JPH0562898B2 - - Google Patents
Info
- Publication number
- JPH0562898B2 JPH0562898B2 JP18190287A JP18190287A JPH0562898B2 JP H0562898 B2 JPH0562898 B2 JP H0562898B2 JP 18190287 A JP18190287 A JP 18190287A JP 18190287 A JP18190287 A JP 18190287A JP H0562898 B2 JPH0562898 B2 JP H0562898B2
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- weight
- parts
- ester
- 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
- 150000002148 esters Chemical class 0.000 claims description 22
- 239000011342 resin composition Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims 6
- 150000002367 halogens Chemical class 0.000 claims 6
- 239000000203 mixture Substances 0.000 description 13
- -1 ester compounds Chemical class 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000010292 electrical insulation Methods 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004808 2-ethylhexylester Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920006385 Geon Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VTBHBNXGFPTBJL-UHFFFAOYSA-N 4-tert-butyl-1-sulfanylidene-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octane Chemical compound C1OP2(=S)OCC1(C(C)(C)C)CO2 VTBHBNXGFPTBJL-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
［産業上の利用分野］
本発明は、硬質、軟質の分野を問わず、優れた
特性を有する含塩素ビニル系樹脂組成物に関す
る。
［従来の技術］
含塩素ビニル系樹脂組成物は、家庭用品や工業
用資材等多方面で使用されている。
近年、係る製品は、小形化が望まれ、又、厳し
い環境において使われることが多くなり、より優
れたゲル化性（加工性）、耐熱性、耐揮発性、耐
移行性、耐抽出性、電気絶縁性、耐熱変形性及び
製品によつて高軟化温度が要求されている。
係る特性を満足するためには、要求される特性
に応じて数種のエステルを樹脂用副資材として選
択し、併用しているのが現状であり、単独のエス
テルでもつてバランスよく全ての特性を満足させ
ることは困難である。
例えば、耐揮発性や電気絶縁性が要求される分
野には、トリメリツト酸トリ（２−エチルヘキシ
ル）等を使用しているが、技術の進展により、よ
り高度の耐揮発性や更には電気絶縁性を要求する
分野が出てきた。
一方、耐抽出性、耐移行性が要求される分野に
は、トリメリツト酸エステルでも満足できず、一
般的にはポリエステル系可塑剤が使用されてい
る。しかし、ポリエステル系可塑剤は、加工性、
耐水性、耐熱性や電気絶縁性が劣り、更に耐抽出
性、耐移行性についても、より一層の特性の向上
が望まれている。
又、硬質製品においては少量のエステルを添加
して溶融粘度を低下させ、加工性の向上を図る
が、この場合、添加量に応じて製品の軟化温度が
低下し、高温での使用に耐えない。この問題を解
決するために固体可塑剤であるフタル酸ジシクロ
ヘキシルを用いる場合もあるが、これとて揮発性
に問題が残る。
［発明が解決しようとする問題点］
本発明者らは、軟質においてはより優れた耐抽
出性、耐熱変形性を有し、硬質分野においては高
軟化温度を保持し得る樹脂組成物を開発すべく、
樹脂用副資材としてのエステル系化合物を種々検
討したところ、特定の構造を有するテトラカルボ
ン酸又は無水物を酸成分として調製されるエステ
ルが有効であることを見い出し、この知見に基づ
いて本発明を完成するに至つた。
［問題点を解決するための手段］
本発明に係る含塩素ビニル系樹脂組成物は、熱
可塑性樹脂に対し、下記の一般式（）で表わさ
れるエステルを配合してなることを特徴とする。
［式中、R1、R2、R3、R4は同一又は異なつ
て、水素原子又は炭素数１〜22のアルキル基若し
くはアルケニル基を表す。但し、R1〜R4の全て
が水素原子であることはない。］
ここで含塩素ビニル系樹脂とは、塩化ビニル又
は塩化ビニルとそれに共重合可能なコモノマーか
ら懸濁重合法、乳化重合法または塊状重合法等の
方法によつて製造されたものが用いられる。そし
て、その平均重合度は、400〜10000の範囲、好ま
しくは、600〜6000の範囲の樹脂である。又、塩
化ビニルに共重合可能なコモノマーは、例えばビ
ニルエステル類、メタクリル酸エステル類、マレ
イン酸エステル類、ビニルエーテル類、α−オレ
フイン類、塩化ビニリデン及び塩化ビニル以外の
ハロゲン化ビニル類等が挙げられるが、これらの
コモノマーは、これに限定されるものではない。
本発明に係るエステルは、相当するジフエニル
スルホン−３，3′，４，4′−テトラカルボン酸類
又はその無水物と所定のアルコールとを常法に従
つてエステル化することにより合成される。
本発明に係るエステルを構成するアルコールの
残基は、炭素数が１〜22のアルキル基又はアルケ
ニル基であつて、具体的にはメチル、エチル、プ
ロピル、ｎ−ブチル、イソブチル、アミル、ヘキ
シル、ヘプチル、ｎ−オクチル、２−エチルヘキ
シル、イソオクチル、イソノニル、ｎ−デシル、
イソデシル、ウンデシル、ドデシル、トリデシ
ル、ミリスチル、セチル、ステアリル、ベヘニ
ル、オレイル等の各基が例示される。
又、アルフオール610（ビスタケミカルフアーイ
ースト社製）、リネボール79（シエル化学(株)製）、
リネボール911（シエル化学(株)製）等の混合系オキ
ソアルコールもアルコール成分として使用するこ
とができる。
当該エステルは、所定のカルボン酸とアルコー
ルから脱水反応によつて得る。その際のエステル
化反応は、無触媒であつてもよいが、通常は酸触
媒、金属アルコラート、金属酸化物等のエステル
化触媒の存在下で反応を行ない、必要に応じて処
理剤などで精製エステルとする。
本発明に係るエステルの配合量は、樹脂組成物
に求められる特性により適宜選択され、例えば樹
脂100重量部に対し、硬質配合物にあつては１〜
30重量部程度、軟質配合物にあつては、20〜200
重量部程度配合される。
又、本発明に係る含塩素ビニル系樹脂組成物に
は、フタル酸ジ（２−エチルヘキシル）、フタン
酸ジイソノニル、アジピン酸ジ（２−エチルヘキ
シル）、トリメリツト酸トリ（２−エチルヘキシ
ル）、液状ポリエステル、リン酸トリクレジル、
エポキシ化大豆油等に代表される汎用可塑剤又は
加工助剤として使用される他のエステルを適宜併
用することができる。
本発明に係る含塩素ビニル系樹脂組成物には、
通常、樹脂用副資材として使用されている安定
剤、滑剤、難燃剤、酸化防止剤、紫外線吸収剤、
充填剤、着色剤、離型剤、防曇剤、帯電防止剤、
架橋剤、防菌剤、防カビ剤、発泡剤等を適宜配合
することができる。
かくして得られた含塩素ビニル系樹脂組成物
は、窓枠、看板、事務器具、電話機、樋、レコー
ド、プレート、容器、パイプ等の硬質製品や、履
物、玩具、家具調度品、床材、包装材、屋根材、
レザー、フイルム、壁紙、ホース、電線、ペース
トゾル成形品、テント、シート、テープ、カーテ
ン等の軟質製品等の各種分野において有用であ
る。
［実施例］
次に、実施例をもつて本発明を詳しく説明す
る。
実施例１〜３、比較例１〜２
下記の組成からなる軟質樹脂組成物を調製し、
耐揮発性、耐移行性、耐抽出性、電気絶縁性及び
耐熱変形等の諸特性を評価した。得られた結果を
第１表に示す。
樹脂組成物の組成
塩化ビニル樹脂
（Geon 101EP（重合度1450）；日本ゼオン(株)
製） 100重量部
エステル（第１表に記載） 50重量部
安定剤（三塩基性硫酸鉛） ３重量部
試験片作成条件
ロール混練 163〜165℃×４分間
プレス成型 165℃×10分間
樹脂組成物の特性評価方法
(1) 電気絶縁性
JIS Ｋ 6723に準じて測定した。
(2) 耐揮発性、耐移行性、耐抽出性
揮発減量、ｎ−ヘキサン抽出及び移行試験は、
各条件下での可塑化PVCの重量損失を測定した。
尚、ｎ−ヘキサン抽出試験の収縮率は、抽出前後
の試験片の寸法を測定することで求めた。
(3) 熱変形性
ダンベル２号試験片に引張加重1200Kg／cm2の分
銅をつるし、ギヤーオーブン内で120℃、2h加熱
した後の試験片の伸びを測定し、変形率を求め
た。
尚、各実施例に供したエステルは、以下の通り
略称する。
TBPS：ジフエニルスルホン−３，3′，４，4′−
テトラカルボン酸テトラｎ−ブチル
THPS：ジフエニルスルホン−３，3′，４，4′−
テトラカルボン酸テトラヘプチル
TOPS：ジフエニルスルホン−３，3′，４，4′−
テトラカルボン酸テトラ−ｎ−オクチル
DOP ：フタル酸ジ−２−エチルヘキシル
TOTM：トリメルツト酸トリ（２−エチルヘキ
シル）
本発明に係る軟質樹脂組成物は、耐揮発性、耐
移行性、高絶縁性可塑剤であるTOTM配合物と
比較しても、シートの耐揮発性、電気絶縁性は同
等若しくはそれ以上である。又、耐移行性、耐油
性と耐熱変形性はTOTM配合物以上の性能を示
し、中でも耐抽出性、耐熱変形性は抜群に優れて
いる。
実施例４〜６、比較例３
下記の組成に従つて得られる樹脂組成物のゲル
化性については、エステル中に分散した樹脂が溶
融して透明化する温度を測定することにより求め
た。得られた結果を第２表に示す。
塩化ビニル樹脂
（Geon 101EP（重合度1450）；日本ゼオン(株)
製） 100重量部
エステル（第２表に記載） 200重量部
溶融温度の測定方法
塩化ビニル樹脂とエステルからなる所定の混合
物0.01ｇをプレパラート上に滴下し、次いで微量
融点測定装置（(株)柳本製作所製）を用いて、混合
物を徐々に加温しながら、混合物が透明になる温
度を求め溶融温度（ゲル化性）とした。
本発明に係るエステルを配合して得られた樹脂
組成物は、従来の耐揮発性、耐移行性及び高電気
絶縁性を有する副資材配合の組成物に比べ、低温
度で溶融することから、当該樹脂組成物はゲル化
性に優れている。
実施例７〜９、比較例４
下記の組成に従つて調製した硬質樹脂組成物の
軟化温度を評価した。評価に際しては、柔軟温度
の測定値（JISK−6745に準抛）をもつて軟化温
度とした。得られた結果を第３表に示す。
塩化ビニル樹脂
（Geon 103EP−８（重合度800）；日本ゼオン
(株)製） 100重量部
エステル（第３表に記載） ５重量部
安定剤（ジブチルスズマレート） 1.5重量部
試験片作成条件
ロール混練 180℃×４分間
プレス成型 180℃×10分間
その結果、硬質配合による本発明の組成物は、
DOP組成物と比べて軟化温度が高く、優れた耐
熱性を示している。
［発明の効果］
ジフエニルスルホン−３，3′，４，4′−テトラ
カルボン酸を酸成分として調製されるエステルを
副資材として配合した含塩素ビニル系樹脂組成物
は、従来の樹脂組成物に比べ、軟質分野において
は、特に耐抽出性、耐熱変形性に優れる外、耐揮
発性、耐移行性、電気絶縁性、ゲル化性等の諸特
性についても同等又はそれ以上の性能を示す。
又、硬質分野においては、軟化温度が高く、可使
温度が向上する等の特徴を有している。
[Industrial Application Field] The present invention relates to a chlorine-containing vinyl resin composition that has excellent properties regardless of whether it is hard or soft. [Prior Art] Chlorine-containing vinyl resin compositions are used in many fields such as household goods and industrial materials. In recent years, such products are desired to be miniaturized and are often used in harsh environments. Electrical insulation, heat deformation resistance, and high softening temperature are required depending on the product. In order to satisfy these properties, the current situation is to select several types of esters as auxiliary materials for resins depending on the required properties and use them in combination. It is difficult to satisfy. For example, tri(2-ethylhexyl trimellitate) is used in fields that require volatility resistance and electrical insulation, but with advances in technology, it has even higher volatility resistance and electrical insulation properties. There are fields that require this. On the other hand, in fields where extraction resistance and migration resistance are required, even trimellitic acid esters are not satisfactory, and polyester plasticizers are generally used. However, polyester plasticizers have poor processability and
It is inferior in water resistance, heat resistance, and electrical insulation, and further improvements in extraction resistance and migration resistance are desired. In addition, for hard products, a small amount of ester is added to lower the melt viscosity and improve processability, but in this case, the softening temperature of the product decreases depending on the amount added, making it difficult to withstand use at high temperatures. . In order to solve this problem, a solid plasticizer, dicyclohexyl phthalate, is sometimes used, but there remains a problem with its volatility. [Problems to be Solved by the Invention] The present inventors have developed a resin composition that has superior extraction resistance and heat deformation resistance in the soft field, and can maintain a high softening temperature in the hard field. As much as possible
After examining various ester compounds as auxiliary materials for resins, we found that esters prepared using tetracarboxylic acids or anhydrides having a specific structure as acid components are effective.Based on this knowledge, we developed the present invention. It was completed. [Means for Solving the Problems] The chlorine-containing vinyl resin composition according to the present invention is characterized by blending an ester represented by the following general formula () with a thermoplastic resin. [In the formula, R 1 , R 2 , R 3 , and R 4 are the same or different and represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 22 carbon atoms. However, not all of R 1 to R 4 are hydrogen atoms. ] Here, the chlorinated vinyl resin used is one manufactured from vinyl chloride or vinyl chloride and a comonomer copolymerizable therewith by a method such as a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method. The resin has an average degree of polymerization of 400 to 10,000, preferably 600 to 6,000. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters, methacrylic esters, maleic esters, vinyl ethers, α-olefins, vinylidene chloride, and vinyl halides other than vinyl chloride. However, these comonomers are not limited thereto. The ester according to the present invention is synthesized by esterifying the corresponding diphenylsulfone-3,3',4,4'-tetracarboxylic acid or its anhydride with a predetermined alcohol according to a conventional method. The alcohol residue constituting the ester according to the present invention is an alkyl group or alkenyl group having 1 to 22 carbon atoms, and specifically, methyl, ethyl, propyl, n-butyl, isobutyl, amyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, isooctyl, isononyl, n-decyl,
Examples include isodecyl, undecyl, dodecyl, tridecyl, myristyl, cetyl, stearyl, behenyl, and oleyl. Also, Alphaol 610 (manufactured by Vista Chemical Far East Co., Ltd.), Lineball 79 (manufactured by Ciel Chemical Co., Ltd.),
Mixed oxo alcohols such as Lineball 911 (manufactured by Ciel Chemical Co., Ltd.) can also be used as the alcohol component. The ester is obtained from a predetermined carboxylic acid and alcohol through a dehydration reaction. The esterification reaction may be carried out without a catalyst, but it is usually carried out in the presence of an esterification catalyst such as an acid catalyst, a metal alcoholate, or a metal oxide, and if necessary, the reaction is purified using a processing agent, etc. Let it be ester. The blending amount of the ester according to the present invention is appropriately selected depending on the properties required of the resin composition.
Approximately 30 parts by weight, 20 to 200 parts for soft compounds
Approximately parts by weight are added. In addition, the chlorine-containing vinyl resin composition according to the present invention includes di(2-ethylhexyl) phthalate, diisononyl phthalate, di(2-ethylhexyl) adipate, tri(2-ethylhexyl) trimellitate, liquid polyester, tricresyl phosphate,
General-purpose plasticizers such as epoxidized soybean oil or other esters used as processing aids can be used in combination as appropriate. The chlorine-containing vinyl resin composition according to the present invention includes:
Stabilizers, lubricants, flame retardants, antioxidants, ultraviolet absorbers, and
Fillers, colorants, mold release agents, antifogging agents, antistatic agents,
A crosslinking agent, antibacterial agent, antifungal agent, foaming agent, etc. can be appropriately added. The thus obtained chlorine-containing vinyl resin composition can be used in hard products such as window frames, signboards, office equipment, telephones, gutters, records, plates, containers, pipes, footwear, toys, furniture, flooring, and packaging. materials, roofing materials,
It is useful in various fields such as leather, films, wallpaper, hoses, electric wires, paste-sol molded products, and soft products such as tents, sheets, tapes, and curtains. [Example] Next, the present invention will be explained in detail with reference to Examples. Examples 1 to 3, Comparative Examples 1 to 2 Soft resin compositions having the following compositions were prepared,
Various properties such as volatility resistance, migration resistance, extraction resistance, electrical insulation, and heat deformation resistance were evaluated. The results obtained are shown in Table 1. Composition of resin composition Vinyl chloride resin (Geon 101EP (degree of polymerization 1450); Nippon Zeon Co., Ltd.
) 100 parts by weight Ester (listed in Table 1) 50 parts by weight Stabilizer (tribasic lead sulfate) 3 parts by weight Test piece preparation conditions Roll kneading 163-165℃ x 4 minutes Press molding 165℃ x 10 minutes Resin composition Method for evaluating properties of objects (1) Electrical insulation Measured according to JIS K 6723. (2) Volatility resistance, migration resistance, extraction resistance Volatilization loss, n-hexane extraction and migration tests are as follows:
The weight loss of plasticized PVC under each condition was measured.
The shrinkage rate in the n-hexane extraction test was determined by measuring the dimensions of the test piece before and after extraction. (3) Thermal deformability A weight with a tensile load of 1200 Kg/cm 2 was suspended from a dumbbell No. 2 test piece, and after heating at 120°C for 2 hours in a gear oven, the elongation of the test piece was measured to determine the deformation rate. The esters used in each example are abbreviated as follows. TBPS: Diphenylsulfone-3,3',4,4'-
Tetra n-butyl tetracarboxylate THPS: Diphenylsulfone-3,3',4,4'-
Tetraheptyl tetracarboxylate TOPS: Diphenylsulfone-3,3',4,4'-
Tetra-n-octyl tetracarboxylate DOP: Di-2-ethylhexyl phthalate TOTM: Tri(2-ethylhexyl trimerutate) The soft resin composition according to the present invention is a volatile-resistant, migration-resistant, and highly insulating plasticizer. Compared to the TOTM formulation, the sheet has the same or better volatility resistance and electrical insulation properties. In addition, migration resistance, oil resistance, and heat deformation resistance are superior to those of TOTM formulations, and extraction resistance and heat deformation resistance are particularly excellent. Examples 4 to 6, Comparative Example 3 The gelling properties of the resin compositions obtained according to the following compositions were determined by measuring the temperature at which the resin dispersed in the ester melts and becomes transparent. The results obtained are shown in Table 2. Vinyl chloride resin (Geon 101EP (degree of polymerization 1450); Nippon Zeon Co., Ltd.
100 parts by weight of ester (listed in Table 2) 200 parts by weight Method for measuring melting temperature 0.01 g of a predetermined mixture consisting of vinyl chloride resin and ester was dropped onto the preparation, and then a micro-melting point measuring device (Yanagimoto Co., Ltd.) was used. The temperature at which the mixture became transparent was determined while gradually heating the mixture using a thermoplastic resin (manufactured by Seisakusho), which was defined as the melting temperature (gelling property). The resin composition obtained by blending the ester according to the present invention melts at a lower temperature than conventional compositions containing secondary materials having volatility resistance, migration resistance, and high electrical insulation properties. The resin composition has excellent gelling properties. Examples 7 to 9, Comparative Example 4 The softening temperature of hard resin compositions prepared according to the following compositions was evaluated. In the evaluation, the measured value of the softening temperature (subject to JISK-6745) was taken as the softening temperature. The results obtained are shown in Table 3. Vinyl chloride resin (Geon 103EP-8 (degree of polymerization 800); Nippon Zeon
Co., Ltd.) 100 parts by weight Ester (listed in Table 3) 5 parts by weight Stabilizer (dibutyl tin malate) 1.5 parts by weight Test piece preparation conditions Roll kneading 180℃ x 4 minutes Press molding 180℃ x 10 minutes As a result, The composition of the invention with a hard formulation comprises:
It has a higher softening temperature than DOP compositions and exhibits excellent heat resistance. [Effect of the invention] A chlorine-containing vinyl resin composition containing an ester prepared from diphenylsulfone-3,3',4,4'-tetracarboxylic acid as an acid component as an auxiliary material is superior to conventional resin compositions. In the soft field, in addition to being particularly excellent in extraction resistance and heat deformation resistance, it also shows equivalent or superior performance in various properties such as volatility resistance, migration resistance, electrical insulation, and gelling properties.
In addition, in the hard field, it has characteristics such as a high softening temperature and an improved usable temperature.
【表】【table】
【表】【table】
Claims (1)
（）で表されるエステルを配合してなることを
特徴とする含ハロゲン系樹脂組成物。 ［式中、R1、R2、R3、R4は同一又は異なつ
て、水素原子又は炭素数１〜22のアルキル基若し
くはアルケニル基を表す。但し、R1〜R4の全て
が水素原子であることはない。］ ２ 含ハロゲン系樹脂100重量部に対し、請求項
１に記載のエステルを１〜30重量部配合してなる
請求項１に記載の含ハロゲン系樹脂組成物。 ３ 含ハロゲン系樹脂100重量部に対し、請求項
１に記載のエステルを20〜200重量部配合してな
る請求項１に記載の含ハロゲン系樹脂組成物。[Scope of Claims] 1. A halogen-containing resin composition characterized by blending an ester represented by the following general formula () into a halogen-containing resin. [In the formula, R 1 , R 2 , R 3 , and R 4 are the same or different and represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 22 carbon atoms. However, not all of R 1 to R 4 are hydrogen atoms. 2. The halogen-containing resin composition according to claim 1, which comprises 1 to 30 parts by weight of the ester according to claim 1, based on 100 parts by weight of the halogen-containing resin. 3. The halogen-containing resin composition according to claim 1, wherein 20 to 200 parts by weight of the ester according to claim 1 is blended with 100 parts by weight of the halogen-containing resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18190287A JPS6424862A (en) | 1987-07-20 | 1987-07-20 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18190287A JPS6424862A (en) | 1987-07-20 | 1987-07-20 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6424862A JPS6424862A (en) | 1989-01-26 |
| JPH0562898B2 true JPH0562898B2 (en) | 1993-09-09 |
Family
ID=16108885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18190287A Granted JPS6424862A (en) | 1987-07-20 | 1987-07-20 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6424862A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006278514A (en) * | 2005-03-28 | 2006-10-12 | Denso Corp | Semiconductor device |
-
1987
- 1987-07-20 JP JP18190287A patent/JPS6424862A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6424862A (en) | 1989-01-26 |
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