JP2008274168A - Styrenic resin composition, extruded foam sheet and container, and flat extruded foam - Google Patents
Styrenic resin composition, extruded foam sheet and container, and flat extruded foam Download PDFInfo
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本発明は、発泡トレー等の発泡容器において製品強度を維持したまま軽量化が可能なスチレン系樹脂組成物およびその材料を用いて押出発泡成形した押出発泡シート、さらに押出発泡シートを真空成型して得られる軽量化容器に関するものである。
また本発明は断熱材等に用いられる板状押出発泡体の断熱性能を維持したまま軽量化が可能なスチレン系樹脂組成物およびその材料を用いた板状押出発泡体に関するものである。
The present invention relates to a styrene-based resin composition that can be reduced in weight while maintaining product strength in a foam container such as a foam tray, an extruded foam sheet formed by extrusion foaming using the material, and a vacuum-molded extruded foam sheet. The present invention relates to a lightweight container obtained.
The present invention also relates to a styrene-based resin composition that can be reduced in weight while maintaining the heat insulation performance of a plate-like extruded foam used for a heat insulating material and the like, and a plate-like extruded foam using the material.
ポリスチレン系樹脂押出発泡シートから熱成形により成形した食品用の簡易容器は、例えば、肉、魚、惣菜等々のトレー、カップめん容器、納豆容器等種々の食品用の簡易容器として汎用的に使われている。このような発泡シートの熱成形による簡易容器においてはコストダウンのために容器の軽量化が計られているが、容器を軽量化すると製品強度が低下してトレーのラッピングの際に容器が割れる等の問題がある。
これに対して押出発泡成形時における発泡セル形態をコントロールしたり、真空成型容器の厚み、特に割れやすい部分の厚みを厚くしたりして軽量化しても容器強度を保つ工夫がされている（非特許文献１）。
Simple containers for foods molded from polystyrene resin extruded foam sheets by thermoforming are widely used as simple containers for various foods such as trays for meat, fish, prepared foods, cup noodle containers, natto containers, etc. Yes. In such a simple container formed by thermoforming a foam sheet, the weight of the container is reduced for cost reduction. However, when the container is lightened, the strength of the product is reduced and the container is broken when the tray is wrapped. There is a problem.
On the other hand, the strength of the container is maintained even if the weight is reduced by controlling the foam cell shape during extrusion foam molding, or by increasing the thickness of the vacuum molded container, particularly the fragile part. Patent Document 1).
また材料としては特定の分岐数を有するスチレン系樹脂を用いる方法（特許文献１）が開示されているが、さらなる軽量化に適した材料が求められている。
さらに断熱材や畳の芯材等に用いられている板状押出発泡体についても軽量化が望まれているが、発泡倍率を上げて軽量化しようとすると発泡セルがうまく形成されず、発泡セルがつながったいわゆる連泡ができて断熱効率が低下したり、また外観が荒れたものになってしまうといった問題があった。
Moreover, although the method (patent document 1) using the styrene resin which has a specific branch number is disclosed as a material, the material suitable for the further weight reduction is calculated | required.
Furthermore, weight reduction is also desired for the plate-like extruded foam used for heat insulating materials and tatami core materials, but when trying to reduce the weight by increasing the foaming ratio, the foam cells are not formed well, and the foam cells. There was a problem that the so-called continuous bubbles were formed and the heat insulation efficiency was lowered, and the appearance was rough.
この問題を解決するために特定のＺ平均分子量および重量平均分子量Ｍｗと数平均分子量Ｍｎの比Ｍｗ／Ｍｎが特定の範囲であるスチレン系樹脂を用いる方法（特許文献２）、Ｚ平均分子量Ｍｚと重量平均分子量Ｍｗの比Ｍｚ／Ｍｗが特定の値以上であるスチレン系樹脂を用いる方法（特許文献３）等が提案されているが、軽量化は十分でなかった。 In order to solve this problem, a method using a styrene-based resin in which the ratio Mw / Mn of a specific Z average molecular weight and weight average molecular weight Mw to number average molecular weight Mn is in a specific range (Patent Document 2), Z average molecular weight Mz and A method using a styrene resin having a weight average molecular weight Mw ratio Mz / Mw of a specific value or more (Patent Document 3) has been proposed, but the weight reduction has not been sufficient.
発泡トレー等の発泡容器において発泡セル形態や容器形状で容器の軽量化を図るには限界があり、さらなる軽量化のために適した材料の登場が望まれていた。また板状押出発泡体の断熱性能を落とすことなく軽量化できる材料が望まれていた。
本発明は、少ない材料で製品強度及び熱強度を維持することができるスチレン系樹脂組成物を提供することを目的とする。また、本発明は当該スチレン系樹脂組成物を押出発泡成形してなる押出発泡シートおよび当該押出発泡シートを真空成形して得られる軽量化容器を提供すること並びに断熱性能を損なうことなく軽量化が可能な板状押出発泡体を提供することを目的とする。
In foaming containers such as foaming trays, there is a limit to reducing the weight of the container in the form of foamed cells and the shape of the container, and the appearance of materials suitable for further weight reduction has been desired. In addition, a material that can be reduced in weight without reducing the heat insulation performance of the plate-like extruded foam has been desired.
An object of this invention is to provide the styrene resin composition which can maintain product intensity | strength and heat intensity with few materials. The present invention also provides an extruded foam sheet obtained by extrusion foam molding of the styrenic resin composition and a weight-reduced container obtained by vacuum molding the extruded foam sheet, and weight reduction without impairing the heat insulation performance. It is an object of the present invention to provide a plate-like extruded foam that can be used.
本発明者らはかかる現状を鑑み、鋭意検討を重ねた結果、特定のメルトマスフローレイトと特定の貯蔵弾性率の角速度依存性を有するスチレン系樹脂組成物を用いることにより、少ない材料で製品強度を維持した発泡容器、あるいは断熱性能を維持した板状押出発泡体が得られることを見出し、本発明を完成させるに至った。
即ち、本発明は、以下に記載する通りのスチレン系樹脂組成物を提供するものである。
As a result of intensive investigations in view of the current situation, the present inventors have achieved a product strength with a small amount of material by using a styrene resin composition having a specific melt mass flow rate and a specific storage elastic modulus having an angular velocity dependency. The inventors have found that a foamed container maintained or a plate-like extruded foam maintaining heat insulation performance can be obtained, and the present invention has been completed.
That is, the present invention provides a styrenic resin composition as described below.
（１）２００℃、４９Ｎ荷重で測定したメルトマスフローレイト（ＭＦＲ）が１．０〜６．０グラム／１０分であって、かつコーン＆プレート型溶融粘弾性測定装置によって２４０℃、角速度０．１ラジアン／秒で測定した貯蔵弾性率Ｇ’（０．１）と角速度１００ラジアン／秒で測定した貯蔵弾性率Ｇ’（１００）の比Ｇ’（０．１）／Ｇ’（１００）が０．００３以上であることを特徴とするスチレン系樹脂組成物。
（２）Ｇ’（０．１）／Ｇ’（１００）が０．００３〜０．００６である上記（１）に記載のスチレン系樹脂組成物。
（３）上記（１）又は（２）に記載のスチレン系樹脂組成物を押出発泡成形してなる押出発泡シート。
（４）上記（３）に記載の押出発泡シートを真空成型して得られる容器。
（５）上記（１）又は（２）記載のスチレン系樹脂組成物を押出発泡成形してなる板状押出発泡体。
(1) Melt mass flow rate (MFR) measured at 200 ° C. under a load of 49 N is 1.0 to 6.0 grams / 10 minutes, and 240 ° C. and angular velocity of 0.1 with a cone and plate type melt viscoelasticity measuring apparatus. The ratio G ′ (0.1) / G ′ (100) of the storage elastic modulus G ′ (0.1) measured at 1 radians / second and the storage elastic modulus G ′ (100) measured at an angular velocity of 100 radians / second is A styrenic resin composition characterized by being 0.003 or more.
(2) The styrenic resin composition according to (1) above, wherein G ′ (0.1) / G ′ (100) is 0.003 to 0.006.
(3) An extruded foam sheet formed by extrusion foam molding of the styrenic resin composition according to the above (1) or (2).
(4) A container obtained by vacuum forming the extruded foam sheet described in (3) above.
(5) A plate-like extruded foam formed by extrusion foam molding of the styrenic resin composition described in (1) or (2) above.
本発明のスチレン系樹脂組成物を用いた押出発泡シートを用いることにより、少量の材料で製品強度に優れた発泡容器を得ることができ、製品のコストダウンに寄与することができる。板状押出発泡体においても同様に少量の材料で断熱性能に優れた製品を得ることができ、製品のコストダウンに寄与することができる。 By using the extruded foam sheet using the styrenic resin composition of the present invention, a foam container having excellent product strength can be obtained with a small amount of material, which can contribute to cost reduction of the product. Similarly, in a plate-like extruded foam, a product having excellent heat insulation performance can be obtained with a small amount of material, which can contribute to cost reduction of the product.
以下、本願発明について具体的に説明する。
本発明のスチレン系樹脂に使用される単量体としてはスチレン、α−メチルスチレン、パラメチルスチレン、エチルスチレン、プロピルスチレン、ブチルスチレン、クロロスチレン、ブロモスチレン等を用いることができる。スチレンが好ましい。本発明に使用されるスチレン系樹脂の目的を損なわない範囲において、スチレンと共重合可能なコモノマーをスチレンと共重合させてもかまわない。スチレンと共重合可能なコモノマーとしては例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステル類、α−メチルスチレン、ｏ−、ｍ−、ｐ−メチルスチレン、ブロモスチレン、ジブロモスチレン、クロロスチレン、ジクロロスチレン等のスチレン以外の芳香族ビニル単量体類、（メタ）アクリル酸、マレイン酸、フマル酸等の不飽和脂肪酸類、無水マレイン酸、無水イタコン酸等の不飽和ジ脂肪酸無水物類，Ｎ−フェニルマレイミド等の不飽和ジ脂肪酸イミド類等が挙げられる。これらの単量体は１種類または２種類以上併用してもかまわない。
Hereinafter, the present invention will be specifically described.
As the monomer used in the styrene resin of the present invention, styrene, α-methylstyrene, paramethylstyrene, ethylstyrene, propylstyrene, butylstyrene, chlorostyrene, bromostyrene and the like can be used. Styrene is preferred. A comonomer copolymerizable with styrene may be copolymerized with styrene within a range not impairing the purpose of the styrene resin used in the present invention. Examples of comonomers copolymerizable with styrene include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, α-methylstyrene, o-, m -, P-methylstyrene, bromostyrene, dibromostyrene, chlorostyrene, dichlorostyrene and other aromatic vinyl monomers other than styrene, (meth) acrylic acid, maleic acid, fumaric acid and other unsaturated fatty acids, anhydrous Examples thereof include unsaturated difatty acid anhydrides such as maleic acid and itaconic anhydride, and unsaturated difatty acid imides such as N-phenylmaleimide. These monomers may be used alone or in combination of two or more.
本発明においては、スチレン系樹脂はスチレン系単量体を熱重合するかまたは有機過酸化物群を重合開始剤として重合することによって得ることができる。有機過酸化物の具体例としては、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン等のパーオキシケタール類、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン等のジアルキルパーオキサイド類、ベンゾイルパーオキサイド、ｍ−トルオイルパーオキサイド等のジアシルパーオキサイド類、ジミリスチルパーオキシジカーボネート等のパーオキシエステル類、シクロヘキサノンパーオキサイド等のケトンパーオキサイド類、ｐ−メンタハイドロパーオキサイド等のハイドロパーオキサイド類、２，２−ビス（４，４−ジターシャリーブチルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジターシャリーアミルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジターシャリーブチルパーオキシシクロヘキシル）ブタン、２，２−ビス（４，４−ジクミルパーオキシシクロヘキシル）プロパンなどの多官能開始剤類を挙げることができる。特に２，２−ビス（４，４−ジターシャリーブチルパーオキシシクロヘキシル）プロパンが好ましい。 In the present invention, the styrenic resin can be obtained by thermally polymerizing a styrenic monomer or polymerizing an organic peroxide group as a polymerization initiator. Specific examples of the organic peroxide include peroxyketals such as 1,1-bis (t-butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. Dialkyl peroxides such as di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diacyl peroxides such as benzoyl peroxide and m-toluoyl peroxide , Peroxyesters such as dimyristylperoxydicarbonate, ketone peroxides such as cyclohexanone peroxide, hydroperoxides such as p-mentahydroperoxide, 2,2-bis (4,4-ditertiary Butylperoxycyclohexyl) propane, 2,2-bis (4,4 Multifunctional initiation of ditertiary amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditertiarybutylperoxycyclohexyl) butane, 2,2-bis (4,4-dicumylperoxycyclohexyl) propane Agents can be mentioned. 2,2-bis (4,4-ditertiary butyl peroxycyclohexyl) propane is particularly preferable.
これらの有機過酸化物はスチレン単量体重合のいずれかの工程にて重合系（重合原料溶液または重合途中の溶液）に添加される。これらの有機過酸化物は重合原料溶液に加えても良いし、重合途中の溶液に必要に応じて複数回に分割して添加しても良い。上記有機過酸化物の添加量は重合原料溶液１００重量部に対して０．０００５〜０．２重量部であり、より好ましい添加量は、０．０１〜０．１重量部である。上記有機過酸化物の添加量が０．０００５重量部未満の場合は開始剤添加の目的の効果を得られない。又、０．２重量部を超える場合は重合時に大量の反応熱が発生するため重合の制御が困難となる場合がある。 These organic peroxides are added to the polymerization system (polymerization raw material solution or solution during polymerization) in any step of styrene monomer polymerization. These organic peroxides may be added to the polymerization raw material solution, or may be added to the solution in the middle of polymerization divided into a plurality of times as necessary. The addition amount of the organic peroxide is 0.0005 to 0.2 parts by weight with respect to 100 parts by weight of the polymerization raw material solution, and a more preferable addition amount is 0.01 to 0.1 parts by weight. When the addition amount of the organic peroxide is less than 0.0005 parts by weight, the intended effect of adding the initiator cannot be obtained. On the other hand, if the amount exceeds 0.2 parts by weight, a large amount of reaction heat is generated during the polymerization, which may make it difficult to control the polymerization.
本発明において、その重合方法には特に制約はなく、通常の塊状重合、溶液重合、懸濁重合等が用いられる。また、本発明においては分子量調整のために、溶媒や連鎖移動剤を使用することも可能である。溶媒としては、トルエン、エチルベンゼン、キシレン等が使用できる。溶媒の使用量は特に限定されるものではないが、０重量％〜５０重量％の範囲の使用が好ましい。連鎖移動剤としてはｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、α−メチルスチレンダイマー等が用いられ、ｎ−ドデシルメルカプタンが好ましい。連鎖移動剤の使用量は０重量％〜１重量％の範囲が好ましい。反応温度は、８０〜２００℃、より好ましくは９０〜１８０℃の範囲である。反応温度が８０℃より低いと生産性が低下し、工業的に不適当である。２００℃を超えると低分子量重合体が多量に生成して好ましくない。目標分子量が重合温度のみで調整できない場合は、開始剤量、溶媒量、連鎖移動剤量等で制御すればよい。反応時間は一般に０．５〜２０時間、より好ましくは２〜１０時間である。反応時間が０．５時間より短いと反応が充分に進行しない。２０時間より長い場合は生産性が低く、工業的に不適当である。 In the present invention, the polymerization method is not particularly limited, and usual bulk polymerization, solution polymerization, suspension polymerization and the like are used. In the present invention, it is also possible to use a solvent or a chain transfer agent for molecular weight adjustment. As the solvent, toluene, ethylbenzene, xylene and the like can be used. Although the usage-amount of a solvent is not specifically limited, Use of the range of 0 weight%-50 weight% is preferable. As the chain transfer agent, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer or the like is used, and n-dodecyl mercaptan is preferable. The amount of chain transfer agent used is preferably in the range of 0% to 1% by weight. The reaction temperature is in the range of 80 to 200 ° C, more preferably 90 to 180 ° C. When the reaction temperature is lower than 80 ° C., the productivity is lowered, which is industrially unsuitable. If it exceeds 200 ° C., a large amount of low molecular weight polymer is produced, which is not preferable. When the target molecular weight cannot be adjusted only by the polymerization temperature, it may be controlled by the initiator amount, the solvent amount, the chain transfer agent amount, or the like. The reaction time is generally 0.5 to 20 hours, more preferably 2 to 10 hours. When the reaction time is shorter than 0.5 hours, the reaction does not proceed sufficiently. If it is longer than 20 hours, the productivity is low and industrially unsuitable.
スチレン系単量体の重合転化率については、特に限定されるものではないが、工業的な見地から、４０％以上であることが望ましい。このようにして得られた重合溶液は、未反応単量体や溶媒を除去することにより、目的とするスチレン系樹脂を分離することができる。懸濁重合の場合はそのまま次の工程に供される。 The polymerization conversion rate of the styrene monomer is not particularly limited, but is preferably 40% or more from an industrial viewpoint. The polymerization solution thus obtained can separate the target styrene resin by removing unreacted monomers and solvent. In the case of suspension polymerization, it is used for the next step as it is.
また、スチレン系樹脂に慣用されている添加剤、例えば酸化防止剤、滑剤、着色剤等を本発明の目的を損なわない範囲で添加してもかまわない。具体的には流動パラフィン、白色鉱油等の可塑剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム等の滑剤、ヘキサブロモシクロドデカン等の難燃剤等があげられる。またペレットの外部潤滑剤として、エチレンビスステアリルアミド、ステアリン酸亜鉛、ステアリン酸マグネシウム等をペレットにまぶしても良い。 In addition, additives commonly used in styrene resins, such as antioxidants, lubricants, colorants, etc., may be added within a range that does not impair the object of the present invention. Specific examples include plasticizers such as liquid paraffin and white mineral oil, lubricants such as stearic acid, palmitic acid, zinc stearate, calcium stearate and magnesium stearate, and flame retardants such as hexabromocyclododecane. Further, as the external lubricant for the pellet, ethylene bisstearylamide, zinc stearate, magnesium stearate or the like may be applied to the pellet.
本発明のスチレン系樹脂の２００℃、４９Ｎ荷重で測定したメルトマスフローレイト（ＭＦＲ）は１．０〜６．０グラム／１０分である。ＭＦＲが１．０グラム／１０分より小さいと外観が荒れたものになる。またＭＦＲが６．０グラム／１０分より大きいと樹脂の粘度が低いため押出発泡成形の際に発泡セルが大きく成長してしまい、製品の強度が低下したり、連泡ができたりする原因となる。好ましいＭＦＲの範囲は１．２〜５．０グラム／１０分である。 The melt mass flow rate (MFR) measured at 200 ° C. and a load of 49 N of the styrene resin of the present invention is 1.0 to 6.0 grams / 10 minutes. When the MFR is smaller than 1.0 gram / 10 minutes, the appearance becomes rough. Also, if the MFR is larger than 6.0 grams / 10 minutes, the viscosity of the resin is low, and the foam cell grows greatly during extrusion foaming, causing the strength of the product to decrease and the cause of continuous foaming. Become. A preferred MFR range is 1.2 to 5.0 grams / 10 minutes.
また本発明のスチレン系樹脂はコーン＆プレート型溶融粘弾性測定装置によって２４０℃、角速度０．１ラジアン／秒で測定した貯蔵弾性率Ｇ’（０．１）と角速度１００ラジアン／秒で測定した貯蔵弾性率Ｇ’（１００）の比Ｇ’（０．１）／Ｇ’（１００）が０．００３以上である。貯蔵弾性率は高分子の緩和時間分布に関係づけられている。Ｇ’（０．１）／Ｇ’（１００）が大きいことは発泡セルが成長する際に相当する低剪断領域での非ニュートン性が大きいことを意味し、０．００３未満であると発泡セルの壁厚みに不均一性を生じて製品強度や断熱性能が低下する。比Ｇ’（０．１）／Ｇ’（１００）の好ましい範囲は０．００３〜０．００６である。なおコーン＆プレート型溶融粘弾性測定装置とは例えばレオメトリックス社のＲＭＳ−８００等として広く知られている。 The styrenic resin of the present invention was measured by a cone and plate type melt viscoelasticity measuring device at 240 ° C. and an angular velocity of 0.1 radians / second and a storage elastic modulus G ′ (0.1) and an angular velocity of 100 radians / second. The ratio G ′ (0.1) / G ′ (100) of the storage elastic modulus G ′ (100) is 0.003 or more. The storage modulus is related to the relaxation time distribution of the polymer. A large G ′ (0.1) / G ′ (100) means a large non-Newtonian property in a low shear region corresponding to the growth of the foam cell, and a foam cell of less than 0.003. As a result, non-uniformity in the wall thickness of the product causes a reduction in product strength and heat insulation performance. A preferable range of the ratio G ′ (0.1) / G ′ (100) is 0.003 to 0.006. The cone-and-plate type melt viscoelasticity measuring apparatus is widely known as, for example, RMS-800 manufactured by Rheometrics.
本発明の樹脂組成物の平均分子量は、重量平均分子量Ｍｗで２０万〜４０万、より好ましくは２５万〜４０万とする。Ｍｗが４０万を超える場合は、溶融体の粘度が高くなり、成形、加工性等が極端に低下し、生産性が悪化する。また２０万未満の場合は、成形体の強度が低下する。またＭｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎは５以上であることが好ましい。またＺ平均分子量ＭｚとＭｗの比Ｍｚ／Ｍｗは２．５以上であることが好ましい。ここでいうＭｗ、Ｍｎ、Ｍｚは、４０℃、テトラヒドロフランを溶媒としてゲルパーミエーションクロマトグラフィーにより測定される。 The average molecular weight of the resin composition of the present invention is 200,000 to 400,000, more preferably 250,000 to 400,000 in terms of weight average molecular weight Mw. When Mw exceeds 400,000, the viscosity of the melt is increased, the molding and workability are extremely lowered, and the productivity is deteriorated. On the other hand, if it is less than 200,000, the strength of the molded product is lowered. Moreover, it is preferable that ratio Mw / Mn of Mw and number average molecular weight Mn is 5 or more. Moreover, it is preferable that ratio Mz / Mw of Z average molecular weight Mz and Mw is 2.5 or more. Mw, Mn, and Mz here are measured by gel permeation chromatography using 40 ° C. and tetrahydrofuran as a solvent.
本発明のスチレン系樹脂組成物による押出発泡シートの製造方法は、通常知られている方法を用いることができる。押出発泡時の発泡剤や発泡核剤については通常用いられる物質を使用できる。発泡剤としてはブタン、ペンタン、フロン、水等を使用することができ、ブタンが好適である。また発泡核剤としてはタルク等を使用できる。ポリスチレン系樹脂押出発泡シートは、厚み０．５ｍｍ〜５．０ｍｍ、見かけ密度５０ｇ／Ｌ〜３００ｇ／Ｌ、坪量８０ｇ／ｍ２〜３００ｇ／ｍ２であることが好ましい。
また、押出発泡シートにフィルムをラミネートしても良い。使用するフィルムの種類として、一般のポリスチレンに使用されるもので差し支えない。
この押出発泡シートを真空成型してトレー等の容器を作る。
As a method for producing an extruded foam sheet using the styrenic resin composition of the present invention, a generally known method can be used. As the foaming agent and foaming nucleating agent during extrusion foaming, commonly used substances can be used. As the foaming agent, butane, pentane, chlorofluorocarbon, water and the like can be used, butane is preferred. Moreover, talc etc. can be used as a foam nucleating agent. Extruded polystyrene resin foam sheet had a thickness of 0.5 mm to 5.0 mm, an apparent density of 50 g / to 300 g / L, it is preferably a basis weight of 80g / m 2 ~300g / m 2 .
Further, a film may be laminated on the extruded foam sheet. As a kind of film to be used, it may be one used for general polystyrene.
A container such as a tray is formed by vacuum forming the extruded foam sheet.
また本発明のスチレン系樹脂組成物による板状押出発泡体の製造方法についても、通常知られている方法を用いることができる。押出発泡時の発泡剤や発泡核剤については通常用いられる物質を使用できる。発泡剤としてはブタン、ペンタン、フロン、水等を使用することができ、ブタンが好適である。また発泡核剤としてはタルク等を使用できる。ポリスチレン系樹脂板状押出発泡体は、厚み１０ｍｍ〜５０ｍｍ、見かけ密度２０ｇ／Ｌ〜１００ｇ／Ｌ、発泡セル径は０．００５〜０．５ｍｍであることが好ましい。
次に、実施例および比較例によって本発明をさらに詳細に説明する。
Also, a generally known method can be used as a method for producing a plate-like extruded foam using the styrene resin composition of the present invention. As the foaming agent and foaming nucleating agent during extrusion foaming, commonly used substances can be used. As the foaming agent, butane, pentane, chlorofluorocarbon, water and the like can be used, butane is preferred. Moreover, talc etc. can be used as a foam nucleating agent. The polystyrene resin plate-like extruded foam preferably has a thickness of 10 mm to 50 mm, an apparent density of 20 g / L to 100 g / L, and a foamed cell diameter of 0.005 to 0.5 mm.
Next, the present invention will be described in more detail with reference to examples and comparative examples.
以下に分析法と発泡体特性の測定法を記す。
（１）メルトマスフローレイト（ＭＦＲ）
ＪＩＳ Ｋ ７２１０にしたがって２００℃、４９Ｎ荷重でメルトマスフローレイト（グラム／１０分）を測定した。
（２）貯蔵弾性率
レオメトリックス社製溶融粘弾性測定装置ＲＭＳ−８００を用いて貯蔵弾性率（Ｐａ）を測定した。
測定は測定温度２４０℃、窒素気流中で行う。コーン＆プレート治具は直径２５ｍｍ、コーンの角度０．１ラジアンのものを用いた。歪みは２０％、角速度１００ラジアン／秒から０．０１ラジアン／秒まで測定を行った。
（３）容器の腰強度
押出発泡シートを図１に示すトレーに真空成型して腰強度（Ｎ）を測定した。トレー容器の大きさは縦１２ｃｍ、横２０ｃｍ、深さ２ｃｍである。トレーの横側面より圧縮して極大荷重を腰強度とした。
（４）分子量
分子量の測定に用いた装置及び条件は次の通りである。
使用装置：東ソー製ＨＬＣ８０２０
分別カラム：東ソー製ＴＳＫ−ｇｅｌ−ＧＭＨ−ＸＬ
測定溶媒：テトラヒドロフラン
試料濃度：スチレン樹脂５ｍｇを１０ｍｌの溶媒に溶解
測定温度：４０℃
流速：０．３５ｍｌ／分。
（５）板状押出発泡体の発泡体密度
発泡体の重量／発泡体の体積から発泡体密度（ｋｇ／ｍ3）を計算した。
（６）板状押出発泡体の平均気泡径
ＡＳＴＭ・Ｄ３５７６−７７に準じて発泡体押出断面の平均気泡径（ｍｍ）を測定した。
（７）板状押出発泡体の独立気泡率
ＡＳＴＭ・Ｄ２８５６−Ａに準じて独立気泡率（％）を測定した。
（８）熱伝導率
下記の装置、条件で熱伝導率（Ｗ／（ｍ・Ｋ））を測定した。
使用装置：京都電子工業株式会社製 熱伝導率計 Ｋｅｍｔｈｅｒｍ ＱＴＭ−Ｄ３
測定温度：室温
The analysis method and the measurement method of foam properties are described below.
(1) Melt mass flow rate (MFR)
The melt mass flow rate (grams / 10 minutes) was measured at 200 ° C. and 49 N load according to JIS K 7210.
(2) Storage elastic modulus The storage elastic modulus (Pa) was measured using a rheometrics melt viscoelasticity measuring device RMS-800.
The measurement is performed at a measurement temperature of 240 ° C. in a nitrogen stream. A cone and plate jig having a diameter of 25 mm and a cone angle of 0.1 radians was used. The strain was measured from 20% and angular velocity from 100 radians / second to 0.01 radians / second.
(3) Waist Strength of Container The extruded foam sheet was vacuum-formed on the tray shown in FIG. 1, and the waist strength (N) was measured. The size of the tray container is 12 cm long, 20 cm wide, and 2 cm deep. Compressed from the side of the tray, the maximum load was used as waist strength.
(4) Molecular weight The apparatus and conditions used for the measurement of molecular weight are as follows.
Equipment used: Tosoh HLC8020
Fractionation column: Tosoh TSK-gel-GMH-XL
Measurement solvent: Tetrahydrofuran Sample concentration: 5 mg of styrene resin dissolved in 10 ml of solvent Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min.
(5) Foam density of plate-like extruded foam The foam density (kg / m 3 ) was calculated from the weight of the foam / volume of the foam.
(6) Average Cell Diameter of Plate Extruded Foam The average cell diameter (mm) of the foam extrusion cross section was measured according to ASTM D3576-77.
(7) Closed cell ratio of plate-like extruded foam The closed cell ratio (%) was measured according to ASTM D2856-A.
(8) Thermal conductivity Thermal conductivity (W / (m · K)) was measured with the following apparatus and conditions.
Equipment used: Thermal conductivity meter, Chemtherm QTM-D3, manufactured by Kyoto Electronics Industry Co., Ltd.
Measurement temperature: room temperature
[実施例１]
［スチレン系樹脂の製造］
スチレン９０重量％、エチルベンゼン１０重量％の混合液１００重量部に対し、２，２−ビス（４，４−ジターシャリーブチルパーオキシシクロヘキシル）プロパンを０．０３５重量部添加した重合液を４．６リットルの完全混合型反応器に０．７８リットル／Ｈｒで連続的に仕込み、１０１℃に調整した。重合体溶液を引き続き、攪拌器を備え３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−１に連続的に仕込んだ。層流型反応器−１の温度を１０５℃／１０８℃／１１０℃に調整した。
完全混合型反応器および層流型反応器−１と並列に接続された、攪拌器を備え、３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−２にスチレン８０重量％、エチルベンゼン２０重量％の混合液１００重量部に対し、１，１−ジ−ｔ−ブチルパーオキシシクロヘキサン０．０７重量部およびｎ−ドデシルメルカプタン０．３５重量部を添加した重合液を０．４２リットル／Ｈｒで連続的に仕込み、層流型反応器−２の温度を１４０℃／１５０℃／１６０℃に順次調節した。
層流型反応器−１と層流型反応器−２の重合体溶液は混合され、混合された重合体溶液を引き続き、静的攪拌器を備え３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−３に連続的に仕込んだ。層流型反応器−３の温度を１２０℃／１３０℃／１４５℃に調整した。
[Example 1]
[Manufacture of styrene resin]
A polymerization solution obtained by adding 0.035 parts by weight of 2,2-bis (4,4-ditertiarybutylperoxycyclohexyl) propane to 100 parts by weight of a mixture of 90% by weight of styrene and 10% by weight of ethylbenzene was 4.6. A liter fully mixed reactor was continuously charged at 0.78 liter / hr and adjusted to 101 ° C. The polymer solution was continuously charged into a 1.5 liter laminar flow reactor-1 equipped with a stirrer and temperature-controlled in 3 zones. The temperature of the laminar flow reactor-1 was adjusted to 105 ° C / 108 ° C / 110 ° C.
80% by weight of styrene was added to a 1.5 liter laminar flow reactor-2 equipped with a stirrer connected in parallel with a fully mixed reactor and laminar flow reactor-1, and temperature controlled in 3 zones, 0.42 liter of a polymerization solution obtained by adding 0.07 part by weight of 1,1-di-t-butylperoxycyclohexane and 0.35 part by weight of n-dodecyl mercaptan to 100 parts by weight of a mixture of 20% by weight of ethylbenzene / Hr was continuously charged, and the temperature of the laminar flow reactor-2 was sequentially adjusted to 140 ° C / 150 ° C / 160 ° C.
The polymer solutions in the laminar flow reactor-1 and the laminar flow reactor-2 are mixed, and the mixed polymer solution is continuously added to 1.5 liters of which temperature can be controlled in three zones with a static stirrer. The laminar flow reactor-3 was continuously charged. The temperature of the laminar flow reactor-3 was adjusted to 120 ° C / 130 ° C / 145 ° C.
重合反応器より連続して排出される重合体溶液を直列に配置した２基の、予熱器として０．６リットルの静的混合器を内蔵した４リットルの脱揮タンクに導いた。予熱器温度を２４０℃とし、脱揮タンク内で２４０℃に保ちながら、１０ｔｏｒｒの減圧下、脱揮後ペレタイズした。重合条件を表１−１に示した。また、得られたポリスチレン樹脂のゲルパーミエイション・クロマトマトグラフィーによる分子量測定、メルトマスフローレイト測定、溶融粘弾性側定を行った。この結果を表２に示した。
メルトマスフローレイトは１．８グラム／１０分であった。２４０℃、角速度０．１および１００ラジアン／秒で測定した、コーン＆プレート型溶融粘弾性測定装置による貯蔵弾性率の比Ｇ’（０．１）／Ｇ’（１００）は０．００４４であった。重量平均分子量は３３．９万であった。
The polymer solution discharged continuously from the polymerization reactor was led to a 4 liter devolatilization tank containing a 0.6 liter static mixer as a preheater and arranged in series. The preheater temperature was 240 ° C., and devolatilization was performed after devolatilization under a reduced pressure of 10 torr while maintaining the temperature in the devolatilization tank at 240 ° C. The polymerization conditions are shown in Table 1-1. In addition, the obtained polystyrene resin was subjected to molecular weight measurement, gel mass flow rate measurement, and melt viscoelasticity determination by gel permeation chromatography. The results are shown in Table 2.
The melt mass flow rate was 1.8 grams / 10 minutes. The storage modulus ratio G ′ (0.1) / G ′ (100) measured at 240 ° C., angular velocity 0.1 and 100 radians / second by a cone and plate type melt viscoelasticity measuring apparatus was 0.0044. It was. The weight average molecular weight was 330,000.
［ポリスチレン樹脂組成物の発泡押出し］
直径１５０ｍｍのサーキュラーダイを備えた押出発泡機を用いて、上記のポリスチレン樹脂組成物１００重量部に対して、発泡核剤としてタルク（平均粒径１．３μｍ）を０．１５重量部、発泡剤として液化ブタンを４重量部添加して押出発泡シートを製造した。樹脂溶融ゾーンの温度は２００〜２３０℃、ロータリークーラー温度は１３０〜１７０℃、ダイス温度を１５０℃に調整した。押出発泡された発泡体を冷却マンドレルで冷却し、円周上の１点でカッターにより切断後、幅１０００ｍｍ、シート厚み：１．９ｍｍ、見かけ密度：１００ｇ／Ｌ（発泡倍率：１０．５倍）、坪量：１８０ｇ／ｍ２のポリスチレン樹脂発泡シートを得た。
［ポリスチレン樹脂組成物発泡シートの熱成形］
上記発泡シートを真空成形して図１に示す形状の発泡トレー容器を得た。この容器について腰強度の測定を行った結果を表２に示す。
[Polystyrene resin composition foam extrusion]
Using an extrusion foaming machine equipped with a circular die having a diameter of 150 mm, 0.15 parts by weight of talc (average particle size 1.3 μm) as a foam nucleating agent with respect to 100 parts by weight of the above polystyrene resin composition, a foaming agent As a result, 4 parts by weight of liquefied butane was added to produce an extruded foam sheet. The temperature of the resin melting zone was adjusted to 200 to 230 ° C, the rotary cooler temperature was adjusted to 130 to 170 ° C, and the die temperature was adjusted to 150 ° C. The extruded foam is cooled with a cooling mandrel, cut with a cutter at one point on the circumference, then width 1000 mm, sheet thickness 1.9 mm, apparent density: 100 g / L (foaming ratio: 10.5 times) A polystyrene resin foam sheet having a basis weight of 180 g / m 2 was obtained.
[Thermoforming of polystyrene resin composition foam sheet]
The foamed sheet was vacuum formed to obtain a foamed tray container having the shape shown in FIG. Table 2 shows the results of measuring the waist strength of this container.
[実施例２]
液化ブタン量を５重量部にして発泡倍率を高くした以外は実施例１と同様に実施した。
結果を表２に示す。
[Example 2]
The same operation as in Example 1 was carried out except that the amount of liquefied butane was 5 parts by weight and the expansion ratio was increased.
The results are shown in Table 2.
[実施例３、４]
重合条件を表１−１のとおり変更した以外は実施例２と同様に実施して、表２に示す性状のポリスチレン樹脂を製造した。結果を表２に示す。
[Examples 3 and 4]
Except having changed superposition | polymerization conditions as shown in Table 1-1, it implemented similarly to Example 2 and manufactured the polystyrene resin of the property shown in Table 2. The results are shown in Table 2.
[比較例１]
［スチレン系樹脂の製造］
スチレン９０重量％、エチルベンゼン１０重量％の混合液１００重量部に対し、２，２−ビス（４，４−ジターシャリーブチルパーオキシシクロヘキシル）プロパンを０．０２７重量部添加した重合液を４．６リットルの完全混合型反応器に０．７２リットル／Ｈｒで連続的に仕込み、１０２℃に調整した。完全混合型反応器と並列に接続された、攪拌器を備え３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−１にスチレン７０重量％、エチルベンゼン３０重量％の混合液１００重量部に対し、１，１−ジ−ｔ−ブチルパーオキシシクロヘキサン０．０２６重量部およびα−メチルスチレンダイマー０．３重量部を添加した重合液を０．２５リットル／Ｈｒで連続的に仕込み、層流型反応器−２の温度を１２５℃／１３０℃／１１２℃に順次調節した。
完全混合型反応器と層流型反応器−１の重合体溶液は混合され、混合された重合体溶液を引き続き、静的攪拌器を備え３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−２およびそれと直列に配された、攪拌器を備え３ゾーンで温度コントロール可能な１．５リットルの層流型反応器−３に連続的に仕込んだ。層流型反応器−２および層流型反応器−３の温度を１１０℃／１２０℃／１３０℃および１４０℃／１５０℃／１６０℃に調整した。
重合反応器より連続して排出される重合体溶液を直列に配置した２基の、予熱器として０．６リットルの静的混合器を内蔵した４リットルの脱揮タンクに導いた。予熱器温度を２４０℃とし、脱揮タンク内で２４０℃に保ちながら、１０ｔｏｒｒの減圧下、脱揮後ペレタイズした。
以下実施例１と同様に実施した。重合条件を表１−２に示す。また結果を表２に示す。
[Comparative Example 1]
[Manufacture of styrene resin]
A polymerization solution obtained by adding 0.027 parts by weight of 2,2-bis (4,4-ditertiarybutylperoxycyclohexyl) propane to 100 parts by weight of a mixture of 90% by weight of styrene and 10% by weight of ethylbenzene was 4.6. A liter fully mixed reactor was continuously charged at 0.72 liter / hr and adjusted to 102 ° C. A 1.5-liter laminar flow reactor-1 equipped with a stirrer and connected in parallel with a fully mixed reactor and capable of temperature control in three zones is mixed with 100 wt.% Of a mixture of 70 wt.% Styrene and 30 wt.% Ethylbenzene. Part of which is a polymerization solution prepared by adding 0.026 part by weight of 1,1-di-t-butylperoxycyclohexane and 0.3 part by weight of α-methylstyrene dimer continuously at 0.25 liter / hr, The temperature of the laminar flow reactor-2 was sequentially adjusted to 125 ° C / 130 ° C / 112 ° C.
The polymer solutions in the fully mixed reactor and laminar flow reactor-1 are mixed, and the mixed polymer solution is continuously added to a 1.5 liter laminar flow having a static stirrer and temperature control in three zones. The reactor was continuously charged in a reactor 1.5 and a 1.5 liter laminar flow reactor-3, which was equipped with a stirrer and was temperature-controlled in three zones. The temperature of laminar flow reactor-2 and laminar flow reactor-3 was adjusted to 110 ° C / 120 ° C / 130 ° C and 140 ° C / 150 ° C / 160 ° C.
The polymer solution discharged continuously from the polymerization reactor was led to a 4 liter devolatilization tank containing a 0.6 liter static mixer as a preheater and arranged in series. The preheater temperature was 240 ° C., and devolatilization was performed after devolatilization under a reduced pressure of 10 torr while maintaining the temperature in the devolatilization tank at 240 ° C.
Thereafter, the same procedure as in Example 1 was performed. The polymerization conditions are shown in Table 1-2. The results are shown in Table 2.
[比較例２、３]
重合条件を表２のとおり変更した以外は比較例１と同様に実施して、表３に示す性状のポリスチレン樹脂を製造した。結果を表２に示す。
[Comparative Examples 2 and 3]
Except having changed polymerization conditions as shown in Table 2, it implemented similarly to the comparative example 1, and manufactured the polystyrene resin of the property shown in Table 3. The results are shown in Table 2.
[実施例５]
実施例１〜４で得たポリスチレン樹脂を用いて板状押出発泡体を製造した。
［ポリスチレン樹脂の板状発泡押出］
ポリスチレン樹脂を、単軸押出機、ミキサー、ロータリークーラー、及びダイからなる押出発泡機を用いて、発泡核剤を樹脂に対して１重量部、発泡剤を樹脂に対して５重量部添加し、厚さ３０ｍｍの板状押出発泡体を製造した。樹脂の溶融ゾーンの温度は１８０〜２００℃、ロータリークーラー温度は１５０〜１６０℃、ダイ温度を１２０〜１３０℃に調整した。発泡核剤には日本ミストロン製、ミストロンベーパーを用い、発泡剤にはＬＰＧ（ノルマルブタン／イソブタン＝７０／３０＜体積分率＞）を用いた。得られた発泡体の発泡体密度、平均気泡径、独立気泡率、熱伝導率測定を行った。この結果を表３に示した。
[Example 5]
A plate-like extruded foam was produced using the polystyrene resin obtained in Examples 1 to 4.
[Plastic foam extrusion of polystyrene resin]
Using polystyrene foam, an extrusion foaming machine consisting of a single screw extruder, a mixer, a rotary cooler, and a die, adding 1 part by weight of the foam nucleating agent to the resin and 5 parts by weight of the foaming agent to the resin, A plate-like extruded foam having a thickness of 30 mm was produced. The temperature of the resin melting zone was adjusted to 180 to 200 ° C, the rotary cooler temperature was adjusted to 150 to 160 ° C, and the die temperature was adjusted to 120 to 130 ° C. As the foam nucleating agent, Mistrone Vapor made by Nippon Mistron was used, and as the foaming agent, LPG (normal butane / isobutane = 70/30 <volume fraction>) was used. The foam density, average cell diameter, closed cell rate, and thermal conductivity of the obtained foam were measured. The results are shown in Table 3.
[実施例６〜８]
発泡剤を６重量部にして発泡倍率を高くした以外は実施例５と同様に実施した。結果を表３に示す。
[Examples 6 to 8]
The same operation as in Example 5 was conducted except that the foaming agent was increased to 6 parts by weight and the expansion ratio was increased. The results are shown in Table 3.
[比較例４〜６]
比較例１〜３のポリスチレン樹脂を用いた以外は比較例１と同様に実施して、板状押出発泡体を製造した。結果を表３に示す。
[Comparative Examples 4 to 6]
Except having used the polystyrene resin of Comparative Examples 1-3, it implemented similarly to the comparative example 1 and manufactured the plate-shaped extrusion foam. The results are shown in Table 3.
本発明は、トレー等の発泡容器および断熱材等の板状押出発泡体向けのスチレン系樹脂組成物として好適である。 The present invention is suitable as a styrene resin composition for foamed containers such as trays and plate-like extruded foams such as heat insulating materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010043171A (en) * | 2008-08-11 | 2010-02-25 | Sekisui Plastics Co Ltd | Method for producing polystyrene resin foamed sheet, polystyrene resin foamed sheet, and container |
| JP2011153261A (en) * | 2010-01-28 | 2011-08-11 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particles, polystyrene-based resin prefoamed particles, polystyrene-based resin foam molding, and method of producing the same |
| JP2015193761A (en) * | 2014-03-31 | 2015-11-05 | 積水化成品工業株式会社 | Polystyrene resin composition for foaming, and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010043171A (en) * | 2008-08-11 | 2010-02-25 | Sekisui Plastics Co Ltd | Method for producing polystyrene resin foamed sheet, polystyrene resin foamed sheet, and container |
| JP2011153261A (en) * | 2010-01-28 | 2011-08-11 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particles, polystyrene-based resin prefoamed particles, polystyrene-based resin foam molding, and method of producing the same |
| JP2015193761A (en) * | 2014-03-31 | 2015-11-05 | 積水化成品工業株式会社 | Polystyrene resin composition for foaming, and application thereof |
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