JPH05202250A - New styrene resin composition - Google Patents
New styrene resin compositionInfo
- Publication number
- JPH05202250A JPH05202250A JP34054491A JP34054491A JPH05202250A JP H05202250 A JPH05202250 A JP H05202250A JP 34054491 A JP34054491 A JP 34054491A JP 34054491 A JP34054491 A JP 34054491A JP H05202250 A JPH05202250 A JP H05202250A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- resin
- terpene
- polymer
- 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.)
- Withdrawn
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 113
- 239000011342 resin composition Substances 0.000 title description 11
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 150000003505 terpenes Chemical class 0.000 claims abstract description 22
- 235000007586 terpenes Nutrition 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 12
- -1 acrylic ester Chemical class 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 229920001890 Novodur Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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組成物に
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。FIELD OF THE INVENTION The present invention relates to a styrene resin composition containing a terpene hydrogenated resin in a 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換える方向にあり、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
望が固まっている。2. Description of the Related Art Styrenic resins 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 tends to increase further. At the same time, in order to expand the fields of use and enhance the productivity of products, there is a strong demand for improvement 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えない。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, a decrease in moldability cannot be avoided by increasing the average molecular weight. The use of a plasticizer to supplement the moldability is also a known method, but 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−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。一方、ブチ
ルアクリレ−トのようなコモノマ−を共重合したスチレ
ン系樹脂も公知である。白色鉱油を添加したスチレン系
樹脂の欠点は改善されるが、強度の低下も大きい。ま
た、メチルメタクリレ−トを共重合したスチレン系樹脂
も公知であるが、スチレン系樹脂の特徴である成形性の
良さが犠牲になっている。In addition, a plasticizer, for example, a styrene resin to which white mineral oil is added, has a plasticizer bleeding out during molding,
It is a well-known fact that a sweating phenomenon is caused, resulting in a decrease in productivity and a decrease in quality of a molded product. On the other hand, a styrene resin obtained by copolymerizing a comonomer such as butyl acrylate is also known. Although the drawbacks of the styrenic resin to which the white mineral oil is added are improved, the strength is greatly reduced. Further, a styrene-based resin obtained by copolymerizing methyl methacrylate is also known, but the good moldability, which is a characteristic of the styrene-based resin, is sacrificed.
【０００５】[0005]
【課題を解決するための手段】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、本発明はビニル芳香族炭化水素単量体とアク
リル酸（メタクリル酸）エステル単量体よりなるスチレ
ン系重合体と、テルペン系水素添加樹脂とからなるスチ
レン系樹脂組成物を提供するものである。Means for Solving the Problems The present inventors have made extensive studies in view of the present situation, and as a result, by blending a terpene-based hydrogenated resin with a styrene-based resin, the moldability, heat resistance, strength and rigidity are improved. It was found that a styrene-based resin composition excellent in quality was obtained, and the present invention was completed.
That is, the present invention provides a styrene resin composition comprising a styrene polymer composed of a vinyl aromatic hydrocarbon monomer and an acrylic acid (methacrylic acid) ester monomer, and a terpene hydrogenated resin. is there.
【０００６】本発明で言うビニル芳香族炭化水素とはス
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であり、これ
ら単独、又は混合して使用することができる。アクリル
酸（メタクリル酸）エステルとは、メチルアクリレ−
ト、エチルアクリレ−ト、ブチルアクリレ−ト、シクロ
ヘキシルアクリレ−ト、メチルメタクリレ−ト、エチル
メタクリレ−ト、ブチルメタクリレ−ト、シクロヘキシ
ルメタクリレ−ト等である。これら単独、又は混合して
使用することが出来る。The vinyl aromatic hydrocarbons referred to in the present invention are styrene, p-methylstyrene, ptbutylstyrene,
It is a styrene-based monomer such as α-methylstyrene, and these can be used alone or in combination. Acrylic acid (methacrylic acid) ester is methyl acrylate
, Ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like. These can be used alone or in combination.
【０００７】スチレン系重合体中のアクリル酸（メタク
リル酸）エステル単量体は１〜６０重量部である。好ま
しくは１〜５５重量部である。６０重量部を越える場合
は、テルペン系水素添加樹脂との相溶性が低下し、透明
性が低下するので好ましくない。又、１重量部未満の場
合は、テルペン系水素添加樹脂を添加しても強度向上の
効果が認められない。The amount of acrylic acid (methacrylic acid) ester monomer in the styrene polymer is 1 to 60 parts by weight. It is preferably 1 to 55 parts by weight. If it exceeds 60 parts by weight, the compatibility with the terpene-based hydrogenated resin is lowered and the transparency is lowered, which is not preferable. When the amount is less than 1 part by weight, the effect of improving the strength is not recognized even if the terpene-based hydrogenated resin is added.
【０００８】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 molecular weight of the styrene resin is not particularly limited, but a styrene resin in the range of 150,000 to 500,000, preferably 180,000 to 450,000 is preferably used. When the molecular weight is smaller than this range, the effect of improving the strength is small even if a terpene-based hydrogenated resin is blended, 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 it deteriorates the property.
【０００９】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、α−メ
チルスチレン、ビニルトルエンが好適に用いられる。テ
ルペンとしては、α−ピネン、β−ピネン、リモネン単
独、又は混合物が好適に用いることができる。The terpene-based hydrogenated resin is a resin obtained by copolymerizing a terpene and an aromatic hydrocarbon and hydrogenating the copolymer. Styrene, α-methylstyrene and vinyltoluene are preferably used as the aromatic hydrocarbon. As the terpene, α-pinene, β-pinene, limonene alone or a mixture can be preferably used.
【００１０】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。１００％水素添
加したものは、スチレン系樹脂との相溶性が低下する
為、１００％未満の水素添加率が好ましい。テルペン系
水素添加樹脂の重合度は特に制約は無いが、重合度１０
００以下、好ましくは５００以下、更に好ましくは２０
０以下である。重合度が１０００を越えるとスチレン系
樹脂との相溶性が低下し、透明性が低下するので好まし
くない。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Ｍ等が用いること
ができる。The hydrogenation rate is not particularly limited, but hydrogenation of 10% or more, preferably 20% or more is preferable. If it is less than 10%, the color tone of the styrene resin deteriorates when exposed to high temperatures, which is not preferable. A 100% hydrogenated product has a low compatibility with a styrene resin, so a hydrogenation ratio of less than 100% is preferable. The degree of polymerization of the terpene-based hydrogenated resin is not particularly limited, but the degree of polymerization is 10
00 or less, preferably 500 or less, more preferably 20
It is 0 or less. If the degree of polymerization exceeds 1000, the compatibility with the styrene resin decreases and the transparency decreases, which is not preferable. As the terpene-based hydrogenated resin, for example, Clearon M manufactured by Yasuhara Chemical Co., Ltd. can be used.
【００１１】テルペン系水素添加樹脂の添加部数は特に
限定しないが、スチレン系重合体１００重量部当たり
０．５〜３０重量部が好ましく、より好ましくは、１〜
２５重量部である。０．５重量部未満では本発明の効果
が十分でなく、又、３０重量部を越える場合は効果が飽
和し、スチレン系樹脂組成物のコストアップを招き好ま
しくない。The number of terpene-based hydrogenated resins added is not particularly limited, but is preferably 0.5 to 30 parts by weight, more preferably 1 to 100 parts by weight per 100 parts by weight of the styrene polymer.
25 parts by weight. If it is less than 0.5 part by weight, the effect of the present invention is not sufficient, and if it exceeds 30 parts by weight, the effect is saturated and the cost of the styrene resin composition is increased, which is not preferable.
【００１２】スチレン系重合体は、公知の方法、溶液重
合、塊状重合、乳化重合により得ることが出来る。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、あるいはアクリル酸（メタクリル酸）エステル単
量体に溶解して重合するか、スチレン系重合体の重合途
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、未反応単量体を
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、スチレン系重合
体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。The styrene polymer can be obtained by a known method such as solution polymerization, bulk polymerization and emulsion polymerization. The terpene-based hydrogenated resin may be added by dissolving it in a styrene-based monomer or an acrylic acid (methacrylic acid) ester monomer for polymerization, or by adding a terpene-based hydrogenated resin during the polymerization of the styrene-based polymer. A method in which the terpene-based hydrogenated resin is added before melting or after the unreacted monomer is removed after the polymerization is completed can be used. It is also possible to mix the styrene polymer and the terpene hydrogenated resin and knead them with an extruder or a molding machine.
【００１３】本発明のスチレン系樹脂組成物は、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、それらの金属塩（カルシュ−
ム、マグネシュ−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。又、本発
明の目的を阻害しない範囲でスチレン−ブタジエンブロ
ック共重合体等の熱可塑性エラストマ−を添加すること
も出来る。The styrenic resin composition of the present invention contains various additives which have been frequently used in conventional styrenic resins, such as stearic acid, behenic acid, and metal salts thereof (calcium-based resin).
, Magnesium, zinc, etc.), ethylenebisstearamide, etc. can also be added. Further, an antioxidant, a colorant, an antistatic agent, etc. can be added. Further, a thermoplastic elastomer such as a styrene-butadiene block copolymer may be added within a range not impairing the object of the present invention.
【００１４】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.
【００１５】[0015]
（スチレン系重合体−１）攪拌機付き１０Ｌ完全混合型
反応機に、スチレン５Ｋｇ、エチルベンゼン０．４Ｋ
ｇ、１，１ビス（ｔ−ブチルパ−オキシ）シクロヘキサ
ン１．２ｇからなる原料溶液を１．８Ｌ／Ｈの速度で供
給する。反応機温度を１２５℃に設定し重合を行う。得
られた重合溶液を押出機に連続的に供給し、押出機で未
反応単量体、溶媒を回収し、スチレン系重合体−１を得
る。 （スチレン系重合体−２）スチレン２．５５Ｋｇ、メチ
ルメタクリレ−ト２．４５Ｋｇ、エチルベンゼン０．４
Ｋｇ、１，１ビス（ｔ−ブチルパ−オキシ）シクロヘキ
サン１ｇからなる原料溶液を３．０Ｌ／Ｈの速度で反応
機に連続的に供給し、反応機温度を１２０℃に設定する
以外、スチレン系重合体−１と同様に操作し、スチレン
系重合体−２を得る。 （スチレン系重合体−３）スチレン４．０Ｋｇ、ブチル
アクリレ−ト１．０Ｋｇ、エチルベンゼン０．４Ｋｇ、
１，１ビス（ｔ−ブチルパ−オキシ）シクロヘキサン
１．２ｇからなる原料溶液を２．０Ｌ／Ｈの速度で反応
機に連続的に供給し、反応機温度を１２５℃に設定する
以外、スチレン系重合体−１と同様に操作し、スチレン
系重合体−３を得る。 （スチレン系重合体−４）スチレン４．５Ｋｇ、ブチル
アクリレ−ト０．５Ｋｇ、エチルベンゼン０．４Ｋｇ、
１，１ビス（ｔ−ブチルパ−オキシ）シクロヘキサン
１．２ｇからなる原料溶液を１．９Ｌ／Ｈの速度で反応
機に連続的に供給し、反応機温度を１２５℃に設定する
以外、スチレン系重合体−１と同様に操作し、スチレン
系重合体−４を得る。(Styrene-based polymer-1) 5 kg of styrene and 0.4 K of ethylbenzene in a 10 L complete mixing type reactor equipped with a stirrer.
A raw material solution consisting of 1.2 g of 1,1 bis (t-butylperoxy) cyclohexane is supplied at a rate of 1.8 L / H. Polymerization is carried out with the reactor temperature set at 125 ° C. The obtained polymerization solution is continuously supplied to the extruder, and the unreacted monomer and the solvent are recovered by the extruder to obtain a styrene polymer-1. (Styrene Polymer-2) Styrene 2.55 Kg, Methyl Methacrylate 2.45 Kg, Ethylbenzene 0.4
A styrene-based material was prepared by continuously supplying a raw material solution containing 1 g of Kg and 1,1 bis (t-butylperoxy) cyclohexane to the reactor at a rate of 3.0 L / H and setting the reactor temperature at 120 ° C. The same operation as in Polymer-1 is performed to obtain Styrene Polymer-2. (Styrene-based polymer-3) 4.0 kg of styrene, 1.0 kg of butyl acrylate, 0.4 kg of ethylbenzene,
A styrene-based solution was prepared by continuously supplying a raw material solution consisting of 1.2 g of 1,1 bis (t-butylperoxy) cyclohexane to the reactor at a rate of 2.0 L / H and setting the reactor temperature at 125 ° C. The same operation as that for the polymer-1 is performed to obtain a styrene polymer-3. (Styrene-based polymer-4) 4.5 kg of styrene, 0.5 kg of butyl acrylate, 0.4 kg of ethylbenzene,
A styrene-based solution was prepared by continuously supplying a raw material solution consisting of 1.2 g of 1,1 bis (t-butylperoxy) cyclohexane to the reactor at a rate of 1.9 L / H and setting the reactor temperature at 125 ° C. The same operation as in Polymer-1 is performed to obtain styrene polymer-4.
【００１６】[0016]
【実施例１〜実施例５】スチレン系重合体１００重量部
当たり、テルペン系水素添加樹脂を表１に示す割合で混
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２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Ｍ１１
５である。Examples 1 to 5 A terpene-based hydrogenated resin was mixed in a ratio shown in Table 1 per 100 parts by weight of a styrene-based polymer and granulated with a 20 mm twin-screw extruder to obtain a styrene-based resin. The physical properties are shown in Table 2. The terpene-based hydrogenated resin used was Clearlon M11 from Yasuhara Chemical Co., Ltd.
It is 5.
【００１７】[0017]
【比較例−１〜比較例−４】スチレン系重合体−１〜ス
チレン系重合体−４単独を用いて、実施例１と同様に物
性を測定する。物性を表２に示す。[Comparative Example-1 to Comparative Example-4] Using styrene-based polymer-1 to styrene-based polymer-4 alone, the physical properties are measured in the same manner as in Example 1. The physical properties are shown in Table 2.
【００１８】[0018]
【比較例−５、比較例−６】スチレン系重合体−１を用
い、表１に示す割合で混合し、実施例１と同様に造粒
し、物性を測定する。物性を表２に示す。[Comparative Example-5, Comparative Example-6] The styrene-based polymer-1 was used, mixed at the ratio shown in Table 1, granulated in the same manner as in Example 1, and the physical properties were measured. The physical properties are shown in Table 2.
【００１９】[0019]
【比較例−７、比較例−８】スチレン系重合体−１を用
い、表１に示す割合でミネラル・オイルと混合し、実施
例１と同様に造粒し、物性を測定する。物性を表２に示
す。本発明のスチレン系樹脂組成物は、ポリスチレンに
テルペン系水素添加樹脂を配合したものに比較し、図１
に示すように、強度の向上が著しい。[Comparative Example-7, Comparative Example-8] The styrene-based polymer-1 was used, mixed with mineral oil in the ratio shown in Table 1, granulated in the same manner as in Example 1, and the physical properties were measured. The physical properties are shown in Table 2. The styrene-based resin composition of the present invention is compared with that obtained by blending polystyrene with a terpene-based hydrogenated resin.
As shown in, the strength is remarkably improved.
【００２０】又、ミネラル・オイルを添加した樹脂に比
較し、耐熱性−流動性バランスが著しく向上しているの
が理解できる。Further, it can be understood that the heat resistance-fluidity balance is remarkably improved as compared with the resin to which mineral oil is added.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【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、ス
チレン系コポリマ−よにも、著しく成形性、耐熱性、強
度、剛性のバランスが優れている。The styrenic resin composition of the present invention is remarkably balanced in moldability, heat resistance, strength and rigidity in comparison with a styrenic resin composition containing a plasticizer and a styrenic copolymer which have been frequently used. Is excellent.
【図１】本発明のスチレン系樹脂組成物、及び従来のス
チレン系樹脂にテルペン系水素添加樹脂、又はミネラル
オイルを添加した時の強度の変化を示す。FIG. 1 shows changes in strength when a terpene-based hydrogenated resin or mineral oil is added to the styrene-based resin composition of the present invention and a conventional styrene-based resin.
Claims (1)
重量部、アクリル酸（メタクリル酸）エステル単量体１
〜６０重量部よりなるスチレン系重合体とテルペン系水
素添加樹脂とからなる新規なスチレン系樹脂組成物1. A vinyl aromatic hydrocarbon monomer 40-99.
Parts by weight, acrylic acid (methacrylic acid) ester monomer 1
To 60 parts by weight of styrenic polymer and terpene hydrogenated resin
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34054491A JPH05202250A (en) | 1991-12-24 | 1991-12-24 | New styrene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34054491A JPH05202250A (en) | 1991-12-24 | 1991-12-24 | New styrene resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05202250A true JPH05202250A (en) | 1993-08-10 |
Family
ID=18338001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34054491A Withdrawn JPH05202250A (en) | 1991-12-24 | 1991-12-24 | New styrene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05202250A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069917A2 (en) | 2003-01-27 | 2004-08-19 | Nova Chemicals Inc. | Foamable interpolymer resin particles containing limonene as a blowing aid |
| CN100362029C (en) * | 2003-04-01 | 2008-01-16 | 深圳市海川实业股份有限公司 | Elastic acrylic ester emulsion |
-
1991
- 1991-12-24 JP JP34054491A patent/JPH05202250A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004069917A2 (en) | 2003-01-27 | 2004-08-19 | Nova Chemicals Inc. | Foamable interpolymer resin particles containing limonene as a blowing aid |
| CN100362029C (en) * | 2003-04-01 | 2008-01-16 | 深圳市海川实业股份有限公司 | Elastic acrylic ester emulsion |
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