JPS6159346B2 - - Google Patents
Info
- Publication number
- JPS6159346B2 JPS6159346B2 JP52051478A JP5147877A JPS6159346B2 JP S6159346 B2 JPS6159346 B2 JP S6159346B2 JP 52051478 A JP52051478 A JP 52051478A JP 5147877 A JP5147877 A JP 5147877A JP S6159346 B2 JPS6159346 B2 JP S6159346B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- acrylate
- polyethylene terephthalate
- present
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 35
- -1 Polytetramethylene terephthalate Polymers 0.000 claims description 33
- 229920000058 polyacrylate Polymers 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- 229920001225 polyester resin Polymers 0.000 claims description 14
- 239000004645 polyester resin Substances 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 229920000874 polytetramethylene terephthalate Polymers 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 9
- 239000012763 reinforcing filler Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229960000878 docusate sodium Drugs 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 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
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Description
本発明はポリテトラメチレンテレフタレート、
ポリエチレンテレフタレート、アクリレート系ゴ
ムを含有するアクリレート系重合体、及び補強充
填剤からなる成形性の改良された強化樹脂組成物
に関する。
ポリテトラメチレンテレフタレート樹脂あるい
はポリエチレンテレフタレート樹脂（以下、ポリ
テトラメチレンテレフタレートあるいはポリエチ
レンテレフタレートと呼ぶ。）のガラス繊維強化
物はその優れた機械的性質、耐熱性、電気絶縁性
等の特性から各種用途に使用されている。
しかしながら、これらのガラス繊維強化物はそ
のガラス繊維の添加により流動性が低下し、薄肉
成形品を得るためには高温高圧で成形する必要が
あり、成形加工上問題がある。
一方、かかるポリエステル樹脂は溶融粘度の温
度依存性が大きく、高圧で成形するとバリが出や
すい問題があつた。すなわち、ガラス繊維強化物
を成形する場合には成形温度、成形圧力を微妙に
バランスさせる必要があるが、そのバランスのと
り方が非常に難しく、その結果、バリ取り等の後
加工を必要としない良好な成形品を得ることが容
易でなかつた。
本発明者らはかかる強化樹脂組成物本来の優れ
た機械的性質、耐熱性、電気絶縁性等の特性を薄
肉成形品においても生かすべく成形加工性の改良
について鋭意研究の結果、特殊な組成物を形成さ
せることにより、上述した欠点を一挙に解決でき
ることを見出し、本発明を完成した。
本発明の要旨とするところは、(a)ポリテトラメ
チレンテレフタレート１〜99重量部とポリエチレ
ンテレフタレート99〜１重量部からなるポリエス
テル樹脂混合物100重量部に対し、(b)アルキルア
クリレート及び／又はアルキルメタクリレート60
重量％以上、これと共重合可能な他のビニル系単
量体40重量％以下及び１分子中に非共役の２重結
合を２個以上有する多官能性単量体０〜５重量％
を共重合して得られるアクリレート系ゴム成分15
〜90重量部の存在下に、芳香族ビニル化合物、シ
アン化ビニル化合物、アクリレート及びメタクリ
レートよりなる群から選ばれる１種以上の単量体
又は単量体混合物85〜10重量部を重合することに
より得られるアクリレート系重合体１〜50重量
部、及び(c)全樹脂組成物に対して５〜60重量％の
補強充填剤よりなる成形性の改良された強化樹脂
組成物にある。
本発明において用いられるポリエステル樹脂混
合物は、ポリテトラメチレンテレフタレート１〜
99重量部とポリエチレンテレフタレート99〜１重
量部（合計100重量部）とからなるポリエステル
樹脂の混合物である。これらのポリエステル樹脂
はジメチルテレフタレートあるいはテレフタル酸
と1.4ブタンジオール又はエチレングリコールか
ら公知の方法で重縮合して得られるものである。
またこれらのポリエステル樹脂は必要に応じてイ
ソフタル酸等のジカルボン酸、1.3−プロパンジ
オール、エチレングリコール、1.4−ブタンジオ
ール等のジオ−ルを少量加えて重縮合したものも
用いることができる。ポリテトラメチレンテレフ
タレート及びポリエチレンテレフタレートの極限
粘度〔η〕としては、テトラクロルエタン／フエ
ノール等量混合溶媒中25℃で測定した値が0.4〜
1.5dl／ｇ、好ましくは0.5〜1.2dl／ｇのものが用
いられる。
本発明におけるポリテトラメチレンテレフタレ
ート１〜99重量部、ポリエチレンテレフタレート
99〜１重量部（合計100重量部）よりなるポリエ
ステル樹脂混合物は本発明の構成成分の主要な成
分の１つであり、かかる混合物を使用することに
よつて、組成物全体の成形加工領域を広くする効
果を奏する。すなわち結晶性重合体は、その融点
を境として溶融粘度が極度に変化するため成形の
温度領域が狭い。それ故本発明の如く、融点の異
なる２つの重合体を混合したものを使用すること
により、温度による溶融粘度の急激な変化が緩和
されるため成形温度領域が広くなる特徴を有する
ものである。本発明のポリエステル樹脂混合物の
混合割合は使用目的に合わせて、前記した組成範
囲内で変化させて使用しうるが、異種成分のポリ
エステルを少なくとも１重量部以上含有している
必要がある。また必要に応じて、他のポリエステ
ル樹脂を添加して用いることもできる。
次にアクリレート系重合体は、炭素数２〜12の
アルキル基を有するアルキルアクリレート及び／
又はアルキルメタクリレート60重量％以上、これ
と共重合可能な他のビニル系単量体40重量％以
下、及び１分子中に非共役の２重結合を２個以上
有する多官能単量体０〜５重量％を共重合して得
られるアクリレート系ゴム成分(a)15〜90重量部の
存在下にスチレン、α−メチルスチレン等の芳香
族ビニル化合物、アクリロニトリル、メタクリロ
ニトリル等のシアン化ビニル化合物、メチルアク
リレート、ブチルアクリレート等のアクリレート
及びメチルメタクリレート、ブチルメタクリレー
ト等のメタクリレートから選択される１種以上の
単量体又は単量体混合物85〜10重量部を重合して
得られる重合体である。炭素数２〜12のアルキル
基を有する単量体としては例えばエチルアクリレ
ート、ブチルアクリレート、２−エチルヘキシル
アクリレート等が使用され、これと共重合可能な
他のビニル単量体としては、メチルメタクリレー
ト、アクリロニトリル、スチレン、エチルビニル
エーテル等が用いられる。また１分子中に非共役
の２重結合を２個以上有する多官能単量体として
は、ジビニルベンゼン、エチレングリコールジメ
タアクリレート、トリアリルシアヌレート、トリ
アリルイソシアヌレート、アリルメタアクリレー
ト等が挙げられる。このアクリレート系重合体に
おいて本発明の目的とする成形性改良のためには
アクリレート系ゴム成分(a)が該アクリレート系重
合体中15〜90重量％含有していることが必要であ
り、15重量％未満の場合には成形加工性が改良さ
れないし、90重量％をこえる場合には組成物中で
の分散性が悪く、均一性に欠けるので好ましくな
い。
補強充填剤としては、ガラス繊維、カーボン繊
維、ホイスカー、石綿、繊維状メタケイ酸カルシ
ウム、ドーソナイト等繊維状の形態のもの、また
弾性率等の向上作用のあるタルク、炭酸カルシウ
ム、ガラスフレーク、ガラスビーズ、クレー、け
い酸、ホワイトカーボン、アルミハク粉、金属粉
等板状、球状、粉末状の形態のものいずれも単独
もしくは併用して用いられる。
本発明の組成物を構成する各成分の配合割合と
しては、ポリテトラメチレンテレフタレート１〜
99重量部とポリエチレンテレフタレート99〜１重
量部のポリエステル樹脂混合物100重量部に対し
てアクリレート系重合体１〜50重量部であり、補
強充填剤は全樹脂組成物の５〜60重量％の範囲で
含有される。本発明に係る樹脂組成物において、
アクリレート系重合体の添加量がポリエステル樹
脂混合物100重量部に対して１重量部未満では成
形性の改良効果が充分でなく、また50重量部を越
えて添加すると機械的性質の低下をもたらすため
好ましくない。成形性の改良効果は本発明の範囲
のポリエステル樹脂混合物とアクリレート系重合
体との併用によつて、はじめて広い成形温度範囲
と成形圧力範囲で良好な成形性を発揮することが
できる。また補強充填剤の添加量が５重量％未満
では補強効果があまり期待されず、逆に60重量％
をこえる場合には成形流動性が低下するので好ま
しくない。
本発明の組成物の製造は、特に限定されない
が、例えばポリテトラメチレンテレフタレート、
ポリエチレンテレフタレート、アクリレート系重
合体、及び補強充填剤をブレンダーで混合し、こ
の混合物を押出機ホツパーに供給し、加熱溶融し
て押出しペレツト状等に賦型して得ることができ
る。
また本発明の組成物には必要に応じて各種改質
剤、添加剤、例えば光又は熱に対する安定剤、硬
化剤、難燃化剤、染顔料等を加えることができ
る。
本発明の組成物は極めて広い成形温度範囲で優
れた成形性を示し、良好な外観を有する成形品が
得られると同時にポリエステル樹脂本来の優れた
機械的、熱的性質等各種特性をそのまま保持し、
電気電子機器部品等の薄肉小型部品や自動車用途
の比較的大型成形品等に有効に使用される。
以下、実施例により本発明を説明するが、実施
例中、部は重量部を、％は重量％を表わす。
実施例１〜３、比較例１〜３
(1) アクリレート系重合体〔Ａ〕の合成
水350部に乳化剤ジオクチルスルホサクシネ
ート２部を溶解し、窒素置換したのち75℃に昇
温する。開始剤として過流酸カリウム0.5部を
水50部に溶解したものを添加し、その後ブチル
アクリレート89部、スチレン10部及びトリアリ
ールイソシアヌレート１部の混合物を１時間に
わたり滴下したのち、さらに１時間重合した。
上記反応混合物にメチルメタクリレート40
部、スチレン10部、ｎ−オクチルメルカプタン
0.1部を添加し、１時間半重合した。全重合率
は96％であつた。反応終了後、上記ラテツクス
を0.05％塩化カルシウム水溶液中に投入、塩析
し、さらに過、水洗後乾燥させて、アクリレ
ート系重合体〔Ａ〕を得た。
(2) 強化樹脂組成物の製造及び評価
フエノール／テトラクロルエタン等重量混合
溶媒中25℃で測定した極限粘度〔η〕＝0.93の
ポリテトラメチレンテレフタレート、〔η〕＝
0.70のポリエチレンテレフタレート、上記アク
リレート系重合体〔Ａ〕、市販繊維長３mmチヨ
ツプドストランド型ガラス繊維及び炭酸カルシ
ウムをそれぞれ表１に示す割合で合計10KgＶ型
ブレンダーに入れ約３分間混合した。この混合
物をシリンダー温度220℃〜260℃の40φベント
式押出機ホツパーに供給して溶融押出しを行な
い、ペレツト状に賦型して本発明の組成物を得
た。
得られたペレツトを36φ射出成形機でシリン
ダー温度250〜290℃、金型温度60〜140℃で成
形し、評価用成形品を得た。なお、使用した金
型は厚さ1.0mm、3.2mm及び6.3mmのテトラピース
及びJIS1号ダンベルの多数個取りのものであ
る。
これらの成形品を用いて成形性、外観、機械
的性質等の評価を行なつた結果を表１に示す。
本発明の組成物から得られる成形品はバリ、
ヒケ等の発生もなく、良好な外観を有してお
り、しかも広い成形温度範囲で高い機械的性質
を示す。
一方、比較例１のようにポリエチレンテレフ
タレートのみでアクリレート系重合体を添加し
ないものは、成形温度250℃では成形できず、
また金型温度が60℃と低いと、成形品のエツジ
部と中央部で外観が異なり不均一であるととも
に、機械的性質にも劣つている。また270℃以
上の成形温度ではバリの発生が多く成形性が極
めて劣つていた。
なお、表１中引張強度はASTM D638、曲げ
強度はASTM D790、アイゾツト（ノツチ付）
衝撃強度はASTM D256に基づいて測定した。
The present invention relates to polytetramethylene terephthalate,
The present invention relates to a reinforced resin composition with improved moldability, comprising polyethylene terephthalate, an acrylate polymer containing acrylate rubber, and a reinforcing filler. Glass fiber reinforced products of polytetramethylene terephthalate resin or polyethylene terephthalate resin (hereinafter referred to as polytetramethylene terephthalate or polyethylene terephthalate) are used for various purposes due to their excellent mechanical properties, heat resistance, electrical insulation properties, etc. has been done. However, the fluidity of these glass fiber reinforced materials decreases due to the addition of glass fibers, and in order to obtain thin-walled molded products, it is necessary to mold them at high temperature and pressure, which poses a problem in molding processing. On the other hand, the melt viscosity of such polyester resins has a large temperature dependence, and burrs tend to form when molded under high pressure. In other words, when molding glass fiber reinforced materials, it is necessary to delicately balance the molding temperature and molding pressure, but it is extremely difficult to achieve this balance. It was not easy to obtain a molded product. The present inventors have conducted intensive research into improving moldability in order to make use of the excellent mechanical properties, heat resistance, electrical insulation properties, etc. inherent to such reinforced resin compositions in thin-walled molded products, and have developed a special composition. The present invention has been completed based on the discovery that the above-mentioned drawbacks can be solved all at once by forming a . The gist of the present invention is that (b) alkyl acrylate and/or alkyl methacrylate is added to 100 parts by weight of a polyester resin mixture consisting of (a) 1 to 99 parts by weight of polytetramethylene terephthalate and 99 to 1 part by weight of polyethylene terephthalate. 60
At least 40% by weight of other vinyl monomers that can be copolymerized with this monomer, and 0 to 5% by weight of polyfunctional monomers having two or more non-conjugated double bonds in one molecule.
Acrylate rubber component 15 obtained by copolymerizing
By polymerizing 85 to 10 parts by weight of one or more monomers or monomer mixtures selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylates and methacrylates in the presence of ~90 parts by weight. There is a reinforced resin composition with improved moldability comprising 1 to 50 parts by weight of the resulting acrylate polymer and (c) 5 to 60% by weight of a reinforcing filler based on the total resin composition. The polyester resin mixture used in the present invention includes polytetramethylene terephthalate 1 to
It is a mixture of polyester resin consisting of 99 parts by weight and 99 to 1 part by weight of polyethylene terephthalate (100 parts by weight in total). These polyester resins are obtained by polycondensation of dimethyl terephthalate or terephthalic acid and 1.4-butanediol or ethylene glycol by a known method.
These polyester resins may also be polycondensed by adding a small amount of dicarboxylic acid such as isophthalic acid or diol such as 1.3-propanediol, ethylene glycol or 1.4-butanediol, if necessary. The intrinsic viscosity [η] of polytetramethylene terephthalate and polyethylene terephthalate is 0.4 to 0.4 when measured at 25°C in a mixed solvent of equal amounts of tetrachloroethane/phenol.
The amount used is 1.5 dl/g, preferably 0.5 to 1.2 dl/g. 1 to 99 parts by weight of polytetramethylene terephthalate in the present invention, polyethylene terephthalate
A polyester resin mixture consisting of 99 to 1 parts by weight (total 100 parts by weight) is one of the main constituents of the present invention, and by using such a mixture, the molding area of the entire composition can be increased. It has a widening effect. That is, since the melt viscosity of a crystalline polymer changes extremely beyond its melting point, the temperature range for molding is narrow. Therefore, by using a mixture of two polymers with different melting points as in the present invention, the rapid change in melt viscosity due to temperature is alleviated, so that the molding temperature range is widened. The mixing ratio of the polyester resin mixture of the present invention can be varied within the composition range described above depending on the purpose of use, but it is necessary to contain at least 1 part by weight of polyester as a different component. Further, other polyester resins may be added and used as necessary. Next, the acrylate polymer is an alkyl acrylate having an alkyl group having 2 to 12 carbon atoms and/or
or 60% by weight or more of alkyl methacrylate, 40% by weight or less of other vinyl monomers copolymerizable with this, and 0 to 5 polyfunctional monomers having two or more nonconjugated double bonds in one molecule. An aromatic vinyl compound such as styrene or α-methylstyrene, a cyanide vinyl compound such as acrylonitrile or methacrylonitrile, in the presence of 15 to 90 parts by weight of an acrylate rubber component (a) obtained by copolymerizing 20% by weight, It is a polymer obtained by polymerizing 85 to 10 parts by weight of one or more monomers or monomer mixtures selected from acrylates such as methyl acrylate and butyl acrylate, and methacrylates such as methyl methacrylate and butyl methacrylate. Examples of monomers having an alkyl group having 2 to 12 carbon atoms include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and other vinyl monomers that can be copolymerized with these include methyl methacrylate and acrylonitrile. , styrene, ethyl vinyl ether, etc. are used. Further, examples of polyfunctional monomers having two or more non-conjugated double bonds in one molecule include divinylbenzene, ethylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, allyl methacrylate, etc. . In order to improve the moldability of this acrylate polymer, which is the objective of the present invention, it is necessary that the acrylate rubber component (a) be contained in the acrylate polymer in an amount of 15 to 90% by weight, and 15% by weight is required. If it is less than 90% by weight, the molding processability will not be improved, and if it exceeds 90% by weight, the dispersibility in the composition will be poor and uniformity will be lacking, which is not preferable. Examples of reinforcing fillers include glass fibers, carbon fibers, whiskers, asbestos, fibrous calcium metasilicate, dawsonite, and other fibrous materials, as well as talc, calcium carbonate, glass flakes, and glass beads that improve elastic modulus. , clay, silicic acid, white carbon, aluminum powder, metal powder, etc. in the form of plates, spheres, and powders can be used alone or in combination. The blending ratio of each component constituting the composition of the present invention is polytetramethylene terephthalate 1 to
The acrylate polymer is 1 to 50 parts by weight per 100 parts by weight of a polyester resin mixture of 99 parts by weight and 99 to 1 part by weight of polyethylene terephthalate, and the reinforcing filler is in the range of 5 to 60% by weight of the total resin composition. Contains. In the resin composition according to the present invention,
If the amount of the acrylate polymer added is less than 1 part by weight per 100 parts by weight of the polyester resin mixture, the moldability improvement effect will not be sufficient, and if it is added in excess of 50 parts by weight, mechanical properties will deteriorate, so it is preferable. do not have. The effect of improving moldability can only be achieved by using a polyester resin mixture within the range of the present invention in combination with an acrylate polymer, and good moldability can be exhibited over a wide molding temperature and molding pressure range. Furthermore, if the amount of reinforcing filler added is less than 5% by weight, the reinforcing effect is not expected to be significant;
If it exceeds this, molding fluidity decreases, which is not preferable. Production of the composition of the present invention is not particularly limited, but for example, polytetramethylene terephthalate, polytetramethylene terephthalate,
It can be obtained by mixing polyethylene terephthalate, an acrylate polymer, and a reinforcing filler in a blender, feeding this mixture into an extruder hopper, heating and melting it, and extruding it into pellets or the like. Furthermore, various modifiers and additives, such as stabilizers against light or heat, curing agents, flame retardants, dyes and pigments, etc., can be added to the composition of the present invention as necessary. The composition of the present invention exhibits excellent moldability over an extremely wide molding temperature range, yielding molded products with good appearance, and at the same time retaining various properties such as excellent mechanical and thermal properties inherent to polyester resin. ,
It is effectively used for thin-walled small parts such as electrical and electronic equipment parts and relatively large molded products for automobiles. The present invention will be explained below with reference to Examples. In the Examples, parts represent parts by weight, and % represents weight %. Examples 1 to 3, Comparative Examples 1 to 3 (1) Synthesis of acrylate polymer [A] 2 parts of emulsifier dioctyl sulfosuccinate was dissolved in 350 parts of water, and after the atmosphere was purged with nitrogen, the temperature was raised to 75°C. A solution of 0.5 parts of potassium persulfate dissolved in 50 parts of water was added as an initiator, and then a mixture of 89 parts of butyl acrylate, 10 parts of styrene, and 1 part of triaryl isocyanurate was added dropwise over 1 hour, and then for another 1 hour. Polymerized. Methyl methacrylate 40 to the above reaction mixture
parts, 10 parts of styrene, n-octyl mercaptan
0.1 part was added and polymerized for 1.5 hours. The total polymerization rate was 96%. After the reaction was completed, the latex was poured into a 0.05% calcium chloride aqueous solution for salting out, filtered, washed with water, and dried to obtain an acrylate polymer [A]. (2) Production and evaluation of reinforced resin composition Polytetramethylene terephthalate with intrinsic viscosity [η] = 0.93 measured at 25°C in a mixed solvent of equal weight of phenol/tetrachloroethane, [η] =
A total of 10 kg of polyethylene terephthalate (10 kg), the above acrylate polymer [A], a commercially available chopped strand type glass fiber with a fiber length of 3 mm, and calcium carbonate in the proportions shown in Table 1 were placed in a V-type blender and mixed for about 3 minutes. This mixture was melt-extruded by feeding it into a hopper of a 40φ vented extruder with a cylinder temperature of 220 DEG C. to 260 DEG C., and shaping it into pellets to obtain the composition of the present invention. The obtained pellets were molded using a 36φ injection molding machine at a cylinder temperature of 250 to 290°C and a mold temperature of 60 to 140°C to obtain a molded product for evaluation. The molds used were those with multiple pieces of tetra pieces and JIS No. 1 dumbbells with thicknesses of 1.0 mm, 3.2 mm, and 6.3 mm. Table 1 shows the results of evaluations of moldability, appearance, mechanical properties, etc. using these molded products. The molded article obtained from the composition of the present invention has no burrs,
It has a good appearance with no sink marks, and exhibits high mechanical properties over a wide molding temperature range. On the other hand, a product containing only polyethylene terephthalate and no acrylate polymer, such as Comparative Example 1, could not be molded at a molding temperature of 250°C.
Furthermore, when the mold temperature is as low as 60°C, the appearance of the molded product differs between the edges and the center and is non-uniform, and the mechanical properties are also poor. Furthermore, at molding temperatures of 270°C or higher, burrs were often generated and moldability was extremely poor. In addition, in Table 1, tensile strength is ASTM D638, bending strength is ASTM D790, Izotsu (notched)
Impact strength was measured based on ASTM D256.
【表】【table】
【表】
実施例４〜７、比較例４〜５
(1) アクリレート系重合体〔Ｂ〕の合成
水350部に乳化剤ジオクチルスルホサクシネ
ート２部を溶解して窒素置換したのち75℃に昇
温する。開始剤として過硫酸カリウム0.5部を
水50部に溶解したものを添加し、その後ブチル
アクリレート80部、エチルアクリレート10部、
アクリロニトリル10部、アクリルメタクリレー
ト１部の混合物を１時間にわたり滴下したのち
さらに１時間重合した。
上記反応混合物にメチルメタクリレート40
部、ｎ−オクチルメルカプタン0.1部の混合物
を滴下し、１時間半重合した。全重合率は97％
であつた。反応終了後、上記ラテツクスを0.05
％塩化カルシウム水溶液中に投入、塩析し、さ
らに過、水洗後乾燥させてアクリレート系重
合体を得た。
(2) 強化樹脂組成物の製造及び評価
極限粘度〔η〕＝0.97のポリテトラメチレン
テレフタレート、〔η〕＝0.82のポリエチレンテ
レフタレート、上記アクリレート系重合体
〔Ｂ〕及びガラス繊維（市販繊維長３mm）ある
いはさらに炭酸カルシウムをそれぞれ表２に示
す割合で合計10KgＶ型ブレンダーに入れ混合し
た。
この混合物を実施例１と同様に押出し、ペレ
ツト状に賦形して組成物を得た。これを用いて
各成形温度で成形性、機械的熱的性質の評価を
行なつた結果を表２に示す。
本発明の組成物は成形性が良好であり、バリ
等の発生もなく光沢の高い良好な成形品が得ら
れる。
一方、比較例４及び比較例５は本発明の組成
物と全く構成成分は同じであるが、アクリレー
ト系重合体〔Ｂ〕の添加量が本発明の範囲外の
ものである。比較例４の如く、アクリレート系
重合体の添加量が少なすぎると成形性の改良効
果が表われず、成形できなかつたりバリを発生
したりするし、比較例５のように過剰に添加す
ると機械的性質や耐熱性が低下する。[Table] Examples 4 to 7, Comparative Examples 4 to 5 (1) Synthesis of acrylate polymer [B] 2 parts of emulsifier dioctyl sulfosuccinate was dissolved in 350 parts of water, the atmosphere was replaced with nitrogen, and the temperature was raised to 75°C. do. As an initiator, 0.5 parts of potassium persulfate dissolved in 50 parts of water was added, followed by 80 parts of butyl acrylate, 10 parts of ethyl acrylate,
A mixture of 10 parts of acrylonitrile and 1 part of acrylic methacrylate was added dropwise over 1 hour, and the mixture was further polymerized for 1 hour. Methyl methacrylate 40 to the above reaction mixture
A mixture of 1 part and 0.1 part of n-octyl mercaptan was added dropwise, and the mixture was polymerized for 1.5 hours. Total polymerization rate is 97%
It was hot. After the reaction is complete, add 0.05% of the above latex.
% calcium chloride aqueous solution, salted out, filtered, washed with water, and dried to obtain an acrylate polymer. (2) Production and evaluation of reinforced resin composition Polytetramethylene terephthalate with intrinsic viscosity [η] = 0.97, polyethylene terephthalate with [η] = 0.82, the above acrylate polymer [B] and glass fiber (commercially available fiber length 3 mm) Alternatively, a total of 10 kg of calcium carbonate was added and mixed in a V-type blender in the proportions shown in Table 2. This mixture was extruded in the same manner as in Example 1 and shaped into pellets to obtain a composition. Table 2 shows the results of evaluation of moldability and mechanical and thermal properties at various molding temperatures using this material. The composition of the present invention has good moldability, and good molded products with high gloss can be obtained without the occurrence of burrs or the like. On the other hand, Comparative Examples 4 and 5 have exactly the same components as the composition of the present invention, but the amount of acrylate polymer [B] added is outside the range of the present invention. As in Comparative Example 4, if the amount of acrylate polymer added is too small, the effect of improving moldability will not appear, and molding will not be possible or burrs will occur.If it is added in excess as in Comparative Example 5, the machine The physical properties and heat resistance deteriorate.
Claims (1)
重量部とポリエチレンテレフタレート99〜１重量
部とからなるポリエステル樹脂混合物100重量部
に対し、(b)アルキルアクリレート及び／又はアル
キルメタクリレート60重量％以上、これと共重合
可能な他のビニル系単量体40重量％以下及び１分
子中に非共役の２重結合を２個以上有する多官能
性単量体０〜５重量％を共重合して得られるアク
リレート系ゴム成分15〜90重量部の存在下に、芳
香族ビニル化合物、シアン化ビニル化合物、アク
リレート及びメタクリレートよりなる群から選ば
れる１種以上の単量体又は単量体混合物85〜10重
量部を重合することにより得られるアクリレート
系重合体１〜50重量部、及び(c)全樹脂組成物に対
して５〜60重量％の補強充填剤よりなる成形性の
改良された強化樹脂組成物。1 (a) Polytetramethylene terephthalate 1-99
(b) 60% by weight or more of alkyl acrylate and/or alkyl methacrylate, and other vinyl monomers copolymerizable with this, based on 100 parts by weight of a polyester resin mixture consisting of 99 to 1 part by weight of polyethylene terephthalate and 99 to 1 part by weight of polyethylene terephthalate. In the presence of 15 to 90 parts by weight of an acrylate rubber component obtained by copolymerizing 40% by weight or less and 0 to 5% by weight of a polyfunctional monomer having two or more non-conjugated double bonds in one molecule. Acrylate polymer 1 obtained by polymerizing 85 to 10 parts by weight of one or more monomers or monomer mixtures selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, acrylates and methacrylates. -50 parts by weight of a reinforcing filler, and (c) 5 to 60% by weight of the total resin composition of a reinforcing filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5147877A JPS53137251A (en) | 1977-05-04 | 1977-05-04 | Reinforced resin composition having improved moldability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5147877A JPS53137251A (en) | 1977-05-04 | 1977-05-04 | Reinforced resin composition having improved moldability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53137251A JPS53137251A (en) | 1978-11-30 |
| JPS6159346B2 true JPS6159346B2 (en) | 1986-12-16 |
Family
ID=12888050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5147877A Granted JPS53137251A (en) | 1977-05-04 | 1977-05-04 | Reinforced resin composition having improved moldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53137251A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1166781A (en) * | 1979-11-19 | 1984-05-01 | Peter Bier | Process for injection molding a rapidly crystallizing polyethylene terephthalate composition at reduced mold temperatures |
| US20060223923A1 (en) * | 2005-02-07 | 2006-10-05 | Serge Cavalli | Thermoplastic vulcanisate blend |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4859148A (en) * | 1971-11-15 | 1973-08-18 | ||
| JPS4954456A (en) * | 1972-04-24 | 1974-05-27 | ||
| JPS4990345A (en) * | 1972-12-29 | 1974-08-29 | ||
| JPS5023449A (en) * | 1973-07-04 | 1975-03-13 | ||
| JPS5125262A (en) * | 1974-08-28 | 1976-03-01 | Hitachi Ltd | Makiagesochi no kafukakenshutsusochi |
| JPS5144158A (en) * | 1974-08-01 | 1976-04-15 | Gen Electric | |
| JPS5156856A (en) * | 1974-09-18 | 1976-05-18 | Basf Ag | Netsukasoseino horiesuteruseikeizairyo |
| JPS51132244A (en) * | 1974-12-13 | 1976-11-17 | Rohm & Haas | Mixed compositions of thermoplastic polymer and multiphase acrylic compound polymers |
-
1977
- 1977-05-04 JP JP5147877A patent/JPS53137251A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4859148A (en) * | 1971-11-15 | 1973-08-18 | ||
| JPS4954456A (en) * | 1972-04-24 | 1974-05-27 | ||
| JPS4990345A (en) * | 1972-12-29 | 1974-08-29 | ||
| JPS5023449A (en) * | 1973-07-04 | 1975-03-13 | ||
| JPS5144158A (en) * | 1974-08-01 | 1976-04-15 | Gen Electric | |
| JPS5125262A (en) * | 1974-08-28 | 1976-03-01 | Hitachi Ltd | Makiagesochi no kafukakenshutsusochi |
| JPS5156856A (en) * | 1974-09-18 | 1976-05-18 | Basf Ag | Netsukasoseino horiesuteruseikeizairyo |
| JPS51132244A (en) * | 1974-12-13 | 1976-11-17 | Rohm & Haas | Mixed compositions of thermoplastic polymer and multiphase acrylic compound polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53137251A (en) | 1978-11-30 |
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