JPH0251935B2 - - Google Patents
Info
- Publication number
- JPH0251935B2 JPH0251935B2 JP33302088A JP33302088A JPH0251935B2 JP H0251935 B2 JPH0251935 B2 JP H0251935B2 JP 33302088 A JP33302088 A JP 33302088A JP 33302088 A JP33302088 A JP 33302088A JP H0251935 B2 JPH0251935 B2 JP H0251935B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- formula
- weight
- carbon atoms
- vinyl chloride
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- -1 mercaptocarboxylic acid ester Chemical class 0.000 description 8
- 239000004801 Chlorinated PVC Substances 0.000 description 7
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 7
- 238000004040 coloring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- NAUUNCGQQSDWHM-UHFFFAOYSA-K 2-(6-methylheptylsulfanyl)acetate octyltin(3+) Chemical compound CCCCCCCC[Sn+3].CC(C)CCCCCSCC([O-])=O.CC(C)CCCCCSCC([O-])=O.CC(C)CCCCCSCC([O-])=O NAUUNCGQQSDWHM-UHFFFAOYSA-K 0.000 description 1
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- BILPJDUODHSEHZ-UHFFFAOYSA-N dimethyltin 2-ethylhexyl 2-sulfanylacetate Chemical compound C[Sn]C.CCCCC(CC)COC(=O)CS.CCCCC(CC)COC(=O)CS BILPJDUODHSEHZ-UHFFFAOYSA-N 0.000 description 1
- VXGIVDFKZKMKQO-UHFFFAOYSA-L dioctyltin isooctylthioglycolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCCCCCC)(CCCCCCCC)SCC(=O)OCC(CC)CCCC VXGIVDFKZKMKQO-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
〔産業上の利用分野〕
本発明はとくに初期着色性が改良された塩素化
塩化ビニル樹脂組成物に関する。
塩素化塩化ビニル樹脂は塩化ビニル樹脂に比べ
て熱変形温度が高いために耐熱性に優れ、電子部
品ケース、銘板、食品容器等の透明加工製品への
用途の拡大が期待されている。
〔従来の技術〕
公知のごとく、塩素化塩化ビニル樹脂（以下
CPVCと称す）も塩化ビニル樹脂（以下PVCと
称す）と同様に熱及び光によつて劣化を受ける。
またCPVCは成形溶融時に一部分解し、初期着色
を生じ、透明製品とするには好ましくない。
そこで熱劣化に対しては、成形加工時に、鉛安
定剤、金属石けん安定剤、有機錫安定剤、エポキ
シ化合物、有機亜リン酸エステル、抗酸化剤等を
添加する方法で、また成形溶融時の初期着色に対
しては、有機錫ビス（メルカプトカルボン酸エス
テル）と塩酸との反応生成物（油状物質）を添加
する方法（特開昭63−248838号）でそれぞれを防
止している。
〔発明が解決しようとする問題点〕
しかしながら上記の熱劣化防止法は熱劣化に対
してはある程度有効であるが、初期着色性を防止
できないし、また上記の初期着色防止法では、該
有機錫化合物と塩酸との反応条件の設定等が困難
で、一定組成の反応油状物質が得られず、一定品
質の工業加工製品にできない欠点がある。
〔問題点を解決するための手段〕
本発明者等は上記欠点を改良するために鋭意研
究の結果、CPVCに特定のアルキル錫メルカプト
カルボン酸エステルと、アルキル錫クロライド又
は／及びメルカプトカルボン酸エステルを併用添
加することにより、初期着色性を改良したCPVC
組成物が得られることを見出し本発明に到つた。
すなわち、本発明は、塩素化塩化ビニル樹脂
100重量部に対し、
(a) 一般式〔〕又は／及び〔〕
（式中R1、R2は炭素数１〜18個のアルキル基
を、R3、R4、R5、R6、R7は炭素数１〜18個の
アルキル基、アルケニル基又は炭素数１〜４個
のアルコキシアルキル基を、ｎは１又は２をそ
れぞれ示す）で表わされるアルキル錫メルカプ
トカルボン酸エステルの１種又は２種以上を
0.01〜５重量部と、
(b) 一般式〔〕又は／及び〔〕
[Industrial Application Field] The present invention particularly relates to a chlorinated vinyl chloride resin composition with improved initial colorability. Chlorinated vinyl chloride resin has a higher heat distortion temperature than vinyl chloride resin, so it has excellent heat resistance, and is expected to find expanded use in transparent processed products such as electronic component cases, nameplates, and food containers. [Prior art] As is well known, chlorinated vinyl chloride resin (hereinafter referred to as
Similar to vinyl chloride resin (hereinafter referred to as PVC), CPVC (hereinafter referred to as PVC) is also subject to deterioration due to heat and light.
Furthermore, CPVC partially decomposes during molding and melting, causing initial coloring, which is not desirable for making transparent products. Therefore, thermal deterioration can be prevented by adding lead stabilizers, metal soap stabilizers, organic tin stabilizers, epoxy compounds, organic phosphite esters, antioxidants, etc. during molding and melting. Initial coloring is prevented by adding a reaction product (oil substance) of organotin bis(mercaptocarboxylic acid ester) and hydrochloric acid (Japanese Patent Application Laid-open No. 248838/1983). [Problems to be Solved by the Invention] However, although the above method for preventing thermal deterioration is effective to some extent against thermal deterioration, it cannot prevent initial discoloration, and the above method for preventing initial discoloration does not prevent the organic tin. It is difficult to set the conditions for the reaction between the compound and hydrochloric acid, and it is difficult to obtain a reaction oil with a certain composition, which makes it impossible to produce industrially processed products of a certain quality. [Means for Solving the Problems] In order to improve the above-mentioned drawbacks, the present inventors have conducted extensive research and have added a specific alkyltin mercaptocarboxylic acid ester, alkyltin chloride or/and mercaptocarboxylic acid ester to CPVC. CPVC with improved initial coloring properties when added together
The inventors discovered that a composition can be obtained and arrived at the present invention. That is, the present invention provides chlorinated vinyl chloride resin.
For 100 parts by weight, (a) General formula [] or/and [] (In the formula, R 1 and R 2 are alkyl groups having 1 to 18 carbon atoms, and R 3 , R 4 , R 5 , R 6 , and R 7 are alkyl groups, alkenyl groups, or alkenyl groups having 1 to 18 carbon atoms. one or more alkyltin mercaptocarboxylic acid esters represented by 1 to 4 alkoxyalkyl groups, n is 1 or 2, respectively)
0.01 to 5 parts by weight, (b) General formula [] or/and []
【式】【formula】
本発明によると、CPVCの加工性と耐熱性（熱
変形温度）を改良でき、CPVCの成形溶融時の分
解を防止し、初期着色を改良できるので、CPVC
組成物を成形加工して、電子部品ケース、銘板、
食品容器等の透明加工食品に利用することができ
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
塩素化塩化ビニル樹脂（HA−15F、徳山積水
工業社製）100部、ジメチル錫ビス（２−エチル
ヘキシルメルカプトアセテート）２部、下記部数
のアルキル錫クロライド及び滑剤（Wax Ｅ、ヘ
キスト社製）１部を添加し、170℃のミキシング
ロールにて厚さ0.5mmのシートを作成し、このシ
ートを６枚重ね、170℃で10分間プレスし、YI
（イエローインデツクス）を全自動測色計カラー
エースTC−Ｐ（東京電色社製）にて測定した。
結果を第１表に示す。
According to the present invention, it is possible to improve the processability and heat resistance (heat distortion temperature) of CPVC, prevent decomposition during molding and melting of CPVC, and improve initial coloring.
The composition can be molded into electronic component cases, nameplates,
It can be used for transparent processed foods such as food containers. [Example] Next, the present invention will be explained with reference to Examples, where parts in the Examples indicate parts by weight. Example 1 100 parts of chlorinated vinyl chloride resin (HA-15F, manufactured by Tokuyama Sekisui Kogyo Co., Ltd.), 2 parts of dimethyltin bis(2-ethylhexylmercaptoacetate), the following parts of alkyltin chloride, and a lubricant (Wax E, manufactured by Hoechst Co., Ltd.) ) was added, a 0.5 mm thick sheet was created using a mixing roll at 170°C, six sheets were stacked and pressed at 170°C for 10 minutes, and YI
(Yellow Index) was measured using a fully automatic colorimeter Color Ace TC-P (manufactured by Tokyo Denshoku Co., Ltd.). The results are shown in Table 1.
【表】【table】
【表】
実施例 ２
塩素化塩化ビニル樹脂（Ｈ−516S、鐘淵化学
社製）100部、メチルメタクリレート・ブタジエ
ン・スチレン樹脂（カネエースＢ−31、鐘淵化学
社製）10部、ジブチル錫ビス（イソオクチルメル
カプトアセテート）３部、下記部数のメルカプト
カルボン酸エステル及び滑剤（Wax Ｅ）１部を
添加し、実施例１と同様にしてプレスシートを作
成し、YIを測定した。
結果を第２表に示す。[Table] Example 2 100 parts of chlorinated vinyl chloride resin (H-516S, manufactured by Kanebuchi Chemical Co., Ltd.), 10 parts of methyl methacrylate-butadiene-styrene resin (Kane Ace B-31, manufactured by Kanebuchi Chemical Co., Ltd.), dibutyltin bis A press sheet was prepared in the same manner as in Example 1 by adding 3 parts of isooctyl mercaptoacetate, the following parts of mercaptocarboxylic acid ester, and 1 part of a lubricant (Wax E), and the YI was measured. The results are shown in Table 2.
【表】【table】
【表】
実施例 ３
塩素化塩化ビニル樹脂（HA−15F）100部、塩
素化ポリエチレン（ダイソラツクＨ−135、ダイ
ソー社製）10部、ジオクチル錫ビス（イソオクチ
ルメルカプトアセテート）1.5部、モノオクチル
錫トリス（イソオクチルメルカプトアセテート）
0.5部、下記部数のアルキル錫クロライドとメル
カプトカルボン酸エステル、及び滑剤（Wax
Ｅ）１部を添加し、実施例１と同様にしてプレス
シートを作成し、YIを測定した。
結果を第３表に示す。[Table] Example 3 100 parts of chlorinated vinyl chloride resin (HA-15F), 10 parts of chlorinated polyethylene (Daisorak H-135, manufactured by Daiso Corporation), 1.5 parts of dioctyltin bis(isooctylmercaptoacetate), monooctyltin Tris (isooctyl mercaptoacetate)
0.5 part, the following parts of alkyltin chloride and mercaptocarboxylic acid ester, and a lubricant (Wax
E) 1 part was added, a press sheet was prepared in the same manner as in Example 1, and YI was measured. The results are shown in Table 3.
【表】
実施例 ４
塩素化塩化ビニル樹脂（Ｈ−516S）100部、メ
チルメタクリレート・ブタジエン・スチレン樹脂
（カネエースＢ）20部、ジブチル錫ジクロライド
2.0部、下記部数のアルキル錫メルカプトカルボ
ン酸エステル、及び滑剤（Wax Ｅ）１部を添加
し、実施例１と同様にしてプレスシートを作成
し、YIを測定した。
結果を第４表に示す。[Table] Example 4 100 parts of chlorinated vinyl chloride resin (H-516S), 20 parts of methyl methacrylate-butadiene-styrene resin (Kane Ace B), dibutyltin dichloride
2.0 parts of alkyltin mercaptocarboxylic acid ester in the following parts, and 1 part of a lubricant (Wax E) were added, a press sheet was prepared in the same manner as in Example 1, and the YI was measured. The results are shown in Table 4.
上記実施例１〜４のイエローインデツクス
（YI）の結果から明らかなように、本発明におい
て、アルキル錫メルカプトカルボン酸エステル
と、アルキル錫クロライド又は（及び）メルカプ
トカルボン酸エステルとを併用添加するとCPVC
の初期着色を改良することができた。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 yellow index (YI) results of Examples 1 to 4 above, in the present invention, when alkyltin mercaptocarboxylic acid ester and alkyltin chloride or (and) mercaptocarboxylic acid ester are added together, CPVC
It was possible to improve the initial coloring of These effects can only be achieved by the configuration of the present invention.
Claims (1)
を、R3、R4、R5、R6、R7は炭素数１〜18個の
アルキル基、アルケニル基又は炭素数１〜４個
のアルコキシアルキル基を、ｎは１又は２をそ
れぞれ示す）で表わされるアルキル錫メルカプ
トカルボン酸エステルの１種又は２種以上を
0.01〜５重量部と、 (b) 一般式〔〕又は／及び〔〕 【式】 【式】 （式中R1及びR2は上記と同意義を有す）で表
わされるアルキル錫クロライドの１種又は２種
以上を0.01〜３重量部又は／及び (c) 一般式〔〕又は／及び〔〕 HS（CH2）oCOOR8 〔〕 HS（CH2）oCOOYOOC（CH2）oSH 〔〕 （式中R8は炭素数１〜18個のアルキル基、ア
ルケニル基又は炭素数１〜４のアルコキシアル
キル基を、Ｙはアルキレン基を、ｎは１又は２
をそれぞれ示す）で表わされるメルカプトカル
ボン酸エステルの１種又は２種以上を0.01〜５
重量部と を添加してなる安定化された塩素化塩化ビニル樹
脂組成物。[Scope of Claims] 1. For 100 parts by weight of chlorinated vinyl chloride resin, (a) General formula [] or/and [] (In the formula, R 1 and R 2 are alkyl groups having 1 to 18 carbon atoms, and R 3 , R 4 , R 5 , R 6 , and R 7 are alkyl groups, alkenyl groups, or alkenyl groups having 1 to 18 carbon atoms. one or more alkyltin mercaptocarboxylic acid esters represented by 1 to 4 alkoxyalkyl groups, n is 1 or 2, respectively)
0.01 to 5 parts by weight, and (b) 1 of an alkyltin chloride represented by the general formula [] or/and [] [Formula] [Formula] (wherein R 1 and R 2 have the same meanings as above) 0.01 to 3 parts by weight of the species or two or more species or/and (c) General formula [] or/and [] HS (CH 2 ) o COOR 8 [] HS (CH 2 ) o COOYOOC (CH 2 ) o SH [ ] (In the formula, R 8 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, or an alkoxyalkyl group having 1 to 4 carbon atoms, Y is an alkylene group, and n is 1 or 2
0.01 to 5 of one or two or more mercaptocarboxylic acid esters represented by
A stabilized chlorinated vinyl chloride resin composition comprising parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33302088A JPH02173146A (en) | 1988-12-27 | 1988-12-27 | Stabilized chlorinated vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33302088A JPH02173146A (en) | 1988-12-27 | 1988-12-27 | Stabilized chlorinated vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02173146A JPH02173146A (en) | 1990-07-04 |
| JPH0251935B2 true JPH0251935B2 (en) | 1990-11-09 |
Family
ID=18261388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33302088A Granted JPH02173146A (en) | 1988-12-27 | 1988-12-27 | Stabilized chlorinated vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02173146A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04198348A (en) * | 1990-11-27 | 1992-07-17 | Sekisui Chem Co Ltd | Chlorinated vinyl chloride resin composition |
| JP2515924B2 (en) * | 1990-11-27 | 1996-07-10 | 積水化学工業株式会社 | Chlorinated vinyl chloride resin composition |
| WO2021039993A1 (en) * | 2019-08-30 | 2021-03-04 | 積水化学工業株式会社 | Chlorinated vinyl chloride resin composition and chlorinated vinyl chloride resin molded body |
-
1988
- 1988-12-27 JP JP33302088A patent/JPH02173146A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02173146A (en) | 1990-07-04 |
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