JPH0245547A - Transparent impact-resistant resin composition - Google Patents
Transparent impact-resistant resin compositionInfo
- Publication number
- JPH0245547A JPH0245547A JP19571188A JP19571188A JPH0245547A JP H0245547 A JPH0245547 A JP H0245547A JP 19571188 A JP19571188 A JP 19571188A JP 19571188 A JP19571188 A JP 19571188A JP H0245547 A JPH0245547 A JP H0245547A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- parts
- formula
- organosilicon compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 21
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 polymethylsiloxane Polymers 0.000 claims abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 5
- 229920006352 transparent thermoplastic Polymers 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims 1
- 239000000088 plastic resin Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 239000000113 methacrylic resin Substances 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 2
- 229920006037 cross link polymer Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 13
- 229920000126 latex Polymers 0.000 description 11
- 239000004816 latex Substances 0.000 description 10
- 239000000306 component Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241000860832 Yoda Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FIHJKUPKCHIPAT-AHIGJZGOSA-N artesunate Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2O[C@@H](OC(=O)CCC(O)=O)[C@@H]4C FIHJKUPKCHIPAT-AHIGJZGOSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- GKPXMGUNTQSFGA-UHFFFAOYSA-N but-2-ynyl 1-methyl-3,6-dihydro-2h-pyridine-5-carboxylate;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC#CCOC(=O)C1=CCCN(C)C1 GKPXMGUNTQSFGA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は透明性が良好で、かつ耐衝撃性に優れる樹脂組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition that has good transparency and excellent impact resistance.
従来、アクリロニトリル−ブタジェン−スチレン共重合
体（ＡＢＥＴ樹脂）、高衝撃性ポリスチレン（Ｈ工ＰＳ
）、耐衝撃性メタクリン樹脂等は耐衝撃性熱可塑性樹脂
として広く用いられている。Conventionally, acrylonitrile-butadiene-styrene copolymer (ABET resin), high impact polystyrene (H-tech PS)
), impact-resistant methacrine resin, etc. are widely used as impact-resistant thermoplastic resins.
一方、アクリロニトリル−スチレン共重合体（ＡＳ樹脂
）、ポリスチレン、メタクリル酸メチル−スチレン共重
合体（ＭＳ樹脂）、メタクリル酸メチル−アクリロニト
リル−スチレン共重合体（ＭＡＳ樹脂）及びメタクリル
樹脂（ＭＭＡ樹脂）等の硬質樹脂等にポリブタジェン、
ブタジェン−スチレン共重合体、ポリアクリル酸アルキ
ルエステル、ブタジェン−アクリル酸アルキルエステル
共重合体等の軟質樹脂を配合する方法が知られている。On the other hand, acrylonitrile-styrene copolymer (AS resin), polystyrene, methyl methacrylate-styrene copolymer (MS resin), methyl methacrylate-acrylonitrile-styrene copolymer (MAS resin), methacrylic resin (MMA resin), etc. Polybutadiene, hard resin, etc.
Methods of blending soft resins such as butadiene-styrene copolymer, polyacrylic acid alkyl ester, butadiene-acrylic acid alkyl ester copolymer are known.
近年は上記方法により得られた樹脂組成物が車間分野を
中心として広範に使用されている。In recent years, resin compositions obtained by the above method have been widely used mainly in the inter-vehicle field.
特に車満用途の場合、低温領域における比較的高度の耐
衝撃性が要求され、特定の構造を有する有機ケイ素化合
物を配合した樹脂組成物が提案されている（特公昭４９
−２９９４７号公報、特公昭６０−２６４５０号公報）
。Particularly in the case of automobile applications, a relatively high degree of impact resistance in the low temperature range is required, and a resin composition containing an organosilicon compound having a specific structure has been proposed (Japanese Patent Publication No. 49
-29947 Publication, Special Publication No. 60-26450)
.
しかしながら、上述の有機ケイ素化合物を配合した樹脂
組成物は低温領域における耐衝撃性は発現されるが、急
激な温度変化（例えば常温から零下３０℃の雰囲気に移
した場合）が起きた場合、色調の変化が認められ外観上
好ましくないものとなる。特Ｋ、有機ケイ素化合物を透
明な樹脂、例えば■工ｐｓ樹脂や耐衝撃性メタクリル樹
脂等に配合した場合、当該樹脂の特徴である透明性が低
下するという問題があった。However, although resin compositions containing the above-mentioned organosilicon compounds exhibit impact resistance in the low temperature range, when a sudden temperature change occurs (for example, when moving from room temperature to -30°C), the color tone may change. Changes are observed and the appearance is unfavorable. When an organosilicon compound is blended into a transparent resin such as a PS resin or an impact-resistant methacrylic resin, there is a problem in that the transparency, which is a characteristic of the resin, decreases.
そこで、本発明者らは従来の耐衝撃性熱可塑性樹脂組成
物がもつ優れた耐衝撃性、耐熱性、流動加工性を保持し
、その優れた透明性を犠牲にすることなく、かつ低温領
域における耐衝撃性に優れた樹脂組成物を得るべく鋭意
検討した結果、本発明に到達したものである。Therefore, the present inventors have developed a method that maintains the excellent impact resistance, heat resistance, and flow processability of conventional impact-resistant thermoplastic resin compositions, without sacrificing its excellent transparency, and in the low-temperature region. The present invention was developed as a result of intensive studies aimed at obtaining a resin composition with excellent impact resistance.
本発明の要旨とするところは、メタクリル酸メチＭを主
要構成単位とする硬質樹脂（１”１９７〜５０重量部、
ブタジェン成分を含む架橋ゴム状重合体にメタクリル酸
メチルを主要構成単位とする硬質樹脂成分をグラフト重
合せしめたグラフト共重合体（■）３〜５０重量部、及
び硬質樹脂（１’）とグラフト共重合体（■）の合計量
１００重量部に対して、下記の一般式
（式中Ｒ１，Ｒ，、Ｒ，はそれぞれ同一であっても異な
っても良込アルキル基を、ｎは１０〜１０００の整数を
示す。）
で表わされる有機ケイ素化合物（ＩＩＩ）ｏ、ｏｏ１〜
α３重量部を添加してなる透明熱可塑性樹脂組成物であ
る。The gist of the present invention is that a hard resin (1" 197 to 50 parts by weight,
3 to 50 parts by weight of a graft copolymer (■) in which a hard resin component having methyl methacrylate as a main constituent unit is grafted onto a crosslinked rubbery polymer containing a butadiene component, and a graft copolymer with a hard resin (1'). With respect to 100 parts by weight of the total amount of the polymer (■), the following general formula (in the formula, R1, R,, R, may be the same or different, each represents a good alkyl group, and n is 10 to 1000 (indicates an integer of ) Organosilicon compound (III) o, oo1~
This is a transparent thermoplastic resin composition in which 3 parts by weight of α is added.
以下、本発明の透明耐衝撃性樹脂組成物について詳ＭＫ
説明する。The details of the transparent impact-resistant resin composition of the present invention are as follows.
explain.
本発明において用いられる硬質樹脂（１）はメタクリル
酸メチルを主要構成単位とする重合体であって、メタク
リル樹脂、ＭＳ樹脂、ＭＡＥ＋樹脂が好ましい。特に耐
候性、透明性の点でメタクリｌし酸メチ／ｌ／６０〜１
００重量部、アクリル酸アルキルエステＩＬ１０〜２０
重量部、及びその他の共重合可能なビニル単量体０〜５
０重量部から成る共重合体が好ましい。アクリル酸アル
ギＶエステルとしてはアクリル酸メチル、アクリル酸エ
チＶ、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘ
キシル、アクリル酸フェニル、アク１１ ｔｖ酸シクロ
ヘキシル等が挙げられる。The hard resin (1) used in the present invention is a polymer having methyl methacrylate as a main constituent unit, and methacrylic resin, MS resin, and MAE+ resin are preferable. Especially in terms of weather resistance and transparency, methacrylic acid methoxyl/l/60~1
00 parts by weight, alkyl ester acrylate IL10-20
Parts by weight, and other copolymerizable vinyl monomers 0-5
Preference is given to copolymers comprising 0 parts by weight. Examples of the algi-V acrylate ester include methyl acrylate, ethyl-V acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and cyclohexyl acrylate.
また、その他の共重合可能なビニＶ単量体としてはアク
リロニトリル、メタクリロニトリル、スチレン、α−メ
チルスチレン、無水マレイン酸、Ｎ−置換マレイミド等
が挙げられる。Other copolymerizable vinyl V monomers include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, maleic anhydride, and N-substituted maleimide.
硬質樹脂（１）は、公知の重合法により製造されたもの
を使用することができる。As the hard resin (1), those manufactured by known polymerization methods can be used.
次Ｋ、グラフト共重合体（ＩＩ）はブタジェン成分を含
む架橋ゴム状重合体にメタクリル酸メチルを主要構成単
位とする硬質樹脂成分をグラフト重合せしめたものであ
るが、透明性、耐衝撃性の点でブタジェン６０〜９０重
量％、アクリル９フルキル工ステル１０〜７０重量％、
及びその他のブタジェンと共重合しつるビニル単量体０
〜５０重量％とからなる架橋ゴム状重合体に、メタクリ
ル酸メチルを８０重量係以上含有する硬質樹脂成分をグ
ラフト重合せしめて得たグラフト共重合体が好寸しい。The next graft copolymer (II) is a crosslinked rubbery polymer containing a butadiene component and a hard resin component whose main constituent unit is methyl methacrylate. 60-90% by weight of butadiene, 10-70% by weight of acrylic 9,
and other vinyl monomers copolymerized with butadiene 0
A graft copolymer obtained by graft-polymerizing a hard resin component containing 80% by weight or more of methyl methacrylate onto a crosslinked rubbery polymer containing 50% by weight is suitable.
ここで、アクリル酸アルキルエステルとしてはアクリル
酸メチル、アクリル酸エチル、アクノル酸ｎ−ブチル、
アクリル酸２−エチルヘキシル、アクリル酸フェニル、
アクリル酸シクロヘキシル等が挙げられる。また、その
他のブタジェンと共重合しうるビニル単量体としてはア
クリロニトリル、メタクリロニトリル、スチレン、α−
メチルスチレン’５Ｌ’＋”挙ケラレル。Here, the acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-butyl acnolate,
2-ethylhexyl acrylate, phenyl acrylate,
Examples include cyclohexyl acrylate. In addition, other vinyl monomers that can be copolymerized with butadiene include acrylonitrile, methacrylonitrile, styrene, α-
Methyl styrene '5L' + "Keralel".
グラフト共重合体（Ｉｎとしては、エクスｌ−マーとし
ての物性の点でガラス転移温度が２５℃以下、特に０℃
以下のものが好ましい。The graft copolymer (In) has a glass transition temperature of 25°C or lower, especially 0°C in terms of physical properties as an exl-mer.
The following are preferred.
グラフト共重合体は、公知の重合法により製造されたも
のを使用することができる。As the graft copolymer, those produced by known polymerization methods can be used.
硬質樹脂（１）とグラフト共重合体（■）の使用割合は
硬質樹脂（１） ｑ ７〜５０重量部に対し、グラフト
共重合体（■）３〜５０重量部の範囲である。グラフト
共重合体（Ｕ）の使用割合が３重量部未満では耐衝撃性
の発現効果が劣ヤ、一方５０重量部を超えると耐熱性や
剛性に劣る傾向となる。The ratio of the hard resin (1) and the graft copolymer (■) is in the range of 3 to 50 parts by weight of the graft copolymer (■) to 7 to 50 parts by weight of the hard resin (1) q. If the proportion of the graft copolymer (U) used is less than 3 parts by weight, the effect of developing impact resistance will be poor, while if it exceeds 50 parts by weight, heat resistance and rigidity will tend to be poor.
さらに、本発明の重要な構成要素である有機ケイ素化合
物（■）は、下記の一般式
（式中Ｒ１，Ｒ，、Ｒ，はそれぞれ同一であって４異な
っても良いアルキＶ基を、ｎは１０〜１０００の整数を
示す。）
で表わされるものである。置換基Ｒ１、Ｒ２＊ ”ｌと
してはメチル、エチル、プロピル、ブチル等のアルキル
基であればよいが、有機ケイ素化合物自体のハンドリン
グ性、コストを考慮した場合、次の一般式
（ｎは１０〜１０００の整数を示す。）で表わされるポ
リメチｌジシロキサンが好まし込。Furthermore, the organosilicon compound (■), which is an important component of the present invention, has the following general formula (wherein R1, R, , R, are each the same and may be 4 different alkyl V groups, n represents an integer from 10 to 1000). The substituents R1 and R2*'l may be any alkyl group such as methyl, ethyl, propyl, butyl, etc., but when considering the handling property and cost of the organosilicon compound itself, the following general formula (n is 10 to (representing an integer of 1000) is preferred.
有機ケイ素化合物（ｍ）の重合度ｎけ、揮発性や樹脂へ
の分散仲を考慮した場合１ｏ〜ｊ ０００の範囲が好ま
しく、１０未満では樹脂との溶融時に揮発分が多く、ま
た成形後成形板の表面にブリードアウトするようになる
。一方、ｎが１０００を超える場合は粘度が高ぐ、樹脂
に対し、均一に分散できなくなる。Considering the degree of polymerization of the organosilicon compound (m), volatility, and dispersion into the resin, a range of 10 to 000 is preferable; if it is less than 10, there will be a large amount of volatile matter when melted with the resin, and the molding after molding will be difficult. It begins to bleed out onto the surface of the board. On the other hand, if n exceeds 1000, the viscosity will be high and it will not be possible to uniformly disperse it in the resin.
有機ケイ素化合物（’［１）としては、上記のポリメチ
ルンロキサンをはじめ種々の市販品、例えばｒ ＫＦ−
９６Ｊ、ｒｘｐ−４２Ｊ、「Ｋｙ−４１３Ｊ、ｒｘＦ−
４１４Ｊ （以上、信越シリコーン■製品）、［ＴＳＦ
−４５１Ｊ （来夏シリコ−ン＠ ｆＪｊ３品）、「５
ＩＩ−２ｏｏ」（東しシリコーン■製品）、「Ｌ−、ａ
ｓＪ （日本ユニカー鞠製品）等を使用することができ
る。As the organosilicon compound ('[1), there are various commercially available products including the above-mentioned polymethylroxane, such as rKF-
96J, rxp-42J, “Ky-413J, rxF-
414J (all Shin-Etsu Silicone products), [TSF
-451J (next summer silicone @ fJj 3 products), “5
II-2oo” (Toshi silicone ■ product), “L-, a
sJ (Japan Unicar Ball Products) etc. can be used.
また、有機ケイ素化合物（ＩＩＩ）の配合量は硬質樹脂
（１）とグラフト共重合体（１１）の合計［１００重量
部に対しα００１〜α５重債部である。The amount of the organosilicon compound (III) is α001 to α5 parts by weight per 100 parts by weight of the total of the hard resin (1) and the graft copolymer (11).
０．００１重量部未満では低温領域における耐衝撃性向
上の効果が見られず、一方ＣＬ３重量部を超えると効果
の増加が認められないばかりでなく、硬質樹脂（１）が
木来持つ透明性が損なわれるようになる。If the amount is less than 0.001 part by weight, no effect of improving impact resistance in the low temperature range is observed, while if it exceeds 3 parts by weight, not only is no increase in the effect observed, but the transparency that the hard resin (1) normally has is not observed. becomes impaired.
本発明の耐衝撃性樹脂組成物において、硬質樹脂（Ｉ）
とグラフト共重合体（ＩＩ）及び有機ケイ素化合物（’
ＩＩＩ’）をブレンド混合する方法としては硬質樹脂（
Ｉ）、グラフト共重合体（Ｕ＞及び有機ケイ素化合物（
ｍ）の６者、もしくは硬質樹脂（１）とグラフト共重合
体（ｎ）の混合物と有機ケイ素化合物（Ｉｎ ’）の２
者をヘンシエルミキサーヤｒＦタンブラ−等により混合
した後、スクリュー式押出機やミキシングロールヲ用い
て１５０〜６００℃で溶融混合する方法が挙げられる。In the impact-resistant resin composition of the present invention, the hard resin (I)
and graft copolymer (II) and organosilicon compound ('
III') is blended with hard resin (III').
I), graft copolymer (U> and organosilicon compound (
6 of m), or 2 of a mixture of hard resin (1) and graft copolymer (n) and organosilicon compound (In')
Examples include a method of mixing the components using a Henschel mixer, rF tumbler, etc., and then melt-mixing at 150 to 600° C. using a screw extruder or mixing roll.
なお溶融混合に際し上記の各樹脂組成物成分の他に、必
要によシ安定剤、滑剤、可塑剤、染顔料、充填剤等を適
宜加えることができる。In addition to the above-mentioned resin composition components, stabilizers, lubricants, plasticizers, dyes and pigments, fillers, etc. can be appropriately added during melt-mixing.
このようにして得られた熱可塑性樹脂組成物を押出成形
機、射出成形機等により成形することにより、常温及び
低温領域忙おける耐衝撃性にすぐれ、かつ急激な温度変
化に伴う色調の変化がなく、特に透明樹脂においてはそ
の透明性が阻害されない成形品を得ることができる。By molding the thermoplastic resin composition obtained in this way using an extrusion molding machine, an injection molding machine, etc., it has excellent impact resistance at room temperature and low temperature, and also resists changes in color tone due to sudden temperature changes. In particular, in the case of transparent resins, it is possible to obtain molded articles whose transparency is not impaired.
以下、実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、実施例中「部」とあるのは「重量部」を、「％」
とあるのは「重量部」をそれぞれ表わす。In addition, "part" in the examples refers to "part by weight" and "%"
``parts by weight'' are indicated respectively.
なお、実施例中の物性評価は以下の方法によった。In addition, physical property evaluation in Examples was performed by the following method.
（１）熱変形温度（℃）はＡＳＴＭ−Ｄ−６４８１に準
拠して測定した。(1) Heat distortion temperature (°C) was measured in accordance with ASTM-D-6481.
（２） アイゾツト衝撃強度（Ｋｇ−α／−２）は、
ＡＳＴＭ−Ｄ−２５６に準拠して測定した。(2) Izod impact strength (Kg-α/-2) is
Measured in accordance with ASTM-D-256.
（３） 光沢度はＡＳＴＭ−Ｄ−６７３−４４に準拠
して測定した。(3) Glossiness was measured in accordance with ASTM-D-673-44.
（４）全光線透過率（引及びヘイズ（チ）はＡＳＴＭ−
Ｄ−１００３−５２に準拠して測定した。(4) Total light transmittance (reduction and haze (CH) are ASTM-
Measured in accordance with D-1003-52.
（５） ブリードアクト性は、成形板を１５０℃のオ
ーブン中で２時間熱曝路した後の光沢度と表面の様子を
観察した。表面外観の判定は下記の通りである。(5) Bleed attack property was determined by observing the glossiness and surface condition after exposing the molded plate to heat for 2 hours in an oven at 150°C. Judgment of surface appearance is as follows.
○・・・ブリードアウトなし
×・・・ブリードアウトが認められる
また、実施例中の硬質樹脂（Ｉ）として下記のものを使
用した。○: No bleed-out ×: Bleed-out observed In addition, the following was used as the hard resin (I) in the examples.
（１１ＭＳ樹脂：メタクリル酸メチルとスチレンの比（
部）が７５：２５で２５℃のク
ロロホルム中で測定した粘度〔η〕
がα０７２ （ｔ１５’）
（２） Ｍ Ｍ Ａ樹脂：メタクリル酸メチルとアクリ
ル酸メチルの比（部）が９７：６で２５
℃のクロロホルム中で測定した粘
度〔η〕がα０５６ （Ｌ／？’）
グラフト共重合体（ＩＩ）として下記の方法によう製造
されたものを用いた。(11MS resin: ratio of methyl methacrylate to styrene (
The viscosity [η] measured in chloroform at 25°C is α072 (t15') (2) M M A resin: the ratio (parts) of methyl methacrylate and methyl acrylate is 97:6. The viscosity [η] measured in chloroform at 25° C. was α056 (L/?’). A graft copolymer (II) produced by the following method was used.
（１） ポリブタジェン系重合体（以下、ＢＲとする
）
ブタジェン１００部を乳化重合して得られだ粒子径、約
ｃＬ２μの重合体に対１−、メタクリル酸メチルとスチ
レンの化ツマー比率（係）が７５ ： ２５のモノマー
混合物６０部をグラフト共重合して得られたラテックス
から常法により重合体を回収し、パウダー状物とした。(1) Polybutadiene-based polymer (hereinafter referred to as BR) The ratio of methyl methacrylate and styrene to the polymer with a particle size of approximately cL 2μ obtained by emulsion polymerization of 100 parts of butadiene (correspondence) A polymer was recovered by a conventional method from a latex obtained by graft copolymerizing 60 parts of a monomer mixture with a ratio of 75:25 to form a powder.
（２） ブタジェン−アクリル酸アルキルエステル系
重合体（以下、ＡＢＲとする）
ブタジェンとアクリル酸ブチルのモノマー比率（俤）が
５０：５０のモノマー混合物を乳化重合して得られた粒
子径約Ｑ、１２μの重合体１００部に対し、メタクリル
酸メチルとアクリル酸エチルの化ツマー比率（係）が９
７：３のモノマー混合物５０部をグラフト共重合して、
得られたラテックスから常法により重合体を回収し、パ
ウダー状物とした。(2) Butadiene-acrylic acid alkyl ester polymer (hereinafter referred to as ABR) Particle diameter of approximately Q obtained by emulsion polymerization of a monomer mixture of butadiene and butyl acrylate in a monomer ratio (忤) of 50:50, The ratio of methyl methacrylate to ethyl acrylate is 9 for 100 parts of 12μ polymer.
Graft copolymerizing 50 parts of a 7:3 monomer mixture,
A polymer was recovered from the obtained latex by a conventional method and made into a powder.
実施例１〜３．比較例１〜３
硬質樹脂（１）、グラフト共重合体（Ｉｌ）、有機ケイ
素化合物（１）として一般式においてｎ＝８３であるジ
メチルポリンロキサンＩ”Ｌ−４５１００センチストー
クス」（日本ユニカー■製品）、及び安定剤を第１表に
示した割合で内容積２０ｔのスーパーミキサー（■用田
製作所Ｗ 、ＳＭＶ−２０タイプ）に入れ攪拌回転数１
８００ ｒｐｍの条件下で３分間ブレンドした。Examples 1-3. Comparative Examples 1 to 3 Hard resin (1), graft copolymer (Il), and organosilicon compound (1) Dimethylpolyrinloxane I"L-45100 centistokes" (Nippon Unicar) where n=83 in the general formula product) and stabilizer in the proportions shown in Table 1 in a super mixer (■ Yoda Seisakusho W, SMV-20 type) with an internal volume of 20 tons, and the stirring speed was 1.
Blended for 3 minutes at 800 rpm.
得られた樹脂組成物のブレンド物を、外径４０間φのス
クリュー型押出機（＠日本製鋼新製、Ｐ−４０−２６Ａ
Ｂ−Ｖ型、Ｌ／Ｄ＝２６ ）を使用し、シリンダー温度
１５０〜２５０℃、ダイ温度２００〜２５０℃で溶層混
練してベレットとした後、下記の条件で射出成形して得
られた試験片を評価し、第２表に示した結果を得た。The resulting blend of resin compositions was transferred to a screw extruder with an outer diameter of 40 mm (@Nippon Steel New Co., Ltd., P-40-26A).
B-V type, L/D = 26), the pellet was made into a pellet by melt layer kneading at a cylinder temperature of 150 to 250°C and a die temperature of 200 to 250°C, and then injection molded under the following conditions. The specimens were evaluated and the results shown in Table 2 were obtained.
射出成形機：■日本製鋼所製、Ｖ−１７−Ｓ５型スクリ
ユ一式自動射出成形機
射出成形条件ニジリンダ−温度２００〜２５０℃金型温
度５５℃
試験片サイズ： １１０ｍＸ １１０１１１１１Ｘ２
＋ｌｌ＋（厚さ）（光沢度、全光線透過率、ヘイズ
測定及び成形品の外観観察用）
７０＋ｍＸ １２．ＳｍＸ ＆２１１１１（厚さ）（ア
イゾツト衝撃強度測定用）
実施例４〜６．比較例４
各成分を第３表に示した本のを用−た以外は実施例１と
同様に実験を行った。結果を第４表に示す。Injection molding machine: Made by Japan Steel Works, V-17-S5 type screw complete automatic injection molding machine Injection molding conditions Niji cylinder temperature 200-250℃ Mold temperature 55℃ Test piece size: 110mX 11011111X2
+ll+ (thickness) (for glossiness, total light transmittance, haze measurement and appearance observation of molded products) 70+mX 12. SmX &21111 (thickness) (for Izot impact strength measurement) Examples 4 to 6. Comparative Example 4 An experiment was conducted in the same manner as in Example 1, except that the ingredients shown in Table 3 were used. The results are shown in Table 4.
／
／
／
比較例５〜６
各成分を第５表に示したものを用いた以外は実施例１と
同様に実験を行った。結果を第６表に示す。/ / / Comparative Examples 5 and 6 An experiment was conducted in the same manner as in Example 1 except that each component shown in Table 5 was used. The results are shown in Table 6.
実施例７
硬質樹脂（Ｉ）としてメタクリル樹脂「アクリベラ）Ｖ
ＨＪ （三菱レイヨン■ｍ品）＆ Ｏｙ４、グラフト共
重合体（（ｒ）として下記の方法によりシ造した重合体
４．０ ｋｌ、実施例１で使用した有機ケイ素化合物（
ＩＩ＋） ２０ ｙ、ステアリン酸モノグリセライドｉ
ｏｐ、安定剤［工ｒｇａｎｏｘ １０７６Ｊ（チバガイ
ギー社製品）ろｏ２及びｒＭａｒｋ ３２９Ｊ（アデカ
・アーガス■製品）４０２を２０１容量のヘンシェルミ
キサーで混合した。この樹脂組成物に対し、実施例１と
同様に実験を行った。Example 7 Methacrylic resin “Acrybella” V as hard resin (I)
HJ (Mitsubishi Rayon m product) & Oy4, graft copolymer (4.0 kl of polymer prepared by the following method as (r), organosilicon compound used in Example 1 (
II+) 20 y, stearic acid monoglyceride i
Op, stabilizer [Rganox 1076J (Ciba Geigy product) RoO2 and rMark 329J (Adeka Argus product) 402 were mixed in a 201 capacity Henschel mixer. Experiments were conducted on this resin composition in the same manner as in Example 1.
結果を第６表に示す。The results are shown in Table 6.
グラフト共重合体（ＩＩ）の製造
１）ゴム状共重合体（１−１）’の製造ブチ７レアクリ
レート ６に９１．３−ブタジェン
４ 〃ジイソプロピルベンゼンヒ
ドロバーオキシＦ ２０ ｙ牛脂脂肪酸カ
リウム １ｏｎ ｔｔＮ−ラウロイルザ
ルコンン酸ナトリウム ５ｏ 〃ビロリン
酸ナトリウム ５ｏ 〃硫酸第一鉄
０．５Ｓ’デキストロース
３０脱イオン水
２０ ゆ上記組成割合の物質の中で、１．３−ブタ
ジェンを除く物質だついては、その中に含まれる酸素を
窒素で置換し、実質上重合反応を阻害しない状態とした
。その後金ての物質をａＯＺオートクレーブに仕込み、
５０℃で重合した。９時間でほぼ重合は完了し、転化率
９７係、粒子予１１７０μｍのゴムラテックス（１−１
）が得られた。Production of graft copolymer (II) 1) Production of rubbery copolymer (1-1)' Buty7 rare acrylate 6 to 91.3-butadiene 4 diisopropylbenzenehydroveroxy F 20 y potassium tallow fatty acid 1 on ttN - Sodium lauroyl sarconate 5o Sodium birophosphate 5o Ferrous sulfate
0.5S' dextrose
30 deionized water
Among the substances having the above composition ratios, the oxygen contained in the substances except 1,3-butadiene was replaced with nitrogen, so that the polymerization reaction was not substantially inhibited. After that, put the gold substance into the aOZ autoclave,
Polymerization was carried out at 50°C. The polymerization was almost completed in 9 hours, the conversion rate was 97%, and the rubber latex (1-1
)was gotten.
ポリマー固型分１０に９を含むゴム状共重合体ラテック
ス（１−１）の入った６０１オートクレープをかき混ぜ
ながら、内温５０℃で１５分間保持した後、下記により
製造したラテックス（Ａ−１）４００１Ｆを加えて６０
分間保持した。A 601 autoclave containing a rubbery copolymer latex (1-1) containing a polymer solid content of 10 to 9 was kept at an internal temperature of 50°C for 15 minutes while stirring, and then the latex (A-1) produced as follows was held at an internal temperature of 50°C for 15 minutes. ) Add 4001F to 60
Hold for minutes.
さらに、５憾硫酸す） ＩＪウム水溶液１ゆを加えて１
時間保持した。得られた肥大化ゴム状重合体（１−１）
’の平均粒子径はＱ、２１μｍであった。Furthermore, add 5 ml of sulfuric acid solution and 1 ml of IJum aqueous solution.
Holds time. Obtained enlarged rubbery polymer (1-1)
The average particle diameter of Q was 21 μm.
２）肥大化用酸基含有共重合体ラテックス（Ａ−１）の
製造
上記組成の混合物を５Ｌのガラス製丸底フラスコにより
、７０℃で１．５時間重合させた後、引続き７０℃で
からなる混合物を１時間かけて滴下し、その後１時間攪
拌を続けて転化率９８％の共重合体ラテックスを得た。2) Production of acid group-containing copolymer latex (A-1) for enlargement The mixture having the above composition was polymerized at 70°C for 1.5 hours in a 5 L glass round bottom flask, and then at 70°C. The mixture was added dropwise over 1 hour, and stirring was continued for 1 hour to obtain a copolymer latex with a conversion rate of 98%.
３）グラフト共重合体（１１）ラテックスの製造肥大化
ゴム状共重合体（１−１）’の重合体固型分１０ゆを含
む肥大化ラテックスの入った、肥大化を行った反応容器
に、脱イオン水９１Ｋｇ、ナトリウムホルムアルデヒド
スＶホキシレート２０ノ、Ｎ−ラウロイＩｖ４ ／Ｌ／
コシン酸ナトナトリウム５０？え内温を７５℃に昇温し
、下記の原料を９０分間にわたり連続的に添加し重合し
た。3) Production of graft copolymer (11) latex: Place the enlarged rubbery copolymer (1-1)' in a reaction vessel containing the enlarged latex containing 10% polymer solids. , 91 kg of deionized water, 20 kg of sodium formaldehyde V oxylate, N-Lauroy Iv4 /L/
Sodium cosinate 50? The internal temperature was raised to 75° C., and the following raw materials were continuously added over 90 minutes for polymerization.
メタクリル酸メチル ４３２０ ？アクリル
酸エチル １８０ 〃ノルマルオクチルメ
ルカプタン ６７５〃クメンヒドロパーオキシ
ド １６ 〃添加終了後、さらに６０分間重合を
継続したメタクリル酸メチルの転化率はほぼ１００チで
あった。Methyl methacrylate 4320? Ethyl acrylate 180 Normal octyl mercaptan 675 Cumene hydroperoxide 16 After the addition, polymerization was continued for an additional 60 minutes, and the conversion rate of methyl methacrylate was approximately 100%.
得られた重合体ラテックスに、スチレン化フェノール５
８２、ジラウリルチオプロピオネ）４４ｉｉ’、ｌ−リ
フエニルフオスファイト５８？を加え、５０℃の温度条
件下、［１２５係の硫酸水により、ラテックス／水＝１
／２で凝集させて、さらに８５℃で５分間保持した。Styrenated phenol 5 was added to the obtained polymer latex.
82, dilaurylthiopropione) 44ii', l-rifenyl phosphite 58? was added, and under a temperature condition of 50°C, latex/water = 1 with sulfuric acid water of 125
The mixture was agglomerated at a temperature of /2 and further held at 85°C for 5 minutes.
得られたスラリ状重合体を洗浄・脱水して、６５℃で３
６時間乾燥り白色の粉末を得た。The obtained slurry polymer was washed and dehydrated, and then heated at 65°C for 3
After drying for 6 hours, a white powder was obtained.
比較例７
実施例８において「Ｌ−４５１００七ンチストークス」
の代わりにフェニル基変性ジメチｌレシロキサンｒｔｚ
−１９７Ｊ （日本ユニカー味製品）を２０２添加した
以外は実施例８と同様に実験を行った。結果を第７表に
示す。Comparative Example 7 “L-45100 Seven-inch Stokes” in Example 8
phenyl-modified dimethyl-resiloxane rtz instead of
The experiment was conducted in the same manner as in Example 8, except that 202 -197J (Nippon Unicar Flavor Product) was added. The results are shown in Table 7.
比較例８
実施例８において「Ｌ−４５１００センチストークス」
を使用しなかった以外は実施例８と同様に実験を行った
。結果を第７表に示す。Comparative Example 8 “L-45100 centistokes” in Example 8
The experiment was conducted in the same manner as in Example 8 except that . The results are shown in Table 7.
第 ７ 表
〔発明の効果〕
本発明の耐衝撃性樹脂組成物は、樹脂本来の特徴を犠牲
にすることなく、これに良好な低温耐衝６性が付与され
、特に透明な樹脂においてはその透明性も阻害されず、
工業１優れた効果を奏する。Table 7 [Effects of the Invention] The impact-resistant resin composition of the present invention imparts good low-temperature impact resistance 6 without sacrificing the original characteristics of the resin, and especially in transparent resins, Transparency is not hindered,
Industry 1: Excellent effect.
特許出願人 三菱レイヨン株式会社 代理人 弁理士 告 澤 敏 夫Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney: Toshio Sawa
Claims (1)
（ I ）９７〜５０重量部、ブタジエン成分を含む架橋
ゴム状重合体にメタクリル酸メチルを主要構成単位とす
る硬質樹脂成分をグラフト重合せしめたグラフト共重合
体（II）５〜５０重量部、及び硬質樹脂（ I ）とグラ
フト共重合体（II）の合計量１００重量部に対して、下
記の一般式 ▲数式、化学式、表等があります▼ （式中Ｒ＿１、Ｒ＿２、Ｒ＿３はそれぞれ同一であつて
も異なつても良いアルキル基を、ｎは１０〜１０００の
整数を示す。） で表わされる有機ケイ素化合物（III）０．００１〜０
．３重量部を添加してなる透明熱可塑性樹脂組成物。 ２）有機ケイ素化合物が下記の一般式 ▲数式、化学式、表等があります▼ （ｎは１０〜１０００の整数を表わす） で示されるポリメチルシロキサンである特許請求の範囲
第１項記載の透明熱可塑性樹脂組成物。[Scope of Claims] 1) 97 to 50 parts by weight of a hard resin (I) containing methyl methacrylate as a main constituent unit, a hard resin component containing methyl methacrylate as a main constituent unit in a crosslinked rubbery polymer containing a butadiene component. 5 to 50 parts by weight of graft copolymer (II) obtained by graft polymerization, and 100 parts by weight of the total amount of hard resin (I) and graft copolymer (II), the following general formula ▲ mathematical formula, chemical formula , tables, etc. ▼ (In the formula, R_1, R_2, and R_3 each represent an alkyl group that may be the same or different, and n represents an integer from 10 to 1000.) Organosilicon compound (III) 0 .001~0
．． A transparent thermoplastic resin composition containing 3 parts by weight. 2) Transparent heat according to claim 1, wherein the organosilicon compound is polymethylsiloxane represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (n represents an integer from 10 to 1000) Plastic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19571188A JP2782199B2 (en) | 1988-08-05 | 1988-08-05 | Transparent impact resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19571188A JP2782199B2 (en) | 1988-08-05 | 1988-08-05 | Transparent impact resistant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245547A true JPH0245547A (en) | 1990-02-15 |
| JP2782199B2 JP2782199B2 (en) | 1998-07-30 |
Family
ID=16345704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19571188A Expired - Fee Related JP2782199B2 (en) | 1988-08-05 | 1988-08-05 | Transparent impact resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2782199B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0591804A1 (en) * | 1992-10-05 | 1994-04-13 | BASF Aktiengesellschaft | Transparent moulding matter |
| EP0599067A1 (en) * | 1992-11-24 | 1994-06-01 | BASF Aktiengesellschaft | Transparent moulding matter |
| EP0606636A1 (en) * | 1993-01-13 | 1994-07-20 | BASF Aktiengesellschaft | Polymethyl methacrylate based moulding materials having improved impact strength |
| WO2012029304A1 (en) * | 2010-08-31 | 2012-03-08 | 株式会社クラレ | Polymer composition and molded product |
| JP2012072274A (en) * | 2010-09-28 | 2012-04-12 | Kuraray Co Ltd | Methacrylic polymer composition and molding |
-
1988
- 1988-08-05 JP JP19571188A patent/JP2782199B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0591804A1 (en) * | 1992-10-05 | 1994-04-13 | BASF Aktiengesellschaft | Transparent moulding matter |
| EP0599067A1 (en) * | 1992-11-24 | 1994-06-01 | BASF Aktiengesellschaft | Transparent moulding matter |
| EP0606636A1 (en) * | 1993-01-13 | 1994-07-20 | BASF Aktiengesellschaft | Polymethyl methacrylate based moulding materials having improved impact strength |
| US5393817A (en) * | 1993-01-13 | 1995-02-28 | Basf Aktiengesellschaft | Molding materials based on polymethyl methacrylate and having improved notched impact strength |
| WO2012029304A1 (en) * | 2010-08-31 | 2012-03-08 | 株式会社クラレ | Polymer composition and molded product |
| US20130225753A1 (en) * | 2010-08-31 | 2013-08-29 | Kuraray Co., Ltd. | Polymer composition and a molded article thereof |
| EP2612883A4 (en) * | 2010-08-31 | 2014-01-22 | Kuraray Co | Polymer composition and molded product |
| JP5844262B2 (en) * | 2010-08-31 | 2016-01-13 | 株式会社クラレ | POLYMER COMPOSITION AND MOLDED ARTICLE |
| JP2012072274A (en) * | 2010-09-28 | 2012-04-12 | Kuraray Co Ltd | Methacrylic polymer composition and molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2782199B2 (en) | 1998-07-30 |
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