JP6348723B2 - Styrenic resin extruded foam - Google Patents
Styrenic resin extruded foam Download PDFInfo
- Publication number
- JP6348723B2 JP6348723B2 JP2014018839A JP2014018839A JP6348723B2 JP 6348723 B2 JP6348723 B2 JP 6348723B2 JP 2014018839 A JP2014018839 A JP 2014018839A JP 2014018839 A JP2014018839 A JP 2014018839A JP 6348723 B2 JP6348723 B2 JP 6348723B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- styrene resin
- extruded foam
- parts
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000006260 foam Substances 0.000 title claims description 155
- 229920001890 Novodur Polymers 0.000 title claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 233
- 229920005989 resin Polymers 0.000 claims description 139
- 239000011347 resin Substances 0.000 claims description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 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 class 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 39
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 239000010439 graphite Substances 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000004088 foaming agent Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 20
- -1 ester compound Chemical class 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 17
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000001282 iso-butane Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229960003750 ethyl chloride Drugs 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 229940077445 dimethyl ether Drugs 0.000 claims description 4
- 238000000691 measurement method Methods 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000009413 insulation Methods 0.000 description 18
- 230000005855 radiation Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(c1ccc(**)cc1)c(cc1)ccc1OCC* Chemical compound CC(C)(c1ccc(**)cc1)c(cc1)ccc1OCC* 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 229910052794 bromium Inorganic materials 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、難燃性および断熱性を両立するスチレン系樹脂押出発泡体、およびその製造方法に関する。 The present invention relates to a styrene resin extruded foam having both flame retardancy and heat insulation, and a method for producing the same.
スチレン系樹脂押出発泡体は、良好な施工性や断熱性から、例えば構造物の断熱材として用いられる。スチレン系樹脂押出発泡体を製造する場合において、スチレン系樹脂を押出機にて加熱溶融し、次いで発泡剤を添加し、冷却させ、これを低圧域に押し出すことにより、スチレン系樹脂押出発泡体を連続的に製造する。スチレン系樹脂押出発泡体には、ＪＩＳ Ａ９５１１記載の押出法ポリスチレンフォーム保温板の燃焼性規格を満たす為、難燃剤が添加される。一般的なポリスチレンの押出加工温度は２３０℃付近であり、この温度付近で難燃剤が分解しないことが要求され、難燃剤の熱安定性を高める添加剤の検討がなされているが、難燃剤の難燃性能は、熱安定性と相反する傾向にあることが知られている。（例えば、特許文献１）
一方、近年は住宅、建築物などの省エネルギー化の要求が高まり、従来以上の高断熱性発泡体の技術開発が望まれている。既に種々の技術が提案されており、スチレン系樹脂押出発泡体の高断熱化は熱線輻射抑制剤として黒鉛（グラファイト）や酸化チタンを添加する技術が主流となっている。（例えば、特許文献２）
一般的なスチレン系樹脂押出発泡体を製造する場合において、押し出されたスチレン系樹脂押出発泡体は切削機を用いてカットするが、その際に発生する発泡体の切削屑、および／または該押出発泡体を押出機などに通して熱処理を行い、リサイクルの原料として再利用することは、同業者間では一般的である。
The styrene resin extruded foam is used as a heat insulating material for a structure because of good workability and heat insulation. In the case of producing a styrene-based resin extruded foam, the styrene-based resin extruded foam is heated and melted in an extruder, then added with a foaming agent, cooled, and extruded into a low-pressure region. Manufacture continuously. In order to satisfy the flammability standard of the extrusion method polystyrene foam heat insulating plate described in JIS A9511, a flame retardant is added to the styrene resin extruded foam. The extrusion temperature of general polystyrene is around 230 ° C., and it is required that the flame retardant does not decompose around this temperature, and an additive for improving the thermal stability of the flame retardant has been studied. It is known that flame retardancy tends to conflict with thermal stability. (For example, Patent Document 1)
On the other hand, in recent years, demands for energy saving of houses, buildings and the like have increased, and technical development of highly heat-insulating foams more than conventional has been desired. Various techniques have already been proposed, and a technique of adding graphite or titanium oxide as a heat ray radiation suppressor has become the mainstream for increasing the heat insulation of styrene resin extruded foam. (For example, Patent Document 2)
In the case of producing a general styrene resin extruded foam, the extruded styrene resin extruded foam is cut using a cutting machine, and the foam cuttings generated at that time and / or the extrusion It is common among traders to heat the foam through an extruder or the like and reuse it as a raw material for recycling.
しかし、グラファイトを含むスチレン系樹脂押出発泡体、および／または該発泡体の切削屑は、グラファイトを含まないスチレン系樹脂押出発泡体、および／または該発泡体の切削屑と比較して、リサイクル原料として熱処理する過程において、大幅に樹脂劣化が進行する。また、ＪＩＳ Ａ９５１１に規定される燃焼性試験において、発泡体の燃焼は、樹脂燃焼と表面ガス燃焼に大別され、樹脂燃焼は難燃剤の増量によりある程度抑えることは可能であるが、発泡体表面のみを溶融するガス延焼は、難燃剤を増量しても抑制には限界があり、発泡体中の可燃性ガスの残存量をコントロールする必要がある。 However, the styrene resin extruded foam containing graphite and / or the cutting waste of the foam is recycled compared to the styrene resin extruded foam not containing graphite and / or the cutting waste of the foam. In the process of heat treatment, the resin progresses greatly. In the flammability test specified in JIS A9511, foam combustion is roughly divided into resin combustion and surface gas combustion. Resin combustion can be suppressed to some extent by increasing the amount of flame retardant. In the case of a gas fire that melts only the flame retardant, there is a limit to suppression even if the amount of the flame retardant is increased, and it is necessary to control the remaining amount of the combustible gas in the foam.
以上のような背景により、グラファイトを含むスチレン系樹脂押出発泡体、及び／または該発泡体の切削屑を、熱処理を行いリサイクル原料として使用したスチレン系樹脂押出発泡体において、優れた難燃性と熱伝導率を両立することが非常に困難という課題があった。 Due to the above background, the styrene resin extruded foam containing graphite and / or the styrene resin extruded foam using the cutting waste of the foam as a recycle raw material after heat treatment, has excellent flame retardancy and There was a problem that it was very difficult to achieve both thermal conductivity.
本発明は、グラファイトを含むスチレン系樹脂押出発泡体が有する前記課題を解決するためになされたものであって、難燃性能、及び断熱性能に優れるスチレン系樹脂押出発泡体、及びその製造方法を提供することを目的とする。特に、リサイクルしたスチレン系樹脂混合物を含有する場合にも、優れた難燃性と熱伝導率を両立することを目的とする。 The present invention has been made to solve the above-mentioned problems of a styrene resin extruded foam containing graphite, and has a styrene resin extruded foam excellent in flame retardancy and heat insulation performance, and a method for producing the same. The purpose is to provide. In particular, even when a recycled styrene resin mixture is contained, the object is to achieve both excellent flame retardancy and thermal conductivity.
本発明者らは、前記課題を解決するために鋭意検討した結果、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
すなわち本発明は、
[１]スチレン系樹脂を主成分とするスチレン系樹脂混合物と発泡剤を用いて押出発泡して得られるスチレン系樹脂押出発泡体であって、スチレン系樹脂１００重量部に対して、（a）グラファイトを１．０重量部以上３．５重量部以下、（b）テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテル、及びテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルより選ばれる少なくとも１種を１．０重量部以上６．０重量部以下、（c）多価アルコール部分エステル化合物を０．１重量部以上０．５重量部以下、含有することを特徴とするスチレン系樹脂押出発泡体。
That is, the present invention
[1] A styrene resin extruded foam obtained by extrusion foaming using a styrene resin mixture containing a styrene resin as a main component and a foaming agent, with respect to 100 parts by weight of the styrene resin (a) 1.0 to 3.5 parts by weight of graphite, (b) tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether, and tetrabromobisphenol-A-bis (2, At least one selected from 3-dibromopropyl) ether is 1.0 part by weight or more and 6.0 parts by weight or less, and (c) 0.1 part by weight or more and 0.5 parts by weight or less of a polyhydric alcohol partial ester compound A styrenic resin extruded foam characterized in that:
［２］前記スチレン系樹脂混合物が、リサイクルしたスチレン系樹脂混合物を１０重量％以上５０重量％以下含むことを特徴とする、［１］に記載のスチレン系樹脂押出発泡体。 [2] The extruded styrene resin foam according to [1], wherein the styrene resin mixture contains a recycled styrene resin mixture in an amount of 10% by weight to 50% by weight.
［３］前記スチレン系樹脂混合物が、リサイクルしたスチレン系樹脂混合物を２５重量％以上４５重量％以下含むことを特徴とする、［２］に記載のスチレン系樹脂押出発泡体。 [3] The styrene resin extruded foam according to [2], wherein the styrene resin mixture contains a recycled styrene resin mixture in an amount of 25 wt% to 45 wt%.
［４］前記多価アルコール部分エステル化合物がジペンタエリスリトールとアジピン酸との反応物であることを特徴とする、［１］〜［３］のいずれかに記載のスチレン系樹脂押出発泡体。 [4] The styrene resin extruded foam according to any one of [1] to [3], wherein the polyhydric alcohol partial ester compound is a reaction product of dipentaerythritol and adipic acid.
［５］前記グラファイトの固定炭素分が８０重量％以上８９重量％以下であることを特徴とする、［１］〜［４］のいずれかに記載のスチレン系樹脂押出発泡体。 [5] The styrene resin extruded foam according to any one of [1] to [4], wherein the fixed carbon content of the graphite is 80 wt% or more and 89 wt% or less.
［６］酸化チタンをスチレン系樹脂１００重量部に対して１．０重量部以上３．５重量部以下含むことを特徴とする、［１］〜［５］のいずれかに記載のスチレン系樹脂押出発泡体。 [6] The styrene resin according to any one of [1] to [5], wherein the titanium oxide is contained in an amount of 1.0 part by weight to 3.5 parts by weight with respect to 100 parts by weight of the styrene resin. Extruded foam.
［７］テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテル及びテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルを含有し、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有率が、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルの含有率に対して３０重量％以上３００重量％以下であることを特徴とする、［１］〜［６］のいずれかに記載のスチレン系樹脂押出発泡体。 [7] Tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether and tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether, and tetrabromobisphenol-A- The content of bis (2,3-dibromo-2-methylpropyl) ether is 30% by weight or more and 300% by weight or less with respect to the content of tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether. The styrene resin extruded foam according to any one of [1] to [6], which is characterized in that it exists.
［８］安定剤としてエポキシ化合物を前記臭素系難燃剤１００重量部に対して４重量部以上２０重量部以下含むことを特徴とする、［１］〜［７］のいずれかに記載のスチレン系樹脂押出発泡体。 [8] The styrenic system according to any one of [1] to [7], comprising an epoxy compound as a stabilizer in an amount of 4 parts by weight to 20 parts by weight with respect to 100 parts by weight of the brominated flame retardant. Resin extruded foam.
［９］前記エポキシ化合物が構造式（１）で示されるビスフェノールＡジグリシジルエーテル型エポキシ樹脂 [9] Bisphenol A diglycidyl ether type epoxy resin in which the epoxy compound is represented by the structural formula (1)
、構造式（２）で示されるクレゾールノボラック型エポキシ樹脂 , A cresol novolac type epoxy resin represented by the structural formula (2)
、構造式（３）で示されるフェノールノボラック型エポキシ樹脂 A phenol novolac epoxy resin represented by the structural formula (3)
よりなる群から選ばれる少なくとも一種である、［１］〜［８］のいずれかに記載のスチレン系樹脂押出発泡体。 The styrene resin extruded foam according to any one of [1] to [8], which is at least one selected from the group consisting of:
［１０］前記発泡剤が少なくとも炭素数が３〜５である飽和炭化水素を含み、更に、水、二酸化炭素、窒素、炭素数が２〜５のアルコール類、ジメチルエーテル、塩化メチル、及び、塩化エチルよりなる群から選ばれる少なくとも一種以上を含むことを特徴とする、［１］〜［９］のいずれかに記載のスチレン系樹脂押出発泡体。 [10] The blowing agent contains at least a saturated hydrocarbon having 3 to 5 carbon atoms, and further includes water, carbon dioxide, nitrogen, alcohols having 2 to 5 carbon atoms, dimethyl ether, methyl chloride, and ethyl chloride. The styrene resin extruded foam according to any one of [1] to [9], comprising at least one selected from the group consisting of:
［１１］前記スチレン系樹脂押出発泡体が、製造から１週間後の該押出発泡体中のイソブタンの残存量が該押出発泡体１ｋｇあたり０．３０ｍｏｌ以上０．６０ｍｏｌ以下であることを特徴とする、［１］〜［１０］のいずれかに記載のスチレン系樹脂押出発泡体。 [11] The extruded foam of the styrenic resin is characterized in that the residual amount of isobutane in the extruded foam after 1 week from production is 0.30 mol or more and 0.60 mol or less per kg of the extruded foam. The styrene resin extruded foam according to any one of [1] to [10].
［１２］ＪＩＳ Ａ９５１１に規定される燃焼性の測定方法Ａに合格し、かつ、延焼長さが１０mm以下であることを特徴とする、［１］〜［１１］のいずれかに記載のスチレン系樹脂押出発泡体。 [12] The styrenic system according to any one of [1] to [11], wherein the flammability measurement method A specified in JIS A9511 is passed and the fire spread length is 10 mm or less. Resin extruded foam.
［１３］ＪＩＳ Ａ９５１１に規定される方法で測定した熱伝導率が０．０２４Ｗ／ｍＫ以下であることを特徴とする、［１］〜［１２］のいずれかに記載のスチレン系樹脂押出発泡体。
に関する。
[13] The styrene resin extruded foam according to any one of [1] to [12], wherein the thermal conductivity measured by a method defined in JIS A9511 is 0.024 W / mK or less. .
About.
本発明によれば、難燃性能及び断熱性能が改善されたスチレン系樹脂押出発泡体を容易に提供することが出来る。さらには、リサイクルしたスチレン系樹脂混合物を含有する場合にも、優れた難燃性と熱伝導率を両立することができる。 ADVANTAGE OF THE INVENTION According to this invention, the styrene-type resin extrusion foam by which the flame retardance performance and the heat insulation performance were improved can be provided easily. Furthermore, even when the recycled styrene resin mixture is contained, both excellent flame retardancy and thermal conductivity can be achieved.
以下、本発明の実施形態を説明する。なお、本実施の形態は本発明の一部にすぎず、本発明の要旨を変更しない範囲で本実施形態を適宜変更できることは言うまでもない。 Embodiments of the present invention will be described below. In addition, this embodiment is only a part of this invention, and it cannot be overemphasized that this embodiment can be suitably changed in the range which does not change the summary of this invention.
本発明で用いられるスチレン系樹脂としては、特に限定はなく、スチレン、メチルスチレン、エチルスチレン、イソプロピルスチレン、ジメチルスチレン、ブロモスチレン、クロロスチレン、ビニルトルエン、ビニルキシレン等のスチレン系単量体の単独重合体、または２種以上の単量体の組み合わせからなる共重合体や；前記スチレン系単量体とジビニルベンゼン、ブタジエン、アクリル酸、メタクリル酸、アクリル酸メチル、メタクリル酸メチル、アクリロニトリル、無水マレイン酸、無水イタコン酸などの単量体の１種または２種以上とを共重合させた共重合体などが挙げられる。 The styrene resin used in the present invention is not particularly limited, and styrene monomers such as styrene, methyl styrene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromo styrene, chloro styrene, vinyl toluene, and vinyl xylene are used alone. A polymer or a copolymer comprising a combination of two or more monomers; the styrene monomer and divinylbenzene, butadiene, acrylate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, maleic anhydride And a copolymer obtained by copolymerizing one or more monomers such as acid and itaconic anhydride.
また、本発明に用いるスチレン系樹脂は、前記スチレン系単量体の単独重合体または共重合体に限られず、前記スチレン系単量体の単独重合体または共重合体と、前記他の単量体の単独重合体または共重合体とのブレンド物であってもよく、ジエン系ゴム強化ポリスチレンやアクリル系ゴム強化ポリスチレンをブレンドすることもできる。さらに、本発明のスチレン系樹脂は、メルトフローレート（以下ＭＦＲ）、成形加工時の溶融粘度、溶融張力などを調整する目的で、分岐構造を有するスチレン系樹脂であってもよい。 Further, the styrene resin used in the present invention is not limited to the homopolymer or copolymer of the styrene monomer, but the homopolymer or copolymer of the styrene monomer and the other single monomer. It may be a blend of the polymer with a homopolymer or copolymer, and may be blended with diene rubber reinforced polystyrene or acrylic rubber reinforced polystyrene. Furthermore, the styrenic resin of the present invention may be a styrenic resin having a branched structure for the purpose of adjusting the melt flow rate (hereinafter referred to as MFR), the melt viscosity at the time of molding, the melt tension, and the like.
また、本発明においては、前述されたスチレン系樹脂のなかでも、経済性・加工性の面からポリスチレン樹脂が特に好適に使用することができる。また、押出発泡体により高い耐熱性が要求される場合には、スチレン‐アクリロニトリル共重合体、（メタ）アクリル酸共重合ポリスチレン、無水マレイン酸変性ポリスチレンを用いることが好ましい。また、押出発泡体により高い耐衝撃性が求められる場合には、ゴム強化ポリスチレンを用いることが好ましい。これらスチレン系樹脂は、単独で使用してもよく、また、共重合成分、分子量や分子量分布、分岐構造、ＭＦＲなどの異なるスチレン系樹脂を２種以上混合して使用してもよい。 In the present invention, among the styrene resins described above, a polystyrene resin can be particularly preferably used from the viewpoint of economy and workability. Further, when high heat resistance is required for the extruded foam, it is preferable to use a styrene-acrylonitrile copolymer, (meth) acrylic acid copolymer polystyrene, or maleic anhydride-modified polystyrene. Moreover, when high impact resistance is calculated | required by an extrusion foam, it is preferable to use rubber reinforced polystyrene. These styrenic resins may be used alone, or two or more different styrenic resins such as copolymerization component, molecular weight, molecular weight distribution, branched structure, and MFR may be mixed and used.
また、本発明で用いられるスチレン系樹脂は、バージンスチレン系樹脂に限定されず、魚箱ＥＰＳ、家電緩衝材、食品発泡ポリスチレントレーなどのスチレン系樹脂発泡体、または、冷蔵庫内装材としてのポリスチレントレーをリサイクルしたスチレン系樹脂も使用できる。 Further, the styrene resin used in the present invention is not limited to virgin styrene resin, but styrene resin foam such as fish box EPS, household appliance cushioning material, food foam polystyrene tray, or polystyrene tray as refrigerator interior material. Recycled styrene resin can also be used.
本発明におけるスチレン系樹脂としては、ＭＦＲが０．５〜２５ｇ／１０分のものを用いることが、押出発泡成形する際の成形加工性に優れ、成形加工時の吐出量、得られた熱可塑性樹脂発泡体の厚みや幅、密度または独立気泡率を所望の値に調整しやすく、発泡性（発泡体の厚みや幅、密度、独立気泡率、表面性などを所望の状況に調整しやすいほど、発泡性が良い）、外観などに優れた熱可塑性樹脂発泡体が得られると共に、圧縮強度、曲げ強度または曲げたわみ量といった機械的強度や、靱性などの特性のバランスがとれた熱可塑性樹脂発泡体が得られる点から、好ましい。さらに、スチレン系樹脂のＭＦＲは、押出機内での溶融混錬時に発生するせん断発熱量、成形加工性および発泡性に対する機械的強度、靱性などのバランスの点から、１〜１２ｇ／１０分が特に好ましい。なお、本発明において、ＭＦＲは、ＪＩＳ Ｋ７２１０（１９９９年）のＡ法、試験条件Ｈにより測定される。 As the styrenic resin in the present invention, one having an MFR of 0.5 to 25 g / 10 min is excellent in molding processability at the time of extrusion foam molding, the discharge amount at the molding process, and the obtained thermoplasticity It is easy to adjust the thickness, width, density, or closed cell ratio of the resin foam to a desired value, and the foamability (the thickness, width, density, closed cell ratio, surface property, etc. of the foam is easily adjusted to the desired situation. Thermoplastic foam with excellent balance of properties such as mechanical strength such as compressive strength, bending strength or bending deflection, and toughness. From the point that a body is obtained, it is preferable. Further, the MFR of the styrenic resin is particularly 1 to 12 g / 10 minutes from the viewpoint of the balance of the shear heating value generated at the time of melt kneading in the extruder, the molding processability, the mechanical strength with respect to the foaming property, the toughness and the like. preferable. In addition, in this invention, MFR is measured by A method and test condition H of JISK7210 (1999).
また、本発明において、バージンスチレン系樹脂とは別に、製造工程等においてスチレン系樹脂押出発泡体を切削した際に発生する切削屑および／または運転スタート時等に発生するスチレン系樹脂押出発泡体、および／またはユーザーから返却されるスチレン系樹脂押出発泡体に熱処理を行い、リサイクルしたスチレン系樹脂混合物も原料として使用することができる。 Further, in the present invention, separately from the virgin styrene-based resin, the cutting waste generated when cutting the styrene-based resin extruded foam in the production process and / or the styrene-based resin extruded foam generated at the start of operation, The styrene resin extruded foam returned from the user can be heat-treated, and a recycled styrene resin mixture can also be used as a raw material.
該リサイクルスチレン系樹脂混合物は、そのまま押出機へ投入しても良いが、一般的には押出機に投入しやすいように、減容化および／または溶融加工（ペレット化）を行なう方が好ましい。なお、ペレット化の際には一般的に押出機によって溶融・混練が行われるが、難燃剤などの影響も含め、樹脂の分子劣化ができる限り抑制される温度、例えば１６０〜２４０℃程度が好ましい。また、スチレン系樹脂押出発泡体および／または該発泡体の切削屑中の発泡剤を脱気する為に、ベント口を設ける事が望ましい。 The recycled styrene-based resin mixture may be put into the extruder as it is, but generally it is preferable to perform volume reduction and / or melt processing (pelletization) so as to be easily put into the extruder. The pelletization is generally performed by melting and kneading with an extruder, and preferably includes a temperature at which molecular degradation of the resin is suppressed as much as possible, including the influence of a flame retardant, for example, about 160 to 240 ° C. . Further, it is desirable to provide a vent port in order to degas the styrene resin extruded foam and / or the foaming agent in the cutting waste of the foam.
本発明におけるリサイクルスチレン系樹脂混合物は、スチレン系樹脂混合物の総和に対し１０重量％以上５０重量％以下含有することが好ましい。発泡体の生産コストと断熱性能等の観点から、リサイクルスチレン系樹脂混合物は、スチレン系樹脂混合物の総和に対し２５重量％以上４５重量％以下含有することがより好ましく、３０重量％以上４０重量％以下含有することが更に好ましい。 The recycled styrene resin mixture in the present invention preferably contains 10% by weight or more and 50% by weight or less based on the total amount of the styrene resin mixture. From the viewpoint of the production cost of the foam and the heat insulation performance, the recycled styrene resin mixture is more preferably contained in an amount of 25% by weight to 45% by weight, more preferably 30% by weight to 40% by weight based on the total of the styrene resin mixture. More preferably, it is contained below.
リサイクルスチレン系樹脂混合物の含有量が１０重量％未満では、リサイクル原料の発生量に対して使用量が不足し、実質的にリサイクル原料を廃棄する必要があるため、生産コストが悪化し、５０重量％を超えると、発泡体の成形性・セル形状肥大などによる断熱性能の悪化等を引き起こす傾向がある。 If the content of the recycled styrene resin mixture is less than 10% by weight, the use amount is insufficient with respect to the amount of the recycled material generated, and it is necessary to substantially discard the recycled material. If it exceeds 100%, there is a tendency to cause deterioration of heat insulation performance due to foam formability, cell shape enlargement, and the like.
本発明においては、熱線輻射抑制剤としてグラファイトを添加することにより、高い断熱性を有する発泡体が得られる。前記熱線輻射抑制剤とは、近赤外または赤外領域（例えば、８００〜３０００ｎｍ程度の波長域）の光を反射・散乱・吸収する特性を有する物質をいう。 In the present invention, a foam having high heat insulating properties can be obtained by adding graphite as a heat ray radiation inhibitor. The said heat ray radiation inhibitor means the substance which has the characteristic to reflect, scatter, and absorb the light of near infrared or infrared region (for example, wavelength range of about 800-3000 nm).
本発明で使用するグラファイトは、例えば、鱗（片）状黒鉛、土状黒鉛、球状黒鉛、人造黒鉛などが挙げられる。これらの中でも、熱線輻射抑制効果が高い点から、主成分が鱗（片）状黒鉛のものを用いることが好ましい。グラファイトの固定炭素分は、得られるスチレン系樹脂押出発泡体の断熱性能と製造コストの観点から、８０重量％以上８９重量％以下のものが好ましい。 Examples of the graphite used in the present invention include scale-like graphite, earthy graphite, spherical graphite, and artificial graphite. Among these, it is preferable to use the one whose main component is scale-like graphite from the viewpoint of a high heat ray radiation suppressing effect. The fixed carbon content of graphite is preferably 80% by weight or more and 89% by weight or less from the viewpoint of heat insulation performance and production cost of the obtained styrene resin extruded foam.
グラファイトの分散粒子径は１５μｍ以下が好ましく、１０μｍ以下がより好ましい。粒径を上記範囲とすることで、グラファイトの比表面積が大きくなり、熱線輻射との衝突確率が高くなるため、熱線輻射抑制効果が高くなる。分散粒径を前記範囲とするためには、一次粒径が１５μｍ以下のものを選択すればよい。 The dispersed particle diameter of graphite is preferably 15 μm or less, and more preferably 10 μm or less. By setting the particle size within the above range, the specific surface area of graphite is increased, and the probability of collision with heat radiation is increased, so that the effect of suppressing heat radiation is enhanced. In order to make the dispersed particle diameter within the above range, a particle having a primary particle diameter of 15 μm or less may be selected.
なお、前記分散粒径とは、発泡板中に分散しているそれぞれの粒子の粒子径の個数基準の算術平均値であり、粒子径は発泡板断面を顕微鏡などにより拡大して計測される。前記一次粒径とは体積平均粒径（ｄ５０）を意味する。 The dispersed particle size is an arithmetic average value based on the number of particles dispersed in the foam plate, and the particle size is measured by enlarging the cross section of the foam plate with a microscope or the like. The primary particle size means a volume average particle size (d50).
本発明におけるグラファイトの含有量は、スチレン系樹脂１００重量部に対して１．０重量部以上３．５重量部以下が好ましく、１．５重量部以上３．０重量部以下がより好ましい。含有量が１．０重量部未満では、十分な熱線輻射抑制効果が得られない。含有量が３．５重量部超では、含有量相応の熱線輻射抑制効果が得られずコストメリットが無い。 The graphite content in the present invention is preferably 1.0 part by weight or more and 3.5 parts by weight or less, and more preferably 1.5 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of the styrene resin. When the content is less than 1.0 part by weight, a sufficient heat ray radiation suppressing effect cannot be obtained. When the content exceeds 3.5 parts by weight, the effect of suppressing heat radiation corresponding to the content cannot be obtained, and there is no cost merit.
尚、本発明におけるグラファイトの含有量は、ＪＩＳ Ｋ ６２２６−２：２００３に準じて測定することが出来る。具体的には、発泡体から約１０ｍｇの試験片を切り出し、熱分析システム：ＥＸＳＴＡＲ６０００を備えた熱重量測定装置：ＴＧ／ＤＴＡ ２２０Ｕ［エスアイアイ・ナノテクノロジー（株）製］を用いて、［１］２００ｍＬ／分の窒素気流下で４０℃から６００℃まで２０℃／分で昇温した後６００℃で１０分保持、［２］２００ｍＬ／分の窒素気流下で６００℃から４００℃まで１０℃／分で降温した後４００℃で５分保持、［３］２００ｍＬ／分の空気気流下で４００℃から８００℃まで２０℃／分で昇温した後８００℃で１５分保持する。以下式（２）、式（３）よりグラファイトの含有量を算出できる。
炭素分＝［３］での減少重量／試験片全量×１００・・・（２）
グラファイト含有量＝炭素分／使用したグラファイトの固定炭素分・・・（３）
本発明で使用することができる熱線輻射抑制剤としては、グラファイトの他に、酸化チタン、硫酸バリウム、酸化亜鉛、酸化アルミニウム、酸化アンチモンなどの白色系粒子を併用することが出来る。これらは、単独で使用しても良く、２種以上を併用しても良い。これらの中でも、線輻射抑制効果が大きい点から、酸化チタンや硫酸バリウムが好ましく、酸化チタンがより好ましい。白色系粒子の分散粒径については、特に限定されるものではないが、効果的に赤外線を反射し、また樹脂への発色性を考慮すれば、例えば、酸化チタンでは０．１μｍ〜１０μｍが好ましく、０．１５μｍ〜５μｍがより好ましい。
In addition, content of the graphite in this invention can be measured according to JISK6226-2: 2003. Specifically, about 10 mg of a test piece was cut out from the foam, and a thermal analysis system: Thermogravimetric measurement apparatus equipped with EXSTAR6000: TG / DTA 220U [manufactured by SII Nanotechnology Co., Ltd.] was used. The temperature was raised from 40 ° C. to 600 ° C. at 20 ° C./min under a nitrogen flow of 200 mL / min and then held at 600 ° C. for 10 minutes. The temperature is lowered at / min and then held at 400 ° C. for 5 minutes. [3] The temperature is raised from 400 ° C. to 800 ° C. at 20 ° C./min under an air stream of 200 mL / min and then held at 800 ° C. for 15 minutes. Hereinafter, the graphite content can be calculated from the formulas (2) and (3).
Carbon content = reduced weight at [3] / total amount of test piece × 100 (2)
Graphite content = carbon content / fixed carbon content of graphite used (3)
As a heat ray radiation inhibitor that can be used in the present invention, white particles such as titanium oxide, barium sulfate, zinc oxide, aluminum oxide, and antimony oxide can be used in combination with graphite. These may be used alone or in combination of two or more. Among these, titanium oxide and barium sulfate are preferable, and titanium oxide is more preferable because the effect of suppressing radiation radiation is large. The dispersed particle diameter of the white particles is not particularly limited, but is preferably 0.1 μm to 10 μm, for example, in the case of titanium oxide, in view of effectively reflecting infrared rays and considering color developability to the resin. 0.15 μm to 5 μm is more preferable.
本発明における白色系粒子の含有量としては、スチレン系樹脂１００重量部に対して、１．０重量部以上３．５重量部以下が好ましく、１．５重量部以上３．０重量部以下がより好ましい。白色系粒子は、グラファイトと比較して熱線輻射抑制効果が小さく、含有量が１．０重量部未満では、上記白色系粒子を含有しても熱線輻射抑制効果は殆どない。３．５重量部超では、含有量相応の熱線輻射抑制効果が得られず、コストメリットがない。 The content of the white particles in the present invention is preferably 1.0 part by weight or more and 3.5 parts by weight or less, and 1.5 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of the styrene resin. More preferred. The white particles have a smaller heat ray radiation suppressing effect than graphite, and if the content is less than 1.0 part by weight, even if the white particles are contained, there is almost no heat ray radiation suppressing effect. If it exceeds 3.5 parts by weight, the effect of suppressing heat radiation corresponding to the content cannot be obtained, and there is no cost merit.
本発明における熱線輻射抑制剤の合計含有量は、スチレン系樹脂１００重量部に対して、１．０重量部以上６．０重量部以下が好ましく、２．０重量部以上５．０重量部以下がより好ましい。熱線輻射抑制剤の合計含有量が１．０重量部未満では、高い断熱性が得られず、６．０重量部超では、押出安定性・成形性が劣ったり、燃焼性が損なわれたりする傾向がある。 The total content of the heat ray radiation inhibitor in the present invention is preferably 1.0 part by weight or more and 6.0 parts by weight or less, and 2.0 parts by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight of the styrene resin. Is more preferable. When the total content of the heat ray radiation suppressor is less than 1.0 part by weight, high heat insulation cannot be obtained, and when it exceeds 6.0 parts by weight, the extrusion stability and formability are inferior or the combustibility is impaired. Tend.
本発明のスチレン系樹脂押出発泡体における臭素系難燃剤の含有量は、ＪＩＳ Ａ９５１１に規定される燃焼性燃焼性の測定方法Ａに合格し、かつ、延焼長さが１０mm以下の難燃性能を示すと共に、更に、発泡体製造時の押出機中でスチレン系樹脂の熱安定性を維持できるように、スチレン系樹脂１００重量部に対して、１．０重量部以上６．０重量部以下である。 The content of the brominated flame retardant in the styrene resin extruded foam of the present invention passes the measurement method A for flammability combustibility defined in JIS A9511, and has a flame spread performance of 10 mm or less. Furthermore, in order to maintain the thermal stability of the styrenic resin in the extruder during the production of the foam, it is 1.0 part by weight or more and 6.0 parts by weight or less with respect to 100 parts by weight of the styrenic resin. is there.
臭素系難燃剤の含有量が１．０重量部未満では、難燃性などの発泡体としての良好な諸特性が得られがたい傾向があり、６．０重量部を超えると、発泡体製造時の安定性、表面性などを損なう場合がある。 If the brominated flame retardant content is less than 1.0 part by weight, good properties as a foam such as flame retardancy tend to be difficult to obtain. If the content exceeds 6.0 parts by weight, foam production The stability and surface properties of the time may be impaired.
本発明における臭素系難燃剤の具体例としては、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテル、およびテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルより選ばれる少なくとも１種からなる臭素系難燃剤を含有することにより、得られるスチレン系樹脂発泡体に難燃性を付与することができる。 Specific examples of the brominated flame retardant in the present invention include tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether and tetrabromobisphenol-A-bis (2,3-dibromopropyl). By containing a brominated flame retardant composed of at least one selected from ether, flame resistance can be imparted to the resulting styrene resin foam.
スチレン系樹脂押出発泡体における臭素系難燃剤の含有率は、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテル及びテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルを含有し、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有率が、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルの含有率に対し、３０重量％以上３００重量％以下であることがより好ましい。 The content of brominated flame retardants in the styrene resin extruded foam is tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether and tetrabromobisphenol-A-bis (2,3-dibromo). Propyl) ether, and the content of tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether is the content of tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether More preferably, it is 30 wt% or more and 300 wt% or less with respect to the rate.
理由は定かではないが、該スチレン系樹脂押出発泡体に含まれるテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有率が、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルの含有率に対し、３０重量％以上３００重量％以下であると、得られる押出発泡体の難燃性能に関しては、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの高い難燃性能が影響するためか、混合相手であるテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルのデメリットであった低い難燃性能を打ち消し、あたかもテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテル単独であるかのような高い難燃性能を発現することができる。一方、得られる押出発泡体の熱安定性に関しては、熱安定性能が低いテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有量を減少させられ、代わりに熱安定性の高いテトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルを含有することができるので、熱安定性は、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルを単独で用いるよりも高くすることができる。 The reason is not clear, but the content of tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether contained in the styrene resin extruded foam is such that tetrabromobisphenol-A-bis ( With respect to the flame retardancy of the resulting extruded foam, the content of 30% by weight to 300% by weight with respect to the content of 2,3-dibromopropyl) ether is about tetrabromobisphenol-A-bis (2,3- Because the high flame retardant performance of dibromo-2-methylpropyl) ether affects, the low flame retardant performance, which was a demerit of tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether, which is the mixing partner, is negated As if tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether alone It can express high flame retardancy such as Luca. On the other hand, regarding the heat stability of the obtained extruded foam, the content of tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether, which has low heat stability performance, can be reduced, Since the highly stable tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether can be contained, the thermal stability is increased to tetrabromobisphenol-A-bis (2,3-dibromo-2-methyl). It can be higher than using propyl) ether alone.
該スチレン系樹脂押出発泡体において、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有率が、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルの含有率に対し、３０重量％未満では、得られる難燃性が低い傾向にあり、３００重量％を超えると、熱安定性が悪化する傾向にある。なお、スチレン系樹脂内での難燃剤の分散・バラツキを考慮して、安定的により高い難燃性、およびより高い熱安定性を得ようとする際には、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピル）エーテルの含有率は、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモプロピル）エーテルの含有率に対し、４０〜２００重量％の範囲であることが更に好ましい。 In the styrene-based resin extruded foam, the content of tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether is tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether. If the content is less than 30% by weight, the flame retardancy obtained tends to be low, and if it exceeds 300% by weight, the thermal stability tends to deteriorate. In consideration of dispersion and variation of the flame retardant in the styrene resin, when trying to stably obtain higher flame retardancy and higher thermal stability, tetrabromobisphenol-A-bis ( The content of 2,3-dibromo-2-methylpropyl) ether is in the range of 40 to 200% by weight with respect to the content of tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether. Further preferred.
本発明においては、安定剤として多価アルコール部分エステル化合物を併用することにより、難燃剤の熱安定性を向上させることが可能であり、リサイクル時においても樹脂・難燃剤の分解を抑制することにより、成形性、難燃性能、断熱性能に優れた発泡体を得ることができる。 In the present invention, it is possible to improve the thermal stability of the flame retardant by using a polyhydric alcohol partial ester compound as a stabilizer, and by suppressing the decomposition of the resin / flame retardant even during recycling Further, it is possible to obtain a foam excellent in moldability, flame retardancy and heat insulation performance.
本発明で用いられる多価アルコール部分エステル化合物としては、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール等の多価アルコールと、酢酸、プロピオン酸等の一価のカルボン酸、または、アジピン酸、グルタミン酸等の二価のカルボン酸との反応物である部分エステルであって、その分子中に一個以上の水酸基を持つ化合物の混合物であり、原料の多価アルコールを少量含有していても良い。 Examples of the polyhydric alcohol partial ester compound used in the present invention include polyhydric alcohols such as pentaerythritol, dipentaerythritol and tripentaerythritol, and monovalent carboxylic acids such as acetic acid and propionic acid, or adipic acid and glutamic acid. It is a partial ester which is a reaction product with the divalent carboxylic acid, and is a mixture of compounds having one or more hydroxyl groups in the molecule, and may contain a small amount of the starting polyhydric alcohol.
具体的な多価アルコール部分エステル化合物としては、ジペンタエリスリトールとアジピン酸との部分エステルおよび多価アルコールとの反応物である、例えば、味の素ファインテクノ（株）製プレンライザーＳＴ−２１０、プレンライザーＳＴ−２２０、等があげられる。 Specific examples of the polyhydric alcohol partial ester compound include a partial ester of dipentaerythritol and adipic acid and a reaction product of a polyhydric alcohol, for example, Ajinomoto Fine Techno Co., Ltd. Plenizer ST-210, Plenizer ST-220, etc.
本発明における多価アルコール部分エステルの含有量は、スチレン系樹脂１００重量部に対して０．１重量部以上０．５重量部以下であることが好ましい。 The content of the polyhydric alcohol partial ester in the present invention is preferably 0.1 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the styrenic resin.
多価アルコール部分エステル化合物の含有量が０．１重量部未満では、熱安定化効果が小さい傾向にある。一方、多価アルコール部分エステル化合物の含有量が０．５重量部を超えると、安定化効果が大きく発揮されてしまい、難燃剤本来の難燃効果を低下させる恐れがある。 When the content of the polyhydric alcohol partial ester compound is less than 0.1 parts by weight, the thermal stabilization effect tends to be small. On the other hand, if the content of the polyhydric alcohol partial ester compound exceeds 0.5 parts by weight, the stabilization effect is greatly exerted, and the inherent flame retarding effect may be reduced.
本発明で用いられる発泡剤としては、特に限定するものではないが、炭素数３〜５の飽和炭化水素を使用することにより、優れた環境適合性を付与することができる。 Although it does not specifically limit as a foaming agent used by this invention, The outstanding environmental compatibility can be provided by using a C3-C5 saturated hydrocarbon.
本発明においては、安定剤としてエポキシ化合物を含有することにより、難燃剤の難燃性能を損なうことなく、熱安定性を向上させることができる。本発明におけるエポキシ化合物の含有量としては、臭素系難燃剤１００重量部に対して、４重量部以上２０重量部以下が好ましい。エポキシ化合物の含有量が４重量部未満であると、難燃剤の安定化効果が十分に発揮されず、難燃剤および樹脂の分解が発生し、樹脂の分子量が低下する傾向にあり、結果として発泡体を形成する気泡径の肥大化が生じ、断熱性能が悪化する傾向にある。又、分子量分布の低下に伴い、発泡体表面の平滑性が悪化し、成形性が悪化する傾向にある。更に、難燃剤の分解によって、他の添加剤もしくは樹脂が黒変し、外観不良に繋がる。また、製品カット時等に発生するスクラップを加熱溶融・混練するリサイクル時においても、難燃剤・樹脂の分解が発生することによって、樹脂の黒色化・分子量分布低下が発生しやすくなる傾向にあり、結果としてリサイクル化が困難となり、コストアップに繋がる。 In the present invention, by including an epoxy compound as a stabilizer, the thermal stability can be improved without impairing the flame retardancy of the flame retardant. As content of the epoxy compound in this invention, 4 to 20 weight part is preferable with respect to 100 weight part of brominated flame retardants. When the content of the epoxy compound is less than 4 parts by weight, the flame retardant stabilizing effect is not sufficiently exhibited, the flame retardant and the resin are decomposed, and the molecular weight of the resin tends to decrease, resulting in foaming. The bubble diameter which forms a body enlarges, and there exists a tendency for heat insulation performance to deteriorate. Further, with the decrease in molecular weight distribution, the smoothness of the foam surface tends to deteriorate and the moldability tends to deteriorate. Furthermore, decomposition of the flame retardant causes other additives or resins to turn black, leading to poor appearance. In addition, even during recycling to melt and knead scrap generated at the time of product cutting etc., decomposition of flame retardant and resin tends to cause blackening of resin and decrease in molecular weight distribution, As a result, recycling becomes difficult, leading to an increase in cost.
一方、エポキシ化合物の含有量が２０重量部を超えると、逆に安定剤の安定化効果が過剰となり、難燃剤が発泡体の燃焼時に効果的に分解できず、難燃性能が低下する傾向にある。 On the other hand, when the content of the epoxy compound exceeds 20 parts by weight, the stabilizing effect of the stabilizer becomes excessive, and the flame retardant cannot be effectively decomposed when the foam is burned, and the flame retardant performance tends to be lowered. is there.
本発明で用いられるエポキシ化合物としては、エポキシ当量が１０００ｇ／ｅｑ未満であることが好ましい。エポキシ基が臭素系難燃剤の分解を抑制し、スチレン系樹脂の熱安定性能を向上させていると考えられることから、エポキシ当量が１０００ｇ／ｅｑ以上であると、難燃剤の分解抑制効果が非常に低いため、結果的に、多量添加する必要があることから、コスト的に現実的ではない。コスト・性能のバランスを鑑みると、５００ｇ／ｅｑ未満であることがより好ましく、４００ｇ／ｅｑ未満であることが更に好ましい。 As an epoxy compound used by this invention, it is preferable that an epoxy equivalent is less than 1000 g / eq. It is thought that the epoxy group suppresses the decomposition of the brominated flame retardant and improves the thermal stability performance of the styrene resin. Therefore, when the epoxy equivalent is 1000 g / eq or more, the decomposition suppressing effect of the flame retardant is very high. Therefore, since it is necessary to add a large amount as a result, it is not practical in terms of cost. In view of the balance between cost and performance, it is more preferably less than 500 g / eq, and still more preferably less than 400 g / eq.
本発明で用いられるエポキシ化合物の化学構造としては、コスト、性能、供給安定性の面から、構造式（１）で示されるビスフェノールＡジグリシジルエーテル型エポキシ樹脂 The chemical structure of the epoxy compound used in the present invention is a bisphenol A diglycidyl ether type epoxy resin represented by the structural formula (1) in terms of cost, performance and supply stability.
、構造式（２）で示されるクレゾールノボラック型エポキシ樹脂 , A cresol novolac type epoxy resin represented by the structural formula (2)
、構造式（３）で示されるフェノールノボラック型エポキシ樹脂 A phenol novolac epoxy resin represented by the structural formula (3)
が望ましい。
また、構造式（４）で示されるビスフェノールＡ骨格に臭素が付加したもの
Is desirable.
Also, bromine added to the bisphenol A skeleton represented by the structural formula (4)
を用いてもよい。これらは、単独で使用しても良いし、２種類以上を混合して使用しても良い。 May be used. These may be used singly or in combination of two or more.
本発明の発泡剤は少なくとも炭素数が３〜５である飽和炭化水素を含み、更に、水、二酸化炭素、窒素、炭素数が２〜５のアルコール類、ジメチルエーテル、塩化メチル、及び、塩化エチルよりなる群から選ばれる少なくとも一種以上を含むことが好ましい。 The blowing agent of the present invention contains at least a saturated hydrocarbon having 3 to 5 carbon atoms, and further includes water, carbon dioxide, nitrogen, alcohols having 2 to 5 carbon atoms, dimethyl ether, methyl chloride, and ethyl chloride. It is preferable to include at least one selected from the group consisting of:
本発明で用いられる炭素数３〜５の飽和炭化水素としては、例えば、プロパン、ｎ−ブタン、ｉ−ブタン、ｎ−ペンタン、ｉ−ペンタン、ネオペンタンなどが挙げられる。これらの炭素数３〜５の飽和炭化水素のなかでは、発泡性の点から、プロパン、ｎ−ブタン、ｉ−ブタン、あるいは、これらの混合物が好ましい。また、発泡体の断熱性能の点から、ｎ−ブタン、ｉ−ブタン（以下、「イソブタン」と呼ぶこともある）、あるいは、これらの混合物が好ましく、特に好ましくはｉ−ブタンである。 Examples of the saturated hydrocarbon having 3 to 5 carbon atoms used in the present invention include propane, n-butane, i-butane, n-pentane, i-pentane, neopentane and the like. Among these saturated hydrocarbons having 3 to 5 carbon atoms, propane, n-butane, i-butane, or a mixture thereof is preferable from the viewpoint of foamability. Further, n-butane, i-butane (hereinafter sometimes referred to as “isobutane”), or a mixture thereof is preferred from the viewpoint of the heat insulating performance of the foam, and i-butane is particularly preferred.
ただし、目的とする発泡倍率、難燃性等の発泡体の諸特性いかんによっては、その使用量などが制限される場合があり、押出発泡成形性などが充分でない場合がある。 However, depending on various properties of the foam, such as the desired foaming ratio and flame retardancy, the amount used may be limited, and the extrusion foam moldability may not be sufficient.
本発明では、さらに、他の発泡剤を用いることにより、発泡体製造時の可塑化効果や助発泡効果が得られ、押出圧力を低減し、安定的に発泡体の製造が可能となる。 In the present invention, by using another foaming agent, a plasticizing effect and an auxiliary foaming effect at the time of foam production can be obtained, the extrusion pressure can be reduced, and the foam can be stably produced.
他の発泡剤としては、例えば、ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル、イソプロピルエーテル、ｎ−ブチルエーテル、ジイソプロピルエーテル、フラン、フルフラール、２−メチルフラン、テトラヒドロフラン、テトラヒドロピランなどのエーテル類；ジメチルケトン、メチルエチルケトン、ジエチルケトン、メチルｎ−プロピルケトン、メチル−ｎ−ブチルケトン、メチル−ｉ−ブチルケトン、メチル−ｎ−アミルケトン、メチル−ｎ−ヘキシルケトン、エチル−ｎ−プロピルケトン、エチル−ｎ−ブチルケトンなどのケトン類；メタノール、エタノール、プロピルアルコール、ｉ−プロピルアルコール、ブチルアルコール、ｉ−ブチルアルコール、ｔ−ブチルアルコールなどの炭素数１〜４の飽和アルコール類；蟻酸メチルエステル、蟻酸エチルエステル、蟻酸プロピルエステル、蟻酸ブチルエステル、蟻酸アミルエステル、プロピオン酸メチルエステル、プロピオン酸エチルエステルなどのカルボン酸エステル類；塩化メチル、塩化エチルなどのハロゲン化アルキル、トランス−１、３、３、３−テトラフルオロプロパ−１−エンなどの有機発泡剤、水、二酸化炭素などの無機発泡剤、アゾ化合物、テトラゾールなどの化学発泡剤などを用いることができる。これら他の発泡剤は、単独で用いてもよいし、２種以上を混合して用いてもよい。 Examples of other foaming agents include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether, furan, furfural, 2-methyl furan, tetrahydrofuran, and tetrahydropyran; dimethyl ketone, methyl ethyl ketone , Diethyl ketone, methyl n-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, ethyl-n-propyl ketone, ethyl-n-butyl ketone, etc. A saturated alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, t-butyl alcohol; Carboxylic acid esters such as acid methyl ester, formic acid ethyl ester, formic acid propyl ester, formic acid butyl ester, formic acid amyl ester, propionic acid methyl ester, propionic acid ethyl ester; alkyl halides such as methyl chloride and ethyl chloride, trans-1 Organic foaming agents such as 3,3,3-tetrafluoroprop-1-ene, inorganic foaming agents such as water and carbon dioxide, chemical foaming agents such as azo compounds and tetrazole, and the like can be used. These other blowing agents may be used alone or in combination of two or more.
他の発泡剤の中では、発泡性、発泡体成形性などの点からは、炭素数１〜４の飽和アルコール、ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル、塩化メチル、塩化エチルなどが好ましく、発泡剤の燃焼性、発泡体の難燃性あるいは後述する断熱性等の点からは、水、二酸化炭素が好ましい。これらの中では、可塑化効果の点からジメチルエーテルが、コスト、気泡径の制御による断熱性向上効果の点から水が特に好ましい。 Among other foaming agents, from the viewpoints of foamability, foam formability, etc., saturated alcohols having 1 to 4 carbon atoms, dimethyl ether, diethyl ether, methyl ethyl ether, methyl chloride, ethyl chloride, etc. are preferable. From the viewpoints of the flammability of the foam, the flame retardancy of the foam, the heat insulation properties described later, and the like, water and carbon dioxide are preferred. Among these, dimethyl ether is particularly preferable from the viewpoint of the plasticizing effect, and water is particularly preferable from the viewpoint of the effect of improving the heat insulation by controlling the cost and the bubble diameter.
本発明で使用される発泡剤として、少なくともイソブタンを含み、更に、水、二酸化炭素、窒素、炭素数が２〜５のアルコール類、ジメチルエーテル、塩化メチル、および塩化エチルよりなる群から選ばれる少なくとも一種以上を含むことが、発泡体の断熱性能、発泡性、発泡成形性などが両立できる点で好ましい。 The blowing agent used in the present invention contains at least isobutane, and at least one selected from the group consisting of water, carbon dioxide, nitrogen, alcohols having 2 to 5 carbon atoms, dimethyl ether, methyl chloride, and ethyl chloride. The inclusion of the above is preferable in that the heat insulation performance, foamability, foam moldability and the like of the foam can be compatible.
発泡剤を添加または注入する際の圧力は、特に制限するものではなく、押出機などの内圧力よりも高い圧力であればよい。 The pressure when adding or injecting the foaming agent is not particularly limited as long as it is higher than the internal pressure of an extruder or the like.
本発明における発泡剤の使用量は、スチレン系樹脂１００重量部に対して、２重量部以上２０重量部以下が好ましく、２重量部以上１０重量部以下がより好ましい。発泡剤の添加量が２重量部より少ないと、発泡倍率が低く、樹脂発泡体としての軽量、断熱などの特性が発揮されにくい場合があり、２０重量部を超えると、過剰な発泡剤量の為、発泡体中にボイドなどの不良を生じる場合がある。 The amount of the foaming agent used in the present invention is preferably 2 parts by weight or more and 20 parts by weight or less, and more preferably 2 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the styrene resin. When the amount of the foaming agent is less than 2 parts by weight, the foaming ratio is low, and the characteristics such as light weight and heat insulation as the resin foam may be difficult to be exhibited. Therefore, defects such as voids may occur in the foam.
本発明においては、スチレン系樹脂押出発泡体製造から１週間後の該押出発泡体中のイソブタンの残存量を、所定量とすることで、ＪＩＳ Ａ９５１１の測定方法Ａに準じた燃焼試験法に合格し、かつ、延焼長さが１０ｍｍ以下を示し、更に、優れた断熱性を有するスチレン系押出発泡体を得ることが出来る。
スチレン系樹脂押出発泡体製造から１週間後の該押出発泡体中のイソブタンの残存量は、該押出発泡体１ｋｇあたり０．３０ｍｏｌ以上０．６０ｍｏｌ以下が好ましく、０．４０ｍｏｌ以上０．５０ｍｏｌ以下がより好ましい。０．３０ｍｏｌ未満では、空気より低い熱伝導率を有するイソブタンの押出発泡体中での量が少なく、押出発泡体へ優れた断熱性を付与できない。一方で、燃焼性の高いイソブタンの量が０．６０ｍｏｌを超えるとＪＩＳ Ａ９５１１に準じた燃焼試験法に不合格となる場合がある。
In the present invention, by passing the residual amount of isobutane in the extruded foam one week after the production of the styrene resin extruded foam to a predetermined amount, the combustion test method according to JIS A9511 measuring method A is passed. In addition, it is possible to obtain a styrene-based extruded foam having a fire spread length of 10 mm or less and having excellent heat insulation.
The residual amount of isobutane in the extruded foam one week after the production of the styrene resin extruded foam is preferably 0.30 mol or more and 0.60 mol or less, and 0.40 mol or more and 0.50 mol or less per kg of the extruded foam. More preferred. If it is less than 0.30 mol, the amount of isobutane having a thermal conductivity lower than that of air in the extruded foam is small, and excellent heat insulating properties cannot be imparted to the extruded foam. On the other hand, if the amount of isobutane having high combustibility exceeds 0.60 mol, the combustion test method according to JIS A9511 may be rejected.
本発明においては、他の発泡剤として水やアルコール類を用いる場合には、安定して押出発泡成形を行うために、吸水性物質を添加することが好ましい。本発明に用いられる吸水性物質の具体例としては、ポリアクリル酸塩系重合体、澱粉−アクリル酸グラフト共重合体、ポリビニルアルコール系重合体、ビニルアルコール−アクリル酸塩系共重合体、エチレン−ビニルアルコール系共重合体、アクリロニトリル−メタクリル酸メチル−ブタジエン系共重合体、ポリエチレンオキサイド系共重合体およびこれらの誘導体などの吸水性高分子の他、表面にシラノール基を有する無水シリカ（酸化ケイ素）［例えば、日本アエロジル（株）製ＡＥＲＯＳＩＬなどが市販されている］などのように表面に水酸基を有する粒子径１０００ｎｍ以下の微粉末；スメクタイト、膨潤性フッ素雲母などの吸水性あるいは水膨潤性の層状珪酸塩並びにこれらの有機化処理品；ゼオライト、活性炭、アルミナ、シリカゲル、多孔質ガラス、活性白土、けい藻土などの多孔性物質等があげられる。 In the present invention, when water or alcohol is used as the other foaming agent, it is preferable to add a water-absorbing substance in order to stably perform extrusion foaming. Specific examples of water-absorbing substances used in the present invention include polyacrylate polymers, starch-acrylic acid graft copolymers, polyvinyl alcohol polymers, vinyl alcohol-acrylate copolymers, ethylene- In addition to water-absorbing polymers such as vinyl alcohol copolymers, acrylonitrile-methyl methacrylate-butadiene copolymers, polyethylene oxide copolymers and derivatives thereof, anhydrous silica (silicon oxide) having silanol groups on the surface [For example, AEROSIL manufactured by Nippon Aerosil Co., Ltd. is commercially available] Fine particle having a hydroxyl group on the surface and having a particle diameter of 1000 nm or less; Water-absorbing or water-swelling layered material such as smectite, swellable fluorine mica Silicates and their organic treated products: zeolite, activated carbon, alumina, silica Gel, porous glass, activated clay, porous material or the like, such as diatomaceous earth and the like.
本発明で用いられる吸水性物質の添加量は、水の添加量などによって、適宜調整されるものであるが、スチレン系樹脂１００重量部に対して、０．０１重量部以上５重量部以下が好ましく、０．１重量部以上３重量部以下がより好ましい。 The addition amount of the water-absorbing substance used in the present invention is appropriately adjusted depending on the addition amount of water and the like, but is 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the styrenic resin. Preferably, it is 0.1 to 3 parts by weight.
本発明においては、必要に応じて、本発明の効果を阻害しない範囲で、脂肪酸金属塩、脂肪酸アミド、脂肪酸エステル、流動パラフィン、オレフィン系ワックスなどの加工助剤、前記以外の難燃剤、難燃助剤、酸化防止剤、帯電防止剤、顔料などの着色剤などの添加剤を含有させることができる。 In the present invention, if necessary, processing aids such as fatty acid metal salts, fatty acid amides, fatty acid esters, liquid paraffin, and olefinic wax, flame retardants other than those described above, and flame retardant, as long as the effects of the present invention are not impaired. Additives such as auxiliaries, antioxidants, antistatic agents, and colorants such as pigments can be contained.
本発明のスチレン系樹脂押出発泡体の製造方法としては、スチレン系樹脂、難燃剤、他の添加剤等を押出機等の加熱溶融手段に供給し、任意の段階で高圧条件下にて発泡剤をスチレン系樹脂に添加し、流動ゲルとなし、押出発泡に適する温度に冷却した後、ダイを通して該流動ゲルを低圧領域に押出発泡して、発泡体を形成することにより製造される。 As a method for producing a styrene resin extruded foam of the present invention, a styrene resin, a flame retardant, other additives and the like are supplied to a heating and melting means such as an extruder, and the foaming agent is subjected to a high pressure condition at any stage. Is added to a styrenic resin to form a fluid gel, cooled to a temperature suitable for extrusion foaming, and then extruded and foamed through a die into a low pressure region to form a foam.
スチレン系樹脂、難燃剤、安定剤、および他の添加剤等の加熱溶融の形態としては、スチレン系樹脂に難燃剤、及びおよび添加剤を混合した後、加熱溶融する；スチレン系樹脂を加熱溶融した後に臭素系難燃剤、及び他の添加剤を添加混合する；予めスチレン系樹脂に臭素系難燃剤、安定剤、及び他の添加剤を混合した後、加熱溶融した組成物を準備し、改めて押出機に供給し加熱溶融する；などが挙げられる。 As a form of heat melting of styrene resin, flame retardant, stabilizer, and other additives, the flame retardant and additive are mixed with styrene resin and then heated and melted; the styrene resin is heated and melted. After adding a brominated flame retardant and other additives, the styrene resin is previously mixed with a brominated flame retardant, stabilizer, and other additives, and then a heated and melted composition is prepared. It is supplied to an extruder and heated and melted.
スチレン系樹脂と発泡剤などの添加剤を加熱溶融混練する際の加熱温度、溶融混練時間および溶融混練手段については、特に制限するものではない。
加熱温度は、使用するスチレン系樹脂が溶融する温度以上であればよいが、難燃剤などの影響も含め、樹脂の分子劣化ができる限り抑制される温度、例えば１６０〜２４０℃程度が好ましく、更に好ましくは２３０℃以下である。
溶融混練時間は、単位時間当たりの押出量、溶融混練手段などによって異なるので一概には決定することができないが、スチレン系樹脂と発泡剤が均一に分散混合するのに要する時間が適宜選ばれる。
There are no particular limitations on the heating temperature, melt kneading time, and melt kneading means when the styrene resin and additives such as a foaming agent are heated and melt kneaded.
The heating temperature may be equal to or higher than the temperature at which the styrenic resin to be used is melted, but preferably includes a temperature at which molecular degradation of the resin is suppressed as much as possible, including the influence of a flame retardant, for example, about 160 to 240 ° C. Preferably it is 230 degrees C or less.
The melt-kneading time varies depending on the amount of extrusion per unit time, the melt-kneading means, etc., and thus cannot be determined unconditionally. However, the time required for uniformly dispersing and mixing the styrene resin and the foaming agent is appropriately selected.
溶融混練手段としては、例えばスクリュー型の押出機などが挙げられるが、通常の押出発泡に用いられているものであれば特に限定はない。 Examples of the melt-kneading means include a screw-type extruder, but there is no particular limitation as long as it is used for ordinary extrusion foaming.
本発明の発泡成形方法は、例えば、押出成形用に使用される開口部が直線のスリット形状を有するスリットダイを通じて、高圧領域から低圧領域へ開放して得られた押出発泡体を、スリットダイと密着又は接して設置された成形金型、及び該成形金型の下流側に隣接して設置された成形ロールなどを用いて、断面積の大きい板状発泡体を成形する方法が用いられる。成形金型の流動面形状調整および金型温度調整によって、所望の発泡体の断面形状、発泡体の表面性、発泡体品質が得られる。 In the foam molding method of the present invention, for example, an extrusion foam obtained by opening from a high-pressure region to a low-pressure region through a slit die having an opening used for extrusion molding having a straight slit shape is used as a slit die. A method of forming a plate-like foam having a large cross-sectional area using a molding die placed in close contact with or in contact with a molding roll placed adjacent to the downstream side of the molding die is used. By adjusting the flow surface shape of the molding die and the mold temperature, the desired cross-sectional shape of the foam, the surface property of the foam, and the quality of the foam can be obtained.
本発明に係るスチレン系樹脂押出発泡体における厚みは特に限定はないが、例えば建築用断熱材や保冷庫用又は保冷車用の断熱材として機能することを考慮した断熱性、曲げ強度及び圧縮強度の観点から、１０ｍｍ以上１６０ｍｍ以下であることが好ましく、２０ｍｍ以上１００ｍｍ以下であることがより好ましい。 The thickness of the styrene-based resin extruded foam according to the present invention is not particularly limited, but for example, heat insulation, bending strength, and compressive strength in consideration of functioning as a heat insulator for a building, a cold storage, or a cold car. In view of the above, it is preferably 10 mm or more and 160 mm or less, and more preferably 20 mm or more and 100 mm or less.
本発明のスチレン系樹脂押出発泡体の密度については、軽量でかつ優れた断熱性および曲げ強度、圧縮強度を付与せしめるためには、１５〜５０ｋｇ／ｍ３であることが好ましく、２５〜４０ｋｇ／ｍ３であることがより好ましい。 The density of the styrene resin extruded foam of the present invention is preferably 15 to 50 kg / m 3, preferably 25 to 40 kg / m 3 in order to give light weight and excellent heat insulating properties, bending strength, and compressive strength. It is more preferable that
かくして、本発明により、ＪＩＳ Ａ９５１１に規定される燃焼性の測定方法Ａに合格し、かつ延焼長さが１０mm以下の難燃性能を示し、更に、ＪＩＳ Ａ９５１１に規定される方法で測定した熱伝導率が０．０２４Ｗ／ｍＫ以下を示す、難燃性能及び断熱性能が改善されたスチレン系樹脂押出発泡体を容易に提供することが出来る。 Thus, according to the present invention, the heat conductivity measured by the method specified in JIS A9511 is shown, which has passed the flammability measuring method A specified in JIS A9511 and exhibits flame retardancy with a fire spread length of 10 mm or less. It is possible to easily provide a styrene resin extruded foam having an improved rate of flame retardancy and heat insulation, and having a rate of 0.024 W / mK or less.
以下、本発明の実施例について説明する。なお、本発明が以下の実施例に限定されないことは勿論である。また、以下の実施例および比較例においては、特に断られない限り、「部」は「重量部」、「％」は「重量％」を表すものとする。 Examples of the present invention will be described below. Needless to say, the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” represents “parts by weight” and “%” represents “% by weight” unless otherwise specified.
実施例および比較例において使用した原料は、次の通りである。
（Ａ）基材樹脂
・スチレン系樹脂 ［ＰＳジャパン（株）製、Ｇ９４０１；ＭＦＲ２．２ｇ／１０分］
（Ｂ）熱線輻射抑制剤
・グラファイト ［（株）丸豊鋳材製作所製、Ｍ−８８５；鱗（片）状黒鉛、一次粒径５．５μｍ、固定炭素分８９％］
・酸化チタン ［堺化学工業（株）製、Ｒ−７Ｅ；一次粒径０．２３ｎｍ］
（Ｃ）難燃剤
・テトラブロモビスフェノール−Ａ−ビス（２、３−ジブロモ−２−メチルプロピル）エーテル、及びテトラブロモビスフェノール−Ａ−ビス（２、３−ジブロモプロピル）エーテルの混合臭素系難燃剤［第一工業製薬（株）製、ＧＲ−１２５Ｐ］
（Ｄ）難燃助剤
・トリフェニルホスフィンオキシド [住友商事ケミカル]
（Ｅ）多価アルコール部分エステル化合物
・ジペンタエリスリトール−アジピン酸反応混合物 ［味の素ファインテクノ製、プレンライザーＳＴ２１０］
（Ｆ）エポキシ化合物
・ビスフェノール−Ａ−グリシジルエーテル ［（株）ＡＤＥＫＡ製、ＥＰ−１３］
・クレゾールノボラック型エポキシ樹脂 [ハンツマンジャパン製、ＥＣＮ−１２８０]
（Ｇ）安定剤
・トリエチレングリコール−ビス−３−（３−ｔ−ブチルー４−ヒドロキシ−５−メチルフェニル）プロピオネート ［Ｓｏｎｇｗｏｎ Ｊａｐａｎ（株）製、ソンノックス２４５０ＦＦ］
（Ｈ）発泡剤
・イソブタン ［三井化学（株）製］
・ジメチルエーテル ［岩谷産業（株）製］
・水 ［水道水］
（Ｉ）その他添加剤
・タルク ［林化成（株）製、タルカンパウダーＰＫ−Ｚ］
・ステアリン酸カルシウム ［堺化学工業（株）製、ＳＣ−Ｐ］
・ベントナイト ［（株）ホージュン製、ベンゲルブライトＫ１１］
・シリカ ［エボニックデグサジャパン（株）製、カープレックスＢＳ−３０４Ｆ］
実施例および比較例にて実施した評価方法は、次の通りである。
The raw materials used in the examples and comparative examples are as follows.
(A) Base resin / styrene resin [manufactured by PS Japan Co., Ltd., G9401; MFR 2.2 g / 10 min]
(B) Heat-ray radiation inhibitor / graphite [Maruho Foundry Mfg. Co., Ltd., M-885; scale (flaky) graphite, primary particle size 5.5 μm, fixed carbon content 89%]
Titanium oxide [manufactured by Sakai Chemical Industry Co., Ltd., R-7E; primary particle size 0.23 nm]
(C) Flame retardant-Mixed brominated flame retardant of tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether and tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether [GR-125P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
(D) Flame retardant aid, triphenylphosphine oxide [Sumitomo Corporation Chemical]
(E) Polyhydric alcohol partial ester compound / dipentaerythritol-adipic acid reaction mixture [manufactured by Ajinomoto Fine-Techno, Pleniser ST210]
(F) Epoxy compound / bisphenol-A-glycidyl ether [manufactured by ADEKA, EP-13]
-Cresol novolac epoxy resin [manufactured by Huntsman Japan, ECN-1280]
(G) Stabilizer / Triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate [Songwon Japan Co., Ltd., Sonnox 2450FF]
(H) Foaming agent, isobutane [Mitsui Chemicals, Inc.]
・ Dimethyl ether [Made by Iwatani Corporation]
・ Water [Tap water]
(I) Other additives
・ Talc [Hayashi Kasei Co., Ltd., Talcan powder PK-Z]
・ Calcium stearate [manufactured by Sakai Chemical Industry Co., Ltd., SC-P]
Bentonite [Hogel Jungle, Wengel Bright K11]
Silica [Evonik Degussa Japan Co., Ltd., Carplex BS-304F]
The evaluation methods implemented in the examples and comparative examples are as follows.
（１）見掛け密度（ｋｇ／ｍ３）
得られたスチレン系樹脂押出発泡体の重量および体積を測定し、以下の式に基づいて発泡体密度を求め、単位をｋｇ／ｍ３に換算した。
見掛け密度（ｇ／ｃｍ３）＝発泡体重量（ｇ）／発泡体体積（ｃｍ３）
（２）イソブタン残存量
得られたスチレン系樹脂押出発泡体をＪＩＳ Ｋ７１００に規定された標準温度状態３級（２３℃±５℃）、および標準湿度状態３級（５０＋２０、−１０％Ｒ．Ｈ．）の条件下に静置し、発泡体を製造してから７日間経過した後のイソブタン残存量を以下の設備、手順にて評価した。
ａ）使用機器；ガスクロマトグラフ ＧＣ−２０１４ [（株）島津製作所製]
ｂ）使用カラム；Ｇ−Ｃｏｌｕｍｎ Ｇ−９５０ ２５ＵＭ ［化学物質評価研究機構製］
ｃ）測定条件；
・注入口温度：６５℃
・カラム温度：８０℃
・検出器温度：１００℃
・キャリーガス：高純度ヘリウム
・キャリーガス流量：３０ｍＬ／分
・検出器：ＴＣＤ
・電流：１２０ｍＡ
約１３０ｃｃの密閉可能なガラス容器（以下、「密閉容器」と言う）に、発泡体から切り出した見掛け密度により異なるが約１．２ｇの試験片を入れ、真空ポンプにより密閉容器内の空気抜きを行った。その後、密閉容器を１７０℃で１０分間加熱し、発泡体中の発泡剤を密閉容器内に取り出した。密閉容器が常温に戻った後、密閉容器内にヘリウムを導入して大気圧に戻した後、マイクロシリンジにより４０μＬのヘリウム、イソブタン、ジメチルエーテル、空気の混合気体を取り出し、上記ａ）〜ｃ）の使用機器、測定条件にて評価した。
(1) Apparent density (kg / m3)
The weight and volume of the obtained styrene resin extruded foam were measured, the foam density was determined based on the following formula, and the unit was converted to kg / m3.
Apparent density (g / cm3) = foam weight (g) / foam volume (cm3)
(2) Residual amount of isobutane Extruded styrene resin foam obtained was classified into standard temperature state class 3 (23 ° C. ± 5 ° C.) and standard humidity state class 3 (50 + 20, −10% RH) as defined in JIS K7100. The remaining amount of isobutane after 7 days from the production of the foam was evaluated by the following equipment and procedure.
a) Equipment used: Gas chromatograph GC-2014 [manufactured by Shimadzu Corporation]
b) Column used: G-Column G-950 25UM [Chemicals Evaluation and Research Institute]
c) Measurement conditions;
・ Inlet temperature: 65 ℃
-Column temperature: 80 ° C
-Detector temperature: 100 ° C
Carry gas: High purity helium Carry gas flow rate: 30 mL / min Detector: TCD
・ Current: 120mA
Put about 1.2g of test piece into an approximately 130cc sealable glass container (hereinafter referred to as "sealed container"), depending on the apparent density cut out from the foam, and evacuate the sealed container with a vacuum pump. It was. Thereafter, the sealed container was heated at 170 ° C. for 10 minutes, and the foaming agent in the foam was taken out into the sealed container. After the airtight container returns to normal temperature, helium is introduced into the airtight container to return to atmospheric pressure, and then 40 μL of a mixed gas of helium, isobutane, dimethyl ether, and air is taken out by a microsyringe, and a) to c) above. Evaluation was performed using the equipment used and the measurement conditions.
（３）発泡体の重量平均分子量保持率（以下、「Ｍｗ保持率」と略す）
押出機内での熱履歴に伴う樹脂劣化の程度を評価する為に、得られた発泡体の重量平均分子量Ｍｗを、ゲル浸透クロマトグラフ法にて、以下の手順により求めた。
(3) Weight average molecular weight retention of foam (hereinafter abbreviated as “Mw retention”)
In order to evaluate the degree of resin deterioration associated with the heat history in the extruder, the weight average molecular weight Mw of the obtained foam was determined by the gel permeation chromatography method according to the following procedure.
ａ）試料濃度：２．５ｍｇ／ｍＬ（溶媒；クロロホルム）
ｂ）使用機器：Ｗａｔｅｒｓ ｅ２６９５
ｃ）使用カラム：ＳＨＯＤＥＸ ＧＰＣ−Ｋ−８０６Ｍ ２本直結
ｄ）測定条件：温度；４０℃、溶媒；クロロホルム、試料注入量；５０μＬ、流速；１．０ｍＬ／ｍｉｎ、検出方法；ＵＶ（２５４ｎｍ）、標準ポリスチレン；ＳＨＯＤＥＸ ＳＴＡＮＤＡＲＤ ＳＭ−１０５
得られた発泡体の重量平均分子量Ｍｗをリサイクル回数が０回の発泡体の重量平均分子量Ｍｗで除した値を、該発泡体のＭｗ保持率として、評価した。
a) Sample concentration: 2.5 mg / mL (solvent; chloroform)
b) Equipment used: Waters e2695
c) Column used: SHODEX GPC-K-806M 2 direct connection d) Measurement conditions: Temperature: 40 ° C., solvent: chloroform, sample injection amount: 50 μL, flow rate: 1.0 mL / min, detection method: UV (254 nm), Standard polystyrene; SHODEX STANDARD SM-105
The value obtained by dividing the weight average molecular weight Mw of the obtained foam by the weight average molecular weight Mw of the foam whose number of recycles was zero was evaluated as the Mw retention rate of the foam.
（４）ＪＩＳ燃焼性、延焼長さ
ＪＩＳ Ａ９５１１：２００６Ｒに準拠し（測定方法Ａを採用）、厚さ１０ｍｍ×長さ２００ｍｍ×幅２５ｍｍの試験片を用い、測定は、スチレン系樹脂押出発泡体の製造後、前記寸法の試験片に切削し、ＪＩＳ Ｋ７１００に規定された標準温度状態３級（２３℃±５℃）、及び標準湿度状態３級（５０＋２０、−１０％Ｒ．Ｈ．）の条件下に静置し、発泡体を製造してから７日間経過した後に行った。
(4) JIS flammability, fire spread length Based on JIS A9511: 2006R (measurement method A is adopted), a test piece having a thickness of 10 mm, a length of 200 mm, and a width of 25 mm is used. After being manufactured, the test piece having the above dimensions was cut, and the standard temperature state class 3 (23 ° C. ± 5 ° C.) and the standard humidity state class 3 (50 + 20, −10% RH) defined in JIS K7100 were cut. The test was carried out after 7 days had passed since the foam was produced.
ＪＩＳ燃焼性の評価基準としては、消炎時間は試験片５個の測定結果の平均値とし、合否判定基準は次の通りとした。
○（合格）：３秒以内に炎が消えて、残じんがなく、燃焼限界指示線を超えて燃焼しないこと、の基準を満たす。
×（不合格）：上記基準を満たさない。
As an evaluation standard for JIS flammability, the extinction time was an average value of the measurement results of five test pieces, and the pass / fail criterion was as follows.
○ (Pass): Satisfies the criteria that the flame disappears within 3 seconds, there is no residue, and the combustion limit indicator line is not combusted.
X (failed): The above criteria are not satisfied.
また、発泡体中に含まれる可燃性ガスの延焼によって、発泡体表面のみを延焼するガス表面燃焼に関して、燃焼限界指示線を超えて延焼した長さ（ｍｍ）を「延焼長さ」として測定した。「延焼長さ」は試験片５個の測定結果の平均値とした。 In addition, regarding the gas surface combustion in which only the surface of the foam is spread by the spread of the combustible gas contained in the foam, the length (mm) that has spread beyond the combustion limit indicator line was measured as the “fire length”. . “Fire spread length” was an average value of the measurement results of five test pieces.
なお、燃焼限界指示線を超えずにガス表面燃焼が消火した場合には、「延焼長さ」はゼロとみなした。 In addition, when the gas surface combustion was extinguished without exceeding the combustion limit indicating line, the “fire spread length” was regarded as zero.
（５）熱伝導率（Ｗ／ｍＫ）
発泡体を製造してから７日間経過したスチレン系樹脂押出発泡体の熱伝導率を、ＪＩＳ Ａ９５１１に準じて測定した。
(5) Thermal conductivity (W / mK)
The thermal conductivity of the styrene resin extruded foam after 7 days from the production of the foam was measured according to JIS A9511.
（実施例１）
［樹脂混合物の作製］
スチレン系樹脂１００重量部に対して、熱線輻射抑制剤としてグラファイト（Ｍ−８８５）２．５重量部、酸化チタン（Ｒ−７Ｅ）１．５重量部、難燃剤として、テトラブロモビスフェノールＡ−ビス（２、３−ジブロモ−２−メチルプロピル）エーテル、及びテトラブロモビスフェノールＡ−ビス（２、３−ジブロモプロピル）エーテルの混合臭素系難燃剤（ＧＲ−１２５Ｐ）３．０重量部、難燃助剤としてトリフェニルホスフィンオキシド１．０重量部、多価アルコール部分エステル化合物として、ジペンタエリスリトール−アジピン酸反応混合物（プレンライザーＳＴ２１０）０．１重量部、安定剤として、ビスフェノール−Ａ−グリシジルエーテル（ＥＰ−１３）０．２重量部、トリエチレングリコール−ビス−３−（３−ｔ−ブチルー４−ヒドロキシ−５−メチルフェニル）プロピオネート（ソンノックス２４５０ＦＦ）０．２重量部、気泡径調整剤として、タルク（タルカンパウダーＰＫ−Ｚ）０．５重量部、滑剤としてステアリン酸カルシウム（ＳＣ−Ｐ）０．２重量部、吸水媒体として、ベントナイト（ベンゲルブライトＫ１１）０．４重量部、シリカ（カープレックスＢＳ−３０４Ｆ）０．４重量部をドライブレンドした。該ドライブレンドしたスチレン系樹脂混合物を「ＧＰ」と称する。
Example 1
[Preparation of resin mixture]
For 100 parts by weight of styrene-based resin, 2.5 parts by weight of graphite (M-885) as a heat radiation inhibitor, 1.5 parts by weight of titanium oxide (R-7E), and tetrabromobisphenol A-bis as a flame retardant (2,3-dibromo-2-methylpropyl) ether and tetrabromobisphenol A-bis (2,3-dibromopropyl) ether mixed brominated flame retardant (GR-125P) 3.0 parts by weight, flame retardant aid 1.0 part by weight of triphenylphosphine oxide as an agent, 0.1 part by weight of dipentaerythritol-adipic acid reaction mixture (Pleniser ST210) as a polyhydric alcohol partial ester compound, and bisphenol-A-glycidyl ether (as stabilizer) EP-13) 0.2 parts by weight, triethylene glycol-bis-3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionate (Sonnox 2450FF) 0.2 parts by weight, as a cell diameter regulator, talc (Talcan powder PK-Z) 0.5 parts by weight, as a lubricant calcium stearate (SC-P) ) 0.2 parts by weight, 0.4 parts by weight of bentonite (Wengerbright K11) and 0.4 parts by weight of silica (Carplex BS-304F) were dry blended as the water-absorbing medium. The dry blended styrenic resin mixture is referred to as “GP”.
ただし、前記グラファイト、酸化チタンは、あらかじめスチレン系樹脂のマスターバッチの形態として投入した。マスターバッチの混合濃度は、スチレン系樹脂／グラファイトを５０重量％／５０重量％とし、スチレン系樹脂／酸化チタンを４０重量％／６０重量％とした。 However, the graphite and titanium oxide were added in advance as a master batch of a styrene resin. The mixing concentration of the master batch was 50% by weight / 50% by weight of styrene resin / graphite and 40% / 60% by weight of styrene resin / titanium oxide.
［押出発泡体の作製］
得られたスチレン系樹脂混合物を口径１５０ｍｍの単軸押出機（第一押出機）と口径２００ｍｍの単軸押出機（第二押出機）、及び冷却機を直列に連結した押出機へ、約９００ｋｇ／ｈｒで供給した。
[Production of extruded foam]
About 900 kg of the resulting styrene-based resin mixture is fed to a single screw extruder (first extruder) having a diameter of 150 mm, a single screw extruder (second extruder) having a diameter of 200 mm, and an extruder in which a cooler is connected in series. / Hr.
第一押出機に供給した樹脂混合物を、樹脂温度２３０℃に加熱して溶融ないし可塑化、混練し、発泡剤（スチレン系樹脂１００重量部に対して、イソブタン３．３重量部、ジメチルエーテル２．４重量部、および水０．７部を第一押出機の先端付近で樹脂中に圧入した。その後、第一押出機に連結された第二押出機及び冷却機中にて、樹脂温度を約１２０℃に冷却し、冷却機先端に設けた厚さ６ｍｍ×幅４００ｍｍの長方形断面の口金（スリットダイ）より大気中へ押出発泡させた後、口金に密着させて設置した成形金型とその下流側に設置した成形ロールにより、厚さ６０ｍｍ×幅１０００ｍｍである断面形状の押出発泡板を得、カッターにて厚み５０ｍｍ×幅９１０ｍｍ×長さ１８２０ｍｍにカットした。上記発泡体をリサイクル０回目の発泡体とする。 The resin mixture supplied to the first extruder is heated to a resin temperature of 230 ° C. to be melted or plasticized, kneaded, and foaming agent (3.3 parts by weight of isobutane, 2. parts of dimethyl ether with respect to 100 parts by weight of styrene resin). 4 parts by weight and 0.7 part of water were press-fitted into the resin near the tip of the first extruder, and then the resin temperature was reduced in the second extruder and the cooler connected to the first extruder. A molding die which is cooled to 120 ° C., extruded and foamed into the atmosphere from a rectangular cross-section die (slit die) having a thickness of 6 mm × width of 400 mm provided at the tip of the cooler, and placed downstream from the die. An extruded foam plate having a cross-sectional shape having a thickness of 60 mm and a width of 1000 mm was obtained by a forming roll installed on the side, and was cut into a thickness of 50 mm, a width of 910 mm, and a length of 1820 mm with a cutter. And foam.
［リサイクルスチレン系樹脂混合物の作製］
得られた発泡体を破砕機にて粉砕したもの、および、カッターにて所定の寸法にカットした際に発生したカット屑を、口径１２０ｍｍの単軸押出機に供給し、樹脂温度を約２３０℃に加熱して溶融ないし可塑化、混練し、オープンベント条件下で発泡体に残存する発泡剤を除去した後、ダイスより吐出させ、ストランドカットにてペレット化を行った。該リサイクルスチレン系樹脂混合物を「ＲＰ」と称する。
[Production of recycled styrene resin mixture]
The obtained foam was pulverized with a crusher, and the cut waste generated when the foam was cut into a predetermined size with a cutter was supplied to a single-screw extruder having a diameter of 120 mm, and the resin temperature was about 230 ° C. The mixture was heated to melt, plasticized, kneaded, the foaming agent remaining in the foam was removed under open vent conditions, then discharged from a die, and pelletized by strand cutting. The recycled styrene resin mixture is referred to as “RP”.
［リサイクルスチレン系樹脂混合物を含有する押出発泡体の作製］
得られたＲＰとＧＰを５０対５０の割合で、口径１５０ｍｍの単軸押出機（第一押出機）と口径２００ｍｍの単軸押出機（第二押出機）、及び冷却機を直列に連結した押出機へ、約９００ｋｇ／ｈｒで供給した以外は、上記押出発泡体の作製条件と同様の操作により、押出発泡体を得た。得られた発泡体を、リサイクル１回目の発泡体とした。
以降、同様のリサイクル樹脂およびリサイクル樹脂含有押出発泡体の作製条件により、リサイクルを２〜５回行った。得られた発泡体の物性を、表１に示す。
[Production of extruded foam containing recycled styrene resin mixture]
The obtained RP and GP were connected in series at a ratio of 50:50, a single screw extruder (first extruder) having a diameter of 150 mm, a single screw extruder (second extruder) having a diameter of 200 mm, and a cooler. Extruded foam was obtained by the same operation as the above-mentioned extruded foam production conditions except that it was supplied to the extruder at about 900 kg / hr. The obtained foam was used as the first foam for recycling.
Thereafter, recycling was performed 2 to 5 times under the same conditions for producing a recycled resin and a recycled resin-containing extruded foam. Table 1 shows the physical properties of the obtained foam.
（実施例２〜７）
表１に示すように、各種配合剤の種類・添加量、及び製造条件を変更した以外は、実施例１と同様の操作により、発泡体を得た。得られた発泡体の物性を、表１に示す。
(Examples 2 to 7)
As shown in Table 1, a foam was obtained in the same manner as in Example 1 except that the types and addition amounts of various compounding agents and the production conditions were changed. Table 1 shows the physical properties of the obtained foam.
（比較例１〜４）
表２に示すように、各種配合剤の種類・添加量、及び製造条件を変更した以外は、実施例１と同様の操作により、発泡体を得た。得られた発泡体の物性を表２に示す。
(Comparative Examples 1-4)
As shown in Table 2, a foam was obtained in the same manner as in Example 1 except that the types and addition amounts of various compounding agents and the production conditions were changed. Table 2 shows the physical properties of the obtained foam.
実施例１〜７と比較例１〜４を比較して明らかなように、熱伝導率が０．０２４Ｗ／ｍＫ以下と高い断熱性を保持しつつ、軽量で断熱性および難燃性に優れた、高性能且つ経済的なスチレン系樹脂押出発泡体を容易に得られることがわかる。 As is clear by comparing Examples 1 to 7 and Comparative Examples 1 to 4, the heat conductivity is 0.024 W / mK or less, while maintaining high heat insulating properties, while being lightweight and excellent in heat insulating properties and flame retardancy. It can be seen that a high-performance and economical styrene resin extruded foam can be easily obtained.
Claims (12)
前記スチレン系樹脂混合物が、リサイクルしたスチレン系樹脂混合物を１０重量％以上５０重量％以下含み、
前記多価アルコール部分エステル化合物が、ペンタエリスリトール、ジペンタエリスリトールおよびトリペンタエリスリトールから選ばれるいずれかの多価アルコールと、一価のカルボン酸または二価のカルボン酸との反応物である部分エステルであることを特徴とするスチレン系樹脂押出発泡体。 A styrene resin extruded foam obtained by extrusion foaming using a styrene resin mixture containing a styrene resin as a main component and a foaming agent, wherein (a) 1 graphite is added to 100 parts by weight of the styrene resin. 0.0 part by weight or more and 3.5 parts by weight or less, (b) tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether, and tetrabromobisphenol-A-bis (2,3-dibromo) 1.0 part by weight or more and 6.0 parts by weight or less of at least one selected from (propyl) ether, (c) 0.1 part by weight or more and 0.5 parts by weight or less of a polyhydric alcohol partial ester compound,
The styrene resin mixture contains a recycled styrene resin mixture in an amount of 10 wt% to 50 wt%,
The polyhydric alcohol partial ester compound is a partial ester which is a reaction product of any polyhydric alcohol selected from pentaerythritol, dipentaerythritol and tripentaerythritol and a monovalent carboxylic acid or a divalent carboxylic acid. styrene resin extruded foam, characterized in that there.
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