JPH0327583B2 - - Google Patents
Info
- Publication number
- JPH0327583B2 JPH0327583B2 JP9270086A JP9270086A JPH0327583B2 JP H0327583 B2 JPH0327583 B2 JP H0327583B2 JP 9270086 A JP9270086 A JP 9270086A JP 9270086 A JP9270086 A JP 9270086A JP H0327583 B2 JPH0327583 B2 JP H0327583B2
- Authority
- JP
- Japan
- Prior art keywords
- dialkyltin
- parts
- weight
- group
- resin
- 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
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- -1 ester salt Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 12
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 11
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 11
- 229920002959 polymer blend Polymers 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 9
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229920006026 co-polymeric resin Polymers 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 5
- 239000000057 synthetic resin Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 claims description 3
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000002347 octyl 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])[H] 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229940049920 malate Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 239000000314 lubricant Substances 0.000 description 2
- 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 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 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 2
- 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 2
- 238000013112 stability test Methods 0.000 description 2
- 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 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000002845 discoloration Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は熱安定性と初期の着色性を改良した安
定化された合成樹脂組成物に関する。
〔従来の技術〕
塩化ビニル樹脂にジアルキル錫メルカプト化合
物又はジアルキル錫マレート化合物を添加すれば
すぐれた熱安定性が得られることは知られてい
る。しかしながら、塩化ビニル樹脂にアクリロニ
トリル・ブタジエン・スチレン共重合樹脂を添加
したポリマーブレンドの加工には、より高温を必
要するため、例えばジアルキル錫マレート化合物
の添加は、該ポリマーブレンドの加工の際、初期
着色性を与え、色調のきびしい製品には不適であ
り、また加熱減量が多く、金型汚染の原因にもな
つた。
〔発明が解決しようとする問題点〕
そこで本発明者等は先に上記ポリマーブレンド
にジアルキル錫マレート化合物とアルキル錫チオ
ジプロピオン酸塩又はアルキル錫ジチオジプロピ
オン酸塩を併用添加して、ジアルキル錫マレート
化合物の添加量を減少させると共に、該ブレンド
樹脂の熱安定性、初期着色性及び耐候性を改良し
たが、その中で熱安定性と初期段階での着色性に
やゝ問題点がみられた。
〔問題点を解決するための手段〕
本発明者等は種々研究の結果、ジアルキル錫マ
レート化合物と有機錫チオジプロピオン酸塩又は
有機錫ジチオジプロピオン酸塩にA型ゼオライト
を併用添加すれば、ブレンド樹脂の高温加工にお
いて、初期段階での着色を防止し、高度に熱安定
化できることを見出し、本発明に到つた。
すなわち、本発明は、塩素含有樹脂30〜70重量
部とアクリロニトリル・ブタジエン・スチレン共
重合樹脂70〜30重量部とからなるポリマーブレン
ド組成物を安定化するに際し、
(a) ジアルキル錫マレイン酸塩又は/及びジアル
キル錫マレイン酸エステル塩を0.01〜5重量部
と
(b) ジアルキル錫チオジプロピオン酸塩又は/及
びジアルキル錫ジチオジプロピオン酸塩を0.01
〜5重量部と
(c) 一般式
(1.0±0.2)M2O・Al2O3・(1.9±0.5)SiO2・
(0.5〜6)H2O
(式中Mは1価のカチオン又はそれと等量の多価
カチオンであり、Na,K,NH4,Ca,Mg,Sr,
Znを示す)
で表わされるA型ゼオライトを0.01〜5重量部と
を併用添加することを特徴とする安定化された合
成樹脂組成物である。
また本発明は上記ポリマーブレンドを安定化す
るに際し、(a)ジアルキル錫マレイン酸塩又は/及
びジアルキル錫マレイン酸エステル塩0.01〜5重
量部と(b)ジアルキル錫チオジプロピオン酸塩又
は/及びジアルキル錫ジチオジプロピオン酸塩
0.01〜5重量部と(c)A型ゼオライト0.01〜5重量
部と(d)ジアルキル錫メルカプト化合物0.01〜5重
量部とを併用添加することを特徴とする安定化さ
れた合成樹脂組成物である。
本発明によつて安定化されるポリマーブレンド
組成物は塩素含有樹脂とアクリロニトリル・ブタ
ジエン・スチレン共重合樹脂とからなつている。
塩素含有樹脂としては、例えば塩化ビニル樹脂又
は塩化ビニリデン樹脂のごとき単独重合体、並び
に塩化ビニルを酢酸ビニル、エチレン、プロピレ
ン、スチレン、イソブチレン、塩化ビニリデン、
無水マレイン酸、ブタジエン、イソプレン、メチ
ルメタクリレート、アクリロニトリル、ジアルキ
ルマレート及び類似物のごときコモノマーの1種
又は2種以上と重合させることによつて形成され
るような共重合体、後塩素化塩化ビニル樹脂、後
塩素化塩化ビニル共重合体、塩素化ポリエチレ
ン、塩化ゴムなどを挙げることができる。またア
クリロニトリル・ブタジエン・スチレン共重合樹
脂としては、通常ABS樹脂として知られている
ものを使用することができる。
本発明においてポリマーブレンド組成物に添加
するジアルキル錫マレイン酸塩としては、例えば
一般式〔1〕の化合物を、またジアルキル錫マレ
イン酸エステル塩としては、例えば一般式〔2〕
及び〔3〕の化合物をそれぞれ挙げることができ
る。
R2Sn(OOCCH=CHCOOR1)2 〔2〕
式中Rは、例えばメチル基、ブチル基、オクチ
ル基、ラウリル基などのアルキル基を、R1は、
例えばメチル基、エチル基、ブチル基、ヘプチル
基、オクチル基、イソオクチル基、2−エチルヘ
キシル基、ノニル基、ラウリル基、セチル基、ス
テアリル基、ベヘニル基、オレイル基、ミリスチ
ル基、ベンジル基、シクロヘキシル基、メトキシ
ブチル基、オキソ法による合成高級アルコールか
ら誘導される高級アルキル基などの炭化水素基
を、nは1〜10の整数をそれぞれ示す。
また本発明において添加するジアルキル錫チオ
ジプロピオン酸塩としては、例えば一般式〔4〕
の構造を反復単位とする化合物を、またジアルキ
ル錫ジチオジプロピオン酸塩としては、例えば一
般式〔5〕の構造を反復単位とする化合物をそれ
ぞれ挙げることができる。
式中Rは、例えばメチル基、ブチル基、オクチ
ル基、ラウリル基などのアルキル基を示す。
さらに本発明において、一般式
(1.0±0.2)M2O・Al2O3・(1.9±0.5)SiO2・
(0.5〜6)H2O
(式中Mは1価のカチオン又はそれと等量の多
価カチオンであり、Na,K,NH4,Ca,Mg,
Sr,Znを示す)
で表わされるA型ゼオライトを添加する。ここで
Mが1価のカチオンである場合にはM2Oはそれ
ぞれNa2O,K2O(NH4)2Oを表わし、Mがそれと
等量の多価カチオンである場合には、M2Oはそ
れぞれCaO,MgO,SrO,ZnOを表わすものと
する。
本発明のポリマーブレンド組成物に(a)一般式
〔1〕〜〔3〕で表わされるジアルキル錫マレー
ト化合物、(b)一般式〔4〕〜〔5〕で表わされる
ジアルキル錫チオジプロピオン酸塩又はジアルキ
ル錫ジチオジプロピオン酸塩及び(c)A型ゼオライ
トを添加して十分に熱安定化できるが、より高度
な熱安定性が必要な場合には、一般式〔6〕で表
わされるジアルキル錫3−メルカプトプロピオン
酸塩、一般式〔7〕で表わされるジアルキル錫ビ
ス(3−メルカプトプロピオン酸エステル)塩及
び一般式〔8〕で表わされるジアルキル錫ビス
(メルカプト酢酸エステル)塩から選ばれるジア
ルキル錫メルカプト化合物をさらに添加すればそ
の目的が達せられる。
R2Sn(SCH2CH2COOR1)2 〔7〕
R2Sn(SCH2COOR1)2 〔8〕
式中Rは、例えばメチル基、ブチル基、オクチ
ル基、ラウリル基などのアルキル基を、R1は、
例えばメチル基、エチル基、ブチル基、ヘプチル
基、オクチル基、イソオクチル基、2−エチルヘ
キシル基、ノニル基、ラウリル基、セチル基、ス
テアリル基、ベヘニル基、オレイル基、ミリスチ
ル基、ベンジル基、メチルベンジル基、シクロヘ
キシル基、メトキシブチル基、オキソ法による合
成高級アルコールから誘導される高級アルキル基
などの炭化水素基を、mは1〜10の整数をそれぞ
れ示す。
本発明において、塩素含有樹脂とアクリロニト
リル・ブタジエン・スチレン樹脂とのポリマーブ
レンド組成物100重量部に対する各安定剤の添加
量は、ジアルキル錫マレイン酸塩又は/及びジア
ルキル錫マレイン酸エステル塩0.01〜5重量部、
ジアルキル錫チオジプロピオン酸塩又は/及びジ
アルキル錫ジチオジプロピオン酸塩0.01〜5重量
部及びA型ゼオライト0.01〜5重量部であり、さ
らに高度な熱安定性が必要な場合には、ジアルキ
ル錫3−メルカプトプロピオン酸塩、ジアルキル
錫ビス(3−メルカプトプロピオン酸エステル)
塩及びジアルキル錫ビス(メルカプト酢酸エステ
ル)塩から選ばれるジアルキル錫メルカプト化合
物を0.01〜5重量部添加すればよい。この添加量
の下限以下の使用では熱安定性の向上はなく、ま
た上限以上の使用は不経済である。
本発明の安定化された合成樹脂組成物に対し、
必要により、公知の安定剤、例えば他の有機錫安
定剤、金属有機酸塩、エポキシ化合物、酸化防止
剤、ホウ酸、ホウ酸塩、無水ホウ酸塩、ホウ酸エ
ステル、紫外線吸収剤、有機亜リン酸エステルを
添加することができる。必要に応じて顔料、充填
剤、滑剤、帯電防止剤、難燃剤、加工助剤も使用
することができる。
〔作 用〕
本発明によると、塩素含有樹脂とアクリロニト
リル・ブタジエン・スチレン共重合樹脂とからな
るブレンド樹脂を高度に熱安定化でき、初期段階
での着色を防止できるため、該樹脂の高温での加
工が容易となる。得られた製品は光に対しても安
定化されており、耐候性が要求される分野にも利
用できる。
〔実施例〕
次に実施例を挙げて本発明を説明するが、実施
例中の部は重量部を示すものとする。
実施例 1
塩化ビニル樹脂(カネビニールS−1007、鐘淵
化学社製)50部とアクリロニトリル・ブタジエ
ン・スチレン樹脂(サイコラツクEx211、宇部サ
イコン社製)50部に下記第1表の安定剤を合計で
4.0部になるように添加し、150℃、3分間テスト
ロールで混練し、厚さ0.5mmのシートを作成した。
各シートを2cm×2cmの大きさに切断後、215℃
のギヤー老化試験機に入れて熱安定性を調べた。
表中の数字は次の評価を示す。以下の熱安定性
試験の表も同じ。
1:乳白色 2:淡黄色 3:黄色
4:黄褐色 5:褐 色 6:黒褐色
結果を第1表に示す。
[Industrial Application Field] The present invention relates to a stabilized synthetic resin composition with improved thermal stability and initial colorability. [Prior Art] It is known that excellent thermal stability can be obtained by adding a dialkyltin mercapto compound or a dialkyltin malate compound to a vinyl chloride resin. However, processing a polymer blend in which acrylonitrile-butadiene-styrene copolymer resin is added to vinyl chloride resin requires higher temperatures. It was unsuitable for producing products with harsh color tones, and it also lost a lot of weight on heating, causing mold contamination. [Problems to be Solved by the Invention] Therefore, the present inventors first added a dialkyltin malate compound and an alkyltin thiodipropionate or an alkyltin dithiodipropionate to the above polymer blend. In addition to reducing the amount of malate compound added, the thermal stability, initial coloring property, and weather resistance of the blend resin were improved, but some problems were observed in the thermal stability and coloring property at the initial stage. Ta. [Means for Solving the Problems] As a result of various studies, the present inventors have found that if A-type zeolite is added in combination to a dialkyltin malate compound and an organotin thiodipropionate or an organotin dithiodipropionate, In high-temperature processing of blended resins, we have discovered that coloring can be prevented in the initial stage and thermal stability can be achieved to a high degree, leading to the present invention. That is, in the present invention, when stabilizing a polymer blend composition consisting of 30 to 70 parts by weight of a chlorine-containing resin and 70 to 30 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin, (a) dialkyltin maleate or / and 0.01 to 5 parts by weight of dialkyltin maleate salt and (b) 0.01 part of dialkyltin thiodipropionate or/and dialkyltin dithiodipropionate.
~5 parts by weight and (c) General formula (1.0±0.2)M 2 O・Al 2 O 3・(1.9±0.5)SiO 2・
(0.5-6) H 2 O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, Na, K, NH 4 , Ca, Mg, Sr,
This is a stabilized synthetic resin composition characterized in that 0.01 to 5 parts by weight of type A zeolite represented by Zn is added in combination. The present invention also provides for stabilizing the above polymer blend by combining (a) 0.01 to 5 parts by weight of dialkyltin maleate or/and dialkyltin maleate salt and (b) dialkyltin thiodipropionate or/and dialkyltin maleate salt. Tin dithiodipropionate
0.01 to 5 parts by weight, (c) 0.01 to 5 parts by weight of A-type zeolite, and (d) 0.01 to 5 parts by weight of dialkyltin mercapto compound. . The polymer blend composition stabilized by the present invention comprises a chlorine-containing resin and an acrylonitrile-butadiene-styrene copolymer resin.
Examples of the chlorine-containing resin include homopolymers such as vinyl chloride resin or vinylidene chloride resin, and vinyl chloride as well as vinyl acetate, ethylene, propylene, styrene, isobutylene, vinylidene chloride, etc.
Copolymers, post-chlorinated vinyl chloride, as formed by polymerization with one or more comonomers such as maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkylmalates and the like. Examples include resin, post-chlorinated vinyl chloride copolymer, chlorinated polyethylene, and chlorinated rubber. Furthermore, as the acrylonitrile-butadiene-styrene copolymer resin, one commonly known as ABS resin can be used. In the present invention, the dialkyltin maleate salt to be added to the polymer blend composition is, for example, a compound of general formula [1], and the dialkyltin maleate salt is, for example, a compound of general formula [2].
and [3] can be mentioned, respectively. R 2 Sn (OOCCH=CHCOOR 1 ) 2 [2] In the formula, R is an alkyl group such as a methyl group, a butyl group, an octyl group, a lauryl group, and R 1 is
For example, methyl group, ethyl group, butyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, lauryl group, cetyl group, stearyl group, behenyl group, oleyl group, myristyl group, benzyl group, cyclohexyl group , a methoxybutyl group, a higher alkyl group derived from a higher alcohol synthesized by the oxo method, and n represents an integer of 1 to 10, respectively. Further, as the dialkyltin thiodipropionate to be added in the present invention, for example, general formula [4]
Examples of the dialkyltin dithiodipropionate include compounds having the structure of general formula [5] as a repeating unit. In the formula, R represents an alkyl group such as a methyl group, a butyl group, an octyl group, or a lauryl group. Furthermore, in the present invention, the general formula (1.0±0.2)M 2 O・Al 2 O 3・(1.9±0.5)SiO 2・
(0.5-6) H 2 O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, Na, K, NH 4 , Ca, Mg,
A type zeolite represented by (Sr, Zn) is added. Here, when M is a monovalent cation, M 2 O represents Na 2 O and K 2 O (NH 4 ) 2 O, respectively, and when M is an equivalent polyvalent cation, M 2 O represents CaO, MgO, SrO, and ZnO, respectively. In the polymer blend composition of the present invention, (a) dialkyltin malate compounds represented by general formulas [1] to [3], (b) dialkyltin thiodipropionates represented by general formulas [4] to [5] Alternatively, it can be sufficiently thermally stabilized by adding dialkyltin dithiodipropionate and (c) type A zeolite, but if a higher degree of thermal stability is required, dialkyltin represented by general formula [6] 3-mercaptopropionate, dialkyltin bis(3-mercaptopropionic acid ester) salt represented by general formula [7], and dialkyltin bis(mercaptoacetate) salt represented by general formula [8] Further addition of mercapto compounds achieves that objective. R 2 Sn (SCH 2 CH 2 COOR 1 ) 2 [7] R 2 Sn (SCH 2 COOR 1 ) 2 [8] In the formula, R represents an alkyl group such as a methyl group, a butyl group, an octyl group, or a lauryl group. , R 1 is
For example, methyl group, ethyl group, butyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, lauryl group, cetyl group, stearyl group, behenyl group, oleyl group, myristyl group, benzyl group, methylbenzyl group. m represents an integer of 1 to 10, respectively. In the present invention, the amount of each stabilizer added to 100 parts by weight of the polymer blend composition of chlorine-containing resin and acrylonitrile-butadiene-styrene resin is 0.01 to 5 parts by weight of dialkyltin maleate or/and dialkyltin maleate salt. Department,
0.01 to 5 parts by weight of dialkyltin thiodipropionate or/and dialkyltin dithiodipropionate and 0.01 to 5 parts by weight of A-type zeolite, and when a higher degree of thermal stability is required, dialkyltin 3 -Mercaptopropionate, dialkyltin bis(3-mercaptopropionate ester)
0.01 to 5 parts by weight of a dialkyltin mercapto compound selected from salts and dialkyltin bis(mercaptoacetate) salts may be added. If the amount added is less than the lower limit, the thermal stability will not be improved, and if the amount is more than the upper limit, it is uneconomical. For the stabilized synthetic resin composition of the present invention,
If necessary, known stabilizers such as other organotin stabilizers, metal organic acid salts, epoxy compounds, antioxidants, boric acid, borates, boric anhydrides, boric acid esters, ultraviolet absorbers, organic substituents, etc. Phosphate esters can be added. Pigments, fillers, lubricants, antistatic agents, flame retardants, and processing aids can also be used as required. [Function] According to the present invention, a blended resin consisting of a chlorine-containing resin and an acrylonitrile-butadiene-styrene copolymer resin can be highly thermally stabilized, and discoloration in the initial stage can be prevented, so that the resin can be stabilized at high temperatures. Processing becomes easier. The resulting product is also stabilized against light and can be used in fields where weather resistance is required. [Example] Next, the present invention will be explained with reference to Examples, where parts in the Examples indicate parts by weight. Example 1 A total of 50 parts of vinyl chloride resin (Kanevinyl S-1007, manufactured by Kanebuchi Kagaku Co., Ltd.) and 50 parts of acrylonitrile-butadiene-styrene resin (Saicolaku Ex211, manufactured by Ube Cycon Co., Ltd.) were combined with the stabilizers listed in Table 1 below.
The mixture was added in an amount of 4.0 parts and kneaded at 150°C for 3 minutes using a test roll to form a sheet with a thickness of 0.5 mm.
After cutting each sheet into 2cm x 2cm size, 215℃
Thermal stability was examined by putting it in a gear aging tester. The numbers in the table indicate the following evaluations. The same applies to the thermal stability test table below. 1: Milky white 2: Pale yellow 3: Yellow 4: Yellowish brown 5: Brown 6: Dark brown The results are shown in Table 1.
【表】
実施例 2
塩化ビニル樹脂(カネビニールS−1007)40部
とアクリロニトリル・ブタジエン・スチレン樹脂
(サイコラツクEx211)60部に下記第2表の安定
剤を合計で5.0部になるように添加し、150℃、3
分間テストロールで混練し、厚さ0.5mmのシート
を作成した。各シートを2cm×2cmの大きさに切
断後、215℃のギヤー老化試験機に入れて熱安定
性を調べた。
結果を第2表に示す。[Table] Example 2 The stabilizers listed in Table 2 below were added to 40 parts of vinyl chloride resin (Kanevinyl S-1007) and 60 parts of acrylonitrile butadiene styrene resin (Cycolac Ex211) for a total of 5.0 parts. , 150℃, 3
The mixture was kneaded using a test roll for a minute to form a sheet with a thickness of 0.5 mm. After each sheet was cut into a size of 2 cm x 2 cm, it was placed in a gear aging tester at 215°C to examine its thermal stability. The results are shown in Table 2.
【表】
実施例 3
後塩素化塩化ビニル樹脂(カネビニールH−
516、鐘淵化学社製)50部とアクリロニトリル・
ブタジエン・スチレン樹脂(サイコラツク
Ex211)50部に下記第3表の安定剤を合計で7.0
部になるように添加し、滑剤としてWaxE(ヘキ
スト社製)1.0部を配合した後、175℃、3分間テ
ストロールで混練し、厚さ0.5mmのシートを作成
した。各シートを2cm×2cmの大きさに切断後、
220℃のギヤー老化試験機に入れて熱安定性を調
べた。
結果を第3表に示す。[Table] Example 3 Post-chlorinated vinyl chloride resin (Kanevinyl H-
516, manufactured by Kanebuchi Kagaku Co., Ltd.) 50 parts and acrylonitrile.
Butadiene/styrene resin
Ex211) 50 parts of the stabilizer listed in Table 3 below for a total of 7.0 parts
After adding 1.0 part of WaxE (manufactured by Hoechst) as a lubricant, the mixture was kneaded with a test roll at 175°C for 3 minutes to form a sheet with a thickness of 0.5 mm. After cutting each sheet into 2cm x 2cm size,
Thermal stability was investigated by placing it in a gear aging tester at 220℃. The results are shown in Table 3.
【表】【table】
【表】
実施例 4
塩化ビニル樹脂(カネビニールS−1007)60部
とアクリロニトリル・ブタジエン・スチレン樹脂
(サイコラツクEx211)40部に下記第4表の安定
剤を合計で3.0部になるように添加し、150℃、3
分間テストロールで混練し、厚さ0.5mmのシート
を作成した。各シートを2cm×2cmの大きさに切
断後、215℃のギヤー老化試験機に入れて熱安定
性を調べた。
結果を第4表に示す。[Table] Example 4 The stabilizers listed in Table 4 below were added to 60 parts of vinyl chloride resin (Kanevinyl S-1007) and 40 parts of acrylonitrile-butadiene-styrene resin (Cycolac Ex211) for a total of 3.0 parts. , 150℃, 3
The mixture was kneaded using a test roll for a minute to form a sheet with a thickness of 0.5 mm. After each sheet was cut into a size of 2 cm x 2 cm, it was placed in a gear aging tester at 215°C to examine its thermal stability. The results are shown in Table 4.
上記実施例1〜3の熱安定性試験結果から明ら
かなように、本発明において、ポリマーブレンド
にジアルキル錫マレイン酸塩又は/及びジアルキ
ル錫マレイン酸エステル塩とジアルキル錫チオ又
はジチオジプロピオン酸塩とA型ゼオライトを併
用すると熱安定性を向上させ、実施例4から明ら
かなように、さらにジアルキル錫メルカプト化合
物を添加すると安定剤の合計量が少なくても熱安
定性を向上した。これらの効果は本発明の構成に
よりはじめて達成されることである。
As is clear from the thermal stability test results of Examples 1 to 3 above, in the present invention, dialkyltin maleate or/and dialkyltin maleate salt and dialkyltin thio or dithiodipropionate are added to the polymer blend. When A-type zeolite was used in combination, the thermal stability was improved, and as is clear from Example 4, when a dialkyltin mercapto compound was further added, the thermal stability was improved even if the total amount of stabilizers was small. These effects can only be achieved by the configuration of the present invention.
Claims (1)
ル・ブタジエン・スチレン共重合樹脂70〜30重量
部とからなるポリマーブレンド組成物を安定化す
るに際し、 (a) ジアルキル錫マレイン酸塩又は/及びジアル
キル錫マレイン酸エステル塩を0.01〜5重量部
と (b) ジアルキル錫チオジプロピオン酸塩又は/及
びジアルキル錫ジチオジプロピオン酸塩を0.01
〜5重量部と (c) 一般式 (1.0±0.2)M2O・Al2O3・(1.9±0.5)SiO2・
(0.5〜6)H2O (式中Mは1価のカチオン又はそれと等量の多価
カチオンであり、Na,K,NH4,Ca,Mg,Sr,
Znを示す) で表わされるA型ゼオライトを0.01〜5重量部と
を併用添加することを特徴とする安定化された合
成樹脂組成物。 2 塩素含有樹脂30〜70重量部とアクリロニトリ
ル・ブタジエン・スチレン共重合樹脂70〜30重量
部とからなるポリマーブレンド組成物を安定化す
るに際し、 (a) ジアルキル錫マレイン酸塩又は/及びジアル
キル錫マレイン酸エステル塩を0.01〜5重量部
と (b) ジアルキル錫チオジプロピオン酸塩又は/及
びジアルキル錫ジチオジプロピオン酸塩を0.01
〜5重量部と (c) 一般式 (1.0±0.2)M2O・Al2O3・(1.9±0.5)SiO2・
(0.5〜6)H2O (式中Mは1価のカチオン又はそれと等量の多価
カチオンであり、Na,K,NH4,Ca,Mg,Sr,
Znを示す) で表わされるA型ゼオライトを0.01〜5重量部と (d) ジアルキル錫3−メルカプトプロピオン酸
塩、ジアルキル錫ビス(3−メルカプトプロピ
オン酸エステル)塩及びジアルキル錫ビス(メ
ルカプト酢酸エステル)塩から選ばれるジアル
キル錫メルカプト化合物を0.01〜5重量部とを
併用添加することを特徴とする安定化された合
成樹脂組成物。[Scope of Claims] 1. In stabilizing a polymer blend composition consisting of 30 to 70 parts by weight of a chlorine-containing resin and 70 to 30 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin, (a) a dialkyltin maleate salt; or/and 0.01 to 5 parts by weight of dialkyltin maleate salt and (b) 0.01 part of dialkyltin thiodipropionate or/and dialkyltin dithiodipropionate.
~5 parts by weight and (c) General formula (1.0±0.2)M 2 O・Al 2 O 3・(1.9±0.5)SiO 2・
(0.5-6) H 2 O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, Na, K, NH 4 , Ca, Mg, Sr,
1. A stabilized synthetic resin composition characterized in that 0.01 to 5 parts by weight of type A zeolite (Zn) is added in combination. 2. When stabilizing a polymer blend composition consisting of 30 to 70 parts by weight of a chlorine-containing resin and 70 to 30 parts by weight of an acrylonitrile-butadiene-styrene copolymer resin, (a) dialkyltin maleate or/and dialkyltin maleate; 0.01 to 5 parts by weight of acid ester salt and (b) 0.01 part of dialkyltin thiodipropionate or/and dialkyltin dithiodipropionate.
~5 parts by weight and (c) General formula (1.0±0.2)M 2 O・Al 2 O 3・(1.9±0.5)SiO 2・
(0.5-6) H 2 O (in the formula, M is a monovalent cation or an equivalent polyvalent cation, Na, K, NH 4 , Ca, Mg, Sr,
(d) dialkyltin 3-mercaptopropionate, dialkyltin bis(3-mercaptopropionate) salt and dialkyltin bis(mercaptoacetate); A stabilized synthetic resin composition characterized in that 0.01 to 5 parts by weight of a dialkyltin mercapto compound selected from salts are added in combination.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9270086A JPS62250045A (en) | 1986-04-21 | 1986-04-21 | Stabilized synthetic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9270086A JPS62250045A (en) | 1986-04-21 | 1986-04-21 | Stabilized synthetic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62250045A JPS62250045A (en) | 1987-10-30 |
JPH0327583B2 true JPH0327583B2 (en) | 1991-04-16 |
Family
ID=14061766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9270086A Granted JPS62250045A (en) | 1986-04-21 | 1986-04-21 | Stabilized synthetic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62250045A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2528688B2 (en) * | 1988-02-29 | 1996-08-28 | 日東化成株式会社 | Improved post-chlorinated vinyl chloride resin composition |
EP1092748A1 (en) * | 1999-10-15 | 2001-04-18 | Albemarle Corporation | Stabilized flame retardant additives and their use |
-
1986
- 1986-04-21 JP JP9270086A patent/JPS62250045A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS62250045A (en) | 1987-10-30 |
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