JPS63178153A - Production of filled propylene polymer composition - Google Patents
Production of filled propylene polymer compositionInfo
- Publication number
- JPS63178153A JPS63178153A JP898787A JP898787A JPS63178153A JP S63178153 A JPS63178153 A JP S63178153A JP 898787 A JP898787 A JP 898787A JP 898787 A JP898787 A JP 898787A JP S63178153 A JPS63178153 A JP S63178153A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- propylene polymer
- inorganic filler
- treated
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011256 inorganic filler Substances 0.000 claims abstract description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 21
- 239000010445 mica Substances 0.000 claims abstract description 21
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 21
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000004898 kneading Methods 0.000 claims abstract description 3
- -1 silane compound Chemical class 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 3
- 229920005604 random copolymer Polymers 0.000 abstract description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RMEHEUYHWNVIMN-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)but-3-enoic acid Chemical compound CC(C)(C)C1=CC(C(C=C)C(O)=O)=CC(C(C)(C)C)=C1O RMEHEUYHWNVIMN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KCJAIHQXOQUWTI-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropan-1-amine Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)CCCN KCJAIHQXOQUWTI-UHFFFAOYSA-N 0.000 description 1
- TVTRDGVFIXILMY-UHFFFAOYSA-N 4-triethoxysilylaniline Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(N)C=C1 TVTRDGVFIXILMY-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- WWOUVFNLIOVAFQ-UHFFFAOYSA-N C(CC)(=O)OC1=CC(=C(C(=C1)C(C=C)(C)C)O)C(C)(C)C Chemical compound C(CC)(=O)OC1=CC(=C(C(=C1)C(C=C)(C)C)O)C(C)(C)C WWOUVFNLIOVAFQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- GVVPGTZRZFNKDS-JXMROGBWSA-N geranyl diphosphate Chemical compound CC(C)=CCC\C(C)=C\CO[P@](O)(=O)OP(O)(O)=O GVVPGTZRZFNKDS-JXMROGBWSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- LHWGFUNMNGDUOR-UHFFFAOYSA-N n'-[3-[dimethoxy(2-phenylethyl)silyl]oxypropyl]ethane-1,2-diamine Chemical compound NCCNCCCO[Si](OC)(OC)CCC1=CC=CC=C1 LHWGFUNMNGDUOR-UHFFFAOYSA-N 0.000 description 1
- JJJXKZYKNMHSMY-UHFFFAOYSA-N n'-[3-[tris(2-ethylhexoxy)silyl]propyl]ethane-1,2-diamine Chemical compound CCCCC(CC)CO[Si](CCCNCCN)(OCC(CC)CCCC)OCC(CC)CCCC JJJXKZYKNMHSMY-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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、フィラー含有プロピレン重合体組成物の製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing filler-containing propylene polymer compositions.
〔従来の技術］
プロピレン重合体は各種無機質フィラーを充填すること
によって剛性、耐熱性、寸法安定性等の機械的及び熱的
性質を改善することはよく知られている。ところが、単
に無機質フィラーをプロピレン重合体に充填するだけで
は、衝撃強度、引張り強度等の機械的強度の低下が著し
く、更に、射出成形品の外観も悪く実用に耐えるものは
得られない。[Prior Art] It is well known that the mechanical and thermal properties of propylene polymers, such as rigidity, heat resistance, and dimensional stability, can be improved by filling them with various inorganic fillers. However, simply filling a propylene polymer with an inorganic filler causes a significant drop in mechanical strength such as impact strength and tensile strength, and furthermore, the appearance of the injection molded product is poor, making it impossible to obtain a product that can be used in practical use.
これらの問題を解決するため、プロピレン重合体に予め
不飽和カルボン酸で変性したプロピレン重合体と無機質
フィラーを配合し、加熱溶融混練し、マトリックスレジ
ンと無機質フィラーの間の接着性を向上させることによ
って機械的な強度、剛性、耐熱性に優れた組成物を製造
することが知られている（例えば、特開昭５６−１４９
４５２号公報、同５Ｂ −０４５２４９号公報）、シか
しながら、この方法では得られる組成物の衝撃強度はほ
とんど改善されない。In order to solve these problems, we blended a propylene polymer modified with an unsaturated carboxylic acid with an inorganic filler into a propylene polymer, heated and melt-kneaded it, and improved the adhesion between the matrix resin and the inorganic filler. It is known to produce compositions with excellent mechanical strength, rigidity, and heat resistance (for example, Japanese Patent Laid-Open No. 56-149
However, this method hardly improves the impact strength of the composition obtained.
一方、予め不飽和カルボン酸で変性したプロピレン重合
体と予め有機シラン化合物で表面処理した無機質フィラ
ーをプロピレン重合体に配合し溶融加熱混練する方法が
知られており（特開昭５９−０６４６４７号公報）、こ
の方法で得られる組成物は、剛性、耐熱性のみならず耐
衝撃性も向上した優れた物性の組成物が得られる極めて
優れた方法である。On the other hand, a method is known in which a propylene polymer modified in advance with an unsaturated carboxylic acid and an inorganic filler whose surface has been previously treated with an organic silane compound are blended into the propylene polymer and then melted and kneaded (see JP-A-59-064647). ), the composition obtained by this method is an extremely excellent method that can yield a composition with excellent physical properties that have improved not only rigidity and heat resistance but also impact resistance.
しかしながら、上記組成物を製造するに際して用いる不
飽和カルボン酸変性プロピレン重合体を製造するために
は、プロピレン重合体と不飽和カルボン酸とを有機過酸
化物の存在下に有機溶剤中で反応させたり、バンバリー
ミキサ−２押出機などの中で溶融加熱混練する必要があ
るため、不飽和カルボン酸変性プロピレン重合体は非常
に高価であり、従って得られるフィラー含有プロピレン
重合体組成物も高価なものになってしまうという問題が
ある。However, in order to produce the unsaturated carboxylic acid-modified propylene polymer used in producing the above composition, it is necessary to react the propylene polymer and the unsaturated carboxylic acid in an organic solvent in the presence of an organic peroxide. The unsaturated carboxylic acid-modified propylene polymer is very expensive because it needs to be melted and heated and kneaded in a Banbury Mixer 2 extruder or the like, and therefore the resulting filler-containing propylene polymer composition is also expensive. The problem is that it becomes.
また、上記溶媒中で製造する前者方法によって製造され
る不飽和カルボン酸変性プロピレン重合体は分子量が低
く、無機質フィラーとプロピレン重合体との間の接着性
を向上させる為に配合量を増加させるに従って、分子量
の低下による物性低下を生じるという問題がある。In addition, the unsaturated carboxylic acid-modified propylene polymer produced by the former method produced in the above-mentioned solvent has a low molecular weight, and in order to improve the adhesion between the inorganic filler and the propylene polymer, the amount of the unsaturated carboxylic acid-modified propylene polymer produced by the former method is increased. However, there is a problem in that physical properties deteriorate due to a decrease in molecular weight.
一方、組成物を製造するのに市場で入手できる造粒され
た不飽和カルボン酸変性プロピレン重合体を用いると配
合時の混合段階で無機質フィラーが分散不良となりやす
く、マトリックスレジンと無ｅ！ｌ質フィラーとの間の
均一な接着状態を得ることが難しくなり、補強効果が十
分でないという問題もある。On the other hand, if a commercially available granulated unsaturated carboxylic acid-modified propylene polymer is used to manufacture the composition, the inorganic filler tends to be poorly dispersed during the mixing stage during compounding, and the matrix resin and the e-free! There is also the problem that it becomes difficult to obtain a uniform adhesion state with the lubricant filler, and that the reinforcing effect is not sufficient.
本発明者らは上記問題を解決すべく鋭意研究を行い、本
発明を完成するに至った。The present inventors have conducted extensive research to solve the above problems and have completed the present invention.
すなわち、本発明は、不飽和カルボン酸及びその誘導体
から選ばれる単量体０．１〜５重Ｍ部、有機過酸化物０
．０１〜１重量部、プロピレン重合体２０〜９０重量部
及びアミノ基を有する有機シラン化合物で表面処理され
た無機質フィラーを溶融加熱混練処理することを特徴と
するフィラー含存プロピレン重合体組成物の製造法であ
る。That is, the present invention comprises 0.1 to 5 parts by weight of a monomer selected from unsaturated carboxylic acids and derivatives thereof, and 0 parts of organic peroxide.
．． 01 to 1 part by weight, 20 to 90 parts by weight of a propylene polymer, and an inorganic filler surface-treated with an organic silane compound having an amino group. It is the law.
本発明で使用されるプロピレン重合体は、プロピレン単
独重合体、プロピレン−エチレンブロック共重合体、プ
ロピレン−エチレンランダム共重合体等であり、これら
は単独であるいは混合して用いられる。The propylene polymer used in the present invention includes a propylene homopolymer, a propylene-ethylene block copolymer, a propylene-ethylene random copolymer, and the like, and these may be used alone or in combination.
本発明で使用される不飽和カルボン酸として、アクリル
酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸
、メサコン酸、シトラコン酸などが例示され、これらの
誘導体としては酸無水物があげられる。なお、不飽和カ
ルボン酸及びその誘導体から選ばれる単量体（以下、単
に単量体と称す）としては、好ましくは上記不飽和カル
ボン酸およびその誘導体である酸無水物が用いられる。Examples of unsaturated carboxylic acids used in the present invention include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid, and examples of derivatives thereof include acid anhydrides. As the monomer selected from unsaturated carboxylic acids and derivatives thereof (hereinafter simply referred to as monomer), preferably the unsaturated carboxylic acids and acid anhydrides thereof are used.
単量体の使用量としてはプロピレン重合体組成物１００
ｆｆｉ１部に対して０．１〜５重量部、好ましくは０．
１〜３重量部である。単量体の使用量が０．１重量部未
満では無機質フィラーとプロピレン重合体との間の接着
性が低下し、その補強効果が十分でない。また、５重量
部を越えた場合では、未反応単量体が増加し成形品の臭
気、色相悪化等、あるいは単量体の単独重合低分子量成
分の増加により物性の低下を生じる。The amount of monomer used is 100% of the propylene polymer composition.
0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight per part of ffi.
It is 1 to 3 parts by weight. If the amount of the monomer used is less than 0.1 part by weight, the adhesiveness between the inorganic filler and the propylene polymer will decrease, and the reinforcing effect will not be sufficient. If the amount exceeds 5 parts by weight, the amount of unreacted monomer increases, causing odor and deterioration of the hue of the molded product, or deterioration of physical properties due to an increase in homopolymerized low molecular weight components of the monomer.
本発明で使用される有機過酸化物としては、２゜４−ジ
クロロベンゾイルパーオキサイド、ベンゾイルパーオキ
サイド、１．１−ジ（ｔ−ブチルパーオキシ）３．３．
５− ）リメチルシクロヘキサン、ジクミルパーオキサ
イド、α、α゛−ビス（ｔ−ブチルパーオキシジイソプ
ロピル）ベンゼン、ｔ−ブチルパーオキシクメン等が挙
げられる。The organic peroxides used in the present invention include 2.4-dichlorobenzoyl peroxide, benzoyl peroxide, 1.1-di(t-butylperoxy)3.3.
5-) Limethylcyclohexane, dicumyl peroxide, α,α゛-bis(t-butylperoxydiisopropyl)benzene, t-butylperoxycumene, and the like.
有機過酸化物の使用量としては、プロピレン重合体組成
物１００重量部に対して０．０１〜１重量部が好適であ
る。有機過酸化物の使用量が、０．０１重量部未満では
単量体のグラフト率が低下し十分な補強効果が得られな
い。また、１重１部を越えた場合ではプロピレン重合体
の劣化や単量体の単独重合低分子量成分の増加により物
性が低下する。The amount of organic peroxide used is preferably 0.01 to 1 part by weight per 100 parts by weight of the propylene polymer composition. If the amount of organic peroxide used is less than 0.01 part by weight, the monomer grafting rate will decrease and a sufficient reinforcing effect will not be obtained. Furthermore, if the amount exceeds 1 part by weight, the physical properties will deteriorate due to deterioration of the propylene polymer and an increase in the homopolymerized low molecular weight component of the monomer.
本発明で使用される無機質フィラーとしては、炭酸カル
シウム、タルク、クレー、ケイ酸カルシウム、硫酸カル
シウム、亜硫酸カルシウム、マイカ、ガラス繊維等が挙
げられる。Examples of the inorganic filler used in the present invention include calcium carbonate, talc, clay, calcium silicate, calcium sulfate, calcium sulfite, mica, and glass fiber.
これらの中でも高アスペクト比であるマイカが補強効果
も高く、等方性であり好適である。ここでマイカとして
は、白マイカ、ソーダマイカ、環マイカ、金マイカ、セ
リサイト等であり、特に好ましくは白マイカ、金マイカ
である。Among these, mica, which has a high aspect ratio, is preferred because it has a high reinforcing effect and is isotropic. Examples of the mica include white mica, soda mica, ring mica, gold mica, and sericite, with white mica and gold mica being particularly preferred.
本発明で使用されるアミノ基を有する有機シラン化合物
としては、４−アミノブチルトリエトキシシラン、（ア
ミノエチル−アミノエチル）フェネチルトリメトキシシ
ラン、Ｎ−（２−アミノエチル）−３−アミノプロピル
メチルジメトキシシラン、Ｎ−（２−アミノエチル）−
３−アミノプロピルトリス（２−エチルヘキソキシ）シ
ラン、ｐ−アミノフェニルトリエトキシシラン、３−ア
ミノプロピルメチルジェトキシシラン、３−アミノプロ
ピルトリエトキシシラン、３−アミノプロピルトリメト
キシシラン、３−アミノプロピルトリス（トリメチルシ
ロキシ）シラン、Ｎ−（２−アミノエチル）−３−アミ
ノプロピルトリメトキシシラン等である。Examples of the organic silane compound having an amino group used in the present invention include 4-aminobutyltriethoxysilane, (aminoethyl-aminoethyl)phenethyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyl. Dimethoxysilane, N-(2-aminoethyl)-
3-aminopropyltris(2-ethylhexoxy)silane, p-aminophenyltriethoxysilane, 3-aminopropylmethyljethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris (trimethylsiloxy)silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and the like.
本発明に於いて無機質フィラーは予め上述のアミノ基を
有する有機シラン化合物で表面処理して用いられる。表
面処理する方法としては、ヘンシェルミキサー、リボン
ブレンダー等で強制撹ｆｌＬでいるところに、アミノ基
を有する有機シラン化合物を直接または低級アルコール
もしくは水で希釈して添加する。あるいは無機質フィラ
ーを低級アルコールもしくは水に分散させスラリー状態
としたのち、有機シラン化合物を直接または低級アルコ
ールもしくは水で希釈したものを添加し、撹拌ののち、
沈澱分離し乾燥する。これらの方法によって無機質フィ
ラー表面に均一に処理することができる。In the present invention, the inorganic filler is used after being surface-treated with the above-mentioned organic silane compound having an amino group. As a method for surface treatment, an organic silane compound having an amino group is added directly or diluted with a lower alcohol or water to the surface under forced stirring using a Henschel mixer, a ribbon blender, or the like. Alternatively, after dispersing the inorganic filler in lower alcohol or water to form a slurry, add the organic silane compound directly or diluted with lower alcohol or water, and after stirring,
Separate the precipitate and dry. By these methods, the surface of the inorganic filler can be uniformly treated.
本発明では上述の各成分の混合方法については特に制限
はなく、単量体、有機過酸化物、プロピレン重合体の３
者を予め混合し、次いで無１ａ質フイラーを加え混合す
ると分散が良好となり、得られる組成物の物性は良好で
ある。具体的には、プロピレン重合体と有機溶剤で溶解
した単量体と有機過酸化物をヘンシェルミキサー、リボ
ンブレンダー等を使用して均一に混合し、プロピレン重
合体表面に単量体と有機過酸化物を均一に付着させ、次
いで表面処理された無機質フィラーを加え再び均一に混
合し溶融加熱混合処理する。また、加熱混練機として押
出機を用いるならば、プロピレン重合体、表面処理され
た無機質フィラーと有機過酸化物をヘンシェルミキサー
、リボンプレンダー等で均一に混合したのち押出機に直
接単量体を供給しながら造粒する方法等が例示できる。In the present invention, there is no particular restriction on the method of mixing the above-mentioned components, and the three components are monomer, organic peroxide, and propylene polymer.
By pre-mixing the filler and then adding and mixing the non-la la filler, the dispersion is good and the resulting composition has good physical properties. Specifically, a propylene polymer, a monomer dissolved in an organic solvent, and an organic peroxide are uniformly mixed using a Henschel mixer, a ribbon blender, etc., and the monomer and organic peroxide are coated on the surface of the propylene polymer. The materials are uniformly adhered, and then the surface-treated inorganic filler is added and mixed uniformly again, followed by melting, heating, and mixing treatment. If an extruder is used as a heating kneader, the propylene polymer, surface-treated inorganic filler, and organic peroxide are uniformly mixed in a Henschel mixer, ribbon blender, etc., and then the monomers are directly added to the extruder. Examples include a method of granulating while feeding.
混練機としてはバンバリーミキサ−、ロール、ニーダ−
が例示でき、押出機としては単軸押出機の使用も可能で
ある。Kneading machines include Banbury mixer, rolls, and kneaders.
For example, a single screw extruder can be used as the extruder.
本発明においては、必要に応じて適宜、公知の種々の酸
化防止剤、中和剤、紫外線吸収剤、静電防止剤、造核剤
等の各種添加剤を加え、耐候性等の物性を改良すること
はもちろん可能である。In the present invention, various known additives such as various antioxidants, neutralizers, ultraviolet absorbers, antistatic agents, and nucleating agents are added as necessary to improve physical properties such as weather resistance. Of course it is possible.
以下、実施例にて本発明を具体的に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
エチレン含量が８．０重量％で、メルトフローインデッ
クスが１０．０ｇ／１０＋ｍｉｎであるプロピレン−エ
チレンブロック共重合体１００重量部に、アセトンに溶
解した無水マレイン酸０．５重量部、ベンゾイルパーオ
キサイド０．１重量部、及び安定剤としてテトラキス〔
メチレン−（３，５−ジ−ｔ−ブチル−４−ヒドロキシ
フェニル）プロピオネート１７２７０，１重量部、水酸
化マグネシウム０．１重量部とステアリン酸カルシウム
０．０５重量部を配合し、ヘンシェルミキサーで均一に
混合した。Example 1 To 100 parts by weight of a propylene-ethylene block copolymer having an ethylene content of 8.0% by weight and a melt flow index of 10.0 g/10+min, 0.5 parts by weight of maleic anhydride dissolved in acetone and benzoyl 0.1 part by weight of peroxide and tetrakis as a stabilizer
Blend 1 part by weight of methylene-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 0.1 part by weight of magnesium hydroxide, and 0.05 part by weight of calcium stearate, and mix uniformly with a Henschel mixer. Mixed.
更に、上記混合物７０重量部に、白マイカ（クラ１θ層
製、クラライトマイカ３００ｗ）を水−エタノール中で
３−アミノプロピルトリエトキシシランで処理し、十分
乾燥して得られた表面処理された白マイカ３０重量部を
加え均一に混合した。Furthermore, 70 parts by weight of the above mixture was treated with white mica (Kura 1θ Layer Co., Ltd., Clarite Mica 300w) in water-ethanol with 3-aminopropyltriethoxysilane, and thoroughly dried to obtain a surface-treated product. 30 parts by weight of white mica was added and mixed uniformly.
この混合物をスクリュー径４５ＩＩ１１のベント付二軸
押出機で２４０’Ｃの温度で混練し造粒した。This mixture was kneaded and granulated using a vented twin-screw extruder with a screw diameter of 45II11 at a temperature of 240'C.
得られたペレットを射出成形機を用いて各種試験片を作
製し、各種物性試験を行った。Various test pieces were prepared from the obtained pellets using an injection molding machine, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
実施例２
実施例１で用いたと同一のエチレン−プロピレンブロッ
ク共重合体１００重量部に、アセトンに溶解した無水マ
レイン酸０．７重量部、ペンゾイルバ−オキサイド０．
１５重量部、及び安定剤としてテトラキス〔メチレン−
（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０．７重量部、水酸化マグネシ
ウム０．７重量部上ステアリン酸カルシウム０．０５重
量部を配合し、ヘンシェルミキサーで均一に混合した。Example 2 To 100 parts by weight of the same ethylene-propylene block copolymer used in Example 1, 0.7 parts by weight of maleic anhydride and 0.7 parts by weight of penzoyl peroxide dissolved in acetone were added.
15 parts by weight, and tetrakis[methylene-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] 0.7 parts by weight of methane, 0.7 parts by weight of magnesium hydroxide, and 0.05 parts by weight of calcium stearate were mixed uniformly using a Henschel mixer.
更に、上記混合物６０重量部に、実施例１と同一の表面
処理された白マイカ４０重量部を加え、均一に混合した
。Further, 40 parts by weight of the same surface-treated white mica as in Example 1 was added to 60 parts by weight of the above mixture, and mixed uniformly.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
実施例３
無水マレイン酸に代えて、アクリル酸０．３重量部を用
いた以外は実施例１と同様にして混合物を得た。Example 3 A mixture was obtained in the same manner as in Example 1 except that 0.3 parts by weight of acrylic acid was used in place of maleic anhydride.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
比較例１
実施例１で用いたと同一のプロピレン−エチレンブロッ
ク共重合体１００重量部に対して無水マレイン成金ｌ
１２．５重量％の無水マレイン酸変性プロピレン重合体
４．５重量部（三井東圧化学■製、ＧＰＰ）及び安定剤
としてテトラキス〔メチレン−（３゜５−ジ−ｔ−ブチ
ル−４−ヒドロキシフェニル）プロピオネートコメタフ
０．１重量部、水酸化マグネシウム０．１重量部とステ
アリン酸カルシウム０．０５重量部を配合し、ヘンシェ
ルミキサーで均一に混合した。更に、上記混合物７０重
量部に、実施例１と同一の表面処理された白マイカ３０
重量部を加え、均一に混合した。Comparative Example 1 Anhydrous maleic alloy was added to 100 parts by weight of the same propylene-ethylene block copolymer used in Example 1.
4.5 parts by weight of 12.5% by weight maleic anhydride-modified propylene polymer (manufactured by Mitsui Toatsu Chemical Co., Ltd., GPP) and tetrakis[methylene-(3゜5-di-t-butyl-4-hydroxy) as a stabilizer. 0.1 part by weight of phenyl)propionate cometaf, 0.1 part by weight of magnesium hydroxide, and 0.05 part by weight of calcium stearate were mixed uniformly using a Henschel mixer. Furthermore, to 70 parts by weight of the above mixture, 30 parts of surface-treated white mica as in Example 1 was added.
Parts by weight were added and mixed uniformly.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
比較例２
実施例１で用いたと同一のプロピレンーエチレンブロッ
ク共重合体１００重量部に、比較例１で用いたと同一の
無水マレイン酸変性プロピレン重合体６．０重量部及び
安定剤としてテトラキス〔メチレン−（３，５−シート
ブチル−４−ヒドロキシフェニル）プロピオネートツメ
タフ０．１１１部、水酸化マグネシウム０．１重量部と
ステアリン酸カルシウム０．０５重量部を配合し、ヘン
シェルミキサーで均一に混合した。更に、上記混合物６
０重量部に、実施例１と同一の表面処理された白マイカ
４０重量部を加え、均一に混合した。Comparative Example 2 100 parts by weight of the same propylene-ethylene block copolymer used in Example 1, 6.0 parts by weight of the same maleic anhydride-modified propylene polymer used in Comparative Example 1, and tetrakis[methylene] as a stabilizer. -(3,5-sheetbutyl-4-hydroxyphenyl)propionate tumetaph 0.111 part, magnesium hydroxide 0.1 part by weight and calcium stearate 0.05 part by weight are blended and mixed uniformly with a Henschel mixer. did. Furthermore, the above mixture 6
To 0 parts by weight, 40 parts by weight of the same surface-treated white mica as in Example 1 was added and mixed uniformly.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
実施例４
無機フィラーとして、白マイカ（クラレ■製、クラライ
トマイカ３００Ｗ）を水−メタノール中でＮ−（２−ア
ミノエチル）−３−アミノプロピルトリメトキシシラン
で処理し、十分乾燥して得られた表面処理された白マイ
カを用いた以外は実施例１と同様にして混合物を得た。Example 4 As an inorganic filler, white mica (Kuraray ■, Clarite Mica 300W) was treated with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in water-methanol and thoroughly dried. A mixture was obtained in the same manner as in Example 1 except that surface-treated white mica was used.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
比較例３
無機フィラーとして、実施例４と同一の表面処理された
白マイカを用いた以外は比較例１と同様にして混合物を
得た。Comparative Example 3 A mixture was obtained in the same manner as in Comparative Example 1, except that the same surface-treated white mica as in Example 4 was used as the inorganic filler.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
実施例５
エチレン含Ｍ９．０重量％で、メルトフローインデック
スが７．５ｇ／１０ｍ１ｎであるプロピレン−エチレン
ブロック共重合体１００重量部に、アセトンで溶解した
無水マレイン酸２重量部とベンゾイルパーオキサイド０
．３重量部、及び安定剤としてテトラキス〔メチレン−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオネートコメタフ０．２重量部、水酸化マグネシ
ウム０．７Ｊｌｉｆｆｉ部とステアリン酸カルシウム０
．０５重量部を配合し、ヘンシェルミキサーで均一に混
合した。更に、上記混合物６０重量部に実施例１と同一
の表面処理された白マイカ４０重量部を加え均一に混合
した。Example 5 2 parts by weight of maleic anhydride dissolved in acetone and 0 parts by weight of benzoyl peroxide were dissolved in 100 parts by weight of a propylene-ethylene block copolymer having an ethylene content of 9.0% by weight and a melt flow index of 7.5 g/10ml.
．． 3 parts by weight, and tetrakis[methylene-
(3,5-di-t-butyl-4-hydroxyphenyl)
0.2 parts by weight of propionate cometaf, 0.7 Jliffi parts of magnesium hydroxide and 0 parts of calcium stearate.
．． 05 parts by weight were blended and mixed uniformly using a Henschel mixer. Furthermore, 40 parts by weight of the same surface-treated white mica as in Example 1 was added to 60 parts by weight of the above mixture and mixed uniformly.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
比較例４
実施例５で用いたと同一のプロピレン−エチレンブロッ
ク共重合体１００重量部に比較例１で用いたと同一の無
水マレイン酸変性プロピレン重合体１６重量部、及び安
定剤としてテトラキス−〔メチレン〔メチレン−（３，
５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピ
オネートコメタフ０．１重量部、水酸化マグネシウム０
．１重量部とステアリン酸カルシウム０．０５重量部を
配合し、ヘンシェルミキサーで均一に混合した。更に、
上記混合物６０重量部に実施例１と同一の表面処理され
た白マイカ４０重量部を加え均一に混合した。Comparative Example 4 100 parts by weight of the same propylene-ethylene block copolymer used in Example 5, 16 parts by weight of the same maleic anhydride-modified propylene polymer used in Comparative Example 1, and tetrakis-[methylene] as a stabilizer. methylene-(3,
5-di-t-butyl-4-hydroxyphenyl) propionate cometaf 0.1 part by weight, magnesium hydroxide 0
．． 1 part by weight and 0.05 part by weight of calcium stearate were mixed uniformly using a Henschel mixer. Furthermore,
40 parts by weight of the same surface-treated white mica as in Example 1 was added to 60 parts by weight of the above mixture and mixed uniformly.
この混合物を実施例１と同様に造粒し、各種試験片を作
製し、各種物性試験を行った。This mixture was granulated in the same manner as in Example 1, various test pieces were prepared, and various physical property tests were conducted.
物性試験の結果を第１表に示す。The results of the physical property tests are shown in Table 1.
実施例にも示すように本発明の方法は特別な変性ポリマ
ーを必要とせず、安価に物性の優れた組成物を製造でき
るだけでなく、得られる組成物は従来の方法で得られる
組成物に比較して格段に優れている。したがって、本発
明の工業的価値は極めて高い。As shown in the examples, the method of the present invention does not require a special modified polymer, and not only can a composition with excellent physical properties be produced at a low cost, but also the resulting composition is superior to that obtained by a conventional method. It's much better. Therefore, the industrial value of the present invention is extremely high.
Claims (1)
体０．１〜５重量部、有機過酸化物０．０１〜１重量部
、プロピレン重合体２０〜９０重量部及びアミノ基を有
する有機シラン化合物で表面処理された無機質フィラー
８０〜１０重量部を溶融加熱混練処理することを特徴と
するフィラー含有プロピレン重合体組成物の製造法。 ２、無機質フィラーがマイカである特許請求の範囲第１
項記載のフィラー含有プロピレン重合体組成物の製造法
。[Claims] 1. 0.1 to 5 parts by weight of a monomer selected from unsaturated carboxylic acids and derivatives thereof, 0.01 to 1 part by weight of an organic peroxide, 20 to 90 parts by weight of a propylene polymer, and A method for producing a filler-containing propylene polymer composition, which comprises melting and heating and kneading 80 to 10 parts by weight of an inorganic filler whose surface has been treated with an organic silane compound having an amino group. 2. Claim 1 in which the inorganic filler is mica
A method for producing a filler-containing propylene polymer composition as described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP898787A JPS63178153A (en) | 1987-01-20 | 1987-01-20 | Production of filled propylene polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP898787A JPS63178153A (en) | 1987-01-20 | 1987-01-20 | Production of filled propylene polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63178153A true JPS63178153A (en) | 1988-07-22 |
Family
ID=11708041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP898787A Pending JPS63178153A (en) | 1987-01-20 | 1987-01-20 | Production of filled propylene polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63178153A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02103245A (en) * | 1988-10-12 | 1990-04-16 | Mitsuboshi Belting Ltd | Glass fiber-reinforced polypropylene resin composition |
| CN109679204A (en) * | 2018-11-29 | 2019-04-26 | 柳州市海达新型材料科技有限公司 | The preparation method of the polypropylene material of height filling inorganic filler |
| CN109734995A (en) * | 2018-11-29 | 2019-05-10 | 柳州市海达新型材料科技有限公司 | Soft sense of touch scratch antibacterial polypropylene material |
| CN111607144A (en) * | 2019-02-25 | 2020-09-01 | 住友电气工业株式会社 | Resin composition, inorganic filler, direct current cable, and method for producing direct current cable |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926937A (en) * | 1972-06-30 | 1974-03-09 | ||
| JPS4941096A (en) * | 1972-08-25 | 1974-04-17 | ||
| JPS57172940A (en) * | 1981-04-17 | 1982-10-25 | Matsushita Electric Ind Co Ltd | Polyolefin composition |
| JPS601236A (en) * | 1983-06-20 | 1985-01-07 | Asahi Chem Ind Co Ltd | Production of glass fiber-reinforced polyolefin resin composition |
| JPS60158240A (en) * | 1984-01-30 | 1985-08-19 | Showa Denko Kk | Polypropylene resin composition |
| JPS6381147A (en) * | 1986-09-24 | 1988-04-12 | Mitsuboshi Belting Ltd | Glass fiber reinforced polypropylene resin composition |
-
1987
- 1987-01-20 JP JP898787A patent/JPS63178153A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926937A (en) * | 1972-06-30 | 1974-03-09 | ||
| JPS4941096A (en) * | 1972-08-25 | 1974-04-17 | ||
| JPS57172940A (en) * | 1981-04-17 | 1982-10-25 | Matsushita Electric Ind Co Ltd | Polyolefin composition |
| JPS601236A (en) * | 1983-06-20 | 1985-01-07 | Asahi Chem Ind Co Ltd | Production of glass fiber-reinforced polyolefin resin composition |
| JPS60158240A (en) * | 1984-01-30 | 1985-08-19 | Showa Denko Kk | Polypropylene resin composition |
| JPS6381147A (en) * | 1986-09-24 | 1988-04-12 | Mitsuboshi Belting Ltd | Glass fiber reinforced polypropylene resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02103245A (en) * | 1988-10-12 | 1990-04-16 | Mitsuboshi Belting Ltd | Glass fiber-reinforced polypropylene resin composition |
| CN109679204A (en) * | 2018-11-29 | 2019-04-26 | 柳州市海达新型材料科技有限公司 | The preparation method of the polypropylene material of height filling inorganic filler |
| CN109734995A (en) * | 2018-11-29 | 2019-05-10 | 柳州市海达新型材料科技有限公司 | Soft sense of touch scratch antibacterial polypropylene material |
| CN111607144A (en) * | 2019-02-25 | 2020-09-01 | 住友电气工业株式会社 | Resin composition, inorganic filler, direct current cable, and method for producing direct current cable |
| CN111607144B (en) * | 2019-02-25 | 2022-05-03 | 住友电气工业株式会社 | Resin composition, inorganic filler, direct current cable, and method for producing direct current cable |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1053685C (en) | Glass fiber reinforced propylene polymer graft composition | |
| US4663369A (en) | Glass-fiber reinforced polypropylene resin composition | |
| EP0265527A1 (en) | Thermoplastic resin composition | |
| US5013789A (en) | Process for producing thermoplastic resin compositions | |
| JPH08134278A (en) | Color master powder composition for molding polypropylene resin, color masterbatch composition, and compound | |
| JPS59149940A (en) | Propylene polymer composition | |
| US4707505A (en) | Glass fiber reinforced propylene-ethylene copolymer base resin composition | |
| JPH0559143B2 (en) | ||
| JPS63178153A (en) | Production of filled propylene polymer composition | |
| JPH03239754A (en) | Fiber-reinforced resin composition | |
| JPH0416499B2 (en) | ||
| JPH0662821B2 (en) | Thermoplastic resin composition | |
| WO1987006249A1 (en) | Thermoplastic resin composition | |
| JPS62158740A (en) | Production of thermoplastic resin composition | |
| JP3321059B2 (en) | Glass fiber reinforced polypropylene resin composition | |
| JPH03115342A (en) | Polypropylene resin composition | |
| JPS63179944A (en) | Production of filler-containing propylene polymer composition | |
| JPH08143739A (en) | Fiber-reinforced polypropylene composition | |
| JP2840394B2 (en) | Fiber reinforced resin composition | |
| JP3356364B2 (en) | Polyolefin resin composition | |
| JPS581738A (en) | polyolefin composition | |
| JPH038382B2 (en) | ||
| JPH0493353A (en) | Thermoplastic resin composition | |
| JP2833333B2 (en) | Thermoplastic resin composition | |
| JP2943252B2 (en) | Resin composition |