JPH01138262A - Polycarbonate resin composition - Google Patents
Polycarbonate resin compositionInfo
- Publication number
- JPH01138262A JPH01138262A JP29640287A JP29640287A JPH01138262A JP H01138262 A JPH01138262 A JP H01138262A JP 29640287 A JP29640287 A JP 29640287A JP 29640287 A JP29640287 A JP 29640287A JP H01138262 A JPH01138262 A JP H01138262A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate
- formula
- mol
- resin composition
- repeating units
- 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 25
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 9
- 239000004431 polycarbonate resin Substances 0.000 title claims description 9
- 239000004417 polycarbonate Substances 0.000 claims abstract description 37
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 18
- 239000003365 glass fiber Substances 0.000 abstract description 15
- 239000000835 fiber Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 238000005299 abrasion Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 4
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 239000011256 inorganic filler Substances 0.000 abstract description 3
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 abstract description 3
- 239000000057 synthetic resin Substances 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract description 2
- 239000004927 clay Substances 0.000 abstract description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical compound OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000951 phenoxy group Chemical class [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 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〕
本発明はポリカーボネート樹脂組成物に関し、詳しくは
新規な構造のポリカーボネートとフッ素樹脂を主成分と
する機械的強度、難燃性ならびに耐摩耗性や摺動特性の
すぐれたポリカーボネート樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polycarbonate resin composition, and more specifically, the present invention relates to a polycarbonate resin composition that has mechanical strength, flame retardance, abrasion resistance, and This invention relates to a polycarbonate resin composition with excellent sliding properties.
(従来の技術及び発明が解決しようとする問題点〕従来
、難燃性を有するポリカーボネートとしては、例えば末
端にハロゲン置換フェノキシ基(ペンタブロモフェノキ
シ基、テトラクロロフェノキシ基、トリブロモフェノキ
シ基など)を有するポリカーボネート(特公昭46−4
0715号公報)をはじめとして様々なものが知られて
いる。(Prior art and problems to be solved by the invention) Conventionally, flame-retardant polycarbonates include, for example, halogen-substituted phenoxy groups (pentabromophenoxy group, tetrachlorophenoxy group, tribromophenoxy group, etc.) at the end. polycarbonate with
Various methods are known, including JP-A-0715).
しかし、これら従来のポリカーボネートは難燃性にはす
ぐれているものの、耐衝撃性等の機械的強度および耐摩
耗性や摺動特性に問題がある。However, although these conventional polycarbonates have excellent flame retardancy, they have problems in mechanical strength such as impact resistance, abrasion resistance, and sliding properties.
そこで、先般、本発明者らのグループは従来のポリカー
ボネートが持つ機械的、光学的性質を維持しながら、難
燃性を大幅に改善した新しい構造のポリカーボネートを
開発することに成功している(特願昭62−29673
号明細書)。Therefore, the group of the present inventors has recently succeeded in developing a polycarbonate with a new structure that has significantly improved flame retardancy while maintaining the mechanical and optical properties of conventional polycarbonate. Gansho 62-29673
No. Specification).
しかしながら、この新規なポリカーボネートは耐摩耗性
や摺動特性に若干の問題がある。However, this new polycarbonate has some problems in wear resistance and sliding properties.
このような状況下で、本発明者らは上記の新規ポリカー
ボネートの長所を維持しつつ、問題点をを解消すべく鋭
意研究を重ねた。Under these circumstances, the inventors of the present invention have conducted intensive research to solve the problems while maintaining the advantages of the above-mentioned new polycarbonate.
その結果、この新規ポリカーボネートにフッ素樹脂を配
合することにより、機械的性質を損なうことなく、耐摩
耗性、摺動特性を大幅に改善するとともに難燃性をも改
善することができることを見出した0本発明はかかる知
見に基づいて完成したものである。すなわち、本発明は
(a)式
で表わされる繰返し単位(n)を有するとともに、末端
位にペンタハロゲノフェノキシ基が結合し、かつ粘度平
均分子量が5000以上であるポリカーボネート及び(
b)フッ素樹脂を主成分とするポリカーボネート樹脂組
成物を提供するものである。As a result, they found that by blending a fluororesin into this new polycarbonate, it was possible to significantly improve abrasion resistance and sliding properties, as well as flame retardance, without impairing mechanical properties. The present invention was completed based on this knowledge. That is, the present invention provides a polycarbonate having a repeating unit (n) represented by formula (a), a pentahalogenophenoxy group bonded to the terminal position, and a viscosity average molecular weight of 5000 or more;
b) A polycarbonate resin composition containing a fluororesin as a main component is provided.
本発明の組成物は、上述の如<(a)ポリカーボネート
及び(b)フッ素樹脂を主成分とするものであるが、こ
こで(a)成分であるポリカーボネートは、式(A)で
表わされる繰返し単位(1)および式(B)で表わされ
る繰返し単位(II)を有するものである。この繰返し
単位(IL(n)のモル分率は、特に制限はなく任意で
あり、使用目的等に応じて適宜選定すればよいが、通常
は繰返し単位(1)のモル分率をm、繰返し単位(II
)のモル分率をnとしたとき、m/(m+ n)=0.
OO5〜0.2、好ましくは0.01〜0.1の範囲
である。The composition of the present invention is mainly composed of (a) a polycarbonate and (b) a fluororesin as described above, where the polycarbonate as the component (a) is a repeating compound represented by the formula (A). It has a unit (1) and a repeating unit (II) represented by formula (B). The molar fraction of this repeating unit (IL(n) is not particularly limited and may be selected as appropriate depending on the purpose of use, etc., but usually the molar fraction of the repeating unit (1) is m, and the molar fraction of the repeating unit (IL(n) is Unit (II
), m/(m+n)=0.
It ranges from OO5 to 0.2, preferably from 0.01 to 0.1.
また、(a)成分であるポリカーボネートは、分子の末
端位、特に両末端にペンタハロゲノフェノキシ基、すな
わち
一般式
(式中、X l 、 X Sはそれぞれハロゲン原子を
示す。なお、X1〜Xsはそれぞれ同じものでも異なる
ものでもよい。)
で表わされる官能基が結合している。In addition, the polycarbonate that is component (a) has a pentahalogenophenoxy group at the terminal position of the molecule, particularly at both ends, that is, the general formula (wherein, X l and X S each represent a halogen atom. They may be the same or different.) The functional groups represented by these are bonded to each other.
さらに、(a)成分のポリカーボネートの重合度につい
ては、粘度平均分子量が5.000以上、好ましくは1
0,000〜30,000の範囲が適当である。ここで
粘度平均分子量が5.000未満のものでは、耐衝撃性
等の機械的強度が充分でない。Furthermore, regarding the degree of polymerization of the polycarbonate component (a), the viscosity average molecular weight is 5.000 or more, preferably 1.
A range of 0,000 to 30,000 is suitable. If the viscosity average molecular weight is less than 5.000, mechanical strength such as impact resistance is insufficient.
このポリカーボネートは、上記繰返し単位(■)。This polycarbonate has the above repeating unit (■).
(I[)を有し、かつ末端位置に一般式(C)のペンタ
ハロゲノフェノキシ基が結合した構成であり、これらの
ランダム共重合体、ブロック共重合体。(I[), and a pentahalogenophenoxy group of general formula (C) is bonded to the terminal position, and these random copolymers and block copolymers.
交互共重合体など様々なものがある。There are various types such as alternating copolymers.
なお、このポリカーボネートの分子鎖中には、繰返し単
位(1) 、(II)以外の繰返し単位が少量混入して
いても差支えない。Note that there is no problem even if a small amount of repeating units other than repeating units (1) and (II) are mixed into the molecular chain of this polycarbonate.
上記(a)成分のポリカーボネートは、様々な方法によ
り製造することができるが、好ましい製造方法としては
特願昭62−29673号明細書に記載された方法をあ
げることができる。The polycarbonate component (a) can be produced by various methods, but a preferred method is the method described in Japanese Patent Application No. 62-29673.
一方、本発明の組成物の(b)成分であるフッ素樹脂と
しては、分子内にフッ素原子を存する樹脂であればどの
ようなものでもよく、中でも分子内に炭素−フッ素結合
を有する樹脂、例えばポリテトラフルオロエチレン、ポ
リクロロトリフルオロエチレン、ポリフッ化ビニル、ポ
リフッ化ヒニリデン、ヘキサフルオロプロピレン−テト
ラフルオロエチレン共重合体、クロロトリフルオロエチ
レン−フッ化ビニリデン共重合体等が好ましく、これら
の中でも特に融点300〜350°Cのポリテトラフル
オロエチレンが好ましい。On the other hand, the fluororesin which is the component (b) of the composition of the present invention may be any resin as long as it has a fluorine atom in its molecule, and in particular, a resin having a carbon-fluorine bond in its molecule, e.g. Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyhynylidene fluoride, hexafluoropropylene-tetrafluoroethylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer, etc. are preferred, and among these, particularly those with a melting point Polytetrafluoroethylene of 300-350°C is preferred.
本発明の組成物は、上記(a))成分と(1))成分を
主成分とするものであり、これら二成分の配合割合は各
成分の種類や組成物の用途等に応じて適宜窓めればよい
が、一般には(a)成分であるポリカーボネート60〜
99重量%、好ましくは70〜95重量%、(b)成分
であるフッ素樹脂1〜40重量%、好ましくは30〜5
重量%の範囲で定める。(a)成分であるポリカーボネ
ートの配合割合が、99重量%を越えると、組成物に充
分な耐摩耗性や摺動特性を付与することができない。ま
た、60重量%未満では耐衝撃性が低下するとともに、
成形品にフローマークが発生しやすくなる。The composition of the present invention has the above-mentioned (a)) component and (1)) component as main components, and the blending ratio of these two components can be adjusted as appropriate depending on the type of each component and the intended use of the composition. Generally, component (a) polycarbonate 60~
99% by weight, preferably 70-95% by weight, 1-40% by weight of fluororesin as component (b), preferably 30-5% by weight
Defined in weight% range. If the blending ratio of the polycarbonate component (a) exceeds 99% by weight, sufficient wear resistance and sliding properties cannot be imparted to the composition. In addition, if it is less than 60% by weight, impact resistance decreases, and
Flow marks are more likely to occur on molded products.
なお、本発明の組成物は、上記(a)成分、(b)成分
以外に、本発明の目的を阻害しない限りにおいて、ガラ
ス繊維や各種の無機質充填剤、添加剤またはその他の合
成樹脂、エラストマー等を必要に応じて配合することが
できる。また、各種の難燃化剤を添加することにより該
組成物の難燃性はさらに向上する。これらの各種添加成
分を説明すれば次の如くである。In addition to the above components (a) and (b), the composition of the present invention may contain glass fibers, various inorganic fillers, additives, other synthetic resins, and elastomers, as long as they do not impede the purpose of the present invention. etc. can be blended as necessary. Furthermore, the flame retardancy of the composition can be further improved by adding various flame retardants. These various additive components are explained as follows.
まず、本発明の樹脂組成物の機械的強度、耐久性または
増量を目的として配合されるガラス繊維としては、各種
のものが使用可能であり、特に制限はないが、例えば従
来から樹脂強化に用いられている含アルカリガラス繊維
、低アルカリガラス繊維、無アルカリガラス繊維などの
ガラス繊維を適宜用いることができる。また、このガラ
ス繊維の形態については特に制限はされず、例えばロー
ビング、チョツプドストランド、ストランド、ミルドフ
ァイバーなどいずれであってもよいが、あまり繊維径が
大きくなり過ぎると、組成物の強度が低下し、かつ外観
が悪くなるおそれがある。−方、繊維径が小さ過ぎると
混練時や成形時に繊維が破断して、組成物の強度が低下
するおそれがある。なお、このガラス繊維は、組成物の
難燃性や機械的強度を一層高める目的で、必要に応じて
アミノシラン系、エポキシシラン系、ボラン系、ビニル
シラン系、メタクリルシラン系などのカップリング剤、
あるいはクロム錯化物、ホウ素化合物などで表面処理し
てもよい。これらのガラス繊維の中でも、特に繊維長1
〜8ffII11、とりわけ2〜7胴であって、繊維径
20μm以下、特に3〜15μmのもので、かつシラン
カップリング剤で表面処理したものが好ましい。First, various kinds of glass fibers can be used for the purpose of increasing the mechanical strength, durability, or weight of the resin composition of the present invention, and there are no particular restrictions. Glass fibers such as alkali-containing glass fibers, low-alkali glass fibers, alkali-free glass fibers, etc., which are currently available, can be used as appropriate. Further, the form of the glass fiber is not particularly limited, and may be any form such as roving, chopped strand, strand, or milled fiber, but if the fiber diameter becomes too large, the strength of the composition will deteriorate. There is a risk that the appearance will deteriorate. On the other hand, if the fiber diameter is too small, the fibers may break during kneading or molding, which may reduce the strength of the composition. In addition, in order to further increase the flame retardancy and mechanical strength of the composition, the glass fibers may be optionally mixed with a coupling agent such as aminosilane, epoxysilane, borane, vinylsilane, methacrylsilane, etc.
Alternatively, the surface may be treated with a chromium complex, a boron compound, or the like. Among these glass fibers, especially fiber length 1
-8ffII11, especially those having 2 to 7 cylinders, having a fiber diameter of 20 μm or less, especially 3 to 15 μm, and having been surface-treated with a silane coupling agent are preferred.
本発明の組成物では、上述のガラス繊維の配合割合は特
に制限はなく、使用目的や所望する性状等に応じて適宜
選定すればよいが、通常は(A)ポリカーボネートと(
B)フッ素樹脂との合計100重量部に対して、ガラス
繊維を1〜40重量部の範囲、好ましくは5〜30重量
部とする。In the composition of the present invention, the blending ratio of the above-mentioned glass fibers is not particularly limited and may be appropriately selected depending on the purpose of use and desired properties, but usually (A) polycarbonate and (
B) The amount of glass fiber is in the range of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, based on a total of 100 parts by weight of the fluororesin.
このガラス繊維を適量配合すれば、難燃性、剛性。By adding an appropriate amount of this glass fiber, it becomes flame retardant and rigid.
寸法安定性が向上する。しかしあまり多量に配合すると
、流動性が低下することとなり好ましくない。Improved dimensional stability. However, if too large a quantity is blended, the fluidity will decrease, which is not preferable.
次に前記無機充填剤としては、例えばカーボンブラック
、硫酸カルシウム、炭酸カルシウム、シリカ、アスベス
ト、タルク、クレー、マイカ、石英粉等が挙げられる。Examples of the inorganic filler include carbon black, calcium sulfate, calcium carbonate, silica, asbestos, talc, clay, mica, and quartz powder.
また、前記添加剤としては、ヒンダードフェノール系、
リン系(亜すン酸エステル系、リン酸エステル系)、ア
ミン系等の酸化防止剤、ベンゾトリアゾール系、ベンゾ
フェノン系の紫外線吸収剤、肪肪族カルボン酸エステル
系。In addition, the additives include hindered phenol,
Phosphorus-based (sulfurous acid ester, phosphate ester), amine-based antioxidants, benzotriazole-based, benzophenone-based ultraviolet absorbers, aliphatic carboxylic acid ester-based.
パラフィン系の外部滑剤、さらには離型剤、帯電防止剤
2着色剤等が挙げられる。ここで上記のヒンダードフェ
ノール系酸化防止剤としては、BHT(2,6−ジ第三
ブチル−p−クレゾール)、チバ・ガイギー社製の「イ
ルガノックス1076J(商品名)、[イルガノックス
l0IOJ(商品名)、エチル社製「エチル330J(
商品名)、住人化学■製「スミライザーGMJ (商品
名)などが好ましく用いられる。その他の合成樹脂とし
ては、ポリエチレン、ポリプロピレン、ポリスチレン、
AS樹脂、ABS樹脂、ポリメチルメタクリレート等の
各樹脂を挙げることができる。また、エラストマーとし
ては、イソブチレン−イソプレンゴム。Examples include a paraffin-based external lubricant, a mold release agent, an antistatic agent, a coloring agent, and the like. Here, the above-mentioned hindered phenolic antioxidants include BHT (2,6-di-tert-butyl-p-cresol), Irganox 1076J (trade name) manufactured by Ciba Geigy, and Irganox 10IOJ (trade name) manufactured by Ciba Geigy. Product name), manufactured by Ethyl Co., Ltd. “Ethyl 330J (
(product name), Sumilizer GMJ (product name) manufactured by Juju Chemical Co., Ltd. are preferably used.Other synthetic resins include polyethylene, polypropylene, polystyrene,
Various resins such as AS resin, ABS resin, and polymethyl methacrylate can be mentioned. Also, as the elastomer, isobutylene-isoprene rubber.
スチレン−ブタジェンゴム、エチレン−プロピレンゴム
、アクリル系エラストマー等が挙げられる。Examples include styrene-butadiene rubber, ethylene-propylene rubber, and acrylic elastomer.
また、難燃剤としてはテトラブロモビスフェノールA
(TBA)、TBAとホスゲンとの反応によるポリカー
ボネートオリゴマー、デカブロモビスフエノールA、臭
素化エポキシ等の難燃剤、更にはSb2O2,アンチモ
ン酸ソーダ等の難燃助剤が挙げられる。In addition, tetrabromobisphenol A is used as a flame retardant.
(TBA), polycarbonate oligomers produced by the reaction of TBA and phosgene, flame retardants such as decabromobisphenol A, and brominated epoxy, and flame retardant aids such as Sb2O2 and sodium antimonate.
本発明のポリカーボネート樹脂組成物は上記の各成分を
配合し、混練することにより得ることができる。配合、
混練は通常の方法を採用することができ、例えばリボン
ブレンダー、ヘンシェルミキサー、バンバリーミキサ−
、ドラムタンブラ−2単軸スクリユ一押出機、二軸スク
リュー押出機。The polycarbonate resin composition of the present invention can be obtained by blending and kneading the above-mentioned components. combination,
The kneading can be done using a conventional method, such as a ribbon blender, Henschel mixer, or Banbury mixer.
, drum tumbler-two single screw extruder, twin screw extruder.
コニーダ、多軸スクリュー押出機等により行うことがで
きる。混純に際しての加熱温度は通常250〜300°
Cが適当である。This can be carried out using a co-kneader, multi-screw extruder, or the like. The heating temperature during mixing is usually 250 to 300°.
C is appropriate.
かくして得られたポリカーボネート樹脂組成物は既知の
種々の成形方法、たとえば射出成形、押出成形、圧縮成
形、カレンダー成形2回転成形等を適用して電気電子機
器、OA機器および自動車等の部品、特に回転部材、移
動部材、駆動部材等の成形品を製造することができる。The polycarbonate resin composition thus obtained can be molded into parts for electrical and electronic equipment, OA equipment, automobiles, etc., especially rotating parts, by applying various known molding methods, such as injection molding, extrusion molding, compression molding, two-turn calendar molding, etc. Molded products such as members, moving members, driving members, etc. can be manufactured.
[実施例] 次に、本発明を実施例により更に詳しく説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
合成例(ビスフェノールへのポリカーボネートオリゴマ
ーの合成)
内容積21の撹拌機付きフラスコの中に、ビスフェノー
ルA91 g、塩化メチレン330n/2および1.7
規定水酸化ナトリウム水溶液560mff1を入れて撹
拌し、水浴冷却しながら、ここにホスゲンを70分間吹
込んだ。得られた反応液を室温下で静置したところ、下
層にオリゴマーの塩化メチレン溶液が分離生成した。こ
のオリゴマー溶液はオリゴマー濃度が300g/lで、
数平均分子量550、クロロホーメート基の濃度が1.
0モル/lのものであった。Synthesis Example (Synthesis of polycarbonate oligomer to bisphenol) In a flask with an internal volume of 21 and equipped with a stirrer, 91 g of bisphenol A, 330 n/2 of methylene chloride, and 1.7 g of methylene chloride were added.
560 mff1 of normal sodium hydroxide aqueous solution was added and stirred, and phosgene was blown therein for 70 minutes while cooling in a water bath. When the resulting reaction solution was allowed to stand at room temperature, a methylene chloride solution of the oligomer was separated and produced in the lower layer. This oligomer solution has an oligomer concentration of 300 g/l,
The number average molecular weight is 550, and the concentration of chloroformate groups is 1.
It was 0 mol/l.
製造例1(ポリカーボネートの製造)
内容積502の撹拌機付き容器に、上記合成例にて合成
したポリカーボネートオリゴマー8ffi。Production Example 1 (Production of Polycarbonate) 8ffi of the polycarbonate oligomer synthesized in the above synthesis example was placed in a container with an internal volume of 502 mm and equipped with a stirrer.
ビスフェノールスルホンの水酸化ナトリウム水溶液〔ビ
スフェノールスルホン123g(0,49モル)、水酸
化ナトリウム69g、水520mjlり640calお
よびトリエチルアミン4.4g(0,043モル)を入
れ、500回転で撹拌した。A sodium hydroxide aqueous solution of bisphenolsulfone [123 g (0.49 mol) of bisphenol sulfone, 69 g of sodium hydroxide, 640 cal/520 mL of water, and 4.4 g (0,043 mol) of triethylamine were added and stirred at 500 rpm.
10分後、ペンタブロモフェノールの水酸化ナトリウム
水溶液〔ペンタブロモフェノール230g(0,47モ
ル)、水酸化ナトリウム37.6g、水2.81’Jを
入れ撹拌した。50分後、ビスフェノールへの水酸化ナ
トリウム水溶液〔ビスフェノールA510g(2,24
モル)、水酸化ナトリウム260g、水4.4E)4.
942および塩化メチレン6iを入れ撹拌した。After 10 minutes, an aqueous sodium hydroxide solution of pentabromophenol [230 g (0.47 mol) of pentabromophenol, 37.6 g of sodium hydroxide, and 2.81'J of water] was added and stirred. After 50 minutes, add sodium hydroxide aqueous solution to bisphenol [bisphenol A 510 g (2,24
mol), sodium hydroxide 260g, water 4.4E)4.
942 and 6i of methylene chloride were added and stirred.
60分撹拌後、得られた反応生成物を水相と生成したコ
ポリマー(繰返し単位(1)と繰返し単位(II)から
なるポリカーボネート)を含有する塩化メチレン相とに
分離した。After stirring for 60 minutes, the resulting reaction product was separated into an aqueous phase and a methylene chloride phase containing the formed copolymer (polycarbonate consisting of repeating unit (1) and repeating unit (II)).
この塩化メチレン相を水、酸(0,1規定塩酸)。This methylene chloride phase was mixed with water and acid (0.1N hydrochloric acid).
水の順に洗浄した。この塩化メチレン相から塩化メチレ
ンを40°Cにて減圧下で除去し、白色の粉体を得た。Washed with water. Methylene chloride was removed from this methylene chloride phase at 40°C under reduced pressure to obtain a white powder.
さらに120 ’C1−昼夜乾燥後、押出機で溶融し、
ペレットにした。このペレットのガラス転移温度(Tg
)を測定したところ、154.2°Cであった。また粘
度平均分子量は18,800であり、ゲルパーミェーシ
ョンクロマトグラフィーにより分子量分布を測定したと
ころ、上記値に単一ピークを有する分布を示した。Further, after drying for 120'C1 day and night, melt it in an extruder,
Made into pellets. The glass transition temperature (Tg
) was measured and found to be 154.2°C. The viscosity average molecular weight was 18,800, and when the molecular weight distribution was measured by gel permeation chromatography, it showed a distribution with a single peak at the above value.
さらに、このコポリマー中の繰返し単位(I)のモル比
を求めたところ、0.024であった。Furthermore, the molar ratio of the repeating unit (I) in this copolymer was determined to be 0.024.
得られたペレットの臭素含有量を測定したところ6.2
wt%であった(サンプルをアルカリ分解し、ホルハル
ト法にて分析したものである)。以下、ここで得られた
ポリカーボネートをPC−1とする。The bromine content of the obtained pellets was measured and was 6.2.
wt% (sample was subjected to alkaline decomposition and analyzed by Holhardt method). Hereinafter, the polycarbonate obtained here will be referred to as PC-1.
製造例2(ポリカーボネートの製造)
内容積501の撹拌機付き容器に、上記合成例にて合成
したポリカーボネートオリゴマー82゜ビスフェノール
スルホンの水酸化ナトリウム水溶液〔ビスフェノールス
ルホン123g(0,49モル)。Production Example 2 (Production of Polycarbonate) In a container with an internal volume of 501 mm and equipped with a stirrer, the polycarbonate oligomer synthesized in the above synthesis example was placed in an aqueous sodium hydroxide solution of 82° bisphenol sulfone [123 g (0.49 mol) of bisphenol sulfone].
水酸化ナトリウム69g、水520n+J2)640m
lおよびトリエチルアミン4.4g
(0,043モル)を入れ、500 rpmで撹拌した
。Sodium hydroxide 69g, water 520n + J2) 640m
1 and 4.4 g (0,043 mol) of triethylamine were added thereto and stirred at 500 rpm.
10分後、ペンタブロモフェノールの水酸化ナトリウム
水溶液〔ペンタブロモフェノール215g(0,44モ
ル)、水酸化ナトリウム35.1g。After 10 minutes, an aqueous sodium hydroxide solution of pentabromophenol [215 g (0.44 mol) of pentabromophenol, 35.1 g of sodium hydroxide].
水2.8ff)を入れ撹拌した。50分後、ビスフェノ
ールAの水酸化ナトリウム水溶液〔ビスフェノールA5
10g(2,24モル)、水酸化ナトリウム260 g
、水4.4f〕4.9fおよび塩化メチレン6℃を入れ
撹拌した。2.8ff of water was added and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A5
10 g (2.24 mol), 260 g of sodium hydroxide
, 4.4f]4.9f of water and 6°C of methylene chloride were added and stirred.
60分撹拌後、得られた反応生成物を水相と生成したコ
ポリマー(繰返し単位(I)と繰返し単位(II)から
なるポリカーボネート)を含存する塩化メチレン相とに
分離した。After stirring for 60 minutes, the resulting reaction product was separated into an aqueous phase and a methylene chloride phase containing the formed copolymer (polycarbonate consisting of repeating units (I) and repeating units (II)).
この塩化メチレン相を水、酸(0,1規定塩酸)。This methylene chloride phase was mixed with water and acid (0.1N hydrochloric acid).
水の順に洗浄した。この塩化メチレン和から塩化メチレ
ンを40°Cにて減圧下で除去し、白色の粉体を得た。Washed with water. Methylene chloride was removed from this methylene chloride sum at 40°C under reduced pressure to obtain a white powder.
さらに120°C1−昼夜乾燥後、押出機で溶融し、ペ
レットにした。このペレットのガラス転移温度(T g
)を測定したところ、153.8°Cであった。また
粘度平均分子量は17,600でアリ、ケルパーミェー
ションクロマトグラフィーにより分子量分布を測定した
ところ、上記値に単一ピークを有する分布を示した。After further drying at 120°C for 1 day and night, the mixture was melted in an extruder and made into pellets. The glass transition temperature (T g
) was measured and found to be 153.8°C. The viscosity average molecular weight was 17,600, and when the molecular weight distribution was measured by Kölper permeation chromatography, it showed a distribution with a single peak at the above value.
さらに、このコポリマー中の繰返し単位(I)のモル比
を求めたところ、0.02であった。Furthermore, the molar ratio of the repeating unit (I) in this copolymer was determined to be 0.02.
得られたペレットの臭素含有量を測定したところ5.8
wt%であった。サンプルをアルカリ分解し、ホルハル
ト法にて分析したものである)。以下、ここで得られた
ポリカーボネートをPC−2とする。The bromine content of the obtained pellets was measured and was found to be 5.8.
It was wt%. The sample was subjected to alkali decomposition and analyzed using the Holhardt method). Hereinafter, the polycarbonate obtained here will be referred to as PC-2.
実施例1〜7および比較例1〜4
第1表に示す各種ポリカーボネート、フッ素樹脂および
ガラス繊維等の他の添加剤の所定量をドラムタンブラ−
で予備混練した後、押出機に供給して温度300°Cで
混練し、ポリカーボネート樹脂組成物を得、これをペレ
ット化した。Examples 1 to 7 and Comparative Examples 1 to 4 Predetermined amounts of various polycarbonate, fluororesin, and other additives such as glass fiber shown in Table 1 were added to a drum tumbler.
After preliminary kneading, the mixture was supplied to an extruder and kneaded at a temperature of 300°C to obtain a polycarbonate resin composition, which was pelletized.
さらに得られたペレットを成形温度300°C3金型温
度80°Cで射出成形して試験片を得た。得られた試験
片の曲げ弾性率、難燃性および動摩擦係数を測定した。Further, the obtained pellets were injection molded at a molding temperature of 300°C and a mold temperature of 80°C to obtain test pieces. The flexural modulus, flame retardance, and coefficient of dynamic friction of the obtained test piece were measured.
結果を第1表に示す。The results are shown in Table 1.
(以下余白)
*1 出光石油化学■製 タフロンA−2200(ビス
フェノールAとホスゲンからのポリカーボネート)
*2 三井フロロケミカル■製 TLP〜IOF〜1(
ポリテトラフルオロエチレン、融点327°C)*3
旭ファイバーグラス■製、 MA409C,直径13μ
、長さ3 mmのアミノシラン処理ガラス繊維
*4 理研ビタミン製 リケマール5100A (ス
テアリン酸モノグリセライド)
*5 グレートレーク社製 BC−58(T B Aと
ホスゲンとからのポリカーボネートオリゴマー)*6
ポリカーボネートとフッ素樹脂の合計100重量部に対
する重量部で示す。(Space below) *1 Taflon A-2200 (polycarbonate made from bisphenol A and phosgene) manufactured by Idemitsu Petrochemical ■2 TLP~IOF~1 (manufactured by Mitsui Fluorochemical ■)
Polytetrafluoroethylene, melting point 327°C) *3
Made of Asahi fiberglass, MA409C, diameter 13μ
, 3 mm long aminosilane-treated glass fiber *4 Riken Vitamin Co., Ltd. Rikemar 5100A (stearic acid monoglyceride) *5 Great Lake Co., Ltd. BC-58 (polycarbonate oligomer from TBA and phosgene) *6
It is expressed in parts by weight based on the total of 100 parts by weight of polycarbonate and fluororesin.
*7 UL規格94に準拠(厚さ3.2薗)*8
ASTM D 1894に準拠、荷重2.0kg*9
ASTM D 1790に準拠*10 厚さ3
閣2幅121.長さ12cmの角板を射出成形(樹脂温
度300°C)L、外観を目視で判定した。*7 Conforms to UL standard 94 (thickness 3.2 mm) *8
Based on ASTM D 1894, load 2.0kg*9
Conforms to ASTM D 1790*10 Thickness 3
Cabinet 2 width 121. A square plate having a length of 12 cm was injection molded (resin temperature: 300°C), and its appearance was visually judged.
(発明の効果〕
叙上の如(、本発明の樹脂組成物は、ポリカーボネート
本来の機械的強度を保持したまま、耐摩耗性、摺動特性
が著しく改善され、また難燃性にすぐれたものである。(Effects of the Invention) As stated above, the resin composition of the present invention has significantly improved abrasion resistance and sliding properties while retaining the mechanical strength inherent to polycarbonate, and has excellent flame retardancy. It is.
したがって、本発明の樹脂組成物は、各種工業材料9例
えば家庭電化製品、OA機器、精密機器。Therefore, the resin composition of the present invention can be used in various industrial materials 9 such as home appliances, OA equipment, and precision equipment.
自動車、建材等に幅広くかつ有効に利用される。Widely and effectively used in automobiles, building materials, etc.
特に本発明の樹脂組成物は、大型射出成形にも適するも
のである。In particular, the resin composition of the present invention is suitable for large-scale injection molding.
じ−一一−−J-11--
Claims (1)
位にペンタハロゲノフェノキシ基が結合し、かつ粘度平
均分子量が5000以上であるポリカーボネート及び(
b)フッ素樹脂を主成分とするポリカーボネート樹脂組
成物。(1) (a) It has a repeating unit (I) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and a repeating unit (II) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the terminal A polycarbonate having a pentahalogenophenoxy group bonded to the position and having a viscosity average molecular weight of 5000 or more and (
b) A polycarbonate resin composition containing a fluororesin as a main component.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29640287A JPH01138262A (en) | 1987-11-25 | 1987-11-25 | Polycarbonate resin composition |
EP88116391A EP0311008A3 (en) | 1987-10-07 | 1988-10-04 | Polycarbonate resin composition |
BR8805161A BR8805161A (en) | 1987-10-07 | 1988-10-06 | POLYCARBONATE RESIN COMPOSITION |
KR1019880013085A KR890006748A (en) | 1987-10-07 | 1988-10-07 | Polycarbonate Resin Composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29640287A JPH01138262A (en) | 1987-11-25 | 1987-11-25 | Polycarbonate resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01138262A true JPH01138262A (en) | 1989-05-31 |
Family
ID=17833082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29640287A Pending JPH01138262A (en) | 1987-10-07 | 1987-11-25 | Polycarbonate resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01138262A (en) |
-
1987
- 1987-11-25 JP JP29640287A patent/JPH01138262A/en active Pending
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