JP4920864B2 - Self-extinguishing foamable styrene resin particles and method for producing the same - Google Patents
Self-extinguishing foamable styrene resin particles and method for producing the same Download PDFInfo
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- JP4920864B2 JP4920864B2 JP2003147876A JP2003147876A JP4920864B2 JP 4920864 B2 JP4920864 B2 JP 4920864B2 JP 2003147876 A JP2003147876 A JP 2003147876A JP 2003147876 A JP2003147876 A JP 2003147876A JP 4920864 B2 JP4920864 B2 JP 4920864B2
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- Prior art keywords
- flame retardant
- styrene resin
- resin particles
- self
- content
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- 239000002245 particle Substances 0.000 title claims description 213
- 229920005989 resin Polymers 0.000 title claims description 190
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- 238000004519 manufacturing process Methods 0.000 title description 19
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- 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 claims description 169
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 42
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- 238000000034 method Methods 0.000 description 26
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- NMZURKQNORVXSV-UHFFFAOYSA-N 6-methyl-2-phenylquinoline Chemical compound C1=CC2=CC(C)=CC=C2N=C1C1=CC=CC=C1 NMZURKQNORVXSV-UHFFFAOYSA-N 0.000 description 2
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
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- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- NJKMYAMRBUSFGT-UHFFFAOYSA-N dodecoxybenzene;sodium Chemical compound [Na].CCCCCCCCCCCCOC1=CC=CC=C1 NJKMYAMRBUSFGT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- MQXVYODZCMMZEM-ZYUZMQFOSA-N mannomustine Chemical compound ClCCNC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CNCCCl MQXVYODZCMMZEM-ZYUZMQFOSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
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Images
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Description
【0001】
【技術分野】
本発明は,製造にあたり複雑な処理工程を必要とせず,少量の難燃剤を添加することで安定した自己消火性を得ることができる自己消火性発泡性スチレン系樹脂粒子に関する。
【0002】
【従来技術】
スチレン系樹脂発泡成形体は軽量性や断熱性に優れているため,住宅用断熱材や保冷箱等に使用されている。
しかしながら,スチレン系樹脂発泡成形体は,その構造上空気を多く含んでおり,燃え易いという欠点を有している。そのため,住宅用断熱材等の自己消火性を要求される用途には,その使用が制限されていた。
【0003】
スチレン系樹脂発泡成形体に自己消火性を付与するために,自己消火性発泡性スチレン系樹脂粒子を材料として発泡成形体を作製することが考えられる。
ここに,自己消火性発泡性スチレン系樹脂粒子の製造方法として,難燃剤を溶剤等に溶解させて発泡剤と共にスチレン系樹脂粒子に含浸させる製造方法がある(特許庁発行の「周知・慣用技術集(発泡成形)」(発行日 昭和57年8月3日)のp28)。
この方法から製造した自己消火性発泡性スチレン系樹脂粒子は,難燃剤が粒子全体にほぼ均一に含浸されるため,所望の自己消火性を発現させるためには多量の難燃剤を溶剤等に溶解させる必要があった。
【0004】
そこで,特開平11−130898号公報,特開平11−255946号公報に,難燃剤の粒子径を小さくして粒子に難燃剤を含浸しやすくさせることで,使用する難燃剤の量を減らす方法が開示されている。
しかし,これらの方法では,予め難燃剤をガラスビーズなどを用いて粉砕する必要があり,製造工程において特殊な操作を必要がある。そのため,製造容易とはいえなかった。
【0005】
【非特許文献1】
特許庁発行の「周知−慣用技術集(発泡成形)」(発行日 昭和57年8月3日)のp28
【0006】
【特許文献1】
特開平11−130898号公報
【特許文献2】
特開平11−255946号公報
【0007】
【解決しようとする課題】
本発明は,かかる従来の問題点に鑑みてなされたもので,製造にあたり複雑な処理工程を必要とせず,少量の難燃剤を添加することで安定した自己消火性を得ることができる自己消火性発泡性スチレン系樹脂粒子及びその製造方法を提供しようとするものである。
【0008】
【課題の解決手段】
説明の都合上,まず参考発明について説明する。
第1の参考発明は,発泡剤と難燃剤とをスチレン系樹脂粒子に含浸させてなる発泡性スチレン系樹脂粒子であって,
上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.1wt%以上であり,
上記発泡性スチレン系樹脂粒子の表層部を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子の表層部の上記難燃剤の含有割合である難燃剤含有量(wt%)Hと,上記発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Tとの含有比H/Tが,1.05以上であることを特徴とする自己消火性発泡性スチレン系樹脂粒子にある。
【0009】
次に,上記参考発明の作用効果につき説明する。
本参考発明においては,上記表層部の難燃剤含有量(wt%)Hと,上記発泡性スチレン系樹脂粒子全体の難燃剤含有量(wt%)Tとの含有比H/Tが,1.05以上であるというように,粒子の表層部に含まれる難燃剤の「含有割合」を他の部分よりも多くすることで,難燃剤の含有量が低くとも優れた自己消火性を得ることができる。
なお,表層部については後述する。
【0010】
以上,第1の参考発明によれば,製造にあたり複雑な処理工程を必要とせず,少量の難燃剤を添加することで安定した自己消火性を得ることができる自己消火性発泡性スチレン系樹脂粒子を得ることができる。
【0011】
次に,第2の参考発明は,発泡剤と難燃剤とをスチレン系樹脂粒子に含浸させてなる発泡性スチレン系樹脂粒子であると共に上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.1wt%以上であり,
上記発泡性スチレン系樹脂粒子の表層部を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子の表層部の上記難燃剤の含有割合である難燃剤含有量(wt%)Hと,上記発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Tとの含有比H/Tが,1.05以上である自己消火性発泡性スチレン系樹脂粒子を製造するに当たり,
密閉容器内でスチレン系樹脂粒子を水性懸濁液中に分散させ,該水性懸濁液に芳香族炭化水素を添加することなく,発泡剤と難燃剤とを添加することを特徴とする自己消火性発泡性スチレン系樹脂粒子の製造方法である。
【0012】
芳香族炭化水素を添加してスチレン系樹脂粒子に難燃剤を含浸させる場合,スチレン系樹脂粒子に難燃剤がほぼ均一に含浸されて,粒子の表層部に含まれる難燃剤の量を多くすることが難しくなり,水性懸濁液に添加する難燃剤の量が少ないと自己消火性の発現が困難になる恐れがある。
また,スチレン系樹脂粒子に含浸された芳香族炭化水素が自己消火性に悪影響を与える恐れがある。
本発明では,芳香族炭化水素を添加しないので,水性懸濁液に添加する難燃剤の量を減らして,粒子の表層部に多くの難燃剤を含有させることができ,優れた自己消火性を得ることができる。
以上,第2の参考発明によれば,製造にあたり複雑な処理工程を必要とせず,少量の難燃剤を添加することで安定した自己消火性を得ることができる自己消火性発泡性スチレン系樹脂粒子の製造方法を得ることができる。
【0013】
次に,本願にかかる発明について説明する。
本発明は,炭素数5の飽和炭化水素の含有量が15vol%以上である化合物からなる発泡剤と難燃剤とを,スチレン系樹脂粒子に,
芳香族炭化水素を添加することなく,含浸させてなる発泡性スチレン系樹脂粒子であって,
上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.1wt%以上であり,
該発泡性スチレン系樹脂粒子の50%平均粒子径が0.5〜2mmであり,
該発泡性スチレン系樹脂粒子を嵩密度20g/Lに発泡させ,得られた発泡粒子を成形して直方体の発泡成形体を得た場合に,
該発泡成形体の表面から厚さ0.3mmまで切り出した切片の切断面において,該切片を構成する発泡粒子の断面の長径をRとしたとき,
t/R=0〜1/10(tは上記切片を構成する発泡粒子表面からの距離)の領域中のスチレン系樹脂に対する該領域中の上記難燃剤の含有割合である難燃剤含有量(wt%)Yと,
該発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Zとの含有比Y/Zが,1.05以上であり,
上記難燃剤含有量(wt%)Zが0.49wt%以上である
ことを特徴とする自己消火性発泡性スチレン系樹脂粒子である(請求項1)。
本発明によれば,優れた自己消火性を有する発泡成形体を得ることができる。
【0014】
【発明の実施の形態】
本発明において,難燃剤のノルマルヘキサンに対する溶解度が20℃において0.1wt%未満の場合には,難燃剤の含浸効率が悪く,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
尚,難燃剤のノルマルヘキサンに対する溶解度は,ノルマルヘキサン100g中に難燃剤20gを入れ,20℃に保ちながら10分撹拌後,上澄み液50gを採取して,ノルマルヘキサンを蒸発させた後の残査量を溶解量とした。
すなわち,『難燃剤のノルマルヘキサンに対する溶解度=ノルマルヘキサンを蒸発させた後の残査量(g)/ノルマルヘキサン量(g)』である。
また,自己消火性とは,JIS A 9511に記載されている方法で燃焼試験を行い,その平均消火秒数が3秒以内のものを自己消火性合格とした。
【0015】
次に,ノルマルヘキサンに対する溶解度が20℃において0.1wt%の難燃剤を含有する発泡性スチレン系樹脂粒子であっても,発泡性スチレン系樹脂粒子表層部の難燃剤含有量(wt%)が,発泡性スチレン系樹脂粒子全体の難燃剤含有量(wt%)に対して1.05倍未満である場合,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
また,含有量の上限は,発泡時のブロッキング量を抑制させるため,1.35倍未満とすることが好ましい。
【0016】
尚,発泡性スチレン系樹脂粒子の難燃剤含有量(wt%)とは,スチレン系樹脂粒子100重量部に含有される難燃剤量で,液クロマトグラフ(カラム:TOSO G2000HHR,溶媒:クロロホルム)により測定した値である。
また,上記難燃剤含有量(wt%)は,発泡性スチレン系樹脂粒子を構成するスチレン系樹脂に対する難燃剤の含有割合を重量%(wt%)で示している。
なお,第1の参考発明においては,上記発泡性スチレン系樹脂粒子の表層部を構成するスチレン系樹脂に対する表層部の上記難燃剤の含有割合である難燃剤含有量(wt%)Hと,上記発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Tとの含有比H/Tを規定している。
【0017】
次に,上記発泡性スチレン系樹脂粒子の表層部について説明する。
上記表層部11とは,図1に示すごとく,樹脂粒子1の長径をRとした場合,t/R=0〜1/10となる領域である。ここにtは樹脂粒子1の表面Sからの距離である。
例えばR=1.0mmの樹脂粒子の場合,t=0.1mmである(後述する実施例1参照)。
【0018】
上記の発泡性スチレン系樹脂粒子とは,発泡剤を含有するスチレン系樹脂粒子である。
ここで,使用する発泡性スチレン系樹脂粒子を構成する樹脂の種類としては,特に制限はないが,例えば,スチレンモノマーが挙げられる。
また,スチレンモノマーと共重合可能なモノマー成分,例えば,アクリル酸メチル,アクリル酸エチル,アクリル酸プロピル,アクリル酸ブチル,アクリル酸−2−エチルヘキシル等のアクリル酸の炭素数が1〜10のアルキルエステル等;メタクリル酸メチル,メタクリル酸エチル,メタクリル酸プロピル,メタクリル酸ブチル,メタクリル酸−2−エチルヘキシル等のメタクリル酸の炭素数が1〜10のアルキルエステル等;α−メチルスチレン,o−メチルスチレン,m−メチルスチレン,p−メチルスチレン,ビニルトルエン,p−エチルスチレン,2,4−ジメチルスチレン,p−メトキシスチレン,p−フェニルスチレン,o−クロロスチレン,m−クロロスチレン,p−クロロスチレン,2,4−ジクロロスチレン,p−n−ブチルスチレン,p−t−ブチルスチレン,p−n−ヘキシルスチレン,p−オクチルスチレン,スチレンスルホン酸,スチレンスルホン酸ナトリウム等;アクリロニトリル,メタクリロニトリル等のニトリル基含有不飽和化合物等の,スチレンモノマー誘導体のモノマーを単独で,または二種以上を組み合わせて,スチレンモノマーと共重合した樹脂を使用することができる。
尚,スチレンモノマー及びスチレンモノマーと共重合可能なモノマー成分を,スチレン系モノマーと称する。
但し,スチレンモノマー以外に,これらのモノマーを併用する場合には,スチレン系樹脂粒子を重合する際のスチレン系モノマーの全重量に対して,スチレンモノマーの重量を,50%以上にすることが好ましい。このような場合,より耐熱性に優れた,均一なスチレン系樹脂粒子を得ることができる。
【0019】
また,上記発泡性スチレン系樹脂粒子は,GPC法により測定した重量平均分子量(Mw)の値が18万〜40万の間にあることが好ましい。
重量平均分子量が18万未満の場合には,得られる発泡成形体の強度が低下する恐れがある。一方,重量平均分子量が40万を越える場合には,発泡性が低下し,目標の発泡倍率(例えば50〜60倍)まで発泡させることが困難になったり,成形時に発泡性スチレン系樹脂粒子同士が融着しにくくなり,発泡成形体強度が低下する恐れがある。より好ましくは20万〜38万,さらに好ましくは22万〜35万である。尚,上記重量平均分子量はGPC法により測定した値である。
【0020】
発泡性スチレン系樹脂粒子を製造する方法としては,例えば特開平7−79376号及び特開平8−253510号に開示されている方法がある。
即ち,まず重合開始剤及び懸濁剤の存在下にて,スチレン系単量体を水性媒体中に分散させる。その後,重合反応を開始し,該重合反応の前後または途中で発泡剤を添加し,発泡性スチレン系樹脂粒子を製造する方法である。
また,他の製造方法としては,押出機内にてスチレン系樹脂と揮発性発泡剤とを溶融混練し,押出機先端のダイの細孔より押出し,直ちに水中へ導入し急冷し,未発泡の状態で粒子化し,発泡性スチレン系樹脂粒子を製造する方法がある。
【0021】
また,押出機中でスチレン系樹脂を溶融混練し,ストランドカット,ホットカット,水中カット等の方法により0.5mg/個〜5mg/個の大きさの粒子とし,得られたスチレン系樹脂の樹脂粒子を密閉容器中に,懸濁剤の存在下で水性媒体に分散させる。その後,揮発性発泡剤を樹脂粒子に含浸させて,発泡性スチレン系樹脂粒子を製造する方法がある(特開2000−178373号)。
発泡性スチレン系樹脂粒子の50%平均粒子径は,0.5〜2mmの範囲の樹脂粒子を用いることが好ましい。形状は特に限定されないが,球状に近いことが望ましい。尚,発泡性スチレン系樹脂粒子の50%粒子径は,発泡性スチレン系樹脂粒子を水に分散させ,形状係数を1としてレーザー回折散乱法(測定装置;独SYMPATEC社製)により50%粒子径を測定した。
【0022】
また,自己消火性発泡性スチレン系樹脂粒子に,メタクリル酸メチル系共重合体,ポリエチレンワックス,タルク,シリカ,エチレンビスステアリルアミド,シリコーンなどの気泡核剤,流動パラフィン,グリセリンジアセトモノラウレート,グリセリントリステアレート,フタル酸ジ−2−エチルヘキシル,アジピン酸ジ−2−エチルヘキシルなどの可塑剤,アルキルジエタノールアミン,グリセリン脂肪酸エステル,アルキルスルホン酸ナトリウムなどの帯電防止剤,フェノール系,リン系,イオウ系などの酸化防止剤,ベンゾトリアゾール系やベンゾフェノン系などの紫外線吸収材,ヒンダードアミン系などの光安定剤,導電性カーボンブラックなどの導電性フィラー,IPBC,TBZ,BCM,TPNなどの有機系抗菌剤,銀系,銅系,亜鉛系,酸化チタン系などの無機系抗菌剤などの添加剤を添加したり,ブタジエンゴム,スチレン−ブタジエンゴム,イソプレンゴム,エチレン−プロピレンゴムなどのゴム成分を添加しても良い。
【0023】
上記発泡剤としては,沸点が90℃以下であるプロパン,ノルマルブタン,イソブタン,ノルマルペンタン,イソペンタン,ネオペンタン,ヘキサン等の脂肪族炭化水素,又はシクロブタン,シクロペンタン,シクロヘキサン等の脂環族炭化水素等が挙げられる。また,これらの脂肪族炭化水素または脂環族炭化水素は,単独で又は混合して使用することができる。
【0024】
発泡剤の含有量はスチレン系樹脂粒子100重量部に対して1〜10重量部であることが好ましい。
1重量部未満の場合は,発泡力が低下し目標の発泡倍率まで発泡させることが困難になったり,スチレン系樹脂粒子に難燃剤を含浸できず,自己消火性の発現が困難になる恐れがある。また,10重量部を超えるとポリスチレン樹脂に対する含浸性に限界があるため経済的に無駄になる恐れがある。更に好ましくは,3〜8重量部の範囲が良い。
【0025】
上記難燃剤としては,臭素を含有する有機化合物が挙げられる。
例えば,1,2,3,4−テトラブロモブタン,1,2,4−トリブロモブタン,テトラブロモペンタン,テトラブロモビスフェノールA,2,2−ビス(4−アリルオキシー3,5−ジブロモフェニル)プロパン,2,2−ビス(4−ヒドロキシエトキシー3,5−ジブロモフェニル)プロパン,2,2−ビス(4−(2,3−ジブロモ)プロピルオキシー3,5−ジブロモフェニル)プロパン,ペンタブロモジフェニルエーテル,ヘキサブロモジフェニルエーテル,オクタブロモジフェニルエーテル,デカブロモジフェニルエーテル,トリブロモフェノール,ジブロムエチルベンゼン,1,2,3,4,5,6−ヘキサブロモシクロヘキサン,1,2,5,6,9,10−ヘキサブロモシクロドデカン,オクタブロモシクロヘキサデカン,1−クロロ−2,3,4,5,6−ペンタブロモシクロヘキサン,トリス−(2,3−ジブロモプロピル)−ホスフェートのようなジブロムプロパノールのエステルもしくはアセタール,トリブロモフェノール,トリブロモスチレン,トリブロモフェノールアリルエーテル,ジブロモエチル−ジブロモシクロヘキサン等があげられる。
【0026】
また,これらの難燃剤は,単独で又は2種以上を混合して使用することができる。
また,自己消火性を高める効果として,公知の難燃助剤を使用しても良い。
上記難燃助剤としては,ジクミルパーオキサイド,クメンハイドロオキシパーオキサイド,2,3−ジメチル−2,3−ジフェニルブタン等の有機過酸化物等が挙げられる。尚,含浸工程において,難燃助剤の分解量をできるだけ抑えるために難燃助剤の10時間半減期温度が100℃以上の有機過酸化物を用いることが好ましい。
難燃助剤の量は,発泡性スチレン系樹脂粒子100重量部に対して1重量部までの量が好ましい。1重量部以上添加しても添加量に見合った効果の向上が見られない。難燃助剤は難燃剤と同様の方法で用いることができる。
【0027】
次に,ノルマルヘキサンに対する溶解度が20℃において0.1wt%以上の難燃剤を含有する発泡性スチレン系樹脂粒子において,発泡性スチレン系樹脂粒子表層部の難燃剤含有量(wt%)が,発泡性スチレン系樹脂粒子全体の難燃剤含有量(wt%)に対して1.15倍以上であることが好ましい。
【0028】
ノルマルヘキサンに対する溶解度が20℃において0.1wt%以上の難燃剤を含有する発泡性スチレン系樹脂粒子であっても,発泡性スチレン系樹脂粒子表層部の難燃剤含有量(wt%)が,発泡性スチレン系樹脂粒子全体の難燃剤含有量(wt%)に対して1.15倍未満である場合,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
【0029】
次に,難燃剤のノルマルヘキサンに対する溶解度が20℃において0.5wt%以上であることが好ましい。
難燃剤のノルマルヘキサンに対する溶解度が20℃において0.5wt%未満の場合には,難燃剤の含浸効率が悪く,少量の難燃剤で安定した自己消火性を発現できない恐れがある。より好ましくは1.5wt%以上であり,更に好ましくは5wt%以上である。
【0030】
次に,上記難燃剤の分解温度が250℃以下であることが好ましい。
これにより,少量の難燃剤で安定した自己消火性を得ることができる。
分解温度が250℃を超える難燃剤を用いる場合,ポリマーの燃焼進展の推進役となる活性なOHラジカルやHラジカルを補足し,安定化させる臭素ラジカルが発生しにくく,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
【0031】
ここで,上記難燃剤の分解温度とは,熱重量分析(昇温速度10℃,窒素雰囲気下)により求めた示差熱減量曲線で,加熱減量開始温度を難燃剤の分解温度とした。好ましくは,アリル構造を有する難燃剤である。
【0032】
次に,難燃剤の融点が70℃〜120℃であることが好ましい。
難燃剤の融点が70℃未満の場合は,得られる自己消火性発泡性スチレン系樹脂粒子が収縮を生じやすく,寸法安定性に問題が出る恐れがある。難燃剤の融点が120℃を超える場合は,難燃剤を自己消火性発泡性スチレン系樹脂粒子に充分に含浸できず,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
【0033】
次に,上記発泡剤は,炭素数5の飽和炭化水素の含有率が15Vol%以上である化合物を用いる。
これにより,少量の難燃剤で安定した自己消火性を発現することができる。
仮に発泡剤中の炭素数5の飽和炭化水素の含有率が15Vol%未満の場合には,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
また,より好ましい炭素数5の飽和炭化水素の含有率は30Vol%以上であり,更に好ましくは50Vol%以上である。
【0034】
また,上記難燃剤含有量(wt%)Zは0.49wt%以上である。
次に,上記難燃剤は,上記スチレン系樹脂粒子100重量部に対して0.5〜10重量部含有されていることが好ましい。
また2重量部を超えると成形性に悪影響を及ぼして美麗な外観の発泡成形体を得ることが難しい。より好ましくは,0.5〜1.5重量部の範囲が良い。
【0035】
次に,上記自己消火性発泡性スチレン系樹脂粒子は,黒鉛粉,カーボンブラック粉,金属粉のうち一種以上を含有していることが好ましい。
これらを含有する自己消火性発泡性スチレン系樹脂粒子は,少量の難燃剤で安定した自己消火性を発現させるだけではなく,熱伝導率が低く,優れた断熱性能を発揮することができる。
尚,金属粉としては,アルミニウム粉,鉄粉,亜鉛粉,金粉,銀粉,銅粉,タングステン粉,チタン粉,モリブデン粉,鉛粉,ニッケル粉などが挙げられる。上記金属粉は単独で用いても,2種類以上混合して用いても良い。また,黄銅粉(銅−亜鉛合金,ブロンズ粉)等の合金の金属粉を用いても良い。
【0036】
黒鉛粉,カーボンブラック粉,金属粉の含有量はスチレン系樹脂粒子100重量部に対して0.1〜20重量部であることが好ましい。
黒鉛粉,カーボンブラック粉,金属粉の50%粒子径は0.1〜100μmであることが好ましい。更に好ましくは,0.5〜50μmである。
尚,50%粒子径は,黒鉛粉,カーボンブラック粉,金属粉をイソプロパノールに分散させ,形状係数を1としてレーザー回折散乱法(測定装置;セイシン企業社製 LMS−24)により50%粒子径を測定した。形状は特に限定されないが,板状や鱗片状が好ましい。更に好ましくは鱗片状である。
【0037】
第2の参考発明にかかる製造方法について説明する。
第2の参考発明において密閉容器とは,密閉可能で,例えば容器内の撹拌,混合が可能,かつ加温可能であるものを用いることが好ましい。このような密閉容器としては,例えば撹拌装置付きオートクレーブ及び密閉可能なミキサー等がある。
また,自己消火性発泡性スチレン系樹脂粒子を製造する具体的な方法としては,例えば,スチレン系樹脂粒子と難燃剤,懸濁剤,界面活性剤を水性懸濁液に分散させ,発泡剤存在下で撹拌しながら加熱する方法がある。なお,スチレン系樹脂粒子,難燃剤及び発泡剤の投入順序に制約はない。
【0038】
難燃剤の使用方法としては,発泡剤を添加する前に,難燃剤を予め水性懸濁液中に分散させておいて,発泡剤を含浸させる際に一緒に含浸させる方法がある。
また,難燃剤の水性懸濁液を工程の最初,或いは途中で添加する方法などがある。
また,発泡剤は,加熱前,加熱中,または所定温度到達後のいずれの状態で添加しても良いし,複数回に分けて添加しても良い。
上記含浸に際しては,スチレン系樹脂粒子は,水性懸濁液の水100重量部に対して20〜120重量部の範囲が好ましく,80〜110重量部の範囲が特に製造コストの面から好ましい。含浸時間は5〜15時間の範囲が好ましいが,これに限定はされない。
【0039】
難燃剤を含浸させる際に用いる懸濁剤は,例えばリン酸三カルシウム,ハイドロキシアパタイト,ピロリン酸マグネシウム,リン酸マグネシウム,水酸化アルミニウム,水酸化第2鉄,水酸化チタン,水酸化マグネシウム,リン酸バリウム,炭酸カルシウム,炭酸マグネシウム,炭酸バリウム,硫酸カルシウム,硫酸バリウム,タルク,カオリン,ベントナイト等の微粒子状の難水溶性無機塩が挙げられる。
中でも,リン酸三カルシウムやハイドロキシアパタイト,ピロリン酸マグネシウムがより好ましい。
懸濁剤の添加量は,スチレン系樹脂粒子100重量部に対して0.05〜3重量部の範囲が好ましい。0.05重量部未満の場合は,スチレン系樹脂粒子を懸濁安定化することができずに樹脂の塊状物が発生することがあり,3重量部を超えると製造コストの面から好ましくない。
【0040】
また,上記懸濁剤に対し,アルキルスルホン酸ナトリウム,アルキルベンベンスルホン酸ナトリウム,ラウリル硫酸ナトリウム,αオレインスルホン酸ナトリウム,ドデシルフェニルオキサイドジスルホン酸ナトリウム等のアニオン系界面活性剤を併用することが好ましい。これにより,優れた懸濁安定化の効果が得られる。
界面活性剤の添加量は,スチレン系樹脂粒子100重量部に対して0.001〜0.1重量部の範囲が好ましい。
また,必要に応じ電解質,例えば塩化リチウム,塩化カリウム,塩化ナトリウム,塩化マグネシウム,塩化カルシウム,硫酸ナトリウム,硝酸ナトリウム,炭酸ナトリウム,重炭酸ナトリウム等の無機塩類等を加えることができる。
【0041】
また,水性懸濁液に染料を添加することにより,自己消火性発泡性スチレン系樹脂粒子を着色することができる。染料としては,一般にスチレン系樹脂に用いられるアゾ系染料,アントラキノン系染料,アジン系染料,キノリン系染料等を使用することができる。
具体的には,ソルベントイエロー33,ソルベントオレンジ60,ソルベントブルー35,ソルベントブルー36,ソルベントレッド111,ソルベントバイオレット13,ソルベントグリーン3等が挙げられる。
これらの染料は,予め溶剤中に溶解あるいは分散させてからスチレン系樹脂粒子と水性懸濁液が入った耐圧容器に添加して発泡剤と共に添加して着色する方法がある。また,難燃剤,難燃助剤と一緒に添加しておいてから発泡剤を添加して含浸着色させる方法がある。
【0042】
染料を予め溶解させずに用いる場合は,均一に含浸させるために染料の粒子径を100μm以下の微細品を用いるか,予めボールミル,ディスパー,ホモジナイザー,アトライターなどの解砕処理機を用い,必要なら水媒体中で染料粒子を100μm以下に微細化しておくことが好ましい。また,ここで挙げた方法に限らず他の公知の手法によっても使用することができる。
【0043】
第2の参考発明において,上記水性懸濁液の温度を上記難燃剤の融点以上に保持することが好ましい。
これにより,難燃剤の含浸効率を高めて,少量の難燃剤で安定した自己消火性を発現させることができる。
水性懸濁液の加熱温度が難燃剤の融点未満である場合には,難燃剤の含浸効率が悪く,少量の難燃剤で安定した自己消火性を発現できない恐れがある。
好ましくは,70〜120℃である。
70℃未満では,難燃剤をスチレン系樹脂粒子に充分に含浸できず,少量の難燃剤で安定した自己消火性を発現できない恐れがある。120℃を超えると,スチレン系樹脂粒子が軟化して,凝結ビーズが発生する恐れがある。
【0044】
また,第2の参考発明も,第1の参考発明と同様に,上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.5wt%以上であることが好ましい。また,上記難燃剤の分解温度が250℃以下であることが好ましい。また,上記難燃剤の融点は70℃〜120℃であることが好ましい。また,上記発泡剤は,炭素数5の飽和炭化水素の含有率が15Vol%以上である化合物からなることが好ましい。また,上記難燃剤は,スチレン系樹脂粒子100重量部に対して0.3〜10重量部含有されていることが好ましい。
【0045】
【実施例】
以下に,実施例及び比較例をあげて本発明をさらに詳述するが,本発明はこれら実施例に限定されるものではない。
(実施例1)
本例の自己消火性発泡性スチレン系樹脂粒子は,発泡剤と難燃剤とをスチレン系樹脂粒子に含浸させてなる粒子で,上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.1wt%以上であり,粒子の表層部における難燃剤含有量(wt%)が,粒子全体の難燃剤含有量(wt%)に対して1.05倍以上である。
発泡剤,難燃剤,スチレン系樹脂粒子については以下に詳述する。また,性能その他は実施例8に詳述する。
【0046】
まず,本例の粒子を得るに用いたスチレン系樹脂粒子Aについて説明する。
撹拌機付き50リットルオートクレーブに,イオン交換水18リットル,難水溶性の無機系懸濁剤としての第3リン酸カルシウム(太平化学産業株式会社製)63g,界面活性剤としてドデシルベンゼンスルホン酸ナトリウム(東京化成工業株式会社製)0.54gを投入した。
次いで撹拌下に,重合開始剤としてベンゾイルパーオキサイド(日本油脂株式会社製,純度75%)を45g(純品換算で33.75g)とt−ブチルパーオキシ2−エチルヘキシルカーボネート13gを溶解させたスチレンモノマー18kgを投入した。
【0047】
撹拌下で30分間室温のまま放置した後,1時間半かけて90℃まで昇温し,更に5時間かけて100℃まで昇温した。その後さらに,120℃まで1時間半かけて昇温し,120℃を2時間半保持した後,4時間かけて30℃まで冷却した。その後,遠心分離機にて脱水,流動乾燥装置で表面付着水分を除去した後,目開きが0.7mmと1.4mmの篩いで篩い分け,粒子径が0.7〜1.4mmのものを用いた。
【0048】
次に,本例にかかる自己消火性発泡性スチレン系樹脂粒子及び製造方法について説明する。
撹拌機付き50リットルオートクレーブに,イオン交換水18リットル,難水溶性の無機系懸濁剤としての第3リン酸カルシウム(太平化学産業株式会社製)160g,界面活性剤としてドデシルベンゼンスルホン酸ナトリウム(東京化成工業株式会社製)1.6g,難燃剤として2,2−ビス(4−アリルオキシ−3,5−ジブロモフェニル)プロパン(帝人化成製;ファイアーガード3200,20℃におけるノルマルヘキサンに対する溶解度=1.9wt%,分解温度239℃,融点115℃)128g,NaCl(並塩)32g,スチレン系樹脂粒子としてスチレン系樹脂粒子Aを16kg投入し180rpmで撹拌した。
【0049】
そして,スチームにより加温し,内温が90℃に到達したところで,発泡剤としてペンタン(ノルマルペンタン約80Vol%,イソペンタン約20Vol%の混合物)1.2kgを30分かけて徐々に添加した。その後,90℃で5時間保持した後,120℃まで昇温し更に6時間保持した後,40℃まで4時間かけて冷却した。
次いで,得られたものを遠心分離器にて脱水し,酸洗浄して粒子の表面の第3リン酸カルシウムを除去した。その後,流動乾燥装置で上面付着水分を除去し,本例にかかる自己消火性発泡性スチレン系樹脂粒子を得た。
【0050】
この自己消火性発泡性スチレン径樹脂粒子の模式図を図1に記載した。
本例にかかる樹脂粒子1は略球形の粒子体である。
上記表層部11とは,樹脂粒子1の長径をRとした場合,t/R=0〜1/10となる領域で,本例の樹脂粒子1についてはR=1.0mm,t=0.1mmである。
【0051】
(実施例2)
本例では,スチレン系樹脂粒子として下記のスチレン系樹脂粒子B,難燃剤を2,4,6−トリブロモフェノールアリルエーテル(第一工業製;ピロガードFR100,20℃におけるノルマルヘキサンに対する溶解度=11.3wt%,分解温度170℃,融点76℃)128g,発泡剤をペンタン(ノルマルペンタン約80Vol%,イソペンタン約20Vol%の混合物)320g,ブタン(ノルマルブタン約70Vol%とイソブタン約30Vol%の混合物)960gにする他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0052】
ここにスチレン系樹脂粒子Bについて説明する。
ポリスチレン(エー・アンド・エム スチレン社製 HH102)を100重量部,アルミペースト(東洋アルミニウム社製0100MSR,アルミニウム粉の含有量約67%,鱗片状アルミニウム粉)3重量部をミキサーで混合した後,Φ30mmの単軸押出機で200〜220℃の温度で溶融混合し,溶融した樹脂を押出機先端のダイよりストランド状に押し出し,直ちに約30℃の水槽に導入して冷却後,ストランドカッターにより,重量が約1mg/個の円柱状のアルミニウム粉を含有するスチレン系樹脂粒子を作成した。
【0053】
(実施例3)
本例では,スチレン系樹脂粒子として下記のスチレン系樹脂粒子C,難燃剤をテトラブロモシクロオクタン(第一工業製;ピロガードFR200,20℃におけるノルマルヘキサンに対する溶解度=1.8wt%,分解温度137℃,融点110℃)160g,難燃助剤としてジクミルパーオキサイド32g,発泡剤をペンタン(ノルマルペンタン約80Vol%,イソペンタン約20Vol%の混合物)560g,ブタン(ノルマルブタン約20Vol%とイソブタン約80Vol%の混合物)960gにする他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0054】
ここにスチレン系樹脂粒子Cについて説明する。
ポリスチレン(エー・アンド・エム スチレン社製 HH102)を100重量部,鱗片状黒鉛粉(エスイーシー社製SNO−5,50%平均粒径:5μm)3重量部をミキサーで混合した後,Φ30mmの単軸押出機で200〜220℃の温度で溶融混合し,溶融した樹脂を押出機先端のダイよりストランド状に押し出し,直ちに約30℃の水槽に導入して冷却後,ストランドカッターにより,重量が約1mg/個の円柱状の黒鉛粉を含有するスチレン系樹脂粒子を作成した。
【0055】
(実施例4)
本例では,スチレン系樹脂粒子として下記のスチレン系樹脂粒子D,難燃剤を1,2,5,6,9,10ヘキサブロモシクロデカン(第一工業製;ピロガードSR−104,20℃におけるノルマルヘキサンに対する溶解度=0.2wt%,分解温度210℃,融点165℃)240g,難燃助剤としてジクミルパーオキサイド80g,発泡剤をイソペンタン800gにする他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0056】
ここにスチレン系樹脂粒子Dについて説明する。
ポリスチレン(エー・アンド・エム スチレン社製 HH102)を100重量部,カーボンブラック試薬(ナカライ社製,50%平均粒子径:5mm)3重量部をミキサーで混合した後,Φ30mmの単軸押出機で200〜220℃の温度で溶融混合し,溶融した樹脂を押出機先端のダイよりストランド状に押し出し,直ちに約30℃の水槽に導入して冷却後,ストランドカッターにより,重量が約1mg/個の円柱状のカーボンブラックを含有するスチレン系樹脂粒子を作成した。
【0057】
(実施例5)
本例は,発泡剤が請求項1の発明の条件と異なるため,参考例として示すものである。
本例では,実施例1の難燃剤を2,4,6−トリブロモフェノールアリルエーテル(第一工業製;ピロガードFR100,20℃におけるノルマルヘキサンに対する溶解度=11.3wt%,分解温度170℃,融点76℃)192g,発泡剤をペンタン(ノルマルペンタン約80Vol%,イソペンタン約20Vol%の混合物)160g,ブタン(ノルマルブタン約70Vol%とイソブタン約30Vol%の混合物)1120gに変え,染料としてオリエント化学工業製「OPLAS YELLOW136」(Solvent
Yellow 33)160gを添加する他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0058】
(実施例6)
本例では,実施例1の難燃剤として2,2−ビス(4−アリルオキシ−3,5−ジブロモフェニル)プロパン(帝人化成製;ファイアーガード3200,20℃におけるノルマルヘキサンに対する溶解度=1.9wt%,分解温度239℃,融点115℃)96gに変え,難燃助剤としてジクミルパーオキサイド48g,染料として青色染料としてのオリエント化学工業製「Oil Blue630」(Solvent Blue 36)16gを添加する他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0059】
(実施例7)
本例では,実施例1の難燃剤を2,4,6−トリブロモフェノールアリルエーテル(第一工業製;ピロガードFR100,20℃におけるノルマルヘキサンに対する溶解度=11.3wt%,分解温度170℃,融点76℃)96gに変え,難燃助剤としてジクミルパーオキサイド48g,染料として,赤色染料としてのオリエント化学工業製「OPLAS RED330」(Solvent RED 111)16gを添加する他は実施例1と同様にして自己消火性発泡性スチレン系樹脂粒子を作製した。
【0060】
(実施例8)
次に,実施例1〜実施例7にかかる自己消火性発泡性スチレン系樹脂粒子を若干発泡させて予備発泡粒子とするために,予備発泡機(株式会社ダイセン工業社製 DYL300)を用いて,常法により嵩密度20g/Lに発泡させた。
そして目開き1cmの篩いを通った上記予備発泡粒子を1日間室温で放置(熟成)した。次いで,水蒸気圧0.07MPaで加熱融着して300mm×75mm×25mmの発泡成形体(A)を得た。この発泡成形体(A)は,(4)発泡性スチレン系樹脂粒子の難燃剤含有量(wt%)に関する評価において用いる。
【0061】
また,得られた予備発泡粒子を発泡ポリスチレン用成形機(ダイセン工業社製:VS−500)で0.7MPaの水蒸気吹き込み圧で20秒間加熱して成形し,発泡成形体(B)を得た。この発泡成形体(B)は,(6)発泡成形体の自己消火性(秒)(7)発泡成形体の熱伝導率の評価において用いる。
上記の発泡成形体(A)及び(B)について,下記の評価方法を行い,その結果を表3に示した。なお,実施例1〜実施例7にかかる自己消火性発泡性スチレン系樹脂粒子については表1に記載した。
【0062】
評価方法
(1)難燃剤のノルマルヘキサンに対する溶解度(wt%)
ノルマルヘキサン100g中に難燃剤20gを入れ,20℃に保ちながら10分攪拌後,上澄み液50gを採取して,ノルマルヘキサンを蒸発させた後の残査量を溶解量とした。
難燃剤のノルマルヘキサンに対する溶解度=ノルマルヘキサンを蒸発させた後の残査量(g)/ノルマルヘキサン量(g)
【0063】
(2)難燃剤の分解温度(℃)
熱重量分析(昇温速度10℃/分,窒素雰囲気下)により求めた示差熱減量開始温度で,過熱減量開始温度を難燃剤の分解温度とした。
(3)難燃剤の融点(℃)
微量融点測定装置(柳本製 MP−S2型)を用いて,1℃/分の昇温で,難燃剤が融解し始める温度を融点とした。
【0064】
(4)発泡性スチレン系樹脂粒子の難燃剤含有量(wt%)
ここに発泡性スチレン系樹脂粒子は非常に小さいため,樹脂粒子の状態から表層部のみを取り出して,そこに含まれる難燃剤含有量を測ることは困難である。そこで,発泡性樹脂粒子全体の難燃剤含有量を次に示す(A)にかかる方法で,表層部の難燃剤含有量を(B)にかかる方法で測定する。
これは発泡性樹脂粒子から発泡成形体を作製した際に,発泡成形体における各発泡粒子は各個の発泡性樹脂粒子と対応しており,また発泡する際に樹脂粒子は全体に膨らんで,発泡の前後で表層部とそれ以外との部分が交わらないと考えられるためである。
【0065】
(A)発泡性スチレン系樹脂粒子全体の難燃剤含有量(wt%)Tについて
発泡性スチレン系樹脂粒子10gをクロロホルム400mリットルに溶解し,その後メタノール1250mリットルに入れて,析出ポリマーを除去した。その後,抽出液を濃縮,蒸発乾固して添加物を取り出した。次に,取り出した添加物を液クロマトグラフ(カラム;TOSO G2000HHR,溶媒;クロロホルム)により分析した。
【0066】
(B)発泡性スチレン系樹脂粒子表層部の難燃剤含有量(wt%)Hについて
各試料にかかる発泡性スチレン系樹脂粒子を発泡,成形して図2に示すごとく,直方体の発泡成形体2を得た。大きさは,a=75mm,b=300mm,c=25mmである。この発泡成形体2の表層を,スーパーデラックススライサー(ワタナベフーマック株式会社製;WSD−2P&3P)で,図3に示すように,厚さd=0.3mmに切り出して,切片21を得た。そして,切片21には多数の発泡粒子25の断面が露出している。
【0067】
この発泡粒子25を拡大した状態を図4に示す。
図4において,各発泡粒子25の表層部251に相当する部分のみを採取して,難燃剤測定用のサンプルとした。このサンプル10gを上記(A)と同様の方法で液クロマトグラフにかけて分析した。
上記(A)及び(B)の測定により,上記発泡性スチレン系樹脂粒子の表層部を構成するスチレン系樹脂に対する表層部の上記難燃剤の含有割合である難燃剤含有量(wt%)Hと,上記発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Tとの含有比H/Tが分かる。
また,発泡性樹脂粒子から発泡成形体を作製した際に,発泡成形体における各発泡粒子は個々の発泡性樹脂粒子と対応している。
それ故,該発泡性スチレン系樹脂粒子を嵩密度20g/Lに発泡させ,得られた発泡粒子を成形して直方体の発泡成形体を得た場合に,
該発泡成形体の表面から厚さ0.3mmまで切り出した切片の切断面において,該切片を構成する発泡粒子断面の長径をRとしたとき,
t/R=0〜1/10(tは前記切片を構成する発泡粒子表面からの距離)の領域中のスチレン系樹脂に対する該領域中の上記難燃剤の含有割合である難燃剤含有量(wt%)Yと,
該発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Z
についても上記と同様である。
このように,上記測定により,該領域中のスチレン系樹脂に対する該領域中の上記難燃剤の含有割合である難燃剤含有量(wt%)Yと,
該発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Zとの含有比Y/Zも分かる。
【0068】
(5)発泡性スチレン系樹脂粒子の発泡剤含有量(wt%)
発泡性スチレン系樹脂粒子の発泡剤含有量は,ガスクロマトグラフ(3mmID×5mS USカラム,キャリアガス(窒素)40ml/min)により測定した。尚,発泡性スチレン系樹脂粒子における発泡剤中の炭素数5の飽和炭化水素比率は,炭素数5の飽和炭化水素含有量を発泡剤含有量で除した値を用いた。
【0069】
(6)発泡成形体の自己消火性(秒)
発泡成形体を200mm×25mm×10mmの寸法の試験体に切り出し,23℃1日間養生し,JIS A 9511に記載されている方法で燃焼試験を行った。燃焼試験数は5回であり,その平均消火秒数が3秒以内のものを自己消火性合格とした。
【0070】
(7)発泡成形体の熱伝導率(W/m・K)
JIS A 1412−2 熱流計法(HFM法)に準じて発泡成形体の熱伝導率を測定した。発泡成形体を200mm×200mm×25mmの寸法の試験体に切り出し,測定装置の加熱板と冷却熱板の間に挟み,試験体温度差30℃,試験体平均温度20℃の条件で測定を行った。
【0071】
そして,実施例1〜7にかかる自己消火性発泡性スチレン系樹脂粒子に関して表1に,上記測定結果について表3に記載した。なお,表1,表3で略語で表記した物質について,正式名称を表5に記載した。
表1,表3より知られるごとく,実施例1〜7に記載した製造方法により,複雑な処理工程を必要とせず,少量の難燃剤で安定した自己消火性を有する自己消火性発泡性スチレン系樹脂粒子を提供することができる。
また,特に実施例2〜4のように,黒鉛粉,カーボンブラック粉,金属粉を含有する自己消火性発泡性スチレン系樹脂粒子では,少量の難燃剤で安定した自己消火性を有するだけでなく,この自己消火性発泡性スチレン系樹脂粒子から製造したスチレン系樹脂発泡成形体の熱伝導率を低くすることができ,断熱材として優れており,建築材料に好適である。
【0072】
(実施例9)
次に,比較のために以下に示す比較例1〜4に基いて上記と同様の評価を行った。
(比較例1)
本例では,実施例1の発泡剤をペンタン(ノルマルペンタン約80%,イソペンタン約20%の混合物)1120gに変え,エチルベンゼン240gを添加する他は実施例1と同様にして発泡性スチレン系樹脂粒子を作製した。
【0073】
(比較例2)
本例では,実施例1の発泡剤をペンタン(ノルマルペンタン約80%,イソペンタン約20%の混合物)1120gに変え,トルエン240gを添加する他は実施例1と同様にして発泡性スチレン系樹脂粒子を作製した。
【0074】
(比較例3)
本例では,実施例1の難燃剤をエチレンビスブロマイド・2,2−ビス(4−(3,5−ジブロモ−4−ヒドロキシフェニル)プロパン縮合物(帝人化成製;ファイアーガード3000,20℃におけるノルマルヘキサンに対する溶解度=0.03wt%,分解温度300℃,融点60−80℃)に変える他は実施例1と同様にして発泡性スチレン系樹脂粒子を作製した。
【0075】
(比較例4)
本例では,実施例1の難燃剤を2,2−ビス(4−(2,3−ジブロモプロポキシ)−3,5−ジブロモフェニル)プロパン(帝人化成製;ファイアーガード3100,20℃におけるノルマルヘキサンに対する溶解度=0.05wt%,分解温度300℃,融点90−105℃)に変える他は実施例1と同様にして発泡性スチレン系樹脂粒子を作製した。
【0076】
そして,比較例1〜4にかかる発泡性スチレン系樹脂粒子に関して表2に,上記測定結果について表4に記載した。なお,表2,表4で略語で表記した物質について,正式名称を表5に記載した。
表2,表4より知られるごとく,比較例1,2にて得られる発泡性スチレン系樹脂粒子は,ノルマルヘキサンに対する溶解度が20℃において0.1wt%以上の難燃剤を含有するが,難燃剤がスチレン系樹脂粒子にほぼ均一に含浸されており,少量の難燃剤で安定した自己消火性が得られなかった。また,比較例3,4のように,難燃剤のノルマルヘキサンに対する溶解度が20℃において0.1wt%未満の場合,難燃剤の含浸効率が悪く,少量の難燃剤で安定した自己消火性が得られなかった。
【0077】
【表1】
【0078】
【表2】
【0079】
【表3】
【0080】
【表4】
【0081】
【表5】
【図面の簡単な説明】
【図1】実施例1における,自己消火性発泡性スチレン系樹脂粒子の模式図。
【図2】実施例8における,発泡成形体とその寸法を示す説明図。
【図3】実施例8における,発泡成形体から切り出した切片を示す説明図。
【図4】実施例8における,切片における発泡粒子とその表層部を示す説明図。
【符号の説明】
1...自己消火性発泡性スチレン系樹脂粒子,
11...表層部,[0001]
【Technical field】
The present invention is a self-extinguishing foaming styrenic resin particle that does not require a complicated processing step for production and can obtain a stable self-extinguishing property by adding a small amount of a flame retardant.For childRelated.
[0002]
[Prior art]
Styrenic resin foam moldings are excellent in lightness and heat insulation, and are therefore used in residential insulation and cold boxes.
However, the styrene resin foamed molded article has a defect that it contains a lot of air due to its structure and is easy to burn. For this reason, its use has been limited to applications that require self-extinguishing properties, such as thermal insulation for homes.
[0003]
In order to impart self-extinguishing properties to a styrene resin foam molded article, it is conceivable to produce a foam molded article using self-extinguishing foamable styrene resin particles as a material.
Here, as a method for producing self-extinguishing foamable styrene resin particles, there is a production method in which a flame retardant is dissolved in a solvent or the like and impregnated with styrene resin particles together with the foaming agent (see “Known and Conventional Technology” Collection (foam molding) "(issued on August 28, 1982) p28).
The self-extinguishing foamable styrene resin particles produced by this method are almost uniformly impregnated with the flame retardant, so a large amount of flame retardant can be dissolved in a solvent to achieve the desired self-extinguishing properties. It was necessary to let them.
[0004]
Therefore, JP-A-11-130898 and JP-A-11-255946 disclose a method of reducing the amount of flame retardant to be used by reducing the particle size of the flame retardant so that the particles are easily impregnated with the flame retardant. It is disclosed.
However, in these methods, it is necessary to pulverize the flame retardant in advance using glass beads or the like, and a special operation is required in the manufacturing process. Therefore, it was not easy to manufacture.
[0005]
[Non-Patent Document 1]
P28 of "Knowledge-Conventional Technology Collection (Foam Molding)" issued by the JPO (issued on August 3, 1982)
[0006]
[Patent Document 1]
JP-A-11-130898
[Patent Document 2]
JP 11-255946 A
[0007]
[Problems to be solved]
The present invention has been made in view of such conventional problems, and does not require complicated processing steps in production, and can provide stable self-extinguishing properties by adding a small amount of flame retardant. An object of the present invention is to provide expandable styrene resin particles and a method for producing the same.
[0008]
[Means for solving problems]
For convenience of explanation, the reference invention will be described first.
FirstReference inventionIs an expandable styrene resin particle obtained by impregnating a styrene resin particle with a foaming agent and a flame retardant,
The flame retardant has a solubility in normal hexane of 0.1 wt% or more at 20 ° C,
For the styrene resin constituting the surface layer of the expandable styrene resin particlesExpandable styrenic resin particlesFlame retardant content (wt%) H, which is the content ratio of the flame retardant in the surface layer portion, and the content of the flame retardant in the entire expandable styrene resin particles with respect to the styrene resin constituting the entire expandable styrene resin particles In the self-extinguishing foamable styrene resin particles, the content ratio H / T to the flame retardant content (wt%) T, which is a ratio, is 1.05 or more.The
[0009]
next,Reference invention aboveThe operational effects of will be described.
BookReference invention, The content ratio H / T between the flame retardant content (wt%) H of the surface layer portion and the flame retardant content (wt%) T of the entire expandable styrene resin particles is 1.05 or more. As described above, by increasing the “content ratio” of the flame retardant contained in the surface layer part of the particles as compared with other parts, it is possible to obtain excellent self-extinguishing properties even if the content of the flame retardant is low.
The surface layer will be described later.
[0010]
more than,First reference inventionAccording to the present invention, it is possible to obtain self-extinguishing foaming styrene resin particles that do not require complicated processing steps for production and can obtain stable self-extinguishing properties by adding a small amount of flame retardant.
[0011]
next,SecondReference inventionIs an expandable styrene resin particle obtained by impregnating a styrene resin particle with a foaming agent and a flame retardant, and the flame retardant has a solubility in normal hexane of 0.1 wt% or more at 20 ° C,
Flame retardant content (wt%) H, which is the content ratio of the flame retardant in the surface layer portion of the expandable styrene resin particle to the styrene resin constituting the surface layer portion of the expandable styrene resin particle, and the expandable styrene The content ratio H / T with the flame retardant content (wt%) T, which is the content ratio of the above-mentioned flame retardant in the entire expandable styrene resin particles to the styrene resin constituting the entire resin particles, is 1.05 or more. In producing certain self-extinguishing foamable styrene resin particles,
Self-extinguishing, characterized in that styrene resin particles are dispersed in an aqueous suspension in an airtight container, and a foaming agent and a flame retardant are added to the aqueous suspension without adding aromatic hydrocarbons. A process for producing expandable styrene resin particlesThe
[0012]
When adding aromatic hydrocarbons and impregnating the styrene resin particles with the flame retardant, the styrene resin particles are almost uniformly impregnated with the flame retardant to increase the amount of the flame retardant contained in the surface layer of the particles. If the amount of flame retardant added to the aqueous suspension is small, it may be difficult to develop self-extinguishing properties.
In addition, aromatic hydrocarbons impregnated in styrene resin particles may adversely affect self-extinguishing properties.
In the present invention, since aromatic hydrocarbons are not added, the amount of the flame retardant added to the aqueous suspension can be reduced, so that many flame retardants can be contained in the surface layer of the particles, and excellent self-extinguishing properties can be obtained. Obtainable.
more than,Second reference inventionAccording to the present invention, it is possible to obtain a method for producing self-extinguishing foamable styrene resin particles that does not require complicated processing steps for production and can obtain stable self-extinguishing properties by adding a small amount of flame retardant. it can.
[0013]
Next, the invention according to the present application will be described.
The present inventionIt consists of a compound whose content of saturated hydrocarbons having 5 carbon atoms is 15 vol% or moreFoaming agent and flame retardant,Styrenic resin particles,
Without adding aromatic hydrocarbons,Expandable styrene resin particles impregnated,
The flame retardant has a solubility in normal hexane of 0.1 wt% or more at 20 ° C,
50% average particle diameter of the expandable styrene resin particles is 0.5 to 2 mm,
When the foamable styrenic resin particles are foamed to a bulk density of 20 g / L, and the resulting foamed particles are molded to obtain a rectangular foam molded product,
When the major axis of the cross-section of the expanded particles constituting the slice is R on the cut surface of the slice cut to a thickness of 0.3 mm from the surface of the foamed molded product,
Flame retardant content (wt) which is the content ratio of the flame retardant in the region to the styrene resin in the region of t / R = 0 to 1/10 (t is the distance from the surface of the expanded particle constituting the slice) %) Y,
The content ratio Y / Z of the flame retardant content (wt%) Z, which is the content ratio of the flame retardant in the whole expandable styrene resin particles to the styrene resin constituting the entire expandable styrene resin particles, is 1 .05 or more,
The flame retardant content (wt%) Z is 0.49 wt% or more.
Self-extinguishing foamable styrene resin particles characterized in that (claim 1).
According to this invention, the foaming molding which has the outstanding self-extinguishing property can be obtained.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
BookIn the invention, when the solubility of the flame retardant in normal hexane is less than 0.1 wt% at 20 ° C., the impregnation efficiency of the flame retardant is poor, and there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of the flame retardant.
The solubility of flame retardant in normal hexane is determined by adding 20 g of flame retardant to 100 g of normal hexane, stirring for 10 minutes while maintaining at 20 ° C., collecting 50 g of supernatant liquid, and evaporating normal hexane. The amount was taken as the dissolved amount.
That is, “Solubility of flame retardant in normal hexane = residual amount after evaporating normal hexane (g) / normal hexane amount (g)”.
In addition, the self-extinguishing property was determined by performing a combustion test by the method described in JIS A 9511 and setting the average fire extinguishing time within 3 seconds as self-extinguishing pass.
[0015]
Next, even in the case of expandable styrene resin particles containing a flame retardant having a solubility in normal hexane of 0.1 wt% at 20 ° C., the flame retardant content (wt%) of the surface layer of the expandable styrene resin particles is When the content of the flame retardant is less than 1.05 times the total content of the expandable styrene resin particles (wt%), there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of flame retardant.
Further, the upper limit of the content is preferably less than 1.35 times in order to suppress the blocking amount at the time of foaming.
[0016]
The flame retardant content (wt%) of the expandable styrene resin particles is the amount of flame retardant contained in 100 parts by weight of the styrene resin particles, and is determined by liquid chromatography (column: TOSO G2000HHR, solvent: chloroform). It is a measured value.
The flame retardant content (wt%) indicates the content ratio of the flame retardant to the styrene resin constituting the expandable styrene resin particles in weight% (wt%).
The first reference invention, The flame retardant content (wt%) H, which is the content ratio of the flame retardant in the surface layer portion to the styrene resin constituting the surface layer portion of the expandable styrene resin particles, and the entire expandable styrene resin particles The content ratio H / T with the flame retardant content (wt%) T, which is the content ratio of the above flame retardant in the entire expandable styrene resin particles with respect to the styrene resin constituting the above, is defined.
[0017]
next,the aboveExpandable styrenic resin particlesThe surface layer will be described.
As shown in FIG. 1, the surface layer portion 11 is a region where t / R = 0 to 1/10, where R is the major axis of the
For example, in the case of resin particles with R = 1.0 mm, t = 0.1 mm (see Example 1 described later).
[0018]
aboveThe expandable styrene resin particles are styrene resin particles containing a foaming agent.
Here, the type of resin constituting the expandable styrene resin particles to be used is not particularly limited, and examples thereof include styrene monomer.
In addition, monomer components copolymerizable with styrene monomers, for example, alkyl esters having 1 to 10 carbon atoms of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate Etc .; alkyl esters having 1 to 10 carbon atoms of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; α-methylstyrene, o-methylstyrene, etc. m-methylstyrene, p-methylstyrene, vinyltoluene, p-ethylstyrene, 2,4-dimethylstyrene, p-methoxystyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, pn- Styrene monomer derivatives such as styrene styrene, pt-butyl styrene, pn-hexyl styrene, p-octyl styrene, styrene sulfonic acid, sodium styrene sulfonate, etc .; nitrile group-containing unsaturated compounds such as acrylonitrile and methacrylonitrile These resins can be used alone or in combination of two or more, and a resin copolymerized with a styrene monomer can be used.
The styrene monomer and the monomer component copolymerizable with the styrene monomer are referred to as a styrene monomer.
However, when these monomers are used in addition to the styrene monomer, the weight of the styrene monomer is preferably 50% or more based on the total weight of the styrene monomer when polymerizing the styrene resin particles. . In such a case, uniform styrene resin particles having better heat resistance can be obtained.
[0019]
Also,the aboveThe expandable styrene resin particles preferably have a weight average molecular weight (Mw) value measured by GPC method of 180,000 to 400,000.
If the weight average molecular weight is less than 180,000, the strength of the resulting foamed molded product may be reduced. On the other hand, when the weight average molecular weight exceeds 400,000, the foaming property is lowered, making it difficult to foam to a target foaming ratio (for example, 50 to 60 times), However, the strength of the foamed molded product may be reduced. More preferably, it is 200,000 to 380,000, and more preferably 220,000 to 350,000. The weight average molecular weight is a value measured by the GPC method.
[0020]
As a method for producing the expandable styrene resin particles, there are methods disclosed in, for example, JP-A-7-79376 and JP-A-8-253510.
That is, first, a styrenic monomer is dispersed in an aqueous medium in the presence of a polymerization initiator and a suspending agent. Thereafter, a polymerization reaction is started, and a foaming agent is added before, during or during the polymerization reaction to produce expandable styrene resin particles.
As another manufacturing method, a styrene resin and a volatile foaming agent are melt-kneaded in an extruder, extruded from the pores of the die at the tip of the extruder, immediately introduced into water, rapidly cooled, and unfoamed. There is a method of producing expandable styrene resin particles by forming particles with the above.
[0021]
Also, a styrene resin is melt-kneaded in an extruder to obtain particles having a size of 0.5 mg / piece to 5 mg / piece by methods such as strand cutting, hot cutting, and underwater cutting, and the resulting styrene resin resin. The particles are dispersed in an aqueous medium in a closed container in the presence of a suspending agent. Thereafter, there is a method of producing expandable styrene resin particles by impregnating resin particles with a volatile foaming agent (Japanese Patent Laid-Open No. 2000-178373).
DepartureIt is preferable to use resin particles in the range of 0.5 to 2 mm as the 50% average particle diameter of the foamed styrene resin particles. The shape is not particularly limited, but is preferably close to a sphere. The 50% particle diameter of the expandable styrene resin particles was determined by dispersing the expandable styrene resin particles in water and setting the shape factor to 1 by a laser diffraction scattering method (measuring device; manufactured by SYMPATEC). Was measured.
[0022]
Also, SelfSelf-extinguishing foamable styrene resin particles, methyl methacrylate copolymer, polyethylene wax, talc, silica, ethylenebisstearylamide, silicone and other cell nucleating agents, liquid paraffin, glycerol diacetomonolaurate, glycerol tristeare Rate, plasticizers such as di-2-ethylhexyl phthalate and di-2-ethylhexyl adipate, antistatic agents such as alkyldiethanolamine, glycerin fatty acid esters, sodium alkylsulfonates, oxidations such as phenols, phosphorus and sulfur Inhibitors, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amines, conductive fillers such as conductive carbon black, organic antibacterials such as IPBC, TBZ, BCM, TPN, silver, Copper-based, sub- System, or adding an additive, such as inorganic antibacterial agents such as titanium oxide, butadiene rubber, styrene - butadiene rubber, isoprene rubber, ethylene - may be added to the rubber component such as propylene rubber.
[0023]
the aboveExamples of the blowing agent include aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, neopentane, and hexane having a boiling point of 90 ° C. or lower, or alicyclic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane. Can be mentioned. These aliphatic hydrocarbons or alicyclic hydrocarbons can be used alone or in combination.
[0024]
The content of the foaming agent is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the styrene resin particles.
If the amount is less than 1 part by weight, the foaming power may decrease, making it difficult to foam to the target foaming ratio, or the styrene resin particles may not be impregnated with a flame retardant, making it difficult to develop self-extinguishing properties. is there. On the other hand, if it exceeds 10 parts by weight, the impregnation property with respect to polystyrene resin is limited, and there is a risk of being wasted economically. More preferably, the range of 3 to 8 parts by weight is good.
[0025]
the aboveExamples of the flame retardant include an organic compound containing bromine.
For example, 1,2,3,4-tetrabromobutane, 1,2,4-tribromobutane, tetrabromopentane, tetrabromobisphenol A, 2,2-bis (4-allyloxy-3,5-dibromophenyl) Propane, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4- (2,3-dibromo) propyloxy-3,5-dibromophenyl) propane, pentabromo Diphenyl ether, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tribromophenol, dibromoethylbenzene, 1,2,3,4,5,6-hexabromocyclohexane, 1,2,5,6,9,10- Hexabromocyclododecane, octabromocyclohexadecane Esters or acetals of dibromopropanol, such as 1-chloro-2,3,4,5,6-pentabromocyclohexane, tris- (2,3-dibromopropyl) -phosphate, tribromophenol, tribromostyrene, tri Examples thereof include bromophenol allyl ether and dibromoethyl-dibromocyclohexane.
[0026]
Moreover, these flame retardants can be used individually or in mixture of 2 or more types.
Moreover, you may use a well-known flame retardant adjuvant as an effect which improves self-extinguishing property.
Examples of the flame retardant aid include organic peroxides such as dicumyl peroxide, cumene hydroxy peroxide, 2,3-dimethyl-2,3-diphenylbutane, and the like. In the impregnation step, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 100 ° C. or higher in order to suppress the decomposition amount of the flame retardant aid as much as possible.
The amount of the flame retardant aid is preferably up to 1 part by weight per 100 parts by weight of the expandable styrene resin particles. Even if it is added in an amount of 1 part by weight or more, the improvement of the effect commensurate with the amount added is not observed. The flame retardant aid can be used in the same manner as the flame retardant.
[0027]
next, NoIn the expandable styrene resin particles containing a flame retardant having a solubility in lumal hexane of 0.1 wt% or more at 20 ° C, the flame retardant content (wt%) of the surface layer of the expandable styrene resin particles is the expandable styrene resin It is preferable that it is 1.15 times or more with respect to the flame retardant content (wt%) of the entire resin particles.Yes.
[0028]
Even in the case of expandable styrene resin particles containing a flame retardant having a solubility in normal hexane of 0.1 wt% or more at 20 ° C., the flame retardant content (wt%) of the surface layer of the expandable styrene resin particles is expanded. When the content is less than 1.15 times the flame retardant content (wt%) of the entire reactive styrenic resin particles, there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of flame retardant.
[0029]
Next, the solubility of the flame retardant in normal hexane is preferably 0.5 wt% or more at 20 ° C.Yes.
If the solubility of the flame retardant in normal hexane is less than 0.5 wt% at 20 ° C, the impregnation efficiency of the flame retardant is poor and there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of flame retardant. More preferably, it is 1.5 wt% or more, More preferably, it is 5 wt% or more.
[0030]
Next, the decomposition temperature of the flame retardant is preferably 250 ° C. or less.Yes.
Thereby, stable self-extinguishing properties can be obtained with a small amount of flame retardant.
When using a flame retardant whose decomposition temperature exceeds 250 ° C, bromine radicals that capture and stabilize active OH radicals and H radicals that promote polymer combustion progress are less likely to be generated and stabilized with a small amount of flame retardant. There is a risk that self-extinguishing properties cannot be achieved.
[0031]
here,the aboveThe decomposition temperature of the flame retardant is a differential heat loss curve obtained by thermogravimetric analysis (temperature increase rate 10 ° C., under nitrogen atmosphere), and the heating loss start temperature is defined as the flame retardant decomposition temperature. Preferably, it is a flame retardant having an allyl structure.
[0032]
Next, the melting point of the flame retardant is preferably 70 ° C to 120 ° C.Yes.
When the melting point of the flame retardant is less than 70 ° C., the resulting self-extinguishing foamable styrene resin particles tend to shrink, which may cause a problem in dimensional stability. If the melting point of the flame retardant exceeds 120 ° C., the flame retardant cannot be sufficiently impregnated into the self-extinguishing foamable styrene resin particles, and there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of the flame retardant.
[0033]
Next, the foaming agent is a compound having a saturated hydrocarbon content of 5 carbon atoms of 15 Vol% or more.Use.
Thereby, the stable self-extinguishing property can be expressed with a small amount of flame retardant.
If the content of the saturated hydrocarbon having 5 carbon atoms in the foaming agent is less than 15 Vol%, there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of flame retardant.
Further, the content of the saturated hydrocarbon having 5 carbon atoms is preferably 30 Vol% or more, and more preferably 50 Vol% or more.
[0034]
The flame retardant content (wt%) Z is 0.49 wt% or more.
Next, the flame retardant is 100 parts by weight of the styrene resin particles.0.5It is preferable that 10-10 weight part is contained.
MaIf it exceeds 2 parts by weight, the moldability is adversely affected, and it is difficult to obtain a foamed molded article having a beautiful appearance. More preferably, the range of 0.5 to 1.5 parts by weight is good.
[0035]
Next, the self-extinguishing foamable styrene resin particles preferably contain one or more of graphite powder, carbon black powder, and metal powder.Yes.
The self-extinguishing foaming styrene resin particles containing them not only exhibit stable self-extinguishing properties with a small amount of flame retardant, but also exhibit low heat conductivity and excellent heat insulation performance.
Examples of the metal powder include aluminum powder, iron powder, zinc powder, gold powder, silver powder, copper powder, tungsten powder, titanium powder, molybdenum powder, lead powder, and nickel powder. The above metal powders may be used alone or in combination of two or more. Also, metal powder of an alloy such as brass powder (copper-zinc alloy, bronze powder) may be used.
[0036]
The content of graphite powder, carbon black powder, and metal powder is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of styrene resin particles.
The 50% particle diameter of graphite powder, carbon black powder, and metal powder is preferably 0.1 to 100 μm. More preferably, it is 0.5-50 micrometers.
The 50% particle size was determined by dispersing graphite powder, carbon black powder, and metal powder in isopropanol, setting the shape factor to 1, and using a laser diffraction scattering method (measuring device: LMS-24 manufactured by Seishin Enterprise Co., Ltd.). It was measured. The shape is not particularly limited, but a plate shape or a scale shape is preferable. More preferably, it is scaly.
[0037]
SecondReference inventionA manufacturing method according to the above will be described.
SecondReference inventionIt is preferable to use a sealed container that can be sealed, for example, can be stirred and mixed in the container and can be heated. Examples of such a sealed container include an autoclave with a stirring device and a mixer that can be sealed.
Also, SelfAs a specific method for producing self-extinguishing foamable styrene resin particles, for example, styrene resin particles, a flame retardant, a suspending agent, and a surfactant are dispersed in an aqueous suspension. There is a method of heating with stirring. In addition, there is no restriction | limiting in the injection | throwing-in order of a styrene resin particle, a flame retardant, and a foaming agent.
[0038]
As a method of using the flame retardant, there is a method in which the flame retardant is dispersed in an aqueous suspension in advance before the foaming agent is added, and impregnated together when the foaming agent is impregnated.
In addition, there is a method of adding an aqueous suspension of a flame retardant at the beginning or in the middle of the process.
Further, the foaming agent may be added before heating, during heating, or after reaching a predetermined temperature, or may be added in a plurality of times.
In the impregnation, the styrenic resin particles are preferably in the range of 20 to 120 parts by weight with respect to 100 parts by weight of the water of the aqueous suspension, and particularly preferably in the range of 80 to 110 parts by weight from the viewpoint of production cost. The impregnation time is preferably in the range of 5 to 15 hours, but is not limited thereto.
[0039]
Suspending agents used when impregnating the flame retardant are, for example, tricalcium phosphate, hydroxyapatite, magnesium pyrophosphate, magnesium phosphate, aluminum hydroxide, ferric hydroxide, titanium hydroxide, magnesium hydroxide, phosphoric acid Examples thereof include particulate water-insoluble inorganic salts such as barium, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, talc, kaolin and bentonite.
Of these, tricalcium phosphate, hydroxyapatite, and magnesium pyrophosphate are more preferable.
The addition amount of the suspending agent is preferably in the range of 0.05 to 3 parts by weight with respect to 100 parts by weight of the styrene resin particles. If the amount is less than 0.05 part by weight, the styrene resin particles cannot be suspended and stabilized, and a resin mass may be generated. If the amount exceeds 3 parts by weight, it is not preferable from the viewpoint of production cost.
[0040]
In addition, it is preferable to use an anionic surfactant such as sodium alkyl sulfonate, sodium alkyl benzone sulfonate, sodium lauryl sulfate, sodium α-olein sulfonate, sodium dodecylphenyl oxide disulfonate, etc. with respect to the suspending agent. As a result, an excellent suspension stabilization effect is obtained.
The addition amount of the surfactant is preferably in the range of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the styrene resin particles.
If necessary, electrolytes such as inorganic salts such as lithium chloride, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, sodium nitrate, sodium carbonate, and sodium bicarbonate can be added.
[0041]
Moreover, self-extinguishing foamable styrene resin particles can be colored by adding a dye to the aqueous suspension. As the dye, azo dyes, anthraquinone dyes, azine dyes, quinoline dyes and the like generally used for styrene resins can be used.
Specifically, solvent yellow 33, solvent orange 60, solvent blue 35, solvent blue 36, solvent red 111, solvent violet 13, solvent green 3, etc. are mentioned.
There is a method in which these dyes are dissolved or dispersed in a solvent in advance and then added to a pressure-resistant container containing styrene resin particles and an aqueous suspension and added together with a foaming agent to be colored. There is also a method of adding impregnation and coloring by adding a foaming agent after adding together with a flame retardant and a flame retardant aid.
[0042]
When using the dye without dissolving it in advance, it is necessary to use a fine product with a dye particle size of 100 μm or less in order to uniformly impregnate, or use a crusher such as a ball mill, disper, homogenizer, or attritor in advance. Therefore, it is preferable to make the dye particles finer to 100 μm or less in an aqueous medium. Moreover, it can be used not only by the method mentioned here but also by other known methods.
[0043]
SecondReference inventionIn this case, it is preferable to maintain the temperature of the aqueous suspension above the melting point of the flame retardant.Yes.
Thereby, the impregnation efficiency of a flame retardant can be improved and the stable self-extinguishing property can be expressed with a small amount of flame retardant.
When the heating temperature of the aqueous suspension is lower than the melting point of the flame retardant, the impregnation efficiency of the flame retardant is poor, and there is a possibility that stable self-extinguishing properties cannot be expressed with a small amount of the flame retardant.
Preferably, it is 70-120 degreeC.
If it is less than 70 degreeC, a flame retardant cannot fully be impregnated with a styrene resin particle, and there exists a possibility that stable self-extinguishing property cannot be expressed with a small amount of flame retardant. If the temperature exceeds 120 ° C., the styrene resin particles may be softened to generate condensed beads.
[0044]
The secondReference inventionAlso the firstReference inventionSimilarly, it is preferable that the flame retardant has a solubility in normal hexane of 0.5 wt% or more at 20 ° C.Yes.The decomposition temperature of the flame retardant is preferably 250 ° C. or lower.Yes.The melting point of the flame retardant is preferably 70 ° C to 120 ° C.Yes.The blowing agent is preferably composed of a compound having a content of saturated hydrocarbons having 5 carbon atoms of 15 Vol% or more.Yes.The flame retardant is preferably contained in an amount of 0.3 to 10 parts by weight with respect to 100 parts by weight of the styrene resin particles.Yes.
[0045]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
Example 1
The self-extinguishing foamable styrene resin particles in this example are particles obtained by impregnating a styrene resin particle with a foaming agent and a flame retardant, and the flame retardant has a solubility in normal hexane of 0.1 wt% or more at 20 ° C. The flame retardant content (wt%) in the surface layer of the particles is 1.05 times or more with respect to the flame retardant content (wt%) of the entire particles.
The foaming agent, flame retardant, and styrene resin particles are described in detail below. The performance and others are described in detail in Example 8.
[0046]
First, the styrene resin particles A used for obtaining the particles of this example will be described.
In a 50 liter autoclave with a stirrer, 18 liters of ion exchange water, 63 g of tricalcium phosphate (made by Taihei Chemical Sangyo Co., Ltd.) as a poorly water-soluble inorganic suspending agent, sodium dodecylbenzenesulfonate (Tokyo Kasei) as a surfactant 0.54 g) (manufactured by Kogyo Co., Ltd.) was added.
Next, under stirring, styrene in which 45 g (33.75 g in terms of pure product) of benzoyl peroxide (manufactured by NOF Corporation, purity: 75%) and 13 g of t-butylperoxy 2-ethylhexyl carbonate were dissolved as a polymerization initiator. 18 kg of monomer was charged.
[0047]
The mixture was allowed to stand at room temperature for 30 minutes under stirring, then heated to 90 ° C. over 1 hour and a half, and further heated to 100 ° C. over 5 hours. Thereafter, the temperature was further raised to 120 ° C. over 1 hour and a half, 120 ° C. was maintained for 2 hours and a half, and then cooled to 30 ° C. over 4 hours. Then, after removing water adhering to the surface with a centrifugal separator and a fluid dryer, sieve with 0.7mm and 1.4mm sieves, and particles with a particle size of 0.7-1.4mm. Using.
[0048]
Next, the self-extinguishing foamable styrene resin particles and the production method according to this example will be described.
In a 50 liter autoclave with a stirrer, 18 liters of ion exchange water, 160 g of tribasic calcium phosphate (made by Taihei Chemical Sangyo Co., Ltd.) as a poorly water-soluble inorganic suspending agent, sodium dodecylbenzenesulfonate (Tokyo Kasei) as a surfactant 1.6 g, 2,2-bis (4-allyloxy-3,5-dibromophenyl) propane (manufactured by Teijin Chemicals; Fireguard 3200, solubility in normal hexane at 20 ° C. = 1.9 wt.) %, Decomposition temperature 239 ° C., melting point 115 ° C.) 128 g, NaCl (normal salt) 32 g, and 16 kg of styrene resin particles A as styrene resin particles were added and stirred at 180 rpm.
[0049]
And when it heated with steam and the internal temperature reached 90 ° C., 1.2 kg of pentane (a mixture of about 80 Vol% of normal pentane and about 20 Vol% of isopentane) as a blowing agent was gradually added over 30 minutes. Then, after maintaining at 90 ° C. for 5 hours, the temperature was raised to 120 ° C., maintained for 6 hours, and then cooled to 40 ° C. over 4 hours.
Subsequently, the obtained product was dehydrated with a centrifugal separator and washed with an acid to remove tertiary calcium phosphate on the surface of the particles. Thereafter, the water adhering to the upper surface was removed with a fluidized dryer, and self-extinguishing foamable styrene resin particles according to this example were obtained.
[0050]
A schematic diagram of the self-extinguishing foamable styrene diameter resin particles is shown in FIG.
The
The surface layer portion 11 is a region where t / R = 0 to 1/10, where R is the major axis of the
[0051]
(Example 2)
In this example, the following styrene resin particles B as the styrene resin particles, and 2,4,6-tribromophenol allyl ether (made by Daiichi Kogyo; Pyroguard FR100, solubility in normal hexane at 20 ° C. = 11. 3 wt%, decomposition temperature 170 ° C., melting point 76 ° C. 128 g, blowing agent pentane (mixture of normal pentane about 80 Vol%, isopentane about 20 Vol%), butane (mixture of normal butane about 70 Vol% and isobutane about 30 Vol%) 960 g Except that, self-extinguishing foamable styrene resin particles were produced in the same manner as in Example 1.
[0052]
Here, the styrene resin particles B will be described.
After mixing 100 parts by weight of polystyrene (HH102 manufactured by A & M Styrene Co., Ltd.) and 3 parts by weight of aluminum paste (0100 MSR manufactured by Toyo Aluminum Co., Ltd., aluminum powder content of about 67%, scaly aluminum powder), Melted and mixed at a temperature of 200 to 220 ° C with a Φ30mm single screw extruder, the molten resin was extruded in a strand form from a die at the tip of the extruder, immediately introduced into a water bath at about 30 ° C, cooled, and then with a strand cutter, Styrenic resin particles containing columnar aluminum powder having a weight of about 1 mg / piece were prepared.
[0053]
(Example 3)
In this example, the following styrene resin particles C as styrene resin particles, flame retardant tetrabromocyclooctane (Daiichi Kogyo; Piroguard FR200, solubility in normal hexane at 20 ° C. = 1.8 wt%, decomposition temperature 137 ° C. , Melting point 110 ° C.) 160 g, dicumyl peroxide 32 g as a flame retardant aid, blowing agent pentane (mixture of normal pentane about 80 Vol%, isopentane about 20 Vol%), butane (normal butane about 20 Vol% and isobutane about 80 Vol%) A self-extinguishing foamable styrene resin particle was prepared in the same manner as in Example 1 except that the mixture was changed to 960 g.
[0054]
Here, the styrene resin particles C will be described.
After mixing 100 parts by weight of polystyrene (HH102 manufactured by A & M Styrene Co., Ltd.) and 3 parts by weight of scaly graphite powder (SNO-5, 50% average particle size: 5 μm manufactured by ESC Co., Ltd.) with a mixer, It is melt-mixed at a temperature of 200 to 220 ° C. with a shaft extruder, and the molten resin is extruded in a strand form from a die at the tip of the extruder, immediately introduced into a water bath at about 30 ° C., cooled, and then weighed by a strand cutter. Styrenic resin particles containing 1 mg / piece of columnar graphite powder were prepared.
[0055]
Example 4
In this example, the following styrene resin particles D as the styrene resin particles, 1,2,5,6,9,10 hexabromocyclodecane (made by Daiichi Kogyo; Piroguard SR-104, normal at 20 ° C.) Self-extinguishing in the same manner as in Example 1 except that the solubility in hexane = 0.2 wt%, decomposition temperature 210 ° C., melting point 165 ° C.) 240 g, dicumyl peroxide 80 g as a flame retardant aid, and foaming agent 800 g. Expandable styrene resin particles were prepared.
[0056]
Here, the styrene resin particles D will be described.
After mixing 100 parts by weight of polystyrene (HH102 manufactured by A & M Styrene Co., Ltd.) and 3 parts by weight of carbon black reagent (manufactured by Nakarai Co., Ltd., 50% average particle size: 5 mm) with a mixer, using a single screw extruder of Φ30 mm The melted resin is melt-mixed at a temperature of 200 to 220 ° C., and the molten resin is extruded in a strand form from a die at the tip of the extruder, immediately introduced into a water bath at about 30 ° C., cooled, and then weighed by a strand cutter with a weight of about 1 mg / piece. Styrenic resin particles containing columnar carbon black were prepared.
[0057]
(Example 5)
This example is shown as a reference example because the foaming agent is different from the conditions of the invention of
In this example, the flame retardant of Example 1 is 2,4,6-tribromophenol allyl ether (Daiichi Kogyo; Pyroguard FR100, solubility in normal hexane at 20 ° C. = 11.3 wt%, decomposition temperature 170 ° C., melting point (76 ° C) 192 g, foaming agent was changed to 160 g of pentane (a mixture of about 80 Vol% of normal pentane and about 20 vol% of isopentane) and 1120 g of butane (a mixture of about 70 vol% of normal butane and about 30 Vol% of isobutane), manufactured by Orient Chemical Industries "OPLAS YELLOW 136" (Solvent
Self-extinguishing foamable styrene resin particles were prepared in the same manner as in Example 1 except that 160 g of Yellow 33) was added.
[0058]
(Example 6)
In this example, 2,2-bis (4-allyloxy-3,5-dibromophenyl) propane (manufactured by Teijin Chemicals; Fireguard 3200, solubility in normal hexane at 20 ° C. = 1.9 wt% as the flame retardant of Example 1 , Decomposition temperature 239 ° C., melting point 115 ° C.) 96 g, except for adding 48 g of dicumyl peroxide as a flame retardant aid and 16 g of “Oil Blue 630” (Solvent Blue 36) manufactured by Orient Chemical Industry as a blue dye Self-extinguishing foamable styrene resin particles were produced in the same manner as in Example 1.
[0059]
(Example 7)
In this example, the flame retardant of Example 1 is 2,4,6-tribromophenol allyl ether (Daiichi Kogyo; Pyroguard FR100, solubility in normal hexane at 20 ° C. = 11.3 wt%, decomposition temperature 170 ° C., melting point 76 g) Dicumyl peroxide 48 g as a flame retardant aid, and 16 g of “OPLAS RED330” (Solvent RED 111) manufactured by Orient Chemical Industry as a red dye are added as a dye. Thus, self-extinguishing foamable styrene resin particles were prepared.
[0060]
(Example 8)
Next, in order to slightly expand the self-extinguishing foamable styrene resin particles according to Example 1 to Example 7 into pre-expanded particles, using a pre-foaming machine (DYL300 manufactured by Daisen Industry Co., Ltd.), It was made to foam to a bulk density of 20 g / L by a conventional method.
The pre-expanded particles that passed through a sieve having an opening of 1 cm were left (aged) at room temperature for 1 day. Subsequently, it was heat-sealed at a water vapor pressure of 0.07 MPa to obtain a foamed molded article (A) of 300 mm × 75 mm × 25 mm. This foamed molded product (A) is used in (4) evaluation regarding the flame retardant content (wt%) of the expandable styrene resin particles.
[0061]
The obtained pre-expanded particles were molded by heating with a foaming polystyrene molding machine (manufactured by Daisen Kogyo Co., Ltd .: VS-500) at a water vapor blowing pressure of 0.7 MPa for 20 seconds to obtain a foam molded product (B). . This foam-molded product (B) is used in (6) self-extinguishing property (second) of the foam-molded product (7) evaluation of thermal conductivity of the foam-molded product.
The foamed molded products (A) and (B) were subjected to the following evaluation methods, and the results are shown in Table 3. The self-extinguishing foamable styrene resin particles according to Examples 1 to 7 are shown in Table 1.
[0062]
Evaluation methods
(1) Solubility of flame retardant in normal hexane (wt%)
20 g of a flame retardant was added to 100 g of normal hexane, stirred for 10 minutes while maintaining at 20 ° C., 50 g of the supernatant was collected, and the residual amount after evaporation of normal hexane was defined as the dissolved amount.
Solubility of flame retardant in normal hexane = residue amount after evaporating normal hexane (g) / normal hexane amount (g)
[0063]
(2) Flame retardant decomposition temperature (℃)
It was the differential heat loss start temperature determined by thermogravimetric analysis (temperature increase rate 10 ° C / min, under nitrogen atmosphere), and the overheat loss start temperature was defined as the flame retardant decomposition temperature.
(3) Melting point of flame retardant (℃)
The temperature at which the flame retardant begins to melt at a temperature rise of 1 ° C./min was determined as the melting point using a trace melting point measuring device (MP-S2 type manufactured by Yanagimoto).
[0064]
(4) Flame retardant content of expandable styrene resin particles (wt%)
Here, since the expandable styrene resin particles are very small, it is difficult to measure only the surface layer portion from the state of the resin particles and measure the content of the flame retardant contained therein. Therefore,EffervescentThe flame retardant content of the entire resin particleShown belowBy the method according to (A), the flame retardant content of the surface layer portion is measured by the method according to (B).
this isEffervescentEach foam particle in the foam molded product is made up of individual pieces when the foam molded product is produced from resin particles.EffervescentThis is because the resin particles correspond to the resin particles, and the resin particles swell all over when foaming, and it is considered that the surface layer portion and other portions do not intersect before and after foaming.
[0065]
(A) Flame retardant content (wt%) of the entire expandable styrene resin particlesAbout T
10 g of expandable styrene resin particles were dissolved in 400 ml of chloroform, and then placed in 1250 ml of methanol to remove the precipitated polymer. Thereafter, the extract was concentrated and evaporated to dryness to remove the additive. Next, the extracted additive was analyzed by a liquid chromatograph (column; TOSO G2000HHR, solvent: chloroform).
[0066]
(B) Flame retardant content (wt%) in the surface layer of expandable styrene resin particlesAbout H
The foamable styrene resin particles applied to each sample were foamed and molded to obtain a rectangular foam molded
[0067]
The expanded state of the expanded
In FIG. 4, only the portion corresponding to the
According to the measurements (A) and (B), the flame retardant content (wt%) H, which is the content ratio of the flame retardant in the surface layer portion relative to the styrene resin constituting the surface layer portion of the expandable styrene resin particles, The content ratio H / T of the flame retardant content (wt%) T, which is the content ratio of the flame retardant in the whole foamable styrene resin particles to the styrene resin constituting the whole foamable styrene resin particles, is known. .
Further, when a foam molded body is produced from the foamable resin particles, each foam particle in the foam molded body corresponds to an individual foamable resin particle.
Therefore,When the foamable styrenic resin particles are foamed to a bulk density of 20 g / L, and the resulting foamed particles are molded to obtain a rectangular foam molded product,
When the major axis of the cross section of the expanded particle constituting the slice is R on the cut surface of the slice cut to a thickness of 0.3 mm from the surface of the foamed molded product,
Flame retardant content (wt) which is the content ratio of the flame retardant in the region to the styrene-based resin in the region of t / R = 0 to 1/10 (t is the distance from the surface of the expanded particle constituting the section) %) Y,
Flame retardant content (wt%) Z, which is the content ratio of the above flame retardant in the entire expandable styrene resin particles to the styrene resin constituting the entire expandable styrene resin particles
Is the same as aboveThe
in this way, By the above measurement, Flame retardant content (wt%) Y, which is the content ratio of the flame retardant in the region to the styrene resin in the region;
Flame retardant content (wt%) Z, which is the content ratio of the above flame retardant in the entire expandable styrene resin particles to the styrene resin constituting the entire expandable styrene resin particlesContent ratioY / ZI understand.
[0068]
(5) Foaming agent content (wt%) of expandable styrene resin particles
The foaming agent content of the expandable styrene resin particles was measured by a gas chromatograph (3 mm ID × 5 mS US column, carrier gas (nitrogen) 40 ml / min). The ratio of the saturated hydrocarbon having 5 carbon atoms in the foaming agent in the expandable styrene resin particles was obtained by dividing the saturated hydrocarbon content having 5 carbon atoms by the foaming agent content.
[0069]
(6) Self-extinguishing properties of foamed molded products (seconds)
The foamed molded body was cut into a test body having dimensions of 200 mm × 25 mm × 10 mm, cured at 23 ° C. for 1 day, and subjected to a combustion test by the method described in JIS A 9511. The number of burning tests was five, and those with an average fire extinguishing time within 3 seconds were regarded as self-extinguishing pass.
[0070]
(7) Thermal conductivity of foamed molded product (W / m · K)
The thermal conductivity of the foamed molded product was measured in accordance with JIS A 1412-2 heat flow meter method (HFM method). The foamed molded body was cut into a test body having a size of 200 mm × 200 mm × 25 mm, and sandwiched between a heating plate and a cooling hot plate of a measuring device, and measurement was performed under the conditions of a test body temperature difference of 30 ° C. and a test body average temperature of 20 ° C.
[0071]
And about the self-extinguishing foamable styrene-type resin particle concerning Examples 1-7, it described in Table 1 and Table 3 about the said measurement result. In addition, the formal names are listed in Table 5 for the substances indicated by abbreviations in Tables 1 and 3.
As is known from Tables 1 and 3, the manufacturing method described in Examples 1 to 7 does not require complicated processing steps, and has a self-extinguishing foaming styrene system having a stable self-extinguishing property with a small amount of flame retardant. Resin particles can be provided.
In particular, as in Examples 2 to 4, the self-extinguishing foamable styrene resin particles containing graphite powder, carbon black powder, and metal powder not only have stable self-extinguishing properties with a small amount of flame retardant. , The thermal conductivity of the styrene resin foam molded body produced from the self-extinguishing foamable styrene resin particles can be lowered, is excellent as a heat insulating material, and is suitable for a building material.
[0072]
Example 9
Next, evaluation similar to the above was performed based on Comparative Examples 1 to 4 shown below for comparison.
(Comparative Example 1)
In this example, expandable styrenic resin particles in the same manner as in Example 1 except that 1120 g of the foaming agent of Example 1 was changed to 1120 g of pentane (a mixture of about 80% normal pentane and about 20% isopentane) and 240 g of ethylbenzene was added. Was made.
[0073]
(Comparative Example 2)
In this example, expandable styrenic resin particles in the same manner as in Example 1 except that 1120 g of the foaming agent of Example 1 was changed to 1120 g of pentane (a mixture of about 80% normal pentane and about 20% isopentane) and 240 g of toluene was added. Was made.
[0074]
(Comparative Example 3)
In this example, the flame retardant of Example 1 is ethylene bisbromide-2,2-bis (4- (3,5-dibromo-4-hydroxyphenyl) propane condensate (manufactured by Teijin Chemicals; Fireguard 3000 at 20 ° C.). Expandable styrene resin particles were prepared in the same manner as in Example 1 except that the solubility in normal hexane was 0.03 wt%, the decomposition temperature was 300 ° C., and the melting point was 60-80 ° C.
[0075]
(Comparative Example 4)
In this example, the flame retardant of Example 1 was 2,2-bis (4- (2,3-dibromopropoxy) -3,5-dibromophenyl) propane (manufactured by Teijin Chemicals; Fireguard 3100, normal hexane at 20 ° C. Expandable styrene resin particles were prepared in the same manner as in Example 1 except that the solubility was 0.05 wt%, the decomposition temperature was 300 ° C., and the melting point was 90-105 ° C.
[0076]
Table 2 shows the expandable styrene resin particles according to Comparative Examples 1 to 4, and Table 4 shows the measurement results. In addition, official names are listed in Table 5 for the substances indicated by abbreviations in Tables 2 and 4.
As known from Tables 2 and 4, the expandable styrene resin particles obtained in Comparative Examples 1 and 2 contain a flame retardant having a solubility in normal hexane of 0.1 wt% or more at 20 ° C. The styrene resin particles were almost uniformly impregnated, and stable self-extinguishing properties could not be obtained with a small amount of flame retardant. In addition, when the solubility of the flame retardant in normal hexane is less than 0.1 wt% at 20 ° C. as in Comparative Examples 3 and 4, the flame retardant impregnation efficiency is poor, and a stable self-extinguishing property is obtained with a small amount of the flame retardant. I couldn't.
[0077]
[Table 1]
[0078]
[Table 2]
[0079]
[Table 3]
[0080]
[Table 4]
[0081]
[Table 5]
[Brief description of the drawings]
1 is a schematic diagram of self-extinguishing foamable styrene resin particles in Example 1. FIG.
FIG. 2 is an explanatory diagram showing a foamed molded product and its dimensions in Example 8.
FIG. 3 is an explanatory diagram showing a section cut out from a foam molded article in Example 8.
4 is an explanatory diagram showing expanded particles and their surface layer portions in a section in Example 8. FIG.
[Explanation of symbols]
1. . . Self-extinguishing foamable styrene resin particles,
11. . . Surface layer,
Claims (1)
芳香族炭化水素を添加することなく,含浸させてなる発泡性スチレン系樹脂粒子であって,
上記難燃剤はノルマルヘキサンに対する溶解度が20℃において0.1wt%以上であり,
該発泡性スチレン系樹脂粒子の50%平均粒子径が0.5〜2mmであり,
該発泡性スチレン系樹脂粒子を嵩密度20g/Lに発泡させ,得られた発泡粒子を成形して直方体の発泡成形体を得た場合に,
該発泡成形体の表面から厚さ0.3mmまで切り出した切片の切断面において,該切片を構成する発泡粒子の断面の長径をRとしたとき,
t/R=0〜1/10(tは上記切片を構成する発泡粒子表面からの距離)の領域中のスチレン系樹脂に対する該領域中の上記難燃剤の含有割合である難燃剤含有量(wt%)Yと,
該発泡性スチレン系樹脂粒子全体を構成するスチレン系樹脂に対する発泡性スチレン系樹脂粒子全体の上記難燃剤の含有割合である難燃剤含有量(wt%)Zとの含有比Y/Zが,1.05以上であり,
上記難燃剤含有量(wt%)Zが0.49wt%以上である
ことを特徴とする自己消火性発泡性スチレン系樹脂粒子。A blowing agent and a flame retardant content of the saturated hydrocarbon having 5 carbon atoms is a compound not less than 15 vol%, the styrene resin particles,
Expandable styrene resin particles impregnated without adding aromatic hydrocarbons ,
The flame retardant has a solubility in normal hexane of 0.1 wt% or more at 20 ° C,
50% average particle diameter of the expandable styrene resin particles is 0.5 to 2 mm,
When the foamable styrenic resin particles are foamed to a bulk density of 20 g / L, and the resulting foamed particles are molded to obtain a rectangular foam molded product,
When the major axis of the cross-section of the expanded particles constituting the slice is R on the cut surface of the slice cut to a thickness of 0.3 mm from the surface of the foamed molded product,
Flame retardant content (wt) which is the content ratio of the flame retardant in the region to the styrene resin in the region of t / R = 0 to 1/10 (t is the distance from the surface of the expanded particle constituting the slice) %) Y,
The content ratio Y / Z of the flame retardant content (wt%) Z, which is the content ratio of the flame retardant in the whole expandable styrene resin particles to the styrene resin constituting the entire expandable styrene resin particles, is 1 .05 or more,
Self-extinguishing foamable styrene resin particles, wherein the flame retardant content (wt%) Z is 0.49 wt% or more .
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