JPH0967486A - Impact resistant styrene-based resin composition - Google Patents
Impact resistant styrene-based resin compositionInfo
- Publication number
- JPH0967486A JPH0967486A JP22398095A JP22398095A JPH0967486A JP H0967486 A JPH0967486 A JP H0967486A JP 22398095 A JP22398095 A JP 22398095A JP 22398095 A JP22398095 A JP 22398095A JP H0967486 A JPH0967486 A JP H0967486A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- styrene
- aromatic compound
- block copolymer
- substituted aromatic
- 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.)
- Pending
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011342 resin composition Substances 0.000 title claims abstract description 14
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 38
- 229920001400 block copolymer Polymers 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 25
- 239000011347 resin Substances 0.000 abstract description 25
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 4
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 20
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- -1 diolefin compound Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000178 monomer Chemical class 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐衝撃性を改良さ
れた硬質塩化ビニル樹脂の代替品として使用可能な、高
耐衝撃性、及び高透明性を兼ね備えたスチレン系樹脂組
成物に関し、更に詳しくは、スチレン系重合体に２種類
の特定の共役ジオレフィンとビニル置換芳香族化合物と
からなるブロック共重合体を特定の割合で加え、スチレ
ン系重合体の透明性を損なうことなく耐衝撃性硬質塩化
ビニル樹脂に匹敵する耐衝撃性を備えた、耐衝撃性スチ
レン系樹脂組成物に関するものである。TECHNICAL FIELD The present invention relates to a styrene resin composition having high impact resistance and high transparency, which can be used as a substitute for a hard vinyl chloride resin having improved impact resistance. Specifically, a block copolymer consisting of two specific conjugated diolefins and a vinyl-substituted aromatic compound is added to a styrene-based polymer in a specific ratio to give impact resistance without impairing the transparency of the styrene-based polymer. The present invention relates to an impact-resistant styrene-based resin composition having impact resistance comparable to that of a hard vinyl chloride resin.
【０００２】[0002]
【従来の技術】従来、透明性を低下させることなく、脆
く耐衝撃強度に劣るポリスチレンの欠点を改良する方法
としてビニル置換芳香族化合物と共役ジオレフィンとか
らなるブロック共重合体をポリスチレンにブレンドする
方法が用いられてきた（特公昭４５−１９３８８号公
報、特公昭４７−４３６１８号公報）。この方法によれ
ば、ビニル置換芳香族化合物含有量が多いブロック共重
合体を用いると透明性は優れるが耐衝撃強度はそれ程改
善されない。逆に、ビニル置換芳香族化合物含有量が少
ないブロック共重合体を用いると耐衝撃強度はある程度
改善されるがポリスチレンに対する相容性が低下し透明
性が失われてしまうため、より効果的な改良方法が望ま
れていた。2. Description of the Related Art Conventionally, a block copolymer comprising a vinyl-substituted aromatic compound and a conjugated diolefin is blended with polystyrene as a method for improving the drawbacks of polystyrene which is brittle and poor in impact strength without lowering transparency. The method has been used (Japanese Patent Publication No. 45-19388 and Japanese Patent Publication No. 47-43618). According to this method, when a block copolymer having a high vinyl substituted aromatic compound content is used, the transparency is excellent, but the impact strength is not so improved. On the other hand, when a block copolymer containing a small amount of vinyl-substituted aromatic compound is used, impact strength is improved to some extent, but compatibility with polystyrene is lowered and transparency is lost, so that more effective improvement is obtained. A method was desired.
【０００３】その後、透明性と耐衝撃性とを両備させる
方法の試みは、例えば、特公昭５６−５０９０３号公
報、特公昭５９−４３０５９号公報にビニル置換芳香族
化合物含有量が少ないビニル置換芳香族化合物と共役ジ
オレフィン化合物とからなるブロック共重合体とビニル
置換芳香族化合物含有量が多いブロック共重合体とをポ
リスチレンにブレンドする方法が記載されている。この
試みでは、耐衝撃性硬質塩化ビニルに匹敵する高透明
性、高耐衝撃性を同時に発現させることは出来なかっ
た。After that, trials of methods for providing both transparency and impact resistance have been made, for example, in JP-B-56-50903 and JP-B-59-43059, in which a vinyl-substituted aromatic compound having a low vinyl-substituted aromatic compound content is used. A method of blending polystyrene with a block copolymer composed of a group compound and a conjugated diolefin compound and a block copolymer having a high vinyl-substituted aromatic compound content is described. In this attempt, it was not possible to simultaneously achieve high transparency and high impact resistance comparable to impact resistant hard vinyl chloride.
【０００４】出願人は、特願平６−６６３２１号におい
て透明性と耐衝撃性が改良されたスチレン系樹脂組成物
に関する出願を行った。先の発明においては確かに透明
性と、耐衝撃性の高度なバランスを実現するには十分で
あったが、耐衝撃性硬質塩化ビニル樹脂に匹敵するほど
の性能を発揮することは出来なかった。The applicant filed an application for a styrene resin composition having improved transparency and impact resistance in Japanese Patent Application No. 6-66321. In the previous invention, it was certainly sufficient to achieve a high degree of balance between transparency and impact resistance, but it could not exhibit performance comparable to impact-resistant hard vinyl chloride resin. .
【０００５】[0005]
【発明が解決しようとする課題】従来技術ではなし得な
かった、耐衝撃性硬質塩化ビニル樹脂に匹敵する、透明
性と、耐衝撃性を兼ね備え他スチレン系樹脂組成物を提
供する。[Problems to be Solved by the Invention] Another styrenic resin composition having both transparency and impact resistance comparable to that of an impact-resistant hard vinyl chloride resin, which cannot be achieved by the prior art, is provided.
【０００６】[0006]
【課題を解決するための手段】本発明は、このような現
状に鑑み、高い透明性を有しかつ、耐衝撃性硬質塩化ビ
ニル樹脂並の耐衝撃性を合わせ持つ、耐衝撃性スチレン
系樹脂組成物を開発することを目的として種々の検討を
行ったところ、各共重合成分の含有量を特定したビニル
置換芳香族化合物含有量が少ないビニル置換芳香族化合
物と共役ジオレフィン化合物とからなるブロック共重合
体とビニル置換芳香族化合物含有量が多いブロック共重
合体とを特定量スチレン系重合体にブレンドし、この
際、スチレン系重合体と、ビニル置換芳香族化合物含有
量が多いビニル置換芳香族化合物と共役ジオレフィン化
合物とからなるブロック共重合体の屈折率の差を０．０
２以下、ビニル置換芳香族化合物含有量が多いブロック
共重合体と、ビニル置換芳香族化合物含有量が少ないブ
ロック共重合体の屈折率の差を０．０３以下とすること
により、本来、相反する透明性と耐衝撃性を高い水準で
バランスさせ、本発明をなすに至った。In view of the above situation, the present invention has an impact-resistant styrenic resin having high transparency and having impact resistance comparable to that of a hard vinyl chloride resin having impact resistance. Various investigations were carried out for the purpose of developing a composition, and a block composed of a vinyl-substituted aromatic compound and a conjugated diolefin compound having a low vinyl-substituted aromatic compound content in which the content of each copolymerization component was specified. A copolymer and a block copolymer having a high vinyl-substituted aromatic compound content are blended with a specific amount of a styrene-based polymer, and at this time, the styrene-based polymer and a vinyl-substituted aromatic compound having a high vinyl-substituted aromatic compound content are blended. The difference in the refractive index of the block copolymer composed of the group compound and the conjugated diolefin compound is 0.0
By setting the difference in refractive index between the block copolymer having a vinyl substitution aromatic compound content of 2 or less and the vinyl substitution aromatic compound content of less than 0.03 to 0.03 or less, there is an inherent conflict. The present invention has been achieved by balancing transparency and impact resistance at a high level.
【０００７】即ち、本発明の前記目的は、（Ａ）スチレ
ン系重合体２４〜４４重量％、（Ｂ）ビニル置換芳香族
化合物の含有量が６５重量％以上７５重量％以下の共役
ジオレフィンとビニル置換芳香族化合物とからなり、ス
チレン系重合体成分（Ａ）との屈折率の差が０．０２以
下であるブロック共重合体５５〜７０重量％、（Ｃ）ビ
ニル置換芳香族化合物の含有量が１５重量％以上５０重
量％以下の共役ジオレフィンとビニル置換芳香族化合物
とからなり、ブロック共重合体成分（Ｂ）との屈折率の
差が０．０３以下であるブロック共重合体７〜１０重量
％よりなる耐衝撃性硬質塩化ビニル樹脂に匹敵する耐衝
撃性を備えた、耐衝撃性スチレン系樹脂組成物によっ
て、容易に達成することができる。That is, the above object of the present invention is to provide a conjugated diolefin having (A) a styrene-based polymer of 24 to 44% by weight and (B) a vinyl-substituted aromatic compound content of 65% by weight or more and 75% by weight or less. 55 to 70% by weight of a block copolymer comprising a vinyl-substituted aromatic compound and having a refractive index difference of 0.02 or less with the styrene-based polymer component (A), and (C) containing a vinyl-substituted aromatic compound. A block copolymer 7 comprising an amount of 15% by weight or more and 50% by weight or less of a conjugated diolefin and a vinyl-substituted aromatic compound and having a difference in refractive index of 0.03 or less with the block copolymer component (B). It can be easily achieved by an impact resistant styrene resin composition having an impact resistance comparable to that of a hard vinyl chloride resin having an impact resistance of 10 to 10% by weight.
【０００８】[0008]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【０００９】本発明で用いるスチレン系重合体とは、ビ
ニル置換芳香族化合物若しくはこれと共重合可能なモノ
マーを重合することにより得たものである。ビニル置換
芳香族化合物と共重合可能なモノマーとしては、α−メ
チルスチレン、ｏ−メチルスチレン，ｐ−メチルスチレ
ン、アクリロニトリル、アクリル酸エステル、メタクリ
ル酸エステル、無水マレイン酸等が挙げられる。特に好
ましいスチレン系重合体としては、ポリスチレン、アク
リロニトリル−スチレン共重合体、アクリル酸エステル
−スチレン共重合体、メタクリル酸エステル−スチレン
共重合体、無水マレイン酸−スチレン共重合体等が挙げ
られ、これらは目的に応じて単独又は二種以上の混合物
として用いることができる。The styrene polymer used in the present invention is obtained by polymerizing a vinyl-substituted aromatic compound or a monomer copolymerizable therewith. Examples of the monomer copolymerizable with the vinyl-substituted aromatic compound include α-methylstyrene, o-methylstyrene, p-methylstyrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride. Particularly preferred styrene-based polymers include polystyrene, acrylonitrile-styrene copolymer, acrylic ester-styrene copolymer, methacrylic acid ester-styrene copolymer, maleic anhydride-styrene copolymer, and the like. Can be used alone or as a mixture of two or more depending on the purpose.
【００１０】成分（Ｂ）、（Ｃ）のブロック共重合体
は、従来公知の方法で製造され、一般に炭化水素溶剤中
でアニオン重合開始剤を用い、共役ジオレフィンとビニ
ル置換芳香族化合物をブロック共重合する。ブロック共
重合体の構造は、一般式（Ｉ）で表される直鎖状ブロッ
ク共重合体、あるいは、一般式（ＩＩ）で表されるラジ
アル状ブロック共重合体として得られるものである。 （Ａ−Ｂ）ｎまたは Ａ（Ｂ−Ａ）ｎまたは Ｂ（Ａ−Ｂ）ｎ …（Ｉ） （式中のＡはビニル置換芳香族化合物を主成分とするブ
ロック、Ｂは共役ジオレフィンを主成分とするブロッ
ク、ｎは１またはそれ以上の整数で一般に１〜６であ
る。） ［（Ｂ−Ａ）ｎ］ｍ＋２−Ｘ ［（Ａ−Ｂ）ｎ］ｍ＋２−Ｘ ［（Ｂ−Ａ）ｎ−Ｂ］ｍ＋２−Ｘ ［（Ａ−Ｂ）ｎ−Ａ］ｍ＋２−Ｘ …（ＩＩ） （式中のＡはビニル置換芳香族化合物を主成分とするブ
ロック、Ｂは共役ジオレフィンを主成分とするブロッ
ク、Ｘは四塩化ケイ素等のカップリング剤、ｎ及びｍは
１またはそれ以上の整数で一般に１〜６である。） 本発明においては、目的に応じて直鎖状ブロック共重合
体とラジアル状ブロック共重合体の混合物、二種類以上
の直鎖状ブロック共重合体の混合物及び二種類以上のラ
ジアル状ブロック共重合体の混合物を用いることができ
る。前記ブロック共重合体においてＡブロックとＢブロ
ックの間の境界は必ずしも明確である必要はなく、ブロ
ック共重合体の構造には完全型のブロック共重合体もテ
ーパー型ブロック共重合体も含みうる。つまり、Ａブロ
ック中に少量のＢ成分を含有していてもよいし、Ｂブロ
ック中に少量のＡ成分を含有していてもよい。さらに、
ブロック共重合体中に複数のＡブロックを有する場合、
全てのＡブロックの分子量、組成が等しい必要はなく、
Ｂブロックについても同様である。The block copolymers of the components (B) and (C) are produced by a conventionally known method, and generally, an anionic polymerization initiator is used in a hydrocarbon solvent to block the conjugated diolefin and the vinyl-substituted aromatic compound. Copolymerize. The structure of the block copolymer is obtained as a linear block copolymer represented by the general formula (I) or a radial block copolymer represented by the general formula (II). (AB) n or A (BA) n or B (AB) n ... (I) (A in the formula is a block containing a vinyl-substituted aromatic compound as a main component, and B is a conjugated diolefin. Block as main component, n is an integer of 1 or more and is generally 1 to 6.) [(B-A) n] m + 2-X [(A-B) n] m + 2-X [(B-A ) N-B] m + 2-X [(AB) n-A] m + 2-X ... (II) (In the formula, A is a block containing a vinyl-substituted aromatic compound as a main component, and B is mainly a conjugated diolefin. Block as component, X is a coupling agent such as silicon tetrachloride, n and m are integers of 1 or more and are generally 1 to 6.) In the present invention, linear block copolymerization is carried out depending on the purpose. Mixture of polymer and radial block copolymer, mixture of two or more linear block copolymers And it is possible to use a mixture of two or more radial shaped block copolymer. In the block copolymer, the boundary between the A block and the B block does not necessarily have to be clear, and the structure of the block copolymer may include a complete block copolymer and a tapered block copolymer. That is, the A block may contain a small amount of the B component, or the B block may contain a small amount of the A component. further,
When the block copolymer has a plurality of A blocks,
The molecular weight and composition of all A blocks need not be the same,
The same applies to the B block.
【００１１】本発明で用いられるブロック共重合体の成
分（Ｂ），（Ｃ）を構成するビニル置換芳香族化合物と
は、スチレン、α−メチルスチレン、ｏ−メチルスチレ
ン，ｐ−メチルスチレン、ビニルナフタレン、ビニルア
ントラセン等で特にスチレンが挙げられる。これらは目
的に応じて単独又は二種以上の混合物として用いること
ができる。又、共役ジオレフィンとは、共役二重結合を
有するジオレフィンであり例えば、１、３−ブタジエ
ン、イソプレン、１、３−ペンタジエン、１、３−ヘキ
サジエン等で特に１、３−ブタジエン及び、イソプレン
が挙げられる。これらは目的に応じて単独又は二種以上
の混合物として用いることができる。The vinyl-substituted aromatic compounds constituting the components (B) and (C) of the block copolymer used in the present invention include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene and vinyl. Naphthalene, vinyl anthracene and the like, especially styrene can be mentioned. These can be used alone or as a mixture of two or more types depending on the purpose. The conjugated diolefin is a diolefin having a conjugated double bond, and is, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, etc., and particularly 1,3-butadiene and isoprene. Is mentioned. These can be used alone or as a mixture of two or more types depending on the purpose.
【００１２】本発明で用いられるブロック共重合体の成
分（Ｂ）、（Ｃ）はそれぞれ、（Ｂ）ビニル置換芳香族
化合物の含有量が６５重量％以上７５重量％以下、共役
ジオレフィン成分が２５重量％以上３５重量％以下含有
し、スチレン系重合体成分（Ａ）との屈折率の差が０．
０２以下であるもの（Ｃ）ビニル置換芳香族化合物の含
有量が１５重量％以上５０重量％以下、共役ジオレフィ
ン成分が５０重量％以上８５重量％以下含有し、ブロッ
ク共重合体成分（Ｂ）との屈折率の差が０．０３以下で
あるものである。ブロック共重合体（Ｂ）中のビニル置
換芳香族化合物の含有量が７５重量％より多い場合に
は、本発明の比率で各成分をブレンドした場合において
も該組成物の耐衝撃性を改善することができない。ま
た、ブロック共重合体（Ｂ）中のビニル置換芳香族化合
物の含有量が６５重量％より少ない場合には、組成物の
耐衝撃性は改善されるが、その反面スチレン系重合体に
対する相容性が低下し透明性を悪化させる結果となる。
ブロック共重合体（Ｃ）中のビニル置換芳香族化合物の
含有量が５０重量％より多い場合には、該組成物の耐衝
撃性は耐衝撃性硬質塩化ビニル樹脂のそれに遠く及ばな
い。また、ブロック共重合体（Ｃ）中のビニル置換芳香
族化合物の含有量が１５重量％より少ない場合には、該
組成物の耐衝撃性が改善できるが、反面スチレン系重合
体に対する相容性が低下し透明性を悪化させる結果とな
る。The components (B) and (C) of the block copolymer used in the present invention each contain (B) a vinyl-substituted aromatic compound in an amount of 65% by weight or more and 75% by weight or less and a conjugated diolefin component. It is contained in an amount of 25% by weight or more and 35% by weight or less, and the difference in refractive index from the styrene polymer component (A) is 0.
No more than 02 (C) The content of the vinyl-substituted aromatic compound is 15% by weight or more and 50% by weight or less, the conjugated diolefin component is contained by 50% by weight or more and 85% by weight or less, and the block copolymer component (B) is contained. The difference in the refractive index between and is 0.03 or less. When the content of the vinyl-substituted aromatic compound in the block copolymer (B) is more than 75% by weight, the impact resistance of the composition is improved even when each component is blended in the ratio of the present invention. I can't. Further, when the content of the vinyl-substituted aromatic compound in the block copolymer (B) is less than 65% by weight, the impact resistance of the composition is improved, but on the other hand, the compatibility with the styrene-based polymer is improved. As a result, the transparency is deteriorated and the transparency is deteriorated.
When the content of the vinyl-substituted aromatic compound in the block copolymer (C) is more than 50% by weight, the impact resistance of the composition is far below that of the impact-resistant hard vinyl chloride resin. Further, when the content of the vinyl-substituted aromatic compound in the block copolymer (C) is less than 15% by weight, the impact resistance of the composition can be improved, but on the other hand, the compatibility with the styrene-based polymer is improved. Results in deterioration of transparency.
【００１３】本発明において用いられるブロック共重合
体の成分（Ｂ）、（Ｃ）の重量平均分子量はそれぞれ、
３０、０００以上、好ましくは５０、０００以上３５
０、０００以下のものである。The weight average molecular weights of the components (B) and (C) of the block copolymer used in the present invention are
30,000 or more, preferably 50,000 or more 35
It is less than 2,000.
【００１４】本発明のスチレン系樹脂組成物は、前記し
た通り各３成分の組成比、および、屈折率を特定するこ
とにより透明性を損なうことなく、耐衝撃性硬質塩化ビ
ニル樹脂に匹敵する、耐衝撃性を発現させる事ができ
る。The styrene resin composition of the present invention is comparable to impact-resistant hard vinyl chloride resin without impairing transparency by specifying the composition ratio of each of the three components and the refractive index as described above. It is possible to develop impact resistance.
【００１５】そのブレンド比を以下に示す。 成分（Ａ）；２４〜４４重量％、好ましくは３０〜３５
重量％ 成分（Ｂ）；５５〜７０重量％、好ましくは６０〜６５
重量％ 成分（Ｃ）； ７〜１０重量％、好ましくは ７〜 ８
重量％ 成分（Ａ）が２４重量％よりも少ない場合には、組成物
の剛性が低くなりその成形品は商品価値を失ってしま
い、また、４４重量％よりも多い場合には、組成物の剛
性は高いが耐衝撃性、特に低温における耐衝撃性を低下
させてしまう。成分（Ｂ）が５５重量％よりも少ない場
合には、組成物の耐衝撃性、透明性を共に低下させてし
まう。７０重量％よりも多い場合には、組成物の剛性は
低くなる。成分（Ｃ）が７重量％よりも少ない場合に
は、組成物の耐衝撃性が耐衝撃性硬質塩化ビニル樹脂の
それに及ばず、１０重量％よりも多い場合には、透明性
が低くなる。The blending ratio is shown below. Component (A); 24-44% by weight, preferably 30-35
% By weight Component (B); 55-70% by weight, preferably 60-65
% By weight Component (C); 7-10% by weight, preferably 7-8
When the content of the component (A) is less than 24% by weight, the rigidity of the composition becomes low and the molded article loses its commercial value. Although it has high rigidity, it lowers impact resistance, especially at low temperatures. When the amount of the component (B) is less than 55% by weight, both impact resistance and transparency of the composition are deteriorated. If it is more than 70% by weight, the rigidity of the composition becomes low. When the amount of the component (C) is less than 7% by weight, the impact resistance of the composition is lower than that of the impact resistant hard vinyl chloride resin, and when it is more than 10% by weight, the transparency is low.
【００１６】さらに、成分（Ａ）と成分（Ｂ）の屈折率
の差が０．０２以下、好ましくは、０．０１以下であ
り、かつ、成分（Ｂ）と成分（Ｃ）の屈折率の差が、
０．０３以下、好ましくは、０．０２以下である。Further, the difference in refractive index between the component (A) and the component (B) is 0.02 or less, preferably 0.01 or less, and the refractive index of the component (B) and the component (C) is different. The difference is
It is 0.03 or less, preferably 0.02 or less.
【００１７】成分（Ａ）と成分（Ｂ）の屈折率の差が
０．０２より大きい、あるいは、成分（Ｂ）と成分
（Ｃ）の屈折率の差が、０．０３より大きい場合、得ら
れ樹脂の透明性が損なわれるばかりか、耐衝撃性までも
劣ってしまう。When the difference in the refractive index between the component (A) and the component (B) is larger than 0.02, or the difference in the refractive index between the component (B) and the component (C) is larger than 0.03, it is obtained. As a result, not only the transparency of the resin is impaired, but also the impact resistance is deteriorated.
【００１８】屈折率を特定することが耐衝撃性の向上に
どの様に寄与しているかは不明であるが上記、組成比と
屈折率の要件を組み合わせることで耐衝撃性と透明性が
飛躍的に改良される。これらの要件のうちいずれを欠い
ても本発明の目的は達成されない。It is not known how specifying the refractive index contributes to the improvement of the impact resistance, but by combining the composition ratio and the refractive index requirements, the impact resistance and the transparency can be dramatically improved. Will be improved. Lacking any of these requirements will not achieve the object of the invention.
【００１９】本発明のスチレン系樹脂組成物は、前記３
成分の重合体以外にも必要に応じて紫外線吸収剤、酸化
防止剤、滑剤、可塑剤、補強材、スリップ剤、アンチブ
ロッキング剤、核剤、架橋剤、帯電防止剤、防曇剤、難
燃剤、顔料、染料等の添加剤が含まれていてもよい。The styrene resin composition of the present invention has the above-mentioned 3
UV absorbers, antioxidants, lubricants, plasticizers, reinforcing materials, slip agents, anti-blocking agents, nucleating agents, cross-linking agents, antistatic agents, antifogging agents, flame retardants, if necessary, in addition to the component polymers. , Pigments, dyes, and other additives may be included.
【００２０】本発明のスチレン系樹脂組成物を得る方法
としては、従来公知の任意の手段を用いることができ
る。例えば、タンブラー型ブレンダー、リボンブレンダ
ー、Ｖ型ブレンダー、ヘンシェルミキサー等において原
料を混合する方法及び前記方法で混合した混合物を押出
機、ニーダー、バンバリーミキサー等で溶融混練する方
法等が用いられる。As a method for obtaining the styrene resin composition of the present invention, any conventionally known means can be used. For example, a method of mixing the raw materials in a tumbler type blender, a ribbon blender, a V type blender, a Henschel mixer, or the like, and a method of melting and kneading the mixture mixed by the above method with an extruder, a kneader, a Banbury mixer, or the like are used.
【００２１】得られた本発明のスチレン系樹脂組成物
は、従来公知の任意の成形加工法を用い、様々な製品に
加工することができる。その加工方法としては、射出成
形、押出成形、押出発泡成形、二軸延伸、中空成形及び
押出成形で得られたフィルム、シート、発泡体の圧空成
形、真空成形等が挙げられる。The styrene resin composition of the present invention thus obtained can be processed into various products by using any conventionally known molding method. Examples of the processing method include injection molding, extrusion molding, extrusion foaming molding, biaxial stretching, blow molding, and pressure molding of a foam, vacuum molding, and the like.
【００２２】以下、実施例により本発明を更に詳細に説
明する。Hereinafter, the present invention will be described in more detail with reference to examples.
【００２３】本実験で使用した樹脂を下に記した。The resins used in this experiment are listed below.
【００２４】 成分Ａ；樹脂１…一般用ポリスチレン、屈折率１．５９ Ｅ１８３（住友化学社製） 成分Ｂ；樹脂２…スチレン含有量７５重量％のスチレン
−ブタジエンブロック共重合体、屈折率１．５７ Ｋレジン（フィリップス社製） 樹脂３…スチレン含有量８０重量％のスチレン−ブタジ
エンブロック共重合体、屈折率１．５８ アサフレックス８１５（旭化成社製） 成分Ｃ；樹脂４…スチレン含有量４５重量％のスチレン
−ブタジエンブロック共重合体、屈折率１．５５ ＴＲ２００３（ＪＳＲ社製） 樹脂５…スチレン含有量４０重量％のスチレン−ブタジ
エンブロック共重合体、屈折率１．５４ タフプレン１２６（旭化成社製） 本実験における評価方法及び基準を下に記した。 落錘衝撃試験…ＡＳＴＭ Ｄ１７０９に準拠。撃芯先端
Ｒ１／２インチ。値が大きいほど耐衝撃性が高い。 曇り度…ＡＳＴＭ Ｄ１００３に準拠。値が小さいほど
透明性が良い。Component A: Resin 1 ... General-purpose polystyrene, refractive index 1.59 E183 (manufactured by Sumitomo Chemical Co., Ltd.) Component B; Resin 2 ... Styrene-butadiene block copolymer having styrene content of 75% by weight, refractive index 1. 57 K resin (manufactured by Philips) Resin 3 ... Styrene-butadiene block copolymer having styrene content of 80% by weight, refractive index 1.58 Asaflex 815 (manufactured by Asahi Kasei Corporation) Component C; Resin 4 ... Styrene content 45% by weight % Styrene-butadiene block copolymer, refractive index 1.55 TR2003 (manufactured by JSR Corp.) Resin 5 ... Styrene content 40% by weight styrene-butadiene block copolymer, refractive index 1.54 Tuffprene 126 (manufactured by Asahi Kasei Corporation) ) The evaluation methods and criteria in this experiment are described below. Drop weight impact test ... Complies with ASTM D1709. Hammer tip R 1/2 inch. The larger the value, the higher the impact resistance. Haze ... Compliant with ASTM D1003. The smaller the value, the better the transparency.
【００２５】[0025]
（実施例１〜４）表１に示した配合割合に従い各成分を
タンブラー型ブレンダーにて混合し、６５ｍｍΦのシー
ト押出機で厚さ０．２５ｍｍのシートを成形した。得ら
れたシートの評価結果を表１に、比較の為に耐衝撃性硬
質塩化ビニル樹脂を用いた厚さ０．２５ｍｍのシートの
評価結果を表２に示した。本発明の配合を用いたシート
は、曇り度が３％以下、落錘衝撃強度が２３℃で１５ｋ
ｇｃｍ以上と、透明性と耐衝撃性が比較に用いた耐衝撃
性硬質塩化ビニル樹脂と同等の高水準でバランスされて
いる。(Examples 1 to 4) The components were mixed in a tumbler type blender in accordance with the blending ratio shown in Table 1, and a sheet having a thickness of 0.25 mm was formed by a sheet extruder having a diameter of 65 mm. The evaluation results of the obtained sheet are shown in Table 1, and for comparison, the evaluation result of the sheet having a thickness of 0.25 mm and using the impact-resistant hard vinyl chloride resin is shown in Table 2. The sheet using the composition of the present invention has a haze of 3% or less and a falling weight impact strength of 15 k at 23 ° C.
With gcm or more, transparency and impact resistance are balanced at the same high level as the impact-resistant hard vinyl chloride resin used for comparison.
【００２６】（比較例１、２）成分Ｃの配合量が７重量
％よりも少ない場合は、透明性は向上するが、落錘衝撃
強度が１０kgcm以下と耐衝撃性硬質塩化ビニル樹脂のそ
れを大きく下回る。(Comparative Examples 1 and 2) When the compounding amount of the component C is less than 7% by weight, the transparency is improved, but the falling weight impact strength is 10 kgcm or less and that of the impact resistant hard vinyl chloride resin. Far below.
【００２７】（比較例３）成分Ｃの配合量が１０重量％
よりも多い場合では、耐衝撃性は十分であるが曇り度が
６％以上と透明性に劣ることが分かる。(Comparative Example 3) The content of component C is 10% by weight.
It can be seen that when the amount is larger than that, the impact resistance is sufficient but the haze is 6% or more and the transparency is poor.
【００２８】（比較例４）成分Ｂと成分Ｃの屈折率の差
が、０．０３以上の場合、耐衝撃性は十分であるが、曇
り度が４％以上と、実施例１と比較して透明性に劣るこ
とが分かる。(Comparative Example 4) When the difference in refractive index between the component B and the component C is 0.03 or more, the impact resistance is sufficient, but the haze is 4% or more. It can be seen that the transparency is poor.
【００２９】（参考例）シート厚み０．２５ｍｍの耐衝
撃性硬質塩化ビニル樹脂（ＰＶＣ樹脂８５重量％とＭＢ
Ｓラテックス１５重量％よりなる）の物性値を表１に示
す。(Reference Example) Impact-resistant hard vinyl chloride resin (PVC resin 85% by weight and MB
Table 1 shows the physical properties of S latex (comprising 15% by weight).
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明のスチレン系樹脂組成物より得ら
れるフィルム、シートは、透明性、耐衝撃性が耐衝撃性
硬質塩化ビニル樹脂に匹敵し、またポリ塩化ビニルと同
様に真空成形が可能で成形性も良好であること、ポリプ
ロピレン、ポリエチレンフィルムに比較して剛性が優れ
ており、非晶性ポリエステルフィルム（Ａ−ＰＥＴ）に
比べ安価で真空成形等の容器成形性に優れていることか
ら、食品やブリスターパック等の包装用途に使用でき
る。The film and sheet obtained from the styrene resin composition of the present invention have transparency and impact resistance comparable to those of hard vinyl chloride resin having impact resistance, and can be vacuum-formed like polyvinyl chloride. Since it has good moldability, it has better rigidity than polypropylene and polyethylene films, is cheaper than amorphous polyester film (A-PET), and has excellent container moldability such as vacuum molding. It can be used for packaging foods, blister packs, etc.
Claims (1)
％、（Ｂ）ビニル置換芳香族化合物の含有量が６５重量
％以上７５重量％以下の共役ジオレフィンとビニル置換
芳香族化合物とからなり、スチレン系重合体成分（Ａ）
との屈折率の差が０．０２以下であるブロック共重合体
５５〜７０重量％、（Ｃ）ビニル置換芳香族化合物の含
有量が１５重量％以上５０重量％以下の共役ジオレフィ
ンとビニル置換芳香族化合物とからなり、ブロック共重
合体成分（Ｂ）との屈折率の差が０．０３以下であるブ
ロック共重合体７〜１０重量％よりなるスチレン系樹脂
組成物。1. A conjugated diolefin and a vinyl-substituted aromatic compound, wherein the content of the styrene polymer (A) is 24 to 44% by weight and the content of the vinyl-substituted aromatic compound (B) is 65% by weight or more and 75% by weight or less. Becomes, styrene polymer component (A)
Block copolymer having a difference in refractive index of 0.02 or less from 55 to 70% by weight, and (C) vinyl substituted aromatic compound content of 15% by weight or more and 50% by weight or less conjugated diolefin and vinyl substitution A styrene-based resin composition comprising an aromatic compound and 7 to 10% by weight of a block copolymer having a refractive index difference of 0.03 or less with respect to the block copolymer component (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22398095A JPH0967486A (en) | 1995-08-31 | 1995-08-31 | Impact resistant styrene-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22398095A JPH0967486A (en) | 1995-08-31 | 1995-08-31 | Impact resistant styrene-based resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0967486A true JPH0967486A (en) | 1997-03-11 |
Family
ID=16806696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22398095A Pending JPH0967486A (en) | 1995-08-31 | 1995-08-31 | Impact resistant styrene-based resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0967486A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032556A1 (en) * | 2006-09-12 | 2008-03-20 | Konami Digital Entertainment Co., Ltd. | Thermoplastic resin blow molded article |
-
1995
- 1995-08-31 JP JP22398095A patent/JPH0967486A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032556A1 (en) * | 2006-09-12 | 2008-03-20 | Konami Digital Entertainment Co., Ltd. | Thermoplastic resin blow molded article |
| JP2008069189A (en) * | 2006-09-12 | 2008-03-27 | Konami Digital Entertainment:Kk | Thermoplastic resin hollow molding |
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