JP2527752B2 - Vinyl chloride resin composition - Google Patents
Vinyl chloride resin compositionInfo
- Publication number
- JP2527752B2 JP2527752B2 JP62165966A JP16596687A JP2527752B2 JP 2527752 B2 JP2527752 B2 JP 2527752B2 JP 62165966 A JP62165966 A JP 62165966A JP 16596687 A JP16596687 A JP 16596687A JP 2527752 B2 JP2527752 B2 JP 2527752B2
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- Prior art keywords
- vinyl chloride
- chloride resin
- weight
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- parts
- 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.)
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は成形加工性（熱流動性）に優れた塩化ビニル
系樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a vinyl chloride resin composition having excellent moldability (heat fluidity).
［従来の技術］ 塩化ビニル系樹脂を押出し加工、カレンダー加工等の
成形加工を行なう際に、加工装置の金属面に該樹脂が粘
着し、流動性が悪化する。このため、塩化ビニル系樹脂
の成形に際しては滑性を付与し、流動性、離型性を高め
てその成形加工性を向上し、且つ熱安定性を補う目的で
種々の滑剤（外部滑剤）が配合されている。[Prior Art] When a vinyl chloride resin is subjected to molding such as extrusion and calendering, the resin adheres to a metal surface of a processing apparatus, resulting in deterioration of fluidity. Therefore, various lubricants (external lubricants) are added for the purpose of imparting lubricity, enhancing fluidity and releasability to improve molding processability of the vinyl chloride resin during molding, and complementing thermal stability. It is compounded.
従来から用いられている滑剤（外部滑剤）としては、
ステアリン酸アマイド、エルカ酸アマイド、オレイン酸
アマイド等の脂肪酸アマイド、ステアリン酸、エルカ酸
等の脂肪酸およびそのカルシウム、亜鉛等の金属塩、ブ
チルステアレート等の脂肪酸エステル、パラフィンワッ
クス、ポリエチレンワックス等があげられる。As a lubricant (external lubricant) that has been conventionally used,
Examples include fatty acid amides such as stearic acid amide, erucic acid amide, and oleic acid amide, fatty acids such as stearic acid and erucic acid, and their metal salts such as calcium and zinc, fatty acid esters such as butyl stearate, paraffin wax, and polyethylene wax. To be
［発明が解決しようとする問題点］ しかしながら、上記滑剤の配合により塩化ビニル系樹
脂の成形加工性は、ある程度改善されているが、未だ充
分とは言いがたい。[Problems to be Solved by the Invention] However, although the molding processability of the vinyl chloride resin has been improved to some extent by the addition of the above-mentioned lubricant, it cannot be said to be sufficient yet.
本発明者は、上記従来技術に鑑み、塩化ビニル系樹脂
の成形加工性（熱流動性）をさらに向上するべく鋭意検
討を重ねた結果、塩化ビニル系樹脂に特定の炭素原子数
を持つα−オレフィン又はその誘導体を少量配合するこ
とにより、塩化ビニル系樹脂の滑性が著しく良好となっ
て、成形加工性が大幅に向上することを見出し、本発明
を完成するに到った。In view of the above-mentioned conventional technique, the present inventor has made earnest studies to further improve the molding processability (heat fluidity) of vinyl chloride resin, and as a result, α- having a specific number of carbon atoms in vinyl chloride resin has been obtained. The inventors have found that the addition of a small amount of an olefin or a derivative thereof significantly improves the slipperiness of the vinyl chloride resin and significantly improves the moldability and has completed the present invention.
すなわち、本発明の目的は、塩化ビニル系樹脂の特定
のα−オレフィン又はその誘導体を配合した成形加工性
に優れた塩化ビニル系樹脂組成物を提供するにある。That is, an object of the present invention is to provide a vinyl chloride-based resin composition which is blended with a specific α-olefin of a vinyl chloride-based resin or a derivative thereof and has excellent moldability.
［問題点を解決するための手段］ しかして、本発明の要旨は、塩化ビニル系樹脂100重
量部に対して、 （ａ）炭素原子数20以上のα−オレインおよび （ｂ）炭素原子数20以上のα−オレフィンと脂肪酸との
熱付加物 から選ばれた少なくとも一種の化合物0.1〜５重量部を
配合してなる塩化ビニル系樹脂組成物に存する。[Means for Solving Problems] Accordingly, the gist of the present invention is that (a) α-olein having 20 or more carbon atoms and (b) 20 carbon atoms per 100 parts by weight of a vinyl chloride resin. A vinyl chloride resin composition comprising 0.1 to 5 parts by weight of at least one compound selected from the above-mentioned thermal adducts of α-olefins and fatty acids.
以下、本発明につきさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明において用いられる塩化ビニル系樹脂として
は、一般に塩化ビニルモノマーを単独で重合させた平均
重合度400〜4000、好ましくは600〜1300のホモポリマ
ー、塩化ビニルを主成分とする平均重合度300〜3000の
共重合体、例えば塩化ビニル−酢酸ビニル共重合体、エ
チレン、プロピレン、アクリル酸エステル、塩化ビニリ
デンなどの塩化ビニルと共重合可能なモノマーの少量と
塩化ビニルとの共重合体、エチレン−酢酸ビニル共重合
体に塩化ビニルをグラフト反応させた共重合体、後塩素
化塩化ビニル樹脂等が挙げられる。As the vinyl chloride resin used in the present invention, generally, a vinyl chloride monomer is polymerized alone to have an average polymerization degree of 400 to 4000, preferably 600 to 1300 homopolymer, an average polymerization degree of vinyl chloride as a main component of 300 to 3000 copolymers, for example, vinyl chloride-vinyl acetate copolymer, ethylene, propylene, acrylic acid ester, vinylidene chloride copolymers of vinyl chloride with a small amount of a monomer copolymerizable with vinyl chloride, ethylene-acetic acid Examples thereof include a copolymer obtained by graft-reacting vinyl chloride on a vinyl copolymer, and a post-chlorinated vinyl chloride resin.
本発明は、上記塩化ビニル系樹脂に熱流動性改良剤と
して炭素原子数20以上のα−オレフィン及び炭素原子数
20以上のα−オレフィンと脂肪酸との熱付加物から選ば
れた少なくとも一種の化合物を配合した組成物にある。The present invention relates to the vinyl chloride resin as a heat fluidity improver having an α-olefin having 20 or more carbon atoms and the number of carbon atoms.
A composition containing at least one compound selected from thermal adducts of 20 or more α-olefins and fatty acids.
上記α−オレフィンは、エチレン性不飽和二重結合を
有する化合物であって、その炭素原子数（炭素数と略称
する。）が20以上、通常20〜500、好ましくは20〜300、
さらに好ましくは30〜100のものである。該α−オレフ
ィンは同一構造を有するものであっても、異なる構造、
異なる炭素数を有するものの混合物であってもよい。例
えば、炭素数20〜28のα−オレフィンの混合物（例え
ば、三菱化成工業（株）製“ダイアレン208"）、炭素数
30〜60のα−オレフィン混合物（同じく“ダイアレン3
0"）等が好適に用いられる（“ダイアレン”は三菱化成
工業（株）の登録商標）。The α-olefin is a compound having an ethylenically unsaturated double bond and has a carbon atom number (abbreviated as carbon number) of 20 or more, usually 20 to 500, preferably 20 to 300,
More preferably, it is 30 to 100. Even though the α-olefin has the same structure, it has a different structure,
It may be a mixture of those having different carbon numbers. For example, a mixture of α-olefins having 20 to 28 carbon atoms (for example, "Dialene 208" manufactured by Mitsubishi Kasei Co., Ltd.), carbon number
A mixture of 30 to 60 α-olefins (also “Dialen 3
0 ") and the like are preferably used (" Dialen "is a registered trademark of Mitsubishi Kasei Co., Ltd.).
炭素数20以上のα−オレフィンと脂肪酸の熱付加物は
α−オレフィンと炭素数２〜30、好ましくは炭素数２〜
20の飽和脂肪酸、例えば酢酸、プロピオン酸、酪酸、吉
草酸、エナント酸、ラウリン酸、ミリスチン酸、ステア
リン酸等との熱付加物で一般式（II）で表わされるもの
が用いられる。The thermal adduct of an α-olefin having 20 or more carbon atoms and a fatty acid is an α-olefin and 2 to 30 carbon atoms, preferably 2 to 30 carbon atoms.
A thermal addition product of 20 saturated fatty acids, for example, acetic acid, propionic acid, butyric acid, valeric acid, enanthic acid, lauric acid, myristic acid, stearic acid, etc., represented by the general formula (II) is used.
（式中、Ｒは一般式（Ｉ）のＲと同じ意味を表わし、
Ｒ″はＨ又は炭素数１〜28の分岐鎖を有していてもよい
アルキル基を示す。） 一般式（II）で示される熱付加物は、α−オレフィン
と脂肪酸とをラジカル重合開始剤、例えば、ジ−ｔ−ブ
チルペルオキシド、ｔ−ブチルヒドロペルオキシド等の
ラジカル発生剤の存在下で熱付加反応させることにより
得られる。 (In the formula, R represents the same meaning as R in formula (I),
R ″ represents H or an alkyl group having 1 to 28 carbon atoms and optionally having a branched chain.) The thermal adduct represented by the general formula (II) is a radical polymerization initiator of α-olefin and fatty acid. , For example, by thermal addition reaction in the presence of a radical generator such as di-t-butyl peroxide, t-butyl hydroperoxide.
これら熱流動性改良剤の配合割合は、塩化ビニル系樹
脂100重量部に対して0.1〜５重量部、好ましくは0.2〜
1.0重量部を配合したものである。熱流動性改良剤の配
合量が下限未満では滑性の改良効果が充分でなく、また
上限より多くても配合量増加に比した以上に滑性改良効
果が期待できず、かえって、コストアップにつながるば
かりでなく、プレートアウトや組成物から得られる成形
品からのブリード等の弊害が生起するので好ましくな
い。The mixing ratio of these heat fluidity improvers is 0.1 to 5 parts by weight, preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
It is a mixture of 1.0 parts by weight. If the blending amount of the heat fluidity improver is less than the lower limit, the effect of improving the slipperiness is not sufficient, and even if it is more than the upper limit, the effect of improving the slipperiness cannot be expected more than the increase in the blending amount, rather increasing the cost. It is not preferable because it not only leads to problems, but also causes adverse effects such as plate-out and bleeding from molded articles obtained from the composition.
本発明の樹脂組成物を製造するには、塩化ビニル系樹
脂と該熱流動性改良剤とをリボンブレンダー、ヘンシエ
ルミキサーなど塩化ビニル系樹脂の成形加工品に慣用の
混合手段を利用して行なうことができ、この際、塩化ビ
ニル系樹脂に通常使用する、例えば、充填剤、加工助
剤、着色剤、紫外線吸収剤、熱安定剤、可塑剤、添加
剤、滑剤等を必要に応じて配合することができる。In order to produce the resin composition of the present invention, the vinyl chloride resin and the heat fluidity improver are used by a conventional blending means such as a ribbon blender or a Henschel mixer for a molded product of the vinyl chloride resin. At this time, it is usually used in vinyl chloride resin, for example, fillers, processing aids, colorants, ultraviolet absorbers, heat stabilizers, plasticizers, additives, lubricants and the like if necessary compounded. can do.
本発明の組成物は、特に、熱安定剤として鉛系安定剤
を併用した場合、成形加工性（熱流動性）が一層向上す
るので、鉛系安定剤を添加して使用するのが好ましい。
鉛系安定剤としては三塩基性硫酸鉛、塩基性硫酸鉛、二
塩基性亜リン酸鉛、二塩基性フタル酸鉛、三塩基性マレ
イン酸鉛、ノルマルサリチル酸鉛、シリカゲル共沈けい
酸鉛、塩基性けい酸鉛、鉛白、二塩基性ステアリン酸
鉛、ステアリン酸鉛、ナフテン酸鉛等が挙げられる。該
鉛系安定剤の配合量としては塩化ビニル系樹脂100重量
部に対して0.5〜７重量部、好ましくは１〜５重量部の
範囲である。勿論、鉛系安定剤以外の安定剤の使用も可
能である。Especially when the composition of the present invention is used in combination with a lead stabilizer as a heat stabilizer, the moldability (heat fluidity) is further improved, and therefore it is preferable to add a lead stabilizer for use.
As the lead-based stabilizer, tribasic lead sulfate, basic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic lead maleate, lead normal salicylate, silica gel lead co-precipitate, Examples thereof include basic lead silicate, lead white, dibasic lead stearate, lead stearate, and lead naphthenate. The content of the lead-based stabilizer is 0.5 to 7 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Of course, it is possible to use stabilizers other than lead-based stabilizers.
［実施例］ 次に本発明を実施例にて詳述するが、本発明はその要
旨を超えない限り、以下の実施例に限定されるものでは
ない。[Examples] Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
実施例１、２ 塩化ビニル樹脂（塩化ビニルホモポリマー、重合度80
0）100重量部に、表１に示す熱流動性改良剤0.5重量
部、鉛系安定剤2.5重量部（三塩基性硫酸鉛1.0重量部及
びステアリン酸鉛1.5重量部の割合）及びステアリン酸
モノグリセライド0.5重量部を添加し、ブレンダーにて2
5℃で10分間混合して塩化ビニル系樹脂組成物とした。Examples 1 and 2 Vinyl chloride resin (vinyl chloride homopolymer, degree of polymerization 80
0) 100 parts by weight, 0.5 part by weight of the heat fluidity improver shown in Table 1, 2.5 parts by weight of a lead-based stabilizer (proportion of 1.0 part by weight of tribasic lead sulfate and 1.5 parts by weight of lead stearate), and monoglyceride stearate. Add 0.5 parts by weight and blend in 2
A vinyl chloride resin composition was obtained by mixing at 5 ° C. for 10 minutes.
この組成物について、または組成物をロールミルで18
0℃、７分間混練した後、0.75mmのシートを成形したも
のについて、次の加工物性評価を行った。その結果を表
１に示す。For this composition or on a roll mill 18
After kneading at 0 ° C. for 7 minutes, a 0.75 mm sheet was molded, and the following processed physical properties were evaluated. Table 1 shows the results.
（１） 熱流動性 シートを約2mm角のペレット状に裁断したものを試料
とし、JIS K7210に準拠し、内径1mmφ、長さ10mmLの割
型ダイスを用いて、ダイス温度180℃及び200℃で170kg/
cm2の加重下で押出速度（フローレート）を測定した。(1) Thermal fluidity A sheet cut into pellets of about 2 mm square is used as a sample, and in accordance with JIS K7210, a split die with an inner diameter of 1 mmφ and a length of 10 mmL is used at a die temperature of 180 ° C and 200 ° C. 170 kg /
The extrusion rate (flow rate) was measured under a load of cm 2 .
（２） 熱安定性 シートを190℃のギヤ・オーブン中で30分間加熱した
際の樹脂の着色変化の度合を観察し、次の評価指標にて
評価した。(2) Thermal stability The degree of color change of the resin when the sheet was heated in a gear oven at 190 ° C. for 30 minutes was observed and evaluated according to the following evaluation index.
◎：着色変化なし、○：着色変化小、 △：着色変化中、×：着色変化大、 （３） ゲル化特性 ブレンドした後の樹脂組成物63gをブラベンダー・プ
ラスティコーダー（185℃、45rpm）で混練し、最大トル
クを示すまでの時間を測定しゲル化時間とした。また最
大トルク後減衰して吸束した時のトルクを定常トルクと
して表示した。◎: No color change, ○: Small color change, △: Medium color change, ×: Large color change, (3) Gelation property 63 g of the resin composition after blending was treated with a Brabender Plasticorder (185 ° C, 45 rpm). ) Was kneaded, and the time until the maximum torque was exhibited was measured and used as the gel time. In addition, the torque when the maximum torque is attenuated and then absorbed is shown as the steady torque.
比較例１〜７ 実施例１において、熱流動性改良剤を表１に記した滑
剤に変えて行なったこと以外は同様にして行った。結果
を表１に示す。Comparative Examples 1 to 7 The same procedure as in Example 1 was repeated except that the lubricant shown in Table 1 was used as the heat fluidity improver. The results are shown in Table 1.
本発明の組成物は、表１の結果から明らかなように、
従来の滑剤の使用に比し、ゲル化時間が同等ないし若干
大きくなる傾向にあるが、低温及び高温両者において熱
流動性が極めて良好であり、成形加工性に極めて優れて
いることが判る。 The composition of the present invention, as is clear from the results in Table 1,
Compared with the use of conventional lubricants, the gelation time tends to be the same or slightly longer, but it can be seen that the heat fluidity is extremely good at both low temperature and high temperature, and the moldability is extremely excellent.
実施例４、５、比較例８、９ 塩化ビニル樹脂（ホモポリマー、平均重合度800）100
重量部に表２に示す熱流動性改良剤0.5重量部、錫系安
定剤（ジブチル錫ジマレート）2.5重量部及びステアリ
ン酸モノグリセライド0.5重量部を添加し、ブレンダー
にて80℃で10分間混合した。この混合物をロールミルで
180℃、７分間混練した後、0.75mmのシートに成形し
た。このシートの約2mm角に裁断したものを試料として1
80℃、200℃で250kg/cm2の加重下の熱流動性を測定し、
またシートの熱安定性試験を行ない表２に示した。Examples 4, 5 and Comparative Examples 8, 9 Vinyl chloride resin (homopolymer, average degree of polymerization 800) 100
0.5 part by weight of the heat fluidity improver shown in Table 2, 2.5 parts by weight of tin stabilizer (dibutyltin dimaleate) and 0.5 part by weight of stearic acid monoglyceride were added to parts by weight, and mixed at 80 ° C. for 10 minutes with a blender. This mixture on a roll mill
After kneading at 180 ° C. for 7 minutes, it was formed into a 0.75 mm sheet. This sheet was cut into about 2 mm square and used as a sample 1
Measure the heat fluidity under load of 250 kg / cm 2 at 80 ℃ and 200 ℃,
Further, the heat stability test of the sheet was conducted and shown in Table 2.
また、熱流動性改良剤と滑剤を含まない組成物及び滑
剤としてステアリン酸を含む組成物からシート成形し同
様のテストを行った。その結果を表２に併記した。Further, a sheet was molded from a composition containing no heat fluidity improver and a lubricant and a composition containing stearic acid as a lubricant, and the same test was conducted. The results are also shown in Table 2.
表２から明らかなように、錫系安定剤を併用した本発
明の組成物は、錫系安定剤併用のもの（実施例１、２）
より熱流動性が劣ってはいるけれども、錫系安定剤を併
用したもの同士を比較すると、本発明の組成物に使用す
る熱流動性改良剤は、従来の滑剤よりも加工性に優れた
物性を与えている。 As is clear from Table 2, the composition of the present invention in which the tin-based stabilizer was used in combination, was used in combination with the tin-based stabilizer (Examples 1 and 2).
Although the thermal fluidity is inferior, the thermal fluidity improver used in the composition of the present invention has physical properties superior in processability to conventional lubricants when compared with those in which tin stabilizers are used in combination. Is giving.
［発明の効果］ 本発明の組成物に用いる熱流動性改良剤は、塩化ビニ
ル系樹脂に配合したとき、従来の滑剤を配合したものよ
り、滑性が良好であり、本発明の塩化ビニル系樹脂組成
物は、成形加工性（熱流動性）及び熱安定性に優れてい
る。該組成物は、カレンダー加工、押出加工、射出成
形、中空成形、真空成形等に好適に使用される。[Effects of the Invention] The thermal fluidity improver used in the composition of the present invention has better lubricity when blended with a vinyl chloride resin than a conventional blend with a lubricant, The resin composition is excellent in molding processability (heat fluidity) and heat stability. The composition is suitably used for calendering, extrusion, injection molding, blow molding, vacuum molding and the like.
Claims (1)
熱付加物 から選ばれた少なくとも一種の化合物0.1〜５重量部を
配合してなる塩化ビニル系樹脂組成物1. A heat-addition product of (a) α-olein having 20 or more carbon atoms and (b) α-olefin having 20 or more carbon atoms and a fatty acid, relative to 100 parts by weight of a vinyl chloride resin. Vinyl chloride resin composition containing 0.1 to 5 parts by weight of at least one compound
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62165966A JP2527752B2 (en) | 1987-07-02 | 1987-07-02 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62165966A JP2527752B2 (en) | 1987-07-02 | 1987-07-02 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6411151A JPS6411151A (en) | 1989-01-13 |
| JP2527752B2 true JP2527752B2 (en) | 1996-08-28 |
Family
ID=15822393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62165966A Expired - Lifetime JP2527752B2 (en) | 1987-07-02 | 1987-07-02 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2527752B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3003797C2 (en) * | 1980-02-02 | 1983-05-11 | Akzo Gmbh, 5600 Wuppertal | Deformation of plastics containing lubricants |
| DE3223694A1 (en) * | 1981-09-17 | 1983-03-24 | Akzo Gmbh, 5600 Wuppertal | COPOLYMERS FROM (ALPHA) - (BETA) -UNSATURED DICARBONIC ACID ESTERS PROCESS FOR THE PRODUCTION AND USE THEREOF |
-
1987
- 1987-07-02 JP JP62165966A patent/JP2527752B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6411151A (en) | 1989-01-13 |
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