JP2968388B2 - Polycarbonate resin composition - Google Patents
Polycarbonate resin compositionInfo
- Publication number
- JP2968388B2 JP2968388B2 JP4107759A JP10775992A JP2968388B2 JP 2968388 B2 JP2968388 B2 JP 2968388B2 JP 4107759 A JP4107759 A JP 4107759A JP 10775992 A JP10775992 A JP 10775992A JP 2968388 B2 JP2968388 B2 JP 2968388B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- polycarbonate resin
- aromatic polycarbonate
- resin composition
- 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.)
- Expired - Lifetime
Links
- 239000004431 polycarbonate resin Substances 0.000 title claims description 23
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000012765 fibrous filler Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 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 17
- 239000000945 filler Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000011156 evaluation Methods 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- -1 carbonyl halide Chemical class 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000013034 phenoxy resin Substances 0.000 description 4
- 229920006287 phenoxy resin Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical compound [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005541 phosphonamide group Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、芳香族ポリカーボネー
トの樹脂組成物、更に詳細には機械的特性、剛性、寸法
安定性に優れ、かつ耐湿熱性、特に成形品を高温多湿な
環境に長時間放置したときの機械的強度低下が少ないカ
メラ、オーディオ、カーオーディオ、ＶＴＲ、ＯＡ、電
動工具部品など幅広い産業分野で有用なポリカーボネー
ト樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition of an aromatic polycarbonate, and more particularly, to a resin composition having excellent mechanical properties, rigidity and dimensional stability. The present invention relates to a polycarbonate resin composition that is useful in a wide range of industrial fields such as cameras, audios, car audios, VTRs, OA, power tool parts, and the like, in which the mechanical strength when left standing is small.
【０００２】[0002]
【従来の技術】繊維強化した芳香族ポリカーボネート樹
脂は、芳香族ポリカーボネート樹脂の優れた特性を維持
し、更に剛性、耐熱性、寸法安定性等に優れたエンジニ
アリングプラスチックとして各種工業分野において幅広
く利用されている。しかしながら、繊維強化芳香族ポリ
カーボネート樹脂は高温多湿な環境に長時間放置すると
ポリカーボネート樹脂と繊維の密着性が低下するために
成形品の機械的強度が著しく低下する欠点を有してい
る。2. Description of the Related Art Fiber-reinforced aromatic polycarbonate resins are widely used in various industrial fields as engineering plastics which maintain the excellent characteristics of aromatic polycarbonate resins and are also excellent in rigidity, heat resistance and dimensional stability. I have. However, the fiber-reinforced aromatic polycarbonate resin has a drawback that when left in a high-temperature and high-humidity environment for a long time, the adhesion between the polycarbonate resin and the fiber is reduced, so that the mechanical strength of the molded product is significantly reduced.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこれら繊維強
化芳香族ポリカーボネート樹脂の優れた特徴を保持し、
同時に耐湿熱性に優れた繊維強化芳香族ポリカーボネー
ト樹脂組成物を提供することにある。The present invention retains the excellent characteristics of these fiber-reinforced aromatic polycarbonate resins,
Another object of the present invention is to provide a fiber-reinforced aromatic polycarbonate resin composition having excellent wet heat resistance.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、特定のヒ
ドロキシ基含有重合体を特定量の範囲内で繊維強化芳香
族ポリカーボネート樹脂に配合した場合、機械的強度を
保持し、かつ耐湿熱性も改良されることを見出だし本発
明に到達したものである。SUMMARY OF THE INVENTION The present inventors have found that when a specific hydroxy group-containing polymer is blended with a fiber-reinforced aromatic polycarbonate resin in a specific amount within a specified range, the mechanical strength is maintained and the heat and humidity resistance is improved. Have also been found to be improved, and the present invention has been achieved.
【０００５】即ち本発明は、成分（Ａ）として芳香族ポ
リカーボネート樹脂５０〜９９．９５重量％、成分
（Ｂ）としてフェノキシ樹脂またはエポキシ樹脂から選
ばれた１種以上のヒドロキシ基含有重合体０．０５〜５
０重量％からなる樹脂成分１００重量部と、成分（Ｃ）
としてＬ／Ｄ≧３の繊維状充填剤を２０重量％以上含有
する充填剤５〜２４０重量部から実質的になる樹脂組成
物であって、且つ本文記載の耐湿熱性試験における４８
時間浸漬試験後においても良好な強度を有する芳香族ポ
リカーボネート樹脂組成物に係わるものである。That is, in the present invention, 50 to 99.95% by weight of an aromatic polycarbonate resin is used as the component (A), and a phenoxy resin or an epoxy resin is used as the component (B).
One or more hydroxy group-containing polymers 0.05 to 5
100 parts by weight of a resin component comprising 0% by weight , and component (C)
Resin composition consisting essentially of 5 to 240 parts by weight of a filler containing 20% by weight or more of a fibrous filler having an L / D ≧ 3
And 48 in the wet heat resistance test described in the text.
The present invention relates to an aromatic polycarbonate resin composition having good strength even after a time immersion test .
【０００６】本発明で使用する芳香族ポリカーボネート
樹脂（Ａ）は、２価フェノールより誘導される粘度平均
分子量１０，０００〜１００，０００、好ましくは１
５，０００〜６０，０００の芳香族ポリカーボネート樹
脂であり、通常２価フェノールとカーボネート前駆体を
溶液法あるいは溶融法で反応せしめて製造される。２価
フェノールの代表的な例を挙げると、２，２−ビス（４
−ヒドロキシフェニル）プロパン［ビスフェノール
Ａ］、ビス（４−ヒドロキシフェニル）メタン、２，２
−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）
プロパン、２，２−ビス（４−ヒドロキシ−３−メチル
フェニル）プロパン、ビス（４−ヒドロキシフェニル）
スルフォン等があげられる。好ましい２価フェノールは
ビス（４−ヒドロキシフェニル）アルカン、特にビスフ
ェノールＡを主原料とするものである。また、カーボネ
ート前駆体としてはカルボニルハライド、カルボニルエ
ステルまたはハロホルメート等が挙げられ、具体的には
ホスゲン、ジフェニルカーボネート、２価フェノールの
ジハロホルメート及びそれらの混合物である。ポリカー
ボネート樹脂を製造するに当たり、前記２価フェノール
を単独でまたは２種以上を使用することができる。ま
た、適当な分子量調節剤、分岐剤、反応を促進するため
の触媒等も使用できる。かくして得られた芳香族ポリカ
ーボネート樹脂の２種以上を混合しても差し支えない。The aromatic polycarbonate resin (A) used in the present invention has a viscosity average molecular weight of 10,000 to 100,000, preferably 1 derived from dihydric phenol.
It is an aromatic polycarbonate resin of 5,000 to 60,000, and is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. A typical example of dihydric phenol is 2,2-bis (4
-Hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 2,2
-Bis (4-hydroxy-3,5-dimethylphenyl)
Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl)
Sulfone and the like. Preferred dihydric phenols are those based on bis (4-hydroxyphenyl) alkane, especially bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. In producing the polycarbonate resin, the dihydric phenol can be used alone or in combination of two or more. In addition, a suitable molecular weight regulator, a branching agent, a catalyst for accelerating the reaction, and the like can be used. Two or more aromatic polycarbonate resins thus obtained may be mixed.
【０００７】本発明において使用するヒドロキシ基含有
重合体（Ｂ）は、フェノキシ樹脂またはエポキシ樹脂で
ある。さらにはビスフェノールＡとエピクロルヒドリン
より合成されるビスフェノールＡ型フェノキシ樹脂，ビ
スフェノールＡ型エポキシ樹脂、ビスフェノールＦとエ
ピクロルヒドリンより合成されるビスフェノールＦ型エ
ポキシ樹脂、フェノールノボラック、O−クレゾールノ
ボラックをグリシジルエーテル化したエポキシ樹脂、臭
素化エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂の
骨格中にダイマー酸を変性したグリシジルエステルやダ
イマー酸ジグリシジルエステル、およびゴム変性、３級
脂肪酸変性による可撓性エポキシ樹脂、水添ビスフェノ
ールＡ型エポキシ樹脂等が特に好ましい。これらヒドロ
キシ基含有重合体を二種以上混合して使用してもよい。[0007] Hydroxy group-containing polymer used in the present invention (B) is a phenoxy resin or epoxy resin
There is . Furthermore, bisphenol A phenoxy resin synthesized from bisphenol A and epichlorohydrin, bisphenol A epoxy resin, bisphenol F epoxy resin synthesized from bisphenol F and epichlorohydrin, phenol novolak, and epoxy resin obtained by glycidyl etherification of O-cresol novolak Glycidyl ester or dimer acid diglycidyl ester obtained by modifying dimer acid in the skeleton of a brominated epoxy resin, bisphenol A epoxy resin, rubber modified tertiary fatty acid modified flexible epoxy resin, hydrogenated bisphenol A epoxy Resins and the like are particularly preferred. Two or more of these hydroxy group-containing polymers may be used as a mixture.
【０００８】上記芳香族ポリカーボネート樹脂に配合す
る充填剤（Ｃ）は、Ｌ／Ｄ≧３の繊維状充填剤を２０重
量％以上含有する充填剤であり、繊維状充填剤として
は、ガラス繊維、カーボン繊維、炭化ケイ素繊維、黄銅
繊維、ステンレス繊維、チタン酸カリウムあるいはほう
酸アルミニウムよりなる繊維もしくはウィスカー、芳香
族ポリアミド繊維等があげられるが、ガラス繊維が好ま
しい。更にアミノ系シランカップリング剤およびまたは
エポキシ系シランカップリング剤で表面処理が施されて
おりエポキシ樹脂およびまたはウレタン樹脂で集束され
たガラス繊維が特に好ましい。Ｌ／Ｄ≧３の繊維状充填
剤以外の充填剤としては、例えばシリカ、タルク、マイ
カ、ガラスビーズ、ガラスフレーク、ガラスパウダー、
金属粉、二硫化モリブデン等で例示される板状、フレー
ク状、粉末状等の充填剤である。かかる充填剤はシラン
カップリング剤やチタネートカップリング剤等で表面処
理されているものが好ましい。The filler (C) to be added to the aromatic polycarbonate resin is a filler containing 20% by weight or more of a fibrous filler having an L / D ≧ 3. Examples include carbon fiber, silicon carbide fiber, brass fiber, stainless steel fiber, fiber made of potassium titanate or aluminum borate, whisker, and aromatic polyamide fiber, and glass fiber is preferable. Further, glass fibers which have been surface-treated with an amino-based silane coupling agent and / or an epoxy-based silane coupling agent and which are bundled with an epoxy resin and / or a urethane resin are particularly preferable. Examples of fillers other than the fibrous filler of L / D ≧ 3 include silica, talc, mica, glass beads, glass flake, glass powder,
Plate-like, flake-like, powder-like fillers exemplified by metal powder, molybdenum disulfide and the like. It is preferable that the filler is surface-treated with a silane coupling agent, a titanate coupling agent, or the like.
【０００９】上記繊維状充填剤は、繊維による補強効果
の目安となるＬ／Ｄ（繊維長／繊維径）が３以上のもの
である。Ｌ／Ｄが３未満の繊維状充填剤を使用したので
は十分な補強効果が得られない。The fibrous filler has an L / D (fiber length / fiber diameter) of 3 or more, which is a measure of the reinforcing effect of the fiber. If a fibrous filler having an L / D of less than 3 is used, a sufficient reinforcing effect cannot be obtained.
【００１０】本発明において使用される樹脂組成物は、
上記３種類の成分を混合することにより製造される。混
合割合は、芳香族ポリカーボネート樹脂５０〜９９．９
５重量％、好ましくは７０〜９９．９０重量％、更に好
ましくは９０〜９９．９０重量％と、ヒドロキシ基含有
重合体０．０５〜５０重量％、好ましくは０．１〜３０
重量％、更に好ましくは０．１〜１０重量％からなる樹
脂成分１００重量部に対して、Ｌ／Ｄ≧３の繊維状充填
剤を２０重量％以上含有する充填剤５〜２４０重量部を
配合してなる。ヒドロキシ基含有重合体が５０重量％を
超えると十分な機械的強度が得られず、０．０５重量％
未満では十分な耐湿熱性が得られない。また、Ｌ／Ｄ≧
３の繊維状充填剤を２０重量％以上含有する充填剤が２
４０重量部を超えると成形性が極端に低下し、５重量部
未満では十分な補強効果が得られない。The resin composition used in the present invention comprises:
It is manufactured by mixing the above three types of components. The mixing ratio is 50 to 99.9 of the aromatic polycarbonate resin.
5% by weight, preferably 70 to 99.90% by weight, more preferably 90 to 99.90% by weight, and 0.05 to 50% by weight, preferably 0.1 to 30% by weight of the hydroxy group-containing polymer.
5 to 240 parts by weight of a filler containing 20% by weight or more of a fibrous filler having an L / D ≧ 3 with respect to 100 parts by weight of a resin component consisting of 0.1 to 10% by weight, more preferably 0.1 to 10% by weight. Do it. If the hydroxy group-containing polymer exceeds 50% by weight, sufficient mechanical strength cannot be obtained and 0.05% by weight
If it is less than this, sufficient moisture and heat resistance cannot be obtained. Also, L / D ≧
The filler containing 20% by weight or more of the fibrous filler of 3 is 2
If it exceeds 40 parts by weight, the moldability will be extremely reduced, and if it is less than 5 parts by weight, a sufficient reinforcing effect will not be obtained.
【００１１】本発明においては、上記芳香族ポリカーボ
ネートとヒドロキシ基含有重合体、充填剤からなる組成
物の調製は、通常の混合機、混練機で実施される。すな
わち、各成分をＶ型ブレンダー、リボンミキサーまたは
タンブラー等に投入し均一に混合した後、一軸または二
軸等の通常の押出機で溶融混練し、冷却後ペレット状に
切断する。この時、ガラス繊維や他の成分の一部を押出
機の途中から添加しても良い。また成分の一部をあらか
じめ混合、混練後、更に残りの成分を添加し押出しても
よい。In the present invention, the preparation of the composition comprising the aromatic polycarbonate, the hydroxy group-containing polymer and the filler is carried out in a usual mixer or kneader. That is, each component is charged into a V-blender, a ribbon mixer, a tumbler, or the like, uniformly mixed, melt-kneaded by a conventional single-screw or twin-screw extruder, cooled, and cut into pellets. At this time, some of the glass fibers and other components may be added in the middle of the extruder. After a part of the components are previously mixed and kneaded, the remaining components may be added and extruded.
【００１２】本発明の組成物には、本発明の目的を損な
わない範囲で難燃剤、難燃助剤、核剤、安定剤（例え
ば、リン酸エステル、亜リン酸エステル等）、酸化防止
剤（例えば、ヒンダードフェノール系化合物等）、光安
定剤、着色剤、発泡剤、滑剤、離型剤、帯電防止剤等を
配合しても良い。 The composition of the present invention contains a flame retardant, a flame retardant auxiliary, a nucleating agent, a stabilizer (for example, a phosphoric ester, a phosphite, etc.) and an antioxidant within a range not to impair the object of the present invention. (For example, a hindered phenol compound), a light stabilizer, a coloring agent, a foaming agent, a lubricant, a release agent, an antistatic agent, and the like .
【００１３】難燃剤としては例えば、臭素化ビスフェノ
ール -Ａ、臭素化ポリスチレン、臭素化ポリカーボネー
ト、トリフェニルホスフェート、ホスホン酸アミド、赤
リン等があげられる。難燃助剤としては例えば、三酸化
アンチモン、アンチモン酸ナトリウム等があげられる。
核剤としては例えばステアリン酸ナトリウム、エチレン
−アクリル酸ナトリウム共重合体等があげられる。Examples of the flame retardant include brominated bisphenol-A, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonamide, and red phosphorus. Examples of the flame retardant aid include antimony trioxide and sodium antimonate.
Examples of the nucleating agent include sodium stearate and ethylene-sodium acrylate copolymer.
【００１４】かくして得られた組成物は、射出成形、押
出成形、圧縮成形または回転成形等の任意の方法で容易
に成形することができる。The composition thus obtained can be easily molded by any method such as injection molding, extrusion molding, compression molding or rotational molding.
【００１５】[0015]
【実施例】本発明を以下の実施例により更に詳細に説明
する。なお、各実施例及び比較例において原料となる芳
香族ポリカーボネート樹脂、ヒドロキシ基含有重合体、
繊維状充填剤、繊維状充填剤以外の充填剤としては、芳
香族ポリカーボネート樹脂はビスフェノールＡ型ポリカ
ーボネート［帝人化成（株）製パンライトＬ−１２５
０、粘度平均分子量２５，０００］、ヒドロキシ基含有
重合体はビスフェノールＡ型フェノキシ樹脂［東都化成
（株）製フェノトートＹＰ−５０］、ビスフェノールＡ
型エポキシ樹脂［東都化成（株）製エポトートＹＤ−７
０２０］、繊維状充填剤は［日東紡（株）製チョップド
ストランド３ＰＥ−９４１］、繊維状充填剤以外の充填
剤は［日本板硝子（株）製ガラスフレークＲＥＦＧ−１
０１］を使用した。The present invention will be described in more detail with reference to the following examples. In each of the Examples and Comparative Examples, an aromatic polycarbonate resin as a raw material, a hydroxy group-containing polymer,
As the fibrous filler and the filler other than the fibrous filler, an aromatic polycarbonate resin is bisphenol A type polycarbonate [Panlite L-125 manufactured by Teijin Chemicals Ltd.]
0, viscosity average molecular weight of 25,000], and a hydroxy group-containing polymer is bisphenol A type phenoxy resin [Phenotote YP-50 manufactured by Toto Kasei Co., Ltd.], bisphenol A
Type epoxy resin [Epototo YD-7 manufactured by Toto Kasei Co., Ltd.]
020], the fibrous filler is [chopped strand 3PE-941 manufactured by Nitto Bo Co., Ltd.], and the filler other than the fibrous filler is [glass flake REFG-1 manufactured by Nippon Sheet Glass Co., Ltd.]
01] was used.
【００１６】また、評価項目の耐湿熱性は以下のように
試験を行い、引張り強さ保持率・曲げ強さ保持率は以下
のように算出した。The wet heat resistance of the evaluation items was tested as follows, and the tensile strength retention and bending strength retention were calculated as follows.
【００１７】評価用試験片を９３℃の熱水浸漬試験機に
て４８時間の浸漬試験を行い、試験片取り出し２４時間
後、引張り強さ（Kgf/cm2 ）はＡＳＴＭ Ｄ−６３８，
曲げ強さ（Kgf/cm2 ）はＡＳＴＭ Ｄ−７９０にしたが
って測定した。The test specimen for evaluation was subjected to a immersion test for 48 hours in a hot water immersion tester at 93 ° C., and after 24 hours, the tensile strength (Kgf / cm 2 ) was measured according to ASTM D-638.
Flexural strength (Kgf / cm 2 ) was measured according to ASTM D-790.
【００１８】引張り強さ保持率は以下の式に準じて算出
した。The tensile strength retention was calculated according to the following equation.
【００１９】[0019]
【数１】 (Equation 1)
【００２０】曲げ強さ保持率は以下の式に準じて算出し
た。The bending strength retention was calculated according to the following equation.
【００２１】[0021]
【数２】 (Equation 2)
【００２２】［実施例１〜１０］ 表１及び表２に示した重量比で芳香族ポリカーボネート
樹脂とヒドロキシ基含有重合体と繊維状充填剤と繊維状
充填剤以外の充填剤をドライブレンドした後、スクリュ
ー径３０ｍｍのベント付一軸押出機［ナカタニ機械
（株）製 ＶＳＫ−３０］を用い、シリンダー設定温度
２９０℃で溶融混練し、ストランドカットにより成形用
ペレットを得た。得られたペレットを１２０℃で５時
間、熱風循環式乾燥機にて乾燥し、射出成形機［住友重
機械工業（株）製ネスタール サイキャップ４８０／１
５０］でシリンダー設定温度３１０℃、型温度１００
℃、冷却時間２６秒、全成形サイクル５５秒で評価用試
験片を得た。評価用試験片は９３℃の熱水浸漬試験機に
て４８時間の浸漬試験を行い試験片取り出し２４時間
後、引張り強さ、曲げ強さを測定し、上式により保持率
を算出した。結果を合わせて表１および表２に示す。[0022] [Examples 1-10] Table 1 and then an aromatic polycarbonate resin and hydroxy group-containing polymer and the fibrous filler and the fibrous filler other than filler were dry-blended at a weight ratio shown in Table 2 Using a single-screw extruder with a screw diameter of 30 mm [VSK-30 manufactured by Nakatani Machinery Co., Ltd.], the mixture was melt-kneaded at a cylinder set temperature of 290 ° C., and a pellet for molding was obtained by strand cutting. The resulting pellet 5 hours at 120 ° C., dried in a hot air circulation type dryer, an injection molding machine [manufactured by Sumitomo Heavy Machinery Industry Co. Nesutaru Sai cap 480/1
50], cylinder set temperature 310 ° C, mold temperature 100
C., a cooling time of 26 seconds, and a total molding cycle of 55 seconds gave test specimens for evaluation. The test specimen for evaluation was subjected to a immersion test for 48 hours using a hot water immersion tester at 93 ° C., and after 24 hours, the tensile strength and the bending strength were measured, and the retention was calculated by the above equation. The results are shown in Tables 1 and 2.
【００２３】［比較例１〜３］ 表３に示した重量比で芳香族ポリカーボネート樹脂と繊
維状充填剤と繊維状充填剤以外の充填剤とを実施例と同
様の方法で溶融混練した。実施例と同様に評価用試験片
を得、９３℃の熱水浸漬試験機にて４８時間の浸漬試験
を行い試験片取り出し２４時間後、引張り強さ、曲げ強
さを測定し、上式により保持率を算出した。結果を合わ
せて表３に示す。[0023] an aromatic polycarbonate resin and the fibrous filler and the fibrous filler other than filler were melt-kneaded in the same manner as in Example at a weight ratio shown in Comparative Examples 1 to 3 Table 3. A test piece for evaluation was obtained in the same manner as in the example, and a immersion test was performed for 48 hours using a hot water immersion tester at 93 ° C., and after 24 hours, the tensile strength and bending strength were measured. The retention was calculated. The results are shown in Table 3.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【発明の効果】本発明の組成物は実施例に示すように耐
湿熱性に優れ、湿熱処理後の引張り強さ、曲げ強さ保持
率高く、高温多湿な環境で使用されるか、船倉など高温
多湿な環境で輸送されることのあるカメラ、オーディ
オ、カーオーディオ、ＶＴＲ、ＯＡ、電動工具部品等に
好適である。As shown in the examples, the composition of the present invention is excellent in wet heat resistance, has high tensile strength and retention of bending strength after wet heat treatment, and is used in a high-temperature and high-humidity environment. It is suitable for cameras, audios, car audios, VTRs, OA, power tool parts and the like that may be transported in humid environments.
Claims (1)
ト樹脂５０〜９９．９５重量％、成分（Ｂ）としてフェ
ノキシ樹脂またはエポキシ樹脂から選ばれた１種以上の
ヒドロキシ基含有重合体０．０５〜５０重量％からなる
樹脂成分１００重量部と、成分（Ｃ）としてＬ／Ｄ≧３
の繊維状充填剤を２０重量％以上含有する充填剤５〜２
４０重量部から実質的になる樹脂組成物であって、且つ
本文記載の耐湿熱性試験における４８時間浸漬試験後に
おいても良好な強度を有する芳香族ポリカーボネート樹
脂組成物。1. A component (A) an aromatic polycarbonate resin from 50 to 99.95% by weight, Fe as component (B)
100 parts by weight of a resin component comprising 0.05 to 50% by weight of at least one hydroxy group-containing polymer selected from a nonoxy resin or an epoxy resin, and L / D ≧ 3 as component (C)
5 to 2 containing at least 20% by weight of a fibrous filler of
A resin composition consisting essentially of 40 parts by weight , and
After 48 hours immersion test in the moisture and heat resistance test described in the text
An aromatic polycarbonate resin composition having good strength .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4107759A JP2968388B2 (en) | 1992-04-27 | 1992-04-27 | Polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4107759A JP2968388B2 (en) | 1992-04-27 | 1992-04-27 | Polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05302025A JPH05302025A (en) | 1993-11-16 |
| JP2968388B2 true JP2968388B2 (en) | 1999-10-25 |
Family
ID=14467272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4107759A Expired - Lifetime JP2968388B2 (en) | 1992-04-27 | 1992-04-27 | Polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2968388B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020196617A1 (en) | 2019-03-26 | 2020-10-01 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition, cured molded article, fiber-reinforced plastic molding material, fiber-reinforced plastic, fiber-reinforced plastic laminated molded body, and methods for producing same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2729765B2 (en) * | 1994-12-07 | 1998-03-18 | 大塚化学株式会社 | Stabilized polycarbonate resin composition |
| DE19547884A1 (en) * | 1995-12-21 | 1997-06-26 | Basf Ag | Molding compounds based on polycarbonates |
| US7572847B2 (en) | 2005-07-21 | 2009-08-11 | Asahi Kasei Chemicals Corporation | Aromatic polycarbonate resin composition and production method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52500B2 (en) * | 1972-10-27 | 1977-01-08 | ||
| JPS5565251A (en) * | 1978-11-09 | 1980-05-16 | Mitsubishi Rayon Co Ltd | Polycarbonate resin composition |
| JPS6153354A (en) * | 1984-08-22 | 1986-03-17 | Dainippon Ink & Chem Inc | Polycarbonate resin composition |
| JPS63245467A (en) * | 1987-04-01 | 1988-10-12 | Toshiba Corp | Resin composition |
| JPH0652363B2 (en) * | 1988-02-08 | 1994-07-06 | 帝人化成株式会社 | Camera parts |
| JPH03220263A (en) * | 1988-06-17 | 1991-09-27 | Mitsui Petrochem Ind Ltd | Polycarbonate resin composition |
-
1992
- 1992-04-27 JP JP4107759A patent/JP2968388B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020196617A1 (en) | 2019-03-26 | 2020-10-01 | 日鉄ケミカル＆マテリアル株式会社 | Resin composition, cured molded article, fiber-reinforced plastic molding material, fiber-reinforced plastic, fiber-reinforced plastic laminated molded body, and methods for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05302025A (en) | 1993-11-16 |
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