JP2015127429A - Component for contact having reduced creaking noise - Google Patents
Component for contact having reduced creaking noise Download PDFInfo
- Publication number
- JP2015127429A JP2015127429A JP2015078458A JP2015078458A JP2015127429A JP 2015127429 A JP2015127429 A JP 2015127429A JP 2015078458 A JP2015078458 A JP 2015078458A JP 2015078458 A JP2015078458 A JP 2015078458A JP 2015127429 A JP2015127429 A JP 2015127429A
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- JP
- Japan
- Prior art keywords
- rubber
- mass
- polymer
- vinyl
- ethylene
- 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
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 115
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 106
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920001971 elastomer Polymers 0.000 claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 50
- 229920002545 silicone oil Polymers 0.000 claims abstract description 50
- 239000004711 α-olefin Substances 0.000 claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005977 Ethylene Substances 0.000 claims abstract description 42
- 239000005060 rubber Substances 0.000 claims abstract description 38
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 30
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 27
- 239000011342 resin composition Substances 0.000 claims abstract description 26
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims description 34
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 22
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 239000003505 polymerization initiator Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 10
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000004898 kneading Methods 0.000 description 7
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 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 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 208000003251 Pruritus Diseases 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000007803 itching Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000011120 plywood Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011094 fiberboard Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 235000021189 garnishes Nutrition 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
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- 244000043261 Hevea brasiliensis Species 0.000 description 2
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- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Air-Conditioning For Vehicles (AREA)
Abstract
Description
本発明は接触用部品に関し、さらに詳しくは、他の部材と接触し、擦れ合うことにより発生する軋み音を大幅に低減させた熱可塑性樹脂組成物製接触用部品に関する。 The present invention relates to a contact part, and more particularly, to a contact part made of a thermoplastic resin composition in which the squeaking noise generated by contacting and rubbing with other members is greatly reduced.
ABS樹脂は、その優れた機械的性質、耐熱性、成形性により自動車内装部品の製造に広範囲に使用されている。 ABS resins are widely used in the manufacture of automotive interior parts due to their excellent mechanical properties, heat resistance, and moldability.
しかし、自動車走行時の振動に伴い、ABS樹脂製自動車内装部品が、該部品同士や該部品とポリ塩化ビニル、クロロプレンゴム、ポリウレタン、天然ゴム、ポリエステルまたはポリエチレン製の内張りシート、フォームなどの他の部材と接触して擦れ合うような場合において、軋み音(擦れ音)を発生することがある。たとえばABS樹脂製のベンチレータには、風量を調整するためにクロロプレンゴム製フォームなどをシール材として使用したバルブシャッターが内部に装着されており、風量調整のためにバルブシャッターを回転させると、ABS樹脂製のベンチレータのケースと他の部材であるシール材のケースとが互いに擦れ合い、軋み音が発生する場合がある。 However, due to vibrations during automobile travel, ABS interior parts made of ABS resin may be used together with other parts and other parts such as polyvinyl chloride, chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheets, foam, etc. In the case where they come into contact with each other and rub against each other, a squeaking noise (friction) may be generated. For example, a ventilator made of ABS resin is equipped with a valve shutter that uses chloroprene rubber foam as a sealing material to adjust the air volume. When the valve shutter is rotated to adjust the air volume, the ABS resin The case of the ventilator made of metal and the case of the sealing material as another member may rub against each other, and a squeaking noise may occur.
また、ABS樹脂、ASA樹脂は非晶性樹脂であるため、結晶性樹脂であるポリエチレン、ポリプロピレン、ポリアセタールなどの樹脂と比較すると摩擦係数が高く、自動車内のエアコン吹き出し口やカーステレオのボタン等のように、他樹脂からなる部材と嵌合する場合には、摩擦係数が大きいために図1に示されるようなスティックスリップ現象が発生し、異音(軋み音)が発生することもよく知られている。上記スティックスリップ現象とは、2つの物体が擦れ合う時に発生するもので、図2(a)のモデルで示されるように駆動速度Vで動く駆動台の上にバネでつながれた物体Mが置かれた場合、物体Mは先ず静摩擦力の作用により駆動速度Vで移動する台とともに図2(b)のように右方向に移動する。そして物体Mがバネによって元に戻されそうとする力が、この静摩擦力と等しくなったとき、物体Mは駆動速度Vと逆の方向に滑り出す。このとき、物体Mは動摩擦力を受けることとなるが、バネの力とこの動摩擦力が等しくなった図2(c)の時点で滑りが止まり、物体Mは再び駆動台に付着した状態となり、再び駆動速度Vと同じ方向に移動することになる(図2(d))。このように物体を滑らせる時に、途中で引っかかったり、滑ったりを繰り返す現象をさして、スティックスリップ現象といい、物体Mは図1に示される経時的な負荷をうける。図1の静摩擦係数μs(図2(b)の時点)と、ノコギリ波形下端のμl(図2(c)の時点)の差のΔμが大きいと、軋み音が発生しやすくなるといわれている。尚、動摩擦係数はμsとμlの中間の値になる。
これらの軋み音は乗車時の快適性、静粛性を損ねる大きな原因となっており、軋み音の低減が強く要求されている。
In addition, since ABS resin and ASA resin are amorphous resins, they have a higher coefficient of friction compared to crystalline resins such as polyethylene, polypropylene, and polyacetal, and are used for air conditioner outlets and car stereo buttons in automobiles. As described above, when mating with a member made of another resin, it is well known that a stick-slip phenomenon as shown in FIG. ing. The stick-slip phenomenon occurs when two objects rub against each other, and an object M connected by a spring is placed on a driving table that moves at a driving speed V as shown in the model of FIG. In this case, the object M first moves to the right as shown in FIG. 2B together with the table that moves at the driving speed V by the action of the static friction force. When the force that the object M is about to return to the original by the spring becomes equal to the static friction force, the object M starts to slide in the direction opposite to the driving speed V. At this time, the object M receives a dynamic frictional force, but when the force of the spring and the dynamic frictional force become equal, the sliding stops and the object M becomes attached to the driving table again. It moves again in the same direction as the drive speed V (FIG. 2D). In this way, when an object is slid, it refers to a phenomenon of repeatedly catching or sliding on the way, which is called a stick-slip phenomenon, and the object M is subjected to a load with time as shown in FIG. It is said that if the difference Δμ between the static friction coefficient μs in FIG. 1 (at the time of FIG. 2B) and μl at the lower end of the sawtooth waveform (at the time of FIG. 2C) is large, itching is likely to occur. The dynamic friction coefficient is an intermediate value between μs and μl.
These squeaking noises are a major cause of impairing comfort and quietness when riding, and there is a strong demand for reduction of squeaking noises.
一方、アモントン・クーロンの法則により求めた摩擦係数の摩擦速度依存性が負の値をとると、スティックスリップ現象が顕著に現れることが知られており(非特許文献1参照)、上記摩擦係数の摩擦速度依存性をゼロに近づけるか、若しくはゼロ以上の正の値とすることで、スティックスリップ現象の発生を抑制し、軋み音の発生を低減させることが可能である。 On the other hand, it is known that the stick-slip phenomenon appears remarkably when the friction speed dependency of the friction coefficient obtained by Ammonton-Coulomb's law takes a negative value (see Non-Patent Document 1). By making the friction speed dependency close to zero or a positive value of zero or more, it is possible to suppress the occurrence of stick-slip phenomenon and reduce the occurrence of squeaking noise.
そこで、これらの軋み音を防止するため、部材表面にテフロン(登録商標)コーティングを施す方法、テフロン(登録商標)テープを装着する方法、シリコーンオイルを塗布する方法などが行なわれてきたが、装着、塗布といった工程は非常に煩雑で手間がかかるばかりでなく、高温下に長時間置かれた場合は効果が持続しないという問題があった。 Therefore, in order to prevent such squeaking noise, a method of applying a Teflon (registered trademark) coating to the surface of the member, a method of mounting a Teflon (registered trademark) tape, a method of applying silicone oil, etc. have been performed. The process such as coating is not only complicated and time-consuming, but also has a problem that the effect is not maintained when it is placed at a high temperature for a long time.
また、自動車内装部品に用いられる材料自体を改質する方法として、ABS樹脂にシリコーンオイルを配合する方法、ABS樹脂にエポキシ含有オレフィン共重合体を配合する方法などが提案されている。たとえば、ポリカーボネート樹脂およびABS樹脂かならなる樹脂に有機ケイ素化合物を配合する技術(特許文献1参照)が、またABS樹脂に難燃剤、難燃助剤およびシリコーンオイルを配合する技術(特許文献2参照)が、またABS樹脂、MBS樹脂およびHIPS(ハイインパクトポリスチレン)樹脂にシリコーンオイルを配合する技術(特許文献3参照)が、またABS樹脂にアルカンスルホネート系界面活性剤を配合する技術(特許文献4参照)が、さらにはABS樹脂にエポキシ基、カルボキシル基および酸無水物基から選ばれる少なくとも1種の反応基を含有する変性ポリオルガノシロキサンを配合し、撥水性を高め浴室内やトイレ内の水回り部品に使用する技術(特許文献5参照)が開示されている。 Further, as a method for modifying the material itself used for automobile interior parts, a method of blending silicone oil with ABS resin, a method of blending an epoxy-containing olefin copolymer with ABS resin, and the like have been proposed. For example, a technique of blending an organosilicon compound into a resin made of polycarbonate resin and ABS resin (see Patent Document 1), and a technique of blending a flame retardant, a flame retardant aid and silicone oil into ABS resin (see Patent Document 2) ), A technique of blending silicone oil into ABS resin, MBS resin and HIPS (high impact polystyrene) resin (see Patent Document 3), and a technique of blending alkanesulfonate surfactant into ABS resin (Patent Document 4). In addition, a modified polyorganosiloxane containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group is added to the ABS resin to increase water repellency and increase the water in the bathroom and toilet. A technique (see Patent Document 5) used for a rotating part is disclosed.
しかしながら、これらの方法による軋み音の低減効果は十分とはいえず、成形直後にはある程度の軋み音防止効果を示しても効果の持続性が乏しく、特に、高温下に長時間置かれた場合にはその効果が大幅に低下するという問題があった。 However, the stagnation noise reduction effect by these methods is not sufficient, and even if it shows a certain level of stagnation noise prevention effect immediately after molding, the effect persists poorly, especially when placed at high temperatures for a long time Has a problem that its effect is greatly reduced.
本発明は、かかる実情に鑑み、部材が擦れ合うときに発生する軋み音の発生が著しく低減され、かつ高温下に長時間置かれた場合においても軋み音低減効果が低下せずに維持され、さらには耐衝撃性に優れた熱可塑性樹脂組成物からなる接触用部品の提供を目的とする。 In view of such circumstances, the present invention significantly reduces the occurrence of squeaking noise that occurs when the members rub against each other, and maintains the squeaking noise reduction effect even when placed under high temperature for a long time, and Is intended to provide a contact component comprising a thermoplastic resin composition having excellent impact resistance.
本発明者らは、上記課題を解決すべく鋭意研究を行った結果、特定のゴム変性ビニル系樹脂に特定のシリコーンオイルを特定量配合することにより、軋み音の発生が著しく低減され、かつ高温下に長時間置かれた場合においても軋み音低減効果が低下せずに維持され、さらには耐衝撃性に優れた熱可塑性樹脂組成物からなる接触用部品が得られることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have significantly reduced the occurrence of squeaking noise by adding a specific amount of a specific silicone oil to a specific rubber-modified vinyl resin, and at a high temperature. It has been found that a contact component made of a thermoplastic resin composition excellent in impact resistance can be obtained, even when left under a long time, the squeaking noise reduction effect is maintained without deterioration. It came to be completed.
本発明によれば、次の接触用部品が提供される。すなわち、
1. ゴム強化ビニル系樹脂〔A〕100質量部に、ASTM D445−46T又はJIS 8803によるウベローデ粘度計により測定した25℃における動粘度が10〜100,000cStであるシリコーンオイル〔B〕0.1〜8質量部を配合してなり、
該ゴム強化ビニル系樹脂〔A〕は、ジエン系ゴム質重合体〔a1〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化ビニル系樹脂〔A1〕と、エチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下にビニル系単量体〔b2〕を重合して得られたゴム強化ビニル系樹脂〔A2〕を含有し、
前記ジエン系ゴム質重合体〔a1〕及び前記エチレン・α−オレフィン系ゴム質重合体〔a2〕の合計量が、前記ゴム強化ビニル系樹脂〔A〕全体を100質量%として5〜30質量%であり、
該ジエン系ゴム質重合体〔a1〕と該エチレン・α−オレフィン系ゴム質重合体〔a2〕の質量比〔a1〕:〔a2〕が10〜85:90〜15であり、
前記ビニル系単量体〔b1〕及び〔b2〕が芳香族ビニル化合物及びシアン化ビニル化合物を含む
熱可塑性樹脂組成物からなることを特徴とする接触用部品。
2. 上記ゴム強化ビニル系樹脂〔A〕が、更に、芳香族ビニル化合物及びシアン化ビニル化合物を含むビニル系単量体〔b3〕の(共)重合体〔C〕を含有してなる上記1に記載の接触用部品。
3. 上記エチレン・α−オレフィン系ゴム質重合体〔a2〕のエチレン:α−オレフィンの質量比が5〜95:95〜5である上記1又は2に記載の接触用部品。
4. 上記エチレン・α−オレフィン系ゴム質重合体〔a2〕が、エチレン・プロピレン共重合体である上記1乃至3の何れかに記載の接触用部品。
5. 上記熱可塑性樹脂組成物又は他の熱可塑性樹脂からなる他の部材と接触し擦れ合う部品に使用される上記1乃至4の何れかに記載の接触用部品。
6. 上記他の熱可塑性樹脂がポリカーボネート/ABSである上記5に記載の接触用部品。
According to the present invention, the following contact parts are provided. That is,
1. Silicone oil [B] 0.1-8 having a kinematic viscosity at 25 ° C. of 10-100,000 cSt measured with ASTM D445-46T or JIS 8803 Ubbelohde viscometer to 100 parts by mass of rubber-reinforced vinyl resin [A] Combining parts by mass,
The rubber-reinforced vinyl resin [A] includes a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of a diene rubber polymer [a1], ethylene A rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of an α-olefin rubber polymer [a2],
The total amount of the diene rubbery polymer [a1] and the ethylene / α-olefin rubbery polymer [a2] is 5 to 30% by mass based on 100% by mass of the entire rubber-reinforced vinyl resin [A]. And
The mass ratio [a1]: [a2] of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] is 10 to 85: 90-15,
The contact component, wherein the vinyl monomers [b1] and [b2] are made of a thermoplastic resin composition containing an aromatic vinyl compound and a vinyl cyanide compound.
2. 2. The rubber-reinforced vinyl resin [A] further comprises a (co) polymer [C] of a vinyl monomer [b3] containing an aromatic vinyl compound and a vinyl cyanide compound. Contact parts.
3. 3. The contact component according to 1 or 2 above, wherein the ethylene / α-olefin rubbery polymer [a2] has an ethylene: α-olefin mass ratio of 5 to 95:95 to 5.
4). 4. The contact part according to any one of 1 to 3, wherein the ethylene / α-olefin rubbery polymer [a2] is an ethylene / propylene copolymer.
5. 5. The contact part according to any one of 1 to 4 above, which is used for a part that comes into contact with and rubs against another member made of the thermoplastic resin composition or another thermoplastic resin.
6). 6. The contact part as described in 5 above, wherein the other thermoplastic resin is polycarbonate / ABS.
本発明によれば、特定のゴム変性ビニル系樹脂に、特定のシリコーンオイルを特定量配合することにより、部材が擦れ合うときに発生する軋み音が著しく低減され、かつ高温下に長時間置かれた場合においても軋み音低減効果が低下しない、熱可塑性樹脂組成物からなる接触用部品を得ることが可能となる。 According to the present invention, by adding a specific amount of a specific silicone oil to a specific rubber-modified vinyl resin, the squeaking noise generated when the members rub against each other is significantly reduced, and the resin is placed at a high temperature for a long time. Even in such a case, it is possible to obtain a contact component made of a thermoplastic resin composition, in which the effect of reducing squeaking noise does not decrease.
以下、本発明を詳細に説明する。
本発明における接触用部品を形成する熱可塑性樹脂組成物は、ゴム強化ビニル系樹脂〔A〕100質量部に、25℃における動粘度が10〜100,000cStであるシリコーンオイル〔B〕0.1〜8質量部を配合してなり、
該ゴム強化ビニル系樹脂〔A〕は、ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕を含有し、
前記ジエン系ゴム質重合体〔a1〕及び上記エチレン・α−オレフィン系ゴム質重合体〔a2〕の合計量が、前記ゴム強化ビニル系樹脂〔A〕全体を100質量%として5〜30質量%であり、
該ジエン系ゴム質重合体〔a1〕と該エチレン・α−オレフィン系ゴム質重合体〔a2〕の質量比〔a1〕:〔a2〕が10〜85:90〜15
であることを特徴とする。
Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition forming the contact component in the present invention is composed of 100 parts by mass of rubber-reinforced vinyl resin [A], silicone oil [B] 0.1 having a kinematic viscosity at 25 ° C. of 10 to 100,000 cSt. ~ 8 parts by mass,
The rubber-reinforced vinyl resin [A] contains a diene rubber polymer [a1] and an ethylene / α-olefin rubber polymer [a2],
The total amount of the diene rubbery polymer [a1] and the ethylene / α-olefin rubbery polymer [a2] is 5 to 30% by mass based on 100% by mass of the entire rubber-reinforced vinyl resin [A]. And
The mass ratio [a1]: [a2] of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] is 10 to 85: 90-15.
It is characterized by being.
尚、本明細書において、「(共)重合」とは、単独重合および共重合を意味し、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味し、「(メタ)アクリレート」とは、アクリレート及び/又はメタクリレートを意味する。 In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.
1.ゴム強化ビニル系樹脂〔A〕(以下、「成分〔A〕」ともいう。):
本発明で使用する成分〔A〕は、ジエン系ゴム質重合体〔a1〕の存在下にビニル系単量体〔b1〕を重合して得られるゴム強化ビニル系樹脂〔A1〕、エチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下にビニル系単量体〔b2〕を重合して得られるゴム強化ビニル系樹脂〔A2〕、及び、必要に応じて、ビニル系単量体〔b3〕の(共)重合体〔C〕との混合物からなるゴム強化ビニル系樹脂である。(共)重合体〔C〕は、ゴム質重合体の非存在下にビニル系単量体〔b3〕を重合して得られる。
1. Rubber-reinforced vinyl resin [A] (hereinafter also referred to as “component [A]”):
The component [A] used in the present invention is a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of a diene rubber polymer [a1], ethylene · α A rubber-reinforced vinyl resin [A2] obtained by polymerizing the vinyl monomer [b2] in the presence of the olefin rubber polymer [a2], and, if necessary, a vinyl monomer [ b3] is a rubber-reinforced vinyl resin made of a mixture with the (co) polymer [C]. The (co) polymer [C] is obtained by polymerizing the vinyl monomer [b3] in the absence of the rubbery polymer.
1−1.ジエン系ゴム質重合体〔a1〕(以下「成分〔a1〕ともいう。):
上記ゴム強化ビニル系樹脂〔A〕に含有されるゴム質重合体は、ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕である。
ジエン系ゴム質重合体〔a1〕としては、ポリブタジエン、ポリイソプレン等の単独重合体;スチレン・ブタジエン共重合体、スチレン・ブタジエン・スチレン共重合体、アクリロニトリル・スチレン・ブタジエン共重合体、アクリロニトリル・ブタジエン共重合体等のブタジエン系共重合体;スチレン・イソプレン共重合体、スチレン・イソプレン・スチレン共重合体、アクリロニトリル・スチレン・イソプレン共重合体等のイソプレン系共重合体等が挙げられる。これらは、ランダム共重合体であっても、ブロック共重合体であってもよく、単独であるいは2種以上を組み合わせて用いることができる。該ジエン系ゴム質重合体〔a1〕は、架橋重合体であってよいし、未架橋重合体であってもよい。
1-1. Diene rubbery polymer [a1] (hereinafter also referred to as “component [a1]”):
The rubbery polymers contained in the rubber-reinforced vinyl resin [A] are a diene rubbery polymer [a1] and an ethylene / α-olefin rubbery polymer [a2].
Examples of the diene rubbery polymer [a1] include homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / styrene / butadiene copolymer, and acrylonitrile / butadiene. Butadiene copolymers such as copolymers; styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, isoprene copolymers such as acrylonitrile / styrene / isoprene copolymers, and the like. These may be random copolymers or block copolymers, and may be used alone or in combination of two or more. The diene rubbery polymer [a1] may be a crosslinked polymer or an uncrosslinked polymer.
1−2.エチレン・α−オレフィン系ゴム質重合体〔a2〕(以下「成分〔a2〕ともいう。):
エチレン・α−オレフィン系ゴム質重合体〔a2〕としては、例えば、エチレン・α−オレフィン共重合体、エチレン・α−オレフィン・非共役ジエン共重合体が挙げられる。該成分〔a2〕を構成するα−オレフィンとしては、例えば、炭素数3〜20のα−オレフィンが挙げられ、具体的には、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン、4−メチル−1−ペンテン、1−ヘプテン、1−オクテン、1−デセン、1−ドデセン、1−ヘキサデセン、1−エイコセンなどが挙げられる。これらのα−オレフィンは、単独でまたは2種以上を混合して使用することができる。α−オレフィンの炭素数は、好ましくは3〜20、より好ましくは3〜12、さらに好ましくは3〜8である。炭素数が20を超えると、共重合性が低下し、成形品の表面外観が十分でなくなる場合がある。エチレン:α−オレフィンの質量比は、通常5〜95:95〜5、好ましくは50〜90:50〜10、より好ましくは60〜88:40〜12である。α−オレフィンの質量比が95を超えると、耐候性が十分でなく、一方、5未満になるとゴム質重合体のゴム弾性が十分でなくなるため、十分な耐衝撃性が発現しない可能性がある。
これらのうち、軋み音低減の観点から、エチレン・α−オレフィン共重合体が好ましく、エチレン・プロピレン共重合体が特に好ましい。
1-2. Ethylene / α-olefin rubbery polymer [a2] (hereinafter also referred to as “component [a2]”):
Examples of the ethylene / α-olefin rubbery polymer [a2] include an ethylene / α-olefin copolymer and an ethylene / α-olefin / non-conjugated diene copolymer. Examples of the α-olefin constituting the component [a2] include α-olefins having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4- Examples include methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. These α-olefins can be used alone or in admixture of two or more. The carbon number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. When the number of carbon atoms exceeds 20, the copolymerizability is lowered and the surface appearance of the molded product may not be sufficient. The mass ratio of ethylene: α-olefin is usually 5 to 95:95 to 5, preferably 50 to 90:50 to 10, more preferably 60 to 88:40 to 12. When the α-olefin mass ratio exceeds 95, the weather resistance is not sufficient. On the other hand, when it is less than 5, the rubber elasticity of the rubbery polymer is not sufficient, so that sufficient impact resistance may not be exhibited. .
Among these, from the viewpoint of reducing squeaking noise, an ethylene / α-olefin copolymer is preferable, and an ethylene / propylene copolymer is particularly preferable.
非共役ジエンとしては、アルケニルノルボルネン類、環状ジエン類、脂肪族ジエン類が挙げられ、好ましくは5−エチリデン−2−ノルボルネンおよびジシクロペンタジエンである。これらの非共役ジエンは、単独でまたは2種以上を混合して使用することができる。非共役ジエンの、ゴム質重合体全量に対する割合は、通常0〜30質量%、好ましくは0〜20質量%、より好ましくは0〜10質量%である。非共役ジエンの割合が30質量%を超えると、成形外観および耐候性が十分でなくなる場合がある。尚、成分〔a1〕における不飽和基量は、ヨウ素価に換算して4〜40の範囲が好ましい。ヨウ素価が40を超えると成形品の成形外観及び耐候性が十分でなくなる場合があり、ヨウ素価が4未満になると成形品の耐衝撃性が十分でなくなる場合がある。
また、成分〔a2〕のムーニー粘度(ML1+4 、100℃;JIS K6300に準拠)は、通常5〜80、好ましくは10〜65、より好ましくは15〜45である。ムーニー粘度が80を超えると、得られるゴム強化ビニル系樹脂の流動性が不十分に、ムーニー粘度が5未満になると、得られる成形品の耐衝撃性が不十分となる場合がある。
Non-conjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, with 5-ethylidene-2-norbornene and dicyclopentadiene being preferred. These non-conjugated dienes can be used alone or in admixture of two or more. The ratio of the nonconjugated diene to the total amount of the rubbery polymer is usually 0 to 30% by mass, preferably 0 to 20% by mass, and more preferably 0 to 10% by mass. If the proportion of the non-conjugated diene exceeds 30% by mass, the molded appearance and weather resistance may not be sufficient. In addition, the amount of unsaturated groups in component [a1] is preferably in the range of 4 to 40 in terms of iodine value. If the iodine value exceeds 40, the molding appearance and weather resistance of the molded product may not be sufficient, and if the iodine value is less than 4, the impact resistance of the molded product may not be sufficient.
Moreover, the Mooney viscosity (ML1 + 4 , 100 degreeC; based on JISK6300) of component [a2] is 5-80 normally, Preferably it is 10-65, More preferably, it is 15-45. When the Mooney viscosity exceeds 80, the fluidity of the resulting rubber-reinforced vinyl resin is insufficient, and when the Mooney viscosity is less than 5, the resulting molded article may have insufficient impact resistance.
また、このエチレン・α−オレフィン系ゴム質重合体〔a2〕には、ブタジエン、イソプレン等の共役ジエン化合物を用いて得られたブロック(共)重合体を水素添加した重合体(共役ジエン部分の二重結合の水素添加率は耐候性の点から90%以上が好ましい。)も含まれる。上記重合体は、架橋重合体であってよいし、未架橋重合体であってもよい。 In addition, this ethylene / α-olefin rubbery polymer [a2] is a polymer obtained by hydrogenating a block (co) polymer obtained by using a conjugated diene compound such as butadiene or isoprene (of a conjugated diene moiety). The hydrogenation rate of the double bond is preferably 90% or more from the viewpoint of weather resistance. The polymer may be a crosslinked polymer or an uncrosslinked polymer.
1−3.ビニル系単量体〔b1〕〜〔b3〕:
上記ビニル系単量体〔b1〕、〔b2〕及び〔b3〕は、いずれも、不飽和結合を有する重合性化合物であれば、特に限定されない。
上記ビニル系単量体〔b1〕、〔b2〕及び〔b3〕は、通常、芳香族ビニル化合物及びシアン化ビニル化合物を含む。その他、必要に応じて、(メタ)アクリル酸エステル、マレイミド化合物等の、他の共重合可能なビニル系単量体、カルボキシル基、酸無水物基、ヒドロキシル基、アミノ基、アミド基、エポキシ基、オキサゾリン基等の官能基を1種以上有する官能基含有ビニル系単量体を併用してもよい。上記ゴム強化ビニル系樹脂〔A1〕及び〔A2〕の形成に用いるビニル系単量体〔b1〕及び〔b2〕は、互いに同一であってもよいし、異なっていてもよい。
また、(共)重合体〔C〕の形成に用いるビニル系単量体〔b3〕は、上記ビニル系単量体〔b1〕及び/又は〔b2〕と同一であってもよいし、異なっていてもよい。
1-3. Vinyl monomers [b1] to [b3]:
The vinyl monomers [b1], [b2] and [b3] are not particularly limited as long as they are all polymerizable compounds having an unsaturated bond.
The vinyl monomers [b1], [b2] and [b3] usually contain an aromatic vinyl compound and a vinyl cyanide compound. In addition, if necessary, other copolymerizable vinyl monomers such as (meth) acrylic acid ester and maleimide compound, carboxyl group, acid anhydride group, hydroxyl group, amino group, amide group, epoxy group A functional group-containing vinyl monomer having at least one functional group such as an oxazoline group may be used in combination. The vinyl monomers [b1] and [b2] used for forming the rubber-reinforced vinyl resins [A1] and [A2] may be the same as or different from each other.
The vinyl monomer [b3] used for forming the (co) polymer [C] may be the same as or different from the vinyl monomer [b1] and / or [b2]. May be.
上記芳香族ビニル化合物としては、少なくとも1つのビニル結合と、少なくとも1つの芳香族環とを有する化合物であれば、特に限定されることなく用いることができる。その例としては、スチレン、α−メチルスチレン、o−メチルスチレン、p−メチルスチレン、ビニルトルエン、β−メチルスチレン、エチルスチレン、p−t−ブチルスチレン、ビニルキシレン、ビニルナフタレン、モノクロロスチレン、ジクロロスチレン、モノブロモスチレン、ジブロモスチレン、フルオロスチレン等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。また、これらのうち、スチレン及びα−メチルスチレンが好ましい。 The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, pt-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.
上記シアン化ビニル化合物としては、アクリロニトリル、メタクリロニトリル等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。また、これらのうち、アクリロニトリルが好ましい。 Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
上記(メタ)アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸2−エチルヘキシル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル等のアクリル酸エステル;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸オクチル、メタクリル酸2−エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸ベンジル等のメタクリル酸エステルが挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。また、これらのうち、メタクリル酸メチルが好ましい。 Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic acid Acrylic esters such as phenyl and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacrylic acid And methacrylic acid esters such as octadecyl acid, cyclohexyl methacrylate, phenyl methacrylate, and benzyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.
上記マレイミド化合物としては、マレイミド、N−メチルマレイミド、N−ブチルマレイミド、N−シクロヘキシルマレイミド、N−フェニルマレイミド等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。また、これらのうち、N−シクロヘキシルマレイミド及びN−フェニルマレイミドが好ましい。
尚、このマレイミド化合物からなる単量体単位を重合体に導入する方法としては、予め、無水マレイン酸を共重合させ、その後、イミド化する方法がある。
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. These can be used alone or in combination of two or more. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.
As a method for introducing a monomer unit comprising this maleimide compound into a polymer, there is a method in which maleic anhydride is copolymerized in advance and then imidized.
上記の官能基含有ビニル系単量体のうち、カルボキシル基を有する不飽和化合物としては、アクリル酸、メタクリル酸、エタクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸、桂皮酸等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。 Among the functional group-containing vinyl monomers, examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. . These can be used alone or in combination of two or more.
酸無水物基を有する不飽和化合物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
ヒドロキシル基を有する不飽和化合物としては、ヒドロキシスチレン、3−ヒドロキシ−1−プロペン、4−ヒドロキシ−1−ブテン、シス−4−ヒドロキシ−2−ブテン、トランス−4−ヒドロキシ−2−ブテン、3−ヒドロキシ−2−メチル−1−プロペン、アクリル酸2−ヒドロキシエチル、メタクリル酸2−ヒドロキシエチル、N−(4−ヒドロキシフェニル)マレイミド等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
Examples of the unsaturated compound having an acid anhydride group include maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used alone or in combination of two or more.
Examples of unsaturated compounds having a hydroxyl group include hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3 -Hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like. These can be used alone or in combination of two or more.
アミノ基を有する不飽和化合物としては、アクリル酸アミノエチル、アクリル酸プロピルアミノエチル、アクリル酸ジメチルアミノメチル、アクリル酸ジエチルアミノメチル、アクリル酸2−ジメチルアミノエチル、メタクリル酸アミノエチル、メタクリル酸プロピルアミノエチル、メタクリル酸ジメチルアミノメチル、メタクリル酸ジエチルアミノメチル、メタクリル酸2−ジメチルアミノエチル、メタクリル酸フェニルアミノエチル、p−アミノスチレン、N−ビニルジエチルアミン、N−アセチルビニルアミン、アクリルアミン、メタクリルアミン、N−メチルアクリルアミン等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
アミド基を有する不飽和化合物としては、アクリルアミド、N−メチルアクリルアミド、メタクリルアミド、N−メチルメタクリルアミド等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
As unsaturated compounds having an amino group, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate , Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N- Examples include methylacrylamine. These can be used alone or in combination of two or more.
Examples of the unsaturated compound having an amide group include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide and the like. These can be used alone or in combination of two or more.
エポキシ基を有する不飽和化合物としては、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。 Examples of the unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.
オキサゾリン基を有する不飽和化合物としては、ビニルオキサゾリン等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。 Examples of the unsaturated compound having an oxazoline group include vinyl oxazoline. These can be used alone or in combination of two or more.
上記ビニル系単量体〔b1〕、〔b2〕及び〔b3〕は、目的、用途等に応じてその種類及び使用量が選択されるが、芳香族ビニル化合物及びシアン化ビニル化合物の合計量は、ビニル系単量体全量100質量%に対して、通常30〜100質量%、好ましくは50〜100質量%、より好ましくは70〜100質量%である。上記他の共重合可能なビニル系単量体の含有量は、ビニル系単量体全体100質量%に対して通常0〜70質量%、好ましくは0〜50質量%、より好ましくは0〜30質量%である。上記官能基含有ビニル系単量体の含有量は、ビニル系単量体全量100質量%に対して、通常0〜40質量%、好ましくは、0〜30質量%、より好ましくは0〜20質量%である。また、芳香族ビニル化合物及びシアン化ビニル化合物の使用比率(芳香族ビニル化合物/シアン化ビニル化合物)は、これらの合計を100質量%とした場合、通常40〜85質量%/15〜60質量%、好ましくは45〜85質量%/15〜55質量%である。 The vinyl monomers [b1], [b2] and [b3] are selected according to their purpose, usage, etc., and their types and amounts used. The total amount of the aromatic vinyl compound and the vinyl cyanide compound is as follows. The total amount of vinyl monomers is 100 to 100% by mass, usually 30 to 100% by mass, preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. The content of the other copolymerizable vinyl monomer is usually 0 to 70% by mass, preferably 0 to 50% by mass, more preferably 0 to 30% with respect to 100% by mass of the whole vinyl monomer. % By mass. The content of the functional group-containing vinyl monomer is usually 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 0 to 20% by mass with respect to 100% by mass of the total amount of the vinyl monomer. %. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound (aromatic vinyl compound / vinyl cyanide compound) is usually 40 to 85% by mass / 15 to 60% by mass when the total of these is 100% by mass. Preferably, it is 45-85 mass% / 15-55 mass%.
1−4.上記ゴム強化ビニル系樹脂〔A〕の製造方法:
上記ゴム強化ビニル系樹脂〔A〕は、ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕を含有する重合体成分であるが、その含有形態は、特に限定されない。
上記ゴム強化ビニル系樹脂〔A〕には、通常、ビニル系単量体の(共)重合体がゴム質重合体にグラフトしているグラフト共重合体と、ゴム質重合体にグラフトしていないビニル系単量体の(共)重合体が含まれる。ただし、このグラフト共重合体に、ビニル系単量体の(共)重合体がグラフトしていない、ゴム質重合体が含まれていてもよい。
従って、上記のジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕の含有態様は、以下に例示される。
(1)ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕の両方が、グラフト共重合体として含有される場合。
(2)ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕のいずれか一方が、グラフト共重合体として含有される場合。
(3)ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕の両方が、未グラフトのゴム質重合体として含有される場合。
これらのうち、(1)が特に好ましい。
1-4. Method for producing the rubber-reinforced vinyl resin [A]:
The rubber-reinforced vinyl resin [A] is a polymer component containing a diene rubber polymer [a1] and an ethylene / α-olefin rubber polymer [a2]. It is not limited.
In the rubber-reinforced vinyl resin [A], a graft copolymer in which a (co) polymer of a vinyl monomer is grafted to a rubber polymer, and a rubber polymer are not grafted. (Co) polymers of vinyl monomers are included. However, this graft copolymer may contain a rubbery polymer to which a (co) polymer of a vinyl monomer is not grafted.
Accordingly, the content of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] is exemplified below.
(1) The case where both the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] are contained as a graft copolymer.
(2) The case where either one of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] is contained as a graft copolymer.
(3) The case where both the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] are contained as an ungrafted rubber polymer.
Of these, (1) is particularly preferred.
上記態様(1)のゴム強化ビニル系樹脂〔A〕としては、以下に例示される。
[i]上記ジエン系ゴム質重合体〔a1〕の存在下に、ビニル系単量体〔b1〕を重合して得られたゴム強化ビニル系樹脂〔A1〕と、上記エチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下に、ビニル系単量体〔b2〕を重合して得られたゴム強化ビニル系樹脂〔A2〕とからなる混合物。
[ii]上記混合物[i]と、ビニル系単量体〔b3〕の(共)重合体(以下、「(共)重合体〔C〕」ともいう。)とからなる混合物。
[iii]上記ジエン系ゴム質重合体〔a1〕及び上記エチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下に、ビニル系単量体〔b1〕を重合して得られたゴム強化ビニル系樹脂〔A3〕。
[iv]上記ゴム強化ビニル系樹脂〔A3〕と、上記(共)重合体〔C〕とからなる混合物。
これらのうち、[i]及び[ii]が生産性の点から好ましく、[ii]が特に好ましい。
尚、上記ゴム強化ビニル系樹脂〔A〕としては、上記[i]、[ii]、[iii]及び[iv]の2種以上の組み合わせであってもよい。
Examples of the rubber-reinforced vinyl resin [A] of the above aspect (1) are as follows.
[I] A rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of the diene rubber polymer [a1], and the ethylene / α-olefin system. A mixture comprising a rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of a rubbery polymer [a2].
[Ii] A mixture comprising the above mixture [i] and a (co) polymer of the vinyl monomer [b3] (hereinafter also referred to as “(co) polymer [C]”).
[Iii] Rubber reinforcement obtained by polymerizing vinyl monomer [b1] in the presence of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] Vinyl resin [A3].
[Iv] A mixture comprising the rubber-reinforced vinyl resin [A3] and the (co) polymer [C].
Among these, [i] and [ii] are preferable from the viewpoint of productivity, and [ii] is particularly preferable.
The rubber-reinforced vinyl resin [A] may be a combination of two or more of the above [i], [ii], [iii] and [iv].
次に、上記のゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕の製造方法について、説明する。
重合方法としては、乳化重合、溶液重合、懸濁重合、塊状重合等の公知の重合方法が挙げられる。いずれにおいても、ゴム質重合体の存在下に、ビニル系単量体を一括投入して反応させてよいし、分割又は連続添加して反応させてもよい。また、ゴム質重合体は、全量又は一部を、ビニル系単量体との重合の途中で添加して反応させてもよい。
尚、ゴム質重合体の使用量は、ゴム質重合体とビニル系単量体の合計を100質量%とした場合、通常5〜80質量%、好ましくは10〜70質量%である。
Next, a method for producing the rubber-reinforced vinyl resins [A1], [A2] and [A3] will be described.
Examples of the polymerization method include known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. In any case, in the presence of the rubbery polymer, the vinyl monomer may be charged all at once, and may be reacted, or may be divided or continuously added for reaction. Further, the rubbery polymer may be added or reacted in the whole or in part during the polymerization with the vinyl monomer.
In addition, the usage-amount of a rubber-like polymer is 5-80 mass% normally when the sum total of a rubber-like polymer and a vinyl-type monomer is 100 mass%, Preferably it is 10-70 mass%.
上記のゴム強化ビニル系樹脂〔A1〕の製造方法は、乳化重合、溶液重合及び懸濁重合が好ましく、乳化重合がより好ましい。上記ゴム強化ビニル系樹脂〔A2〕の製造方法は、乳化重合、溶液重合及び塊状重合が好ましく、溶液重合がより好ましい。上記ゴム強化ビニル系樹脂〔A3〕の製造方法は、乳化重合及び溶液重合が好ましい。
上記のゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕を乳化重合で製造する場合には、通常、重合開始剤、連鎖移動剤、乳化剤、水等が用いられる。尚、上記ゴム質重合体がラテックス状でなく、固形状である場合には、再乳化によりラテックス状として使用することができる。
As the method for producing the rubber-reinforced vinyl resin [A1], emulsion polymerization, solution polymerization and suspension polymerization are preferable, and emulsion polymerization is more preferable. As the method for producing the rubber-reinforced vinyl resin [A2], emulsion polymerization, solution polymerization and bulk polymerization are preferable, and solution polymerization is more preferable. As the method for producing the rubber-reinforced vinyl resin [A3], emulsion polymerization and solution polymerization are preferable.
When the above rubber-reinforced vinyl resins [A1], [A2] and [A3] are produced by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, water and the like are usually used. In addition, when the said rubbery polymer is not a latex form but a solid form, it can be used as a latex form by re-emulsification.
重合開始剤としては、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド等の有機過酸化物と、含糖ピロリン酸処方、スルホキシレート処方等で代表される還元剤との組み合わせによるレドックス系重合開始剤;過硫酸カリウム等の過硫酸塩;ベンゾイルパーオキサイド(BPO)、ラウロイルパーオキサイド、t−ブチルパーオキシラウレイト、t−ブチルパーオキシモノカーボネート等の過酸化物;2,2’−アゾビス(イソブチロニトリル)等のアゾ系重合開始剤等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。上記重合開始剤の使用量は、上記ビニル系単量体〔b1〕又は〔b2〕の全量に対し、通常、0.05〜5質量%、好ましくは0.1〜1質量%である。
上記重合開始剤は、通常、反応系に一括添加又は連続添加される。
As the polymerization initiator, a combination of an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, etc. Redox polymerization initiators by: persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxymonocarbonate; Examples thereof include azo polymerization initiators such as 2′-azobis (isobutyronitrile). These can be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.05 to 5% by mass, preferably 0.1 to 1% by mass, based on the total amount of the vinyl monomer [b1] or [b2].
The polymerization initiator is usually added all at once or continuously to the reaction system.
連鎖移動剤としては、オクチルメルカプタン、n−ドデシルメルカプタン、t−ドデシルメルカプタン、n−ヘキシルメルカプタン、n−ヘキサデシルメルカプタン、n−テトラデシルメルカプタン、t−テトラデシルメルカプタン等のメルカプタン類;ターピノーレン類、α−メチルスチレンのダイマー、テトラエチルチウラムスルフィド、アクロレイン、メタクロレイン、アリルアルコール、2−エチルヘキシルチオグリコール等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。上記連鎖移動剤の使用量は、上記ビニル系単量体〔b1〕又は〔b2〕の全量に対し、通常、0.05〜2質量%である。 Examples of chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan; terpinolenes, α -Methylstyrene dimer, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2% by mass with respect to the total amount of the vinyl monomer [b1] or [b2].
乳化剤としては、アニオン系界面活性剤及びノニオン系界面活性剤が挙げられる。アニオン系界面活性剤としては、高級アルコールの硫酸エステル;ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩;ラウリル硫酸ナトリウム等の脂肪族スルホン酸塩;ロジン酸塩、リン酸塩等が挙げられる。また、ノニオン系界面活性剤としては、ポリエチレングリコールのアルキルエステル型化合物、アルキルエーテル型化合物等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。上記乳化剤の使用量は、上記ビニル系単量体〔b1〕又は〔b2〕の全量に対し、通常、0.3〜5質量%である。 Examples of the emulsifier include anionic surfactants and nonionic surfactants. Examples of the anionic surfactant include sulfates of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; rosinates and phosphates. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5 mass% normally with respect to the whole quantity of the said vinylic monomer [b1] or [b2].
乳化重合は、用いるビニル系単量体〔b1〕又は〔b2〕、重合開始剤等の種類、量に応じ、公知の条件で行うことができる。上記乳化重合により得られたラテックスは、通常、凝固剤により凝固させ、重合体成分を粉末状とし、その後、これを水洗、乾燥することによって精製される。この凝固剤としては、塩化カルシウム、硫酸マグネシウム、塩化マグネシウム、塩化ナトリウム等の無機塩;硫酸、塩酸等の無機酸;酢酸、乳酸、クエン酸等の有機酸等が用いられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。また、要求される性能に応じて、凝固後にアルカリ成分又は酸成分を添加し中和処理した後、洗浄してもよい。 Emulsion polymerization can be performed under known conditions according to the type and amount of the vinyl monomer [b1] or [b2] used, the polymerization initiator, and the like. The latex obtained by the above emulsion polymerization is usually purified by coagulating with a coagulant to form a polymer component in powder form, and then washing with water and drying. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, lactic acid, and citric acid. These can be used alone or in combination of two or more. Further, depending on the required performance, washing may be carried out after adding an alkali component or an acid component after solidification to neutralize it.
上記のゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕を溶液重合により製造する場合には、通常、溶媒、重合開始剤、連鎖移動剤等が用いられる。
溶媒としては、公知のラジカル重合で使用される不活性重合溶媒、例えば、エチルベンゼン、トルエン等の芳香族炭化水素;メチルエチルケトン、アセトン等のケトン類;ジクロルメチレン、四塩化炭素等のハロゲン化炭化水素;アセトニトリル、ジメチルホルムアミド、N−メチルピロリドン等を用いることができる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
When the above rubber-reinforced vinyl resins [A1], [A2] and [A3] are produced by solution polymerization, usually a solvent, a polymerization initiator, a chain transfer agent and the like are used.
Examples of the solvent include inert polymerization solvents used in known radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene; ketones such as methyl ethyl ketone and acetone; halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride. Acetonitrile, dimethylformamide, N-methylpyrrolidone and the like can be used. These can be used alone or in combination of two or more.
重合開始剤としては、ケトンパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、ハイドロパーオキサイド等の有機過酸化物が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
連鎖移動剤としては、メルカプタン類、ターピノーレン類、α−メチルスチレンのダイマー等が挙げられる。これらは、単独であるいは2種以上を組み合わせて用いることができる。
Examples of the polymerization initiator include organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide. These can be used alone or in combination of two or more.
Examples of chain transfer agents include mercaptans, terpinolenes, α-methylstyrene dimers, and the like. These can be used alone or in combination of two or more.
溶液重合は、用いるビニル系単量体〔b1〕又は〔b2〕、重合開始剤等の種類に応じ、公知の条件で行うことができる。重合温度は、通常80〜140℃の範囲である。尚、溶液重合に際し、重合開始剤を使用せずに製造することもできる。 Solution polymerization can be carried out under known conditions depending on the type of vinyl monomer [b1] or [b2] used, the polymerization initiator, and the like. The polymerization temperature is usually in the range of 80 to 140 ° C. In addition, in the case of solution polymerization, it can also manufacture without using a polymerization initiator.
塊状重合及び懸濁重合による場合も、公知の方法を適用することができる。これらの方法において用いる重合開始剤、連鎖移動剤等は、例えば溶液重合において例示した化合物を用いることができる。 Also in the case of bulk polymerization and suspension polymerization, known methods can be applied. As the polymerization initiator, chain transfer agent and the like used in these methods, for example, compounds exemplified in solution polymerization can be used.
1−5.ゴム強化ビニル系樹脂〔A〕の物性:
上記のようにして得られた、ゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕のグラフト率は、いずれも、通常10〜150質量%、好ましくは20〜120質量%である。このグラフト率が10質量%未満では、グラフト共重合体とビニル系単量体〔b1〕又は〔b2〕の(共)重合体との界面強度が劣るため、耐衝撃性が十分でない場合がある。一方、150質量%を超えると、ゴム質重合体表面におけるビニル系単量体〔b1〕又は〔b2〕の(共)重合体からなる層が厚くなり、また、ゴム質重合体の内部にグラフトした上記(共)重合体からなる層が発達するため、ゴム弾性が低下し、その結果、耐衝撃性が低下する場合がある。
1-5. Physical properties of rubber-reinforced vinyl resin [A]:
The graft ratios of the rubber-reinforced vinyl resins [A1], [A2] and [A3] obtained as described above are usually 10 to 150% by mass, preferably 20 to 120% by mass. When the graft ratio is less than 10% by mass, the interfacial strength between the graft copolymer and the (co) polymer of the vinyl monomer [b1] or [b2] is inferior, and the impact resistance may not be sufficient. . On the other hand, if it exceeds 150% by mass, the layer made of the (co) polymer of the vinyl monomer [b1] or [b2] on the surface of the rubber polymer becomes thick, and the rubber polymer is grafted inside. Since the layer made of the (co) polymer is developed, the rubber elasticity is lowered, and as a result, the impact resistance may be lowered.
上記グラフト率は、下記式により求めることができる。 The graft ratio can be determined by the following formula.
グラフト率(質量%)={(S−T)/T}×100 Graft ratio (mass%) = {(S−T) / T} × 100
上記式中、Sはゴム強化ビニル系樹脂1グラムをアセトン(ゴム質重合体がアクリル系ゴムの場合はアセトニトリル)20mlに投入し、25℃の温度条件下で、振とう機により2時間振とうした後、5℃の温度条件下で、遠心分離機(回転数;23,000rpm)で60分間遠心分離し、不溶分と可溶分とを分離して得られる不溶分の質量(g)であり、Tはゴム強化ビニル系樹脂1グラムに含まれるゴム質重合体の質量(g)である。このゴム質重合体の質量は、重合処方及び重合転化率から算出する方法、赤外線吸収スペクトル(IR)により求める方法等により得ることができる。 In the above formula, S represents 1 gram of rubber-reinforced vinyl resin in 20 ml of acetone (acetonitrile when the rubbery polymer is an acrylic rubber) and shakes with a shaker for 2 hours at 25 ° C. After that, the mass (g) of insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate the insoluble matter and the soluble matter. Yes, T is the mass (g) of the rubbery polymer contained in 1 gram of rubber-reinforced vinyl resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.
また、上記ゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕のアセトン可溶分の極限粘度[η](メチルエチルケトン中、30℃で測定)は、いずれも、通常0.1〜1.5dl/g、好ましくは0.2〜1.0dl/gである。極限粘度[η]が上記範囲内にあれば、成形加工性及び耐衝撃性の物性バランスに優れる。 In addition, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble components of the rubber-reinforced vinyl resins [A1], [A2] and [A3] is usually 0.1 to 1. 0.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
なお、上記極限粘度[η]の測定は下記方法で行った。まず、上記ゴム強化ビニル系樹脂〔A1〕、〔A2〕及び〔A3〕のアセトン可溶分をメチルエチルケトンに溶解させ、濃度の異なるものを5点作った。ウベローデ粘度管を用い、30℃で各濃度の還元粘度を測定した結果から、極限粘度[η]を求めた。単位は、dl/gである。
上記極限粘度は、製造時に用いる連鎖移動剤の種類及び使用量、重合開始剤の種類及び使用量、重合温度等を適宜選択することにより調整することができる。
The intrinsic viscosity [η] was measured by the following method. First, acetone-soluble components of the rubber-reinforced vinyl resins [A1], [A2], and [A3] were dissolved in methyl ethyl ketone, and five different concentrations were prepared. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.
上記のように、本発明に係るゴム強化ビニル系樹脂〔A〕は、別々に調製したゴム強化ビニル系樹脂〔A1〕及び〔A2〕の混合物を用いてなるものであってよいし、ジエン系ゴム質重合体〔a1〕及びエチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下に、ビニル系単量体〔b1〕を重合して得られたゴム強化ビニル系樹脂〔A3〕を用いてなるものであってもよい。従って、前者のような、複数のゴム強化ビニル系樹脂を用いる場合には、各製造工程で得られた各樹脂の混合物を用いてもよいが、他の方法として、例えば、乳化重合により各樹脂を各々含むラテックスを製造してから、ラテックス同士を混合し、その後、凝固する等により得ることができる。 As described above, the rubber-reinforced vinyl resin [A] according to the present invention may be a mixture of separately prepared rubber-reinforced vinyl resins [A1] and [A2]. Rubber reinforced vinyl resin [A3] obtained by polymerizing vinyl monomer [b1] in the presence of rubber polymer [a1] and ethylene / α-olefin rubber polymer [a2] It may be used. Therefore, when using a plurality of rubber-reinforced vinyl resins such as the former, a mixture of resins obtained in each manufacturing process may be used, but as another method, for example, each resin is obtained by emulsion polymerization. Can be obtained by mixing latexes and then coagulating them.
1−6.(共)重合体〔C〕の製造方法:
また、上記(共)重合体〔C〕は、重合開始剤等の存在下、ビニル系単量体〔b3〕を、溶液重合、塊状重合、乳化重合、懸濁重合等の公知の方法で重合することにより製造することができる。これらの重合は、重合開始剤を用いる触媒重合であってもよく、重合開始剤を用いない熱重合であってもよい。
1-6. Production method of (co) polymer [C]:
In addition, the (co) polymer [C] is obtained by polymerizing the vinyl monomer [b3] by a known method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization in the presence of a polymerization initiator or the like. Can be manufactured. These polymerizations may be catalytic polymerization using a polymerization initiator, or may be thermal polymerization without using a polymerization initiator.
1−7.(共)重合体〔C〕の物性:
上記重合体〔C〕の極限粘度[η](メチルエチルケトン中、30℃で測定)は、通常0.1〜1.5dl/g、好ましくは0.2〜1.0dl/gである。極限粘度[η]が上記範囲内にあれば、成形加工性と耐衝撃性の物性バランスに優れる。
1-7. Physical properties of (co) polymer [C]:
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the polymer [C] is usually 0.1 to 1.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.
なお、上記極限粘度[η]の測定は下記方法で行った。まず、上記(共)重合体〔C〕をメチルエチルケトンに溶解させ、濃度の異なるものを5点作った。ウベローデ粘度管を用い、30℃で各濃度の還元粘度を測定した結果から、極限粘度[η]を求めた。単位は、dl/gである。
上記極限粘度は、製造時に用いる連鎖移動剤の種類及び使用量、重合開始剤の種類及び使用量、重合温度等を適宜選択することにより調整することができる。
The intrinsic viscosity [η] was measured by the following method. First, the above (co) polymer [C] was dissolved in methyl ethyl ketone to prepare 5 samples having different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl / g.
The intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.
2.シリコーンオイル〔B〕(以下、「成分〔B〕」ともいう。):
本発明で使用する成分〔B〕としてのシリコーンオイルは、25℃における動粘度の他は特に制限されず、ポリオルガノシロキサン構造を持つものであれば周知のものを用いることができる。シリコーンオイル〔B〕は、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル等の未変性シリコーンオイルであってもよいし、ポリオルガノシロキサン構造中の側鎖の一部及び/又はポリオルガノシロキサン構造の片末端部分、又は、ポリオルガノシロキサン構造の両末端部分に各種有機基が導入された変性シリコーンオイルであってもよい。上記変性シリコーンオイルとしては、アルキル変性シリコーンオイル、ポリエーテル変性シリコーンオイル、フッ素変性シリコーンオイル、高級アルコキシ変性シリコーンオイル、高級脂肪酸変性シリコーンオイル、メチルスチリル変性シリコーンオイル、メチル塩素化フェニルシリコーンオイル、メチルハイドロジエンシリコーンオイル、アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシル変性シリコーンオイル、アクリル変性シリコーンオイル、メタクリル変性シリコーンオイル、メルカプト変性シリコーンオイル、フェノール変性シリコーンオイル、カルビノール変性シリコーンオイル等を使用することができる。
尚、これらのシリコーンオイルは、単独で使用してもよく、また2種以上を組み合わせて使用してもよい。
2. Silicone oil [B] (hereinafter also referred to as “component [B]”):
The silicone oil as the component [B] used in the present invention is not particularly limited except the kinematic viscosity at 25 ° C. Any known oil can be used as long as it has a polyorganosiloxane structure. The silicone oil [B] may be an unmodified silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, or a part of side chains in the polyorganosiloxane structure and / or polyorgano It may be a modified silicone oil in which various organic groups are introduced into one terminal part of the siloxane structure or both terminal parts of the polyorganosiloxane structure. Examples of the modified silicone oil include alkyl modified silicone oil, polyether modified silicone oil, fluorine modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid modified silicone oil, methyl styryl modified silicone oil, methyl chlorinated phenyl silicone oil, methyl hydro Diene silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone oil, etc. may be used. it can.
These silicone oils may be used alone or in combination of two or more.
また、本発明で使用するシリコーンオイル〔B〕の25℃における動粘度は、10〜100,000cSt、好ましくは、10〜50,000cSt、より好ましくは25〜50,000cSt、更により好ましくは50〜30,000cSt、特に好ましくは200〜15,000cStである。該シリコーンオイル〔B〕の25℃における動粘度が10cSt未満では、軋み音の低減効果が劣り、一方、動粘度が100,000cStを超えると、ゴム強化ビニル系樹脂〔A〕における該シリコーンオイル〔B〕の分散性が悪くなり、耐衝撃性、軋み音低減効果が安定して発現せず、溶融混練時の押出加工性も低下する。 The kinematic viscosity at 25 ° C. of the silicone oil [B] used in the present invention is 10 to 100,000 cSt, preferably 10 to 50,000 cSt, more preferably 25 to 50,000 cSt, and still more preferably 50 to 30,000 cSt, particularly preferably 200 to 15,000 cSt. When the kinematic viscosity at 25 ° C. of the silicone oil [B] is less than 10 cSt, the effect of reducing the squeaking noise is inferior. On the other hand, when the kinematic viscosity exceeds 100,000 cSt, the silicone oil [B] in the rubber-reinforced vinyl resin [A] [ The dispersibility of B] is deteriorated, the impact resistance and the stagnation noise reduction effect are not stably exhibited, and the extrusion processability at the time of melt-kneading is also lowered.
シリコーンオイルの動粘度の測定は、ASTM D445−46T(JIS 8803でも可)によるウベローデ粘度計により測定した。 The kinematic viscosity of the silicone oil was measured by an Ubbelohde viscometer according to ASTM D445-46T (JIS 8803 is acceptable).
3.熱可塑性樹脂組成物:
本発明における熱可塑性樹脂組成物は、上記成分〔A〕、上記成分〔B〕、及び、所望により上記成分〔C〕を所定の配合比率で混合し、溶融混練することにより得られる。
3. Thermoplastic resin composition:
The thermoplastic resin composition in the present invention can be obtained by mixing the above-mentioned component [A], the above-mentioned component [B] and, if desired, the above-mentioned component [C] at a predetermined blending ratio and melt-kneading.
上記ゴム強化ビニル系樹脂〔A〕100質量部に対する上記シリコーンオイル〔B〕の配合量は、0.1〜8質量部、好ましくは0.2〜6質量部、より好ましくは0.5〜5質量部、特に好ましくは2.5〜3.5質量部である。上記成分〔B〕の配合量が0.1質量部未満では、軋み音の低減効果が得られない。一方、上記成分〔B〕の配合量が8質量部を超えると、成形品の外観や耐衝撃性が低下したり、溶融混連が困難になる。 The compounding amount of the silicone oil [B] with respect to 100 parts by mass of the rubber-reinforced vinyl resin [A] is 0.1 to 8 parts by mass, preferably 0.2 to 6 parts by mass, more preferably 0.5 to 5 parts. Part by mass, particularly preferably 2.5 to 3.5 parts by mass. If the amount of the component [B] is less than 0.1 parts by mass, the effect of reducing the squeaking noise cannot be obtained. On the other hand, when the compounding amount of the component [B] exceeds 8 parts by mass, the appearance and impact resistance of the molded product are deteriorated, and melt-mixing becomes difficult.
上記成分〔A〕中の上記ジエン系ゴム質重合体〔a1〕及び上記エチレン・α−オレフィン系ゴム質重合体〔a2〕の合計量は、上記ゴム強化ビニル系樹脂〔A〕全体を100質量%として5〜30質量%であり、好ましくは5〜25質量%、より好ましくは8〜20質量%、特に好ましくは10〜18質量%である。この合計量が5質量%未満では耐衝撃性に劣り、一方、30質量%を超えると耐熱性が低下する。 The total amount of the diene rubbery polymer [a1] and the ethylene / α-olefin rubbery polymer [a2] in the component [A] is 100 masses of the whole rubber-reinforced vinyl resin [A]. % Is 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 8 to 20% by mass, and particularly preferably 10 to 18% by mass. When the total amount is less than 5% by mass, the impact resistance is inferior, whereas when it exceeds 30% by mass, the heat resistance is lowered.
また、上記成分〔A〕中の上記ジエン系ゴム質重合体〔a1〕と上記エチレン・α−オレフィン系ゴム質重合体〔a2〕の質量比〔a1〕:〔a2〕は10〜85:90〜15、好ましくは20〜80:80〜20、より好ましくは25〜75:75〜25である。各ゴム質重合体の質量比をこの範囲とすることにより、軋み音低減効果、耐衝撃性及び耐熱性が優れる。 The mass ratio [a1]: [a2] of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] in the component [A] is 10 to 85:90. -15, preferably 20-80: 80-20, more preferably 25-75: 75-25. By setting the mass ratio of each rubbery polymer within this range, the squeaking noise reduction effect, impact resistance and heat resistance are excellent.
上記の如く成分〔A〕と成分〔B〕、及び必要に応じ、更に成分〔C〕からなる本発明の熱可塑性樹脂組成物は、必要に応じて、充填剤、造核剤、滑剤、熱安定剤、酸化防止剤、紫外線吸収剤、難燃剤、老化防止剤、可塑剤、抗菌剤、着色剤等の各種添加剤を、本発明の目的を損なわない範囲で含有することができる。 As described above, the thermoplastic resin composition of the present invention comprising the component [A] and the component [B], and further, if necessary, the component [C], can be filled with a filler, a nucleating agent, a lubricant, a heat Various additives such as a stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, an antibacterial agent, and a colorant can be contained within a range that does not impair the object of the present invention.
さらに、本発明の熱可塑性樹脂組成物は、必要に応じて、他の樹脂、例えばポリエチレン、ポリプロピレン、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリカーボネート、ポリフェニレンサルファイド、ポリアミド等を、本発明の目的を損なわない範囲で含有することができる。 Furthermore, the thermoplastic resin composition of the present invention can be added to other resins such as polyethylene, polypropylene, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene sulfide, polyamide, and the like, as necessary. Can be contained.
本発明の熱可塑性樹脂組成物は、各成分を所定の配合比で、タンブラーミキサーやヘンシェルミキサーなどで混合した後、一軸押出機、二軸押出機、バンバリーミキサー、ニーダー、ロール、フィーダールーダー等の混合機を用いて、適当な条件下で溶融混練して製造することができる。好ましい混練機は、二軸押出機である。さらに、それぞれの成分を混練するに際しては、それぞれの成分を一括して混練しても、多段、分割配合して混練してもよい。尚、バンバリーミキサー、ニーダー等で混練した後、押出機によりペレット化することもできる。また、充填材のうち繊維状のものは、混練中での切断を防止するためにサイドフィーダーにより押出機の途中から供給する方が好ましい。溶融混練温度は、通常200〜300℃、好ましくは220〜280℃である。 The thermoplastic resin composition of the present invention is prepared by mixing each component at a predetermined mixing ratio using a tumbler mixer, a Henschel mixer, etc. It can be produced by melt-kneading under suitable conditions using a mixer. A preferred kneader is a twin screw extruder. Furthermore, when each component is kneaded, each component may be kneaded in a lump or may be kneaded in multiple stages. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. Moreover, it is more preferable to supply the fibrous thing among fillers from the middle of an extruder with a side feeder in order to prevent the cutting | disconnection in kneading | mixing. The melt kneading temperature is usually 200 to 300 ° C, preferably 220 to 280 ° C.
4.接触用部品:
本発明の接触用部品は、上記熱可塑性樹脂組成物を成形して得られる。該熱可塑樹脂組成物から本発明の接触用部品を製造する方法には何等制限はなく、射出成形、射出圧縮成形、ガスアシスト成形、プレス成形、カレンダー成形、ブロー成形、Tダイ押出成形、異形押出成形、フィルム成形等公知の方法により製造することができる。
4). Contact parts:
The contact component of the present invention is obtained by molding the thermoplastic resin composition. There is no limitation on the method for producing the contact component of the present invention from the thermoplastic resin composition, and injection molding, injection compression molding, gas assist molding, press molding, calender molding, blow molding, T-die extrusion molding, irregular shape It can be produced by a known method such as extrusion molding or film molding.
本発明の接触用部品が接触する他の部材に特に制限はなく、例えば、本発明のゴム強化ビニル系樹脂〔A〕を含む熱可塑性樹脂、熱硬化性樹脂、ゴム、有機質材料、無機質材料、金属材料等が挙げられる。
熱可塑性樹脂としては、例えば、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、AS樹脂、ABS樹脂、AES樹脂、ASA樹脂、ポリメチルメタクリレート、ポリスチレン、耐衝撃性ポリスチレン、EVA、ポリアミド(PA)、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート(PC)、ポリ乳酸、PC/ABS、PC/AES、PA/ABS、PA/AES等が挙げられる。これらは、単独で又は2種以上の組み合わせで使用できる。
熱硬化性樹脂としては、例えば、フェノール樹脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂等が挙げられる。これらは、単独で又は2種以上を組み合わせて使用できる。
ゴムとしては、クロロプレンゴム、ポリブタジエンゴム、エチレン・プロピレンゴム、SEBS、SBS、SIS等の各種合成ゴム、天然ゴム等が挙げられる。これらは、単独で又は2種以上を組み合わせて使用できる。
有機質材料としては、例えば、インシュレーションボード、MDF(中質繊維板)、ハードボード、パーティクルボード、ランバーコア、LVL(単板積層材)、OSB(配向性ボード)、PSL(パララム)、WB(ウェハーボード)、硬質繊維板、軟質繊維板、ランバーコア合板、ボードコア合板、特殊コア−合板、ベニアコア−ベニヤ板、タップ樹脂を含浸させた紙の積層シート・板、(古)紙等を砕いた細かい小片・線状体に接着剤を混合して加熱圧縮したボード、各種の木材等が挙げられる。これらは、単独で又は2種以上を組み合わせて使用できる。
無機質材料としては、例えば、ケイ酸カルシウムボード、フレキシブルボード、ホモセメントボード、石膏ボード、シージング石膏ボード、強化石膏ボード、石膏ラスボード、化粧石膏ボード、複合石膏ボード、各種セラミック、ガラス等が挙げられる。これらは、単独で又は2種以上を組み合わせて使用できる。
更に、金属材料としては、鉄、アルミニウム、銅、各種の合金等が挙げられる。これらは、単独で又は2種以上を組み合わせて使用できる。
これらの中で、熱可塑性樹脂、熱硬化性樹脂、ゴムが好ましく、ABS、AES、PC/ABS、PC/AESが特に好ましい。
There is no particular limitation on the other members that come into contact with the contact component of the present invention. A metal material etc. are mentioned.
Examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, AS resin, ABS resin, AES resin, ASA resin, polymethyl methacrylate, polystyrene, high impact polystyrene, EVA, polyamide (PA), polyethylene terephthalate, poly Examples include butylene terephthalate, polycarbonate (PC), polylactic acid, PC / ABS, PC / AES, PA / ABS, and PA / AES. These can be used alone or in combination of two or more.
Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, melamine resin, and unsaturated polyester resin. These can be used alone or in combination of two or more.
Examples of the rubber include chloroprene rubber, polybutadiene rubber, ethylene / propylene rubber, various synthetic rubbers such as SEBS, SBS, and SIS, and natural rubber. These can be used alone or in combination of two or more.
Examples of the organic material include insulation board, MDF (medium fiber board), hard board, particle board, lumbar core, LVL (single board laminate), OSB (orientation board), PSL (pararam), WB (wafer). Board), hard fiberboard, soft fiberboard, lumbar core plywood, board core plywood, special core-plywood, veneer core-plywood, laminated sheet / board of paper impregnated with tap resin, small pieces of crushed (old) paper, etc. -Boards obtained by mixing a linear body with an adhesive and heating and compressing, various kinds of wood, and the like. These can be used alone or in combination of two or more.
Examples of the inorganic material include calcium silicate board, flexible board, homocement board, gypsum board, sizing gypsum board, reinforced gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, and glass. These can be used alone or in combination of two or more.
Furthermore, iron, aluminum, copper, various alloys, etc. are mentioned as a metal material. These can be used alone or in combination of two or more.
Among these, a thermoplastic resin, a thermosetting resin, and rubber are preferable, and ABS, AES, PC / ABS, and PC / AES are particularly preferable.
本発明の接触用部品は、他の部材と接触し、擦れ合うことにより発生する軋み音を大幅に低減させることが可能で、このような接触用部品としてはドアトリム、ドアライニング、ピラーガーニッシュ、コンソール、ドアポケット、ベンチレータ、ダクト、エアコン、メーターバイザー、インパネアッパーガーニッシュ、インパネロアガーニッシュ、A/T インジケーター、オンオフスイッチ類(スライド部、スライドプレート)、グリルフロントデフロスター、グリルサイドデフロスター、リッドクラスター、カバーインストロアー、マスク類(マスクスイッチ、マスクラジオなど)、グローブボックス、ポケット類(ポケットデッキ、ポケットカードなど)、カップホルダー、スイッチボックス、ステアリングホイールホーンパッド等を挙げることができる。その中でも、自動車用ベンチレータとして好適に用いることができ、自動車用ベンチレータ及び自動車用エアコンの板状羽根、バルブシャッター、ルーバー等として特に好適に用いることができる。この様に他の部材との嵌合部を有する部品に好適である。 The contact component of the present invention can greatly reduce the squeaking noise generated by contacting and rubbing with other members, such as a door trim, door lining, pillar garnish, console, Door pocket, ventilator, duct, air conditioner, meter visor, instrument panel upper garnish, instrument panel upper garnish, A / T indicator, on / off switch (slide part, slide plate), grill front defroster, grill side defroster, lid cluster, cover intro , Masks (mask switches, mask radios, etc.), glove boxes, pockets (pocket decks, pocket cards, etc.), cup holders, switch boxes, steering wheel horn pads, etc. be able to. Among them, it can be suitably used as an automobile ventilator, and can be particularly suitably used as a plate-shaped blade, a valve shutter, a louver and the like of an automobile ventilator and an automobile air conditioner. Thus, it is suitable for a component having a fitting portion with another member.
以下、実施例を挙げ、本発明をさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に何等制約されるものではない。尚、実施例中、部および%は特に断らない限り質量基準である。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited at all to the following Example, unless the summary is exceeded. In the examples, parts and% are based on mass unless otherwise specified.
(1)評価方法:
下記の実施例及び比較例における、各種評価項目の測定方法を以下に示す。
(1) Evaluation method:
The measuring methods of various evaluation items in the following examples and comparative examples are shown below.
(1−1)軋み音評価(摩擦係数の摩擦速度依存性):
日精樹脂工業株式会社製の電動射出成形機「エルジェクト NEX30」(型式名)を用い、表1に記載の熱可塑性樹脂組成物及びテクノポリマー株式会社製のPC/ABS「CK43」(商品名)からなる、内径20mm、外径24.8mm、高さ15mmの円筒型の試験片を射出成形し、その後、両試験片を80℃のギアオーブンに400時間放置した。次に、株式会社オリエンテック製の摩耗摩擦試験器「EFM−III −EN」(商品名)を用い、回転側に接触相手として「CK43」からなる試験片をセットし、固定側に表1に記載の熱可塑性樹脂組成物からなる試験片をセットし、荷重3kg、回転速度(摩擦速度)50mm/s、100mm/s、150mm/sの条件で、摩擦速度に対する摩擦係数の傾きを測定した。
(1-1) Evaluation of stagnation noise (friction speed dependence of friction coefficient):
Using an electric injection molding machine “Erject NEX30” (model name) manufactured by Nissei Plastic Industry Co., Ltd., the thermoplastic resin composition shown in Table 1 and PC / ABS “CK43” (trade name) manufactured by Technopolymer Co., Ltd. A cylindrical test piece having an inner diameter of 20 mm, an outer diameter of 24.8 mm, and a height of 15 mm was injection molded, and then both test pieces were left in a gear oven at 80 ° C. for 400 hours. Next, using a wear friction tester “EFM-III-EN” (trade name) manufactured by Orientec Co., Ltd., set a test piece consisting of “CK43” as a contact partner on the rotating side, and in Table 1 on the fixed side The test piece which consists of the thermoplastic resin composition of description was set, and the inclination of the friction coefficient with respect to a friction speed was measured on the conditions of load 3kg and rotation speed (friction speed) 50mm / s, 100mm / s, 150mm / s.
(1−2)軋み音評価(実用評価):
株式会社日本製鋼所製の射出成形機「J−100E」(型式名)を用い、表1に記載の熱可塑性樹脂組成物及びテクノポリマー株式会社製のPC/ABS「CK43」(商品名)からなる、ISOダンベル試験片を射出成形し、その後、両試験片を80℃のギアオーブンに200時間および400時間放置した。次に、80℃のギアオーブンに200時間および400時間放置した、上記表1に記載の熱可塑性樹脂組成物からなるISOダンベル試験片5枚と、「CK43」からなるISOダンベル試験片5枚を交互に重ね合わせ、この両端を手でひねって軋み音の発生の状況を評価した。評価は5回行い、下記評価基準に基づき判定を行った。
◎:5回の評価全てにおいて、軋み音の発生はなかった。
○:5回の評価全てにおいて、軋み音の発生は僅かであった。
△:5回の評価において、軋み音の発生が顕著な場合が含まれていた。
×:5回の評価全てにおいて、軋み音の発生が顕著であった。
(1-2) Itching sound evaluation (practical evaluation):
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., from the thermoplastic resin composition described in Table 1 and PC / ABS “CK43” (trade name) manufactured by Techno Polymer Co., Ltd. The ISO dumbbell specimens were injection molded, and then both specimens were left in a gear oven at 80 ° C. for 200 hours and 400 hours. Next, 5 ISO dumbbell test pieces made of the thermoplastic resin composition shown in Table 1 and 5 ISO dumbbell test pieces made of “CK43” were left in a gear oven at 80 ° C. for 200 hours and 400 hours. The situation of the generation of itchiness was evaluated by alternately overlapping and twisting both ends by hand. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
(Double-circle): There was no generation | occurrence | production of a squeaking sound in all five evaluations.
○: In all five evaluations, the occurrence of itching was slight.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.
(1−3)落錘衝撃強度:
日精樹脂工業株式会社製の電動射出成形機「エルジェクト NEX30」(型式名)を用い、表1に記載の熱可塑性樹脂組成物からなる、80mm×55mm×2.4mmの平板型の試験片を射出成形した。試験片は、55mmの一方の辺の中央に4mm×1mmのサイドゲートを備え、成形時の樹脂温度は240℃、金型温度は50℃であった。次に、株式会社島津製作所の島津ハイドロショット・高速パンクチャー衝撃試験機「HITS−P10」(型式名)を用い、以下に示す条件で上記試験片を打ち抜いて破壊エネルギー(J)を測定した。
測定温度 : 23℃
打ち抜き速度 : 6.7mm/s
打ち抜き試験用ジグのストライカ先端 : φ12.7mm
試験片受け台のダイス径 : 43mm
(1-3) Drop weight impact strength:
Using an electric injection molding machine “Erject NEX30” (model name) manufactured by Nissei Plastic Industrial Co., Ltd., an 80 mm × 55 mm × 2.4 mm flat plate type test piece made of the thermoplastic resin composition shown in Table 1 Injection molded. The test piece was provided with a side gate of 4 mm × 1 mm at the center of one side of 55 mm, the resin temperature during molding was 240 ° C., and the mold temperature was 50 ° C. Next, using the Shimadzu hydro-shot / high-speed puncture impact tester “HITS-P10” (model name) manufactured by Shimadzu Corporation, the test piece was punched under the following conditions to measure the fracture energy (J).
Measurement temperature: 23 ° C
Punching speed: 6.7mm / s
Punching test jig striker tip: φ12.7mm
Die diameter of specimen holder: 43 mm
(2−1)成分〔A〕
A−1:ABS−1
攪拌機付き重合器に、水280部および重量平均粒子径0.26μm、ゲル分率90%のポリブタジエンラテックス60部(固形分換算)、ナトリウムホルムアルデヒドスルホキシレート0.3部、硫酸第一鉄0.0025部、エチレンジアミン四酢酸二ナトリウム0.01部を仕込み、脱酸素後、窒素気流中で撹拌しながら60℃に加熱した後、アクリロニトリル10部、スチレン30部、t−ドデシルメルカプタン0.2部、クメンハイドロパーオキサイド0.3部からなる単量体混合物を60℃で5時間かけて連続的に滴下した。滴下終了後、重合温度を65℃にし、1時間撹拌続けた後、重合を終了させ、グラフト共重合体のラテックスを得た。重合転化率は98%であった。その後、得られたラテックスに、2,2′−メチレン−ビス(4−エチレン−6−t−ブチルフェノール)0.2部を添加し、塩化カルシウムを添加して凝固し、洗浄、濾過および乾燥工程を経てパウダー状の樹脂組成物を得た。得られた樹脂組成物のグラフト率は40%、アセトン可溶分の極限粘度[η]は0.38dl/gであった。
(2-1) Component [A]
A-1: ABS-1
In a polymerization vessel equipped with a stirrer, 280 parts of water, 60 parts of a polybutadiene latex having a weight average particle size of 0.26 μm and a gel fraction of 90% (in terms of solid content), 0.3 part of sodium formaldehyde sulfoxylate, 0.1 part of ferrous sulfate. 0025 parts, 0.01 parts of disodium ethylenediaminetetraacetate, after deoxygenation, heated to 60 ° C. with stirring in a nitrogen stream, 10 parts of acrylonitrile, 30 parts of styrene, 0.2 parts of t-dodecyl mercaptan, A monomer mixture consisting of 0.3 part of cumene hydroperoxide was continuously added dropwise at 60 ° C. over 5 hours. After completion of the dropwise addition, the polymerization temperature was set to 65 ° C. and stirring was continued for 1 hour, and then the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Thereafter, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-tert-butylphenol) is added to the obtained latex, and calcium chloride is added to coagulate, washing, filtering and drying steps. After that, a powdery resin composition was obtained. The graft ratio of the obtained resin composition was 40%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.38 dl / g.
A−2:AES−1
リボン型攪拌機翼、助剤連続添加装置、温度計などを装備した容積20リットルのステンレス製オートクレーブに、エチレン・α−オレフィン系ゴム(エチレン/プロピレン=78/22(%)、ムーニー粘度(ML1+4 ,100℃)20である、エチレン・プロピレン共重合体)22部、スチレン55部、アクリロニトリル23部、t−ドデシルメルカプタン0.5部、トルエン110部を仕込み、内温を75℃に昇温して、オートクレーブ内容物を1時間攪拌して均一溶液とした。その後、t−ブチルパーオキシイソプロピルモノカーボネート0.45部を添加し、内温を更に昇温して、100℃に達した後は、この温度を保持しながら、攪拌回転数100rpmとして重合反応を行った。重合反応開始後4時間目から、内温を120℃に昇温し、この温度を保持しながら更に2時間反応を行って重合反応を終了した。その後、内温を100℃まで冷却し、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェノール)−プロピオネート0.2部を添加した後、反応混合物をオートクレーブより抜き出し、水蒸気蒸留により未反応物と溶媒を留去し、さらに40mmφベント付き押出機(シリンダー温度220℃、真空度760mmHg)を用いて揮発分を実質的に脱気させ、ペレット化した。得られたエチレン・α−オレフィン系ゴム強化ビニル系樹脂のグラフト率は70%、アセトン可溶分の極限粘度[η]は0.47dl/gであった。
A-2: AES-1
A 20 liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., was charged with ethylene / α-olefin rubber (ethylene / propylene = 78/22 (%), Mooney viscosity (ML 1 ). +4 , 100 ° C.) 20 parts ethylene / propylene copolymer) 22 parts, 55 parts of styrene, 23 parts of acrylonitrile, 0.5 part of t-dodecyl mercaptan, 110 parts of toluene, and the internal temperature was raised to 75 ° C. Warm and stir the autoclave contents for 1 hour to make a homogeneous solution. Thereafter, 0.45 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), and pelletized. The resulting ethylene / α-olefin rubber-reinforced vinyl resin had a graft rate of 70% and an intrinsic viscosity [η] of acetone-soluble content of 0.47 dl / g.
A−3:AES−2
リボン型攪拌機翼、助剤連続添加装置、温度計などを装備した容積20リットルのステンレス製オートクレーブに、エチレン・α−オレフィン系ゴム(エチレン/プロピレン/ジシクロペンタジエン=63/32/5(%)、ムーニー粘度(ML1+4 ,100℃)33である、エチレン・プロピレン・ジシクロペンタジエン共重合体)30部、スチレン45部、アクリロニトリル25部、t−ドデシルメルカプタン0.5部、トルエン140部を仕込み、内温を75℃に昇温して、オートクレーブ内容物を1時間攪拌して均一溶液とした。その後、t−ブチルパーオキシイソプロピルモノカーボネート0.45部を添加し、内温を更に昇温して、100℃に達した後は、この温度を保持しながら、攪拌回転数100rpmとして重合反応を行った。重合反応開始後4時間目から、内温を120℃に昇温し、この温度を保持しながら更に2時間反応を行って重合反応を終了した。その後、内温を100℃まで冷却し、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェノール)−プロピオネート0.2部を添加した後、反応混合物をオートクレーブより抜き出し、水蒸気蒸留により未反応物と溶媒とを留去し、さらに40mmφベント付き押出機(シリンダー温度220℃、真空度760mmHg)を用いて揮発分を実質的に脱気させ、ペレット化した。得られたエチレン・α−オレフィン系ゴム強化ビニル系樹脂のグラフト率は60%、アセトン可溶分の極限粘度[η]は0.45dl/gであった。
A-3: AES-2
In a 20 liter stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary agent addition device, thermometer, etc., ethylene / α-olefin rubber (ethylene / propylene / dicyclopentadiene = 63/32/5 (%)) 30 parts of an ethylene / propylene / dicyclopentadiene copolymer having a Mooney viscosity (ML 1 + 4 , 100 ° C.) of 33, 45 parts of styrene, 25 parts of acrylonitrile, 0.5 part of t-dodecyl mercaptan, 140 parts of toluene The internal temperature was raised to 75 ° C., and the autoclave contents were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.45 part of t-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and the solvent were distilled off by distillation, and the volatile matter was substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), and pelletized. The resulting ethylene / α-olefin rubber-reinforced vinyl resin had a graft rate of 60% and an intrinsic viscosity [η] of acetone-soluble content of 0.45 dl / g.
A−4:ABS−2
撹拌機を備えたガラス製反応容器に、イオン交換水75部、ロジン酸カリウム0.8部、t−ドデシルメルカプタン0.15部、ポリブタジエンラテックス(重量平均粒子径:0.26μm、ゲル含率90%)20部(固形分換算)、スチレン15部及びアクリロニトリル5部を入れ、窒素気流中で攪拌しながら昇温した。内温が45℃に達した時点でピロリン酸ナトリウム0.2部、硫酸第一鉄7水和物0.01部及びブドウ糖0.2部をイオン交換水20部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド0.1部を加えて重合を開始し、1時間重合させた。次いで、イオン交換水50部、ロジン酸カリウム0.7部、スチレン45部、アクリロニトリル15部、t−ドデシルメルカプタン0.08部及びクメンハイドロパーオキサイド0.015部を4時間かけて連続的に添加した。1時間重合させた後2,2´−メチレン−ビス(4−エチレン−6−t−ブチルフェノール)0.2部を添加し重合を完結させた。このラテックスに硫酸マグネシウムを添加し、樹脂成分を凝固させた。その後、水洗、更に乾燥することによりポリブタジエン系グラフト共重合体を得た。グラフト率は62%、アセトン可溶分の極限粘度[η]は0.38dl/gであった。
A-4: ABS-2
In a glass reaction vessel equipped with a stirrer, 75 parts of ion exchange water, 0.8 part of potassium rosinate, 0.15 part of t-dodecyl mercaptan, polybutadiene latex (weight average particle size: 0.26 μm, gel content 90) %) 20 parts (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the temperature was increased while stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. Thereafter, 0.1 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Subsequently, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 45 parts of styrene, 15 parts of acrylonitrile, 0.08 part of t-dodecyl mercaptan and 0.015 part of cumene hydroperoxide are continuously added over 4 hours. did. After polymerization for 1 hour, 0.2 part of 2,2'-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the polybutadiene type graft copolymer was obtained by washing with water and further drying. The graft ratio was 62%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.38 dl / g.
C−1:AS−1
撹拌機付き重合容器に、水250部およびパルミチン酸ナトリウム1.0部を投入し、脱酸素後、窒素気流中で撹拌しながら70℃まで加熱した。さらにナトリウムホルムアルデヒドスルホキシレート0.4部、硫酸第一鉄0.0025部、エチレンジアミン四酢酸二ナトリウム0.01部を仕込み後、α−メチルスチレン70部、アクリロニトリル25部、スチレン5部、t−ドデシルメルカプタン0.5部、クメンハイドロパーオキサイド0.2部からなる単量体混合物を、重合温度70℃で連続的に7時間かけて滴下した。滴下終了後、重合温度を75℃にし、1時間撹拌を続けて重合を終了させ、共重合体のラテックスを得た。重合転化率は99%であった。その後、得られたラテックスを塩化カルシウムを添加して凝固し、洗浄、濾過および乾燥工程を経てパウダー状の共重合体を得た。得られた共重合体のアセトン可溶分の極限粘度[η]は0.40dl/gであった。
C-1: AS-1
In a polymerization vessel equipped with a stirrer, 250 parts of water and 1.0 part of sodium palmitate were charged, and after deoxygenation, the mixture was heated to 70 ° C. with stirring in a nitrogen stream. Further, 0.4 parts of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate and 0.01 part of disodium ethylenediaminetetraacetate were added, and then 70 parts of α-methylstyrene, 25 parts of acrylonitrile, 5 parts of styrene, t- A monomer mixture composed of 0.5 parts of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide was continuously added dropwise at a polymerization temperature of 70 ° C. over 7 hours. After completion of the dropping, the polymerization temperature was set to 75 ° C., and stirring was continued for 1 hour to complete the polymerization, thereby obtaining a copolymer latex. The polymerization conversion rate was 99%. Thereafter, the obtained latex was coagulated by adding calcium chloride, and a powdery copolymer was obtained through washing, filtration and drying steps. The intrinsic viscosity [η] of the acetone-soluble component of the obtained copolymer was 0.40 dl / g.
(2−2)成分〔B〕(シリコーンオイル):
B−1:ジメチルシリコーンオイル;KF−96H−10,000cSt(商品名:信越シリコーン株式会社製)、25℃の動粘度は10000cStであった。
(2-2) Component [B] (silicone oil):
B-1: Dimethyl silicone oil; KF-96H-10,000 cSt (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.), the kinematic viscosity at 25 ° C. was 10,000 cSt.
B−2:ジメチルシリコーンオイル;KF−96−100cSt(商品名:信越シリコーン株式会社製)、25℃の動粘度は100cStであった。 B-2: Dimethyl silicone oil; KF-96-100 cSt (trade name: manufactured by Shin-Etsu Silicone), kinematic viscosity at 25 ° C. was 100 cSt.
B−3:ジメチルシリコーンオイル;KF−96H−50,000cSt(商品名:信越シリコーン株式会社製);25℃の動粘度は50,000cStであった。 B-3: Dimethyl silicone oil; KF-96H-50,000 cSt (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.); The kinematic viscosity at 25 ° C. was 50,000 cSt.
B−4:ジメチルシリコーンオイル;KF−96L−5cSt(商品名:信越シリコーン株式会社製)、25℃の動粘度は5cStであった。 B-4: Dimethyl silicone oil; KF-96L-5cSt (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.), kinematic viscosity at 25 ° C. was 5 cSt.
B−5:ジメチルシリコーンオイル;KF−96H−300,000cSt(商品名:信越シリコーン株式会社製)、25℃の動粘度は300,000cStであった。 B-5: Dimethyl silicone oil; KF-96H-300,000 cSt (trade name: manufactured by Shin-Etsu Silicone), kinematic viscosity at 25 ° C. was 300,000 cSt.
(2−3)添加剤:
D−1:エチレン・ビスステアリン酸アマイド;カオーワックス EB−P(商品名:花王株式会社製)
D−2:1,3,5−トリス(3,5−ジ−t−ブチル−4−ハイドロキシベンジル)−s−トリアジン−2,4,6−(1H,3H,5H)トリオン;アデカスタブ AO−20(商品名:株式会社ADEKA製)
D−3:ビス(2,4−ジ−t−ブチルフェニル)ペンタエリストールジホスファイト;アデカスタブ PEP−24G(商品名:株式会社ADEKA製)
(2-3) Additive:
D-1: Ethylene bis-stearic acid amide; Kao wax EB-P (trade name: manufactured by Kao Corporation)
D-2: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione; Adekastab AO- 20 (Product name: Made by ADEKA Corporation)
D-3: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; ADK STAB PEP-24G (trade name: manufactured by ADEKA Corporation)
実施例1〜9及び比較例1〜5
表1に記載の配合割合で、上記成分〔A〕〜〔D〕をヘンシェルミキサーにより混合した後、二軸押出機(日本製鋼所製、TEX44、バレル設定温度250℃)で混練し、ペレット化した。得られたペレットで評価用の各試験片を成形した。そして得られた試験片を用いて、前記の方法で評価した。以上の評価結果を表1に示した。
Examples 1-9 and Comparative Examples 1-5
After mixing the above components [A] to [D] with a Henschel mixer at the blending ratio shown in Table 1, they are kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX44, barrel set temperature 250 ° C.) and pelletized. did. Each test piece for evaluation was shape | molded with the obtained pellet. And it evaluated by the said method using the obtained test piece. The above evaluation results are shown in Table 1.
表1から明らかように、実施例1〜9に代表される本発明の熱可塑性樹脂組成物は、本発明の目的とする軋み音が低減され、更に、耐衝撃性をバランス良く備えた成形品を提供することができる。
これに対し、比較例1は、エチレン・α−オレフィン系ゴム質重合体〔a2〕を含まない例であり、軋み音の低減効果に劣る。比較例2は、ジエン系ゴム質重合体〔a1〕を含まない例であり、落錘衝撃強度に劣る。比較例3は、本発明のシリコーンオイル〔B〕の配合量が多すぎる例で、溶融混練が困難で、かつシリコーンオイルが成形品表面にブリードアウトして実用上使用不可能なため、これら評価を行わなかった。比較例4は、本発明における動粘度を満たさないシリコーンオイルを用いた例であり、動粘度が小さすぎるため、軋み音の低減効果に劣る。比較例5は、本発明における動粘度を満たさないシリコーンオイルを用いた例であり、動粘度が大きすぎるため、溶融混練が困難で評価を行わなかった。
As can be seen from Table 1, the thermoplastic resin compositions of the present invention represented by Examples 1 to 9 are molded articles with reduced squeak noise that is the object of the present invention, and further having a good balance of impact resistance. Can be provided.
On the other hand, Comparative Example 1 is an example that does not contain the ethylene / α-olefin rubbery polymer [a2], and is inferior in the effect of reducing the squeaking noise. Comparative Example 2 is an example not containing the diene rubbery polymer [a1], and is inferior in falling weight impact strength. Comparative Example 3 is an example in which the blending amount of the silicone oil [B] of the present invention is too large, and melt kneading is difficult, and the silicone oil bleeds out on the surface of the molded product and cannot be used practically. Did not do. Comparative Example 4 is an example using a silicone oil that does not satisfy the kinematic viscosity in the present invention. Since the kinematic viscosity is too small, the effect of reducing the squeaking noise is inferior. Comparative Example 5 is an example using a silicone oil that does not satisfy the kinematic viscosity in the present invention. Since the kinematic viscosity was too large, melt kneading was difficult and evaluation was not performed.
本発明の接触用部品は、部材が擦れ合うときに発生する軋み音が著しく低減され、かつ高温下に長時間置かれた場合においても軋み音低減効果が低下せずに維持され、さらには耐衝撃性に優れた熱可塑性樹脂組成物からなる接触用部品を提供することができ、自動車用ベンチレータ等に好適に使用することができる。特に、他の部材との嵌合部を有する部品に好適に使用することができる。 The contact component according to the present invention significantly reduces the squeaking noise that occurs when the members rub against each other, and maintains the squeaking noise reduction effect even when left at high temperatures for a long time. It is possible to provide a contact component comprising a thermoplastic resin composition having excellent properties, and it can be suitably used for an automobile ventilator or the like. In particular, it can be suitably used for a component having a fitting portion with another member.
M 物体
V 駆動速度
μs 静摩擦係数
μl ノコギリ波形下端
Δμ μs−μl
M Object V Drive speed μs Static friction coefficient μl Sawtooth waveform lower end Δμ μs-μl
Claims (6)
該ゴム強化ビニル系樹脂〔A〕は、ジエン系ゴム質重合体〔a1〕の存在下にビニル系単量体〔b1〕を重合して得られたゴム強化ビニル系樹脂〔A1〕と、エチレン・α−オレフィン系ゴム質重合体〔a2〕の存在下にビニル系単量体〔b2〕を重合して得られたゴム強化ビニル系樹脂〔A2〕を含有し、
前記ジエン系ゴム質重合体〔a1〕及び前記エチレン・α−オレフィン系ゴム質重合体〔a2〕の合計量が、前記ゴム強化ビニル系樹脂〔A〕全体を100質量%として5〜30質量%であり、
該ジエン系ゴム質重合体〔a1〕と該エチレン・α−オレフィン系ゴム質重合体〔a2〕の質量比〔a1〕:〔a2〕が10〜85:90〜15であり、
前記ビニル系単量体〔b1〕及び〔b2〕が芳香族ビニル化合物及びシアン化ビニル化合物を含む
熱可塑性樹脂組成物からなることを特徴とする接触用部品。 Silicone oil [B] 0.1-8 having a kinematic viscosity at 25 ° C. of 10-100,000 cSt measured with ASTM D445-46T or JIS 8803 Ubbelohde viscometer to 100 parts by mass of rubber-reinforced vinyl resin [A] Combining parts by mass,
The rubber-reinforced vinyl resin [A] includes a rubber-reinforced vinyl resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of a diene rubber polymer [a1], ethylene A rubber-reinforced vinyl resin [A2] obtained by polymerizing a vinyl monomer [b2] in the presence of an α-olefin rubber polymer [a2],
The total amount of the diene rubbery polymer [a1] and the ethylene / α-olefin rubbery polymer [a2] is 5 to 30% by mass based on 100% by mass of the entire rubber-reinforced vinyl resin [A]. And
The mass ratio [a1]: [a2] of the diene rubber polymer [a1] and the ethylene / α-olefin rubber polymer [a2] is 10 to 85: 90-15,
The contact component, wherein the vinyl monomers [b1] and [b2] are made of a thermoplastic resin composition containing an aromatic vinyl compound and a vinyl cyanide compound.
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US9708482B2 (en) | 2013-04-08 | 2017-07-18 | Techno Polymer Co., Ltd. | Contacting component and structure containing said contacting component |
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MX2019001668A (en) | 2016-08-09 | 2019-09-19 | Techno Umg Co Ltd | Thermoplastic resin composition having reduced impact noise and molded body having reduced impact noise. |
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