JP2018513252A - 垂直方向に伸長された気泡を有する断熱発泡体 - Google Patents
垂直方向に伸長された気泡を有する断熱発泡体 Download PDFInfo
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- JP2018513252A JP2018513252A JP2017553880A JP2017553880A JP2018513252A JP 2018513252 A JP2018513252 A JP 2018513252A JP 2017553880 A JP2017553880 A JP 2017553880A JP 2017553880 A JP2017553880 A JP 2017553880A JP 2018513252 A JP2018513252 A JP 2018513252A
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- Prior art keywords
- foam
- less
- polymer
- blowing agent
- ratio
- Prior art date
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- Granted
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- 238000001125 extrusion Methods 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
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- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 8
- 229920002959 polymer blend Polymers 0.000 claims description 32
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 19
- 229920000638 styrene acrylonitrile Polymers 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 210000002421 cell wall Anatomy 0.000 description 10
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- 238000010998 test method Methods 0.000 description 6
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- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 2
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- MMJXXOIUVNOFPL-UHFFFAOYSA-N 1,1,1,2-tetrafluorobut-2-ene Chemical compound CC=C(F)C(F)(F)F MMJXXOIUVNOFPL-UHFFFAOYSA-N 0.000 description 1
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- PVYYRPAHXQUHAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluorobut-1-ene Chemical compound FC=C(F)C(F)(F)C(F)(F)F PVYYRPAHXQUHAW-UHFFFAOYSA-N 0.000 description 1
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- FFTOUVYEKNGDCM-UHFFFAOYSA-N 1,3,3-trifluoroprop-1-ene Chemical compound FC=CC(F)F FFTOUVYEKNGDCM-UHFFFAOYSA-N 0.000 description 1
- HBNHMHOVKXPSOO-UHFFFAOYSA-N 1,4,4,4-tetrafluorobut-1-ene Chemical compound FC=CCC(F)(F)F HBNHMHOVKXPSOO-UHFFFAOYSA-N 0.000 description 1
- AIQOHQPVTDYQKZ-UHFFFAOYSA-N 1-bromo-1-fluorobut-1-ene Chemical compound CCC=C(F)Br AIQOHQPVTDYQKZ-UHFFFAOYSA-N 0.000 description 1
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-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
- YZXSQDNPKVBDOG-UHFFFAOYSA-N 2,2-difluoropropane Chemical compound CC(C)(F)F YZXSQDNPKVBDOG-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- FAOACLKUNWKVPH-UHFFFAOYSA-N 2,3,3,4,4,4-hexafluorobut-1-ene Chemical compound FC(=C)C(F)(F)C(F)(F)F FAOACLKUNWKVPH-UHFFFAOYSA-N 0.000 description 1
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- JMRIJKGIVGYIAD-UHFFFAOYSA-N 2,3,3-trifluoroprop-1-ene Chemical compound FC(F)C(F)=C JMRIJKGIVGYIAD-UHFFFAOYSA-N 0.000 description 1
- SGGPUNTZIKXDMQ-UHFFFAOYSA-N 2,3-difluoroprop-1-ene Chemical compound FCC(F)=C SGGPUNTZIKXDMQ-UHFFFAOYSA-N 0.000 description 1
- DKSYJUPLFVFPRY-UHFFFAOYSA-N 2,4,4,4-tetrafluorobut-1-ene Chemical compound FC(=C)CC(F)(F)F DKSYJUPLFVFPRY-UHFFFAOYSA-N 0.000 description 1
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- WCNKHTIPPVQEQW-UHFFFAOYSA-N 4,4,4-trifluorobut-1-ene Chemical compound FC(F)(F)CC=C WCNKHTIPPVQEQW-UHFFFAOYSA-N 0.000 description 1
- ABCATIFGNSHDMN-UHFFFAOYSA-N 4,4-difluorobut-1-ene Chemical compound FC(F)CC=C ABCATIFGNSHDMN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
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- 239000006233 lamp black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
- B29C44/352—Means for giving the foam different characteristics in different directions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/36—Feeding the material to be shaped
- B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
- B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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Abstract
Description
押出ポリスチレン(XPS)発泡体は、断熱材として有用である。XPS発泡体は、建築構造物及び容器の断熱材として長く使われてきた。エネルギー効率に対する常に増大する欲動と共に、XPS発泡体などの断熱製品の断熱特性を向上させることに対する常に増大する欲動が存在する。したがって、XSPを通る熱伝導率をどのように低下させるかを特定することが望ましい。
k=a/(a*b*c)1/3
で定義され、aは垂直方向の平均気泡サイズであり、bは横(水平)方向の平均気泡サイズであり、cは縦(押出)方向の平均気泡サイズである。
圧縮バランス=CF=σV/[(σE+σH)/2]
気泡の周りに等方性ポリマーマトリックス構造及び所与の気泡異方性比を有する発泡体についてのCFを計算するための理論モデルは、Gibson及びAshby、Cellular Solids、Structure&Properties、chapter6.3、Pergamon Press、First Edition、 (1988)、pages182−197によって展開され、公表された。そのモデルは、気泡異方性比が与えられた場合の発泡体の理論CFを計算するために使用できる。発泡体がGibson及びAshbyによって予測されたCF値よりも小さいCF値を有する場合、垂直方向の気泡壁は、等方性の気泡構造において予想されるよりも薄くなければならないこと、すなわち、気泡構造は等方性気泡構造において予期されるよりも垂直方向の方で薄いことを意味する。垂直方向の壁が薄くなると、垂直方向のストラットが弱くなることをもたらし、垂直方向の圧縮強度値が低くなると予期される。壁が垂直方向に薄くされている場合、圧縮強度がより大きい垂直方向に垂直な平面内で壁がより厚いことになる。
P比=CF/Gibson−Ashby CF
P比が1である場合、発泡体は、気泡の周囲に等方性ポリマーマトリックス構造を有する。P比が1より大きい場合、発泡体は、垂直方向においてより大きなポリマーマトリックス構造を有し、垂直方向に垂直な平面においてより小さい。P比が1より小さい場合、発泡体は、垂直方向においてより小さなポリマーマトリックス構造を有し、垂直方向に垂直な平面においてより大きい。特に、P比を決定するために、ストラット比1が理論的計算によって選択された。なぜなら、この選択は理論的に最も低いCF値をもたらしたからである。結果として、P比が1未満であることが判明した場合、それは人為的に低いストラット比値選択のためではなく、実際には垂直気泡構造の薄さのためであった。ストラット比が1のとき、Gibson−Ashby CF値はk4.8である。
ポリマー樹脂100重量部に基づく重量部に関して、4重量部の二酸化炭素、0.9重量部の水、及び1重量部のイソブタンからなるフッ素フリーの発泡剤組成物を用いて、比較例(Comp Ex)CE1及びCE2ならびに実施例(Exs)1〜4を調製。二酸化炭素、水、及び炭化水素発泡剤の総モルパーセントは、発泡剤の総モル数に基づいて、それぞれ57.5、31.6、及び10.9モルパーセントである。
以下の本明細書に記載のフッ素化成分を含む発泡剤を使用することを除いて、フッ素フリー実施例及び比較例と同様の方法で、比較例3及び4ならびに実施例5〜9を調製する。さもなければ、表1の代わりに表2に与えられた特性を有するフッ素を含有しない実施例及び比較例について記載したのと同様の方法で発泡体を調製する。同様に、比較例2、C4及び実施例5〜9の発泡体特性を表2に示す。
米国特許第7,919,538号は、赤外線減衰剤を含有するSANコポリマー発泡体の教示を提供する。米国特許第7,919,538号は、その実施例の「長期熱伝導率」値を報告しているが、熱伝導率値が方法EN8301(コラム5、ライン42−43参照)に準拠して測定され、発泡体の製造の14日後に測定されたことを理解することが重要である。米国特許第7,919,538号の「長期熱伝導率」値は、本明細書で報告される25年値とは対照的に、14日値である。したがって、米国特許第7,919,538号から本発明のものへの発泡体の公正な比較を行うために、米国特許第7,919,538号の発泡体を、本発明で使用される本方法及び分析に従って評価した。
Claims (10)
- 押出ポリマー発泡体であって、前記発泡体がポリマーマトリックスの中にある気泡を画定する前記ポリマーマトリックスを含み、前記発泡体が、
(a)前記ポリマーマトリックスが、スチレンアクリロニトリルコポリマー、及び前記ポリマーマトリックス中に分散された、発泡体の重量に基づいて0.1〜10重量パーセントの赤外線減衰剤を含むことと、
(b)前記気泡が、
i.150マイクロメートル以下の、前記発泡体の垂直方向の平均サイズ、
ii.1を超える、垂直方向の平均気泡サイズの、押出方向の平均気泡サイズに対する比率、
iii.1.1を超える、気泡異方性比、となるようなASTM D−3576によって測定される、前記発泡体の垂直、水平、及び押出方向の平均サイズを有することと、
(c)ASTM D1621に準拠して測定される圧縮強度値と共に、0.7以下のP比を有することと、
(d)ガスクロマトグラフィーによって測定される、前記気泡中の、発泡体1キログラム当たり0.2モル未満の炭化水素発泡剤を有することと、
(e)ASTM D1622によって測定される、1立方メートル当たり20〜48キログラムの密度を有することと、
(f)EN13164の切断技術によって測定される25年熱伝導率に関して、フッ素化発泡剤を使用しない場合、0.030ワット/メートルケルビン以下、フッ素化発泡剤を含有する場合、0.029ワット/メートルケルビン未満の平均25年熱伝導率を有することと、を特徴とする押出ポリマー発泡体。 - ASTM D6226−05によって測定される、30パーセント未満の連続気泡含有率を有することをさらに特徴とする、請求項1に記載の押出ポリマー発泡体。
- 圧縮強度が、ASTM D1621によって測定される場合、200キロパスカルを超える垂直の圧縮強度を有し、0.45未満の、前記垂直方向の圧縮強度の、前記垂直、水平、及び押出方向の圧縮強度の合計に対する比率を有することをさらに特徴とする、請求項1または2に記載の押出ポリマー発泡体。
- 前記気泡中に、フッ素化発泡剤を含有することをさらに特徴とする、請求項1〜3のいずれか一項に記載の押出ポリマー発泡体。
- 前記ポリマーマトリックスが、前記ポリマーマトリックス中のポリマーの総重量に基づいて、90重量パーセントを超えるスチレンアクリロニトリルコポリマーを含むことをさらに特徴とする、請求項1〜4のいずれか一項に記載の押出ポリマー発泡体。
- ポリマー発泡体が、100ナノメートル以下の寸法を有する針状粒子を含まない、請求項1〜5のいずれか一項に記載の押出ポリマー発泡体。
- 前記ポリマーマトリックスが、前記ポリマーマトリックス中のポリマーの総重量に基づいて、90重量パーセントを超えるスチレンアクリロニトリルコポリマーを含み、前記赤外線減衰剤がカーボンブラック及びグラファイトからなる群から選択され、前記発泡体の前記P比が0.60以下であり、前記気泡がフッ素化発泡剤を含み、前記発泡体の前記25年熱伝導率が0.027ワット/メートルケルビン以下であることをさらに特徴とする、請求項1〜6のいずれか一項に記載の押出ポリマー発泡体。
- 請求項1に記載の押出ポリマー発泡体を調製する方法であって、
(a)スチレンアクリロニトリルコポリマー、発泡性ポリマー混合物重量に基づいて0.1〜10重量パーセントの赤外線減衰剤、及び発泡剤の総モル数に基づいて20モルパーセント未満の炭化水素を含む発泡剤、を含む発泡性ポリマー混合物を提供すること、及び前記発泡剤の膨張を防止する初期圧力で前記発泡性ポリマー混合物を提供することと、
(b)前記発泡性ポリマー混合物を、6メガパスカルを超えるダイ圧力、及び摂氏110〜135度の範囲の発泡温度で、ダイを通して、前記初期圧力未満の圧力領域に押出することと、
(c)膨張が4〜12の範囲の垂直ブローアップ比、及び1〜2の範囲の押出ブローアップ比を達成するように、前記発泡性ポリマー混合物の前記膨張を制御しながら、前記発泡性ポリマー混合物をポリマー発泡体に膨張させることを含む、方法。 - 前記発泡剤が、フッ素化発泡剤、発泡剤の総モル数に基づくモルパーセントで、20モルパーセント未満の炭化水素、及び15モルパーセントを超える水を含むことをさらに特徴とする、請求項8に記載の方法。
- 前記発泡性ポリマー混合物が、前記発泡性ポリマー混合物中のポリマーの総重量に基づいて、90重量パーセントを超えるスチレンアクリロニトリルコポリマーを含むことをさらに特徴とする、請求項8または9に記載の方法。
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