JPS61179250A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has improved processability and gives moldings having improved hardness, strength, heat distortion temp., etc., by blending a tetracarboxylic tetraester contg. at least two (in total) of cycloalkyl and/or aryl groups with a vinyl chloride resin. CONSTITUTION:1-30pts.wt. tetraester of a 3,4-dicarboxy-1,2,3,4- tetrahydronaphthyl-1-succinic dianhydride contg. at least two groups (in total) of cycloalkyl and aryl groups and having the formula (wherein R<1>-R<4> are each cycloalkyl, aryl, 1-8C alkyl) is blended with 100pts.wt. vinyl chloride resin (e.g. vinyl chloride homopolymer or vinyl chloride/ethylene copolymer) to obtain the desired vinyl chloride resin compsn. An example of the compd. of the formula is tetra(cyclohexyl) ester of 3,4-dicarboxy-1,2,3,4- tetrahydronaphthyl-1-succinic dianhydride.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、加工性に優れ、かつ高い硬度、強度を有する
硬質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 hard vinyl chloride resin composition that has excellent processability and high hardness and strength.

［従来の技術］ 塩化ビニル系樹脂組成物は、その優れた物理的・化学的
特性により、現在最も広く利用されている樹脂の一つで
ある。しかしながら、塩化ビニル系樹脂組成物には熱分
解温度が低く、加工時の熱劣化が著しいという大きな欠
点がある。特に硬質分野においては、近年、性能向上の
ために、より重合度の高い樹脂が使用される方向にあっ
て、安定剤、滑剤だけでは加士時の熱劣化を防ぐことが
困難となってきており、大幅に加工性を改善し得る添加
剤の開発が望まれている。[Prior Art] Vinyl chloride resin compositions are currently one of the most widely used resins due to their excellent physical and chemical properties. However, vinyl chloride resin compositions have a major drawback in that they have a low thermal decomposition temperature and are subject to significant thermal deterioration during processing. Particularly in the hard field, in recent years there has been a trend toward using resins with higher polymerization degrees to improve performance, and it has become difficult to prevent thermal deterioration during heating with stabilizers and lubricants alone. Therefore, it is desired to develop additives that can significantly improve processability.

一方、融点が高く、かつ極性の強い化合物を少量添加し
た場合、加工時には通常の可塑剤と同等の加工性の改善
がなされるとともに、得られた成形物の硬度、強度が向
上し得ることが知られており、その様な化合物は一般に
「反可塑剤」と呼ばれている。On the other hand, when a small amount of a compound with a high melting point and strong polarity is added, the processability can be improved to the same extent as a normal plasticizer during processing, and the hardness and strength of the resulting molded product can be improved. are known, and such compounds are commonly referred to as "antiplasticizers."

［発明が解決しようとする問題点］ そこで、本発明者らは上記の問題を解決する添加削とし
て反可塑剤に着目し、従来の二塩基酸エステル等より優
れた新規な反可塑剤を開発すべく鋭意検討をかさねた結
果、特定の構造を有するテトラカルボン酸テトラエステ
ルが良好な加工性改善効果および反可塑化効果を示すこ
とを見出し、本発明を完成するに至った。[Problems to be Solved by the Invention] Therefore, the present inventors focused on antiplasticizers as an additive to solve the above problems, and developed a new antiplasticizer that is superior to conventional dibasic acid esters. As a result of extensive research, the present invention was completed based on the discovery that a tetracarboxylic acid tetraester having a specific structure exhibits good processability improvement effects and anti-plasticization effects.

即ち、本発明は、シクロアルキル基および／またはアリ
ール基を合計２個以上含む、下記の一般式で示される３
、４−ジカルボキシ−１，２，３゜４−テトラヒドロナ
フチル−１−］］ハク酸−二無水物以下、ＴＤＡと略称
する）のテトラエステルを特定量配合することを特徴と
する、加工性に優れ、かつ高い硬度、強度を有する硬質
塩化ビニル系樹脂組成物を提供することを目的とするも
のである。That is, the present invention relates to 3 containing a total of two or more cycloalkyl groups and/or aryl groups, represented by the following general formula.
, 4-dicarboxy-1,2,3゜4-tetrahydronaphthyl-1-]] succinic acid dianhydride (hereinafter abbreviated as TDA). The object of the present invention is to provide a hard vinyl chloride resin composition that has excellent hardness and strength.

（式中、Ｒ１−Ｒ４はシクロアルキル基、アリール基、
炭素数１〜８のアルキル基を示す〉［問題点を解決する
ための手段］ 上記のテトラカルボン酸テトラエステルの一般式におい
てＲ１−Ｒ４で示されるシクロアルキル基としては、シ
クロペンチル基、シクロヘキシル基、メチルシクロヘキ
シル基等、アリール基としてはフェニル基、クレジル基
、プチルフＪニル基、オクチルフェニル基、ノニルフェ
ニル基、キシレニル基、ナフチル基、ブチルナフチル基
、ベンジル基、メチルベンジル基等が例示される。また
、メチル基、エチル基、プロピル基、ブチル基、ペンチ
ル基、ヘキシル基、ヘプチル基、オクチル基等のアルキ
ル基を１ないし２個含んでいてもよい。(In the formula, R1-R4 are a cycloalkyl group, an aryl group,
Indicates an alkyl group having 1 to 8 carbon atoms> [Means for solving the problem] In the general formula of the above tetracarboxylic acid tetraester, the cycloalkyl group represented by R1-R4 includes a cyclopentyl group, a cyclohexyl group, Examples of the aryl group such as methylcyclohexyl group include phenyl group, cresyl group, butylphenyl group, octylphenyl group, nonylphenyl group, xylenyl group, naphthyl group, butylnaphthyl group, benzyl group, and methylbenzyl group. Further, it may contain one or two alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group.

当該テトラエステルの配合量は、塩化ビニル系樹脂組成
物’１００重量部当たり１〜３０重量部、好ましくは５
礼２５重量部である。１重量部未満の場合、充分な加工
性の改善、反可塑化の効果が得られず、３０重量部を越
える場合には成形物の柔軟温度が著しく低下するため、
いずれも所期の目的を満足することが出来ない。The compounding amount of the tetraester is 1 to 30 parts by weight, preferably 5 parts by weight per 100 parts by weight of the vinyl chloride resin composition.
It is 25 parts by weight. If it is less than 1 part by weight, sufficient improvement in workability and anti-plasticization effect cannot be obtained, and if it exceeds 30 parts by weight, the flexibility temperature of the molded product will be significantly lowered.
Neither of these methods can satisfy the intended purpose.

本発明において用いられる塩化ビニル系樹脂組成物とは
、塩化ビニルホモポリマーもしくは塩化ビニルを構造単
位の一種とする共重合体である。The vinyl chloride resin composition used in the present invention is a vinyl chloride homopolymer or a copolymer having vinyl chloride as a type of structural unit.

当該共重合体としては、塩化ビニル−エチレンコポリマ
ー、塩化ビニル−プロピレンコポリマー、塩化ビニル−
酢酸ビニルコポリマー等が挙げられる。また、これらの
樹脂は乳化重合法、懸濁重合法、塊状重合法などいずれ
の重合法によって製造されたものでもよい。Examples of the copolymer include vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, and vinyl chloride-ethylene copolymer.
Examples include vinyl acetate copolymer. Further, these resins may be produced by any polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization.

本発明における組成物には必要に応じて熱・光安定剤、
滑剤、紫外線吸収剤、帯電防止剤、着色剤、充填剤、難
燃剤、発泡剤等の添加剤を適宜加えることができる。The composition of the present invention may optionally include a heat/light stabilizer,
Additives such as lubricants, ultraviolet absorbers, antistatic agents, colorants, fillers, flame retardants, foaming agents, and the like can be added as appropriate.

本発明に係る塩化ビニル系樹脂組成物は用途に応じて押
出加工、射出成形、カレンダー加工、真空成形、ブロー
成形等の常法による成形加工が施され、それぞれの分野
での素材として提供される。The vinyl chloride resin composition according to the present invention is subjected to molding processing by conventional methods such as extrusion processing, injection molding, calendar processing, vacuum forming, blow molding, etc. depending on the purpose, and is provided as a material in each field. .

かくして得られる本発明に係る塩化ビニル系樹脂組成物
は、一般に硬質塩化ビニル系樹脂の用いられているシー
ト、パイプ、フィルム、成形品等に幅広く使用すること
が出来るものである。The vinyl chloride resin composition according to the present invention thus obtained can be widely used in sheets, pipes, films, molded products, etc. in which hard vinyl chloride resins are generally used.

［実施例］ 以下に本発明を更に詳しく説明するために実施例並びに
比較例を示す。[Examples] Examples and comparative examples are shown below to explain the present invention in more detail.

実施例１ 塩化ビニル樹脂（平均重合度１４５０）１００重量部に
ＴＤＡテトラ（シフ日ヘキシル）エステル１０重量部、
ステアリン酸カルシウム０．３重量部、ステアリン酸亜
鉛０．２重量部、エポキシ化大豆油２重量部を加え、混
合した。得られた混合物のゲル化特性をプラストグラフ
試験機を用いて測定した。次に混合物を混練ロールを用
いて１７５℃で５分間混練し、素練りシートを作成した
。Example 1 100 parts by weight of vinyl chloride resin (average degree of polymerization 1450), 10 parts by weight of TDA tetra (Schiff's hexyl) ester,
0.3 parts by weight of calcium stearate, 0.2 parts by weight of zinc stearate, and 2 parts by weight of epoxidized soybean oil were added and mixed. The gelation properties of the resulting mixture were measured using a plastograph tester. Next, the mixture was kneaded for 5 minutes at 175° C. using a kneading roll to create a masticated sheet.

得られた素練りシートを更に１８０℃、１００Ｋｇ／　
ｃＭで１０分間プレス成形し、厚さ１＃のプレスシート
を作成した。得られたプレスシートより所定の試験片を
切り扱き、柔軟温度および引張特性を測定した。結果を
表に示す。次に、試験方法を以下に示す。The obtained masticated sheet was further heated at 180°C and 100 kg/
Press molding was performed for 10 minutes at cM to create a press sheet with a thickness of 1#. Predetermined test pieces were cut and handled from the obtained press sheet, and the softening temperature and tensile properties were measured. The results are shown in the table. Next, the test method is shown below.

ゲル化特性 プラストグラフ試験機を用いて、チャンバ一温度１８０
℃、ローター回転数毎分４０回転にて配合組成物６０９
をチャンバーに投入し、３分間の予熱時間をおいて混線
を開始し、急激にトルクが上昇し、最大トルクに達する
点をゲル化点とし、その時のトルク、温度を測定した。Using a gelling property plastograph tester, the chamber temperature was 180°C.
Compounded composition 609 at a rotor speed of 40 revolutions per minute.
was put into the chamber, and after a preheating time of 3 minutes, crosstalk was started, the torque rapidly increased, and the point at which the maximum torque was reached was defined as the gelation point, and the torque and temperature at that time were measured.

引張特性 ＪＩＳＫ６７２３に準拠して測定を行なった。tensile properties Measurement was performed in accordance with JISK6723.

柔軟温度 Ｊ　ｌ５Ｋ６７４５に準拠して測定を行なった。flexible temperature Measurements were carried out in accordance with J　5K6745.

実施例２〜３ ＴＤＡテトラ（シクロヘキシル〉エステルの配合量を夫
々５．２５重量部とした他は、実施例１に準じて同様の
試験を行なった。結果を表に示す。Examples 2 to 3 The same tests as in Example 1 were conducted except that the amount of TDA tetra(cyclohexyl) ester was 5.25 parts by weight.The results are shown in the table.

実施例４ 実施例１のＴＤＡテトラ（シクロヘキシル）エステルを
ＴＤＡテトラ（ベンジル）エステルに置き換えて同様の
試験を行なった。結果を表に示す。Example 4 A similar test was conducted except that TDA tetra(cyclohexyl) ester in Example 1 was replaced with TDA tetra(benzyl) ester. The results are shown in the table.

実施例５ 実施例１のＴＤ△テトラ（シクロヘキシル）エステルを
ＴＤＡジ（ｎ−ブチル）ジ（シクロヘキシル）エステル
に置き換えて同様の試験を行なった。結果を表に示す。Example 5 A similar test was conducted in Example 1 except that TDΔtetra(cyclohexyl) ester was replaced with TDA di(n-butyl) di(cyclohexyl) ester. The results are shown in the table.

実施例６ 実施例１のＴＤＡテトラ（シクロヘキシル）エステルを
ＴＤＡジ（ｎ−ブチル）ジ（ベンジル）エステルに置き
換えて同様の試験を行なった。結果を表に示す。Example 6 A similar test was conducted except that TDA tetra(cyclohexyl) ester in Example 1 was replaced with TDA di(n-butyl) di(benzyl) ester. The results are shown in the table.

比較例１〜２ 実施例１および３のＴＤＡテトラ（シクロヘキシル）ニ
［ステルをフタル酸ジ（２−エチルヘキシル）エステル
に置き換えて同様の試験を行なった。Comparative Examples 1 to 2 Similar tests were conducted except that TDAtetra(cyclohexyl) di[ester in Examples 1 and 3 was replaced with phthalic acid di(2-ethylhexyl) ester.

結果を表に示す。The results are shown in the table.

比較例３〜４ 実施例１および３のＴＤＡテトラ（シクロヘキシル）エ
ステルをフタル酸ジ（シクロヘキシル〉エステルに置き
換えて同様の試験を行なった。結果を表に示す。Comparative Examples 3 to 4 Similar tests were conducted by replacing TDA tetra(cyclohexyl) ester in Examples 1 and 3 with phthalic acid di(cyclohexyl) ester.The results are shown in the table.

比較例５ 実施例１のＴＤＡテトラ（シクロヘキシル）エステルを
扱いた配合組成にて同様の試験を行なった。結果を表に
示す。Comparative Example 5 A similar test was conducted using the formulation of Example 1 using TDA tetra(cyclohexyl) ester. The results are shown in the table.

［発明の効果］ 表から明らかなように、本発明組成物は非常に優れた硬
度、強度、および加工性を示し、かつ充分なる熱変形温
度を有している。[Effects of the Invention] As is clear from the table, the composition of the present invention exhibits excellent hardness, strength, and processability, and has a sufficient heat distortion temperature.

Claims (1)

【特許請求の範囲】 塩化ビニル系樹脂１００重量部当たり、シクロアルキル
基および／またはアリール基を合計２個以上含む、次の
一般式で示されるテトラカルボン酸テトラエステル１〜
３０重量部を配合することを特徴とする塩化ビニル系樹
脂組成物。 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１〜Ｒ＾４はシクロアルキル基、アリール
基、炭素数１〜８のアルキル基を示す）[Scope of Claims] 1 to 2 tetracarboxylic acid tetraesters represented by the following general formula, containing a total of two or more cycloalkyl groups and/or aryl groups per 100 parts by weight of vinyl chloride resin.
A vinyl chloride resin composition, characterized in that it contains 30 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 to R^4 represent a cycloalkyl group, an aryl group, or an alkyl group having 1 to 8 carbon atoms.)