JPH06248135A - Thermoplastic resin composition excellent in weatherability - Google Patents
Thermoplastic resin composition excellent in weatherabilityInfo
- Publication number
- JPH06248135A JPH06248135A JP5331226A JP33122693A JPH06248135A JP H06248135 A JPH06248135 A JP H06248135A JP 5331226 A JP5331226 A JP 5331226A JP 33122693 A JP33122693 A JP 33122693A JP H06248135 A JPH06248135 A JP H06248135A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin composition
- component
- vinyl
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【0001】[0001]
【発明の利用分野】本発明は、熱可塑性樹脂に関するも
のであり、より詳細には優秀な耐候性を持ちながら、衝
撃強度等諸般の機械的物性も優れたスチレン系熱可塑性
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 relates to a thermoplastic resin, and more particularly to a styrene-based thermoplastic resin composition having excellent weather resistance and excellent mechanical properties such as impact strength. Is.
【0002】[0002]
【従来の技術】ABS樹脂は、アクリロニトリルとブタ
ジエン及びスチレンの共重合体樹脂であり、一般に耐衝
撃特性や引張特性等の各々の物理的な特性及び耐薬品
性、成形加工性等が優れ、家電製品や各種の事務機器等
に広く使用されている樹脂である。2. Description of the Related Art ABS resin is a copolymer resin of acrylonitrile, butadiene and styrene, and generally has excellent physical properties such as impact resistance and tensile property, chemical resistance, molding processability, etc. This resin is widely used in products and various office equipment.
【0003】しかしながら、このABS樹脂はその成分
中の一つであるブタジエンゴムの二重結合に起因して紫
外線又は酸素により酸化反応がおこりやすく、変色及び
物性低下が甚だしいため、耐候性が要求される電子製品
や屋外使用製品等に適用するには限界があった。However, the ABS resin is apt to undergo an oxidation reaction due to ultraviolet rays or oxygen due to the double bond of butadiene rubber, which is one of its components, and thus discoloration and deterioration of physical properties are serious, and therefore weather resistance is required. There was a limit in applying it to electronic products and outdoor products.
【0004】このような問題点を解決するがために、米
国特許第3,886,233号公報、第4,007,2
34号公報等に開示されているように、ブタジエンゴム
の代りに二重結合がないか、ほとんどないエチレン−プ
ロピレンゴム(以下、“EPR”と称す)又はエチレン
−プロピレン−ジエンゴム(以下“EPDM”と称す)
にSANをグラフト重合して衝撃補強材として使用する
か、又は米国特許第4,528,328号公報に開示さ
れているように、アクリルゴムのグラフト重合体を用い
て高い耐衝撃性及び耐候性を得る方法等がある。In order to solve such problems, US Pat. Nos. 3,886,233 and 4,007,2 have been proposed.
As disclosed in Japanese Patent Publication No. 34, etc., ethylene-propylene rubber (hereinafter referred to as "EPR") or ethylene-propylene-diene rubber (hereinafter referred to as "EPDM") having no or almost no double bond in place of butadiene rubber. Called)
Is used as an impact reinforcing material by graft polymerization of SAN, or as described in US Pat. No. 4,528,328, a high impact resistance and weather resistance is obtained by using a graft polymer of acrylic rubber. There is a method to obtain.
【0005】しかしながら、上記のグラフト重合体は流
動性が非常に低く、加工条件に制限があり、複雑な製造
工程を経なければならないという欠点がある。However, the above-mentioned graft polymer has the drawbacks that it has a very low fluidity, the processing conditions are limited, and a complicated manufacturing process is required.
【0006】一方、特公昭第39−17057号公報、
同第41−6351号公報等には、ブタジエンゴムの代
りに塩素化ポリエチレンをアクリロニトリル−スチレン
共重合体と重合またはブレンドさせたACS(アクリロ
ニトリル−塩素化ポリエチレン−スチレン)樹脂を製造
したが、これは耐熱特性及び耐候性は優れているが、耐
衝撃性等の機械的な物性が多少劣るという短所がある。On the other hand, Japanese Patent Publication No. 39-17057,
No. 41-6351 discloses an ACS (acrylonitrile-chlorinated polyethylene-styrene) resin produced by polymerizing or blending chlorinated polyethylene with an acrylonitrile-styrene copolymer instead of butadiene rubber. Although it has excellent heat resistance and weather resistance, it has a drawback that mechanical properties such as impact resistance are somewhat inferior.
【0007】ACS樹脂のこのような短所を解決するた
めに特公昭第48−44933号公報には塩素化ポリエ
チレン(以下“CPE”と称す)及び少量のEPR又は
EPDMをスチレン系樹脂の衝撃補強材に使用して耐衝
撃性等の機械的物性を改善したが、この技術には衝撃強
度改善効果が低く、層状剥離が生じる等の問題点があ
る。In order to solve such disadvantages of the ACS resin, Japanese Patent Publication No. 48-44933 discloses a chlorinated polyethylene (hereinafter referred to as "CPE") and a small amount of EPR or EPDM as an impact reinforcement of a styrene resin. Although the mechanical properties such as impact resistance have been improved by using it, this technique has a problem that impact strength improving effect is low and delamination occurs.
【0008】上記の問題点を解決するため、欧州特許第
37609号及び米国特許第4,341,884号、同
第4,468,487号等では上記の組成物の中でEP
DMの量を増加させて結晶性CPEを使用している。In order to solve the above-mentioned problems, EP 37609 and US Pat. Nos. 4,341,884 and 4,468,487 disclose EP in the above composition.
Crystalline CPE is used with increasing amounts of DM.
【0009】しかしながら、この方法もまた機械的物性
改善には限界が有り、層状剥離の防止には効果が無かっ
た。However, this method also has a limit in improving the mechanical properties and is not effective in preventing delamination.
【0010】[0010]
【発明が解決しようとする課題】本発明は、ACS樹脂
が持っている上記の問題点を解決するためのものであ
り、既存の熱可塑性樹脂と比べて優秀な機械的物性を持
ち、層状剥離現象の発生率が低く、耐候性に優れた樹脂
組成物を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned problems of the ACS resin, has excellent mechanical properties as compared with existing thermoplastic resins, and has delamination. An object of the present invention is to provide a resin composition having a low occurrence rate of phenomena and excellent weather resistance.
【0011】[0011]
【課題を解決するための手段および作用】本発明者達
は、上記の目的のために鋭意研究を重ねた結果、スチレ
ン系樹脂及びCPE、変性エチレン−プロピレン系ゴム
及びビニル系衝撃補強材を適切な比率で調整して使用す
れば上記の目的を達成することを明らかにした。Means and Actions for Solving the Problems As a result of intensive studies for the above purpose, the present inventors have found that styrene resin and CPE, modified ethylene-propylene rubber and vinyl impact reinforcement are suitable. It was clarified that the above-mentioned object can be achieved by adjusting and using it at various ratios.
【0012】本発明は、次のような組成を持つことを特
徴とする。The present invention is characterized by having the following composition.
【0013】(A)芳香族ビニル系単量体60〜85w
t%にシアン化ビニル系単量体40〜15wt%及びこ
れらと重合可能な他のビニル系単量体0〜40wt%を
混合して重合したスチレン系重合体50〜85wt%; (B)塩素含量20〜40wt%のCPE10〜35w
t%; (C)エチレン−プロピレン系ゴム100重量部(以下
“部”と略称する)に対して有機過酸化物0〜2部及び
カルボキシル基又は無水カルボキシル基を持つ反応性単
量体1.5〜6部を溶融混練して製造した変性エチレン
−プロピレン系ゴム5〜35wt%; (D)ビニル系グラフト共重合体0〜10wt% を配合、溶融混練して製造することを特徴とする。(A) Aromatic vinyl monomer 60-85w
50% to 85% by weight of a styrene polymer obtained by mixing 40% to 15% by weight of a vinyl cyanide monomer and 0% to 40% by weight of another vinyl monomer that can be polymerized with t%, and polymerized (B) chlorine CPE10-35w with a content of 20-40wt%
t%; (C) Reactive monomer having 0 to 2 parts of organic peroxide and 100 to 100 parts by weight of ethylene-propylene rubber (hereinafter abbreviated as "part") and a carboxyl group or an anhydrous carboxyl group. Modified ethylene-propylene rubber 5 to 35 wt% produced by melt-kneading 5 to 6 parts; and (D) vinyl graft copolymer 0 to 10 wt% are blended and melt-kneaded to produce.
【0014】以下、本発明をさらに詳細に説明する。The present invention will be described in more detail below.
【0015】本発明の構成成分(A)であるビニル系共
重合体構成成分としては上記に列挙した芳香族ビニル単
量体、シアン化ビニル単量体を使用することができ、重
合可能な他のビニル単量体としてはアクリル酸及びメタ
クリル酸のメチル、エチル、プロピル、n−ブチル等の
(メタ)アクリル酸エステル単量体、マレイミド、N−
メチルマレイミド、N−フェニルマレイミド等のような
マレイミド、アクリルアミドである。As the vinyl-based copolymer constituting component of the component (A) of the present invention, the aromatic vinyl monomer and vinyl cyanide monomer listed above can be used, and they can be polymerized. Examples of the vinyl monomer include (meth) acrylic acid ester monomers such as methyl, ethyl, propyl and n-butyl of acrylic acid and methacrylic acid, maleimide, N-
Maleimides such as methylmaleimide, N-phenylmaleimide, etc., acrylamide.
【0016】構成成分(A)の製造方法としては、乳化
重合、懸濁重合、塊状重合、連続重合等の様な公知の重
合法の中の何れも使用可能である。As the method for producing the constituent component (A), any of known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization and continuous polymerization can be used.
【0017】本組成物の構成成分(B)であるCPEは
溶液、懸濁又は気相反応を通じてポリエチレンを塩素化
させて製造することができ、その製法は米国特許第3,
935,181号公報、同第4,197,386号公報
等に開示されたのを使用することができる。The component (B) of the composition, CPE, can be produced by chlorinating polyethylene through a solution, suspension or gas phase reaction, and the production method is described in US Pat.
Those disclosed in Japanese Patent No. 935,181 and Japanese Patent No. 4,197,386 can be used.
【0018】CPEの塩素含量は、構成成分(C)との
相容性及び衝撃補強効果を考慮した時、20〜40wt
%が適当である。構成成分(B)の適切な組成比は、組
成物全体に対して10〜35wt%であるが、望ましく
は13〜25wt%である。The chlorine content of CPE is 20 to 40 wt% in consideration of the compatibility with the constituent component (C) and the impact reinforcing effect.
% Is appropriate. A suitable composition ratio of the component (B) is 10 to 35 wt% with respect to the entire composition, and preferably 13 to 25 wt%.
【0019】CPEが組成物全体に対して10wt%未
満であると、引張強度、硬度及び耐熱特性は向上する
が、伸率、耐衝撃性は急激に低下し、一方35wt%を
越えると耐衝撃特性は優秀であるが成形時に有毒ガスが
発生し、また引張強度、硬度、耐候性が低下するので実
用には適さないという問題が発生する。When the CPE is less than 10 wt% with respect to the entire composition, the tensile strength, hardness and heat resistance are improved, but the elongation and impact resistance sharply decrease, while when it exceeds 35 wt%, the impact resistance is increased. Although the characteristics are excellent, toxic gas is generated at the time of molding, and the tensile strength, hardness, and weather resistance are deteriorated, which causes a problem that it is not suitable for practical use.
【0020】本組成物の構成成分(C)の変性エチレン
−プロピレン系ゴムを構成する、エチレン−プロピレン
系ゴムとしてはエチレン−プロピレンゴム(以下“EP
R”と称す)、エチレン−プロピレン−ジエンゴム(以
下EPDM”と称す)を用いることが出来る。この中の
EPDMのジエン成分としては1,4−ヘキサジエン、
ジシクロペンタジエン、5−ビニルノボネン、2,5−
エチリデンノボネン等を使用することができ、その組成
はEPDM100部に対して2〜8部を使用することが
できる。As the ethylene-propylene rubber constituting the modified ethylene-propylene rubber as the constituent component (C) of the present composition, ethylene-propylene rubber (hereinafter referred to as "EP
R ") and ethylene-propylene-diene rubber (hereinafter referred to as EPDM") can be used. The diene component of EPDM in this is 1,4-hexadiene,
Dicyclopentadiene, 5-vinyl nobonene, 2,5-
Ethylidene nobonene or the like can be used, and the composition thereof can be 2 to 8 parts based on 100 parts of EPDM.
【0021】成分(C)の製造に用いる有機過酸化物と
しては、ジイソプロピルベンゼンハイドロパーオキサイ
ド、ジ−t−ブチルパーオキサイド、t−ブチルクミル
パーオキサイド、ジクミルパーオキサイド、ジ−t−ブ
チルジパーオキシフタレイト、スクシニックアシドパー
オキサイド、t−ブチルパーオキシベンゾエイト、t−
ブチルパーオキシマレイン酸、メチルエチルケトンパー
オキサイド、シクロヘキサノンパーオキサイド等を使用
することができ、この中でも反応性及び加工性を考慮し
てジクミルパーオキサイドを使用するのが良い。Examples of the organic peroxide used for the production of the component (C) include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide and di-t-butyldioxide. Peroxyphthalate, succinic acid peroxide, t-butyl peroxybenzoate, t-
Butyl peroxymaleic acid, methyl ethyl ketone peroxide, cyclohexanone peroxide and the like can be used. Among them, it is preferable to use dicumyl peroxide in consideration of reactivity and processability.
【0022】成分(C)の製造に用いるカルボキシル基
又は無水カルボキシル基を持つ反応性単量体としてはマ
レイン酸、無水マレイン酸、フマル酸、アクリル酸、メ
タクリル酸エステル等が使用可能で、この中でも無水マ
レイン酸の使用が望ましい。Maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid ester and the like can be used as the reactive monomer having a carboxyl group or a carboxyl anhydride group used for the production of the component (C). The use of maleic anhydride is preferred.
【0023】変性エチレン−プロピレン系ゴムの製造
時、有機過酸化物を2部を越えて混合すると、架橋反応
によりゴム性質が減少して衝撃補強効果が低下し、反応
性単量体の量が1.5部未満、および6部を越える場合
においても耐衝撃効果が減少する。又、構成成分(C)
の変性エチレン−プロピレン系ゴムの割合が樹脂組成物
全体に対して5〜35wt%の範囲を外れると、衝撃補
強効果が不足する。When more than 2 parts of the organic peroxide is mixed during the production of the modified ethylene-propylene rubber, the rubber property is reduced by the cross-linking reaction, the impact-reinforcing effect is lowered, and the amount of the reactive monomer is reduced. If it is less than 1.5 parts or exceeds 6 parts, the impact resistance effect is reduced. Also, the constituent component (C)
If the ratio of the modified ethylene-propylene rubber of 3 is out of the range of 5 to 35 wt% with respect to the entire resin composition, the impact reinforcing effect is insufficient.
【0024】構成成分(C)の製造方法は、EPR又は
EPDMに有機過酸化物、反応性単量体を配合した後、
バンバリミキサ又はベント式押出機を使用して溶融混練
状態でEPR又はEPDMを変性させて製造する。The component (C) is produced by mixing EPR or EPDM with an organic peroxide or a reactive monomer,
It is manufactured by modifying EPR or EPDM in a melt-kneaded state using a Banbury mixer or a vent type extruder.
【0025】本組成物の構成成分(D)であるビニル系
グラフト重合体の主鎖成分(a)はメチルメタクリル
酸、ブチルメタクリル酸、ブチルアクリル酸等のエステ
ル化合物又は酢酸ビニルの様なカルボキシル基を含有す
る単量体とエチレン、プロピレン等のオレフィン系単量
体との共重合体であるが、その中でエチレン/酢酸ビニ
ル、エチレン/エチルアクリレート等を好適に使用する
ことができる。The main chain component (a) of the vinyl-based graft polymer which is the constituent component (D) of the present composition is an ester compound such as methylmethacrylic acid, butylmethacrylic acid or butylacrylic acid, or a carboxyl group such as vinyl acetate. Among these, it is a copolymer of a monomer containing ethylene with an olefinic monomer such as ethylene or propylene, and among them, ethylene / vinyl acetate, ethylene / ethyl acrylate and the like can be preferably used.
【0026】側鎖成分(b)としては、スチレン系単量
体とシアン化ビニル系単量体の共重合体等が使用される
が、その中でスチレンとアクリロニトリルの共重合体の
使用が最も望ましい。主鎖(a)成分中、カルボキシル
基を含有する単量体の量が5wt%未満、または40w
t%を越える場合には衝撃補強効果が劣り、又、構成成
分(D)中の主鎖(a)の量が40wt%未満、または
90wt%を越える場合にも衝撃補強効果が劣る。As the side chain component (b), a copolymer of a styrene-based monomer and a vinyl cyanide-based monomer or the like is used. Among them, a styrene-acrylonitrile copolymer is most used. desirable. In the main chain component (a), the amount of the monomer containing a carboxyl group is less than 5 wt% or 40 w
When it exceeds t%, the impact reinforcing effect is poor, and when the amount of the main chain (a) in the constituent component (D) is less than 40 wt% or exceeds 90 wt%, the impact reinforcing effect is poor.
【0027】構成成分(D)の割合が組成物全体に対し
て10wt%を越える場合には引張強度等の機械的物性
が低下する。When the ratio of the constituent component (D) exceeds 10 wt% with respect to the entire composition, mechanical properties such as tensile strength are deteriorated.
【0028】本樹脂組成物の製造方法は特別に制限され
ない。例えば、(A)ビニル系共重合体と、(B)CP
E、(C)変性エチレン−プロピレン系ゴム及び(D)
ビニル系グラフト重合体を混合した後、バンバリミキサ
又はベント式押出機を使用して通常の方法で製造するこ
とができる。The method for producing the present resin composition is not particularly limited. For example, (A) vinyl-based copolymer and (B) CP
E, (C) modified ethylene-propylene rubber and (D)
After the vinyl-based graft polymer is mixed, it can be produced by a usual method using a Banbury mixer or a vent type extruder.
【0029】上記の如く本発明の熱可塑性樹脂組成物
は、従来の提示されたものとは異なり、カルボキシル基
を持つ反応性モノマーで変性したエチレン−プロピレン
系ゴムを添加使用することによって、機械的物性が向上
し、表面層状剥離現象が減少し、耐候性が向上する。こ
れは変性エチレン−プロピレン系ゴムとCPE及び他の
成分の間での好ましい相互作用に起因すると推測され
る。As described above, the thermoplastic resin composition of the present invention differs from the conventional ones by mechanically adding an ethylene-propylene rubber modified with a reactive monomer having a carboxyl group. The physical properties are improved, the surface delamination phenomenon is reduced, and the weather resistance is improved. It is speculated that this is due to the favorable interaction between the modified ethylene-propylene rubber and CPE and other components.
【0030】図1、図2及び図3から分かるように変性
エチレン−プロピレン系ゴムを使用する時、EPR、又
はEPDMを使用する場合に比べてゴム粒子の分散程度
が良好になり、ゴム粒子とマトリックス樹脂との相互作
用が増加している。As can be seen from FIGS. 1, 2 and 3, when the modified ethylene-propylene rubber is used, the degree of dispersion of the rubber particles becomes better as compared with the case where EPR or EPDM is used. Interaction with matrix resin is increasing.
【0031】上記の熱可塑性樹脂組成物には必要に応じ
て難燃剤、滑剤、熱安定剤、光安定剤、顔料等を添加し
て使用することができる。If necessary, flame retardants, lubricants, heat stabilizers, light stabilizers, pigments, etc. may be added to the above thermoplastic resin composition for use.
【0032】[0032]
【実施例】本発明の実施例を以下に説明する。EXAMPLES Examples of the present invention will be described below.
【0033】製造実施例 (1)重合体(A) (A)−1:反応器にスチレン730g、アクリロニト
リル270g、t−ドデシルメルカプタン5gを入れて
懸濁重合して製造した。 Production Example (1) Polymer (A) (A) -1: Produced by suspension polymerization by adding 730 g of styrene, 270 g of acrylonitrile and 5 g of t-dodecyl mercaptan to a reactor.
【0034】(A)−2:反応器にα−メチルスチレン
710g、アクリロニトリル290g、t−ドデシルメ
ルカプタン5gを入れて乳化重合して製造した。(A) -2: 710 g of α-methylstyrene, 290 g of acrylonitrile and 5 g of t-dodecyl mercaptan were placed in a reactor and emulsion-polymerized.
【0035】(2)重合体(B) 次のCPE3種を使用した。(2) Polymer (B) The following 3 types of CPE were used.
【0036】(B)−1:TYRIN3615(米国ダ
ウケミカル製品CPE、塩素含量36wt%) (B)−2:DAISOLAC J−230(日本大正
製品CPE、塩素含量30wt%) (B)−3:DAISOLAC MR104(日本大正
製品CPE、塩素含量40wt%) (3)重合体(C) EPR(韓国琴湖イーピーゴム社製KEP020P)又
はEPDM(韓国琴湖イーピーゴム社製KEP570
P)と無水マレイン酸(以下“MA”と称する)、ジク
ミルパーオキサイド(以下“DCP”と称する)を表1
に示した割合で混合した後、L/D=34、φ=40m
mの二軸押出機を使用してペレット状の重合体(C)−
1〜(C)−6を製造した。この時、シリンダーの温度
は150〜190℃、スクリュー回転数は400rpm
に設定した。(B) -1: TYRIN 3615 (CPE of Dow Chemical Product of the United States, chlorine content 36 wt%) (B) -2: DAISOLAC J-230 (CPE of Nihon Taisho product, chlorine content 30 wt%) (B) -3: DAISOLAC MR104 (Nippon Taisho CPE, chlorine content 40 wt%) (3) Polymer (C) EPR (KEP020P manufactured by Kotoko EP Rubber, Korea) or EPDM (KEP570 manufactured by Koto EP Rubber, Korea)
P), maleic anhydride (hereinafter referred to as “MA”), and dicumyl peroxide (hereinafter referred to as “DCP”) are shown in Table 1.
After mixing at the ratio shown in, L / D = 34, φ = 40 m
pelletized polymer (C) -using a twin screw extruder
1- (C) -6 were manufactured. At this time, the cylinder temperature is 150 to 190 ° C, and the screw rotation speed is 400 rpm.
Set to.
【0037】[0037]
【表1】 [Table 1]
【0038】上記の結果の中で、グラフト化されたMA
の含量は、製造されたペレットをトルエン/メタノール
溶液で再沈澱させた後、赤外線分光器でMAの特性バン
ド(1785cm−1)の面積を測定して算出した。上
記の結果中、ゲル含量はソクスレー蒸溜法(8時間蒸
溜)により残留ゲルの重さを測定して算出した。Among the above results, the grafted MA
The content of was calculated by reprecipitating the produced pellet with a toluene / methanol solution and then measuring the area of the characteristic band (1785 cm −1 ) of MA with an infrared spectroscope. Among the above results, the gel content was calculated by measuring the weight of the residual gel by the Soxhlet distillation method (distillation for 8 hours).
【0039】(4)重合体(D) 日本油脂社製のモディパーA6400((D)−1)、
A5400((D)−2)を使用し、各成分の記号と組
成は下記の表2のようである。(4) Polymer (D) MODIPER A6400 ((D) -1) manufactured by NOF CORPORATION,
A5400 ((D) -2) was used, and the symbols and compositions of each component are as shown in Table 2 below.
【0040】[0040]
【表2】 [Table 2]
【0041】実施例1〜5及び比較例1〜4 実施例1〜5及び比較例1〜4は、重合体(A)、
(B)、(C)を下記の表4のように一定の比率で混合
後、L/D=34、φ=40mmの二軸押出機を使用し
てペレットを製造した後、このペレットを射出成形して
機械的物性及び耐候性測定試験片を製作し、下記の表3
の如き試験方法及び試験条件で測定した。その結果を表
4に示す。 Examples 1 to 5 and Comparative Examples 1 to 4 Examples 1 to 5 and Comparative Examples 1 to 4 are polymers (A),
After mixing (B) and (C) at a constant ratio as shown in Table 4 below, pellets were produced using a twin-screw extruder with L / D = 34 and φ = 40 mm, and then the pellets were injected. Molded to prepare a test piece for measuring mechanical properties and weather resistance, and shown in Table 3 below.
The test method and test conditions as described above were used for measurement. The results are shown in Table 4.
【0042】この時のシリンダー温度は180〜210
℃に設定した。The cylinder temperature at this time is 180 to 210.
It was set to ° C.
【0043】[0043]
【表3】 [Table 3]
【0044】[0044]
【表4】 [Table 4]
【0045】上記の表4の結果でMA変性EPR又はE
PDMを使用すると、EPR、EPDMを使用した場合
より引張強度、衝撃強度等の機械的物性が向上する程度
が大きく、表面剥離性が良好になるのが分かる。但し、
MA含量が1.5部未満、または6部を越える変性EP
Rを使用する場合(比較例1、2)にはかえって伸率や
衝撃強度が減少し表面剥離の改善効果も不足する。Based on the results in Table 4 above, MA modified EPR or E
It can be seen that when PDM is used, mechanical properties such as tensile strength and impact strength are improved to a greater extent than when EPR and EPDM are used, and the surface releasability is improved. However,
Modified EP with MA content less than 1.5 parts or more than 6 parts
When R is used (Comparative Examples 1 and 2), the elongation and impact strength are rather reduced, and the effect of improving surface peeling is also insufficient.
【0046】実施例6、7及び比較例5〜12 実施例6、7及び比較例5〜12では、CPE及び変性
EPRの含量による機械的物性と耐候性の変化を測定し
た。その結果を下記の表5に示す。押出、射出及び特性
測定方法は実施例1〜5と同じである。 Examples 6 and 7 and Comparative Examples 5 to 12 In Examples 6 and 7 and Comparative Examples 5 to 12, changes in mechanical properties and weather resistance depending on the contents of CPE and modified EPR were measured. The results are shown in Table 5 below. Extrusion, injection and property measurement methods are the same as in Examples 1-5.
【0047】[0047]
【表5】 [Table 5]
【0048】上記の表5の結果から分かるように、CP
E変性EPRを単独に使用した場合より混用使用した場
合に引張強度や伸率、衝撃強度が大きく向上される。重
合体(B)(CPE)の含量が10wt%未満以下であ
る比較例5の場合、衝撃強度が非常に低いし、CPEが
過剰に使用された比較例6の場合、引張強度及び耐候性
が非常に低下することになる。As can be seen from the results in Table 5 above, CP
When the E-modified EPR is used alone, the tensile strength, the elongation and the impact strength are improved more than when the E-modified EPR is used alone. In the case of Comparative Example 5 in which the content of the polymer (B) (CPE) is less than 10 wt% or less, the impact strength is very low, and in the case of Comparative Example 6 in which CPE is used excessively, the tensile strength and the weather resistance are It will be very low.
【0049】上記の実施例6、7及び比較例5〜10に
は酸化防止剤と共に光安定剤が0.2重量部ずつ添加さ
れている。In Examples 6 and 7 and Comparative Examples 5 to 10, 0.2 parts by weight of a light stabilizer was added together with an antioxidant.
【0050】実施例8〜13及び比較例13〜15 実施例8〜13及び比較例13〜15では、衝撃補強材
としてビニル系グラフト重合剤を添加して物性特性及び
表面剥離性を測定した。その結果は、下記の表6のよう
になった。押出、射出及び物性測定方法は上記の実施例
1〜5と同じである。 Examples 8 to 13 and Comparative Examples 13 to 15 In Examples 8 to 13 and Comparative Examples 13 to 15, a vinyl-based graft polymerizing agent was added as an impact reinforcing material, and the physical properties and surface releasability were measured. The results are shown in Table 6 below. The extrusion, injection and physical property measurement methods are the same as those in Examples 1 to 5 above.
【0051】[0051]
【表6】 [Table 6]
【0052】上記の表6の結果から、EVAを添加した
場合と比較した時、重合体(D)−1、(D)−2を添
加した場合の方が良好な物性を現わし、又、(D)−2
よりも(D)−1の物性改良効果がより良好であり、
(D)−1、(D)−2とも10wt%を越えると物性
改良効果が減少することが分かる。From the results shown in Table 6 above, when compared with the case where EVA was added, the cases where the polymers (D) -1 and (D) -2 were added exhibited better physical properties, and (D) -2
Than (D) -1 is more effective in improving the physical properties,
It can be seen that the effect of improving the physical properties decreases when both (D) -1 and (D) -2 exceed 10 wt%.
【0053】[0053]
【発明の効果】以上の実施例及び比較例により確認した
ように、本発明の組成物においては重合工程の省略が可
能でありながら優秀な機械的物性と耐候性を持つと同時
に表面の層状剥離性が大きく改善される。As confirmed by the above Examples and Comparative Examples, in the composition of the present invention, it is possible to omit the polymerization step, while having excellent mechanical properties and weather resistance, and at the same time, delaminate the surface. Sex is greatly improved.
【図1】本発明の構成成分中のエチレンープロピレン系
ゴムとして、エチレンープロピレンゴム(EPR)を使
用した場合(比較例3)の破断面の形態を現す2000
倍倍率の電子顕微鏡写真(SEM)であり、FIG. 1 shows the morphology of a fracture surface when ethylene-propylene rubber (EPR) is used as the ethylene-propylene rubber in the constituent components of the present invention (Comparative Example 3).
It is an electron micrograph (SEM) of a magnification,
【図2】本発明の構成成分中のエチレンープロピレン系
ゴムとしてエチレンープロピレン−ジエンゴム(EPD
M)を同一な条件に使用した場合(比較例4)の破断面
の形態を現した2000倍倍率電子顕微鏡写真(SE
M)であり、FIG. 2 is an ethylene-propylene-diene rubber (EPD) as an ethylene-propylene rubber in the constituent components of the present invention.
(M) was used under the same conditions (Comparative Example 4), the morphology of the fracture surface was observed at a magnification of 2000 times (SE).
M),
【図3】本発明の構成成分中のエチレンープロピレン系
ゴムとして変性エチレンープロピレンゴムを同一な条件
で使用した場合(実施例2)の破断面の形態を現した2
000倍倍率の電子顕微鏡写真(SEM)である。FIG. 3 shows the morphology of a fracture surface when modified ethylene-propylene rubber is used as the ethylene-propylene rubber in the constituents of the present invention under the same conditions (Example 2).
It is an electron micrograph (SEM) at a magnification of 000.
Claims (8)
%、 (B)塩素化ポリエチレン 10〜35wt%、 (C)変性エチレン−プロピレン系ゴム 5〜35wt
%及び (D)ビニル系グラフト共重合体 0〜10wt% にて構成されることを特徴とする熱可塑性樹脂組成物。1. A styrene-based polymer (A) 50 to 85 wt.
%, (B) chlorinated polyethylene 10 to 35 wt%, (C) modified ethylene-propylene rubber 5 to 35 wt%
% And (D) vinyl-based graft copolymer 0 to 10 wt%, a thermoplastic resin composition.
含量が20〜40wt%であることを特徴とする請求項
1の熱可塑性樹脂組成物。2. The thermoplastic resin composition according to claim 1, wherein the component (B) chlorinated polyethylene has a chlorine content of 20 to 40 wt%.
系ゴムは、エチレン−プロピレンゴム100部に対して
有機過酸化物0〜2部及びカルボキシル基又は無水カル
ボキシル基を持つ反応性単量体1.5〜6部を溶融混練
して製造されることを特徴とする請求項1の熱可塑性樹
脂組成物。3. The component (C) modified ethylene-propylene rubber is a reactive monomer 1 having 0 to 2 parts of an organic peroxide and a carboxyl group or an anhydrous carboxyl group with respect to 100 parts of ethylene-propylene rubber. The thermoplastic resin composition according to claim 1, which is produced by melt-kneading 5 to 6 parts.
系ゴムは、エチレン−プロピレン−ジエンゴム100部
に対して有機過酸化物0〜2部及びカルボキシル基又は
無水カルボキシル基を持つ反応性単量体1.5〜6部を
溶融混練して製造されることを特徴とする請求項1の熱
可塑性樹脂組成物。4. The component (C) modified ethylene-propylene rubber is a reactive monomer having 0 to 2 parts of an organic peroxide and 100 parts of an ethylene-propylene-diene rubber and a carboxyl group or an anhydrous carboxyl group. The thermoplastic resin composition according to claim 1, which is produced by melt-kneading 1.5 to 6 parts.
は、主鎖成分としてエステル化合物を持つことを特徴と
する請求項1の熱可塑性樹脂組成物。5. The thermoplastic resin composition according to claim 1, wherein the component (D) vinyl-based graft copolymer has an ester compound as a main chain component.
は、主鎖成分としてカルボキシル基を含有する単量体と
オレフィン系単量体の共重合体を持つことを特徴とする
請求項1の熱可塑性樹脂組成物。6. The vinyl graft copolymer as the component (D) has a copolymer of a monomer having a carboxyl group and an olefin monomer as a main chain component. The thermoplastic resin composition.
は、側鎖成分としてスチレン系単量体とシアン化ビニル
系単量体の共重合体を持つことを特徴とする請求項1の
熱可塑性樹脂組成物。7. The component (D) vinyl-based graft copolymer has a copolymer of a styrene-based monomer and a vinyl cyanide-based monomer as a side chain component. Thermoplastic resin composition.
基を持つ反応性単量体は、マレイン酸、無水マレイン
酸、フマル酸、アクリル酸、メタクリル酸エステルの中
で選択された一種であることを特徴とする請求項3また
は4に記載の熱可塑性樹脂組成物。8. The reactive monomer having a carboxyl group or a carboxyl anhydride group is one selected from maleic acid, maleic anhydride, fumaric acid, acrylic acid, and methacrylic acid ester. The thermoplastic resin composition according to claim 3 or 4.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1993-2127 | 1993-02-16 | ||
KR1019930002127A KR960007315B1 (en) | 1993-02-16 | 1993-02-16 | Excellent weather-resistance having thermoplastic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06248135A true JPH06248135A (en) | 1994-09-06 |
JP2852485B2 JP2852485B2 (en) | 1999-02-03 |
Family
ID=19350855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5331226A Expired - Lifetime JP2852485B2 (en) | 1993-02-16 | 1993-12-27 | Thermoplastic resin composition with excellent weather resistance |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2852485B2 (en) |
KR (1) | KR960007315B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101805425A (en) * | 2010-03-30 | 2010-08-18 | 扬州市政兴树脂有限公司 | Solid thermoplastic acrylic resin special for PP (polypropylene) and preparation method thereof |
CN116082784A (en) * | 2023-04-10 | 2023-05-09 | 佛山市塑聚新材料科技有限公司 | Flame-retardant composite material and preparation method and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100765696B1 (en) * | 2005-09-28 | 2007-10-11 | 주식회사 엘지화학 | Halogen free flame retardant thermoplastic resin composition using organic peroxides |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62104808A (en) * | 1985-10-31 | 1987-05-15 | Japan Synthetic Rubber Co Ltd | Production of modified ethylene-alpha-olefin copolymer composition |
JPS62181358A (en) * | 1986-02-04 | 1987-08-08 | Mitsubishi Chem Ind Ltd | Asphalt modifier for surface layer reproducing construction method in asphalt pavement |
JPS641765A (en) * | 1987-06-23 | 1989-01-06 | Calp Corp | Composite resin composition of high specific gravity |
-
1993
- 1993-02-16 KR KR1019930002127A patent/KR960007315B1/en not_active IP Right Cessation
- 1993-12-27 JP JP5331226A patent/JP2852485B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62104808A (en) * | 1985-10-31 | 1987-05-15 | Japan Synthetic Rubber Co Ltd | Production of modified ethylene-alpha-olefin copolymer composition |
JPS62181358A (en) * | 1986-02-04 | 1987-08-08 | Mitsubishi Chem Ind Ltd | Asphalt modifier for surface layer reproducing construction method in asphalt pavement |
JPS641765A (en) * | 1987-06-23 | 1989-01-06 | Calp Corp | Composite resin composition of high specific gravity |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101805425A (en) * | 2010-03-30 | 2010-08-18 | 扬州市政兴树脂有限公司 | Solid thermoplastic acrylic resin special for PP (polypropylene) and preparation method thereof |
CN116082784A (en) * | 2023-04-10 | 2023-05-09 | 佛山市塑聚新材料科技有限公司 | Flame-retardant composite material and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
KR940019796A (en) | 1994-09-15 |
JP2852485B2 (en) | 1999-02-03 |
KR960007315B1 (en) | 1996-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3596126B2 (en) | Method for producing rubber-reinforced thermoplastic resin | |
AU596833B2 (en) | Blend comprising EPDM graft terpolymer and acrylate rubber | |
JP2852485B2 (en) | Thermoplastic resin composition with excellent weather resistance | |
EP0190334A1 (en) | Polyblends of a copolymer of a vinyl aromatic monomer and an unsaturated dicarboxylic acid anhydride with a methyl methacrylate homopolymer or copolymer | |
JP3472308B2 (en) | Impact resistant methacrylic resin | |
JPS6013837A (en) | Treated product of impact-resistant resin | |
JP3389627B2 (en) | Graft copolymer and method for producing the same | |
KR0182360B1 (en) | Thermoplastic resin composition | |
JPS62205149A (en) | Weather-resistant resin composition having improved impact resistance and rib strength | |
JPH0657049A (en) | Compatibilizing agent and thermoplastic resin composition blended with the same | |
JPS6397655A (en) | Non-rigid polypropylene resin composition | |
JPH07252329A (en) | Heat-resistant methacrylic resin | |
US5834558A (en) | Weather resistant theromplastic resin composition | |
JPH0291147A (en) | Blend comprising large amount of epdm graft terpolymer and relatively small amount of acrylate rubber | |
JPH0665444A (en) | Modifying agent composition and thermoplastic resin composition using the same | |
JPS60177071A (en) | Matte thermoplastic resin composition | |
JPH02178346A (en) | Thermoplastic resin composition | |
JPH0665426A (en) | Resin composition | |
JPH0657051A (en) | Thermoplastic resin composition | |
JPS58145716A (en) | Graft polymer composition | |
JPS62132953A (en) | Weather-resistant resin composition having improved chemical resistance and rib strength | |
JPH0370762A (en) | Resin composition | |
JPH0657048A (en) | Thermoplastic resin composition | |
JPH06179753A (en) | Production of thermoplastic resin | |
JPH0621199B2 (en) | Thermoplastic resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071120 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081120 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091120 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091120 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101120 Year of fee payment: 12 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111120 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111120 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121120 Year of fee payment: 14 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121120 Year of fee payment: 14 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131120 Year of fee payment: 15 |
|
EXPY | Cancellation because of completion of term |