JP5437606B2 - Rubber-modified styrenic resin composition, and sheet and container using the same - Google Patents
Rubber-modified styrenic resin composition, and sheet and container using the same Download PDFInfo
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- JP5437606B2 JP5437606B2 JP2008202930A JP2008202930A JP5437606B2 JP 5437606 B2 JP5437606 B2 JP 5437606B2 JP 2008202930 A JP2008202930 A JP 2008202930A JP 2008202930 A JP2008202930 A JP 2008202930A JP 5437606 B2 JP5437606 B2 JP 5437606B2
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- 239000011342 resin composition Substances 0.000 title claims description 52
- 229920001890 Novodur Polymers 0.000 title claims description 21
- 150000003440 styrenes Chemical class 0.000 claims description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 230000008961 swelling Effects 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229940057995 liquid paraffin Drugs 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 38
- 239000002994 raw material Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 26
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 239000005063 High cis polybutadiene Substances 0.000 description 12
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000013305 food Nutrition 0.000 description 9
- 239000005064 Low cis polybutadiene Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 235000021185 dessert Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- -1 for example Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000003068 static effect Effects 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
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Wrappers (AREA)
Description
本発明は、ゴム変性スチレン系樹脂組成物に関し、より詳しくは、油やミルクと直接接する食品容器に好適に用いることができるゴム変性スチレン系樹脂組成物に関する。 The present invention relates to a rubber-modified styrenic resin composition, and more particularly to a rubber-modified styrenic resin composition that can be suitably used for food containers that are in direct contact with oil or milk.
耐衝撃性ポリスチレン〔ハイインパクトポリスチレン(HIPS)〕に代表されるゴム変性ポリスチレンは、耐衝撃性、成形性、寸法安定性に優れた樹脂であることから、電化製品、家庭製品、食品容器等の成形材料、包装材料として幅広く使用されている。 Rubber-modified polystyrene, typified by high-impact polystyrene (high-impact polystyrene (HIPS)), is a resin with excellent impact resistance, moldability, and dimensional stability, so it can be used in electrical appliances, household products, food containers, etc. Widely used as molding material and packaging material.
しかしながら、周知の如く、通常のゴム変性ポリスチレン系樹脂は、脂肪や油、及び有機溶媒との接触により短期間のうちに環境応力割れを生じるという問題がある。 However, as is well known, ordinary rubber-modified polystyrene resins have the problem of causing environmental stress cracks in a short period of time due to contact with fats, oils, and organic solvents.
耐油性を改良するために例えばポリオレフィン系樹脂やポリフェニレンエーテル樹脂をゴム変性ポリスチレン基材樹脂に添加する方法や、ゴム変性ポリスチレン基材樹脂をポリオレフィン系樹脂等の保護材で被覆し多層構造とする方法があるが、いずれも加工コストが大幅に増加する。 In order to improve oil resistance, for example, a method of adding a polyolefin resin or polyphenylene ether resin to a rubber-modified polystyrene base resin, or a method of coating a rubber-modified polystyrene base resin with a protective material such as a polyolefin resin to form a multilayer structure However, both of them significantly increase the processing cost.
また、その他の方法として、特許文献1〜3には、ゴムの分散粒子径を大粒子径化する方法が開示されているが、粒子径を大きくすることにより材料の剛性が著しく低下する。 As other methods, Patent Documents 1 to 3 disclose a method of increasing the dispersed particle diameter of rubber, but the rigidity of the material is significantly reduced by increasing the particle diameter.
食品容器向けシート分野では食用油やミルク等と接触する機会が多いため長時間の耐油性が必要とされることが多くあるが、特に飲料容器蓋材等には、それ以外にも嵌合性を最適とするための適度なコシが求められる。コシを上げるためには容器の厚みを増す方法があるが、コスト高となるため望ましくない。また近年、容器包装リサイクル法の施行により、容器の薄肉軽量化の動きがあり、軽量化後も剛性と強度を保つ材料の開発が望まれている。 In the field of food container seats, there are many opportunities to come in contact with edible oil or milk, so long-term oil resistance is often required. Appropriate stiffness is required to optimize There is a method of increasing the thickness of the container in order to increase the stiffness, but this is not desirable because it increases the cost. In recent years, with the enforcement of the Containers and Packaging Recycling Law, there has been a movement to reduce the thickness and weight of containers, and the development of materials that maintain rigidity and strength after weight reduction is desired.
そこで、本発明は、曲げ弾性率及び衝撃強度などの機械的特性に優れ、かつ耐油性、耐薬品性に優れ、主に油に直接接する食品容器や包装材料に好適に使用することができるゴム変性スチレン系樹脂組成物を提供することを目的とする。 Accordingly, the present invention is a rubber that is excellent in mechanical properties such as flexural modulus and impact strength, and excellent in oil resistance and chemical resistance, and can be suitably used for food containers and packaging materials mainly in direct contact with oil. An object is to provide a modified styrenic resin composition.
本発明者等は、上記目的を達成するため、鋭意研究を進めたところ、ゴム変性スチレン系樹脂中におけるゴム状分散粒子の体積中位粒子径、ゲル分、グラフト率、膨潤比を特定の範囲とすることによって上記課題が達成できることを見出した。 The inventors of the present invention have made extensive studies to achieve the above object, and have found that the volume-average particle diameter, gel content, graft ratio, and swelling ratio of rubber-like dispersed particles in the rubber-modified styrenic resin are within a specific range. It has been found that the above problems can be achieved.
即ち、本発明のゴム変性スチレン系樹脂組成物は、ポリブタジエンの存在下、スチレン系単量体をグラフト重合してなるゴム変性スチレン系樹脂であって、ゴム状分散粒子の体積中位粒子径が4〜10μmであり、ゲル分が22〜35質量%、グラフト率が1.30〜2.00、膨潤度が12〜20であり、流動パラフィンを1〜3質量%含むことを特徴とする。 That is, the rubber-modified styrene resin composition of the present invention is a rubber-modified styrene resin obtained by graft polymerization of a styrene monomer in the presence of polybutadiene, and the volume-median particle size of rubber-like dispersed particles is is 4 to 10 [mu] m, the gel fraction is 22-35% by weight, graft ratio from 1.30 to 2.00, a degree of swelling Ri der 12-20, characterized in that it comprises a liquid paraffin 1-3% by weight .
本発明のゴム変性スチレン系樹脂組成物は、耐油性、耐薬品性が向上し、しかも衝撃強度と剛性に優れるため、食品向け嵌合容器に好適に使用することができ、さらにシートの薄肉軽量化が可能となる。 The rubber-modified styrene-based resin composition of the present invention has improved oil resistance and chemical resistance, and is excellent in impact strength and rigidity, so that it can be suitably used for food fitting containers, and the sheet is thin and lightweight. Can be realized.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のゴム変性スチレン系樹脂組成物は、ポリブタジエンの存在下、スチレン系単量体をグラフト重合して得られるものである。重合方法としては公知の方法、例えば、塊状重合法、塊状・懸濁二段重合法、溶液重合法等により製造することができる。 The rubber-modified styrene resin composition of the present invention is obtained by graft polymerization of a styrene monomer in the presence of polybutadiene. As the polymerization method, it can be produced by a known method, for example, a bulk polymerization method, a bulk / suspension two-stage polymerization method, a solution polymerization method or the like.
スチレン系単量体としては、スチレン、α−メチルスチレン、o−メチルスチレン、p−メチルスチレン等の単独または混合物をいい、特に好ましくはスチレンである。また、これらのスチレン系単量体に共重合可能な単量体、例えばアクリロニトリル、メタクリル酸エステル、アクリル酸エステル等の単量体も本発明の効果を損なわない程度であれば共重合することができる。 As a styrene-type monomer, styrene, (alpha) -methylstyrene, o-methylstyrene, p-methylstyrene etc. are individual or a mixture, Especially preferably, it is styrene. In addition, monomers that can be copolymerized with these styrenic monomers, for example, monomers such as acrylonitrile, methacrylic acid esters, and acrylic acid esters, can be copolymerized as long as the effects of the present invention are not impaired. it can.
また、ポリブタジエンとしては、1,4−シス構造が90モル%以上のハイシスポリブタジエンと、1,4−シス構造が15〜40モル%のローシスポリブタジエンのいずれを用いてもよく、また混合物であっても良いが、特に好ましいのはハイシスポリブタジエンである。ハイシスポリブタジエンを用いた場合、剛性と耐衝撃性の面で優れた物性のものが得られる。 As the polybutadiene, either a high cis polybutadiene having a 1,4-cis structure of 90 mol% or more and a low cis polybutadiene having a 1,4-cis structure of 15 to 40 mol% may be used. Particularly preferred is high-cis polybutadiene. When high-cis polybutadiene is used, a material having excellent physical properties in terms of rigidity and impact resistance can be obtained.
本発明のゴム変性スチレン系樹脂組成物のゴム状分散粒子の体積中位粒子径は4〜10μmであり、好ましくは4〜8μmである。体積中位粒子径が4μm未満では樹脂組成物の耐油性が低下し、10μmを超えると樹脂組成物の剛性が著しく低下する。粒子径を調整する方法としては、重合工程においてゴム粒子の相転域での攪拌速度を調整する方法や、原料液中の連鎖移動開始剤の量を調整する方法などが挙げられる。なお、本発明において、ゴム状分散粒子の体積中位粒子径は、ゴム変性スチレン系樹脂組成物をジメチルホルムアミドに溶解させ、レーザー回折方式粒度分布測定装置(コールター社製レーザー回折方式粒子アナライザーLS−230型:アパチャーチューブのオリフィス径30μm)により測定して求めた体積基準の粒径分布曲線の50体積%粒子径をいう。 The volume median particle diameter of the rubber-like dispersed particles of the rubber-modified styrenic resin composition of the present invention is 4 to 10 μm, preferably 4 to 8 μm. When the volume median particle diameter is less than 4 μm, the oil resistance of the resin composition is lowered, and when it exceeds 10 μm, the rigidity of the resin composition is significantly lowered. Examples of the method for adjusting the particle diameter include a method for adjusting the stirring speed in the phase transition region of the rubber particles in the polymerization step, a method for adjusting the amount of the chain transfer initiator in the raw material liquid, and the like. In the present invention, the volume-average particle size of the rubber-like dispersed particles is determined by dissolving a rubber-modified styrene resin composition in dimethylformamide and measuring a laser diffraction particle size distribution analyzer (Laser diffraction particle analyzer LS- manufactured by Coulter). 230 type: 50 volume% particle diameter of a volume-based particle size distribution curve obtained by measurement using an aperture tube orifice diameter of 30 μm).
本発明のゴム変性スチレン系樹脂組成物のゲル分は22〜35質量%であり、好ましくは22〜28質量%である。ゲル分が22質量%未満では樹脂組成物の耐油性が低下し、35質量%を超えると樹脂組成物の剛性が低下する。ゲル分を調整する方法としては、重合工程においてゴム含有量を調整する方法、開始剤量を調整する方法の他、重合後にブレンドにより調整する方法などが挙げられる。ゲル分は、ゴム変性スチレン系樹脂組成物中のゴム状分散粒子の割合であり、質量Wのゴム変性スチレン系樹脂組成物をメチルエチルケトンに5%の割合で溶解し、その溶液を遠心分離して不溶分を沈降せしめ、デカンテーションにより上澄み液を除去して不溶分を得、70℃で15時間程度真空乾燥し、20分間デシケーター中で冷却した後、乾燥した不溶分の質量Gを測定して次のように求めることができる。 The gel content of the rubber-modified styrene resin composition of the present invention is 22 to 35% by mass, preferably 22 to 28% by mass. When the gel content is less than 22% by mass, the oil resistance of the resin composition is lowered, and when it exceeds 35% by mass, the rigidity of the resin composition is lowered. Examples of the method for adjusting the gel content include a method of adjusting the rubber content in the polymerization step, a method of adjusting the initiator amount, and a method of adjusting by blending after polymerization. The gel content is the ratio of rubber-like dispersed particles in the rubber-modified styrene resin composition. The rubber-modified styrene resin composition having a mass W is dissolved in methyl ethyl ketone at a ratio of 5%, and the solution is centrifuged. The insoluble matter is allowed to settle, the supernatant is removed by decantation to obtain an insoluble matter, vacuum dried at 70 ° C. for about 15 hours, cooled in a desiccator for 20 minutes, and then the mass G of the dried insoluble matter is measured. It can be obtained as follows.
ゲル分(ゴム状分散粒子量)(質量%)=(G/W)×100 Gel content (amount of rubber-like dispersed particles) (mass%) = (G / W) × 100
本発明のゴム変性スチレン系樹脂組成物のグラフト率は1.00〜2.00であり、好ましくは1.20〜1.55である。グラフト率が1.00未満であると樹脂組成物の耐油性を保つために多くのゴム分が必要となり、グラフト率が2.00を超えると樹脂組成物の剛性が低下する。グラフト率を調整する方法としては、重合工程において開始剤の量を下げる方法があるが、反応器の形式や用いるゴム種によっても変わる。グラフト率は、ゴム変性スチレン系樹脂組成物中のゲル分(質量%)とゴム変性スチレン系樹脂組成物中のゴム分(質量%)から次のように求めることができる。 The graft ratio of the rubber-modified styrene resin composition of the present invention is 1.00 to 2.00, preferably 1.20 to 1.55. If the graft ratio is less than 1.00, a large amount of rubber is required to maintain the oil resistance of the resin composition, and if the graft ratio exceeds 2.00, the rigidity of the resin composition decreases. As a method of adjusting the graft ratio, there is a method of reducing the amount of the initiator in the polymerization step, but it varies depending on the type of the reactor and the rubber type used. The graft ratio can be determined from the gel content (mass%) in the rubber-modified styrenic resin composition and the rubber content (mass%) in the rubber-modified styrene resin composition as follows.
グラフト率=(ゲル分−ゴム分)/ゴム分 Graft rate = (gel content-rubber content) / rubber content
なお、ゴム変性スチレン系樹脂組成物中のゴム分は、ゴム変性スチレン系樹脂組成物をクロロホルムに溶解させ、一定量の一塩化ヨウ素/四塩化炭素溶液を加え暗所に約1時間放置後、ヨウ化カリウム溶液を加え、過剰の一塩化ヨウ素を0.1Nチオ硫酸ナトリウム/エタノール水溶液で滴定し、付加した一塩化ヨウ素量から求めることができる。 The rubber content in the rubber-modified styrenic resin composition is obtained by dissolving the rubber-modified styrenic resin composition in chloroform, adding a certain amount of iodine monochloride / carbon tetrachloride solution and leaving it in the dark for about 1 hour. Potassium iodide solution is added, excess iodine monochloride is titrated with 0.1N sodium thiosulfate / ethanol aqueous solution, and the amount of iodine monochloride added can be determined.
本発明のゴム変性スチレン系樹脂組成物の膨潤度SIは12〜20であり、好ましくは13〜17である。膨潤度SIが12未満であると樹脂組成物の強度が低下し、膨潤度SIが20を超えると樹脂組成物の強度と剛性が低下する。膨潤度SIを調整する方法としては、脱揮工程における温度条件を調整する方法がある。なお、膨潤度SIは、樹脂組成物をトルエンに溶解し、その溶液を遠心分離して不溶分を沈降せしめ、デカンテーションにより上澄み液を除去してトルエンで膨潤した不溶分の質量Sを測定し、続いてトルエンで膨潤した不溶分を70℃で15時間真空乾燥し、20分間デシケーター中で冷却した後、不溶分の乾燥質量Dを測定して次のように求めることができる。 The swelling degree SI of the rubber-modified styrenic resin composition of the present invention is 12 to 20, preferably 13 to 17. When the degree of swelling SI is less than 12, the strength of the resin composition decreases, and when the degree of swelling SI exceeds 20, the strength and rigidity of the resin composition decrease. As a method of adjusting the degree of swelling SI, there is a method of adjusting temperature conditions in the devolatilization step. The degree of swelling SI is obtained by dissolving the resin composition in toluene, centrifuging the solution to settle the insoluble matter, removing the supernatant by decantation, and measuring the mass S of the insoluble matter swollen with toluene. Subsequently, the insoluble matter swollen with toluene is vacuum-dried at 70 ° C. for 15 hours, cooled in a desiccator for 20 minutes, and then the dry mass D of the insoluble matter is measured to obtain as follows.
膨潤度SI=S/D Swelling degree SI = S / D
本発明のゴム変性スチレン系樹脂組成物は、流動パラフィンを1〜3質量%含むことが好ましく、1〜2質量%含むことがより好ましい。流動パラフィンが1質量%未満では樹脂組成物の耐油性、成形流動性が低下する場合があり、流動パラフィンが3質量%以上では、耐油性、耐熱性が低下すると同時に成形性が悪化する恐れがある。なお、流動パラフィンは、沸点的には潤滑油留分に属する、きわめて純度の高い液状飽和炭化水素の混合物であると定義される公知のもの(ホワイトオイルと称される)であれば差し支えない。 The rubber-modified styrenic resin composition of the present invention preferably contains 1 to 3 mass%, more preferably 1 to 2 mass% of liquid paraffin. If the liquid paraffin is less than 1% by mass, the oil resistance and molding fluidity of the resin composition may be lowered. If the liquid paraffin is 3% by mass or more, the oil resistance and heat resistance may be lowered and the moldability may be deteriorated. is there. The liquid paraffin may be a known one (referred to as white oil) that is defined as a mixture of liquid saturated hydrocarbons having a very high purity and belonging to the lubricating oil fraction in terms of boiling point.
本発明のゴム変性スチレン系樹脂組成物の曲げ弾性率は好ましくは1600Mpa以上であり、さらに好ましくは1800Mpa以上である。曲げ弾性率が1600Mpa未満であるとシートや容器、蓋類等を成形した際のコシが不十分となることが多い。 The flexural modulus of the rubber-modified styrene resin composition of the present invention is preferably 1600 Mpa or more, and more preferably 1800 Mpa or more. When the bending elastic modulus is less than 1600 MPa, the stiffness when molding a sheet, a container, a lid or the like is often insufficient.
本発明のゴム変性スチレン系樹脂組成物は、その物性を損なわない範囲で1種類以上のゴム変性スチレン系樹脂、あるいはゴム変性していないスチレン系樹脂をブレンドすることができる。また、そのブレンド方法には特に制限はなく、ゴム変性スチレン系樹脂とゴム変性していないスチレン系樹脂を混合し、押出機により再造粒する方法、あるいは、ゴム変性スチレン系樹脂とゴム変性していないスチレン系樹脂を混合したものを、ヘンシェルミキサー、リボンブレンダー、スーパーミキサー、及びVブレンダー等でドライブレンドする方法がある。 The rubber-modified styrenic resin composition of the present invention can be blended with one or more kinds of rubber-modified styrenic resins or styrene-based resins that are not rubber-modified as long as the physical properties thereof are not impaired. The blending method is not particularly limited, and a method in which a rubber-modified styrene resin and a rubber-modified styrene resin are mixed and re-granulated by an extruder, or a rubber-modified styrene resin and a rubber-modified styrene resin are modified. There is a method of dry blending an unmixed styrene resin with a Henschel mixer, a ribbon blender, a super mixer, a V blender, or the like.
本発明のゴム変性スチレン系樹脂組成物は、必要に応じて、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、高級脂肪酸、高級脂肪酸塩、難燃剤、着色剤、顔料等の添加剤を添加することができる。 The rubber-modified styrenic resin composition of the present invention is optionally added with an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a higher fatty acid, a higher fatty acid salt, a flame retardant, a colorant, a pigment, and the like. An agent can be added.
本発明のゴム変性スチレン系樹脂組成物は、押出成形、射出成形、射出中空成形等の公知の成形法によって各種成形品を成形することができ、各種発泡成形技術と組み合わせて、発泡成形体を成型することもできる。更にTダイシート押出機、二軸延伸加工装置、インフレーション加工装置を用いて、シートやフィルムに成形することができる。成形品がシートの場合、単層であっても良いし、多層シートの最外層のうち油等と接触する恐れのある少なくとも一方の面に用いても良い。シートの厚みに特に制限はないが成形品のコシを上げるために0.2mm以上とするのが好ましい。 The rubber-modified styrenic resin composition of the present invention can be molded into various molded products by known molding methods such as extrusion molding, injection molding, injection hollow molding, etc., and combined with various foam molding techniques, It can also be molded. Furthermore, it can shape | mold into a sheet | seat or a film using a T-die sheet extruder, a biaxial stretching processing apparatus, and an inflation processing apparatus. When the molded product is a sheet, it may be a single layer or may be used on at least one surface of the outermost layer of the multilayer sheet that may come into contact with oil or the like. Although there is no restriction | limiting in particular in the thickness of a sheet | seat, It is preferable to set it as 0.2 mm or more in order to raise the stiffness of a molded article.
本発明のゴム変性スチレン系樹脂組成物よりなるシートは、加熱され、種々の形状に二次成形され、各種食品容器、食品包装に用いることができる。食品容器、食品包装の具体的な例としては、コップ、デザート容器、アイスクリーム容器、冷菓容器、ヨーグルト容器、乳飲料容器、乳酸菌飲料容器、一般飲料容器、ミルクポーション、惣菜容器、弁当箱、豆腐容器、それらの蓋類、卵容器、青果用容器、ミートトレーなどが挙げられる。 The sheet made of the rubber-modified styrene resin composition of the present invention is heated and secondarily formed into various shapes, and can be used for various food containers and food packaging. Specific examples of food containers and food packaging include cups, dessert containers, ice cream containers, frozen dessert containers, yogurt containers, milk drink containers, lactic acid bacteria drink containers, general drink containers, milk potions, sugar beet containers, lunch boxes, tofu Containers, their lids, egg containers, fruit and vegetable containers, meat trays and the like.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.
尚、実施例で使用したポリブタジエンは以下の通りである。 The polybutadiene used in the examples is as follows.
(1)ハイシスポリブタジエン
宇部興産社製「BR−15HB」1,4−シス構造:97モル%
(1) High cis polybutadiene "BR-15HB" 1,4-cis structure manufactured by Ube Industries, Ltd .: 97 mol%
(2)ローシスポリブタジエン
旭化成社製「ジエン55AE」1,4−シス構造:35モル%
(2) Low-cis polybutadiene "Diene 55AE" 1,4-cis structure manufactured by Asahi Kasei Corporation: 35 mol%
また、実施例で使用したゴム変性スチレン系樹脂組成物は以下のように製造した。 Moreover, the rubber-modified styrene resin composition used in the examples was produced as follows.
(1)HIPS−1の製造
下記第1〜第4反応器を直列に接続して重合工程を構成した。
(1) Production of HIPS-1 The following first to fourth reactors were connected in series to constitute a polymerization step.
第1反応器:容積25Lの攪拌翼付完全混合型反応器
第2反応器:容積25Lの攪拌翼付プラグフロー型反応器
第3反応器:容積50Lの攪拌翼付プラグフロー型反応器
第4反応器:容積50Lのスタティックミキサー式プラグフロー反応器
First reactor: 25 L capacity mixing bladed complete mixing reactor Second reactor: 25 L capacity plug flow reactor with stirring blade Third reactor: 50 L capacity plug flow reactor with stirring blade Reactor: Static mixer type plug flow reactor with 50L capacity
各反応器での条件は以下の通りとした。 The conditions in each reactor were as follows.
第1反応器:[攪拌数]100rpm、[反応温度]125℃
第2反応器:[攪拌数]60rpm、[反応温度]反応液の流れ方向に128〜130℃の温度勾配がつくように調整
第3反応器:[攪拌数]30rpm、[反応温度]反応液の流れ方向に128〜130℃の温度勾配がつくように調整
第4反応器:[反応温度]流れ方向に140〜165℃の温度勾配がつくように調整
First reactor: [Number of stirring] 100 rpm, [Reaction temperature] 125 ° C.
Second reactor: [Number of stirring] 60 rpm, [Reaction temperature] Adjusted so that a temperature gradient of 128 to 130 ° C. is formed in the flow direction of the reaction liquid. Third reactor: [Number of stirring] 30 rpm, [Reaction temperature] Reaction liquid 4th reactor: [Reaction temperature] Adjusted to have a temperature gradient of 140 to 165 ° C in the flow direction
また、原料液としては、以下のものを用いた。 Moreover, the following were used as a raw material liquid.
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.025質量%添加した原料液 Raw material liquid in which 0.025% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene and 7.5% by mass of high-cis polybutadiene are dissolved.
まず、原料液を23L/hrの供給速度で第1反応器に連続的に供給し重合した後、第2反応器に連続的に装入して重合した。第1反応器の出口では、いまだポリブタジエンが分散粒子化(相反転)していない状態で、第2反応器の出口では分散粒子化が終了した状態となり、このときの重合転化率は28%であった。次いで、第2反応器の出口からの重合液を第3反応器に連続的に装入し、このときの重合転化率は42%であった。さらに第4反応器にて重合転化率が70%になるまで重合を進行させた。 First, the raw material liquid was continuously supplied to the first reactor at a supply rate of 23 L / hr for polymerization, and then charged continuously into the second reactor for polymerization. At the outlet of the first reactor, polybutadiene has not yet been dispersed and phase-reversed (phase inversion), and at the outlet of the second reactor, dispersion of particles has been completed. The polymerization conversion rate at this time is 28%. there were. Subsequently, the polymerization liquid from the outlet of the second reactor was continuously charged into the third reactor, and the polymerization conversion rate at this time was 42%. Furthermore, the polymerization was allowed to proceed in the fourth reactor until the polymerization conversion reached 70%.
得られた重合液を直列に2段より構成される予熱器付き真空脱揮槽に導入し、未反応スチレン及びエチルベンゼンを分離した後、ストランド状に押し出しして冷却した後、切断してペレットとした。なお、1段目の脱揮槽内の樹脂温度は200℃に設定し、真空脱揮槽の圧力は53.3kPa(400torr)とし、2段目の脱揮槽内の樹脂温度は245℃に設定し、真空脱揮槽の圧力は2.7Pa(20torr)とした。 The obtained polymerization liquid was introduced into a vacuum devolatilization tank equipped with a preheater composed of two stages in series, and after separating unreacted styrene and ethylbenzene, it was extruded into a strand and cooled, then cut into pellets and did. The resin temperature in the first devolatilization tank is set to 200 ° C., the pressure in the vacuum devolatilization tank is 53.3 kPa (400 torr), and the resin temperature in the second devolatilization tank is 245 ° C. The pressure in the vacuum devolatilization tank was set to 2.7 Pa (20 torr).
得られたゴム変性スチレン系樹脂組成物HIPS−1の特性を表1に示す。 Table 1 shows the properties of the rubber-modified styrene-based resin composition HIPS-1.
(2)HIPS−2の製造
以下の原料液を用いた以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(2) Production of HIPS-2 A rubber-modified styrene resin composition was produced in the same manner as in the production of HIPS-1, except that the following raw material liquid was used. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.035質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.035% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene and 7.5% by mass of high-cis polybutadiene are dissolved.
(3)HIPS−3の製造
以下の原料液を用いた以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(3) Production of HIPS-3 A rubber-modified styrene resin composition was produced in the same manner as in the production of HIPS-1, except that the following raw material solutions were used. The characteristics are shown in Table 1.
<原料液>
スチレン単量体77.6質量%、エチルベンゼン13.7質量%、ハイシスポリブタジエン8.7質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.025質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.025% by mass of t-dodecyl mercaptan is added to a solution in which 77.6% by mass of styrene monomer, 13.7% by mass of ethylbenzene, and 8.7% by mass of high-cis polybutadiene are dissolved.
(4)HIPS−4の製造
以下の原料液を用いた以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(4) Production of HIPS-4 A rubber-modified styrene resin composition was produced in the same manner as in the production of HIPS-1, except that the following raw material liquid was used. The characteristics are shown in Table 1.
<原料液>
スチレン単量体77.6質量%、エチルベンゼン13.7質量%、ハイシスポリブタジエン8.7質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.035質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.035% by mass of t-dodecyl mercaptan is added to a solution in which 77.6% by mass of styrene monomer, 13.7% by mass of ethylbenzene, and 8.7% by mass of high-cis polybutadiene are dissolved.
(5)HIPS−5の製造
以下の原料液を用い、第2反応器の出口からの重合液に対し、t−ブチルクミルパーオキサイドを0.030質量%添加し、第3,第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更し、2段目の脱気槽内の樹脂温度を260℃とした以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(5) Production of HIPS-5 Using the following raw material liquid, 0.030% by mass of t-butylcumyl peroxide was added to the polymerization liquid from the outlet of the second reactor, and the third and fourth reactors were added. The rubber-modified styrene was manufactured in the same manner as in the production of HIPS-1, except that the conditions (number of stirring and / or reaction temperature) were changed as follows and the resin temperature in the second stage deaeration tank was changed to 260 ° C. A resin composition was produced. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.030質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.030% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene and 7.5% by mass of high-cis polybutadiene are dissolved.
<条件>
第3反応器:[反応温度]128℃
第4反応器:[反応温度]流れ方向に137〜165℃の温度勾配がつくように調整
<Conditions>
Third reactor: [reaction temperature] 128 ° C
Fourth reactor: [Reaction temperature] Adjusted to have a temperature gradient of 137 to 165 ° C in the flow direction.
(6)HIPS−6の製造
以下の原料液を用い、第2反応器の出口からの重合液に対し、t−ブチルクミルパーオキサイドを0.030質量%添加し、第3,第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更した以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(6) Production of HIPS-6 Using the following raw material liquid, 0.030% by mass of t-butylcumyl peroxide was added to the polymerization liquid from the outlet of the second reactor, and the third and fourth reactors were added. A rubber-modified styrenic resin composition was produced in the same manner as in the production of HIPS-1, except that the conditions (number of stirring and / or reaction temperature) were changed as follows. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.045質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.045% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene and 7.5% by mass of high-cis polybutadiene are dissolved.
<条件>
第3反応器:[反応温度]128℃
第4反応器:[反応温度]流れ方向に137〜165℃の温度勾配がつくように調整
<Conditions>
Third reactor: [reaction temperature] 128 ° C
Fourth reactor: [Reaction temperature] Adjusted to have a temperature gradient of 137 to 165 ° C in the flow direction.
(7)HIPS−7の製造
以下の原料液を用い、第2〜第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更した以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(7) Production of HIPS-7 Using the following raw material liquid, the same as the production of HIPS-1, except that the conditions of the second to fourth reactors (stirring number and / or reaction temperature) were changed as follows. Thus, a rubber-modified styrene resin composition was produced. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.4質量%、エチルベンゼン13.8質量%、ローシスポリブタジエン7.8質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.030質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.030% by mass of t-dodecyl mercaptan is added to a solution in which 78.4% by mass of styrene monomer, 13.8% by mass of ethylbenzene and 7.8% by mass of low-cis polybutadiene are dissolved.
<条件>
第2反応器:[攪拌数]70rpm、[反応温度]反応液の流れ方向に128〜129℃の温度勾配がつくように調整
第3反応器:[反応温度]反応液の流れ方向に130〜135℃の温度勾配がつくように調整
第4反応器:[反応温度]流れ方向に139〜165℃の温度勾配がつくように調整
<Conditions>
Second reactor: [Number of stirring] 70 rpm, [Reaction temperature] Adjusted so that a temperature gradient of 128 to 129 ° C. is formed in the flow direction of the reaction solution. Third reactor: [Reaction temperature] 130 to 130 in the flow direction of the reaction solution Adjust so that a temperature gradient of 135 ° C is obtained. Fourth reactor: [Reaction temperature] Adjust so that a temperature gradient of 139 to 165 ° C is applied in the flow direction.
(8)HIPS−8の製造
以下の原料液を用いた以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(8) Production of HIPS-8 A rubber-modified styrene resin composition was produced in the same manner as in the production of HIPS-1, except that the following raw material liquid was used. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.015質量%添加した原料液
<Raw material liquid>
Raw material solution in which 0.015% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene, and 7.5% by mass of high-cis polybutadiene are dissolved.
(9)HIPS−9の製造
以下の原料液を用い、第2反応器の出口からの重合液に対し、t−ブチルクミルパーオキサイドを0.030質量%添加し、第2〜第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更し、2段目の脱気槽内の樹脂温度を260℃とした以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(9) Production of HIPS-9 Using the following raw material liquid, 0.030% by mass of t-butylcumyl peroxide was added to the polymerization liquid from the outlet of the second reactor, and the second to fourth reactors were added. The rubber-modified styrene was manufactured in the same manner as in the production of HIPS-1, except that the conditions (number of stirring and / or reaction temperature) were changed as follows and the resin temperature in the second stage deaeration tank was changed to 260 ° C. A resin composition was produced. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.6質量%、エチルベンゼン13.9質量%、ハイシスポリブタジエン7.5質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.005質量%添加した原料液
<Raw material liquid>
Raw material solution in which 0.005% by mass of t-dodecyl mercaptan is added to a solution in which 78.6% by mass of styrene monomer, 13.9% by mass of ethylbenzene and 7.5% by mass of high-cis polybutadiene are dissolved.
<条件>
第2反応器:[攪拌数]80rpm
第3反応器:反応温度]128℃
第4反応器:[反応温度]流れ方向に137〜165℃の温度勾配がつくように調整
<Conditions>
Second reactor: [Number of stirring] 80 rpm
Third reactor: reaction temperature] 128 ° C
Fourth reactor: [Reaction temperature] Adjusted to have a temperature gradient of 137 to 165 ° C in the flow direction.
(10)HIPS−10の製造
以下の原料液を用い、第2反応器の出口からの重合液に対し、t−ブチルクミルパーオキサイドを0.020質量%添加し、第2、第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更し、2段目の脱気槽内の樹脂温度を260℃とした以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(10) Production of HIPS-10 Using the following raw material liquid, 0.020% by mass of t-butylcumyl peroxide was added to the polymerization liquid from the outlet of the second reactor, and the second and fourth reactors were added. The rubber-modified styrene was manufactured in the same manner as in the production of HIPS-1, except that the conditions (number of stirring and / or reaction temperature) were changed as follows and the resin temperature in the second stage deaeration tank was changed to 260 ° C. A resin composition was produced. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.4質量%、エチルベンゼン13.9質量%、ローシスポリブタジエン7.8質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.015質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.015% by mass of t-dodecyl mercaptan is added to a solution in which 78.4% by mass of styrene monomer, 13.9% by mass of ethylbenzene, and 7.8% by mass of low-cis polybutadiene are dissolved.
<条件>
第2反応器:[攪拌数]110rpm、[反応温度]反応液の流れ方向に128〜129℃の温度勾配がつくように調整
第4反応器:[反応温度]流れ方向に134〜165℃の温度勾配がつくように調整
<Conditions>
Second reactor: [Number of stirring] 110 rpm, [Reaction temperature] Adjusted so that a temperature gradient of 128 to 129 ° C. is formed in the flow direction of the reaction solution Fourth reactor: [Reaction temperature] 134 to 165 ° C. in the flow direction Adjust to create a temperature gradient
(11)HIPS−11の製造
以下の原料液を用い、第2〜第4反応器の条件(攪拌数及び/又は反応温度)を以下のように変更し、2段目の脱気槽内の樹脂温度を260℃とした以外は、HIPS−1の製造と同様にしてゴム変性スチレン系樹脂組成物を製造した。その特性を表1に示す。
(11) Production of HIPS-11 Using the following raw material liquid, the conditions of the second to fourth reactors (stirring number and / or reaction temperature) were changed as follows, and the inside of the second stage deaeration tank A rubber-modified styrene resin composition was produced in the same manner as in the production of HIPS-1, except that the resin temperature was 260 ° C. The characteristics are shown in Table 1.
<原料液>
スチレン単量体78.4質量%、エチルベンゼン13.9質量%、ローシスポリブタジエン7.8質量%を溶解させた溶液に対してt−ドデシルメルカプタン0.030質量%添加した原料液
<Raw material liquid>
Raw material liquid in which 0.030% by mass of t-dodecyl mercaptan is added to a solution in which 78.4% by mass of styrene monomer, 13.9% by mass of ethylbenzene, and 7.8% by mass of low-cis polybutadiene are dissolved.
<条件>
第2反応器:[攪拌数]70rpm、[反応温度]反応液の流れ方向に128〜129℃の温度勾配がつくように調整
第3反応器:[反応温度]反応液の流れ方向に130〜135℃の温度勾配がつくように調整
第4反応器:[反応温度]流れ方向に139〜165℃の温度勾配がつくように調整
<Conditions>
Second reactor: [Number of stirring] 70 rpm, [Reaction temperature] Adjusted so that a temperature gradient of 128 to 129 ° C. is formed in the flow direction of the reaction solution. Third reactor: [Reaction temperature] 130 to 130 in the flow direction of the reaction solution Adjust so that a temperature gradient of 135 ° C is obtained. Fourth reactor: [Reaction temperature] Adjust so that a temperature gradient of 139 to 165 ° C is applied in the flow direction.
<実施例1〜7、比較例1〜6>
ゴム変性スチレン系樹脂組成物に対して流動パラフィンを表2の割合で加え、二軸押出機を用いてブレンドしペレット化した。得られたペレットについて、下記条件にて物性測定を行った。その結果を表2に示す。
<Example 1-7, Comparative Example 1-6>
Liquid paraffin was added to the rubber-modified styrenic resin composition in the ratio shown in Table 2, blended using a twin screw extruder, and pelletized. About the obtained pellet, the physical-property measurement was performed on the following conditions. The results are shown in Table 2.
(1)メルトマスフローレート
射出成形機を用いて試験片を作成し、JIS K−7210に基づき200℃、49N荷重の条件により求めた。
(1) Melt Mass Flow Rate A test piece was prepared using an injection molding machine, and was determined under the conditions of 200 ° C. and 49 N load based on JIS K-7210.
(2)ビカット軟化温度
射出成形機を用いて試験片を作成し、JIS K−7206に基づき49N荷重の条件により求めた。
(2) Vicat softening temperature A test piece was prepared using an injection molding machine, and was determined under a 49 N load condition based on JIS K-7206.
(3)曲げ弾性率(剛性)
射出成形機を用いて試験片を作成し、JIS K−7171により求めた。
(3) Flexural modulus (rigidity)
Test pieces were prepared using an injection molding machine and determined according to JIS K-7171.
(4)シャルピー衝撃強度(耐衝撃性)
射出成形機を用いて試験片を作成し、JIS K−7111により求めた。
(4) Charpy impact strength (impact resistance)
Test pieces were prepared using an injection molding machine and determined according to JIS K-7111.
(5)耐油性
単軸シート押出機を用いてシート成形し、厚み0.4mmのシートを作成した。得られたシートからTD方向に長さ180mm、幅15mmの短冊を切り出し、定歪み冶具に150mm幅まで弓状に曲げて取り付けた後、試験片の中央部に1cmの幅でガーゼを置き、下記油(a)〜(c)を0.5mL塗布した。
(5) Oil resistance Sheets were formed using a single screw sheet extruder to produce a 0.4 mm thick sheet. A strip with a length of 180 mm and a width of 15 mm was cut out in the TD direction from the obtained sheet, attached to a constant strain jig by bending it into a bow shape to a width of 150 mm, and then gauze was placed with a width of 1 cm at the center of the test piece. 0.5 mL of oil (a)-(c) was apply | coated.
(a)日清オイリオグループ社製、日清サラダ油(商品名)
(b)タカナシ乳業社製、特選北海道産 純生クリーム47(商品名)
(c)東京めいらく社製、生クリーム入りスジャータ(商品名)
(A) Nisshin Oillio Group, Nissin salad oil (trade name)
(B) Pure fresh cream 47 (trade name), manufactured by Takashi Dairy & Co., Ltd.
(C) Tokyo Meiraku Co., Ltd. Sujata with fresh cream
24時間後の外観を観察し、クラックが発生しないものを○、クラックの発生するものを△、破断するものを×として評価した。 The appearance after 24 hours was observed, and the case where no crack was generated was evaluated as ◯, the case where a crack was generated was evaluated as Δ, and the case where it was broken was evaluated as ×.
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