JPH051195A - Flexible vinyl chloride-based resin composition for extrusion molding - Google Patents
Flexible vinyl chloride-based resin composition for extrusion moldingInfo
- Publication number
- JPH051195A JPH051195A JP3183153A JP18315391A JPH051195A JP H051195 A JPH051195 A JP H051195A JP 3183153 A JP3183153 A JP 3183153A JP 18315391 A JP18315391 A JP 18315391A JP H051195 A JPH051195 A JP H051195A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- weight
- parts
- resin composition
- pts
- 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.)
- Pending
Links
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、明色系のカラーに着色
した成形体を押出成形法で成形する分野に於いて、環境
保全の観点からその使用が抑制される原料を一切使用せ
ずに成形体の耐候性と成形加工時熱安定性とが共に優れ
た押出成形用軟質塩化ビニル系樹脂組成物を提供するも
のである。更に詳しくは、環境保全の観点からその使用
が抑制される原料、例えば、鉛、バリウム、カドミウム
等を一切使用していない押出成形用軟質塩化ビニル系樹
脂組成物であって、その成形体を自動車用外装材、屋外
用建築材などとして明色系のカラーに着色して使用する
際の耐候性に関する二つの特性、すなわち、成形体の
ポリマー分子の主として紫外線や熱などの外的環境によ
る実質的な劣化が起こらずいつまで長もちするか（以
下、長期耐候性と称す）、この実質的な劣化が発生し
始める以前の極く初期の曝露時期（数カ月）に一時的に
淡黄色に変色する度合（以下、初期耐候帯色性と称
す）、がいずれも良好であり、また押出成形に於ける成
形加工時熱安定性が良好であり、これらの特性が共に優
れた屋外用途に好適な樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not use any raw materials whose use is suppressed from the viewpoint of environmental protection in the field of molding a molded product colored in a light color by an extrusion molding method. In addition, the present invention provides a soft vinyl chloride resin composition for extrusion molding, which is excellent in both weather resistance and heat stability during molding. More specifically, it is a soft vinyl chloride resin composition for extrusion molding that does not use any raw materials whose use is suppressed from the viewpoint of environmental protection, for example, lead, barium, cadmium, etc. Two properties related to weather resistance when used by coloring with light color as exterior material for exterior, building material for outdoor use, that is, the polymer molecule of the molded body is mainly due to external environment such as ultraviolet ray and heat. How long does it occur without any significant deterioration (hereinafter referred to as long-term weathering resistance), or the degree of temporary discoloration to a pale yellow color at the very early exposure time (a few months) before this substantial deterioration begins ( (Hereinafter, referred to as initial weathering color resistance)) is good, and also has good thermal stability at the time of molding processing in extrusion molding, and a resin composition suitable for outdoor use that has both of these characteristics. Concern It is intended.
【０００２】[0002]
【従来の技術】塩化ビニル系樹脂は安価であり、可塑剤
などを添加することにより容易に軟質化させることがで
きるため、自動車部品分野、建材分野などで多量に使用
されている。自動車用外装材や屋外用建築材は、長期間
に亙り、過酷な環境に曝されて使用されるため耐候性が
強く要求され、これに応えた軟質塩化ビニル系樹脂組成
物が開発されて屋外用途に広く使用されてきている。こ
れらの組成物は、熱安定剤としてＢａ−Ｚｎ系熱安定剤
を、紫外線吸収剤としてベンゾフェノン系化合物やシア
ノアクリレート化合物を使用することを骨子とする技術
に基づくものである。従来、上記のような用途に耐候性
良好な成形体を押出成形法で成形して使用する場合は、
熱安定剤としてＢａ−Ｚｎ系熱安定剤が用いられＣａ−
Ｚｎ系熱安定剤は用いられなかった。その理由は、Ｃａ
−Ｚｎ系熱安定剤は熱安定化の性能が弱く、押出成形時
に「焼け」などの問題を生ずるからであった。しかし、
最近は、環境保全の観点からＢａ−Ｚｎ系熱安定剤の使
用を抑制する動きがあり、これに対応できる技術が必要
となってきた。従来はこれらの用途に於ける成形体は黒
色に着色したものであり、この場合は屋外曝露テストや
サンシャインウェザロメーターテストで評価される長期
耐候性の改良のみが技術的課題であり、紫外線照射など
による劣化が発生し始める以前の曝露期間の極く初期に
一時的に淡黄色に変色する現象の程度、すなわち初期耐
候帯色性は全く問題にされなかった。しかし、最近は屋
外用途で明色系のカラーに着色した材料を使用する要求
が高まり、これまで見過ごされてきた初期耐候帯色性を
長期耐候性と同様に重要視する必要が出てきた。2. Description of the Related Art Vinyl chloride resins are inexpensive and can be easily softened by adding a plasticizer or the like, and are therefore used in large quantities in the fields of automobile parts and building materials. Automotive exterior materials and outdoor building materials are strongly required to have weather resistance because they are exposed to harsh environments for a long period of time, and a soft vinyl chloride resin composition that meets these requirements has been developed. It has been widely used for purposes. These compositions are based on a technique that uses Ba—Zn heat stabilizers as heat stabilizers and benzophenone compounds and cyanoacrylate compounds as ultraviolet absorbers. Conventionally, when using a molded article having good weather resistance for the above-mentioned applications by extrusion molding,
As the heat stabilizer, a Ba-Zn heat stabilizer is used and Ca-
No Zn-based heat stabilizer was used. The reason is Ca
This is because the Zn-based heat stabilizer has a weak heat stabilizing property and causes problems such as "burning" during extrusion molding. But,
Recently, from the viewpoint of environmental protection, there has been a movement to suppress the use of Ba—Zn heat stabilizers, and a technique capable of coping with this has been required. Conventionally, molded products for these applications are colored in black, and in this case, the only technical issue is to improve the long-term weather resistance evaluated by the outdoor exposure test and the sunshine weatherometer test. The degree of the phenomenon of temporary discoloration to pale yellow, that is, the initial weathering tint, was not considered at all very early in the exposure period before the deterioration due to the occurrence of deterioration. However, recently, there has been an increasing demand for using a material colored in a light-colored color for outdoor use, and it has become necessary to attach importance to the overlooked initial weathering tint as well as long-term weathering.
【０００３】また、明色系のカラーに着色した軟質塩化
ビニル系樹脂組成物を押出成形法で成形する際の成形加
工時熱安定性が低いために成形体が熱による変色を受け
る現象があるが、これも黒色の用途に於いては問題にさ
れなかった。In addition, when a soft vinyl chloride resin composition colored in a light color is molded by an extrusion molding method, it has a low thermal stability during the molding process, so that the molded article may be discolored by heat. However, this too was not a problem in black applications.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、明色系のカ
ラーに着色された屋外用途の成形体の材料として、押出
成形に供される従来の技術による耐候性軟質塩化ビニル
系樹脂組成物が、環境保全の観点から抑制される原料を
使用しており、且つ成形体の初期耐候帯色性及び長期耐
候性といった耐候性に関する特性と押出成形を行なう際
の成形加工時熱安定性が不充分であるという問題を解決
するものである。DISCLOSURE OF THE INVENTION The present invention provides a weather-resistant soft vinyl chloride resin composition according to the prior art which is used for extrusion molding as a material for a molded article for outdoor use which is colored in a light color. However, it uses raw materials that are suppressed from the viewpoint of environmental protection, and the characteristics related to weather resistance such as initial weathering coloration and long-term weather resistance of the molded product and the thermal stability during molding during extrusion molding are unsatisfactory. It solves the problem of being sufficient.
【０００５】[0005]
【課題を解決するための手段】本発明は、塩化ビニル系
樹脂１００重量部に対して、（ａ）ベンゾフェノン系及
び／又はシアノアクリレート系紫外線吸収剤を２．５〜
６．０重量部、（ｂ）ハイドロタルサイト類化合物の１
種以上を０．２〜５．０重量部、（ｃ）Ｃａ−Ｚｎ系熱
安定剤の１種以上を１．０〜４．５重量部、及び（ｄ）
可塑剤を２５〜２００重量部、を配合して得られる、環
境保全の観点からその使用が抑制される原料を一切使用
していない軟質塩化ビニル系樹脂組成物を屋外用途の明
色系のカラーに着色した成形体の材料として使用すれば
成形体の長期耐候性及び初期耐候帯色性といった耐候性
に関する特性が良好で、且つ押出成形法で成形する際の
成形加工時熱安定性が良好であることを見出したことに
よるものである。上記の組成物に、更にメタクリル酸メ
チルを主成分とする共重合体であって、濃度０．４ｇ／
１００mlのトルエン溶液の３０℃で測定した比粘度が
２．５以上のメタクリル酸メチル系共重合体を塩化ビニ
ル系樹脂１００重量部に対して１〜３０重量部配合する
ことによりこれらの特性を一段と高めることができ、更
に可塑剤としてフタル酸系可塑剤、トリメリット酸系可
塑剤あるいはアジピン酸系可塑剤を使用したときこれら
の特性が特に優れていることを見出したことによるもの
である。According to the present invention, (a) a benzophenone-based and / or cyanoacrylate-based ultraviolet absorber is added in an amount of 2.5 to 100 parts by weight of a vinyl chloride resin.
6.0 parts by weight, (b) 1 of hydrotalcite compound
0.2 to 5.0 parts by weight of one or more kinds, (c) 1.0 to 4.5 parts by weight of one or more kinds of Ca-Zn heat stabilizers, and (d)
A soft vinyl chloride resin composition obtained by blending 25 to 200 parts by weight of a plasticizer, which does not use any raw material whose use is suppressed from the viewpoint of environmental protection, is a bright color for outdoor use. When used as a material for a colored molded article, the molded article has good weatherability characteristics such as long-term weatherability and initial weathering tint resistance, and good thermal stability during molding during extrusion molding. This is due to the discovery of something. In addition to the above composition, a copolymer containing methyl methacrylate as a main component and having a concentration of 0.4 g /
These characteristics are further improved by blending 1 to 30 parts by weight of a methyl methacrylate copolymer having a specific viscosity of 2.5 or more in 100 ml of a toluene solution measured at 30 ° C. with 100 parts by weight of vinyl chloride resin. This is because it has been found that these properties are particularly excellent when a phthalic acid plasticizer, a trimellitic acid plasticizer or an adipic acid plasticizer is used as the plasticizer.
【０００６】本発明で使用する塩化ビニル系樹脂とは、
塩化ビニルモノマーを単独重合させた塩化ビニル樹脂、
８５重量％以上の塩化ビニルを含有する塩化ビニル系共
重合樹脂、及びテトラヒドロフランに不溶な塩化ビニル
ゲル分２〜６５重量％を含む部分架橋塩化ビニル系樹脂
をいい、これらを単独もしくは２種以上混合して使用す
る。塩化ビニル系共重合樹脂としては、たとえば塩化ビ
ニル−酢酸ビニル共重合樹脂などの塩化ビニルとアルキ
ルビニルエステルとの共重合樹脂、塩化ビニル−エチレ
ン共重合樹脂、塩化ビニル−プロピレン共重合樹脂など
の塩化ビニルとオレフィン類との共重合樹脂、塩化ビニ
ルとアクリル酸又はそのエステルとの共重合樹脂、塩化
ビニルとメタクリル酸又はそのエステルとの共重合樹
脂、塩化ビニルとアルキルビニルエーテルとの共重合樹
脂などが使用できる。また、部分架橋塩化ビニル系樹脂
としては、架橋剤としてジアリルフタレートなどのジア
リル化合物、ポリエチレングリコール（メタ）アクリレ
ートなどのジ（メタ）アクリレート化合物などを使用し
て得られる部分架橋塩化ビニル系樹脂が使用できる。塩
化ビニル系樹脂の平均重合度（ＪＩＳ Ｋ ６７２１）
は４００〜４５００であることが好ましい。平均重合度
が４００未満では耐候性が低くなり、また平均重合度が
４５００を越えると押出成形時の溶融粘度が高くなって
成形加工時熱安定性が悪くなるので好ましくない。The vinyl chloride resin used in the present invention is
Vinyl chloride resin homopolymerized with vinyl chloride monomer,
A vinyl chloride-based copolymer resin containing 85% by weight or more of vinyl chloride and a partially crosslinked vinyl chloride-based resin containing 2 to 65% by weight of vinyl chloride gel insoluble in tetrahydrofuran. These are used alone or in combination of two or more. To use. Examples of the vinyl chloride-based copolymer resin include vinyl chloride-vinyl acetate copolymer resin and other vinyl chloride-alkyl vinyl ester copolymer resins, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin and other chloride resins. Copolymer resin of vinyl and olefins, copolymer resin of vinyl chloride and acrylic acid or its ester, copolymer resin of vinyl chloride and methacrylic acid or its ester, copolymer resin of vinyl chloride and alkyl vinyl ether, etc. Can be used. As the partially crosslinked vinyl chloride resin, a partially crosslinked vinyl chloride resin obtained by using a diallyl compound such as diallyl phthalate or a di (meth) acrylate compound such as polyethylene glycol (meth) acrylate as a crosslinking agent is used. it can. Average degree of polymerization of vinyl chloride resin (JIS K 6721)
Is preferably 400 to 4500. If the average degree of polymerization is less than 400, the weather resistance will be low, and if the average degree of polymerization is more than 4500, the melt viscosity during extrusion will be high and the thermal stability during molding will be poor, such being undesirable.
【０００７】本発明で使用するベンゾフェノン系紫外線
吸収剤又はシアノアクリレート系紫外線吸収剤は、それ
ぞれ単独で使用してもよく、両者を併用してもよい。紫
外線吸収剤の使用量は、塩化ビニル系樹脂１００重量部
に対して２．５〜６．０重量部の範囲である。使用量が
２．５重量部未満では紫外線吸収能力が不充分であり、
このため屋外曝露テストやサンシャインウェザロメータ
ーテストを行なうと紫外線による劣化が著しく進行す
る。紫外線による劣化は、ハイドロタルサイト類化合物
を併用すると一層著しく進行するので紫外線吸収剤を増
量する必要がある。すなわち、ハイドロタルサイト類化
合物を併用しない従来の技術に於いては、ベンゾフェノ
ン系紫外線吸収剤やシアノアクリレート系紫外線吸収剤
は塩化ビニル系樹脂１００重量部に対して０．２〜２．
０重量部の使用量で充分な効果を発揮することができる
が、本発明のハイドロタルサイト類化合物を併用する系
では、ベンゾフェノン系紫外線吸収剤やシアノアクリレ
ート系紫外線吸収剤の使用量は塩化ビニル系樹脂１００
重量部に対して２．５重量部以上にする必要がある。逆
に６．０重量部を越えて使用しても、紫外線吸収能力は
飽和して増量の効果は現れない。The benzophenone type ultraviolet absorber or the cyanoacrylate type ultraviolet absorber used in the present invention may be used alone or in combination. The amount of the ultraviolet absorber used is in the range of 2.5 to 6.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If the amount used is less than 2.5 parts by weight, the ultraviolet absorption capacity is insufficient,
For this reason, when exposed to an outdoor exposure test or a sunshine weatherometer test, deterioration due to ultraviolet rays significantly progresses. Deterioration due to ultraviolet light proceeds more remarkably when a hydrotalcite compound is used in combination, so it is necessary to increase the amount of the ultraviolet light absorber. That is, in the conventional technique in which the hydrotalcite compound is not used in combination, the benzophenone-based UV absorber or the cyanoacrylate-based UV absorber is added in an amount of 0.2 to 2.
A sufficient effect can be exhibited with the use amount of 0 parts by weight, but in the system in which the hydrotalcite compound of the present invention is used in combination, the use amount of the benzophenone ultraviolet absorber or the cyanoacrylate ultraviolet absorber is vinyl chloride. Resin 100
It should be 2.5 parts by weight or more with respect to parts by weight. On the contrary, even if it is used in an amount exceeding 6.0 parts by weight, the ultraviolet absorbing ability is saturated and the effect of increasing the amount does not appear.
【０００８】本発明で使用するハイドロタルサイト類化
合物は、一般式
Mg1-x Alx (OH)2(CO3)X/2 ・mH2O
（０＜ｘ≦０．５、ｍは正の数）
で表示される化合物であり、これら化合物の１種以上を
使用する。該化合物は、後述するＣａ−Ｚｎ系熱安定剤
と組み合わせて使用することにより、塩化ビニル系樹脂
の熱安定剤として非常に優れた効果を発揮する。塩化ビ
ニル系樹脂の熱安定剤としてはこれらの化合物のほかに
も種々のものがあるが、ハイドロタルサイト類化合物と
Ｃａ−Ｚｎ系熱安定剤とを組み合わせて使用する本発明
の熱安定剤系以外のものは使用すべきでない。すなわ
ち、錫系熱安定剤は、塩化ビニル系樹脂の熱安定性の改
良効果は優れているが、耐候性を低下させる。また、鉛
系熱安定剤、Ｂａ−Ｚｎ系熱安定剤、Ｃｄ−Ｂａ系熱安
定剤などは、環境保全の観点からその使用は抑制され
る。また、ハイドロタルサイト類化合物を併用しないで
Ｃａ−Ｚｎ系熱安定剤だけを単独で使用すると、熱安定
性の改良効果が不充分である。ハイドロタルサイト類化
合物の使用量は、塩化ビニル系樹脂１００重量部に対し
て０．２〜５．０重量部である。使用量が０．２重量部
未満では得られる軟質塩化ビニル系樹脂組成物の熱安定
性が不充分であり、使用量が５．０重量部を越えると耐
候性が悪化する。The hydrotalcite compound used in the present invention has a general formula Mg 1-x Al x (OH) 2 (CO 3 ) X / 2 · mH 2 O (0 <x ≦ 0.5, m is a positive value). The number of) is a compound and one or more of these compounds are used. When used in combination with the below-described Ca-Zn heat stabilizer, the compound exhibits a very excellent effect as a heat stabilizer for vinyl chloride resin. There are various other heat stabilizers for vinyl chloride resins in addition to these compounds, but the heat stabilizer system of the present invention comprising a combination of a hydrotalcite compound and a Ca—Zn heat stabilizer is used. Other than that should not be used. That is, the tin-based heat stabilizer has an excellent effect of improving the thermal stability of the vinyl chloride-based resin, but reduces the weather resistance. Further, the use of lead-based heat stabilizers, Ba-Zn-based heat stabilizers, Cd-Ba-based heat stabilizers, etc. is suppressed from the viewpoint of environmental protection. Further, if only the Ca-Zn heat stabilizer is used alone without using the hydrotalcite compound in combination, the effect of improving the heat stability is insufficient. The amount of the hydrotalcite compound used is 0.2 to 5.0 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount used is less than 0.2 parts by weight, the thermal stability of the obtained soft vinyl chloride resin composition will be insufficient, and if the amount used exceeds 5.0 parts by weight, the weather resistance will deteriorate.
【０００９】本発明で使用するＣａ−Ｚｎ系熱安定剤の
使用量は、塩化ビニル系樹脂１００重量部に対して１．
０〜４．５重量部である。使用量が１．０重量部未満で
は得られる軟質塩化ビニル系樹脂組成物の熱安定性が不
充分であり、使用量が４．５重量部を越えるとＣａ−Ｚ
ｎ系熱安定剤が成形体の表面にブルームする問題が生じ
る。The amount of the Ca-Zn heat stabilizer used in the present invention is 1 to 100 parts by weight of the vinyl chloride resin.
0 to 4.5 parts by weight. If the amount used is less than 1.0 part by weight, the thermal stability of the resulting soft vinyl chloride resin composition is insufficient, and if the amount used exceeds 4.5 parts by weight, Ca-Z
There is a problem that the n-type heat stabilizer blooms on the surface of the molded body.
【００１０】本発明で使用する可塑剤は、塩化ビニル系
樹脂に通常使用される可塑剤であればよい。すなわち、
フタル酸系、トリメリット酸系、アジピン酸系、ポリエ
ステル系などの可塑剤であるが、これらのうち、フタル
酸系、トリメリット酸系、アジピン酸系の可塑剤が好ま
しく、フタル酸系、トリメリット酸系の可塑剤が最も好
ましい。これらは単独で使用してもよく２種以上を組み
合わせて使用してもよい。The plasticizer used in the present invention may be any plasticizer usually used for vinyl chloride resins. That is,
Among the plasticizers such as phthalic acid-based, trimellitic acid-based, adipic acid-based, polyester-based, among these, phthalic acid-based, trimellitic acid-based and adipic acid-based plasticizers are preferable, and phthalic acid-based Most preferred are melitic acid-based plasticizers. These may be used alone or in combination of two or more.
【００１１】本発明の軟質塩化ビニル系樹脂組成物は、
メタクリル酸メチルを主成分とする共重合体を配合する
ことが好ましい。該共重合体の分子量は、濃度０．４ｇ
／１００mlのトルエン溶液の３０℃で測定した比粘度で
表示する場合、その値が２．５以上であることが好まし
い。比粘度が２．５未満では組成物の混練効果が不充分
となり、また押出成形性が良くないので好ましくない。
該共重合体の使用量は、塩化ビニル系樹脂１００重量部
に対して１〜３０重量部が好ましい。使用量が１重量部
未満では組成物の混練効果が不充分であり、使用量が３
０重量部を越えると組成物の溶融粘度が高くなり過ぎ押
出成形を行なう際の成形加工時熱安定性が低下するので
好ましくない。The soft vinyl chloride resin composition of the present invention comprises
It is preferable to add a copolymer containing methyl methacrylate as a main component. The molecular weight of the copolymer is 0.4 g in concentration.
When expressed as the specific viscosity of a / 100 ml toluene solution measured at 30 ° C., the value is preferably 2.5 or more. If the specific viscosity is less than 2.5, the kneading effect of the composition will be insufficient and the extrusion moldability will be poor, such being undesirable.
The amount of the copolymer used is preferably 1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount used is less than 1 part by weight, the kneading effect of the composition is insufficient and the amount used is 3
If it exceeds 0 parts by weight, the melt viscosity of the composition becomes too high and the thermal stability at the time of molding during extrusion molding is deteriorated, which is not preferable.
【００１２】[0012]
【実施例】以下、本発明を実施例に基づき更に詳しく説
明するが、本発明はこれらに限定されるものではない。
実施例１〜８、比較例１〜６
表１、表２及び表３に示す重量部数の塩化ビニル樹脂、
紫外線吸収剤、ハイドロタルサイト類化合物、熱安定
剤、可塑剤、メタクリル酸メチル系共重合体をリボンブ
レンダーにより混合しドライアップさせた。得られたパ
ウダー状の組成物を１７５℃で７分間ロール混練し、厚
さ約２mmの素練りシートを得た。これを更に１８０℃で
熱プレスし厚さ１mmのシートを作製した。このシートを
使用して耐候性を測定した。一方、前記素練りシートを
約２mm四方に切断してペレット状にし、これを使用して
ブラベンダープラストグラフにより成形加工時熱安定性
を評価した。評価結果を表１、表２、表３及び表４に示
す。尚、比較例６は、本発明者らが開発し特許出願中の
ものである。表１、表２、表３及び表４から明らかなと
おり、本発明の組成物は、環境保全の観点から抑制され
る原料を一切使用していないが、初期耐候帯色性及び長
期耐候性並びに成形加工時熱安定性が共に優れたもので
あった。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. Examples 1 to 8 and Comparative Examples 1 to 6 Vinyl chloride resins having the parts by weight shown in Table 1, Table 2 and Table 3,
An ultraviolet absorber, a hydrotalcite compound, a heat stabilizer, a plasticizer, and a methyl methacrylate copolymer were mixed with a ribbon blender and dried up. The obtained powdery composition was roll-kneaded at 175 ° C. for 7 minutes to obtain a masticated sheet having a thickness of about 2 mm. This was further hot pressed at 180 ° C. to prepare a sheet having a thickness of 1 mm. The weather resistance was measured using this sheet. On the other hand, the masticated sheet was cut into a pellet shape by cutting it into a square of about 2 mm, and this was used to evaluate the thermal stability at the time of molding by Brabender Plastograph. The evaluation results are shown in Table 1, Table 2, Table 3 and Table 4. Comparative Example 6 is a patent developed by the present inventors and pending a patent. As is clear from Table 1, Table 2, Table 3 and Table 4, the composition of the present invention does not use any raw materials suppressed from the viewpoint of environmental protection, but the initial weather resistance and long-term weather resistance and The heat stability during molding was excellent.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】[0015]
【表３】 [Table 3]
【００１６】[0016]
【表４】 [Table 4]
【００１７】注１：２−ヒドロキシ−４−オクトキシベ
ンゾフェノン
注２：エチル−２−シアノ−３，３−ジフェニルアクリ
レート
注３：ハイドロタルサイト類化合物の商品名（協和化学
工業株式会社）
注４：ジイソノニルフタレート
注５：ジイソノニルアジペート
注６：トリ−２−エチルヘキシルトリメリテート
＊１：サンシャインウェザロメーターを用い８３℃で３
００hrs 照射後の変色の度合を下式によるHunterの色差
法で表示する。ΔＥが小さいほど変色の度合が小さいこ
とを示す。
ΔＥ＝〔（Δａ）2 ＋（Δｂ）2 ＋（ΔＬ）2〕1/2
＊２：サンシャインウェザロメーターを用い８３℃で３
０００hrs 照射後の変色の度合を下式によるHunterの色
差法で表示する。ΔＥが小さいほど変色の度合が小さい
ことを示す。
ΔＥ＝〔（Δａ）2 ＋（Δｂ）2 ＋（ΔＬ）2〕1/2
＊３：ブラベンダープラストグラフによるトルクの上昇
開始時までの時間（分）
チャンバー温度：２１０℃
ローター回転数：１００rpm
ペレット充填量：６０ｇ* 1: 2-Hydroxy-4-octoxybenzophenone * 2: Ethyl-2-cyano-3,3-diphenyl acrylate * 3: Trade name of hydrotalcite compounds (Kyowa Chemical Industry Co., Ltd.) * 4 : Diisononyl phthalate * 5: Diisononyl adipate * 6: Tri-2-ethylhexyl trimellitate * 1: 3 at 83 ° C using a sunshine weatherometer
The degree of discoloration after irradiation for 00 hrs is displayed by the Hunter color difference method according to the following formula. The smaller ΔE indicates the smaller degree of discoloration. ΔE = [(Δa) 2 + (Δb) 2 + (ΔL) 2 ] 1/2 * 2: 3 at 83 ° C. using a sunshine weatherometer
The degree of discoloration after irradiation for 000 hrs is displayed by the Hunter color difference method according to the following formula. The smaller ΔE indicates the smaller degree of discoloration. ΔE = [(Δa) 2 + (Δb) 2 + (ΔL) 2 ] 1/2 * 3: Time (minutes) until the start of torque increase according to Brabender Plastograph Chamber temperature: 210 ° C Rotor speed: 100 rpm Pellet filling amount: 60g
【００１８】[0018]
【発明の効果】以上に述べたとおり、本発明の軟質塩化
ビニル系樹脂組成物は、環境保全の観点からその使用が
抑制される原料を一切使用せず、且つ初期耐候帯色性及
び長期耐候性並びに押出成形法で成形する際の熱安定性
が共に優れている。Industrial Applicability As described above, the soft vinyl chloride resin composition of the present invention does not use any raw materials whose use is suppressed from the viewpoint of environmental protection, and has an initial weather resistance and long-term weather resistance. And the thermal stability during extrusion molding are excellent.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 //(Ｃ０８Ｌ 27/06 33:12） 7242−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // (C08L 27/06 33:12) 7242-4J
Claims (3)
て、下記（ａ）〜（ｄ）を配合してなる押出成形用軟質
塩化ビニル系樹脂組成物； （ａ）ベンゾフェノン系及び／又はシアノアクリレート
系紫外線吸収剤を２．５〜６．０重量部、 （ｂ）ハイドロタルサイト類化合物の１種以上を０．２
〜５．０重量部、 （ｃ）Ｃａ−Ｚｎ系熱安定剤の１種以上を１．０〜４．
５重量部、及び （ｄ）可塑剤を２５〜２００重量部。1. A soft vinyl chloride resin composition for extrusion molding, comprising 100 parts by weight of a vinyl chloride resin and (a) to (d) below; (a) benzophenone and / or cyanoacrylate. 2.5 to 6.0 parts by weight of a UV absorber, and (b) 0.2 of one or more hydrotalcite compounds.
To 5.0 parts by weight, and (c) one or more Ca-Zn heat stabilizers in an amount of 1.0 to 4.
5 parts by weight, and 25 to 200 parts by weight of (d) plasticizer.
合体であって、該共重合体０．４ｇを含む１００mlのト
ルエン溶液の３０℃で測定した比粘度が２．５以上のメ
タクリル酸メチル系共重合体を１〜３０重量部配合して
なる請求項１記載の樹脂組成物。2. A copolymer containing methyl methacrylate as a main component, wherein 100 ml of a toluene solution containing 0.4 g of the copolymer has a specific viscosity measured at 30 ° C. of 2.5 or more. The resin composition according to claim 1, which comprises 1 to 30 parts by weight of a system copolymer.
系、及びアジピン酸系の可塑剤から選択される１種以上
である請求項１又は２記載の樹脂組成物。3. The resin composition according to claim 1, wherein the plasticizer is at least one selected from phthalic acid-based, trimellitic acid-based, and adipic acid-based plasticizers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3183153A JPH051195A (en) | 1991-06-26 | 1991-06-26 | Flexible vinyl chloride-based resin composition for extrusion molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3183153A JPH051195A (en) | 1991-06-26 | 1991-06-26 | Flexible vinyl chloride-based resin composition for extrusion molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH051195A true JPH051195A (en) | 1993-01-08 |
Family
ID=16130727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3183153A Pending JPH051195A (en) | 1991-06-26 | 1991-06-26 | Flexible vinyl chloride-based resin composition for extrusion molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH051195A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322206A (en) * | 1993-05-14 | 1994-11-22 | Sumika Color Kk | Vinyl chloride resin composition |
| US6162540A (en) * | 1999-03-23 | 2000-12-19 | Sumitomo Wiring Systems, Ltd. | Insulated wire |
| US8084721B2 (en) | 2007-10-26 | 2011-12-27 | Calsonic Kansei Corporation | Electrical heating apparatus, method of manufacturing heat generator unit and pressing jig for use in manufacturing thereof |
-
1991
- 1991-06-26 JP JP3183153A patent/JPH051195A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322206A (en) * | 1993-05-14 | 1994-11-22 | Sumika Color Kk | Vinyl chloride resin composition |
| US6162540A (en) * | 1999-03-23 | 2000-12-19 | Sumitomo Wiring Systems, Ltd. | Insulated wire |
| US8084721B2 (en) | 2007-10-26 | 2011-12-27 | Calsonic Kansei Corporation | Electrical heating apparatus, method of manufacturing heat generator unit and pressing jig for use in manufacturing thereof |
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