・未反応モノマーを樹脂成分から分離する分離回収工程
での回収の出口の樹脂平均温度（ＴAV）を１７０〜２８
０℃の範囲とし、回収の出口の樹脂温度を変動させ、Ｔ
AVに対する回収の出口の温度の変動率（Ｔde）と１時間
当たりの温度の変動回数（ＮCT）の積を調整することに
より、成形加工後の成形物表面に観察される粒子Ｂは生
成する。ＴdeとＮCTの積が大きくなるほど最終的には成
形物で粒子Ｂとなるゴム粒子の数を増加させることがで
きる。For example, the ratio of the area of the particles B observed in the molded article 1 is generated by a change in the recovery temperature in the separation and recovery step of the ABS resin production step by the solution or bulk polymerization method.
For example, the resin average temperature (T AV ) at the outlet of the recovery in the separation and recovery step of separating the solvent and unreacted monomer from the resin component in the ABS resin production process by the bulk polymerization method is 170 to 28.
0 ° C., and the resin temperature at the outlet of the recovery is varied.
By adjusting the product of the temperature fluctuation rate (T de ) at the recovery outlet with respect to AV and the number of temperature fluctuations per hour (N CT ), particles B observed on the surface of the molded product after the molding process are formed. I do. As the product of T de and N CT increases, the number of rubber particles that eventually become particles B in the molded product can be increased.
【００２９】本発明で言う回収温度の平均値（ＴAV）は
下記式（数１）で算出される。The average value (T AV ) of the recovery temperature referred to in the present invention is calculated by the following equation (Equation 1).
【００３０】[0030]
【数１】 本発明で言う温度変動率（Ｔde：１時間あたりの温度変
動率）は下記式（数２）で算出される。(Equation 1) The temperature fluctuation rate (T de : temperature fluctuation rate per hour) referred to in the present invention is calculated by the following equation (Equation 2).
【００３１】[0031]
【数２】温度変動率（Ｔde）＝（（Ｔmax −Ｔmin ）／
ＴAV）×１００ （但しＴmax は１時間当たりの回収温度の最大温度、Ｔ
min は最小温度） また１時間当たりの温度の変動回数を毎時温度変動回数
（ＮCT）とよび（但し温度変動率０．５％以内の変動は
無視する）、時間に対し温度の微分値が正負に変化する
回数をさす。## EQU2 ## Temperature fluctuation rate (T de ) = ((T max −T min ) /
T AV ) × 100 (where T max is the maximum recovery temperature per hour, T
The minimum number of temperature fluctuations per hour is called the number of temperature fluctuations per hour (N CT ) (however, fluctuations within a temperature fluctuation rate of 0.5% are ignored). Indicates the number of times that changes to positive or negative.
【００３２】本発明において回収温度の平均値ＴAV、温
度変動率Ｔde、及び１時間当たりの温度の変動回数ＮCT
は３時間以上の回収温度の平均値を一定にして運転し、
その区間の測定値から算出する。In the present invention, the average value T AV of the recovery temperature, the temperature fluctuation rate T de , and the number of temperature fluctuations N CT per hour
Operates with the average value of the recovery temperature for 3 hours or more constant,
It is calculated from the measured value in that section.
【００３３】上記ＴdeとＮCTの積（Ｆ）を調整すること
により成形加工後成形物表面で粒子Ｂとなりうる粒子が
生成する。本発明では上記Ｆの値が０．５〜１５０のも
のが使用でき、特にＦの値が異なる２種以上の樹脂を混
合して使用すると好ましい結果を与える。この際も混合
比とＦ値から平均値を求めてこれが０．５〜１５０の範
囲に入るものが使用できる。例えばＦが０．５〜１５で
は粒子Ｂは０．０１〜１％生成し、得られた樹脂のゴム
粒子平均径が０．０５〜１μｍ、好ましくは０．１〜
０．８μｍであれば光沢の高い樹脂が得られる。Ｆが３
５を越えて１５０以下であれば粒子Ｂは４０〜９０％生
成し、ゴム粒子平均径が０．５〜３、μｍ、好ましくは
１〜２．５μｍであれば、艶消し効果のある樹脂が得ら
れる。本発明の方法では、例えば粒子Ｂを０．０１〜１
％含有する光沢の高い樹脂を剪断効果の高い押出機によ
り処理することによりさらに高い光沢の成形物が得られ
る樹脂にすることが可能であり、艶消し効果のある樹脂
についても、１つの樹脂から用途によって適当な光沢に
調整することができる。By adjusting the product (F) of the above-mentioned T de and N CT , particles which can become particles B on the surface of the molded product after the molding process are generated. In the present invention, those having a value of F of 0.5 to 150 can be used. Particularly, a mixture of two or more resins having different values of F gives a preferable result. In this case, an average value obtained from the mixing ratio and the F value and falling within the range of 0.5 to 150 can be used. For example, when F is 0.5 to 15, particles B are formed in an amount of 0.01 to 1%, and the average particle diameter of the obtained resin is 0.05 to 1 μm, preferably 0.1 to 1 μm.
If it is 0.8 μm, a resin with high gloss can be obtained. F is 3
If it exceeds 5 and is 150 or less, 40 to 90% of the particles B are formed, and if the average particle diameter of the rubber particles is 0.5 to 3 μm, preferably 1 to 2.5 μm, a resin having a matting effect is obtained. can get. In the method of the present invention, for example, the particles B are contained in an amount of 0.01 to 1
% By treating the high-gloss resin with an extruder having a high shearing effect, it is possible to obtain a resin having a higher glossy molded product. It can be adjusted to an appropriate gloss depending on the application.
【００３４】例えば上記の方法で得られた樹脂を溶融状
態で押出機に送入する。ここで使用する押出機はニーデ
ィングディスクまたはローターが設置されている２軸押
出機であり、分離回収工程出口からニーディングゾーン
との間に水を添加する部分と、ニーディングゾーンと同
時またはその直前部に添加した水を蒸発させる部分とを
有する２軸押出機を用いる。添加する水の割合は、１時
間あたり押出機が処理する樹脂量１００重量部に対して
０〜１５重量部、好ましくは１〜１０重量部、より好ま
しくは１〜７重量部である。ニーディングゾーンより前
の部分で水を添加し、蒸発させることによって樹脂温を
下げ、ニーディングゾーンでの樹脂にかかる剪断力を高
めることができる。水の他に低沸点の有機溶媒を混合し
て使用しても良い。For example, the resin obtained by the above method is fed into an extruder in a molten state. The extruder used here is a twin-screw extruder in which a kneading disk or a rotor is installed, and a part for adding water between the separation and recovery step outlet and the kneading zone, and a part simultaneously or simultaneously with the kneading zone. A twin screw extruder having a portion for evaporating the added water in the immediately preceding portion is used. The proportion of water to be added is 0 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 7 parts by weight, per 100 parts by weight of the resin processed by the extruder per hour. By adding and evaporating water in a portion before the kneading zone, the temperature of the resin can be lowered and the shearing force applied to the resin in the kneading zone can be increased. A low boiling organic solvent may be used in combination with water.
【００３５】本発明においてニーディングゾーンより前
の部分で水を添加する部分を持たない場合はニーディン
グゾーンと同時または直前部で押出機のシリンダー温度
を回収工程出口の樹脂温の０〜６０％低下、より高光沢
の製品が得たい場合は１５〜６０％低下させることによ
り本発明の効果が得られる。但し大型の押出機の場合、
樹脂温を低下させることは困難であるので水を添加する
方法の方が好ましい。本発明においては分離回収工程で
の温度の変動の程度と、押し出し工程での樹脂にかかる
剪断の程度によって、得られた樹脂の表面モルフォロジ
ーが決められる。押し出し工程で樹脂にかかる剪断の程
度は、例えば同方向回転噛合型２軸押出機で２条のニー
ディングディスクを装着している場合、下記式（数３）
（数４）で表される剪断指標（Ｓ）を用いる。In the present invention, in the case where there is no portion to which water is added in the portion before the kneading zone, the cylinder temperature of the extruder is adjusted to 0 to 60% of the resin temperature at the outlet of the recovery step simultaneously with or immediately before the kneading zone. If it is desired to obtain a product having a lower gloss and a higher gloss, the effect of the present invention can be obtained by reducing the product by 15 to 60%. However, in the case of a large extruder,
Since it is difficult to lower the resin temperature, the method of adding water is preferred. In the present invention, the surface morphology of the obtained resin is determined by the degree of temperature fluctuation in the separation and recovery step and the degree of shear applied to the resin in the extrusion step. The degree of shear applied to the resin in the extrusion step is determined by, for example, the following formula (Equation 3) when two kneading disks are mounted in a co-rotating meshing twin screw extruder.
The shear index (S) represented by (Equation 4) is used.
【００３６】[0036]
【数３】γm ＝（ｄＮＥ＋ＤＮＥ）×π×Ｎ／｛（ＤＢ
−ｄＮＥ）／２｝ ｄＮＥ：ニーディングディスクの短径（ｍｍ） ＤＮＥ：ニーディングディスクの長径（ｍｍ） Ｎ ：１秒間あたりのスクリュー回転数（ｒｐｓ） ＤＢ ：シリンダーの直径（ｍｍ）Γ m = (dNE + DNE) × π × N / ｛(DB
−dNE) / 2｝ dNE: short diameter of the kneading disk (mm) DNE: long diameter of the kneading disk (mm) N: number of rotations of the screw per second (rps) DB: diameter of the cylinder (mm)
【００３７】[0037]
【数４】Ｓ＝（３５０−Ｔ1 ）×０．０２×γm ×（θ
／６０）×Ｌ／１００ Ｔ1 ：ニーディングゾーン入口の樹脂温度（℃） θ ：押出機中の樹脂の滞留時間（ｓｅｃ） Ｌ ：スクリュー有効長に対するニーディングゾーン
の割合（％） このＳとＢ1により粒子Ｂの変化率（ＢD）が決まる。粒
子Ｂの変化率ＢDは下記式（数５）により求められる。S = (350−T 1 ) × 0.02 × γ m × (θ
/ 60) × L / 100 T 1 : Resin temperature at inlet of kneading zone (° C.) θ: Residence time of resin in extruder (sec) L: Ratio of kneading zone to effective screw length (%) The change rate (B D ) of the particle B is determined by B 1 . The change rate BD of the particles B is obtained by the following equation (Equation 5).
【００３８】[0038]
【数５】ＢD＝（Ｂ1−Ｂ2）／Ｂ1×１００ 上記Ｂ1・Ｓを用いて粒子Ｂの変化率ＢDを考えると、例
えばＢ1が０．０１〜１０％の場合、Ｓが１００以下で
ＢDは０〜３０％、Ｓが１４０を超える範囲でＢ D４０〜
７０％となる。例えばＢ1は４０〜９０％の場合、Ｓが
６０以下でＢD０〜３０％、Ｓが１００を越える範囲で
ＢDは５０〜９０％となる。(Equation 5) BD= (B1-BTwo) / B1× 100 above B1・ Change rate B of particle B using SDGiven the example
For example, B1Is 0.01 to 10%, S is 100 or less
BDIs 0 to 30%, and B is in the range where S exceeds 140. D40 ~
70%. For example, B1Is 40-90%, S is
B below 60D0-30%, S exceeds 100
BDIs 50 to 90%.
【００３９】即ち、あるＢ1をもつ成形物１となるよう
なＡＢＳ樹脂を製造しておけば、Ｓを変えることにより
様々なモルフォロジーの製品を得ることができる。同方
向回転噛合型スクリューとは２軸押出機のスクリューの
タイプであり、２本のスクリューが同じ方向に回転する
ものである。また噛合型とは２本のスクリューの山と谷
がスクリュー軸を結ぶ線上で完全に噛み合っているもの
である。That is, if an ABS resin is produced so as to be a molded product 1 having a certain B 1 , various morphological products can be obtained by changing S. The co-rotating mesh screw is a screw type of a twin-screw extruder in which two screws rotate in the same direction. The meshing type is a type in which the ridges and valleys of two screws are completely meshed on a line connecting the screw shafts.
【００４０】本願での剪断指標（Ｓ）は２０〜３００、
好ましくは３０〜２５０、さらに好ましくは５０〜２０
０である。The shear index (S) in the present application is 20 to 300,
Preferably 30 to 250, more preferably 50 to 20
0.
【００４１】本発明の方法により得られた樹脂の成形物
は衝撃強度等他の物性を低下することなく表面特性をコ
ントロールできるため、電機機器やコンピューター等の
産業分野の部品として幅広く有用であり、また化粧品容
器や玩具・文房具等の成形物として特に有用である。Since the resin molded product obtained by the method of the present invention can control the surface characteristics without deteriorating other physical properties such as impact strength, it is widely useful as a component in industrial fields such as electric appliances and computers. Further, it is particularly useful as a molded product such as a cosmetic container, a toy, and a stationery.
【００４２】次に実施例により本発明を更に詳細に説明
するが、本発明はこれらの実施例により限定されるもの
ではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００４３】[0043]
【実施例】以下、実施例により本発明を更に詳細に説明
する。性能評価は下記の基準で測定した。 （１）光沢測定 ＪＩＳＫ７１０５中の光沢度の測定（６０°鏡面光沢）
の測定法に準じて１０ｍｍ×５０ｍｍの試験片３個につ
いて光沢を測定し、その平均値を求めた。 （２）衝撃強度の測 衝撃強度は成形物を切り出し試験片とし、Ｉｚｏｄ衝撃
試験法（ＪＩＳ−Ｋ７１１０）で行なった。 （３）耐熱温度の測定 ビカット軟化点はＡＳＴＭ ＤＩ５２５に準拠して、成
形物から試験片を切り出したサンプルを用いて評価し
た。 （４）ゴム粒子形態の測定 ＴＥＭ（透過型電子顕微鏡）の超薄切片法により、ゴム
粒子形状を測定した。 （５）ゴム粒子平均径の測定 成形物２の成形前のペレットを超薄切片法による電子顕
微鏡写真を撮影し、写真中のゴム粒子５００〜７００個
の短径及び長径をそれぞれ測定して、その平均値を粒子
径とし、次式により体積平均径を求めた。 体積平均径＝ΣｎＤ4／ΣｎＤ3 （但しｎは粒子径Ｄμmのゴムの個数である。） 参考例 スチレン７４．５重量部、アクリロニトリル２５．５重
量部、エチルベンゼン２５重量部、ゴム状重合体（スチ
レン−ブタジエンブロック共重合体 溶液粘度１０ｃｔ
ｓ ５％スチレン溶液 ２５℃）１２重量部、有機過酸
化物〔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〕０．０４重量部、メル
カプタン０．２重量部よりなる原料溶液を作成した。こ
の原料を３段の撹拌式重合槽列反応器にて重合を行なっ
た。１段目の槽から原料溶液を連続的に供給した。１段
目の槽の反応温度１００℃、２段目の槽では１２０℃、
３段目の槽では１３０℃とした。３段目の槽より重合液
を予熱器と減圧室より成る分離回収工程に導いた。分離
回収工程の出口での樹脂の平均温度（Ｔav）を２４０
℃、温度変動率（Ｔde）を８％、１時間あたりの変動回
数（Ｎ）１０回として回収工程から出た樹脂の一部を射
出成形した（成形物１）。得られた成型物の表面を電子
顕微鏡で観察した。分離回収工程から出た樹脂を表１に
示す押出機Ａにて、ニーディングゾーン３０％、スクリ
ュー回転数３．３ｒｐｓの条件でシリンダー温度を２３
０℃として、水を添加することなく処理した後、射出成
形を行った。結果を表２に示す。ニーディングゾーン入
り口の温度（Ｔ1）は２４０℃で あった。成形物２の光
沢は２１％となり、成形物１とほとんど光沢は変わらず
良好な艶消し性を有している。なお温度変動率及び１時
間当たりの温度変動率は、予熱器のジャケットの熱媒の
平均温度及び流量で調節した。なお本実験に使用したペ
レットは、３時間を１ロットとして混合して使用した。The present invention will be described in more detail with reference to the following examples. The performance evaluation was measured according to the following criteria. (1) Gloss measurement Measurement of glossiness in JIS K7105 (60 ° specular gloss)
The gloss was measured for three test pieces of 10 mm × 50 mm in accordance with the measurement method described above, and the average value was obtained. (2) Measurement of Impact Strength The impact strength was measured according to the Izod impact test method (JIS-K7110) by cutting a molded product into a test piece. (3) Measurement of heat resistance temperature The Vicat softening point was evaluated using a sample obtained by cutting a test piece from a molded product in accordance with ASTM DI525. (4) Measurement of Rubber Particle Shape The rubber particle shape was measured by an ultra-thin section method using a TEM (transmission electron microscope). (5) Measurement of average particle diameter of rubber particles An electron micrograph was taken of the pellet before molding of the molded product 2 by an ultra-thin section method, and the short diameter and long diameter of 500 to 700 rubber particles in the photograph were measured, respectively. The average value was defined as the particle diameter, and the volume average diameter was determined by the following equation. Volume average diameter = ΣnD 4 / ΣnD 3 (where n is the number of rubbers having a particle diameter of D μm) Reference Example 74.5 parts by weight of styrene, 25.5 parts by weight of acrylonitrile, 25 parts by weight of ethylbenzene, rubbery polymer ( Styrene-butadiene block copolymer Solution viscosity 10ct
s 5% styrene solution 25 ° C.) 12 parts by weight, organic peroxide [1,1-bis (t-butylperoxy) 3,3
[5-Trimethylcyclohexane] 0.04 parts by weight and a raw material solution comprising 0.2 parts by weight of mercaptan were prepared. This raw material was polymerized in a three-stage stirred polymerization tank row reactor. The raw material solution was continuously supplied from the first tank. The reaction temperature of the first tank is 100 ° C, the second tank is 120 ° C,
The temperature was set to 130 ° C. in the third tank. From the third tank, the polymerization liquid was led to a separation and recovery step comprising a preheater and a decompression chamber. The average temperature (T av ) of the resin at the outlet of the separation and recovery step is 240
C., the temperature fluctuation rate (T de ) was 8%, and the number of fluctuations per hour (N) was 10 times, and a part of the resin discharged from the recovery step was injection-molded (molded product 1). The surface of the obtained molded product was observed with an electron microscope. The resin discharged from the separation / recovery step was subjected to extruder A shown in Table 1 at a kneading zone of 30% and a screw rotation speed of 3.3 rps at a cylinder temperature of 23 rpm.
After treatment at 0 ° C. without adding water, injection molding was performed. Table 2 shows the results. The temperature at the entrance of the kneading zone (T 1 ) was 240 ° C. The gloss of the molded article 2 was 21%, and the gloss was almost the same as that of the molded article 1 and had a good matting property. The temperature fluctuation rate and the temperature fluctuation rate per hour were adjusted by the average temperature and the flow rate of the heating medium in the jacket of the preheater. Note that the pellets used in this experiment were mixed and used for three hours as one lot.
【００４４】実施例Ａ−１ 回収工程を出た樹脂を、シリンダーの温度を２３０℃
と、スクリュウーの回転数を４．８ｒｐｓとする以外は
参考例と同じ条件で樹脂を製造し、成形物２を得た。ニ
ーディングゾーン入り口の温度（Ｔ1）は２３５℃であ
った。成形物２の光沢は３０％となり、光沢が向上し
た。Example A-1 The resin exiting the recovery step was heated at a cylinder temperature of 230 ° C.
A resin was produced under the same conditions as in Reference Example except that the screw rotation speed was changed to 4.8 rps, and a molded product 2 was obtained. The temperature at the entrance of the kneading zone (T 1 ) was 235 ° C. The gloss of the molded product 2 was 30%, and the gloss was improved.
【００４５】実施例Ａ−２ 押出機で水を樹脂の押出量に対して１重量％添加し、シ
リンダー温度を２２５℃とする以外は参考例と同じとし
た。結果を表２に示す。Ｔ1は２３０℃であった。光沢
は ３３．２％となり、さらに光沢が向上した。Example A-2 The procedure was the same as that of Reference Example except that water was added by 1% by weight based on the amount of resin extruded by an extruder and the cylinder temperature was set to 225 ° C. Table 2 shows the results. T 1 was 230 ° C. The gloss was 33.2%, further improving the gloss.
【００４６】実施例Ａ−３ 押出機で水の添加量を７重量％とし、シリンダー温度を
１６０℃とする以外は参考例と同じとした。結果を表２
に示す。Ｔ1は１７７℃であった。光沢は４２％とな
り、さらに光沢が向上した。Example A-3 The procedure was the same as that of the reference example except that the amount of water added was 7% by weight and the cylinder temperature was 160 ° C. in the extruder. Table 2 shows the results
Shown in T 1 was 177 ° C. The gloss was 42%, which was further improved.
【００４７】実施例Ａ−４ 押出機のスクリュー回転数を６．０ｒｐｓ、押出機で水
の添加量を１重量％とし、シリンダー温度を２２５℃と
する以外は参考例と同じとした。結果を表２に示す。Ｔ
1は２３３℃であった。光沢は３８％となり、光沢が向
上した。Example A-4 The procedure was the same as that of the reference example, except that the screw speed of the extruder was 6.0 rps, the amount of water added was 1% by weight in the extruder, and the cylinder temperature was 225 ° C. Table 2 shows the results. T
1 was 233 ° C. The gloss was 38%, and the gloss was improved.
【００４８】比較例Ｂ−１ 回収工程を出た樹脂を表１に示す押出機Ｂで処理する以
外は実施例Ａ−２と同じとした。結果を表−２に示す。
得られた成形物２の光沢は２１％、でほとんど光沢は向
上しなかった。Comparative Example B-1 The procedure of Example A-2 was repeated, except that the resin that had gone through the recovery step was treated in the extruder B shown in Table 1. Table 2 shows the results.
The gloss of the obtained molded article 2 was 21%, and the gloss was hardly improved.
【００４９】比較例Ｂ−２ 回収工程を出た樹脂を表１に示す押出機Ｂで処理する以
外は実施例Ａ−３と同とした。結果を表−２に示す。得
られた成形物２の光沢は２２％、でほとんど光沢は向上
しなかった。Comparative Example B-2 The procedure of Example A-3 was repeated, except that the resin that had gone through the recovery step was treated with an extruder B shown in Table 1. Table 2 shows the results. The gloss of the obtained molded article 2 was 22%, and the gloss was hardly improved.
【００５０】比較例Ｂ−３ 回収工程を出た樹脂を表１に示す押出機Ｂで処理する以
外は実施例Ａ−４と同とした。結果を表−２に示す。得
られた成形物２の光沢は２１％、でほとんど光沢は向上
しなかった。この様に１軸フルフライトスクリューでは
剪断指標を変えても光沢はほとんど変化しない。Comparative Example B-3 The procedure of Example A-4 was repeated, except that the resin that had gone through the recovery step was treated in the extruder B shown in Table 1. Table 2 shows the results. The gloss of the obtained molded article 2 was 21%, and the gloss was hardly improved. As described above, in the single-axis full flight screw, the gloss hardly changes even when the shear index is changed.
【００５１】実施例Ｃ−１ エチルベンゼン ２０重量部、ゴム状重合体 １０重量
部、有機過酸化物 ０．０３重量部を用いて参考例と同
様に重合し、回収工程での回収温度の平均値（Ｔ AV）を
２３５℃、温度変動率を２％、１時間当たりの変動回数
を４回とする押出機でのシリンダー温度を２２０とする
以外は実施例Ａ−２と同じ条件とした。結果を表３に示
す。Ｔ1は２２３℃であった。得られた成形物の光沢は
成形物 １が７５％、成型物２が８４．３％となり光沢
が向上した。Example C-1 Ethylbenzene 20 parts by weight, rubbery polymer 10 parts by weight
Parts and 0.03 parts by weight of organic peroxide
Polymerized in the same manner, and the average value (T AV)
235 ° C, temperature fluctuation rate 2%, number of fluctuations per hour
The temperature of the cylinder in the extruder is set to 220 times
Except for this, the conditions were the same as those of Example A-2. The results are shown in Table 3.
You. T1Was 223 ° C. The gloss of the obtained molded product is
Molded product 1 has 75% gloss and molded product 2 has 84.3% gloss
Improved.
【００５２】実施例Ｃ−２ 押出機で水を７重量％添加し、シリンダー温度を１５５
℃とする以外は実施例Ｃ−１と同じとした。結果を表３
に示す。Ｔ1は１５８℃であった。得られた成形物の光
沢は８９．４％となり、さらに光沢が向上した。Example C-2 Water was added by 7% by weight in an extruder, and the cylinder temperature was adjusted to 155.
It was the same as Example C-1 except that the temperature was changed to ° C. Table 3 shows the results
Shown in T 1 was 158 ° C. The gloss of the obtained molded product was 89.4%, and the gloss was further improved.
【００５３】実施例Ｃ−３ 押出機で水を１０重量％添加し、シリンダー温度を１２
５℃とする以外は実施例Ｃ−１と同じとした。結果を表
３に示す。Ｔ1は１２６℃であった。得られた成形物の
光沢は９５．３％となり、さらに光沢が向上した。Example C-3 10% by weight of water was added by an extruder, and the cylinder temperature was adjusted to 12%.
It was the same as Example C-1 except that the temperature was 5 ° C. Table 3 shows the results. T 1 was 126 ° C. The gloss of the obtained molded product was 95.3%, and the gloss was further improved.
【００５４】実施例Ｃ−４ 押出機のスクリュー回転数を６．０ｒｐｓとする以外は
実施例Ｃ−１と同じとした。結果を表３に示す。Ｔ1は
２２５℃であった。得られた成形物の光 沢は８５．５
％となり光沢が向上した。Example C-4 The procedure was the same as Example C-1 except that the screw rotation speed of the extruder was 6.0 rps. Table 3 shows the results. T 1 was 225 ° C. The resulting molded article has a luster of 85.5.
% And the gloss was improved.
【００５５】比較例Ｄ−１ ポリブタジエンラテックス（ゴム粒子径０．３μｍ）２
０重量部の存在下でスチレン７０％、アクリロニトリル
３０％からなる単量体混合物８０重量部を乳化重合し
た。得られたグラフト共重合体は硫酸で凝固し、苛性ソ
ーダで中和・洗浄・濾過・乾燥してＡＢＳ樹脂を得た。
得られた樹脂を表１に示す押出機Ｃでシリンダー２４０
℃、スクリュー回転数１．５ｒｐｓで溶融し、その溶融
樹脂を押出機Ａに送入し実施例Ｃ−１と同じ条件で処理
した。押出機Ｃによる処理前の樹脂の成形物を成形物
１、押出機Ａによる処理後の成形物を成形物２として結
果を表−３に示す。押出機Ａのニーディングゾーン入口
の温度をＴ1とすると、Ｔ1は２２４℃であった。成形物
１の光沢は７８％であり、成形物２の光沢も７８％と変
化しなかった。Comparative Example D-1 Polybutadiene latex (rubber particle diameter 0.3 μm) 2
In the presence of 0 parts by weight, 80 parts by weight of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile was emulsion-polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered and dried to obtain an ABS resin.
The obtained resin was extruded into a cylinder 240 using an extruder C shown in Table 1.
C. and a screw rotation number of 1.5 rps, and the molten resin was fed into an extruder A and processed under the same conditions as in Example C-1. The results are shown in Table 3 where the molded product of the resin before the treatment by the extruder C was molded product 1 and the molded product after the treatment by the extruder A was molded product 2. Assuming that the temperature at the entrance of the kneading zone of the extruder A was T 1 , T 1 was 224 ° C. The gloss of the molded product 1 was 78%, and the gloss of the molded product 2 was not changed to 78%.
【００５６】比較例Ｄ−２ 押出機Ａに水を樹脂に対して７重量％添加し、シリンダ
ー温度を１５５℃とする以外は比較例Ｄ−１と同じとし
た。結果を表３に示す。成形物２の光沢が７８．３％と
、ほとんど向上していない。Comparative Example D-2 The same operation as in Comparative Example D-1 was carried out except that water was added to the extruder A in an amount of 7% by weight based on the weight of the resin and the cylinder temperature was set to 155 ° C. Table 3 shows the results. The gloss of the molded product 2 was 78.3%, which was hardly improved.
【００５７】比較例Ｄ−３ 押出機Ａのスクリューの回転数を６ｒｐｓとする以外は
比較例Ｄ−４と同じとした。結果を表３に示す。Ｔ1は
２２５℃であった。成形物２の光沢が７８％と、ほとん
ど向上していない。乳化重合ＡＢＳでは剪断指標が異な
る２軸押出機を用いても、光沢をコントロールする事は
出来ない。Comparative Example D-3 The procedure was the same as Comparative Example D-4, except that the number of revolutions of the screw of the extruder A was changed to 6 rps. Table 3 shows the results. T 1 was 225 ° C. The gloss of the molded product 2 was 78%, which was almost not improved. In emulsion polymerization ABS, gloss cannot be controlled even if a twin-screw extruder having a different shear index is used.
【００５８】[0058]
【表１】 [Table 1]
【００５９】[0059]
【表２】 [Table 2]
【００６０】[0060]
【表３】 [Table 3]
【００６１】[0061]
【発明の効果】本発明の方法により成形物の表面におけ
るゴム粒子モルフォロジーが自由に変えられるのでＡＢ
Ｓ樹脂の表面の特徴を極めて容易に発現させることがで
き、例えば光沢・艶消しを任意にコントロールできる。Since the morphology of rubber particles on the surface of a molded product can be freely changed by the method of the present invention, AB
The characteristics of the surface of the S resin can be expressed extremely easily, and for example, gloss / mat can be arbitrarily controlled.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森田 尚夫 大阪府高石市高砂１丁目６番地 三井東 圧化学株式会社内 (72)発明者 高久 真人 大阪府高石市高砂１丁目６番地 三井東 圧化学株式会社内 (72)発明者 白藤 朋史 大阪府高石市高砂１丁目６番地 三井東 圧化学株式会社内 (56)参考文献 特開 昭62−280205（ＪＰ，Ａ) 特開 昭62−158750（ＪＰ，Ａ) 特開 昭52−24290（ＪＰ，Ａ) 特開 平８−3234（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 279/00 - 279/06 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Morio Nao 1-6-6 Takasago, Takaishi City, Osaka Prefecture Inside Mitsui East Pressure Chemical Co., Ltd. (72) Inventor Masato Takaku 1-6-6 Takasago, Takaishi City, Osaka Prefecture Mitsui East Pressure Chemical Co., Ltd. (72) Inventor Tomofumi Shirato 1-6-6 Takasago, Takaishi City, Osaka Prefecture Mitsui East Pressure Chemical Co., Ltd. (56) References JP-A-62-280205 (JP, A) JP-A-62-158750 JP-A-52-24290 (JP, A) JP-A-8-3234 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 279/00-279/06
Claims (8)
アクリロニトリル系単量体、及びゴム状重合体を含む原
料を重合工程に供給し、該単量体の一部もしくは全量を
重合させてゴム状重合体粒子（ゴム粒子）形成を含む重
合体を重合する工程の後、重合体、未反応単量体および
／または溶剤を含む混合液を加熱し、同時にまたは加熱
後減圧室に導入して単量体および／または溶剤を樹脂成
分と分離する分離回収工程を持ち、この分離回収工程を
出る樹脂を射出成形して得られた成形物（成形物１）の
表面から０．５〜１．５μｍの深さに存在するゴム粒子
が、成形物表面との平行面を超薄切片法による電子顕微
鏡写真で観察する時、 長径ａと短径ｂの比率ａ／ｂが１．５以下の粒子Ａ、
及び 長径ａと短径ｂの比率ａ／ｂが５以上である粒子Ｂ の少なくとも２種類の形態を有し、且つ超薄切片法によ
る電子顕微鏡写真で観察されるゴム粒子の全面積を１０
０％とした時に粒子Ａの面積が少なくとも１０％以上、
粒子Ｂの面積が０．０１〜９０％であるＡＢＳ樹脂を、
［II］分離回収工程を出た後、ニーディングディスクま
たはローターを有する２軸押出機により剪断を与えるこ
とによって、得られた成形物（成形物２）の表面を上記
と同じ方法で、即ち成形物表面から０．５〜１．５μｍ
の深さの平行面を超薄切片法による電子顕微鏡写真で観
察し、粒子Ｂの面積を上記成形物１で観察された粒子Ｂ
の割合を１００％とするとき０〜９５％となる様にコン
トロールする事を特徴とする多様な表面モルフォロジー
を有するＡＢＳ系樹脂の製造方法。[I] A raw material containing at least a styrene-based monomer, an acrylonitrile-based monomer, and a rubbery polymer is supplied to a polymerization step, and a part or all of the monomer is polymerized to obtain a rubber. After the step of polymerizing the polymer including the formation of the polymer particles (rubber particles), the mixed solution containing the polymer, the unreacted monomer and / or the solvent is heated and introduced into the decompression chamber simultaneously or after heating. A separation / recovery step of separating the monomer and / or the solvent from the resin component, and from the surface of a molded product (molded product 1) obtained by injection-molding the resin exiting the separation / recovery process, from 0.5 to 1. When a rubber particle existing at a depth of 5 μm is observed with an electron micrograph taken by an ultra-thin section method in a plane parallel to the surface of the molded product, particles having a ratio a / b of major axis a to minor axis b of 1.5 or less are obtained. A,
And at least two types of particles B having a ratio a / b of the major axis a to the minor axis b of 5 or more, and the total area of the rubber particles observed in the electron micrograph by the ultra-thin section method is 10%.
0%, the area of the particles A is at least 10% or more,
ABS resin having an area of particles B of 0.01 to 90%,
[II] After leaving the separation and recovery step, the surface of the obtained molded product (molded product 2) is subjected to shearing by a twin-screw extruder having a kneading disk or a rotor in the same manner as described above, that is, by molding. 0.5 to 1.5 μm from the object surface
Is observed by an electron micrograph by an ultra-thin section method, and the area of the particle B is determined by the particle B observed in the molded article 1.
The method for producing an ABS-based resin having various surface morphologies, wherein the ratio is controlled so as to be 0 to 95% when the proportion of the resin is 100%.
アクリロニトリル系単量体、及びゴム状重合体を含む原
料を重合工程に供給し、該単量体の一部もしくは全量を
重合させてゴム粒子形成を含む重合体を重合する工程の
後、重合体、未反応単量体および／または溶剤を含む混
合液を加熱し、同時にまたは加熱後減圧室に導入して単
量体および／または溶剤を樹脂成分と分離する分離回収
工程を持ち、この分離回収工程を出る樹脂を射出成形し
て得られた成形物（成形物１）の表面から０．５〜１．
５μｍの深さに存在するゴム粒子が、成形物表面との平
行面を超薄切片法による電子顕微鏡写真で観察する時、 長径ａと短径ｂの比率ａ／ｂが１．５以下の粒子Ａ、
及び 長径ａと短径ｂの比率ａ／ｂが５以上である粒子Ｂ の少なくとも２種類の形態を有し、且つ超薄切片法によ
る電子顕微鏡写真で観察されるゴム粒子の全面積を１０
０％とした時に粒子Ａの面積が少なくとも１０％以上、
粒子Ｂの面積が０．０１〜９０％であるＡＢＳ樹脂を、
［II］分離回収工程を出た後、ニーディングディスクま
たはローターを有する２軸押出機であり、分離回収工程
出口とニーディングディスクまたはローターが設置され
ている部分との間に、樹脂に水を添加する部分と添加し
た水を蒸発させる部分を有し、且つ添加した水を蒸発さ
せる部分はニーディングディスクが設置されている部分
と同時またはその直前部に設けられた押出機を用いて剪
断を与えることによって、得られた成形物（成形物２）
の表面を上記と同じ方法で、即ち成形物表面から０．５
〜１．５μｍの深さの平行面を超薄切片法による電子顕
微鏡写真で観察し、粒子Ｂの面積を上記成形物１で観察
された粒子Ｂの割合を１００％とするとき０〜９５％と
なる様にコントロールする事を特徴とする多様な表面モ
ルフォロジーを有するＡＢＳ系樹脂の製造方法。2. [I] A raw material containing at least a styrene-based monomer, an acrylonitrile-based monomer, and a rubbery polymer is supplied to a polymerization step, and a part or all of the monomer is polymerized to obtain a rubber. After the step of polymerizing the polymer including the particle formation, the mixed solution containing the polymer, the unreacted monomer and / or the solvent is heated, and simultaneously or after heating, introduced into a reduced-pressure chamber to introduce the monomer and / or the solvent. Is separated from the resin component by a separation / recovery step, and the resin exiting the separation / recovery step is injection-molded from the surface of a molded article (molded article 1) obtained by injection molding.
When a rubber particle existing at a depth of 5 μm is observed with an electron micrograph taken by an ultra-thin section method in a plane parallel to the surface of the molded product, particles having a ratio a / b of major axis a to minor axis b of 1.5 or less are obtained. A,
And at least two types of particles B having a ratio a / b of the major axis a to the minor axis b of 5 or more, and the total area of the rubber particles observed in the electron micrograph by the ultra-thin section method is 10%.
0%, the area of the particles A is at least 10% or more,
ABS resin having an area of particles B of 0.01 to 90%,
[II] A twin-screw extruder having a kneading disk or rotor after exiting the separation / recovery step, wherein water is applied to the resin between the separation / recovery step outlet and the portion where the kneading disk or rotor is installed. It has a part to be added and a part to evaporate the added water, and the part to evaporate the added water is subjected to shearing by using an extruder provided at the same time as or immediately in front of the part where the kneading disk is installed. The molded product obtained by giving (molded product 2)
Surface in the same manner as above, i.e., 0.5
A parallel plane having a depth of about 1.5 μm is observed with an electron micrograph by an ultra-thin section method, and the area of the particles B is 0 to 95% when the proportion of the particles B observed in the molded article 1 is 100%. A method for producing an ABS resin having various surface morphologies, characterized in that the resin is controlled to be as follows.
合が単位時間当たりの樹脂の押出量１００重量部に対し
て０〜１５重量部であることを特徴とするＡＢＳ系樹脂
の製造方法。3. The method for producing an ABS resin according to claim 2, wherein the proportion of water to be added is 0 to 15 parts by weight based on 100 parts by weight of the resin extruded per unit time.
ディングディスクが設置されている部分、またはその直
前部で押出機シリンダーの温度を回収工程出口の樹脂温
の０〜６０％低下させた温度とすることを特徴とするＡ
ＢＳ系樹脂の製造方法。4. The method according to claim 1, wherein the temperature of the extruder cylinder is reduced by 0 to 60% of the resin temperature at the outlet of the recovery step at a portion where the kneading disk is installed in the extruder or immediately before the portion. A characterized by temperature
A method for producing a BS resin.
ディングディスクが設置されている部分、またはその直
前部で押出機シリンダーの温度を回収工程出口の樹脂温
の０〜６０％低下させた温度とすることを特徴とするＡ
ＢＳ系樹脂の製造方法。5. The method according to claim 2, wherein the temperature of the extruder cylinder is reduced by 0 to 60% of the resin temperature at the outlet of the recovery step at the portion where the kneading disk is installed in the extruder or immediately before the portion. A characterized by temperature
A method for producing a BS resin.
のスクリューの長さ（Ｌ）とシリンダー径（Ｄ）の比Ｌ
／Ｄが１０〜５０であって、ニーディングゾーンがスク
リュー有効長の５〜６０％である２軸押出機を用いるこ
とを特徴とするＡＢＳ系樹脂の製造方法。6. The method according to claim 1, wherein the ratio of the length (L) of the screw of the extruder to the diameter of the cylinder (D) is L.
A method for producing an ABS resin, wherein a twin screw extruder having a / D of 10 to 50 and a kneading zone of 5 to 60% of the effective screw length is used.
機が、シリンダー径（Ｄ）と、スクリューエレメントの
溝深さ（ｄ）の比Ｄ／ｄが３〜１２であるスクリューエ
レメントが、スクリューの有効長の４０〜９５％のセグ
メントを占めることを特徴とするＡＢＳ樹脂の製造方
法。7. The extruder used in the method according to claim 1 or 2, wherein a screw element having a ratio D / d of a cylinder diameter (D) and a groove depth (d) of the screw element of 3 to 12 is: A method for producing an ABS resin, wherein the segment occupies 40 to 95% of the effective length of the screw.
ディスクまたはローターを備えた２軸押出機として同方
向回転噛合型２軸押出機であって、下記式で表される剪
断指標Ｓが２０〜３００である条件で用いることを特徴
とする多様な表面モルフォロジーを有するＡＢＳ系樹脂
の製造方法。 γm ＝（ｄＮＥ＋ＤＮＥ）×π×Ｎ／｛（ＤＢ−ｄＮ
Ｅ）／２｝ ｄＮＥ：ニーディングディスクの短径（ｍｍ） ＤＮＥ：ニーディングディスクの長径（ｍｍ） Ｎ ：１秒間あたりのスクリュー回転数（ｒｐｓ） ＤＢ ：シリンダーの直径（ｍｍ） Ｓ＝（３５０−Ｔ1 ）×０．０２×γm ×（θ／６０）
×Ｌ／１００ Ｔ1 ：ニーディングゾーン入口の樹脂温度（℃） θ ：押出機中の樹脂の滞留時間（ｓｅｃ） Ｌ ：スクリュー有効長に対するニーディングゾーン
の割合（％）8. A twin-screw extruder equipped with the kneading disk or rotor according to claim 1 or 2, which is a co-rotating mesh twin-screw extruder, wherein a shear index S represented by the following formula is 20: A method for producing an ABS-based resin having various surface morphologies, wherein the method is used under the condition of ~ 300. γ m = (dNE + DNE) × π × N / ｛(DB−dN
E) / 2｝ dNE: short diameter of the kneading disc (mm) DNE: long diameter of the kneading disc (mm) N: number of screw rotations per second (rps) DB: diameter of cylinder (mm) S = (350) −T 1 ) × 0.02 × γ m × (θ / 60)
× L / 100 T 1 : Resin temperature at inlet of kneading zone (° C.) θ: Residence time of resin in extruder (sec) L: Ratio of kneading zone to effective screw length (%)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21852694A JP3325399B2 (en) | 1994-09-13 | 1994-09-13 | Method for producing ABS resin having various surface morphologies |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21852694A JP3325399B2 (en) | 1994-09-13 | 1994-09-13 | Method for producing ABS resin having various surface morphologies |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0881523A JPH0881523A (en) | 1996-03-26 |
| JP3325399B2 true JP3325399B2 (en) | 2002-09-17 |
Family
ID=16721315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21852694A Expired - Fee Related JP3325399B2 (en) | 1994-09-13 | 1994-09-13 | Method for producing ABS resin having various surface morphologies |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3325399B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3341102B2 (en) * | 1996-01-17 | 2002-11-05 | 住友化学工業株式会社 | Thermoplastic resin molding |
| JP5092260B2 (en) * | 2005-09-21 | 2012-12-05 | 住友化学株式会社 | Process for producing olefin polymer |
-
1994
- 1994-09-13 JP JP21852694A patent/JP3325399B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0881523A (en) | 1996-03-26 |
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