JP3141751B2 - Rubber-modified styrenic resin composition and molded article thereof - Google Patents
Rubber-modified styrenic resin composition and molded article thereofInfo
- Publication number
- JP3141751B2 JP3141751B2 JP07254857A JP25485795A JP3141751B2 JP 3141751 B2 JP3141751 B2 JP 3141751B2 JP 07254857 A JP07254857 A JP 07254857A JP 25485795 A JP25485795 A JP 25485795A JP 3141751 B2 JP3141751 B2 JP 3141751B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- resin composition
- component
- weight
- ethylene
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、面衝撃強度に優れ
たゴム変性スチレン系樹脂組成物及びその成形品に関す
るものであり、更に詳しくは面衝撃強度が大幅に向上し
ていると同時に、他の物性については低下していないゴ
ム変性スチレン系樹脂組成物及びその成形品に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-modified styrenic resin composition having excellent surface impact strength and a molded product thereof. More particularly, the present invention relates to a rubber composition having improved surface impact strength. The present invention relates to a rubber-modified styrenic resin composition whose physical properties have not been reduced and a molded article thereof.
【０００２】[0002]
【従来の技術】ＯＡ機器、家電製品などの用途分野で
は、成形時の加工性、加工製品の仕上がり寸法精度、引
っ張り及び曲げなどの機械的物性、耐熱性などの諸物性
のバランスが良いことが必要とされるが、特に外装材料
ということから衝撃強度の向上が一段と求められてい
る。かかる要求は近年ますます高水準に及んでいる。ま
た、包装材料として用いる際も高水準の衝撃強度と外観
が求められる。緩衝材として用いる場合には、具備すべ
き必須の特性の一つとして、衝撃吸収性に優れることが
あげられる。ところが、ゴム変性スチレン系樹脂組成物
は、上記のすべての要求を十分に満足するという観点に
鑑み、必ずしも十分であるとはいい難い物であった。ゴ
ム変性スチレン系樹脂の耐衝撃強度を向上させる技術と
しては、特公平３−４１１０４号公報にあるように有機
ポリシロキサン及びエチレン−不飽和カルボン酸エステ
ル共重合体を特定量添加する方法が知られている。しか
し、有機ポリシロキサンが必須成分であり、添加の手間
と費用がかかった。2. Description of the Related Art In application fields such as OA equipment and home electric appliances, it is necessary to have a good balance of workability at the time of molding, finished dimensional accuracy of the processed product, mechanical properties such as tension and bending, and physical properties such as heat resistance. Although it is required, improvement of impact strength is further demanded especially because of the exterior material. Such demands have reached an increasingly high level in recent years. Also, when used as a packaging material, a high level of impact strength and appearance are required. When used as a cushioning material, one of the essential properties to be provided is that it has excellent shock absorption. However, the rubber-modified styrenic resin composition is not necessarily satisfactory in view of sufficiently satisfying all the above requirements. As a technique for improving the impact resistance of a rubber-modified styrenic resin, there is known a method of adding a specific amount of an organic polysiloxane and an ethylene-unsaturated carboxylic acid ester copolymer as disclosed in JP-B-3-41104. ing. However, the organic polysiloxane is an essential component, and it has been troublesome and expensive to add.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
問題点を解決し、比較的少量のブレンド添加で衝撃強度
に優れ、かつ成形性他の物性などにも優れ、外装材、包
装材、発泡成形体に要求される性能に優れたゴム変性ス
チレン系樹脂組成物及びその成形品を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to provide an excellent impact strength by adding a relatively small amount of a blend, and to be excellent in moldability and other physical properties. Another object of the present invention is to provide a rubber-modified styrenic resin composition excellent in performance required for a foamed molded article and a molded article thereof.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意検討の結果、本発明に到達したもの
である。すなわち、本発明のうち一の発明は、下記
（Ａ）成分１００重量部及び（Ｂ）成分を０．１〜１０
重量部含有するゴム変性スチレン系樹脂組成物に係るも
のである。 （Ａ）：軟質成分粒子を５〜３５重量％含有し、該軟質
成分粒子の平均粒子径が０．５〜２．５μｍであり、該
軟質成分粒子の膨潤度が３〜３０であり、該軟質成分粒
子がサラミ構造を有するゴム変性スチレン系樹脂 （Ｂ）：溶解性パラメータ（ＳＰ）が８．４５〜８．７
０であり、かつポリマー中に芳香族ビニル化合物単位を
含有しないポリマー（ただし、エチレン−不飽和カルボ
ン酸エステル共重合体を除く）また、本発明のうち、他
の発明は、上記のゴム変性スチレン系樹脂組成物を用い
た射出成形品、押し出し成形品又は発泡成形品に係るも
のである。以下、詳細に説明する。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and have reached the present invention. That is, one invention of the present invention comprises 100 parts by weight of the following component (A) and 0.1 to 10 parts of the component (B).
It relates to a rubber-modified styrenic resin composition containing parts by weight. (A): a soft component particles contained 5 to 35% by weight, an average particle diameter of the soft quality component particles 0.5 to 2.5 .mu.m, swelling degree of soft matter component particles is 3 to 30, wherein Soft ingredient grains
Rubber-modified styrene-based resin having a salami structure as a child (B): solubility parameter (SP) is 8.45 to 8.7
0, and a polymer containing no aromatic vinyl compound unit in the polymer (except for the ethylene-unsaturated carboxylic acid ester copolymer). The present invention relates to an injection molded article, an extrusion molded article, or a foam molded article using the resin composition. The details will be described below.
【０００５】[0005]
【発明の実施の形態】本発明で用いる（Ａ）ゴム変性ス
チレン系樹脂は、ゴム状重合体の存在下、一種もしくは
二種以上のスチレン系単量体、又は一種もしくは二種以
上のスチレン系単量体及びこれと共重合可能な化合物と
を重合して得られるゴム変性スチレン系樹脂である。BEST MODE FOR CARRYING OUT THE INVENTION The rubber-modified styrenic resin (A) used in the present invention comprises one or more styrene-based monomers, or one or more styrene-based monomers in the presence of a rubbery polymer. A rubber-modified styrenic resin obtained by polymerizing a monomer and a compound copolymerizable therewith.
【０００６】本発明で用いられる（Ａ）ゴム変性スチレ
ン系樹脂の原料であるスチレン系単量体としては、例え
ばスチレン、α−メチルスチレンなどのα−アルキル置
換スチレン、ｐ−メチルスチレンなどの核置換アルキル
スチレンなどがあげられる。また、スチレン系単量体と
共重合可能な化合物としては、例えばアクリロニトリ
ル、メタクリロニトリル、メタクリル酸、メチルメタク
リレートなどのビニルモノマー、さらには無水マレイン
酸、マレイミド、核置換マレイミドなどがあげられる。
また、ゴム状重合体としては、例えばポリブタジエン、
スチレン−ブタジエン共重合体類、エチレン−プロピレ
ン−非共役ジエンの三元共重合体類等が使用されるが、
その中でもポリブタジエン及びスチレン−ブタジエン共
重合体類が好ましい。ポリブタジエンとしては、シス含
有率の高いハイシスポリブタジエン、シス含有率の低い
ローシスポリブタジエン共に用いることができる。The styrene monomer which is a raw material of the rubber-modified styrene resin (A) used in the present invention includes, for example, nuclei such as α-alkyl-substituted styrene such as styrene and α-methylstyrene, and p-methylstyrene. And substituted alkylstyrene. Examples of the compound copolymerizable with the styrene monomer include vinyl monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, and methyl methacrylate, as well as maleic anhydride, maleimide, and a nucleus-substituted maleimide.
Further, as the rubbery polymer, for example, polybutadiene,
Styrene-butadiene copolymers, ethylene-propylene-non-conjugated diene terpolymers and the like are used,
Among them, polybutadiene and styrene-butadiene copolymers are preferred. As polybutadiene, both high cis polybutadiene having a high cis content and low cis polybutadiene having a low cis content can be used.
【０００７】本発明の（Ａ）ゴム変性スチレン系樹脂中
の軟質成分粒子の含有量は５〜３５重量％である。その
含有量が５重量％未満では衝撃強度の改良が十分でな
く、３５重量％より多くなると衝撃強度以外の物性、例
えば剛性、耐熱性が低下するので好ましくない。なお、
本発明において（Ａ）ゴム変性スチレン系樹脂中の軟質
成分粒子の含有量は、次の方法により測定される。すな
わち、試料であるゴム変性スチレン系樹脂約０．５ｇを
秤量（重量：Ｗ1 ）採取し、該試料を室温（２３℃程
度）においてメチルエチルケトン／メタノール混合溶媒
（体積比１０／１）５０ｍｌに溶解させる。次に、該溶
解時の不溶分を遠心分離により単離し、該不溶分を乾燥
してその重量（Ｗ2 ）を測定する。ゴム変性スチレン系
樹脂中の軟質成分粒子の含有量は（Ｗ2 ／Ｗ1 ）×１０
０（％）により求められる。また該軟質成分粒子の平均
粒子径は０．１〜２．５μｍである。これが０．１μｍ
未満では面衝撃強度の改良が十分でなく、２．５μｍよ
り大きいと光沢などの外観が低下して好ましくない。な
お、ここで平均粒子径とは次のように定義される。すな
わち、ゴム変性スチレン系樹脂の超薄切片を作成し、そ
の透過型電子顕微鏡写真を撮り、写真中の軟質成分粒子
径を測定し、下式によって計算されるものである。The content of the soft component particles in the rubber-modified styrene resin (A) of the present invention is 5 to 35% by weight. If the content is less than 5% by weight, the impact strength is not sufficiently improved, and if it exceeds 35% by weight, physical properties other than the impact strength, for example, rigidity and heat resistance are undesirably reduced. In addition,
In the present invention, the content of the soft component particles in the rubber-modified styrene resin (A) is measured by the following method. Specifically, about 0.5 g of a rubber-modified styrene resin as a sample was weighed (weight: W 1 ), and the sample was dissolved in 50 ml of a methyl ethyl ketone / methanol mixed solvent (volume ratio: 10/1) at room temperature (about 23 ° C.). Let it. Next, the insoluble matter at the time of the dissolution is isolated by centrifugation, the insoluble matter is dried, and its weight (W 2 ) is measured. The content of the soft component particles in the rubber-modified styrene resin is (W 2 / W 1 ) × 10
It is determined by 0 (%). The average particle diameter of the soft component particles is 0.1 to 2.5 μm. This is 0.1 μm
If it is less than 2.5 μm, the surface impact strength is not sufficiently improved, and if it is more than 2.5 μm, the appearance such as gloss decreases, which is not preferable. Here, the average particle diameter is defined as follows. That is, an ultra-thin section of a rubber-modified styrene resin is prepared, a transmission electron micrograph thereof is taken, the particle diameter of the soft component in the photograph is measured, and it is calculated by the following equation.
【０００８】[0008]
【数１】平均粒子径＝ΣｎｉＤｉ／Σｎｉ ここでｎｉは粒子径Ｄｉの粒子数である。[Equation 1] Average particle size = ΣniDi / Σni where ni is the number of particles having a particle size Di.
【０００９】本発明において、（Ａ）ゴム変性スチレン
系樹脂中の軟質成分粒子は、ゴム状重合体からなる連続
相中に複数のスチレン系樹脂の小粒子が分散して存在す
る、いわゆるサラミ構造を有するもである。なお、軟質
成分粒子の構造の観察は、上記の平均粒子径の測定と同
様、透過型電子顕微鏡を用いて行われる。本発明の
（Ａ）ゴム変性スチレン系樹脂中の軟質成分粒子の膨潤
度は３〜３０、好ましくは８〜２０である。膨潤度が３
未満であればその樹脂を含む組成物は衝撃強度に劣り、
３０より大であると剛性や外観に劣り、実用上好ましく
ない。なお、本発明の（Ａ）ゴム変性スチレン系樹脂の
軟質成分粒子の膨潤度は次の方法により求められる。す
なわち、試料であるゴム変性スチレン系樹脂約１．０ｇ
を５０ｍｌのトルエンに室温で溶解し、一昼夜放置す
る。得られたトルエン溶液を遠心分離機（１００００ｒ
ｐｍ×３０分間）にかけ、不溶分を分離する。上澄み液
を捨て、不溶分を秤量し、その重量をａとする。次に、
該不溶分を真空乾燥機にて乾燥（７０℃×３時間）し、
乾燥後の重量をｂとする。膨潤度は（ａ−ｂ）／ｂによ
り求められる。本発明において用いられる（Ａ）ゴム変
性スチレン系樹脂の製造方法は、塊状重合法又は塊状・
懸濁二段重合法が用いられる。そして、重合反応時のゴ
ム状重合体濃度、攪拌速度、温度などを調整することに
より、本発明で必要とされる、軟質成分粒子の含有量、
該粒子の平均粒子径、膨潤度等の条件を充足するゴム変
性スチレン系樹脂を得ることができる。[0009] In the present invention, (A) the soft component particles children in the rubber-modified styrenic resin, the small particles of a plurality of the styrene resin in a continuous phase consisting of rubber-like polymer is present in a dispersed, so-called salami It also has a structure. The observation of the structure of the soft component particles is performed using a transmission electron microscope as in the measurement of the average particle diameter described above. The swelling degree of the soft component particles in the rubber-modified styrenic resin (A) of the present invention is 3 to 30, preferably 8 to 20. 3 degree of swelling
If less than the composition containing the resin is inferior in impact strength,
If it is larger than 30, the rigidity and appearance are inferior, which is not practically preferable. The degree of swelling of the soft component particles of the rubber-modified styrene resin (A) of the present invention can be determined by the following method. That is, about 1.0 g of a rubber-modified styrene resin as a sample
Is dissolved in 50 ml of toluene at room temperature and left overnight. The obtained toluene solution is centrifuged (10000 r).
pm × 30 minutes) to separate insoluble matter. The supernatant is discarded, the insoluble matter is weighed, and the weight is defined as a. next,
The insolubles were dried with a vacuum dryer (70 ° C. × 3 hours),
Let b be the weight after drying. The degree of swelling is determined by (ab) / b. The method for producing the rubber-modified styrenic resin (A) used in the present invention may be a bulk polymerization method or a bulk polymerization method.
A suspension two-stage polymerization method is used. Then, by adjusting the rubber-like polymer concentration during the polymerization reaction, stirring speed, temperature and the like, the content of the soft component particles required in the present invention,
A rubber-modified styrenic resin that satisfies the conditions such as the average particle size and swelling degree of the particles can be obtained.
【００１０】次に本発明では組成物中に（Ｂ）溶解性パ
ラメータ（ＳＰ）が８．４５〜８．７０であり、かつ芳
香族ビニル化合物単位を含有しないポリマーでエチレン
−不飽和カルボン酸エステル共重合体を除く物を（Ａ）
ゴム変性スチレン系樹脂１００重量部に対して０．１〜
１０重量部含有するが、含有量が０．１重量部未満では
衝撃強度改良の効果が十分でなく、１０重量部より多い
と耐熱性等の他の物性が低下し、好ましくない。なお、
本発明の組成物中の（Ｂ）成分の含有量は、組成物の超
薄切片を作成し、その透過型電子顕微鏡写真を取り、写
真中に占める（Ｂ）成分の面積割合から換算して求める
ことができる。その他に、ＮＭＲやＩＲ等の分光器を用
いてその吸収ピークから求める方法、溶媒により分別す
る方法などを用いることができる。また、本発明の
（Ｂ）成分の溶解性パラメータ（ＳＰ）は８．４５〜
８．７０であり、８．４５より小さいか又は８．７０よ
り大きいと衝撃強度改良の効果が十分でない。なお、こ
こで溶解性パラメータとはＨｉｌｄｅｂｒａｎｄ−Ｓｃ
ａｔｃｈａｒｄの理論によって分子間の引き合う力を定
義したものである。詳しい解説は高分子科学の一般的な
教科書、たとえば”ポリマーブレンド、秋本三郎ら、
（株）シーエムシー、第４刷、１２５〜１４４頁（１９
９１年）”等に記載されている。しかし、この溶解性パ
ラメータは粘度法や膨潤度法等の実験により求める方法
及び分子構造から計算により求める方法等があり、方法
により値が若干異なる。そこで、Ｓｍａｌｌによって提
案された分子構造から計算により求める方法をここでは
用いた。この方法及び理論は”ジャーナル・オブ・アプ
ライド・ケミストリー（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐ
ｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）、３巻、７１〜８０頁
（１９５３年）”に詳しく記載されている。これにより
溶解性パラメータは次式を用いて算出した。Next, in the present invention, a polymer having (B) a solubility parameter (SP) of 8.45 to 8.70 and containing no aromatic vinyl compound unit in the composition is an ethylene-unsaturated carboxylic acid ester. (A) excluding the copolymer
0.1 to 100 parts by weight of rubber-modified styrenic resin
Although the content is 10 parts by weight, if the content is less than 0.1 part by weight, the effect of improving the impact strength is not sufficient, and if the content is more than 10 parts by weight, other physical properties such as heat resistance deteriorate, which is not preferable. In addition,
The content of the component (B) in the composition of the present invention is determined by preparing an ultrathin section of the composition, taking a transmission electron micrograph, and converting the area ratio of the component (B) in the photograph. You can ask. In addition, a method of obtaining from the absorption peak using a spectroscope such as NMR or IR, a method of performing fractionation using a solvent, and the like can be used. The solubility parameter (SP) of the component (B) of the present invention is 8.45 to
When it is 8.70, and is smaller than 8.45 or larger than 8.70, the effect of improving the impact strength is not sufficient. Here, the solubility parameter is Hildebrand-Sc.
Attraction's theory defines the attractive force between molecules. Detailed explanations are given in general textbooks of polymer science such as "Polymer Blend, Saburo Akimoto et al.
CMC Co., Ltd., 4th printing, pages 125-144 (19
However, the solubility parameter includes a method obtained by experiments such as a viscosity method and a degree of swelling method and a method obtained by calculation from a molecular structure, and the value is slightly different depending on the method. The method used by calculation from the molecular structure proposed by Small, Inc., was used here.This method and theory is described in the Journal of Applied Chemistry (Journal of Applied Chemistry).
Lied Chemistry, Vol. 3, pages 71-80 (1953) ", whereby the solubility parameter was calculated using the following equation.
【００１１】[0011]
【数２】 Ｆｉは分子を構成する原子又は原子団、結合型など構成
グループのモル吸引力、Ｖはモル容積、ρは密度、Ｍは
分子量を示し、高分子の場合は繰り返し単位（つまりモ
ノマー単位）の分子量を示す。Ｆｉの値は、上記２つの
文献に記載されているＳｍａｌｌの値を用いた。共重合
体のρ、ΣＦｉ又はＭについては、共重合体を構成する
モノマー単位の各単独重合体のρ、ΣＦｉ又はＭの数値
にモノマー単位のモル分率を乗じたものの和を計算して
用いた。また、本発明で用いられる（Ｂ）成分はポリマ
ー中に芳香族ビニル化合物単位を含有しないポリマーで
ある。ポリマー中に芳香族ビニル化合物単位を有するポ
リマーを用いた組成物は衝撃強度が劣る。芳香族ビニル
化合物としては、たとえばスチレン、α−メチルスチレ
ンなどのα−アルキル置換スチレン、ｐ−メチルスチレ
ンなどの核置換アルキルスチレンなどがあげられる。ま
た、本発明で用いられる（Ｂ）成分はエチレン−不飽和
カルボン酸エステル共重合体を含有しないが、エチレン
−不飽和カルボン酸エステル共重合体の例としては、エ
チレン−メチルメタクリレート共重合体、エチレン−エ
チルメタクリレート共重合体、エチレン−エチルアクリ
レート共重合体、エチレン−メチルアクリレート共重合
体等があげられる。また、本発明で用いられる（Ｂ）成
分の溶融性パラメーター（ＳＰ）が８．４５〜８．７０
であるポリマーとしては、不飽和カルボン酸又は酢酸ビ
ニルのうち１つ以上のビニルモノマーとエチレンとの共
重合体があげられる。その例としてはエチレン−不飽和
カルボン酸共重合体、エチレン−酢酸ビニル共重合体、
エチレン−不飽和カルボン酸−酢酸ビニル３元共重合
体、エチレンと２種類以上の不飽和カルボン酸とからな
る多元共重合体等があげられる。(Equation 2) Fi is the molar attractive force of the constituent groups such as atoms or atomic groups constituting the molecule, bond type, etc., V is the molar volume, ρ is the density, M is the molecular weight. In the case of a polymer, the molecular weight of a repeating unit (that is, monomer unit) Is shown. As the value of Fi, the value of Small described in the above two documents was used. For ρ, ΔFi or M of the copolymer, the sum of the values of ρ, ΔFi or M of each homopolymer of the monomer units constituting the copolymer multiplied by the mole fraction of the monomer units is used. Was. The component (B) used in the present invention is a polymer containing no aromatic vinyl compound unit in the polymer. A composition using a polymer having an aromatic vinyl compound unit in the polymer has poor impact strength. Examples of the aromatic vinyl compound include α-alkyl-substituted styrenes such as styrene and α-methylstyrene, and nuclear-substituted alkylstyrenes such as p-methylstyrene. Although the component (B) used in the present invention does not contain an ethylene-unsaturated carboxylic acid ester copolymer, examples of the ethylene-unsaturated carboxylic acid ester copolymer include an ethylene-methyl methacrylate copolymer, Examples include an ethylene-ethyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-methyl acrylate copolymer. Further, the meltability parameter (SP) of the component (B) used in the present invention is 8.45 to 8.70.
Examples of the polymer are copolymers of ethylene with one or more vinyl monomers of unsaturated carboxylic acid or vinyl acetate. Examples thereof are ethylene-unsaturated carboxylic acid copolymer, ethylene-vinyl acetate copolymer,
Examples include an ethylene-unsaturated carboxylic acid-vinyl acetate terpolymer, and a multi-component copolymer composed of ethylene and two or more kinds of unsaturated carboxylic acids.
【００１２】不飽和カルボン酸の具体的な例としてはア
クリル酸、メタクリル酸があげられる。本発明で用いら
れる不飽和カルボン酸又は酢酸ビニルのうち１つ以上の
ビニルモノマーとエチレンとの共重合体の好ましい例と
してはエチレン−アクリル酸共重合体、エチレン−メタ
クリル酸共重合体、エチレン−酢酸ビニル、エチレン−
アクリル酸−酢酸ビニル共重合体、エチレン−メタクリ
ル酸−酢酸ビニル共重合体等があげられる。不飽和カル
ボン酸単位又は酢酸ビニル単位の共重合体中の比率は５
〜６０重量％が好ましい。また共重合体中の上記ビニル
モノマーとエチレンの結合様式（たとえばランダム、ブ
ロック、交互）等については何等限定されない。また該
共重合体のメルトフローレート（ＪＩＳ Ｋ７２１０に
準拠、温度１９０℃、荷重２．１６ｋｇｆによる）は特
に限定されないが、１〜５００ｇ／１０分程度が好まし
い。Specific examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. Preferred examples of the copolymer of ethylene and one or more vinyl monomers of the unsaturated carboxylic acid or vinyl acetate used in the present invention include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene- Vinyl acetate, ethylene-
Acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer and the like can be mentioned. The ratio of unsaturated carboxylic acid units or vinyl acetate units in the copolymer is 5
~ 60% by weight is preferred. Further, there is no particular limitation on the bonding mode (for example, random, block, alternate) between the vinyl monomer and ethylene in the copolymer. The melt flow rate of the copolymer (according to JIS K7210, at a temperature of 190 ° C. and a load of 2.16 kgf) is not particularly limited, but is preferably about 1 to 500 g / 10 minutes.
【００１３】本発明のゴム変性スチレン系樹脂組成物を
得るには、各成分の所定量を、ヘンシェルミキサー、タ
ンブラーなどの混合装置でドライブレンドするか、一軸
又は二軸のスクリュー押し出し機、バンバリーミキサー
等の混練機を用い、１８０〜２６０℃の温度で十分に加
熱混練し、その後造粒すればよい。なお、必要に応じ
て、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、帯電
防止剤、ミネラルオイル、シリコンオイルなどの添加剤
を使用することができる。これらの添加剤は、上記ドラ
イブレンド又は混練時に添加してもよいが、ゴム変性ス
チレン系樹脂を重合により合成する際に重合工程で添加
してもよい。In order to obtain the rubber-modified styrenic resin composition of the present invention, a predetermined amount of each component is dry-blended with a mixing device such as a Henschel mixer or a tumbler, or a single-screw or twin-screw extruder, a Banbury mixer The mixture may be sufficiently heated and kneaded at a temperature of 180 to 260 ° C. using a kneader such as the above, followed by granulation. Note that additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, mineral oil, and silicone oil can be used as needed. These additives may be added at the time of the above-mentioned dry blending or kneading, but may be added at the polymerization step when the rubber-modified styrene resin is synthesized by polymerization.
【００１４】本発明のゴム変性スチレン系樹脂組成物を
用いた射出成形品は、一般に使用されている射出成形機
を用いて得ることができる。An injection molded article using the rubber-modified styrene resin composition of the present invention can be obtained by using a commonly used injection molding machine.
【００１５】本発明のゴム変性スチレン系樹脂組成物を
用いた押し出し成形品は、一般に使用されている押し出
し成形機を用いて得ることができる。本発明のゴム変性
スチレン系樹脂組成物を押し出し成形して押し出し成形
品とする方法としては、特に制限はないが、たとえば押
し出し機にて溶融した後、Ｔ−ダイから押し出しする方
法、押し出し機よりシート状に押し出しした後、テンタ
ー方式あるいはインフレーション方式により２軸延伸す
る方法などあげることができる。An extruded product using the rubber-modified styrenic resin composition of the present invention can be obtained by using a generally used extruder. The method for extruding the rubber-modified styrenic resin composition of the present invention to obtain an extruded product is not particularly limited. For example, a method of extruding from a T-die after melting with an extruder, After extruding into a sheet, biaxial stretching may be performed by a tenter method or an inflation method.
【００１６】本発明のゴム変性スチレン系樹脂組成物を
発泡して発泡体とする方法としては、特に制限はない
が、たとえば分散型発泡剤とゴム変性スチレン系樹脂組
成物を押し出し機で溶融混練し、発泡させる方法；ゴム
変性スチレン系樹脂組成物を押し出し機で溶融させ蒸発
型発泡剤をシリンダー途中から直接圧入し、混練、発泡
させる方法；ゴム変性スチレン系樹脂組成物からなる小
ペレット又はビーズを押し出し機又は水系懸濁液中で蒸
発型発泡剤を含浸させ、その含浸ペレット又はビーズを
水蒸気で発泡させる方法；などがあげられる。The method of foaming the rubber-modified styrenic resin composition of the present invention to form a foam is not particularly limited. For example, a dispersion-type foaming agent and the rubber-modified styrenic resin composition are melt-kneaded by an extruder. A method in which a rubber-modified styrene-based resin composition is melted by an extruder and an evaporating foaming agent is directly press-fitted from the middle of a cylinder, kneaded and foamed; small pellets or beads made of the rubber-modified styrene-based resin composition Impregnated with an evaporating foaming agent in an extruder or an aqueous suspension, and foaming the impregnated pellets or beads with steam.
【００１７】本発明のゴム変性スチレン系樹脂組成物の
用途は、その特徴を生かした射出成形加工品分野、押し
出しシート加工品分野及び発泡成形加工品分野が適して
いる。すなわち、弱電機器、事務機器、電話機、ＯＡ機
器等の外装材や食品容器など包装材などが具体的な用途
としてあげられる。また、ガラス製品や各種の精密機器
製品に加わる外部からの衝撃を吸収し、該製品を保護す
るいわゆる緩衝材として、樹脂組成物を発泡して得られ
る発泡体を用いることができる。The rubber-modified styrenic resin composition of the present invention is suitably used in the fields of injection-molded products, extruded sheet products, and foam-formed products, taking advantage of its features. That is, specific applications include exterior materials such as light electrical appliances, office equipment, telephones, and OA appliances, and packaging materials such as food containers. In addition, a foam obtained by foaming a resin composition can be used as a so-called cushioning material that absorbs external impact applied to glass products and various precision equipment products and protects the products.
【００１８】[0018]
【実施例】以下実施例により本発明を詳しく説明する
が、本発明はこれら実施例により何等限定をされる物で
はない。測定及び評価方法は以下の通りである。なお、
下記以外の項目については、前記の説明の通り行った。 （１）曲げ弾性率（剛性） ＪＩＳ Ｋ７２０３に準拠して測定した。 （２）ビカット軟化点（耐熱性） ＪＩＳ Ｋ７２０６、Ｂ法に準拠して測定した。 （３）落錘インパクト 厚さ２ｍｍの平板を射出成形し、東洋精機製作所の「落
錘型グラフィックインパクトテスター」を用いて、高さ
８０ｃｍより質量７．５ｋｇの重錘を試験片平面上へ自
然落下させ、重錘下部に設けてあるストライカによって
試験片を完全破壊又は貫通させる。この際の亀裂発生に
要したエネルギー値を求めた。なお、成形機は東芝ＩＳ
−１５０Ｅを用い、金型温度４０℃、サンプル形状１５
０×９０×２ｍｍとした。 （４）アイゾット衝撃強度 ＪＩＳ Ｋ７１１０に準拠して測定した。なお、試験片
厚み３ｍｍ、ノッチ付き、測定温度２３℃とした。 （５）表面光沢（表面外観） 厚さ２ｍｍの平板を射出成形し、その中央部をＪＩＳ
Ｋ７１０５の４５度鏡面光沢度測定法の規格に準拠して
測定した。なお、成形機は東芝ＩＳ−１５０Ｅを用い、
金型温度４０℃、サンプル形状１５０×９０×２ｍｍと
した。また、樹脂シートについても、同様に測定した。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The measurement and evaluation methods are as follows. In addition,
Items other than those described below were performed as described above. (1) Flexural modulus (rigidity) Measured according to JIS K7203. (2) Vicat softening point (heat resistance) Measured according to JIS K7206, B method. (3) Drop Weight Impact A flat plate having a thickness of 2 mm is injection molded, and a weight of 7.5 kg in mass from a height of 80 cm is naturally placed on the plane of the test piece using a “drop weight type graphic impact tester” manufactured by Toyo Seiki Seisaku-sho, Ltd. The specimen is dropped, and the test piece is completely broken or penetrated by a striker provided below the weight. The energy value required for crack generation at this time was determined. The molding machine is Toshiba IS
Using -150E, mold temperature 40 ° C, sample shape 15
It was set to 0 × 90 × 2 mm. (4) Izod impact strength Measured according to JIS K7110. The test piece had a thickness of 3 mm, a notch, and a measurement temperature of 23 ° C. (5) Surface gloss (surface appearance) A flat plate with a thickness of 2 mm is injection molded, and the central part is JIS
It was measured according to the standard of K7105 45 degree specular gloss measurement method. The molding machine used was Toshiba IS-150E,
The mold temperature was 40 ° C. and the sample shape was 150 × 90 × 2 mm. In addition, the measurement was similarly performed for the resin sheet.
【００１９】実施例１〜３及び比較例１〜６ 表１及び２に示した成分を４０ｍｍφ押し出し機にて２
２０℃で溶融させ、混練、造粒してペレットを得た。得
られたペレットをテストピースもしくは平板に射出成形
し、評価を行った。なお、用いた（Ａ）ゴム変性スチレ
ン系樹脂は、連続塊状重合法により、次のようにして合
成した。 Ａ１：攪拌型重合槽に、スチレン９２．５重量％、ポリ
ブタジエン４重量％及びエチルベンゼン３．５重量％か
らなる混合液を送液し、温度１４０℃、攪拌速度４５ｒ
ｐｍの条件にて転化率２１％まで重合させた。続いて、
得られた混合液を満液型重合槽に移送しそこで転化率７
０％まで重合させ、次いで内容物を２４０℃の脱気槽に
移送しそこで揮発成分を除去し、次いで得られた重合物
を溶融押し出し機及びペレタイザーに通し、ペレット状
のゴム変性スチレン系樹脂を得た。 Ａ２：攪拌型重合槽に、スチレン８８重量％、ポリブタ
ジエン７重量％、エチルベンゼン３．５重量％及びミネ
ラルオイル１．５重量％からなる混合液を送液し、温度
１４０℃、攪拌速度４０ｒｐｍの条件にて転化率１８％
まで重合させた。続いて、得られた混合液を満液型重合
槽に移送しそこで転化率７０％まで重合させ、次いで内
容物を２４０℃の脱気槽に移送しそこで揮発成分を除去
し、次いで得られた重合物を溶融押し出し機及びペレタ
イザーに通し、ペレット状のゴム変性スチレン系樹脂を
得た。また、用いた（Ｂ）成分はそれぞれ次のとおりで
ある。 Ｂ１：エチレン−酢酸ビニル共重合体（住友化学工業
製、商品名スミテートＲＢ−１１、酢酸ビニル含量４１
重量％、メルトフローレート６０ｇ／１０分）、 Ｂ２：ポリプロピレン（住友化学工業製、商品名ノーブ
レンＡＤ５７１（メルトフローレート０．２ｇ／１０
分）、 Ｂ３：ポリエチレン（住友化学工業製、商品名スミカセ
ンα ＦＺ１０３−０（メルトフローレート０．９ｇ／
１０分）、 Ｂ４：ポリメチルメタクリレート（住友化学工業製、商
品名スミペックス−ＢＭＨＧ、メルトフローレート０．
５ｇ／１０分）、 Ｂ５：スチレン−アクリロニトリル共重合体（三菱モン
サント化成製、商品名サンレックスＳＡＮ−Ｃ、アクリ
ロニトリル含量３３重量％、メルトフローレート０．５
ｇ／１０分）。 メルトフローレートはＪＩＳ Ｋ７２１０に従い、温度
１９０℃、荷重２．１６ｋｇｆで測定した。また、これ
らの（Ｂ）成分の溶解性パラメータ（ＳＰ）を表３に示
した。シリコンオイルとしては、東レシリコーン製シリ
コンオイル、ＳＨ２００（１０００センチストークス）
を用いた。Examples 1 to 3 and Comparative Examples 1 to 6 The components shown in Tables 1 and 2 were extruded by a 40 mmφ extruder.
The mixture was melted at 20 ° C., kneaded and granulated to obtain pellets. The obtained pellet was injection molded into a test piece or a flat plate and evaluated. The rubber-modified styrenic resin (A) used was synthesized by a continuous bulk polymerization method as follows. A1: A mixed solution composed of 92.5% by weight of styrene, 4% by weight of polybutadiene and 3.5% by weight of ethylbenzene was sent to a stirring-type polymerization tank at a temperature of 140 ° C. and a stirring speed of 45 r.
Under a condition of pm, polymerization was carried out up to a conversion rate of 21%. continue,
The obtained mixture was transferred to a full-type polymerization tank, where the conversion rate was 7%.
0%, then the contents are transferred to a degassing tank at 240 ° C. to remove volatile components therefrom, and then the obtained polymer is passed through a melt extruder and a pelletizer to pelletize rubber-modified styrene resin. Obtained. A2: A mixed solution composed of 88% by weight of styrene, 7% by weight of polybutadiene, 3.5% by weight of ethylbenzene and 1.5% by weight of mineral oil was sent to a stirring-type polymerization tank at a temperature of 140 ° C. and a stirring speed of 40 rpm. 18% conversion rate
The polymerization was carried out until: Subsequently, the obtained mixed solution was transferred to a full polymerization tank where polymerization was performed to a conversion rate of 70%, and then the contents were transferred to a deaeration tank at 240 ° C. to remove volatile components, and then obtained. The polymer was passed through a melt extruder and a pelletizer to obtain a pelletized rubber-modified styrene resin. The components (B) used are as follows. B1: Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumitate RB-11, vinyl acetate content 41)
B2: Polypropylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Noblen AD571 (melt flow rate: 0.2 g / 10 min.)
B3: Polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen α FZ103-0 (melt flow rate 0.9 g /
B4: Polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMIPEX-BMHG, melt flow rate: 0.1%).
B5: Styrene-acrylonitrile copolymer (manufactured by Mitsubishi Monsanto Kasei, trade name Sunlex SAN-C, acrylonitrile content 33% by weight, melt flow rate 0.5)
g / 10 minutes). The melt flow rate was measured at a temperature of 190 ° C. and a load of 2.16 kgf according to JIS K7210. Table 3 shows the solubility parameter (SP) of the component (B). As silicone oil, Toray silicone silicone oil, SH200 (1000 centistokes)
Was used.
【００２０】結果から次のことがわかる。表１におい
て、本発明の実施例１は衝撃強度に優れる。一方、
（Ｂ）成分を含有しない比較例１は衝撃強度に劣る。Ｓ
Ｐが規定範囲外のポリマーを（Ｂ）成分として含有する
比較例２〜５は衝撃強度に劣る。ポリマー中に芳香族ビ
ニル化合物単位を含有するポリマーを（Ｂ）成分として
含む比較例５は衝撃強度に劣る。表２において、本発明
の実施例２及び３は衝撃強度に優れる。一方、（Ｂ）成
分を含有しない比較例６は衝撃強度に劣る。The following can be seen from the results. In Table 1, Example 1 of the present invention is excellent in impact strength. on the other hand,
Comparative Example 1 containing no component (B) is inferior in impact strength. S
Comparative Examples 2 to 5, in which P contains a polymer out of the specified range as the component (B), are inferior in impact strength. Comparative Example 5, which contains a polymer containing an aromatic vinyl compound unit in the polymer as the component (B), is inferior in impact strength. In Table 2, Examples 2 and 3 of the present invention are excellent in impact strength. On the other hand, Comparative Example 6 containing no component (B) is inferior in impact strength.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】表１及び２の共通の注を次に示す。 ＊１ （Ａ）：ゴム変性スチレン系樹脂（スチレン系単
量体としてはスチレンを用いた。） ＊２ （Ｂ）：表３に示したポリマー ＊３ （Ｃ）：シリコンオイル ＊４ ＳＡＬ：サラミ構造The following notes are common to Tables 1 and 2. * 1 (A): Rubber-modified styrene resin (styrene was used as the styrene monomer) * 2 (B): Polymer shown in Table 3 * 3 (C): Silicon oil * 4 SAL: Salami Construction
【００２４】[0024]
【表３】 [Table 3]
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 23:08） Ｂ２９Ｋ 96:02 (56)参考文献 特開 平３−220255（ＪＰ，Ａ) 特開 平８−151500（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 51/04 B29C 39/02 B29C 45/00 B29C 47/00 C08L 23/08 B29K 96:02 Continuation of the front page (51) Int.Cl. 7 Identification code FI C08L 23:08) B29K 96:02 (56) References JP-A-3-220255 (JP, A) JP-A 8-151500 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08L 51/04 B29C 39/02 B29C 45/00 B29C 47/00 C08L 23/08 B29K 96:02
Claims (6)
（Ｂ）成分を０．１〜１０重量部含有するゴム変性スチ
レン系樹脂組成物。 （Ａ）：軟質成分粒子を５〜３５重量％含有し、該軟質
成分粒子の平均粒子径が０．５〜２．５μｍであり、該
軟質成分粒子の膨潤度が３〜３０であり、該軟質成分粒
子がサラミ構造を有するゴム変性スチレン系樹脂 （Ｂ）：溶解性パラメータ（ＳＰ）が８．４５〜８．７
０であり、かつポリマー中に芳香族ビニル化合物単位を
含有しないポリマー（ただし、エチレン−不飽和カルボ
ン酸エステル共重合体を除く）(1) 100 parts by weight of the following component (A):
A rubber-modified styrenic resin composition containing 0.1 to 10 parts by weight of the component (B). (A): a soft component particles contained 5 to 35% by weight, an average particle diameter of the soft quality component particles 0.5 to 2.5 .mu.m, swelling degree of soft matter component particles is 3 to 30, wherein Soft ingredient grains
Rubber-modified styrene-based resin having a salami structure as a child (B): solubility parameter (SP) is 8.45 to 8.7
0 and a polymer containing no aromatic vinyl compound unit in the polymer (excluding an ethylene-unsaturated carboxylic acid ester copolymer)
ニルのうち１つ以上のビニルモノマーとエチレンから成
る共重合体である請求項１記載の樹脂組成物。2. The resin composition according to claim 1, wherein the component (B) is a copolymer comprising at least one vinyl monomer of unsaturated carboxylic acid or vinyl acetate and ethylene.
体である請求項１記載の樹脂組成物。3. The resin composition according to claim 1, wherein the component (B) is an ethylene-vinyl acetate copolymer.
ゴム変性スチレン樹脂組成物を用いた射出成形品。4. An injection-molded article using the rubber-modified styrene resin composition according to claim 2 or 3.
ム変性スチレン樹脂組成物を用いた押し出し成形品。5. An extruded product using the rubber-modified styrene resin composition according to claim 1, 2 or 3.
ム変性スチレン樹脂組成物を用いた発泡成形品。6. A foam molded article using the rubber-modified styrene resin composition according to claim 1, 2 or 3.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07254857A JP3141751B2 (en) | 1995-10-02 | 1995-10-02 | Rubber-modified styrenic resin composition and molded article thereof |
| KR1019960043753A KR100449059B1 (en) | 1995-10-02 | 1996-10-02 | Rubber modified syrene-based resin composition and formed article thereof |
| CN96114442A CN1105142C (en) | 1995-10-02 | 1996-10-02 | Rubber modified styron composition and article formed thereof |
| KR1019960046379A KR970021181A (en) | 1995-10-02 | 1996-10-16 | Laminates comprising a nonwoven fabric blended with thermoplastic films and methods for making the same |
| KR1019960048061A KR100291764B1 (en) | 1995-10-02 | 1996-10-24 | Resin composition tablet for mold cleaning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07254857A JP3141751B2 (en) | 1995-10-02 | 1995-10-02 | Rubber-modified styrenic resin composition and molded article thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0995587A JPH0995587A (en) | 1997-04-08 |
| JP3141751B2 true JP3141751B2 (en) | 2001-03-05 |
Family
ID=17270814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07254857A Expired - Fee Related JP3141751B2 (en) | 1995-10-02 | 1995-10-02 | Rubber-modified styrenic resin composition and molded article thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3141751B2 (en) |
| KR (1) | KR100449059B1 (en) |
| CN (1) | CN1105142C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3141791B2 (en) * | 1996-10-01 | 2001-03-05 | 住友化学工業株式会社 | Rubber-modified styrenic resin composition and molded article thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767644A (en) * | 1980-10-14 | 1982-04-24 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JPS60177071A (en) * | 1984-02-21 | 1985-09-11 | Sumitomo Naugatuck Co Ltd | Matte thermoplastic resin composition |
| JPS62143957A (en) * | 1985-12-18 | 1987-06-27 | Sumitomo Chem Co Ltd | Styrenic resin composition |
| JPH0742383B2 (en) * | 1990-01-26 | 1995-05-10 | 出光石油化学株式会社 | Thermoplastic resin composition |
| US5388572A (en) * | 1993-10-26 | 1995-02-14 | Tenax Corporation (A Connecticut Corp.) | Dry powder medicament inhalator having an inhalation-activated piston to aerosolize dose and deliver same |
-
1995
- 1995-10-02 JP JP07254857A patent/JP3141751B2/en not_active Expired - Fee Related
-
1996
- 1996-10-02 CN CN96114442A patent/CN1105142C/en not_active Expired - Fee Related
- 1996-10-02 KR KR1019960043753A patent/KR100449059B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0995587A (en) | 1997-04-08 |
| KR100449059B1 (en) | 2005-01-15 |
| KR970021190A (en) | 1997-05-28 |
| CN1105142C (en) | 2003-04-09 |
| CN1156737A (en) | 1997-08-13 |
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