JPS63284241A - Fiber-reinforced resin composition - Google Patents
Fiber-reinforced resin compositionInfo
- Publication number
- JPS63284241A JPS63284241A JP11827587A JP11827587A JPS63284241A JP S63284241 A JPS63284241 A JP S63284241A JP 11827587 A JP11827587 A JP 11827587A JP 11827587 A JP11827587 A JP 11827587A JP S63284241 A JPS63284241 A JP S63284241A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- components
- parts
- component
- total amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 17
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000000454 talc Substances 0.000 claims abstract description 18
- 229910052623 talc Inorganic materials 0.000 claims abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000004611 light stabiliser Substances 0.000 claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 14
- -1 phosphorus compound Chemical class 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 235000012222 talc Nutrition 0.000 description 16
- 238000000465 moulding Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229940116351 sebacate Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000010332 dry classification Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010333 wet classification Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LGKVAJZZWOFYSZ-UHFFFAOYSA-N 1,1-bis(2-tert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C)C(C)(C)C LGKVAJZZWOFYSZ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ADVWVIQNAOXLCV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperazine Chemical compound CC1(C)CNCC(C)(C)N1 ADVWVIQNAOXLCV-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000020719 Satsuma Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000860832 Yoda Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は繊維で補強された樹脂組成物に係り、特に高温
時での寸法安定性および耐候性が要求される分野、例え
ばフェンダ−、ドアパネル、バンパー、バンパースカー
ト、フェーシャ−等の車両外装部品等の用途に用いられ
るla!補強樹脂組成物に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a fiber-reinforced resin composition, particularly in fields where dimensional stability and weather resistance at high temperatures are required, such as fenders and door panels. , la! is used for vehicle exterior parts such as bumpers, bumper skirts, and fascias. The present invention relates to a reinforced resin composition.
フィラー等で補強されたプロピレン系樹脂組成物は、そ
の成形加工性や物性が優れており、経済的にも有利であ
るため、自動車部品の分野を始め、各種の工業部品に幅
広く使用されている。Propylene-based resin compositions reinforced with fillers, etc. have excellent moldability and physical properties, and are economically advantageous, so they are widely used in the field of automobile parts and various other industrial parts. .
ところが、前記補強のためのフィラーとして炭酸カルシ
ウムや硫酸バリウムを用いた場合には、高温時の寸法安
定性が不充分である。However, when calcium carbonate or barium sulfate is used as the reinforcing filler, the dimensional stability at high temperatures is insufficient.
また例えば、ガラス繊維をフィラーとして用いた場合に
は高温時の寸法安定性は良くなるが、成形反りや物性低
下、特に衝撃強度の低下という問題を生ずる。For example, when glass fiber is used as a filler, the dimensional stability at high temperatures is improved, but problems such as molding warpage and deterioration of physical properties, particularly impact strength, occur.
これらの問題を解決する手法としては、フィラーとして
微細ta維(ホイスカ)を用いる補強方法が提案されて
いる。中でもチタン酸カリウムの微細繊維をフィラーと
して用いたものは高温時の寸法安定性や成形反りが改善
されるほか、物性上も優れているので、プロピレン系に
限らず各種のプラスチックに対し、あるいは他のフィラ
ーとの併用補強材として多数提案されている(例えば、
特開昭el−99848号、特開昭59−13f133
8号、特開昭59−140245号、特開昭58−21
3032号、各明細書参照)。As a method for solving these problems, a reinforcing method using fine Ta fibers (whiskers) as a filler has been proposed. Among them, products using fine fibers of potassium titanate as a filler not only improve dimensional stability and mold warping at high temperatures, but also have excellent physical properties, so they can be used not only for propylene-based plastics but also for various other plastics. A number of reinforcement materials have been proposed for use in combination with fillers (for example,
JP-A No. 1984-99848, JP-A No. 59-13F133
No. 8, JP-A-59-140245, JP-A-58-21
No. 3032, see each specification).
しかしながら、これまで提案されてきたチタン酸カリウ
ム含有樹脂組成物は、必ずしも耐候性が充分とはいえず
、長時問屋外に暴露されるような用途、例えば車両の外
装部材には適さない場合が多かった。However, the potassium titanate-containing resin compositions that have been proposed so far do not necessarily have sufficient weather resistance, and may not be suitable for applications that are exposed to the outdoors for long periods of time, such as vehicle exterior parts. There were many.
そこで、本発明者等は先に特定形状のチタン酸カリウム
繊維及び特定の光安定剤を配合することにより、良好な
高温時の寸法安定性や成形反り抑制に加えて良好な耐候
性を有する繊維補強樹脂組成物を提案した(特願昭81
−297253号明細書参照)。Therefore, the present inventors first blended potassium titanate fibers with a specific shape and a specific light stabilizer to create fibers that had good dimensional stability at high temperatures, suppressed molding warping, and had good weather resistance. proposed a reinforcing resin composition (patent application 1981)
-297253).
しかしながら、該am補強樹脂組成物においても用途に
よっては高温時の寸法安定性や成形反り抑制は良好でも
耐候性が充分とはいえず、例えば、車両用外装部材とし
ては適さない場合が多かった。However, depending on the application, the am-reinforced resin composition may have good dimensional stability at high temperatures and suppress molding warpage, but may not have sufficient weather resistance, and is often unsuitable for use as an exterior member for a vehicle, for example.
本発明者等は、車両、特に自動車の外装部材として適用
可能な著しく耐候性の優れたプロピレン系樹脂組成物を
探究してきた結果、特定形状のチタン酸カリウム繊維、
特定のリン化合物および特定の光安定剤などを配合する
ことにより上記の目的を達成したものである。The present inventors have been searching for a propylene resin composition with extremely excellent weather resistance that can be applied to exterior parts of vehicles, especially automobiles, and as a result, they have found that potassium titanate fibers of a specific shape,
The above objective was achieved by blending a specific phosphorus compound and a specific light stabilizer.
即ち本発明は、下記(a)〜mの各成分からなることを
特徴とする繊維補強樹脂組成物である。That is, the present invention is a fiber-reinforced resin composition characterized by comprising each of the following components (a) to m.
(a)結晶性プロピレン系重合体:
(e)成分及び/又は(n成分を含むときは(a) 、
(b) 、 (e)び(f)成分の合計量に対して4
0〜98重量tであり、(e)成分及び(f)成分を含
まないときは(a)及び(b)成分の合計量に対して7
0〜99重量2
(b)平均m雄径が0.1〜1用■で、かつ、平均アス
ペクト比が5以上のチタン酸カリウム繊Ia:
(a) 、 (b) 、 (a)及び(f)成分の合計
量に対して30〜1重量2
(e)一般式
(式中、R1は炭素数8〜30のアルキル基。(a) Crystalline propylene polymer: (a) when containing component (e) and/or (n component),
4 for the total amount of components (b), (e) and (f).
0 to 98 weight tons, and if component (e) and (f) are not included, 7 to the total amount of components (a) and (b).
0 to 99 weight 2 (b) Potassium titanate fiber Ia with an average male diameter of 0.1 to 1 and an average aspect ratio of 5 or more: (a), (b), (a) and ( f) 30 to 1 weight 2 based on the total amount of components (e) General formula (wherein R1 is an alkyl group having 8 to 30 carbon atoms.
シクロアルキル基又は芳香族の基であり、R2は炭素数
1〜30のアルキル基、シクロアルキル基、又は芳香族
の基であり、l(l、R2はともに同一化合物中で異な
っていてもよい RMはt−ブチル基である。)
で表わされる構造を有するリン化合物:(a) 、 (
b) 、 (e)及び(f) Jli分の合計量100
重量部に対して0.01〜0.5重量部(d)ヒンダー
ドアミン系光安定剤:
(a) 、 (b)、 (e)及び(f)成分の合計量
100重量部に対して0.01〜2重量部
(e)平均粒径が51Lm以下のタルク:0〜30重量
2
CF>プロピレン含量が20〜60重量2で、ムーニー
粘度ML1+4(100℃)が5〜120のエチレン・
プロピレン共重合体ゴム:
θ〜40重量2゜
〔発明の詳細な説明〕
薩裟虚宏
(a)結晶性プロピレン系重合体
本発明で用いられる(a)成分のプロピレン系重合体(
以下、PPと略称する)は、立体規則性を有するプロピ
レンの単独重合体(ポリプロピレン)、フロピレン以外
の他のα−オレフィン、好ましくは例えばエチレン、ブ
テン−1、ペンテン−1、ヘキセン−1、ヘプテン−1
、オクテン−1等の炭素数8以下のα−オレフィン、特
に好ましくはエチレン、ブテン−1を40重量2以下、
好ましくは30重量2以下含有する、プロピレンとα−
オレフィンとの二元以上のブロックまたはランダム共重
合体、もしくはこれらの重合体を融化、塩素化、スルホ
ン化、グリシジル化、あるいは不飽和有機酸等による変
性等で変性したもの等である。It is a cycloalkyl group or an aromatic group, R2 is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, or an aromatic group, and l (l and R2 may be different in the same compound. RM is a t-butyl group.) A phosphorus compound having the structure represented by: (a), (
b), (e) and (f) Total amount for Jli 100
0.01 to 0.5 parts by weight per part by weight (d) Hindered amine light stabilizer: Total amount of components (a), (b), (e) and (f) 0.01 to 0.5 parts by weight per 100 parts by weight. 01-2 parts by weight (e) Talc with an average particle size of 51 Lm or less: 0-30 weight 2 CF> Ethylene with a propylene content of 20-60 weight 2 and a Mooney viscosity ML1+4 (100°C) of 5-120.
Propylene copolymer rubber: θ ~ 40 weight 2° [Detailed description of the invention] Urohiro Satsuma (a) Crystalline propylene polymer The propylene polymer (a) component used in the present invention (
(hereinafter abbreviated as PP) is a stereoregular propylene homopolymer (polypropylene), other α-olefins other than propylene, preferably ethylene, butene-1, pentene-1, hexene-1, heptene-1, etc. -1
, octene-1 and other α-olefins having 8 or less carbon atoms, particularly preferably ethylene, butene-1, 40% by weight or less,
Preferably containing 30% by weight or less, propylene and α-
These include two or more block or random copolymers with olefins, or those modified by melting, chlorinating, sulfonating, glycidylating, or modifying with unsaturated organic acids.
これらのPPのうち、プロピレン単独重合部分の密度が
0.908以上で、重合体全体のエチレン含量が3重量
2以上であり、そのMFRが4g/10分以上のプロピ
レン・エチレン−ブロック共重合体が好ましい、特にプ
ロピレン単独重合部分の密度が0゜907以上で1重合
体全体のエチレン含量が3〜7重量$ 、 MFRが5
0〜120 g/10分のものが好ましく、さらに、こ
のプロピレン・エチレン−ブロック共重合体でエチレン
含量20〜50重量工の常温キシレン可溶分を5〜15
重量2含むものがより好ましい。Among these PPs, propylene/ethylene block copolymers have a density of the propylene homopolymerized portion of 0.908 or more, an ethylene content of the entire polymer of 3 weight 2 or more, and an MFR of 4 g/10 minutes or more. is preferable, especially when the density of the propylene homopolymerized portion is 0°907 or more, the ethylene content of the whole polymer is 3 to 7 wt.$, and the MFR is 5
0 to 120 g/10 min is preferable, and furthermore, this propylene/ethylene block copolymer has an ethylene content of 20 to 50 g/wt/xylene solubles at room temperature of 5 to 15 g/10 min.
It is more preferable that the weight is 2.
ここで、密度はJIS−に7112 、 MFRはJI
S−に7210(230℃、2.18Kg)に準拠し、
また、エチレン含量はNMR法にて測定される値であり
、常温キシレン可溶分は2gの試料を沸騰キシレン60
0g中に20分間浸漬して溶解させた後、室温まで冷却
し、 G4型ガラスフィルターでろ過および乾燥して求
めた固相重量から逆算した値である。Here, the density is JIS-7112, and the MFR is JIS-7112.
Based on S-7210 (230℃, 2.18Kg),
In addition, the ethylene content is a value measured by NMR method, and the xylene soluble content at room temperature is 2 g of sample mixed with boiling xylene 60%.
The value was calculated back from the weight of the solid phase obtained by immersing it in 0 g for 20 minutes to dissolve it, cooling it to room temperature, filtering it with a G4 type glass filter, and drying it.
ここでこのPPは2種以上の併用混合物であってもよい
。Here, this PP may be a mixture of two or more types.
(b)チタン酸カリウム繊維
次に本発明で用いる (b)成分のチタン酸カリウム繊
維は、その平均繊維直径が0.1〜1島層で、かつ平均
アスペクト比(繊維長と繊維直径の比の平均値)が5以
上のものである。なかでも平均直径が0.54gm以下
、平均アスペクト比が7以上、とりわけ10以上のもの
が好ましい、この繊維の製造法は特に問わないが、その
形状は先の範囲内にあることが必要である。ここでその
PH値はlO以下であることが望ましく、特に7〜3.
5、とりわけ7〜Bのものが好ましい、ここでチタン酸
カリウムのp)I値は、繊維を水中分散させた場合の測
定値であって、例えば100−の水中にチタン酸カリウ
ム1gを24時間浸漬後、測定される。また、繊維直径
及びア・スペクト比は樹脂中に混線分散させた後、その
断面を顕微鏡にて観察測定した値である。(b) Potassium titanate fiber Next, the potassium titanate fiber used in the present invention (b) has an average fiber diameter of 0.1 to 1 island layer, and an average aspect ratio (ratio of fiber length to fiber diameter). average value) is 5 or more. Among these, fibers with an average diameter of 0.54 gm or less and an average aspect ratio of 7 or more, especially 10 or more are preferred.The manufacturing method of this fiber is not particularly limited, but the shape must be within the above range. . Here, the pH value is desirably 1O or less, particularly 7 to 3.
5, especially those from 7 to B are preferred, where the p)I value of potassium titanate is the value measured when the fibers are dispersed in water, for example 1 g of potassium titanate in 100-g water for 24 hours. Measured after immersion. Further, the fiber diameter and aspect ratio are values obtained by cross-dispersing the fibers in the resin and then observing and measuring the cross section thereof using a microscope.
(C)リン化合物
次に、本発明で用いる(C)成分のリン化合物は次に示
すものである。すなわち、本化合物は次の一般式(I)
又は(n)で表わされる構造を有するもので、式中R1
は炭素数8〜30のアルキル基、シクロアルキル基又は
芳香族の基であり、R2は炭素数1〜30のアルキル基
、シクロアルキル基又は芳香族の基であり R’、Rz
はともに同一化合物中で異なっていてもよい R1はt
−ブチルである。(C) Phosphorus Compound Next, the phosphorus compound as component (C) used in the present invention is shown below. That is, the present compound has the following general formula (I)
or (n), in which R1
is an alkyl group, cycloalkyl group, or aromatic group having 8 to 30 carbon atoms; R2 is an alkyl group, cycloalkyl group, or aromatic group having 1 to 30 carbon atoms; R', Rz
may be different in the same compound R1 is t
-Butyl.
及び/又は
上記化合物(I)の具体例としては、例えば、(1)ジ
ステアリルペンタエリスリトールジホスファイト
(2)ビス(2,4−ジ−t−ブチルフェニル)ペンタ
エリスリトールジホスファイト
(3)ビス(2−t−ブチル−4−メチルフェニル)ペ
ンタエリスリトールジホスファイト
(4)ビス(2,8,ジ−t−ブチル−4−メチルフェ
ニル)ペンタエリスリトールジホスファイト等が挙げら
れ、化合物(II)に関しては、(5)テトラキス(2
,4−ジ−t−ブチルフェニル)−4゜4°−ビフェニ
レンホスファイト
(6)テトラキス(2−t−ブチル−4−メチル−フェ
ニル)−4,4−ビフェニレンホスフォナイト等が挙げ
られる。And/or specific examples of the above compound (I) include (1) distearyl pentaerythritol diphosphite (2) bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite (3) Bis(2-t-butyl-4-methylphenyl)pentaerythritol diphosphite (4)bis(2,8,di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, etc., and the compound ( Regarding II), (5) tetrakis (2
, 4-di-t-butylphenyl)-4°4°-biphenylene phosphite (6) tetrakis(2-t-butyl-4-methyl-phenyl)-4,4-biphenylene phosphonite.
なかでも前記(1) 、 (2) 、 (4)及び(5
)の化合物が好ましく、とりわけ(2)及び(5)の化
合物が好ましい。Among them, the above (1), (2), (4) and (5)
) are preferred, and (2) and (5) are particularly preferred.
これらのリン化合物の添加量は、(a) 、 (b)、
(e)及び(f)合計量100重量部に対して0.01
〜0.5重量部、好ましくは0.03〜0.3重量部で
ある。The amounts of these phosphorus compounds added are (a), (b),
(e) and (f) 0.01 per 100 parts by weight of the total amount
-0.5 parts by weight, preferably 0.03-0.3 parts by weight.
(d)ヒンダードアミン系光安定剤
法に、本発明で用いる(d)成分のヒンダードアミン系
光安定剤としては、例えば
(7)ビス−2,2,8,8−テトラメチル−4−ピペ
リジルセバケート
(8)テトラキス(2,2,8,El−テトラメチル−
4−ピペリジル) 1,2,3.4−ブタンテトラカル
ボキシレート
(9) 2− (3,5−ジ−t−ブチル−4−ヒドロ
キシベンジル)2−n−ブチルマロン酸ビス(1,2,
2,6,8−ぺ−フタメチル−4−ピペリジル)
(10)1.1’−(1,2−エタンジイル)ビス(3
,3,5,5−テトラメチルピペラジン)
(11))リス(2,2,2,2−テトラメチル−4−
ピペリジル)−ドデシル−1,2,3,4−ブタンテト
ラカルボキシレート
(12) )リス(1,2,2,8,El−ペンタメチ
ル−4−ピペリジル)−ドデシル−1,2,3,4−ブ
タンテトラカルボキシレート
(13)ビス−1,2,2,8,8−ペンタメチル−4
−ピペリジル−セバケート
(14)ポリ[(El−(1,1,3,3−テトラメチ
ルブチル)イミノ−1,3,5−トリアジン−2,4−
ジイル) ((2゜2.6.8−テトラメチル−4−
ピペリジル)イミノ)ヘキサメチレン((2,2,8,
13−テトラメチル−4−ピペリジル)イミノ)1
などであるが、これらに限定されない、なかでも(7)
、 (8) 、 (14)の化合物が好ましく、とり
わけ(7)の化合物が好ましい。(d) Hindered amine light stabilizer In the method, the hindered amine light stabilizer as component (d) used in the present invention is, for example, (7) bis-2,2,8,8-tetramethyl-4-piperidyl sebacate. (8) Tetrakis(2,2,8,El-tetramethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate (9) 2-(3,5-di-t-butyl-4-hydroxybenzyl)2-n-butylmalonic acid bis(1,2,
2,6,8-pe-phthamethyl-4-piperidyl) (10) 1.1'-(1,2-ethanediyl)bis(3
,3,5,5-tetramethylpiperazine) (11)) Lis(2,2,2,2-tetramethyl-4-
piperidyl)-dodecyl-1,2,3,4-butanetetracarboxylate (12)) lis(1,2,2,8,El-pentamethyl-4-piperidyl)-dodecyl-1,2,3,4- Butane tetracarboxylate (13) bis-1,2,2,8,8-pentamethyl-4
-piperidyl-sebacate (14) poly[(El-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-
diyl) ((2゜2.6.8-tetramethyl-4-
piperidyl)imino)hexamethylene((2,2,8,
13-tetramethyl-4-piperidyl)imino)1, among others, but not limited to (7)
, (8) and (14) are preferred, and the compound (7) is particularly preferred.
この(d)成分の添加量は、(a) 、 (b) 、
(e)及びCnの合計量100重量部に対して0.01
〜2重量部、好ましくは0.03〜1重量部である。ま
た、これら以外の紫外線吸収剤等の耐光性付与剤を併用
することによりさらに耐候性を向上させることができる
。The amount of component (d) added is (a), (b),
0.01 per 100 parts by weight of the total amount of (e) and Cn
~2 parts by weight, preferably 0.03 to 1 part by weight. Further, weather resistance can be further improved by using a light resistance imparting agent other than these, such as an ultraviolet absorber.
(e)タルク
本発明において用いることのできる (e)成分のタル
クは、平均粒径が51L11以下のものである。(e) Talc The talc component (e) that can be used in the present invention has an average particle size of 51L11 or less.
タルクの添加は高温時の寸法安定性、成形反り抑制、剛
性等を向上させる効果を有し、なかでも比表面積が35
,000 cボッg以上で、平均粒径が0.2〜2.5
延鵬であり、粒度分布が実質的に15弘層以下であって
、粒子寸法10用層以下のものが95%以上、51L厘
以下のものが80X以上、IIL11以下のものが5〜
50%で、かつ、平均アスペクト比が5以上のものが好
ましく、更に好ましくは比表面積が37.000cm″
/g以上で、平均粒径が0.3〜2.2ル■、粒度分布
が粒子全部が実質的に15IL11以下で、10IL■
以下のものが97%以上、5gm以下のものが82X以
上、かつ、 lpm以下のものが10〜45%であって
、平均アスペクト比が8以上のものである。The addition of talc has the effect of improving dimensional stability at high temperatures, suppressing molding warpage, and rigidity, among others, with a specific surface area of 35
,000 cbog or more, with an average particle size of 0.2 to 2.5
The particle size distribution is substantially 15 layers or less, 95% or more of particles with a particle size of 10 layers or less, 80X or more of particles with a particle size of 51 L or less, and 5 to 11 layers or less.
50% and an average aspect ratio of 5 or more, more preferably a specific surface area of 37.000 cm''
/g or more, the average particle size is 0.3 to 2.2 l■, the particle size distribution is substantially all the particles are 15IL11 or less, and 10IL■
The following items are 97% or more, 5 gm or less are 82X or more, and lpm or less are 10 to 45%, and the average aspect ratio is 8 or more.
ここで、比表面積の測定は、常法の、いわゆる空気透過
法に基いて、恒圧通気式表面積測定装置、例えば島津製
作所製粉体比表面積測定装置5S−20型等で行なわれ
る。また、粒度分布の測定は、液相沈降方式の光透過法
による積算分布値である。IM定装置としては、例えば
島津製作所製5A−cp型(例えば5A−CP 2−2
0)がある。Here, the specific surface area is measured using a constant pressure aeration type surface area measuring device, such as powder specific surface area measuring device 5S-20 manufactured by Shimadzu Corporation, based on a conventional method, the so-called air permeation method. Further, the particle size distribution is measured by an integrated distribution value by a light transmission method using a liquid phase sedimentation method. As an IM determination device, for example, 5A-CP type manufactured by Shimadzu Corporation (for example, 5A-CP 2-2
0).
一方、平均粒径は、粒度分布の測定装置と同じ装置で測
定した粒度の累積分布曲線における50%の点での粒径
値である。ここで、測定に用いる分散媒としてはアルコ
ール30重量2程度の水溶液を用いることが、タルクの
分散度を高め、測定し易くするので好ましい、また、平
均アスペクト比とはタルクの縦又は横のいずれかの長さ
と厚みの比の平均値であり、その測定は顕微鏡にて観察
する方法によった。On the other hand, the average particle size is the particle size value at the 50% point in the particle size cumulative distribution curve measured with the same device as the particle size distribution measuring device. Here, it is preferable to use an aqueous solution of about 30 parts alcohol by weight 2 parts as the dispersion medium used in the measurement because it increases the degree of dispersion of talc and makes it easier to measure. It is the average value of the ratio of length to thickness, and its measurement was performed by observation using a microscope.
また、樹脂中に分散しているフィラーの上記諸物性は、
この組成物を有機溶媒で沸点抽出する方法、例えばキシ
レン中130〜140℃で数時間浸漬溶解し、それを円
筒濾紙を通してタルクと樹脂を分離する方法か、又はこ
の組成物を焼成する方法等で取り出したフィラーについ
て、上記の方法で求めることができる。In addition, the above physical properties of the filler dispersed in the resin are:
A method of extracting the boiling point of this composition with an organic solvent, such as a method of immersing and dissolving it in xylene at 130 to 140°C for several hours and separating the talc and resin through a thimble filter paper, or a method of baking this composition, etc. The extracted filler can be determined by the method described above.
平均粒径1.5路1以下のタルクは湿式分級で得られ易
く、同0.7g■以上のタルクは乾式分級で得られ易い
、このようなタルクは、例えば次のような分級方法によ
って製造される。Talc with an average particle size of 1.5 g or less can be easily obtained by wet classification, and talc with an average particle size of 0.7 g or more can be obtained by dry classification. Such talc can be produced, for example, by the following classification method. be done.
即ち、タルク原石をチューブミル型粉砕機、衝撃式粉砕
機、ミクロンミル型粉砕機、遠心ローラー型しイモンド
ミル等の装置で粉砕し、微粉砕を要する場合には更にミ
クロンミル、ジェット型粉砕機、ジェット・オ・マイザ
ー、ミクロナイf−、ジェットパルペライザー、撹拌摩
砕ミル(タワーミル)、振動ミル、コロイドミル等で乾
式又は湿式微粉砕する0次に、これらの粉砕したタルク
をサイクロン、マルチロン、ミクロンセパレーター、ミ
クロンプレックス、サイクロネアセパレーター、ウルト
ラセパレーター、ジェットクロン、クラシフロン、レー
キ分級機、ハイドロサイクロン、水力分級機、遠心分級
機等の装置で、−回又は複数回繰り返して乾式又は湿式
分級し、その物性を調整する。That is, raw talc is crushed using equipment such as a tube mill type crusher, impact type crusher, micron mill type crusher, centrifugal roller type Imond mill, etc., and if fine crushing is required, a micron mill, jet type crusher, etc. Dry or wet pulverization is performed using a jet-o-mizer, micronizer, jet pulpelizer, stirring mill (tower mill), vibration mill, colloid mill, etc. Next, the pulverized talc is pulverized using a cyclone, multilon, etc. Dry or wet classification is performed repeatedly one or more times using a device such as a micron separator, micronplex, cyclonea separator, ultra separator, jet chron, classiflon, rake classifier, hydrocyclone, hydraulic classifier, centrifugal classifier, etc. Adjust its physical properties.
タルクの原石としては中国産、豪州産、米国産等が好ま
しいが、とりわけ中国産が好ましい、また、これらのタ
ルクは各種エステル類やグリコール類、カップリング剤
、脂肪酸やその金属塩類、界面活性剤等で表面処理して
も良く、その処理は性能向上に有効である。Talc from China, Australia, the United States, etc. is preferred as raw talc, but talc from China is especially preferred.In addition, these talcs can be used for various esters, glycols, coupling agents, fatty acids and their metal salts, and surfactants. Surface treatment may also be carried out, and this treatment is effective in improving performance.
(f)エチレン・プロピレン共重合体ゴムまた、本発明
で用いることのできる (f)成分のエチレン・プロピ
レン系共重合体ゴム(1!PR)としてはエチレン拳プ
ロピレン二元共重合体ゴム(EPM)又はエチレン・プ
ロピレン・非共役ジエン三元共重合体ゴム(EPDM)
であって、プロピレン含量(重量)が20〜8oz、好
ましくは25〜50駕、ムーニー粘度ML1+4(10
0℃)が5〜120、好ましくは35〜70、とりわけ
好ましくは40〜60のもので、更にEPD)1ではヨ
ウ素価が20以下のものが好ましい。(f) Ethylene-propylene copolymer rubber Also, the ethylene-propylene copolymer rubber (1!PR) of component (f) that can be used in the present invention is ethylene-propylene binary copolymer rubber (EPM). ) or ethylene/propylene/non-conjugated diene terpolymer rubber (EPDM)
, the propylene content (weight) is 20 to 8 oz, preferably 25 to 50 oz, and the Mooney viscosity is ML1+4 (10
0°C) is 5 to 120, preferably 35 to 70, particularly preferably 40 to 60, and further preferably has an iodine value of 20 or less in EPD)1.
ここでプロピレン含量が20を未満、6oz超過のもの
は組成物の耐衝撃性が不十分であり、ムーニー粘度が5
未満のものは塗装性が劣り、更には成形デラミネーショ
ンが発生し易く、一方、120超過のものは外観(フロ
ーマーク他)、塗装性、塗装光沢変化防止性が劣るので
いずれも好ましくない、ここでムーニー粘度範囲が5〜
120(好ましくは35〜70)であれば、そのEPR
は2種類以上の併用であってもよい0例えば、EPMと
EPDM、高粘度量と低粘度量のブレンドでもよく、そ
の際、粘度範囲外のものを併用しても差し支えない。If the propylene content is less than 20 oz or more than 6 oz, the impact resistance of the composition is insufficient, and the Mooney viscosity is 5 oz.
If it is less than 120, the paintability is poor and mold delamination is likely to occur, while if it is more than 120, the appearance (flow marks, etc.), paintability, and prevention of paint gloss change are poor, so both are unfavorable. Mooney viscosity range is 5~
120 (preferably 35-70), its EPR
For example, a blend of EPM and EPDM, a high viscosity amount and a low viscosity amount may be used, and in this case, it is also possible to use materials outside the viscosity range in combination.
屹立■涜
以上のような(a)〜(f)成分の配合割合は(a)+
(b)+(e)+(f)合計100重量2 (部)に対
して、それぞれ
(a) : (e)及び/又は(f)成分を含むとき4
0〜98重量2、好ましくは50〜95重量t
(e)及び/又は(f)成分を含まないとき70〜99
重量2、好ましくは80〜97重量2(b):1〜30
重量! 、 好* L < t* 3〜20重量2(c
):0.01〜0.5重量部、好ましくは0.03〜0
.3重量部
(d):0.01〜2重量部、好ましくは0.03〜1
重量部
(e)0〜30重量2、好ましくは5〜25重量す(f
)0〜40重量駕、好ましくは5〜35重量2である。The blending ratio of ingredients (a) to (f) as above is (a) +
(b) + (e) + (f) Total 100 weight 2 (parts), when each contains (a): (e) and/or (f) component 4
0-98 weight 2, preferably 50-95 weight t 70-99 when not containing component (e) and/or (f)
Weight 2, preferably 80-97 Weight 2(b): 1-30
weight! , Good * L < t * 3~20 Weight 2 (c
): 0.01 to 0.5 parts by weight, preferably 0.03 to 0
.. 3 parts by weight (d): 0.01 to 2 parts by weight, preferably 0.03 to 1 part by weight
Part by weight (e) 0-30 weight 2, preferably 5-25 weight (f
) 0 to 40 weight units, preferably 5 to 35 weight units.
上記範囲外のものは耐候性が不充分となり、好ましくな
い。If it is outside the above range, the weather resistance will be insufficient, which is not preferable.
そ
本発明の組成物は、上記各成分の外に、本発明の効果を
著しく損わない範囲で、他の付加的配合成分を添加する
ことができる。In addition to the above-mentioned components, the composition of the present invention may contain other additional components as long as the effects of the present invention are not significantly impaired.
それらの付加的配合成分としては、本発明で用いる (
b)成分及び(e)成分以外の処理区は無処理の無機又
は有機フィラー、本発明で用いる (c)成分以外の各
種酸化防止剤、本発明で用いる (f)成分のEPR以
外のゴム又体ラテックス成分、本発明で用いる (a)
成分以外の熱可塑性樹脂又は熱硬化性樹脂、その他、顔
料1分散剤、架橋剤、発泡剤、難燃剤、核材、帯電防止
剤、塗装性改良剤がある。ここで高密度ポリエチレンの
2〜5重量2を添加することは、塗装性や外観の向上に
有効的である。Those additional ingredients used in the present invention include (
Treatment areas other than component b) and component (e) include untreated inorganic or organic fillers, various antioxidants other than component (c) used in the present invention, and rubbers other than EPR of component (f) used in the present invention. Body latex component used in the present invention (a)
In addition to the components, there are thermoplastic resins or thermosetting resins, pigment dispersants, crosslinking agents, foaming agents, flame retardants, core materials, antistatic agents, and paintability improvers. Adding 2 to 5 parts by weight of high-density polyethylene is effective for improving paintability and appearance.
糺り上皿11
本発明の樹脂組成物は、−軸押出機、二軸押出機、バン
バリーミキサ−、ロール、ブラベンダープラストグラフ
、ニーグー等の通常の混線機を用いて製造することがで
きる0通常は押出機等で混練してベレット状のコンパウ
ンドにした後、加工に供するが、特殊な場合は、前記6
成分を直接各種成形機に供給し、成形機内で混練しなが
ら成形することもできる。また、予めフィラーやEPR
を(必要に応じて各種添加剤と共に)高濃度に混練して
マスターバッチとし、それを別途プロピレン重合体等で
希釈しながらブレンドコンパウンディングしたり、成形
したりすることもできる。Squeezing plate 11 The resin composition of the present invention can be produced using a conventional mixing machine such as a screw extruder, twin screw extruder, Banbury mixer, roll, Brabender Plastograph, Nigoo, etc. Usually, it is kneaded with an extruder etc. to form a pellet-shaped compound and then subjected to processing, but in special cases,
It is also possible to directly supply the components to various molding machines and mold them while kneading them within the molding machine. In addition, filler or EPR may be used in advance.
It is also possible to knead the mixture to a high concentration (with various additives as necessary) to form a masterbatch, which can then be separately diluted with a propylene polymer or the like for blend compounding or molding.
本発明の樹脂組成物の成形加工法としては特に限定され
るものではなく、押出成形、中空成形、射出成形、シー
ト成形、熟成形、回転成形、積層成形等があり、これら
成形法の違いを問わず、いずれの成形品においても本発
明の樹脂組成物の効果は発揮されるが、なかでも射出成
形による成形が最も適している。The molding method for the resin composition of the present invention is not particularly limited, and includes extrusion molding, blow molding, injection molding, sheet molding, aging molding, rotational molding, and lamination molding. Although the effects of the resin composition of the present invention can be exhibited in any molded product, molding by injection molding is the most suitable.
肚差
このようにして得られた本発明の繊維強化樹脂組成物は
、従来のチタン酸カリウム系フィラー補強樹脂組成物に
は無い耐候性を有する外、優れた高温時における寸法安
定性、高度な物性バランス(剛性〜低温衝撃強度)、良
好な外観、成形加工性を有し、また、ヒケ、反りも目立
たず、印刷性や接着性、耐傷性も良好で、ウェルドライ
ンも目立ち難く、ウェルド強度や引張伸び性も良好であ
り、特に長時問屋外 露される用途、例えば自動車外装
部品用として高度な適性を有するものである。The fiber-reinforced resin composition of the present invention thus obtained has weather resistance not found in conventional potassium titanate filler-reinforced resin compositions, as well as excellent dimensional stability at high temperatures and high It has a good balance of physical properties (rigidity to low-temperature impact strength), good appearance, and moldability.In addition, sink marks and warping are not noticeable, and printability, adhesion, and scratch resistance are good, and weld lines are not noticeable and weld strength. It also has good tensile elongation and is highly suitable for applications that are exposed to the outdoors for long periods of time, such as automotive exterior parts.
以下に実施例を示して本発明を具体的に説明する。ここ
で用いた各種測定法は次の通りである。EXAMPLES The present invention will be specifically described below with reference to Examples. The various measurement methods used here are as follows.
(1)耐候性:
射出成形 (多機製作所製インラインスクリュー型射出
成形機(230℃))にて100X100×2麿層のシ
ートを成形し、該シートをスガ試験機社製すンシャイン
型つェイザーメーターを用い、83℃、雨ありの条件で
1800時間照射処理し、そのシートの表面外観状態を
拡大鏡にて観察した。(1) Weather resistance: A sheet of 100 x 100 x 2 layers was molded using injection molding (an in-line screw injection molding machine (230°C) manufactured by Taki Seisakusho), and the sheet was molded using a sunshine type molding machine manufactured by Suga Test Instruments Co., Ltd. Using an isermeter, the sheet was irradiated for 1800 hours at 83° C. in the presence of rain, and the surface appearance of the sheet was observed using a magnifying glass.
(2)寸法安定性: ASTM−0996に準じて線膨
張係数を測定、但し、温度範囲は23℃〜80℃で、そ
の試片は100 X 100 X 3mmの射出成形シ
ートからの切出片(80,×10×3Il■)を用いた
。また、測定値は樹脂の流れ方向(タテ)のものである
。(2) Dimensional stability: The coefficient of linear expansion was measured according to ASTM-0996, however, the temperature range was 23°C to 80°C. 80, × 10 × 3 Il■) was used. Furthermore, the measured values are in the flow direction (vertical) of the resin.
(3)成形反り性: 200X 200■■厚の円板
状試片(グー) :1mm径のピンポイント)を射出成
形し、これを23℃、50%RHの雰囲気で72時間放
置後、それを定盤上に静置し、その最大変形量を成形反
り量としてノギスで測定した。(3) Molding warpage resistance: A 200X 200■■ thick disc-shaped specimen (Goo: 1mm diameter pinpoint) was injection molded, and after being left in an atmosphere of 23°C and 50% RH for 72 hours, it was was placed on a surface plate, and the maximum amount of deformation was measured using calipers as the amount of molding warpage.
(4)剛性: JIS−に7203準拠。(4) Rigidity: Compliant with JIS-7203.
測定温度23℃、試片は上記射出成形による。The measurement temperature was 23° C., and the specimens were injection molded as described above.
(5)衝撃強度(アイゾツト) : JIS−に71
10準拠。(5) Impact strength (Izot): JIS-71
10 compliant.
測定温度−30℃、試片は同上。Measurement temperature was -30°C, and the specimen was the same as above.
以下の実施例および比較例で用いた(a)〜(6)成分
及びその性状を以下に示す。The components (a) to (6) used in the following Examples and Comparative Examples and their properties are shown below.
(a)成分:
プロピレン・エチレン−ブロック共重合体(b)成分:
チタン酸カリウムm維
平均繊維直径: 0.3IL鳳、
平均アスペクト比:12、
pH(水中分散)=8
(C)成分ニリン化合物
C−1= ビス(2,4−ジ−t−ブチルフェニル)
ペンタエリス、リドールージホスファイト
C−2: テトラキス(2,4−ジ−t−ブチルフエ
ニ(f)成分(EPR)
一/−ノ 1.−ノAJ! 、 つり4&凰!
+−−−軒# 、 ■ル)−4,4°−ビフェニレンホ
スフォナイトC−3: )リス(2,4−ジ−t−ブ
チルフェニル)ボスファイト
(d)成分(光安定剤)
ヒンダードアミン系
D−1: ビス−2,2,8,8−テトラメチル−4
−ピペリジルセバケート
D−2= ポリ[(8−(1,1,3,3−テトラメ
チルブチル)イミノ−1,3,5−トリアジン−2,4
−ジイル) ((2、2,8,8−テトラメチル−4−
ピペリジル)イミノ)へキサメチレン((2,2゜6.
6−テトラメチル−4−ピペリジル)イミノ)】
ベンゾエート系
D−3: 2,4−ジ−t−ブチルフェニル−3,5
−ジー七−ブチルー4−ヒドロキシベンゾエート
(e)成分(タルク)
/ ” シv/ −t2 里、”HLBLk 、4”
l?011L 、”実施例1〜4及び比較例1〜
5
上記示した各成分を第1表に示す通りの配合割合で配合
し、その配合物100重量部当り、更にテトラキス[メ
チレン−3−(3°−5”−ジ−t−ブチル−4°−ヒ
ドロキシフェニル)プロピオネート] メタン0゜10
重量部、2−(2’−ヒドロキシ−3°−t−ブチル−
5°−メチルフェニル
重量部およびカーボンブラックと酸化チタンを主成分と
した灰色顔料3.5重量部を配合し、用田製作所製スー
パーミキサーにて2分聞易合した後、FCM二軸混線機
にて230℃で混練造粒して組成物ペレットを得た.こ
の後、スクリューインライン射出成形機にて230℃で
試片を成形し,その寸法安定性、耐候性、剛性、衝撃強
度を評価した.結果は第1表に示す。Component (a): Propylene/ethylene block copolymer (b) Component:
Potassium titanate m-fiber average fiber diameter: 0.3IL, average aspect ratio: 12, pH (dispersed in water) = 8 (C) component niline compound C-1 = bis(2,4-di-t-butylphenyl)
Pentaeris, ridoru diphosphite C-2: Tetrakis (2,4-di-t-butylpheni(f) component (EPR) 1/-no 1.-no AJ!, Tsuri 4&凰!
+--- Eaves #, ■ Le) -4,4°-biphenylene phosphonite C-3: ) Lis(2,4-di-t-butylphenyl)bosphite (d) component (light stabilizer) Hindered amine System D-1: Bis-2,2,8,8-tetramethyl-4
-piperidyl sebacate D-2= poly[(8-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4
-diyl) ((2,2,8,8-tetramethyl-4-
piperidyl)imino)hexamethylene((2,2゜6.
6-tetramethyl-4-piperidyl)imino)] Benzoate D-3: 2,4-di-t-butylphenyl-3,5
-Di-7-butyl-4-hydroxybenzoate (e) component (talc) / ``Shiv/-t2ri, ``HLBLk, 4''
l? 011L, “Examples 1 to 4 and Comparative Examples 1 to
5 The above-mentioned components were blended in the proportions shown in Table 1, and per 100 parts by weight of the blend, tetrakis[methylene-3-(3°-5”-di-t-butyl-4° -Hydroxyphenyl)propionate] Methane 0°10
Parts by weight, 2-(2'-hydroxy-3°-t-butyl-
5 parts by weight of methylphenyl and 3.5 parts by weight of a gray pigment mainly composed of carbon black and titanium oxide were blended and mixed for 2 minutes in a super mixer made by Yoda Seisakusho, and then mixed in an FCM twin-shaft mixer. The mixture was kneaded and granulated at 230°C to obtain composition pellets. Thereafter, specimens were molded at 230°C using a screw in-line injection molding machine, and their dimensional stability, weather resistance, rigidity, and impact strength were evaluated. The results are shown in Table 1.
その結果、実施例1〜4の組成物は良好な品質バランス
を示したのに対し、比較例1〜5は品質バランスが不良
であった。As a result, the compositions of Examples 1 to 4 showed a good quality balance, whereas the compositions of Comparative Examples 1 to 5 had a poor quality balance.
また、比較例5に示す様にチタン酸カリウム繊維を含ま
ない樹脂組成物においては寸法安定性や剛性の点におい
て問題があることが明らかである。Furthermore, as shown in Comparative Example 5, it is clear that resin compositions that do not contain potassium titanate fibers have problems in terms of dimensional stability and rigidity.
本発明の繊維補強樹脂組成物は、耐候性が特に優れ、さ
らに高温度での寸法安定性も良好であるので車両の外装
部品等素材として優れたものであり、工業的に極めて有
用なものである。The fiber-reinforced resin composition of the present invention has particularly excellent weather resistance and also has good dimensional stability at high temperatures, so it is excellent as a material for vehicle exterior parts and is extremely useful industrially. be.
Claims (1)
とする繊維補強樹脂組成物。 (a)結晶性プロピレン系重合体: (e)成分及び/又は(f)成分を含むときは(a)、
(b)、(e)び(f)成分の合計量に対して40〜9
8重量%であり、(e)成分及び(f)成分を含まない
ときは(a)及び(b)成分の合計量に対して70〜9
9重量% (b)平均繊維径が0.1〜1μmで、かつ、平均アス
ペクト比が5以上のチタン酸カリウム 繊維: (a)、(b)、(e)及び(f)成分の合計量に対し
て30〜1重量% (c)一般式 ▲数式、化学式、表等があります▼( I ) 及び/又は ▲数式、化学式、表等があります▼(II) (式中、R^1は炭素数8〜30のアルキル基、シクロ
アルキル基又は芳香族の基であり、 R^2は炭素数1〜30のアルキル基、シクロアルキル
基、又は芳香族の基であり、R^1、R^2はともに同
一化合物中で異なっていてもよい、R^3はt−ブチル
基である。) で表わされる構造を有するリン化合物: (a)、(b)、(e)及び(f)成分の合計量 10
0重量部に対して0.01〜0.5重量部 (d)ヒンダ−ドアミン系光安定剤: (a)、(b)、(e)及び(f)成分の合計量 10
0重量部に対して0.01〜2重量部 (e)平均粒径が5μm以下のタルク: 0〜30重量% (f)プロピレン含量が20〜60重量%で、ムーニー
粘度ML_1_+_4(100℃)が5〜120のエチ
レン・プロピレン共重合体ゴム: 0〜40重量%。(1) A fiber-reinforced resin composition comprising the following components (a) to (f). (a) Crystalline propylene polymer: (a) when containing component (e) and/or component (f),
40 to 9 for the total amount of components (b), (e) and (f)
8% by weight, and when component (e) and (f) are not included, it is 70 to 9% based on the total amount of components (a) and (b).
9% by weight (b) Potassium titanate fibers with an average fiber diameter of 0.1 to 1 μm and an average aspect ratio of 5 or more: Total amount of components (a), (b), (e) and (f) (c) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^1 is It is an alkyl group, cycloalkyl group, or aromatic group having 8 to 30 carbon atoms, R^2 is an alkyl group, cycloalkyl group, or aromatic group having 1 to 30 carbon atoms, and R^1, R Both ^2 may be different in the same compound, R^3 is a t-butyl group.) Phosphorus compounds having the structure represented by: (a), (b), (e) and (f) Total amount of ingredients 10
0.01 to 0.5 parts by weight relative to 0 parts by weight (d) Hindered amine light stabilizer: Total amount of components (a), (b), (e) and (f) 10
0.01 to 2 parts by weight relative to 0 parts by weight (e) Talc with an average particle diameter of 5 μm or less: 0 to 30% by weight (f) Propylene content of 20 to 60% by weight, Mooney viscosity ML_1_+_4 (100°C) Ethylene-propylene copolymer rubber having a weight of 5 to 120: 0 to 40% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11827587A JPS63284241A (en) | 1987-05-15 | 1987-05-15 | Fiber-reinforced resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11827587A JPS63284241A (en) | 1987-05-15 | 1987-05-15 | Fiber-reinforced resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63284241A true JPS63284241A (en) | 1988-11-21 |
Family
ID=14732617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11827587A Pending JPS63284241A (en) | 1987-05-15 | 1987-05-15 | Fiber-reinforced resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63284241A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04139252A (en) * | 1990-09-28 | 1992-05-13 | Mitsubishi Petrochem Co Ltd | Propylene resin composition |
JPH1134097A (en) * | 1997-07-15 | 1999-02-09 | Chisso Corp | Outer door handle molded product composed of long fiber glass reinforced propylene resin |
WO2012132537A1 (en) * | 2011-03-31 | 2012-10-04 | ゲイツ・ユニッタ・アジア株式会社 | Friction transmission belt |
JP2017149852A (en) * | 2016-02-25 | 2017-08-31 | 株式会社Adeka | Polyolefin resin composition and automotive interior and exterior materials prepared therewith |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6169848A (en) * | 1984-09-13 | 1986-04-10 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
JPS61255953A (en) * | 1985-05-09 | 1986-11-13 | Mitsubishi Petrochem Co Ltd | Pigmented propylene polymer composition having good weather resistance |
JPS624733A (en) * | 1985-07-02 | 1987-01-10 | Mitsubishi Petrochem Co Ltd | Inorganic filler-containing polyolefin composition |
JPS6291545A (en) * | 1985-10-17 | 1987-04-27 | Idemitsu Petrochem Co Ltd | Polyolefin resin composition |
-
1987
- 1987-05-15 JP JP11827587A patent/JPS63284241A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6169848A (en) * | 1984-09-13 | 1986-04-10 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
JPS61255953A (en) * | 1985-05-09 | 1986-11-13 | Mitsubishi Petrochem Co Ltd | Pigmented propylene polymer composition having good weather resistance |
JPS624733A (en) * | 1985-07-02 | 1987-01-10 | Mitsubishi Petrochem Co Ltd | Inorganic filler-containing polyolefin composition |
JPS6291545A (en) * | 1985-10-17 | 1987-04-27 | Idemitsu Petrochem Co Ltd | Polyolefin resin composition |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04139252A (en) * | 1990-09-28 | 1992-05-13 | Mitsubishi Petrochem Co Ltd | Propylene resin composition |
JPH1134097A (en) * | 1997-07-15 | 1999-02-09 | Chisso Corp | Outer door handle molded product composed of long fiber glass reinforced propylene resin |
WO2012132537A1 (en) * | 2011-03-31 | 2012-10-04 | ゲイツ・ユニッタ・アジア株式会社 | Friction transmission belt |
JP2012215212A (en) * | 2011-03-31 | 2012-11-08 | Gates Unitta Asia Co | Friction transmission belt |
US9194458B2 (en) | 2011-03-31 | 2015-11-24 | Gates Corporation | Friction transmission belt |
JP2017149852A (en) * | 2016-02-25 | 2017-08-31 | 株式会社Adeka | Polyolefin resin composition and automotive interior and exterior materials prepared therewith |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE19821937B4 (en) | Polypropylene-based resin composition, injection-molded article thereof, and use of a polypropylene-based resin composition for producing molded articles | |
JP3352282B2 (en) | Thermoplastic resin composition and injection molded article thereof | |
JPH04372637A (en) | Thermoplastic polymer composition | |
US20110245387A1 (en) | Method for preparing rubber/nanoclay masterbatches, and method for preparing high strength, high impact-resistant polypropylene/nanoclay/rubber composites using same | |
JP2006321914A (en) | Polypropylene resin composition for exterior automotive trim and exterior automotive trim using the same | |
JP3347289B2 (en) | Propylene resin composition | |
JP3270322B2 (en) | Thermoplastic resin composition with improved mold contamination | |
DE69305864T2 (en) | LOW-VISCOSE THERMOPLASTIC POLYOLEFINE | |
JPH0456649A (en) | Automobile bumper made of resin | |
JP3117850B2 (en) | Thermoplastic polymer composition | |
JP2000026697A (en) | Propylene resin composition | |
GB2213156A (en) | Filler reinforced plastic composition | |
DE102018211722B4 (en) | Polypropylene composite resin composition with silylated microfibrillated cellulose, method for producing a vehicle interior material using the same, and vehicle pillar garnish using the same | |
JP2003105163A (en) | Polypropylene based resin composition | |
EP0771854A2 (en) | Crystalline thermoplastic resin composition | |
JPS63284241A (en) | Fiber-reinforced resin composition | |
US20040116560A1 (en) | Impact modified thermoplastic olefin compositions | |
JP2007332272A (en) | Propylene-based block copolymer composition for automobile exterior and exterior member for automobile | |
JPH01204946A (en) | Thermoplastic resin composition for automotive bumper | |
US5567759A (en) | Propylene polymer composition | |
DE102017210696B4 (en) | Polyolefin resin composition, polyolefin masterbatch, process for producing a polyolefin masterbatch and article formed therefrom | |
US20020077396A1 (en) | Polypropylene resin composition | |
EP2074156B1 (en) | Compatibilizers for producing nanocomposites, microcomposites and polymer blends and process for obtaining them. | |
JPH0995592A (en) | Polypropylene resin composition | |
JPS63150341A (en) | Fiber-reinforced resin composition |