JP2528688B2 - Improved post-chlorinated vinyl chloride resin composition - Google Patents
Improved post-chlorinated vinyl chloride resin compositionInfo
- Publication number
- JP2528688B2 JP2528688B2 JP63047059A JP4705988A JP2528688B2 JP 2528688 B2 JP2528688 B2 JP 2528688B2 JP 63047059 A JP63047059 A JP 63047059A JP 4705988 A JP4705988 A JP 4705988A JP 2528688 B2 JP2528688 B2 JP 2528688B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- parts
- weight
- chloride resin
- chlorinated vinyl
- 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 - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は加工性と耐熱性が改良された後塩素化塩化ビ
ニル樹脂組成物に関する。The present invention relates to a post-chlorinated vinyl chloride resin composition having improved processability and heat resistance.
後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すぐれ，給湯管，地中線
用ケーブル防護管等に利用されている。Since post-chlorinated vinyl chloride resin has a higher heat distortion temperature than vinyl chloride resin, it has excellent heat resistance and is used for hot water supply pipes, underground cable protection pipes, etc.
公知の如く，後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
及び光によって劣化を受ける。CPVCの加熱による劣化を
防止するために，成型加工時に，三塩基性硫酸鉛，二塩
基性亜硫酸鉛等の鉛安定剤，ステアリン酸鉛，ステアリ
ン酸バリウム，ステアリン酸カルシウム等の金属石けん
類，ジブチル錫マレートポリマー，ジブチル錫ビス（モ
ノアルキルマレート），ジブチル錫ビス（２−エチルヘ
キシルメルカプトアセテート），ジオクチル錫ビス（イ
ソオクチルメルカプトアセテート），ジメチル錫ビス
（イソオクチルメルカプトアセテート）等の有機錫系安
定剤，エポキシ化合物，有機亜リン酸エステル，抗酸化
剤等が使用され，熱安定性を得ている。As is well known, post-chlorinated vinyl chloride resin (hereinafter referred to as CPVC), like vinyl chloride resin (hereinafter referred to as PVC), is deteriorated by heat and light. In order to prevent deterioration of CPVC due to heating, lead stabilizers such as tribasic lead sulfate and dibasic lead sulfite, lead stearate, barium stearate, metallic soaps such as calcium stearate, dibutyltin, etc. Organotin stable such as malate polymer, dibutyltin bis (monoalkyl maleate), dibutyltin bis (2-ethylhexylmercaptoacetate), dioctyltin bis (isooctylmercaptoacetate), dimethyltin bis (isooctylmercaptoacetate) Uses agents, epoxy compounds, organic phosphites, antioxidants, etc. to obtain thermal stability.
しかしながら，上記添加剤において，有機錫系安定剤
の使用はCPVCの熱変形温度（耐熱性）を低下させたり，
例えば押出成形加工において，吐出量の低下や金型内で
の分解による製品表面の肌荒れを生じ，満足できる製品
とすることはできなかった。従って，これらの欠点のな
い加工性と耐熱性にすぐれたCPVCの出現が望まれてい
た。However, in the above additives, the use of an organotin stabilizer lowers the heat distortion temperature (heat resistance) of CPVC,
For example, in the extrusion molding process, it was not possible to obtain a satisfactory product because the discharge amount was lowered and the product surface was roughened due to decomposition in the mold. Therefore, the advent of CPVC, which is excellent in workability and heat resistance without these defects, has been desired.
本発明者等は上記欠点を改良するため鋭意研究の結
果,CPVCに特定の有機錫カルボキシレートとＡ型ゼオラ
イトを併用添加することにより，加工性と耐熱性のすぐ
れたCPVC組成物が得られることを見出し，本発明に到っ
た。The inventors of the present invention have conducted intensive studies to improve the above-mentioned drawbacks, and as a result, by adding a specific organotin carboxylate and A-type zeolite together to CPVC, a CPVC composition having excellent processability and heat resistance can be obtained. The present invention has been completed and the present invention has been achieved.
すなわち，本発明は，後塩素化塩化ビニル樹脂100重
量部又は塩化ビニル樹脂を20重量％以下で含有する後塩
素化塩化ビニル樹脂100重量部に対して衝撃強化剤５〜2
0重量部を配合してなる樹脂組成物において， （ａ）一般式 R2Sn（OOCR1）２ （式中Ｒは炭素数１〜12個を有するアルキル基をR1は炭
素数11〜21個を有するアルキル基又はアルケニル基をそ
れぞれ示す）で表わされる有機錫カルボキシレートを0.
3〜2.0重量部と （ｂ）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0.1〜2.0重量部と を添加してなる改良された後塩素化塩化ビニル樹脂組成
物である。That is, the present invention is based on 100 parts by weight of a post-chlorinated vinyl chloride resin or 100 parts by weight of a post-chlorinated vinyl chloride resin containing 20% by weight or less of a vinyl chloride resin, and an impact toughening agent of 5 to 2 parts.
In a resin composition containing 0 part by weight, (a) a general formula R 2 Sn (OOCR 1 ) 2 (wherein R is an alkyl group having 1 to 12 carbons, R 1 is 11 to 21 carbons). Represents an alkyl group or an alkenyl group each having 1).
3 to 2.0 parts by weight and (b) 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 (where M is a monovalent cation) Or 0.1 to 2.0 parts by weight of an A-type zeolite represented by Na, K, NH 4 , Ca, Mg, Sr, Zn, which is an equivalent amount of polyvalent cation, It is a chlorinated vinyl chloride resin composition.
上記一般式〔Ｉ〕で表わされる有機錫カルボキシレー
トとしては，例えばジアルキル錫ジラウレート，ジアル
キル錫ジミリステート，ジアルキル錫ジパルミテート，
ジアルキル錫ジステアレート，ジアルキル錫ジベヘネー
ト，ジアルキル錫ジオレート，ジアルキル錫ジリシノレ
ート，ジアルキル錫ジリノレート，ジアルキル錫ジ（12
−ヒドロキシステアレート）などが挙げられる。ここで
ジアルキル錫としては，例えばジメチル錫，ジブチル
錫，ジオクチル錫，ジラウリル錫などを挙げることがで
きる。Examples of the organic tin carboxylate represented by the above general formula [I] include dialkyltin dilaurate, dialkyltin dimyristate, dialkyltin dipalmitate,
Dialkyltin distearate, dialkyltin dibehenate, dialkyltin dioleate, dialkyltin diricinolate, dialkyltin dilinoleate, dialkyltin di (12
-Hydroxy stearate) and the like. Examples of the dialkyl tin include dimethyl tin, dibutyl tin, dioctyl tin, and dilauryl tin.
また上記一般式〔III〕で表わされるＡ型ゼオライト
において,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,Zn
Oを表わすものとする。In the A-type zeolite represented by the above general formula [III], when M is a monovalent cation, M 2 O represents Na 2 O, K 2 O, (NH 4 ) 2 O, respectively, and M is If the amount of polyvalent cation is equal to that, M 2 O is CaO, MgO, SrO, Zn, respectively.
Shall represent O.
本発明に使用するCPVCは，例えばPVCを単独，又は塩
素化炭化水素溶媒と共に，水に懸濁し塩素を付加した公
知方法で作られるもので，塩素含有量が63〜70の範囲の
ものがよい。これより塩素含有量が低いものは耐熱性が
不充分でありまたこれより塩素含有量が多いものは溶融
粘度が高く，加工性が悪くなる。The CPVC used in the present invention is made by a known method in which, for example, PVC alone or with a chlorinated hydrocarbon solvent is suspended in water and chlorine is added, and the chlorine content is preferably in the range of 63 to 70. . If the chlorine content is lower than this, the heat resistance is insufficient, and if the chlorine content is higher than this, the melt viscosity is high and the processability becomes poor.
本発明に使用する衝撃強化剤としては，例えば30〜40
％の塩素を含有する塩素化ポリエチレン，アクリル酸エ
ステルを主体とする共重合ゴムにメチルメタクリレー
ト，スチレン，アクリロニトリル等の単量体をグラフト
重合した多成分系樹脂，アクリロニトリル・ブタジエン
・スチレン樹脂，メタルメタクリレート・ブタジエン・
スチレン樹脂，酢酸ビニル・エチレン共重合体樹脂など
が挙げられる。Examples of the impact strengthening agent used in the present invention include 30 to 40
% Polychlorinated Polyethylene Containing Chlorine, Acrylic Ester-Based Copolymer Rubber Graft Polymerized with Monomers such as Methyl Methacrylate, Styrene, Acrylonitrile, Acrylonitrile-Butadiene-Styrene Resin, Metal Methacrylate ·butadiene·
Examples include styrene resin and vinyl acetate / ethylene copolymer resin.
本発明においては,CPVC100重量部又はPVCを20重量％
以下で含有するCPVC100重量部に対して衝撃強化剤５〜2
0重量部を配合した樹脂組成物に，有機錫カルボキシレ
ート0.3〜2.0重量部とＡ型ゼオライト0.1〜2.0重量部を
添加した場合に，加工性と耐熱性が改良されたCPVC組成
物を得ることができる。In the present invention, 100 parts by weight of CPVC or 20% by weight of PVC is used.
Impact strengthener 5 to 2 per 100 parts by weight of CPVC contained below
To obtain a CPVC composition with improved processability and heat resistance when 0.3 to 2.0 parts by weight of organotin carboxylate and 0.1 to 2.0 parts by weight of A-type zeolite are added to a resin composition containing 0 parts by weight. You can
有機錫カルボキシレート又はＡ型ゼオライトの添加量
が上記範囲外であると，次のように加工性又は耐熱性に
おいて優れたCPVC製品が得られない。すなわち，例えば
押出成形加工において，有機錫カルボキシレートの添加
量が0.3重量部より少ないと，トルク及び背圧の低下も
吐出量の増加もなく,2.0重量部より多いと，トルク及び
背圧が低下し，吐出量は増加するが，耐熱性（熱変形温
度）が悪化する。またＡ型ゼオライトの添加量が0.1重
量部より少ないと，吐出量の増加はなく耐熱性が悪化
し,2.0重量部より多いと，トルク及び背圧が高くて加工
性が悪化し，また結晶水が遊離し，発泡のため製品の外
観を損ねる。If the addition amount of the organotin carboxylate or A-type zeolite is out of the above range, a CPVC product excellent in processability or heat resistance cannot be obtained as follows. That is, for example, in extrusion molding, if the addition amount of organotin carboxylate is less than 0.3 parts by weight, there is no decrease in torque and back pressure and discharge amount, and if it is more than 2.0 parts by weight, the torque and back pressure decrease. However, the discharge amount increases, but the heat resistance (heat distortion temperature) deteriorates. When the amount of A-type zeolite added is less than 0.1 parts by weight, the discharge amount does not increase and heat resistance deteriorates, and when it is more than 2.0 parts by weight, the torque and back pressure are high and the workability deteriorates. Are released, and the appearance of the product is impaired due to foaming.
本発明のCPVC組成物には，必要に応じて公知の種々の
熱及び光に対する安定剤，滑剤，充填剤，顔料等を添加
することができる。そして，ロールミル，リボンブレン
ダー，ヘンシェルミキサー，バンバリミキサー等の公知
の混合装置を用いて所望の成形物に成形できる。Various known heat and light stabilizers, lubricants, fillers, pigments and the like can be added to the CPVC composition of the present invention as necessary. Then, it can be molded into a desired molded product using a known mixing device such as a roll mill, a ribbon blender, a Henschel mixer, or a Banbury mixer.
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に耐衝撃性を与えているので,CPVC
組成物を押出成形加工して，給湯管や地中線用ケーブル
防護管等に利用することができる。According to the present invention, the workability and heat resistance (heat distortion temperature) of CPVC can be improved and impact resistance is imparted to CPVC.
The composition can be extruded and used as a hot water supply pipe or a cable protection pipe for underground cables.
〔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。[Examples] Next, the present invention will be described with reference to examples, but parts in the examples represent parts by weight.
実施例 １ 後塩素化塩化ビニル樹脂（カネビニールＨ−701,鐘淵
化学社製）100部，衝撃強化剤として，アクリルゴム・
メチルメタクリレート・アクリロニトリル共重合体（カ
ネエースFM,鐘淵化学社製）10部，下記第１表の安定剤
を合計で２部，滑剤として,Wax OP（ヘキスト社製）１
部,EW−100（理研ビタミン社製）１部及びHiwax 200P三
井石油化学社製）0.5部を配合し，ヘンシェルミキサー
にて120℃になるまで混合してコンパウンドを調製し
た。これを20mm押出成形機にて５×10mmの角棒に押出
し，トルク，背圧，吐出量を測定することにより加工性
を調べた。またJIS K 7206に従ってビカット軟化点試験
を行ない，樹脂組成物の耐熱性を評価した。Example 1 100 parts of post-chlorinated vinyl chloride resin (Kanevinyl H-701, manufactured by Kanegafuchi Chemical Co., Ltd.), acrylic rubber
Methylmethacrylate-acrylonitrile copolymer (Kaneace FM, manufactured by Kanebuchi Chemical Co., Ltd.) 10 parts, 2 parts in total of the stabilizers shown in Table 1 below, and Wax OP (manufactured by Hoechst) as a lubricant 1
Part, EW-100 (manufactured by Riken Vitamin Co., Ltd.) and 0.5 part of Hiwax 200P manufactured by Mitsui Petrochemical Co., Ltd. were mixed and mixed with a Henschel mixer to 120 ° C. to prepare a compound. This was extruded into a 5 × 10 mm square bar using a 20 mm extrusion molding machine, and the workability was investigated by measuring the torque, back pressure, and discharge rate. Also, a Vicat softening point test was performed according to JIS K 7206 to evaluate the heat resistance of the resin composition.
押出成形条件は次の通りであった。 The extrusion molding conditions were as follows.
シリンダー:C1 C2 ダイス 温度（℃）:165 195 195 回転数:40rpm 結果を第１表に示す。Cylinder: C 1 C 2 Die Temperature (℃): 165 195 195 Revolution: 40 rpm The results are shown in Table 1.
実施例 ２ 後塩素化塩化ビニル樹脂（カネビニールＨ−701）85
部，塩化ビニル樹脂（カネビニールＳ−1001,鐘淵化学
社製）15部，衝撃強化剤として塩素化ポリエチレン（ダ
イソラックＨ−135,大阪曹達社製）15部，下記第２表の
安定剤を各部数，滑剤として,Wax OP1部,EW−100 1部及
びHiwax 200P 0.5部を配合し，ヘンシェルミキサーにて
120℃になるまで混合してコンパウンドを調製した。こ
れを実施例１と全く同様にして押出成形を行い，トル
ク，背圧，吐出量を測定し，またビカット軟化点を調べ
た。 Example 2 Post-chlorinated vinyl chloride resin (Kanevinyl H-701) 85
Parts, vinyl chloride resin (Kanevinyl S-1001, manufactured by Kanegafuchi Chemical Co., Ltd.), 15 parts of chlorinated polyethylene (Daisolak H-135, manufactured by Osaka Soda Co., Ltd.) as an impact strengthener, and stabilizers shown in Table 2 below. Mix each part with 1 part of Wax OP, 1 part of EW-100 and 0.5 part of Hiwax 200P as a lubricant and use a Henschel mixer.
A compound was prepared by mixing until the temperature reached 120 ° C. Extrusion molding was performed in the same manner as in Example 1, torque, back pressure, and discharge amount were measured, and the Vicat softening point was examined.
結果を第２表に示す。 The results are shown in Table 2.
〔発明の効果〕 上記実施例１〜２の押出加工試験及びビカット軟化点
の結果から明らかなように，本発明において，ジアルキ
ル錫ジカルボキシレートとＡ型ゼオライトを特定量併用
添加するとCPVCの熱変形温度を低下させることなく，加
工性を向上させることができた。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。 [Effects of the Invention] As is clear from the results of the extrusion test and the Vicat softening point of Examples 1 and 2, in the present invention, when dialkyltin dicarboxylate and A-type zeolite are added together in a specific amount, the thermal deformation of CPVC is caused. The workability could be improved without lowering the temperature. These effects are achieved only by the constitution of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 27:06 Ｃ０８Ｌ 27:06 55:02） 55:02） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area C08L 27:06 C08L 27:06 55:02) 55:02)
Claims (1)
化ビニル樹脂を20重量％以下で含有する後塩素化塩化ビ
ニル樹脂100重量部に対して衝撃強化剤５〜20重量部を
配合してなる樹脂組成物において， （ａ）一般式 R2Sn（OOCR1）２ （式中Ｒは炭素数１〜12個を有するアルキル基を,R1は
炭素数11〜21個を有するアルキル基又はアルケニル基を
それぞれ示す）で表わされる有機錫カルボキシレートを
0.3〜2.0重量部と （ｂ）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0.1〜2.0重量部と を添加してなる改良された後塩素化塩化ビニル樹脂組成
物。1. A mixture of 100 parts by weight of a post-chlorinated vinyl chloride resin or 100 parts by weight of a post-chlorinated vinyl chloride resin containing 20% by weight or less of a vinyl chloride resin with 5 to 20 parts by weight of an impact enhancer. In the resin composition, (a) R 2 Sn (OOCR 1 ) 2 (wherein R is an alkyl group having 1 to 12 carbon atoms, R 1 is an alkyl group having 11 to 21 carbon atoms or An organotin carboxylate represented by
0.3 to 2.0 parts by weight (b) 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 (M in the formula is a monovalent cation Or 0.1 to 2.0 parts by weight of an A-type zeolite represented by Na, K, NH 4 , Ca, Mg, Sr, Zn, which is an equivalent amount of polyvalent cation, Chlorinated vinyl chloride resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047059A JP2528688B2 (en) | 1988-02-29 | 1988-02-29 | Improved post-chlorinated vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047059A JP2528688B2 (en) | 1988-02-29 | 1988-02-29 | Improved post-chlorinated vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01221447A JPH01221447A (en) | 1989-09-04 |
| JP2528688B2 true JP2528688B2 (en) | 1996-08-28 |
Family
ID=12764582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63047059A Expired - Fee Related JP2528688B2 (en) | 1988-02-29 | 1988-02-29 | Improved post-chlorinated vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2528688B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7593149B2 (en) | 2006-01-11 | 2009-09-22 | Ricoh Company, Ltd. | Optical scanning unit having more maintenance-friendly adjustable lens having a support member with first and second faces, an adjusting member and moving member opposite the adjusting member, and image forming apparatus including the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0658594B1 (en) * | 1993-12-14 | 1999-03-31 | Witco Vinyl Additives GmbH | Stabilizer for chlorine-containing polymers |
| TW411352B (en) * | 1995-06-30 | 2000-11-11 | Witco Vinyl Additives Gmbh | Composition of containing a stabilised halogen-containing polymer |
| CN103897241A (en) * | 2012-12-27 | 2014-07-02 | 山西博亮硅业有限公司 | Heat conductive plastics and manufacturing method thereof |
| CN111040344A (en) * | 2019-12-31 | 2020-04-21 | 永川区嵘鑫塑料厂 | Antistatic heat-resistant high-transparency PVC/CPVC alloy pipe and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115338A (en) * | 1980-02-14 | 1981-09-10 | Nippon Carbide Ind Co Ltd | Transparent chlorinated vinyl chloride resin composition |
| JPS62250045A (en) * | 1986-04-21 | 1987-10-30 | Nitto Kasei Kk | Stabilized synthetic resin composition |
-
1988
- 1988-02-29 JP JP63047059A patent/JP2528688B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7593149B2 (en) | 2006-01-11 | 2009-09-22 | Ricoh Company, Ltd. | Optical scanning unit having more maintenance-friendly adjustable lens having a support member with first and second faces, an adjusting member and moving member opposite the adjusting member, and image forming apparatus including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01221447A (en) | 1989-09-04 |
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