JPS6030342B2 - Thermoplastic resin composition with excellent light blocking properties - Google Patents

Description

【発明の詳細な説明】 本発明は、遮光性にすぐれた熱可塑性樹脂組成物に関し
、さらに詳しくは、塩素化ポリエチレン及びアクリロニ
トリルースチレン共重合体よりなる二成分系樹脂組成物
、または塩素化ポリエチレン、アクリロニトリルースチ
レン共重合体及びポリ塩化ビニルよりなる三成分系樹脂
組成物に対し、酸化チタンを配してなる遮光性にすぐれ
た熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition with excellent light-shielding properties, and more specifically, a two-component resin composition comprising chlorinated polyethylene and acrylonitrile-styrene copolymer, or a chlorinated polyethylene , relates to a thermoplastic resin composition with excellent light-shielding properties, which is made by disposing titanium oxide in a three-component resin composition consisting of an acrylonitrile-styrene copolymer and polyvinyl chloride.

塩素化ポリエチレンとアクリロニトリルースチレン共重
合体よりなる二成分系樹脂組成物、及び塩素化ポリエチ
レン、アクリロニトリルースチレン共重合体及びポＩＪ
塩化ビニルよりなる三成分系樹脂組成物は、耐候・性、
耐衝撃性及び難燃性等のすぐれた樹脂組成物として知ら
れ、現在主として建築、車繭及び電気機器部品等の成形
材料として用いられているが、近年、エレクトロニクス
技術の進歩に伴ない、時計や電卓その他計測品等のデジ
タル表示板の材料として、その適用範囲を広めつつある
。Two-component resin composition consisting of chlorinated polyethylene and acrylonitrile styrene copolymer, and chlorinated polyethylene, acrylonitrile styrene copolymer and poly-IJ
The three-component resin composition made of vinyl chloride has excellent weather resistance,
Known as a resin composition with excellent impact resistance and flame retardancy, it is currently used mainly as a molding material for buildings, car cocoons, and electrical equipment parts. The scope of its application is expanding as a material for digital display boards such as calculators, calculators, and other measuring products.

しかし、このような用途に上記二成分系樹脂組成物また
は三成分系樹脂組成物を用いた場合、得られる表示板の
遮光性が不十分であるため、数字、記号、パターン等が
不鮮明で表示効果が充分でないという欠点を有する。従
って、上記二成分系樹脂組成物または三成分系樹脂組成
物の遮光性を改良することは、これら組成物が物性面で
上記の諸特長を有するため、極めて有意義なことである
。本発明者らは、塩素化ポリエチレンとアクリロニトリ
ルースチレン共重合体よりなる二成分系樹脂組成物また
は塩素化ポリエチレン、アクリロニトリルースチレン共
重合体及びポリ塩化ビニルよりなる三成分系樹脂組成物
の遮光性について種々研究した結果、酸化チタンを上記
二成分系樹脂組成物または三成分系樹脂組成物に添加す
ることによって、二成分系樹脂組成物または三成分系樹
脂組成物の遮光性が著しく改善され、しかも良好な物性
を有する成形体が得られることを見出し、本発明に到達
した。However, when the above-mentioned two-component resin composition or three-component resin composition is used for such applications, the light-shielding properties of the resulting display board are insufficient, so numbers, symbols, patterns, etc. are unclear and displayed. It has the disadvantage of not being sufficiently effective. Therefore, it is extremely meaningful to improve the light-shielding properties of the two-component resin composition or the three-component resin composition, since these compositions have the above-mentioned features in terms of physical properties. The present inventors have demonstrated the light-shielding properties of two-component resin compositions made of chlorinated polyethylene and acrylonitrile-loustyrene copolymer or three-component resin compositions made of chlorinated polyethylene, acrylonitrile-loustyrene copolymer, and polyvinyl chloride. As a result of various studies, it was found that by adding titanium oxide to the two-component resin composition or three-component resin composition, the light-shielding properties of the two-component resin composition or three-component resin composition were significantly improved. Moreover, it was discovered that a molded article having good physical properties could be obtained, and the present invention was achieved.

本発明は、風塩素含有率２０〜５の重量％の塩素化ポリ
エチレン５〜４５重量部、曲アクリロニトリルースチレ
ン共重合体９５〜５５重量部及び【ｑポリ塩化ビニル０
〜３の重量部の総計１０の重量部に対し、皿酸化チタン
５〜３の重量部を配してなる熱可塑性樹脂組成物に関す
る。The present invention comprises 5 to 45 parts by weight of chlorinated polyethylene with a wind chlorine content of 20 to 5% by weight, 95 to 55 parts by weight of bent acrylonitrile-styrene copolymer, and [q polyvinyl chloride 0
The present invention relates to a thermoplastic resin composition comprising 5 to 3 parts by weight of dish titanium oxide for a total of 10 parts by weight of 3 parts by weight.

本発明において用いられる塩素化ポリエチレンとしては
、重量平均分子量が５方以上、好ましくは１０〜５０万
のポリエチレンを塩素化した塩素化ポリエチレンのほか
、エチレンープロピレン共重合体またはエチレンープテ
ン−１共重合体のごときエチレン共重合体を塩素化した
もの、′ポリエチレンをクロロスルホン化したものがあ
げられる。The chlorinated polyethylene used in the present invention includes chlorinated polyethylene obtained by chlorinating polyethylene with a weight average molecular weight of 5 or more, preferably 100,000 to 500,000, as well as ethylene-propylene copolymer or ethylene-butene-1 copolymer. Examples include chlorinated ethylene copolymers such as ethylene copolymers, and chlorosulfonated polyethylene.

塩素化ポリエチレンは、塩素含有率２０〜５の重量％よ
り好適には３０〜４の重量％のものが組成物の耐衝撃性
を向上させる上で好適である。また本発明において用い
られるアクリロニトリルースチレン共重合体としては、
アクリロニトリルとスチレンを溶液重合法または乳化重
合法等任意の方法により共重合せしめたものであり、共
重合体中のァクリロニトリルのスチレンに対する比率は
１０〜９の重量％の範囲で選択されらる。The chlorinated polyethylene preferably has a chlorine content of 20 to 5% by weight, more preferably 30 to 4% by weight, in order to improve the impact resistance of the composition. Furthermore, the acrylonitrile-styrene copolymer used in the present invention includes:
Acrylonitrile and styrene are copolymerized by any method such as solution polymerization or emulsion polymerization, and the ratio of acrylonitrile to styrene in the copolymer is selected in the range of 10 to 9% by weight.

アクリロニトリルの比率が大きくなると同一塩素化ポリ
エチレン量の場合、抗張力、耐衝撃性が向上し、一方、
スチレンの比率が大きくなると加工性が増大する。次に
所望に応じて配合されるポリ塩化ビニルとしては、重合
度５００〜２０００、好ましくは７００〜１５００の硬
質ポリ塩化ビニルであり、また塩化ビニルを少なくとも
８の重量％含有する塩化ビニルと酢酸ビニル、塩化ビニ
リデンまたはその他のビニル系モノマーとの共重合体、
後塩素化ポリ塩化ビニルも用いられる。When the ratio of acrylonitrile increases, the tensile strength and impact resistance improve for the same amount of chlorinated polyethylene;
Processability increases as the proportion of styrene increases. Next, the polyvinyl chloride to be blended as desired is hard polyvinyl chloride with a degree of polymerization of 500 to 2000, preferably 700 to 1500, and vinyl chloride containing at least 8% by weight of vinyl chloride and vinyl acetate. , copolymers with vinylidene chloride or other vinyl monomers,
Post-chlorinated polyvinyl chloride is also used.

本発明において用いられる酸化チタンとは、平均粒径０
．２〜０．５〃、比重３．８〜４．５で少なくとも７０
％はルチル型の二酸化チタンが好ましい。The titanium oxide used in the present invention has an average particle size of 0.
．． 2-0.5〃, specific gravity 3.8-4.5 and at least 70
% is preferably rutile-type titanium dioxide.

以上述べた各成分を混合して目的とする樹脂組成物を調
製するにあたり、各成分の浪合割合は「風塩素化ポリエ
チレン５〜４５重量部、好ましくは１０〜４の重量部、
‘Ｂ’アクリロニトリルースチレン共重合体９５〜５５
重量部、好ましくは９０〜６の重量部及びに’ポリ塩化
ビニル０〜３の重量部、好ましくは０〜２の重量部の総
計１０の重量部に対し、■酸化チタン５〜３の重量部で
あることが必要である。When preparing the desired resin composition by mixing each component described above, the proportion of each component is "5 to 45 parts by weight, preferably 10 to 4 parts by weight of air-chlorinated polyethylene,
'B' Acrylonitrile-styrene copolymer 95-55
5 to 3 parts by weight of titanium oxide to a total of 10 parts by weight, preferably 90 to 6 parts by weight, and 0 to 3 parts by weight, preferably 0 to 2 parts by weight of polyvinyl chloride. It is necessary that

これらの混合割合は、本発明者らが種々実験、検討した
結果得たものであって、遮光性及びその他の各種性状に
基づく組成物の実用性の見地から臨界的な値である。即
ち、塩素化ポリエチレンの配合割合が５重量部以下では
、樹脂組成物は硬質となり、抗張力は向上するが耐衝撃
性が低下するので好ましくない。また、塩素化ポリエチ
レンの配合割合が４５重量部以上では、樹脂組成物の耐
衝撃性が向上するが抗張力及び加工性が低下するので望
ましくない。一方、所望に応じて加えられるポリ塩化ビ
ニルの配合割合が３の重量部以上では、樹脂組成物の耐
衝撃性及び加工性が低下するばかりか、成形体が着色す
るので好ましくない。酸化チタンの配合量は、全樹脂量
の総計１００重量部に対し、５〜３の重量部、好ましく
は１０〜２５重量部である。These mixing ratios were obtained as a result of various experiments and studies by the present inventors, and are critical values from the viewpoint of practicality of the composition based on light-shielding properties and various other properties. That is, if the blending ratio of chlorinated polyethylene is 5 parts by weight or less, the resin composition becomes hard and the tensile strength improves, but the impact resistance decreases, which is not preferable. Moreover, if the blending ratio of chlorinated polyethylene is 45 parts by weight or more, the impact resistance of the resin composition will improve, but the tensile strength and processability will decrease, which is not desirable. On the other hand, if the blending ratio of polyvinyl chloride added as desired is 3 parts by weight or more, not only the impact resistance and processability of the resin composition will deteriorate, but also the molded article will be colored, which is not preferable. The amount of titanium oxide to be blended is 5 to 3 parts by weight, preferably 10 to 25 parts by weight, based on a total of 100 parts by weight of all resins.

酸化チタンの配合量が５重量部以下では、本発明の効果
は得られず、一方、酸化チタンの配合量が３の重量部以
上では、成形加工が困難になるばかりか、酸化チタンの
樹脂成分への分散が悪くなり、成形体の外観が不良とな
るので好ましくない。本発明の樹脂組成物は、雛燃剤を
さらに添加してその難燃性を向上させることができる。If the amount of titanium oxide is less than 5 parts by weight, the effect of the present invention cannot be obtained. On the other hand, if the amount of titanium oxide is more than 3 parts by weight, not only will molding become difficult, but the resin component of titanium oxide This is not preferable because the dispersion in the molded product becomes poor and the appearance of the molded product becomes poor. The flame retardance of the resin composition of the present invention can be improved by further adding a flame retardant.

難燃剤としては、公知のハロゲン化ェステル、りん酸ェ
ステル、芳香族ハロゲン化物等いずれの簸燃剤を使用し
てもよいが、とくに塩素化パラフィン、パークロロベン
タシクロデカン及びその変性物、ヘキサブロモベンゼン
、テトラブロムビスフエノールＡ、デカブロムビフェニ
ルエーテル等のハロゲン系鎚燃剤、アンチモン系化合物
が本発明の樹脂組成物の諸特性を変える度合が小さく、
且つ難燃性を著しく向上させる利点を有するので好適に
使用される。ハロゲン系鶏燃剤及びアンチモン系化合物
の添加量は、全樹脂量の総計１０の重量部に対して、前
者は５〜２の重量部、後者は３〜１の重量部である。本
発明の樹脂組成物を調製するには、所定成分を例えば熱
ロール、バンバリーミキサー、押出機等速常の方法で行
なうことができる。As the flame retardant, any known elutriation agents such as halogenated esters, phosphate esters, aromatic halides, etc. may be used, but in particular, chlorinated paraffin, perchlorobentacyclodecane and its modified products, hexabromobenzene , tetrabromubisphenol A, decabromubiphenyl ether, and other halogen-based retardants, and antimony-based compounds have a small degree of altering the various properties of the resin composition of the present invention,
Moreover, it has the advantage of significantly improving flame retardancy, so it is preferably used. The amount of the halogen-based chicken retardant and the antimony-based compound added is 5 to 2 parts by weight for the former and 3 to 1 part by weight for the latter to a total of 10 parts by weight of the total resin amount. In order to prepare the resin composition of the present invention, predetermined components can be prepared by a conventional method such as using a heated roll, a Banbury mixer, or an extruder.

この際、必要に応じて種々の添加剤、例えば安定剤、酸
化防止剤、滑剤、可塑剤、帯電防止剤、充填剤等を配合
することができる。以下、実施例及び比較例によって本
発明を具体的に示す。At this time, various additives such as stabilizers, antioxidants, lubricants, plasticizers, antistatic agents, fillers, etc. can be added as necessary. The present invention will be specifically illustrated below with reference to Examples and Comparative Examples.

例において特記しない限り、部は重量部を表わす。なお
、成形材料の物性は、次記に準じて測定した。遮光性（
光透過率） 厚さ０．４柳の試験片を用い、色差計による光の透過率
を測定色相 肉眼観察による 抗張力 ＡＳＴＭ Ｄ６３８ 耐衝撃性 ＡＳＴＭ Ｄ２５６−７３ 加工性 ＡＳＴＭＤ１２３８−７３により、１９０００、１０ｋ
９の荷重で測定した。In the examples, unless otherwise specified, parts refer to parts by weight. In addition, the physical properties of the molding material were measured according to the following. Light blocking property (
Light transmittance) Measurement of light transmittance using a color difference meter using a willow test piece with a thickness of 0.4 Hue Tensile strength by visual observation ASTM D638 Impact resistance ASTM D256-73 Workability 19000, 10k according to ASTM D1238-73
It was measured with a load of 9.

光沢 ガードナーグロスメーターを用いて、 ＡＳＴＭダンベル１号の表面光沢を測定し、それを光の
反射率で表示した。Gloss The surface gloss of ASTM dumbbell No. 1 was measured using a Gardner gloss meter, and the surface gloss was expressed as light reflectance.

難燃性 厚さ１．６側の試験片を用い、ＵＬ−９迫垂直燃焼試験
法による燃焼試験実施例 １〜１０、及び比較例 １〜
６ 重量平均分子量２０万のポリエチレンを塩素化して得ら
れた塩素含有率３の重量％の塩素化ポリエチレン（昭和
電工（株）社製、ェラスレン３０１Ａ、ＣＩＰＥと略記
する）、アクリロニトリルースチレン共重合体（アクリ
ロニトリル２５重量％、ＡＳと略記する）、ポリ塩化ビ
ニル（日本ゼオン（株）社製、重合度１０００、ＰＶＣ
と略記する）及び酸化チタン（平均粒径０．５仏、比重
４．０、Ｔｉ０２と略記する）の各成分を第１表記載の
割合で配合し、次いでジプチル錫マレェート２重量部を
加え、２００００の６５肋？押出機（ベントタィプ）で
混練した。Combustion test examples 1 to 10 and comparative examples 1 to 10 according to the UL-9 near-vertical combustion test method using test pieces with a flame retardant thickness of 1.6
6 Chlorinated polyethylene with a chlorine content of 3% by weight obtained by chlorinating polyethylene with a weight average molecular weight of 200,000 (manufactured by Showa Denko Co., Ltd., Elasthrene 301A, abbreviated as CIPE), acrylonitrile styrene copolymer (acrylonitrile 25% by weight, abbreviated as AS), polyvinyl chloride (manufactured by Nippon Zeon Co., Ltd., polymerization degree 1000, PVC
) and titanium oxide (average particle size: 0.5 French, specific gravity: 4.0, abbreviated as Ti02) in the proportions listed in Table 1, then 2 parts by weight of diptyltin maleate were added, 20,000 65 ribs? The mixture was kneaded using an extruder (bent type).

次いで、組成物を３オンスの射出成形機を用いてシリン
ダー温度をホッパ一部からスクリュー先端方向に１６０
−１８０一２００ｑｏとし、射出圧力８０ｋ９／仇、金
型温度５０ｑ０に設定して、それぞれ所定の試験片に成
形した。この試験片を用いて、遮光性、色相、抗張力、
耐衝撃性、光沢及び難燃性試験を行なつた。これらの試
験と共に比較のため、ＡＳ単独のもの、ＣＩＰＥとＡＳ
の配合量が本発明の範囲外のもの、ＣＩＰＥとＡＳの二
成分からなるもの、Ｔｉ０２の配合量が本発明の範囲外
のもの、ＣＩＰＥとＰＶＣの三成分からなるもの、及び
ＰＶＣの配合量が本発明の範囲外のものについても同様
に行なった。その結果を第１表に示した。第 １ 表 第１表から明らかなごとく、本発明の組成物はいずれも
遮光性が改善され、物性的にバランスがとれていること
がわかる。Then, the composition was put into a 3-ounce injection molding machine, and the cylinder temperature was increased to 160°C from the hopper part toward the screw tip.
-180 - 200 qo, injection pressure 80k9/2, mold temperature 50q0, and molded into predetermined test pieces. Using this test piece, light shielding property, hue, tensile strength,
Impact resistance, gloss and flame retardancy tests were conducted. Along with these tests, for comparison, AS alone, CIPE and AS
Those in which the blending amount is outside the scope of the present invention, those consisting of two components of CIPE and AS, those in which the blending amount of Ti02 is outside the range of the present invention, those consisting of three components of CIPE and PVC, and the blending amount of PVC However, the same procedure was carried out for those outside the scope of the present invention. The results are shown in Table 1. Table 1 As is clear from Table 1, all of the compositions of the present invention have improved light-shielding properties and are well-balanced in terms of physical properties.

実施例 １１〜１４、及び比較例 ７〜８重量平均分子
量２０万のポリエチレンを塩素化して得られた塩素含有
率４の重量％の塩素化ポリエチレン（昭和電工（株）社
製、ェラスレン４０１Ａ、ＣＩＰＥと略記する）、アク
リロニトリルースチレン共重合体（アクリロニトリル２
３重量％、ＡＳと略記する）、ポリ塩化ビニル（日本ゼ
オン（株）社製、Ｓ９０１、重合度１０００、ＰＶＣと
略記する）、酸化チタン（平均粒径０．５仏、比重４．
０、Ｔｉ０２と略記する）、ヘキサブロムベンゼン（Ｈ
ＢＢと略記する）及び三酸化アンチモン（Ｓｂ２０３と
略記する）の各成分を第２表記載の割合で配合し、以後
の操作は実施例１〜１０、及び比較例１−６と全く同様
に行ない、各物性値を測定した。Examples 11 to 14 and Comparative Examples 7 to 8 Chlorinated polyethylene with a chlorine content of 4% by weight obtained by chlorinating polyethylene with a weight average molecular weight of 200,000 (manufactured by Showa Denko K.K., Elasthrene 401A, CIPE) ), acrylonitrile styrene copolymer (acrylonitrile 2
3% by weight, abbreviated as AS), polyvinyl chloride (manufactured by Nippon Zeon Co., Ltd., S901, degree of polymerization 1000, abbreviated as PVC), titanium oxide (average particle size 0.5 F, specific gravity 4.
0, abbreviated as Ti02), hexabromobenzene (H
BB) and antimony trioxide (abbreviated as Sb203) were mixed in the proportions listed in Table 2, and the subsequent operations were carried out in exactly the same manner as in Examples 1 to 10 and Comparative Examples 1 to 6. , each physical property value was measured.

その結果を第２表に示した。第２表 第２表から明らかなごとく、ＨＢＢとＳＱ０３、または
ＳＱ０３単独を添加しても、遮光性及びその他の物性を
変える度合が小さく、且つ難燃性が向上することがわか
る。The results are shown in Table 2. As is clear from Table 2, even if HBB and SQ03, or SQ03 alone is added, the degree of change in light shielding properties and other physical properties is small, and flame retardancy is improved.

Claims (1)

【特許請求の範囲】[Claims] １ （Ａ）塩素含有率２０〜５０重量％の塩素化ポリエ
チレン５〜４５重量部、（Ｂ）アクリロニトリル−スチ
レン共重合体９５〜５５重量部及び（Ｃ）ポリ塩化ビニ
ル０〜３０重量部の総計１００重量部に対し、（Ｄ）酸
化チタン５〜３０重量部を配してなる遮光性にすぐれた
熱可塑性樹脂組成物。1 Total of (A) 5 to 45 parts by weight of chlorinated polyethylene with a chlorine content of 20 to 50% by weight, (B) 95 to 55 parts by weight of acrylonitrile-styrene copolymer, and (C) 0 to 30 parts by weight of polyvinyl chloride. A thermoplastic resin composition with excellent light-shielding properties, comprising 5 to 30 parts by weight of (D) titanium oxide per 100 parts by weight.