JP2546936B2 - Styrene resin composition - Google Patents
Styrene resin compositionInfo
- Publication number
- JP2546936B2 JP2546936B2 JP3144650A JP14465091A JP2546936B2 JP 2546936 B2 JP2546936 B2 JP 2546936B2 JP 3144650 A JP3144650 A JP 3144650A JP 14465091 A JP14465091 A JP 14465091A JP 2546936 B2 JP2546936 B2 JP 2546936B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- resin
- terpene
- styrene resin
- resin composition
- 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 - Lifetime
Links
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- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はスチレン系樹脂中にテル
ペン系水素添加樹脂を含有するスチレン系樹脂に関する
ものである。更に詳細には、耐熱性、成形性、強度、剛
性のバランスに優れたスチレン系樹脂組成物を提供する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene resin containing a terpene hydrogenated resin in the styrene resin. More specifically, the present invention provides a styrene resin composition having an excellent balance of heat resistance, moldability, strength and rigidity.
【０００２】[0002]
【従来の技術及び課題】スチレン系樹脂は、透明性、成
形性、剛性に優れた樹脂であるところから、以前から、
家庭用品、電化製品等の成形材料として広く用いられて
きた。最近、原材料の高騰から、他の高品位樹脂を比較
的コストの安い樹脂に切り替える方向にあり、スチレン
系樹脂に対する需要は一層増大の傾向にある。これとと
もに、利用分野を拡大するため、及び製品の生産性を高
めるために、スチレン系樹脂の強度、成形性の改良の要
望が高まっている。2. Description of the Related Art Styrenic resins are resins that are excellent in transparency, moldability, and rigidity.
It has been widely used as a molding material for household products and electric appliances. Recently, due to soaring raw materials, there is a tendency to switch to other low-grade resins from other high-grade resins, and the demand for styrene-based resins is increasing. At the same time, in order to expand the fields of use and increase the productivity of products, there is an increasing demand for improvements in the strength and moldability of styrene resins.
【０００３】これまで、強度の高いスチレン系樹脂を得
るには、平均分子量を大きくすればよいことは公知の事
実である。しかし、平均分子量を大きくすることによ
り、成形性の低下は免れない。又、成形性を補う為に可
塑剤の使用も公知の方法であるが、可塑剤を添加するこ
とにより、耐熱性、剛性が低下し、強度も低下する。製
品の生産性を高める為高速成形が望まれている分野もあ
り、分子量を高めること、及び可塑剤の使用による強度
向上、成形性向上だけでは対応出来ない。It is a known fact that the average molecular weight should be increased to obtain a styrene resin having high strength. However, if the average molecular weight is increased, the moldability is unavoidable. Although the use of a plasticizer to supplement the moldability is a known method, the addition of the plasticizer lowers heat resistance and rigidity, and also lowers strength. In some fields, high-speed molding is desired in order to improve the productivity of products, and it cannot be dealt with only by increasing the molecular weight and improving the strength and moldability by using a plasticizer.
【０００４】又、可塑剤、例えば白色鉱油を添加したス
チレン系樹脂は、成形時に可塑剤がブリードアウトし、
スエッティング現象を呈し生産性の低下、成形品の品質
低下を招くことはよく知られた事実である。Further, in a styrene resin to which a plasticizer such as white mineral oil is added, the plasticizer bleeds out during molding,
It is a well-known fact that it causes a sweating phenomenon, which lowers the productivity and the quality of molded products.
【０００５】[0005]
【課題を解決するための課題】本発明者らはかかる現状
を鑑み、鋭意検討を重ねた結果、テルペン系水素添加樹
脂をスチレン系樹脂に配合することにより、成形性、耐
熱性、強度、剛性バラに優れたスチレン系樹脂組成物が
得られることを見いだし、本発明を完成するに至った。
すなわち、本発明は、スチレン系樹脂とテルペン系水素
添加樹脂とからなるスチレン系樹脂を提供するものであ
る。DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the present situation, and as a result, by combining a terpene-based hydrogenated resin with a styrene-based resin, the moldability, heat resistance, strength and rigidity of the resin have been improved. It was found that a styrene-based resin composition excellent in individuality was obtained, and the present invention was completed.
That is, the present invention provides a styrene resin composed of a styrene resin and a terpene hydrogenated resin.
【０００６】本発明で言うスチレン系樹脂とはスチレ
ン、ｐ−メチルスチレン、ｐ−ｔブチルスチレン、α−
メチルスチレン等のスチレン系単量体単独又は混合物を
重合して得られる樹脂、スチレン系単量体と共重合可能
な単量体例えば、アクリロニトリル、ブチルアクリレー
ト、メチルアクリレート、エチルアクリレート、メチル
メタクリレート、エチルメタクリレート、ブチルメタク
リレート、アクリル酸、メタクリル酸、無水マレイン酸
等とのスチレン共重合体樹脂、ゴム状弾性体を分散粒子
として含有する上記のスチレン系樹脂、スチレン系共重
合体樹脂である。スチレン系樹脂の分子量は特に限定さ
れるものではないが１５００００〜５０００００好まし
くは１８００００〜４５００００の範囲のスチレン系樹
脂が好適に用いられる。この範囲より分子量が小さい
と、テルペン系水素添加樹脂を配合しても強度向上の効
果は小さく、この範囲より高い分子量を有するスチレン
系樹脂は成形性が悪くなり、又、スチレン系樹脂そのも
のの生産性が低下し好ましくない。The styrene resin referred to in the present invention is styrene, p-methylstyrene, ptbutylstyrene, α-
Resin obtained by polymerizing a styrene monomer such as methylstyrene alone or a mixture, a monomer copolymerizable with a styrene monomer, for example, acrylonitrile, butyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl A styrene copolymer resin with methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, etc., and the above styrene resin and styrene copolymer resin containing a rubber-like elastic material as dispersed particles. The molecular weight of the styrene resin is not particularly limited, but a styrene resin having a molecular weight in the range of 150,000 to 500000, preferably 180,000 to 450,000 is preferably used. If the molecular weight is smaller than this range, the effect of improving the strength is small even if a terpene-based hydrogenated resin is added, the styrene-based resin having a molecular weight higher than this range has poor moldability, and the production of the styrene-based resin itself It is not preferable because the property deteriorates.
【０００７】テルペン系水素添加樹脂は、テルペンと芳
香族炭化水素を共重合し、この共重合体を水素添加した
樹脂である。芳香族炭化水素としてはスチレンが好適に
用いられる。水素添加率は特に制限はないが、１０％以
上、好ましくは２０％以上水素添加したものが好まし
い。１０％未満の場合、高温に曝された時スチレン系樹
脂の色調が悪くなるので好ましくない。The terpene-based hydrogenated resin is a resin obtained by copolymerizing a terpene and an aromatic hydrocarbon and hydrogenating the copolymer. Styrene is preferably used as the aromatic hydrocarbon. The hydrogenation rate is not particularly limited, but hydrogenation of 10% or more, preferably 20% or more is preferable. When it is less than 10%, the color tone of the styrene resin deteriorates when exposed to high temperatures, which is not preferable.
【０００８】テルペン系水素添加樹脂としては、例え
ば、ヤスハラケミカル株式会社のクリアロンＰ、クリア
ロンＭ等が用いることができる。テルペン系水素添加樹
脂の添加方法としては、スチレン系単量体、あるいはス
チレン系単量体と共重合可能な単量体混合物に溶解して
重合するか、スチレン系重合体、あるいはスチレン系共
重合体の重合途中にテルペン系水素添加樹脂を溶融し
て、あるいは溶媒に溶解して添加するか、重合が終了
し、未反応スチレン系単量体等を除去する前、又は後に
テルペン系水素添加樹脂を添加する等の方法を用いるこ
とができる。又、スチレン系樹脂とテルペン系水素添加
樹脂を混合し、押出機あるいは成形機等で混練すること
も可能である。As the terpene-based hydrogenated resin, for example, Clearon P, Clearon M manufactured by Yasuhara Chemical Co., Ltd. can be used. The terpene-based hydrogenated resin may be added by dissolving in a styrene-based monomer or a monomer mixture copolymerizable with the styrene-based monomer and polymerizing, or by adding a styrene-based polymer or a styrene-based copolymer. The terpene-based hydrogenated resin is melted during the polymerization of the combined polymer or added by dissolving it in a solvent, or before or after the polymerization is completed and unreacted styrene-based monomers are removed. Can be used. It is also possible to mix a styrene resin and a terpene hydrogenated resin and knead them with an extruder or a molding machine.
【０００９】スチレン系樹脂とテルペン系樹脂の割合
は、スチレン系樹脂１００重量部当たりテルペン系樹脂
０．５〜３０重量部が好ましい。さらに、好ましくは、
スチレン系樹脂１００重量部当たりテルペン系樹脂０．
５〜３０重量部である。本発明のスチレン系樹脂は、従
来のスチレン系樹脂で多用されていた各種添加剤、例え
ばステアリン酸、ベヘニン酸、それらの金属えん（カル
シューム、マグネシューム、亜鉛等）、エチレンビスス
テアロアミド等を添加することもできる又、酸化防止
剤、着色剤、帯電防止剤等を添加することもできる。The ratio of the styrene resin to the terpene resin is preferably 0.5 to 30 parts by weight per 100 parts by weight of the styrene resin. Further, preferably,
Terpene resin per 100 parts by weight of styrene resin.
5 to 30 parts by weight. The styrene-based resin of the present invention is added with various additives which are frequently used in conventional styrene-based resins, such as stearic acid, behenic acid, their metal noodles (calcium, magnesium, zinc, etc.), ethylenebisstearoamide and the like. It is also possible to add an antioxidant, a coloring agent, an antistatic agent or the like.
【００１０】以下、実施例で更に詳しく説明する。但
し、本発明はこれらの実施例によって何ら限定されるも
のではない。Hereinafter, the present invention will be described in more detail. However, the present invention is not limited to these examples.
【００１１】[0011]
（スチレン系重合体−１）攪拌機付き１０Ｌオートクレ
ーブに、スチレン５ｋｇ、エチルベンゼン０．２ｋｇ、
１，１ビス（ｔ−ブチルパーオキシ）シクロヘキサン
１．２ｇを仕込み、１１０℃で３時間、１３０℃で３時
間、１５０℃で２時間重合後、押出機で未反応スチレ
ン、エチルベンゼンを回収し、スチレン系重合体−１を
得る。(Styrene-based polymer-1) In a 10 L autoclave equipped with a stirrer, 5 kg of styrene, 0.2 kg of ethylbenzene,
1.2 g of 1,1 bis (t-butylperoxy) cyclohexane was charged, and after polymerization at 110 ° C. for 3 hours, 130 ° C. for 3 hours and 150 ° C. for 2 hours, unreacted styrene and ethylbenzene were recovered by an extruder, Styrene polymer-1 is obtained.
【００１２】ＧＰＣで測定した重量平均分子量は３４
６，０００である。 （スチレン系重合体−２）攪拌機付き１０Ｌオートクレ
ーブに、スチレン５ｋｇ、エチルベンゼン０．５ｋｇ、
１，１ビス（ｔ−ブチルパーオキシ）シクロヘキサン１
ｇを仕込み、１２０℃で２時間、１４０℃で２時間、１
５０℃で２時間重合後、押出機で未反応スチレン、エチ
ルベンゼンを回収し、スチレン系重合体−２を得る。The weight average molecular weight measured by GPC is 34.
6,000. (Styrene-based polymer-2) In a 10 L autoclave equipped with a stirrer, 5 kg of styrene, 0.5 kg of ethylbenzene,
1,1 bis (t-butylperoxy) cyclohexane 1
g, charge at 120 ° C for 2 hours, 140 ° C for 2 hours, 1
After polymerization at 50 ° C. for 2 hours, unreacted styrene and ethylbenzene are recovered by an extruder to obtain styrene polymer-2.
【００１３】ＧＰＣで測定した重量平均分子量は２９
７，０００である。The weight average molecular weight measured by GPC is 29.
7,000.
【００１４】[0014]
【実施例−１〜実施例−３】スチレン系重合体−１ １
００重量部当たり、テルペン系水素添加樹脂を２，４，
６重量部混合し、２０ｍｍ二軸押出機で造粒し、スチレ
ン系樹脂を得る。物性を表１に示す。なお、用いたテル
ペン系水素添加樹脂はヤスハラケミカル（株）のクリア
ロンＰである。[Example-1 to Example-3] Styrenic polymer-11
The terpene-based hydrogenated resin is added in an amount of 2, 4 per 100 parts by weight.
6 parts by weight are mixed and granulated with a 20 mm twin-screw extruder to obtain a styrene resin. The physical properties are shown in Table 1. The terpene-based hydrogenated resin used was Clearon P from Yasuhara Chemical Co., Ltd.
【００１５】[0015]
【実施例−４〜実施例−６】スチレン系重合体−２を用
いる以外、実施例−１と同様に操作し、スチレン系樹脂
をえる。物性を表１に示す。[Examples 4 to 6] A styrene resin is obtained by the same procedure as in Example 1 except that the styrene polymer-2 is used. The physical properties are shown in Table 1.
【００１６】[0016]
【比較例−１〜比較例−３】テルペン系水素添加樹脂の
変わりにミネラル・オイルを用いる以外、実施例−１と
同様に操作し、スチレン系樹脂を得る。物性を表１に示
す。[Comparative Example-1 to Comparative Example-3] A styrene-based resin is obtained in the same manner as in Example-1 except that mineral oil is used instead of the terpene-based hydrogenated resin. The physical properties are shown in Table 1.
【００１７】[0017]
【比較例−４〜比較例−６】テルペン系水素添加樹脂の
変わりにミネラル・オイルを用いる以外、実施例−４と
同様に操作し、スチレン系樹脂を得る。物性を表１に示
す。[Comparative Example-4 to Comparative Example-6] A styrene-based resin is obtained in the same manner as in Example-4 except that mineral oil is used instead of the terpene-based hydrogenated resin. The physical properties are shown in Table 1.
【００１８】[0018]
【比較例−７、比較例−８】スチレン系重合体−１、ス
チレン系重合体−２の物性を表１に示す。本発明のスチ
レン系樹脂組成物は、耐熱性、剛性が変化せず、かつ図
１に示したように、ミネラルオイルを添加したスチレン
系樹脂よりも流動性−強度バランスが優れている。[Comparative Example-7, Comparative Example-8] Table 1 shows the physical properties of styrene-based polymer-1 and styrene-based polymer-2. The styrene-based resin composition of the present invention does not change in heat resistance and rigidity, and as shown in FIG. 1, has a better fluidity-strength balance than the styrene-based resin to which mineral oil is added.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【本発明の効果】本発明のスチレン系樹脂組成物は、従
来多用されていた可塑剤を含むスチレン系樹脂組成物よ
りも、著しく成形性、耐熱性、強度、剛性のバランスが
優れている。EFFECTS OF THE INVENTION The styrene resin composition of the present invention is remarkably excellent in balance of moldability, heat resistance, strength and rigidity, as compared with the styrene resin composition containing a plasticizer which has been frequently used.
【図１】本発明のスチレン系樹脂組成物、及び従来のス
チレン系樹脂の流動性と強度の関係を表す。FIG. 1 shows the relationship between fluidity and strength of a styrene resin composition of the present invention and a conventional styrene resin.
Claims (1)
系単量体を共重合し当該共重合体を水素添加した樹脂か
らなり、スチレン系樹脂１００重量部当たり、テルペン
及びスチレン系単量体を共重合し当該共重合体を水素添
加した樹脂０．５〜３０重量部であることを特徴とする
スチレン系樹脂組成物。1. A styrene resin, terpene and styrene.
Is it a resin obtained by copolymerizing a system monomer and hydrogenating the copolymer?
Rannahli, styrene resin per 100 parts by weight of a terpene
And styrene monomer are copolymerized and the copolymer is hydrogenated.
A styrene-based resin composition, wherein the added resin is 0.5 to 30 parts by weight .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3144650A JP2546936B2 (en) | 1991-06-17 | 1991-06-17 | Styrene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3144650A JP2546936B2 (en) | 1991-06-17 | 1991-06-17 | Styrene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04370131A JPH04370131A (en) | 1992-12-22 |
| JP2546936B2 true JP2546936B2 (en) | 1996-10-23 |
Family
ID=15367017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3144650A Expired - Lifetime JP2546936B2 (en) | 1991-06-17 | 1991-06-17 | Styrene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546936B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10040877B2 (en) * | 2012-03-06 | 2018-08-07 | Sumitomo Rubber Industries, Ltd. | Hydrogenated branched conjugated diene copolymer, rubber composition and pneumatic tire |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3621219A1 (en) * | 1986-06-25 | 1988-01-07 | Hoechst Ag | HIGH-SHRINKABLE FILMS BASED ON STYROL BUTADIENE BLOCK COPOLYMERS AND METHOD FOR THE PRODUCTION THEREOF |
-
1991
- 1991-06-17 JP JP3144650A patent/JP2546936B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04370131A (en) | 1992-12-22 |
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