JPH0224346A - Fiber-reinforced thermoplastic resin composition - Google Patents
Fiber-reinforced thermoplastic resin compositionInfo
- Publication number
- JPH0224346A JPH0224346A JP17536488A JP17536488A JPH0224346A JP H0224346 A JPH0224346 A JP H0224346A JP 17536488 A JP17536488 A JP 17536488A JP 17536488 A JP17536488 A JP 17536488A JP H0224346 A JPH0224346 A JP H0224346A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- graft copolymer
- pts
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 12
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 10
- 229920001225 polyester resin Polymers 0.000 claims abstract description 6
- 239000004645 polyester resin Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000012744 reinforcing agent Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 30
- -1 polybutylene terephthalate Polymers 0.000 abstract description 28
- 229920000728 polyester Polymers 0.000 abstract description 26
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000003365 glass fiber Substances 0.000 abstract description 8
- 229920002857 polybutadiene Polymers 0.000 abstract description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002787 reinforcement Effects 0.000 abstract 2
- 229920001971 elastomer Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- URRLLRVIUROMEQ-UHFFFAOYSA-N anthracene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 URRLLRVIUROMEQ-UHFFFAOYSA-N 0.000 description 1
- XAAYMWLCUICVSL-UHFFFAOYSA-N anthracene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 XAAYMWLCUICVSL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は耐衝撃性、成形加工性に優れた繊維強化熱可塑
性樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fiber-reinforced thermoplastic resin composition having excellent impact resistance and moldability.
［従来の技術］
芳香族ポリエステル樹脂（以下ポリエステルと略称する
）は優れた機械的性質、電気的性質、耐薬品性、耐熱性
、低吸湿性、加工性などを有しており、エンジニアリン
グプラスチックとして広く使用されているが、耐衝撃性
に劣るという欠点がある。[Prior art] Aromatic polyester resin (hereinafter abbreviated as polyester) has excellent mechanical properties, electrical properties, chemical resistance, heat resistance, low moisture absorption, processability, etc., and is used as an engineering plastic. Although widely used, it has the disadvantage of poor impact resistance.
ポリエステルの耐衝撃性を改良するための一般的な方法
として、ガラス繊維等の繊維状強化剤を添加する方法が
知られている。しかしながら、繊維状強化剤をポリエス
テルに添加した場合、耐衝撃性向上効果は不十分であり
、しかも、繊維状強化剤が配向するために、成形収縮率
に大きな異方性を生じ、そりが発生してしまう。A commonly known method for improving the impact resistance of polyester is to add a fibrous reinforcing agent such as glass fiber. However, when a fibrous reinforcing agent is added to polyester, the effect of improving impact resistance is insufficient, and the orientation of the fibrous reinforcing agent causes large anisotropy in the molding shrinkage rate, causing warping. Resulting in.
そこで、ポリエステルの耐衝撃性を改良し、しかも、そ
りの発生を防止することを目的に、ポリエステル、ガラ
ス繊維、およびスチレン系重合体とのブレンドが提案さ
れている（例えば特開昭５０−１１４６号公報、特開昭
５０−２３４４８号公報、特開昭５２−８６４４６号公
報等）。Therefore, in order to improve the impact resistance of polyester and prevent the occurrence of warpage, blends of polyester, glass fiber, and styrene polymers have been proposed (for example, in JP-A No. 50-1146 JP-A-50-23448, JP-A-52-86446, etc.).
さらに、ポリエステルとの相溶性を上げる目的で、メタ
クリル酸エステルをグラフト共重合したゴム状重合体と
ポリエステル、充填剤のブレンドが提案されている（例
えば、特開昭５７−１３８２５７号公報等）。Further, for the purpose of increasing compatibility with polyester, a blend of a rubbery polymer obtained by graft copolymerizing a methacrylic acid ester, polyester, and a filler has been proposed (for example, Japanese Patent Application Laid-Open No. 138257/1983).
さらに、メタクリル酸エステルをグラフト共重合したゴ
ム状重合体、ポリエステル、充填剤の混合物にエポキシ
化合物をブレンドする方法が提案されている（例えば、
特開昭６１−１５１２６２号公報等）。Furthermore, a method has been proposed in which an epoxy compound is blended into a mixture of a rubber-like polymer obtained by graft copolymerizing a methacrylic acid ester, a polyester, and a filler (for example,
(Japanese Unexamined Patent Publication No. 151262/1983, etc.).
［発明が解決しようとする課題］
しかし、前記したような方法では、ポリエステルの耐衝
撃性および成形加工性を十分に満足できるレベルまで改
良することは難しい。[Problems to be Solved by the Invention] However, with the methods described above, it is difficult to improve the impact resistance and moldability of polyester to a fully satisfactory level.
例えば、ポリエステル、ガラス繊維およびスチレン系重
合体とのブレンドでは、そりの問題は大幅に改良される
が、ポリエステルとスチレン系重合体との相溶性が本質
的に悪いために、耐衝撃性は満足のできるレベルではな
い。For example, blends of polyester, glass fiber, and styrenic polymers greatly improve the warping problem, but the impact resistance is unsatisfactory due to the inherently poor compatibility of polyester with styrenic polymers. It is not at the level where it can be done.
メタクリル酸エステルを導入した場合にも、相溶性はほ
とんど改良されず、耐衝撃性の向上効果は不十分である
。Even when methacrylic acid ester is introduced, the compatibility is hardly improved and the effect of improving impact resistance is insufficient.
エポキシ化合物を添加した場合は、エポキシ化合物が局
在化して硬化するために、本質的に流動性が悪くなる。When an epoxy compound is added, the epoxy compound is localized and hardened, resulting in essentially poor fluidity.
本発明の課題は、ポリエステルの成形加工性を損うこと
なく耐衝撃性を改良し、耐熱性、耐薬品性、機械物性に
優れる樹脂組成物を提供することにある。An object of the present invention is to provide a resin composition that improves impact resistance without impairing the moldability of polyester and has excellent heat resistance, chemical resistance, and mechanical properties.
［課題を解決するための手段］
すなわち、本発明は上記課題を解決するために次の構成
をとる。[Means for Solving the Problems] That is, the present invention takes the following configuration in order to solve the above problems.
（Ａ）（ａ）ジエン系ゴム１０〜８５重量部に、（ｂ）
（イ）芳香族ビニル５０〜９０重量（ロ）シアン化ビニ
ル９〜５０重量
％
（ハ）α、β−不飽和カルボン酸
０．１〜２０重世％
からなる単量体混合物９０〜１５重量
部をグラフト共重合してなるグラフト
共重合体または該グラフト共重合体と
残りの単量体が共重合した共重合体と
からなるグラフト共重合体組成物１〜
９４重量部と
（Ｂ）芳香族ポリエステル樹脂１〜９４重量部と（Ｃ）
繊維状強化剤５〜７０重量部
からなり、（Ａ）、（Ｂ）および（Ｃ）の合計量が１０
０重量部である繊維強化熱可塑性樹脂組成物。(A) (a) 10 to 85 parts by weight of diene rubber, (b)
(a) 50-90% by weight of aromatic vinyl (b) 9-50% by weight of vinyl cyanide (c) 90-15% by weight of a monomer mixture consisting of 0.1-20% by weight of α,β-unsaturated carboxylic acid 1 to 94 parts by weight of a graft copolymer composition comprising a graft copolymer obtained by graft copolymerizing a part of the monomer, or a copolymer obtained by copolymerizing the graft copolymer and the remaining monomer, and (B) aromatic 1 to 94 parts by weight of Group polyester resin and (C)
It consists of 5 to 70 parts by weight of fibrous reinforcing agent, and the total amount of (A), (B) and (C) is 10
0 parts by weight of a fiber-reinforced thermoplastic resin composition.
本発明の特徴はジエン系ゴムのグラフト成分として、芳
香族ビニルとシアン化ビニルおよびα。The feature of the present invention is that aromatic vinyl, vinyl cyanide, and α are used as graft components of diene rubber.
β−不飽和カルボン酸の３成分を必須としてグラフト共
重合したグラフト共重合体（組成物）と、ポリエステル
および繊維状強化剤をブレンドすることである。α、β
−不飽和カルボン酸を共重合したグラフト共重合体（組
成物）および繊維状強化剤を含むことにより、樹脂組成
物の耐衝撃性は十分に高く、成形品のソリの発生も抑制
される。This method involves blending a graft copolymer (composition) obtained by graft copolymerizing essential components of β-unsaturated carboxylic acid with a polyester and a fibrous reinforcing agent. α, β
- By including the graft copolymer (composition) copolymerized with unsaturated carboxylic acid and the fibrous reinforcing agent, the impact resistance of the resin composition is sufficiently high, and the occurrence of warpage in the molded product is suppressed.
以下、本発明を具体的に説明する。The present invention will be specifically explained below.
本発明におけるグラフト共重合体またはグラフト共重合
体組成物（Ａ）とは、（ａ）と（ｂ）の合計を１００重
量部として、ジエン系ゴム（ａ）１０〜８５重量部に、
芳香族ビニル（イ）５０〜９０重量％とシアン化ビニル
（ロ）９〜５０重量％とα、β−不飽和カルボン酸（ハ
）０．１〜２０量量％の合計が１００重量％からなる単
量体混合物（ｂ）１５〜９０重量部の全量をグラフト共
重合してなるグラフト共重合体または該単量体混合物の
一部をグラフト共重合してなるグラフト共重合体と、残
りの重合体が共重合した共重合体とのグラフト共重合体
組成物である。この場合、α。The graft copolymer or graft copolymer composition (A) in the present invention refers to 10 to 85 parts by weight of the diene rubber (a), with the total of (a) and (b) being 100 parts by weight.
The total of 50 to 90% by weight of aromatic vinyl (a), 9 to 50% by weight of vinyl cyanide (b), and 0.1 to 20% by weight of α,β-unsaturated carboxylic acid (c) is from 100% by weight. A graft copolymer obtained by graft copolymerizing a total amount of 15 to 90 parts by weight of the monomer mixture (b), or a graft copolymer obtained by graft copolymerizing a part of the monomer mixture, and the remaining It is a graft copolymer composition with a copolymer obtained by copolymerizing the polymer. In this case, α.
β−不飽和カルボン酸は、全量をグラフト共重合体に共
重合するか、グラフト共重合体および残りの単量体が共
重合した共重合体に分割して共重合するか、あるいは全
量を残りの単量体が共重合した共重合体に共重合するこ
とができる。The β-unsaturated carboxylic acid can be copolymerized in its entirety into a graft copolymer, divided into a copolymer in which the graft copolymer and the remaining monomer are copolymerized, or the entire amount can be copolymerized with the remaining monomer. The monomers can be copolymerized to form a copolymer.
本発明で最も重要なことは、グラフト共重合体またはグ
ラフト共重合体組成物（Ａ）において芳香族ビニル（イ
）、シアン化ビニル（ロ）およびα、β−不飽和カルボ
ン酸（ハ）を必須とする単量体混合物（ｂ）をジエン系
ゴム（ａ）にグラフト共重合したグラフト共重合体を用
いることである。The most important thing in the present invention is that the graft copolymer or graft copolymer composition (A) contains aromatic vinyl (a), vinyl cyanide (b), and α,β-unsaturated carboxylic acid (c). It is to use a graft copolymer obtained by graft copolymerizing the essential monomer mixture (b) to the diene rubber (a).
本発明におけるジエン系ゴム（ａ）としては、ポリブタ
ジェンゴム、アクリロニトリル−ブタジェン共重合体ゴ
ム、スチレン−ブタジェン共重合体ゴム、ポリイソプレ
ンゴム等があり、なかでもポリブタジェンゴム、スチレ
ン−ブタジェン共重合体ゴム等が好ましい。The diene rubber (a) in the present invention includes polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. Among them, polybutadiene rubber, styrene-butadiene copolymer rubber, etc. Copolymer rubber and the like are preferred.
本発明における単量体混合物（ｂ）中の芳香族ビニル（
イ）としては、スチレン、α−メチルスチレン、ｐ−メ
チルスチレン、ｐ−ｔ−ブチルスチレン等が挙げられ、
なかでもスチレン、α−メチルスチレン等が好ましい。Aromatic vinyl (
Examples of a) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, etc.
Among them, styrene, α-methylstyrene, etc. are preferred.
本発明における単量体混合物（ｂ）中のシアン化ビニル
（ロ）としては、アクリロニトリル、メタクリロニトリ
ル等が挙げられ、ながでもアクリロニトリルが好ましい
。Examples of the vinyl cyanide (b) in the monomer mixture (b) in the present invention include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.
本発明における単量体混合物（ｂ）中のα、β−不飽和
カルボン酸（ハ）としては、アクリル酸、メタクリル酸
などが挙げられ、これらは２種以上併用することができ
る。Examples of the α,β-unsaturated carboxylic acid (c) in the monomer mixture (b) in the present invention include acrylic acid and methacrylic acid, and two or more of these can be used in combination.
また、（イ）、（ロ）、（ハ）の単量体の合計１００重
量部に対して、７０重量部以下の範囲で共電−合可能な
他の単量体をグラフト共重合することも可能である。Furthermore, with respect to a total of 100 parts by weight of the monomers (a), (b), and (c), 70 parts by weight or less of other monomers capable of coelectrification may be graft copolymerized. is also possible.
共重合可能な他の単量体として、メタクリル酸メチル、
メタクリル酸エチル、メタクリル酸１−ブチル、メタク
リル酸シクロヘキシル、アクリル酸グリシジル、メタク
リル酸グリシジル等のα。Other copolymerizable monomers include methyl methacrylate,
α of ethyl methacrylate, 1-butyl methacrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, etc.
β−不飽和カルボン酸エステル類、無水マレイン酸、無
水イタコン酸等のα、β−不飽和ジカルボン酸無水物類
、Ｎ−フェニルマレイミド、Ｎ−メチルマレイミド、Ｎ
−ｔ−ブチルマレイミドなどのα、β−不飽和カルボン
酸のイミド化合物類等が挙げられる。β-unsaturated carboxylic acid esters, α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-methylmaleimide, N
Examples include imide compounds of α,β-unsaturated carboxylic acids such as -t-butylmaleimide.
グラフト共重合体またはグラフト共重合体組成物（Ａ）
におけるジエン系ゴム（ａ）の組成比は、（ａ）と（ｂ
）の合計を１００重量部として１０〜８５重量部、好ま
しくは１２〜８０重量部、特に好ましくは１５〜７０重
量部である。Graft copolymer or graft copolymer composition (A)
The composition ratio of diene rubber (a) in (a) and (b) is
) is 10 to 85 parts by weight, preferably 12 to 80 parts by weight, particularly preferably 15 to 70 parts by weight.
また、本発明における単量体混合物（ｂ）中の芳香族ビ
ニル（イ）、シアン化ビニル（ロ）、α。Furthermore, aromatic vinyl (a), vinyl cyanide (b), and α in the monomer mixture (b) in the present invention.
β−不飽和カルボン酸（ハ）の各組成比は、（イ）が５
０〜９０重量％、好ましくは５５〜８５重量％、特に好
ましくは５７〜８２重量、（ロ）が９〜５０重量％、好
ましくは１５〜４５重合％、特に好ましくは１８〜４３
重量％である。Each composition ratio of β-unsaturated carboxylic acid (c) is (a) is 5
0 to 90% by weight, preferably 55 to 85% by weight, particularly preferably 57 to 82% by weight, 9 to 50% by weight of (b), preferably 15 to 45% by weight, particularly preferably 18 to 43% by weight
Weight%.
（ハ）については０．１〜２０重量％の範囲で用いられ
るが、好ましくは０．２〜１０重量％、特に好ましくは
０．５〜８重量％の範囲で用いられる。(iii) is used in a range of 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight.
（ａ）が（ａ）と（ｂ） （７）合計１００重量部に対
して１０重量部未満の場合、ならびに（イ）、（ロ）、
（ハ）の合計１００重量％に対して（イ）が９０重量％
を越えた場合、および（ロ）が９重量％未満の場合は、
得られる組成物の耐衝撃性が低いため好ましくない。ま
た（ａ）が（ａ）と（ｂ）の合計１００重量部に対して
８５重量部を越えた場合、ならびに（イ）、（ロ）、（
ハ）の合計１００重量％に対して（イ）が５０重量％未
満の場合および（ロ）が５０重量％を越えた場合は、得
られる組成物の成形加工性が劣るので実用的でない。さ
らに、（ハ）が０．１重量％未満では得られる組成物の
耐衝撃性が低く、２０重量％を越″えると（Ａ）の製造
時架橋反応を起こし易く、一定品質のものを得るのが困
難となり、実用的でない。グラフト共重合体またはグラ
フト共重合体組成物（Ａ）の製造方法に関しては特に制
限はなく、塊状重合、溶液重合、塊状懸濁重合、懸濁重
合、乳化重合等通常の方法が用いられる。単量体の仕込
み方法に関しても特に制限はなく、初期に一括添加して
もよく、また共重合体の組成分布の生成を防止するため
に、仕込み単量体の一部または全部を連続仕込みまたは
分割仕込みしながら重合してもよい。When (a) is less than 10 parts by weight based on the total of (a) and (b) (7) 100 parts by weight, and (a), (b),
(B) is 90% by weight relative to the total 100% by weight of (C).
and (b) is less than 9% by weight,
This is not preferred because the resulting composition has low impact resistance. In addition, if (a) exceeds 85 parts by weight based on the total of 100 parts by weight of (a) and (b), and (a), (b), (
If (a) is less than 50% by weight or if (b) is more than 50% by weight with respect to the total 100% by weight of c), the moldability of the resulting composition will be poor and it is not practical. Furthermore, if (c) is less than 0.1% by weight, the resulting composition will have low impact resistance, and if it exceeds 20% by weight, crosslinking reaction will easily occur during the production of (A), resulting in a constant quality product. There are no particular restrictions on the method for producing the graft copolymer or graft copolymer composition (A), and bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are possible. There are no particular restrictions on the method of charging the monomers, and they may be added all at once at the initial stage. Polymerization may be carried out while part or all of the mixture is continuously or dividedly charged.
また、別々に（グラフト）共重合した樹脂をブレンドす
ることによって、上記の組成物を得ることも可能である
。It is also possible to obtain the above compositions by blending separately (graft) copolymerized resins.
本発明における芳香族ポリエステル樹脂（Ｂ）とは、芳
香環を重合体の連鎖単位に有するポリエステルで、芳香
族ジカルボン酸（あるいはそのエステル形成性誘導体）
と、ジオール（あるいはそのエステル形成性誘導体）と
を主成分とする重縮合反応により得られる重合体ないし
共重合体である。The aromatic polyester resin (B) in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is an aromatic dicarboxylic acid (or its ester-forming derivative).
It is a polymer or copolymer obtained by a polycondensation reaction containing as main components a diol (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof).
ここでいう芳香族ジカルボン酸としては、テレフタル酸
、イソフタル酸、オルトフタル酸、１゜５−ナフタレン
ジカルボン酸、２，５−ナフタレンジカルボン酸、２，
６−ナフタレンジカルボン酸、２． ２’−ビフェニル
ジカルボン酸、３゜３′−ビフェニルジカルボン酸、４
．４’ −ビフェニルジカルボン酸、４．４’ −ジフ
ェニルエーテルジカルボン酸、４．４’ −ジフェニル
メタンジカルボン酸、４．４’ −ジフェニルスルフォ
ンジカルボン酸、４．４’ −ジフェニルイソプロピリ
デンジカルボン酸、１，２−ビス（フェノキシ）エタン
−４，４′−ジカルボン酸、２，５−アントラセンジカ
ルボン酸、２，６−アントラセンジカルボン酸、４．４
’ −ｐ−ターフェニレンジカルボン酸、２，５−ピリ
ジンジカルボン酸などであり、中でもテレフタル酸が好
ましい。The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1°5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,
6-naphthalene dicarboxylic acid, 2. 2'-biphenyldicarboxylic acid, 3゜3'-biphenyldicarboxylic acid, 4
．． 4'-biphenyl dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, 4.4'-diphenylmethane dicarboxylic acid, 4.4'-diphenylsulfone dicarboxylic acid, 4.4'-diphenylisopropylidene dicarboxylic acid, 1,2- Bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4.4
'-p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, etc., and among them, terephthalic acid is preferred.
これらの芳香族ジカルボン酸は２種以上を混合して使用
してもよい。なお少量であれば、これらの芳香族ジカル
ボン酸と共に、アジピン酸、アゼライン酸、ドデカンジ
オン酸、セバシン酸などの脂肪族ジカルボン酸、シクロ
ヘキサンジカルボン酸などの脂環族ジカルボン酸を一種
以上混合して使用することができる。Two or more of these aromatic dicarboxylic acids may be used in combination. If the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. can do.
またジオール成分としては、エチレングリコール、プロ
ピレングリコール、ブチレングリコール、ヘキシレング
リコール、ネオペンチルグリコール、２−メチル−１，
３−プロパンジオール、ジエチレングリコール、トリエ
チレングリコール等の脂肪族ジオール、１，４−シクロ
ヘキサンジメタツールなどの脂環族ジオール等、および
それらの混合物などがあげられる。なお少量であれば、
分子量４００〜６，０００の長鎖ジオール、すなわち、
ポリエチレングリコール、ポリ−１，３−プロピレング
リコール、ポリテトラメチレングリコールなどを一種以
上共重合せしめてもよい。Diol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,
Examples include aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, and mixtures thereof. Furthermore, if it is a small amount,
Long chain diols with a molecular weight of 400 to 6,000, i.e.
One or more types of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.
具体的な芳香族ポリエステルとしては、ポリエチレンテ
レフタレート、ポリプロピレンテレフタレート、ポリブ
チレンテレフタレート、ポリエチレンナフタレート、ポ
リブチレンナフタレート、ポリエチレン−１，２−ビス
（フェノキシ）エタン−４，４′−ジカルボキシレート
などのほか、ポリエチレンイソフタレート／テレフタレ
ート、ポリブチレンテレフタレート／イソフタレート、
ポリブチレンテレフタレート／デカンジカルボキシレー
トなどの共重合ポリエステルがあげられる。Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, etc. In addition, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate,
Examples include copolymerized polyesters such as polybutylene terephthalate/decane dicarboxylate.
これらのうち機械的性質、成形性などのバランスのとれ
たポリブチレンテレフタレートおよびポリエチレンテレ
フタレートが好ましく使用できる。Among these, polybutylene terephthalate and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used.
本発明における芳香族ポリエステルは、０．５％の０−
クロルフェノール溶液を２５℃で測定した相対粘度が、
１．１５〜３．０、特に１．３〜２．５のものが好まし
い。相対粘度が１．１５未満の場合には、得られる成形
品の衝撃強度が低く、３．０より大きい場合には成形品
表面の光沢が悪く実用的でない。The aromatic polyester in the present invention contains 0.5% 0-
The relative viscosity of the chlorophenol solution measured at 25°C is
1.15-3.0, especially 1.3-2.5 is preferred. If the relative viscosity is less than 1.15, the resulting molded product will have low impact strength, and if it is greater than 3.0, the surface of the molded product will have poor gloss, making it impractical.
本発明における繊維状強化剤とは、ガラス繊維（表面を
カップリング剤等で処理したものを含む）、炭素繊維、
金属繊維、アスベスト、セラミック繊維、有機繊維等が
挙げられ、中でもチョツプドストランドタイプのガラス
繊維が最も好ましく用いられる。In the present invention, fibrous reinforcing agents include glass fibers (including those whose surfaces have been treated with a coupling agent, etc.), carbon fibers,
Examples include metal fibers, asbestos, ceramic fibers, and organic fibers, among which chopped strand type glass fibers are most preferably used.
本発明の繊維強化熱可塑性樹脂組成物において、グラフ
ト共重合体またはグラフト共重合体組成物（Ａ）と芳香
族ポリエステル（Ｂ）および繊維状強化剤（Ｃ）の配合
割合は、（Ａ）が１〜９４重量部、好ましくは２〜９０
重量部、特に好ましくは５〜８５重量部、（Ｂ）が１〜
９４重量部、好ましくは２〜９０重量部、特に好ましく
は５〜８５重量部、（Ｃ）が５〜７０重量部、好ましく
は７〜６５重量部、特に好ましくは１０〜６０重量部で
、かつ（Ａ）、（Ｂ）および（Ｃ）の合計量が１００重
量部となる割合である。（Ａ）が１重量部未満で（Ｂ）
が９４重量部を越えた場合、（Ｃ）が５重量部未満、７
０重量部を越えた場合は組成物の耐衝撃性が劣り、（Ａ
）が９４重量部を越え、かつ（Ｂ）が１重量部未満の場
合は組成物の耐薬品性が劣るので好ましくない。In the fiber-reinforced thermoplastic resin composition of the present invention, the blending ratio of the graft copolymer or graft copolymer composition (A), aromatic polyester (B), and fibrous reinforcing agent (C) is such that (A) 1 to 94 parts by weight, preferably 2 to 90 parts by weight
Parts by weight, particularly preferably 5 to 85 parts by weight, 1 to 85 parts by weight of (B)
94 parts by weight, preferably 2 to 90 parts by weight, particularly preferably 5 to 85 parts by weight, 5 to 70 parts by weight, preferably 7 to 65 parts by weight, particularly preferably 10 to 60 parts by weight of (C), and The ratio is such that the total amount of (A), (B) and (C) is 100 parts by weight. (A) is less than 1 part by weight (B)
exceeds 94 parts by weight, (C) is less than 5 parts by weight, 7
If it exceeds 0 parts by weight, the impact resistance of the composition will be poor, and (A
) is more than 94 parts by weight and (B) is less than 1 part by weight, which is not preferred because the chemical resistance of the composition will be poor.
本発明の繊維強化熱可塑性樹脂組成物中のα。α in the fiber-reinforced thermoplastic resin composition of the present invention.
β−不飽和カルボン酸残基の含有量は特に制限はないが
、樹脂の耐衝撃性および流動性の点から、通常０．００
０１５〜１６．０重量％、特に０゜０１〜１０重量％の
範囲となるようにグラフト共重合体またはグラフト共重
合体組成物（Ａ）中のα、β−不飽和カルボン酸の共重
合量および繊維強化熱可塑性樹脂組成物中のグラフト共
重合体またはグラフト共重合体組成物（Ａ）の配合曾を
選ぶのが好ましい。The content of β-unsaturated carboxylic acid residues is not particularly limited, but from the viewpoint of resin impact resistance and fluidity, it is usually 0.000.
The copolymerized amount of α, β-unsaturated carboxylic acid in the graft copolymer or graft copolymer composition (A) is in the range of 0.015 to 16.0% by weight, particularly 0.01 to 10% by weight. It is preferable to select the proportion of the graft copolymer or graft copolymer composition (A) in the fiber-reinforced thermoplastic resin composition.
本発明の繊維強化熱可塑性樹脂組成物の製造方法に関し
ては特に制限はなく、通常公知の方法を採用することが
できる。すなわち、グラフト共重合体またはグラフト共
重合体組成物（Ａ）、ポリエステル（Ｂ）よび繊維状強
化剤（Ｃ）をペレット、粉末、細片状態等で、高速撹拌
機等を用いて均一混合した後、十分な混練能力のある一
軸または多軸の押出機で溶融混練する方法およびバンバ
リーミキサ−やゴムロール機を用いて溶融混練する方法
等、種々の方法を採用することができる。There are no particular restrictions on the method for producing the fiber-reinforced thermoplastic resin composition of the present invention, and generally known methods can be employed. That is, the graft copolymer or graft copolymer composition (A), polyester (B), and fibrous reinforcing agent (C) were uniformly mixed in the form of pellets, powder, small pieces, etc. using a high-speed stirrer or the like. After that, various methods can be employed, such as melt-kneading using a single-screw or multi-screw extruder with sufficient kneading capacity, and melt-kneading using a Banbury mixer or rubber roll machine.
本発明の繊維強化熱可塑性樹脂組成物は、ゲラフート共
重合体またはグラフト共重合体組成物（Ａ）、ポリエス
テル（Ｂ）、および繊維状強化剤（Ｃ）の他に、必要に
応じてポリスチレン（ＰＳ）、スチレン／アクリロニト
リル共重合体（ＳＡＮ）、ポリメタクリル酸メチル（Ｐ
ＭＭＡ）、スチレン／メタクリル酸メチル／アクリロニ
トリル共重合体、α−メチルスチレン／アクリロニトリ
ル共重合体、α−メチルスチレン／スチレン／アクリロ
ニトリル共重合体、α−メチルスチレン／メタクリル酸
メチル／アクリロニトリル共重合体、ｐ−メチルスチレ
ン／アクリロニトリル共重合体、スチレン／Ｎ−フェニ
ルマレイミド共重合体等のビニル系重合体、メタクリル
酸−ブタジェン−スチレン三元共重合体（ＭＢＳ）樹脂
、ＡＥＳ樹脂、ＡＡＳ樹脂、ポリカーボネート、ポリカ
プロアミド（ナイロン６）、ポリヘキサメチレンアジパ
ミド（ナイロン６６）等熱可塑性樹脂を適宜混合したり
、ポリエチレン、ポリプロピレン、エチレン／プロピレ
ン共重合体、エチレン／ブテン−１共重合体、エチレン
／プロピレン／ジシクロペンタジェン共重合体、エチレ
ン／プロピレン１５−エチリデン２−ノルボルネン共重
合体、エチレン／酢酸ビニル共重合体およびエチレン／
アクリル酸ブチル共重合体等のポリオレフィン系ゴムを
適宜混合することによって、さらに望ましい物性、特性
に調節することも可能である。また目的に応じて顔料や
染料、金属フレーク等の補強材や充填材、熱安定剤、酸
化防止剤、紫外線吸収剤、光安定剤、滑剤、可塑剤、帯
電防止剤および難燃剤等を添加することができる。The fiber-reinforced thermoplastic resin composition of the present invention contains polystyrene ( PS), styrene/acrylonitrile copolymer (SAN), polymethyl methacrylate (P
MMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, Vinyl polymers such as p-methylstyrene/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, methacrylic acid-butadiene-styrene terpolymer (MBS) resin, AES resin, AAS resin, polycarbonate, Thermoplastic resins such as polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 66) may be appropriately mixed, or polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/ Propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene 2-norbornene copolymer, ethylene/vinyl acetate copolymer and ethylene/
By appropriately mixing polyolefin rubber such as butyl acrylate copolymer, it is also possible to adjust the physical properties and characteristics to more desirable values. Depending on the purpose, reinforcing materials and fillers such as pigments, dyes, and metal flakes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, antistatic agents, and flame retardants may also be added. be able to.
［実 施 例］
以下、実施例および比較例によって本発明をさらに詳し
く説明する。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
成形加工性の評価として、そり量を測定した。As an evaluation of moldability, the amount of warpage was measured.
そり量は、厚さ０．５ｍｍのフィルムゲートをもつ８０
Ｘ８０Ｘ１ｍｍの角板を成形し、平板上に静置してその
一端を軽くおさえ、もっとも浮き上りの大きい他端と平
板間の距離を測定した。The amount of warpage is 80 with a film gate of 0.5 mm thickness.
A square plate measuring 80 mm x 1 mm was formed, placed on a flat plate, one end of which was lightly pressed, and the distance between the other end and the flat plate where the bulge was the largest was measured.
耐衝撃性の評価として１／２′アイゾツト衝撃強さをＡ
ＳＴＭ Ｄ２５６−５６に従って測定した。As an evaluation of impact resistance, 1/2′ isot impact strength is A.
Measured according to STM D256-56.
耐薬品性は、射出成形した角板をメタノールおよびガソ
リンに２３℃、２４時間浸漬して角板表面を目視で観察
した。Chemical resistance was determined by immersing an injection-molded square plate in methanol and gasoline at 23°C for 24 hours, and visually observing the surface of the square plate.
なお、以下の部数および％は、それぞれ重量部および重
合％を表わす。Note that the following parts and percentages represent parts by weight and polymerization percentage, respectively.
参考例１
次の処方により、グラフト共重合体Ａ−１〜Ａ−６を製
造した。Reference Example 1 Graft copolymers A-1 to A-6 were manufactured according to the following formulations.
Ａ−１：ポリブタジェンラテックス（ゴム粒子径０．２
５μ、ゲル含率８０％）６０部（固形分換算）の存在下
でスチレン７０％、アクリロニトリル２０％、メタクリ
ル酸１０％からなる単量体混合物４０部を乳化重合した
。得られたグラフト共重合体は硫酸マグネシウムで凝固
し、洗浄、ろ過、乾燥してパウダー状のグラフト共重合
体（Ａ−１）を調製した。A-1: Polybutadiene latex (rubber particle size 0.2
40 parts of a monomer mixture consisting of 70% styrene, 20% acrylonitrile, and 10% methacrylic acid was emulsion polymerized in the presence of 60 parts (in terms of solid content) (5μ, gel content 80%). The obtained graft copolymer was coagulated with magnesium sulfate, washed, filtered, and dried to prepare a powdery graft copolymer (A-1).
Ａ−２： Ａ−１で使用したポリブタジェンラテックス
４０部（固形分換算）の存在下でメタクリル酸メチル１
３％、スチレン７０％、アクリロニトリル１５％、アク
リル酸２％からなる単量体混合物６０部を乳化重合した
後、Ａ−１と同様にしてパウダー状のグラフト共重合体
（Ａ−２）を調製した。A-2: 1 methyl methacrylate in the presence of 40 parts of the polybutadiene latex used in A-1 (calculated as solid content)
After emulsion polymerization of 60 parts of a monomer mixture consisting of 3% styrene, 70% styrene, 15% acrylonitrile, and 2% acrylic acid, a powdery graft copolymer (A-2) was prepared in the same manner as A-1. did.
Ａ−３ニジエンＮＦ３５Ａ （旭化成■製）２０部をス
チレン４５部、α−メチルスチレン１１部、アクリロニ
トリル２０部、メタクリル酸４部に溶゛解した後、塊状
重合してグラフト共重合体（Ａ−３）を調製した。After dissolving 20 parts of A-3 Nidiene NF35A (manufactured by Asahi Kasei ■) in 45 parts of styrene, 11 parts of α-methylstyrene, 20 parts of acrylonitrile, and 4 parts of methacrylic acid, bulk polymerization was performed to obtain a graft copolymer (A-3). 3) was prepared.
Ａ−４ニジエンＮＦ３５Ａ （旭化成■製）２０部をス
チレン５０部、アクリロニトリル１８部、メタクリル酸
メチル１０部、アクリル酸２部に溶解した後、塊状重合
してグラフト共重合体（Ａ−４）を調製した。After dissolving 20 parts of A-4 Nidiene NF35A (manufactured by Asahi Kasei) in 50 parts of styrene, 18 parts of acrylonitrile, 10 parts of methyl methacrylate, and 2 parts of acrylic acid, bulk polymerization was performed to obtain a graft copolymer (A-4). Prepared.
Ａ−５： Ａ−１で使用したポリブタジェンラテックス
５０部（固形分換算）の存在下でスチレン９５％、メタ
クリル酸５％からなる単量体混合物５０部を乳化重合し
た後、Ａ−１と同様にしてパウダー状のグラフト共重合
体（Ａ−５）を調製した。A-5: After emulsion polymerization of 50 parts of a monomer mixture consisting of 95% styrene and 5% methacrylic acid in the presence of 50 parts (solid content equivalent) of the polybutadiene latex used in A-1, A-1 A powdery graft copolymer (A-5) was prepared in the same manner as above.
Ａ＝６：Ａ−１で使用したポリブタジェンラテックス６
０部（固形分換算）の存在下で、スチレン７５％、アク
リロニトリル２５％からなる単量体混合物４０部を乳化
重合した後、Ａ−１と同様にしてパウダー状のグラフト
共重合体（Ａ−６）を調製した。A=6: Polybutadiene latex 6 used in A-1
After emulsion polymerizing 40 parts of a monomer mixture consisting of 75% styrene and 25% acrylonitrile in the presence of 0 parts (solid content), a powdery graft copolymer (A-1) was prepared in the same manner as A-1. 6) was prepared.
実施例１〜８
参考例１で製造したＡ−１〜Ａ−４、ポリエステルとし
てＰＢＴ−１２００Ｌ （東し■製ポリブチレンテレフ
タレート）およびエポキシ処理した３ｎｕａチヨツプド
ストランドタイプのガラス繊維を、それぞれ表−１の配
合割合でヘンシェルミキサーで混合し、次に４０ｎｕｅ
φ押出機により押出温度２５０℃で押出し、それぞれペ
レット化した後、各ペレットについて成形温度２５０℃
、金型温度６０℃の条件で射出成形に供し、各試験片を
作製しそれについて物性の評価を行なった。これらの結
果を表−１に示す。Examples 1 to 8 A-1 to A-4 produced in Reference Example 1, PBT-1200L (polybutylene terephthalate manufactured by Toshi ■) as the polyester, and 3nua chopped strand type glass fiber treated with epoxy were used, respectively. Mix with a Henschel mixer at the mixing ratio shown in Table 1, then 40 nu
After extruding with a φ extruder at an extrusion temperature of 250°C and pelletizing each pellet, the molding temperature was 250°C for each pellet.
The specimens were subjected to injection molding at a mold temperature of 60° C., and the physical properties of each specimen were evaluated. These results are shown in Table-1.
比較例１〜４
参考例１で製造したＡ−１〜Ａ−６、ポリエステルとし
てＰＢＴ−１２００Ｌ （東し■製ポリブチレンテレフ
タレート）、およびエポキシ処理した３ｍｍチョツプド
ストランドタイプのガラス繊維をそれぞれ表−１の配合
割合でヘンシェルミキサーで混合し、次に４０ｍｍφ押
出機により押出温度２５０℃で押出し、それぞれペレッ
ト化した後、各ペレットについて成形温度２５０°Ｃ１
金型温度６０℃の条件で射出成形に供し、各試験片を作
製し、それについて物性の評価を行なった。これらの結
果を表−１に併せて示す。Comparative Examples 1 to 4 A-1 to A-6 manufactured in Reference Example 1, PBT-1200L (polybutylene terephthalate manufactured by Toshi ■) as polyester, and 3 mm chopped strand type glass fiber treated with epoxy are shown in the table. -1 blending ratio in a Henschel mixer, then extruded with a 40 mmφ extruder at an extrusion temperature of 250°C, pelletized, and then molded at a molding temperature of 250°C for each pellet.
Each test piece was prepared by injection molding at a mold temperature of 60° C., and its physical properties were evaluated. These results are also shown in Table-1.
以下余白
実施例９〜１６
ポリエステルとしてＰＥＴ−Ｊ１３５ （三井ペット樹
脂側製ポリエチレンテレフタレート）を用い、押出温度
を２８０℃とした以外は、実施例１〜８と同様の条件で
行なった。配合割合および物性の測定結果を表−２に示
す。Blank Examples 9 to 16 Examples 9 to 16 were conducted under the same conditions as Examples 1 to 8, except that PET-J135 (polyethylene terephthalate manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester and the extrusion temperature was 280°C. Table 2 shows the blending ratio and measurement results of physical properties.
比較例８〜１４
ポリエステルとしてＰＥＴ−Ｊ１３５ （三井ペット樹
脂■製ポリエチレンテレフタレート）を用い、押出温度
を２８０℃成形温度を２８０℃とした以外は、比較例１
〜７と同様の条件で行なった。Comparative Examples 8 to 14 Comparative Example 1 except that PET-J135 (polyethylene terephthalate manufactured by Mitsui Pet Resin ■) was used as the polyester and the extrusion temperature was 280°C and the molding temperature was 280°C.
It was carried out under the same conditions as in 7.
配合割合および特性の測定結果は表−２に示す。The blending ratio and measurement results of properties are shown in Table 2.
以下余白
実施例および比較例より、次のことが明らかである。す
なわち、本発明により得られたものは、いずれも耐衝撃
性、成形加工性、耐薬品性に優れている。それに対して
、α、β−不飽和カルボン酸を共重合しないグラフト共
重合体（Ａ−６）では耐衝撃性が劣り、グラフト成分と
してシアン化ビニルを含まない芳香族ビニルとα、β−
不飽和カルボン酸のみグラフトしたグラフト共重合体（
・Ａ−５）では、耐衝撃性は不十分である。繊維状強化
剤の■が規定量をはずれている場合は耐衝撃性に劣る。The following is clear from the following margin examples and comparative examples. That is, the products obtained according to the present invention are excellent in impact resistance, moldability, and chemical resistance. On the other hand, the graft copolymer (A-6) in which α,β-unsaturated carboxylic acid is not copolymerized has poor impact resistance, and the graft copolymer (A-6), which does not contain vinyl cyanide as a graft component, and α,β-
Graft copolymer with only unsaturated carboxylic acid grafted (
-A-5) has insufficient impact resistance. If the amount of ■ in the fibrous reinforcing agent is outside the specified amount, the impact resistance will be poor.
［発明の効果］
本発明の繊維強化熱可塑性樹脂組成物は、ジエン系ゴム
に芳香族ビニルおよびα、β−不飽和カルボン酸をグラ
フト共重合してなるグラフト共重合体またはグラフト共
重合体組成物（Ａ）、芳香族ポリエステル（Ｂ）および
繊維状強化剤（Ｃ）を特定の割合で配合しているが、特
にカルボキシル基の存在のため（Ａ）、（Ｂ）および（
Ｃ）の相溶性が極めて良好である。更に本発明の繊維強
化熱可塑性樹脂組成物は、グラフト共重合体と繊維状強
化剤をブレンドすることにより、ポリエステルの耐衝撃
性および成形加工性を改良しており、耐熱性、耐薬品性
、機械物性を活かした種々の用途に用いることができる
。[Effects of the Invention] The fiber-reinforced thermoplastic resin composition of the present invention is a graft copolymer or a graft copolymer composition obtained by graft copolymerizing an aromatic vinyl and an α,β-unsaturated carboxylic acid to a diene rubber. (A), aromatic polyester (B) and fibrous reinforcing agent (C) are blended in a specific ratio, but due to the presence of carboxyl groups in particular, (A), (B) and (
The compatibility of C) is extremely good. Furthermore, the fiber-reinforced thermoplastic resin composition of the present invention improves the impact resistance and moldability of polyester by blending a graft copolymer and a fibrous reinforcing agent, and improves heat resistance, chemical resistance, It can be used in various applications that take advantage of its mechanical properties.
Claims (1)
（イ）芳香族ビニル５０〜９０重量 ％ （ロ）シアン化ビニル９〜５０重量 ％ （ハ）α，β−不飽和カルボン酸 ０．１〜２０重量％ からなる単量体混合物９０〜１５重量 部をグラフト共重合してなるグラフト 共重合体または該グラフト共重合体と 残りの単量体が共重合した共重合体と からなるグラフト共重合体組成物１〜 ９４重量部と （Ｂ）芳香族ポリエステル樹脂１〜９４重量部と（Ｃ）
繊維状強化剤５〜７０重量部 からなり、（Ａ）、（Ｂ）および（Ｃ）の合計量が１０
０重量部である繊維強化熱可塑性樹脂組成物。[Claims] (A) (a) 10 to 85 parts by weight of diene rubber, (b)
(a) 50-90% by weight of aromatic vinyl (b) 9-50% by weight of vinyl cyanide (c) 90-15% by weight of a monomer mixture consisting of 0.1-20% by weight of α,β-unsaturated carboxylic acid 1 to 94 parts by weight of a graft copolymer composition comprising a graft copolymer obtained by graft copolymerizing a part of the monomer, or a copolymer obtained by copolymerizing the graft copolymer and the remaining monomer, and (B) aromatic 1 to 94 parts by weight of Group polyester resin and (C)
It consists of 5 to 70 parts by weight of fibrous reinforcing agent, and the total amount of (A), (B) and (C) is 10
0 parts by weight of a fiber-reinforced thermoplastic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63175364A JPH075815B2 (en) | 1988-07-13 | 1988-07-13 | Fiber-reinforced thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63175364A JPH075815B2 (en) | 1988-07-13 | 1988-07-13 | Fiber-reinforced thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0224346A true JPH0224346A (en) | 1990-01-26 |
| JPH075815B2 JPH075815B2 (en) | 1995-01-25 |
Family
ID=15994794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63175364A Expired - Lifetime JPH075815B2 (en) | 1988-07-13 | 1988-07-13 | Fiber-reinforced thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075815B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6197878B1 (en) | 1997-08-28 | 2001-03-06 | Eastman Chemical Company | Diol latex compositions and modified condensation polymers |
| US6329462B1 (en) | 1999-06-18 | 2001-12-11 | Eastman Chemical Company | Nylon 6/silicone blends |
| US6340726B1 (en) | 1999-03-03 | 2002-01-22 | Eastman Chemical Company | Silicone polymer diol compositions and condensation polymer/silicone polymer blends |
| US6353052B1 (en) | 1999-06-18 | 2002-03-05 | Eastman Chemical Company | Amide-type polymer/silicone polymer blends and processes of making the same |
| US6403698B1 (en) | 1999-03-03 | 2002-06-11 | Eastman Chemical Company | Polyamide/emulsion polymer blends |
| US6699931B2 (en) | 2001-04-09 | 2004-03-02 | Eastman Chemical Company | Modified alkyd compositions comprising diol latex compositions and processes of making the same |
| US6844390B2 (en) | 2001-04-09 | 2005-01-18 | Eastman Chemical Company | Modified alkyd compositions comprising polyol latex compositions and processes of making them |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5423656A (en) * | 1977-07-25 | 1979-02-22 | Toray Ind Inc | Fiber-reinforced thermoplastic polyester resin composition |
| JPS5832656A (en) * | 1980-11-03 | 1983-02-25 | モンサント・カンパニ− | Thermoplastic composition |
| JPS6039093A (en) * | 1983-08-10 | 1985-02-28 | 三菱重工業株式会社 | Wrist mechanism of robot |
-
1988
- 1988-07-13 JP JP63175364A patent/JPH075815B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5423656A (en) * | 1977-07-25 | 1979-02-22 | Toray Ind Inc | Fiber-reinforced thermoplastic polyester resin composition |
| JPS5832656A (en) * | 1980-11-03 | 1983-02-25 | モンサント・カンパニ− | Thermoplastic composition |
| JPS6039093A (en) * | 1983-08-10 | 1985-02-28 | 三菱重工業株式会社 | Wrist mechanism of robot |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6197878B1 (en) | 1997-08-28 | 2001-03-06 | Eastman Chemical Company | Diol latex compositions and modified condensation polymers |
| US6417239B1 (en) | 1997-08-28 | 2002-07-09 | Eastman Chemical Company | Methods of making modified condensation polymers |
| US6417269B1 (en) | 1997-08-28 | 2002-07-09 | Eastman Chemical Company | Methods of making modified condensation polymers |
| US6340726B1 (en) | 1999-03-03 | 2002-01-22 | Eastman Chemical Company | Silicone polymer diol compositions and condensation polymer/silicone polymer blends |
| US6403698B1 (en) | 1999-03-03 | 2002-06-11 | Eastman Chemical Company | Polyamide/emulsion polymer blends |
| US6329462B1 (en) | 1999-06-18 | 2001-12-11 | Eastman Chemical Company | Nylon 6/silicone blends |
| US6353052B1 (en) | 1999-06-18 | 2002-03-05 | Eastman Chemical Company | Amide-type polymer/silicone polymer blends and processes of making the same |
| US6699931B2 (en) | 2001-04-09 | 2004-03-02 | Eastman Chemical Company | Modified alkyd compositions comprising diol latex compositions and processes of making the same |
| US6844390B2 (en) | 2001-04-09 | 2005-01-18 | Eastman Chemical Company | Modified alkyd compositions comprising polyol latex compositions and processes of making them |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH075815B2 (en) | 1995-01-25 |
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