JP6972401B1 - 発泡スチレン樹脂用難燃剤組成物、難燃性発泡スチレン系樹脂組成物及びその押出発泡成形体 - Google Patents
発泡スチレン樹脂用難燃剤組成物、難燃性発泡スチレン系樹脂組成物及びその押出発泡成形体 Download PDFInfo
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- JP6972401B1 JP6972401B1 JP2021016840A JP2021016840A JP6972401B1 JP 6972401 B1 JP6972401 B1 JP 6972401B1 JP 2021016840 A JP2021016840 A JP 2021016840A JP 2021016840 A JP2021016840 A JP 2021016840A JP 6972401 B1 JP6972401 B1 JP 6972401B1
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- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
Description
に関する。
項1
少なくとも下記の成分(B1)、成分(C)及び成分(D)、
(B1)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)、
(C)脂肪酸亜鉛、及び、
(D)脂肪酸金属塩(ただし、前記(C)成分は除く)
を含み、
前記成分(B1)100質量部あたりの前記成分(C)の含有量が0.1〜15質量部であり、
前記成分(B1)100質量部あたりの前記成分(D)の含有量が1〜35質量部である、発泡スチレン樹脂用難燃剤組成物。
項2
前記成分(B1)以外に難燃剤として成分(B2)を含有し、
前記成分(B2)は、含臭素難燃剤である、項1に記載の発泡スチレン樹脂用難燃剤組成物。
項3
前記成分(B2)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)、トリス(2,3−ジブロモプロピル)イソシアヌレート、トリス(トリブロモフェノキシ)トリアジン、及び、臭素化エポキシオリゴマーからなる群より選択される少なくとも1種を含む、項1又は2に記載の発泡スチレン樹脂用難燃剤組成物。
項4
前記成分(B1)及び前記成分(B2)の総量に対して、前記成分(B1)の含有割合が10〜99質量%である、項2又は3に記載の発泡スチレン樹脂用難燃剤組成物。
項5
項1〜4のいずれか1項に記載の発泡スチレン樹脂用難燃剤組成物と、成分(A)スチレン系樹脂とを含む、難燃性発泡スチレン系樹脂組成物。
項6
項5に記載の難燃性発泡スチレン系樹脂組成物の押出発泡成形体。
本発明の発泡スチレン樹脂用難燃剤組成物は、少なくとも下記の成分(B1)、成分(C)及び成分(D)を含む。
(B1)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)、
(C)脂肪酸亜鉛、及び、
(D)脂肪酸金属塩(ただし、前記(C)成分は除く)。
難燃剤組成物に含まれる成分(B1)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)であって、難燃剤としての役割を果たす成分である。つまり、成分(B1)は臭素系難燃剤である。
難燃剤組成物は、本発明の効果が阻害されない限り、成分(B1)以外の難燃剤を含むこともでき、この場合、難燃性及び耐熱性が向上することもある。成分(B1)以外の難燃剤として、成分(B1)以外の臭素系難燃剤を挙げることができる。以下、この臭素系難燃剤を「成分(B2)」と略記する。
難燃剤組成物に含まれる成分(C)は、脂肪酸亜鉛である。難燃剤組成物が脂肪酸亜鉛を含むことで、難燃剤組成物は、押出発泡成形体に優れた難燃性及び耐熱性を付与することができ、特に難燃性能を向上させることができる。
{成分(C)の質量/成分(B1)の質量}×100
の値が0.1〜15の範囲である。これにより、成分(B1)の難燃剤の効果を高めることができ、優れた難燃性能を発揮することができる。
難燃剤組成物に含まれる成分(D)は、脂肪酸金属塩である。ただし、斯かる(D)脂肪酸金属塩は前記(C)成分、つまり、前記脂肪酸亜鉛以外を意味する。要するに、成分(D)において、脂肪酸金属塩の金属は亜鉛以外である。
{成分(D)の質量/成分(B1)の質量}×100
の値が1〜35の範囲である。これにより、難燃性能をさらに高めることができ、また、押出発泡成形体に優れた耐熱性を付与でき、成形性に優れる押出発泡成形体を得ることができる。
難燃剤組成物は、成分(A)〜(D)以外に、例えば、成分(E)として熱安定剤を含むことができる。なお、難燃剤組成物は成分(E)を含まず、後記するスチレン系樹脂組成物が成分(E)を含むこともできる。熱安定剤は、発泡成形体の熱安定性をさらに向上させることができる。
難燃剤組成物は、成分(A)〜(D)以外に、例えば、成分(F)として難燃増強剤を含むことができる。なお、難燃剤組成物は成分(F)を含まず、後記するスチレン系樹脂組成物が成分(F)を含むこともできる。難燃増強剤は、発泡成形体の熱安定性をさらに向上させることができる。
難燃剤脂組成物は、成分(A)〜(D)以外に、例えば、成分(H)として発泡核剤を含むことができる。なお、難燃剤組成物は成分(H)を含まず、後記するスチレン系樹脂組成物が成分(H)を含むこともできる。発泡核剤は、スチレン系樹脂組成物の発泡成形体の気泡を形成しやすくし、気泡径の調整も容易になるので発泡成形体の強度等の調節に役立ちやすい。
難燃剤脂組成物は、上記各成分以外にも、本発明の効果を損なわない範囲内で、その他の各種成分を含むことができる。難燃剤脂組成物がその他成分を含む場合、その含有割合は特に限定されず、例えば、前記(B1)、成分(C)及び成分(D)の全質量に対して、50質量%以下とすることができ、好ましくは30質量%以下、より好ましくは10質量%以下、さらに好ましくは1質量%以下である。
本発明の難燃性発泡スチレン系樹脂組成物(スチレン系樹脂組成物)は、前記難燃剤組成物に加えて、さらに成分(A)スチレン系樹脂を含む。つまり、本発明の発泡スチレン樹脂用難燃剤組成物は、成分(A)、成分(B1)、成分(C)及び成分(D)を含む。(A)スチレン系樹脂
(B1)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)
(C)脂肪酸亜鉛、及び、
(D)脂肪酸金属塩(ただし、前記(C)成分は除く)
を含む。
念のための注記に過ぎないが、前記成分(B1)100質量部あたりの前記成分(C)の含有量が0.1〜15質量部であり、前記成分(B1)100質量部あたりの前記成分(D)の含有量が1〜35質量部である。
押出発泡工程;スチレン系樹脂組成物を押出機内で溶融混合し、(G)成分としての発泡剤(G)を押出機内に圧入し、次いで、押出機口金から大気中へ押出す工程。
(A)スチレン系樹脂
・GP−PS(PSジャパン社製「PSJポリスチレン G9305」
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)(第一工業製薬社製「ピロガード SR−130」)
・B2−1: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)(第一工業製薬社製「ピロガード SR−720N」)
・B2−2:トリス(2,3−ジブロモプロピル)イソシアヌレート(第一工業製薬社製「ピロガード SR−750」)
・B2−3:トリス(トリブロモフェノキシ)トリアジン(第一工業製薬社製「ピロガード SR−245」)
・B2−4:臭素化エポキシオリゴマー(阪本薬品工業社製「SR−T1000」)
(C)脂肪酸亜鉛
・C−1:ステアリン酸亜鉛(日東化成工業社製「Zn−St」)
・C−2:12−ヒドロキシステアリン酸亜鉛(日東化成工業社製「ZS−6」)
・C−3:モンタン酸亜鉛(日東化成工業社製「ZS−8」)
・C−4:オレイン酸亜鉛
・C−5:ラウリン酸亜鉛(日東化成工業社製「ZS−3」)
(D)脂肪酸金属塩
・D−1:ステアリン酸カルシウム(日東化成工業社製「Ca−St」)
・D−2:ステアリン酸マグネシウム(日東化成工業社製「Mg−St」)
・D−3:ステアリン酸アルミニウム(日東化成工業社製「Al−St」)
・D−4:ステアリン酸リチウム(日東化成工業社製「LI−ST」)
・D−5:ステアリン酸ナトリウム(日東化成工業社製「NA−ST」)
・D−6:12−ヒドロキシステアリン酸カルシウム(日東化成工業社製「CS−6」)
・D−7:ラウリン酸カルシウム(日東化成工業社製「CS−3」)
・D−8:ラウリン酸マグネシウム
・D−9:モンタン酸カルシウム(日東化成工業社製「CS−8」)
・D−10:モンタン酸マグネシウム(日東化成工業社製「MS−8」)
(E)熱安定剤
ビス(2,6−ジ−t−ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト(ADEKA社製「アデカスタブPEP−36」)
(F)難燃増強剤
・F−1:2,3−ジメチル−2,3−ジフェニルブタン(日油社製「ノフマーBC−90」)
・F−2:トリフェニルホスフェート(大八化学工業社製「TPP」)
(G)発泡剤
・G−1:イソブタン
・G−2:ジメチルエーテル
(H)発泡核剤
・タルクMS(日本タルク工業(株)製)
後掲の表1に示す配合割合で発泡剤を除く各成分を、口径65mmの押出機に投入し、機内を200℃に加熱して溶融して可塑化し、混練を続けることで、押出機内でスチレン系樹脂組成物を調製した。押出機は、口径65mmから口径90mmに直列連結した二段押出機を使用した。各成分の配合量は、表1に示すように、成分(A)を100質量部、成分(B1)を0.9質量部、成分(B2)としてB2−1を2.1質量部、成分(C)としてC−1を0.03質量部、成分(D)としてD−1を0.1質量部、成分(E)を0.05質量部とした。
表1及び表2に示すように各成分の種類と配合量を変更したこと以外は実施例1と同様の方法で押出発泡成形体を得た。
後掲の表3に示すように各成分の種類と配合量を変更したこと以外は実施例1と同様の方法で押出発泡成形体を得た。
<難燃性>
JISK−7201に従って酸素指数を測定し、下記判断基準に基づいて難燃性能を評価した。
◎:酸素指数が26.5以上であり、特に優れた難燃性を有していた。
〇:酸素指数が26.0以上26.5未満であり、優れた難燃性を有していた。
×:酸素指数が26.0未満であり、優れた難燃性を有していなかった。
各実施例及び比較例で得られた発泡成形体の黄変度合い(YI:イエローインデックス)から、発泡成形体の耐熱性を評価した。具体的に、試験中の押出発泡成形体をカッターでスライスしてボードとし、2軸ロールで圧縮した後粉砕機で粗砕した。粗砕物をラボプラストミルに投入し、200℃で溶融混練後すぐ取り出して冷却プレスにて3.2mm厚の板状に成形した。このように得られた板状成形品を220℃の熱プレスにて40分加熱後、冷却プレスにて冷却した。冷却後の板状成形品を塩化メチレンに10質量%となるように溶解させ、溶解液を0.45μmのフィルターに通し濾過した後の溶解液を耐熱試験サンプルとした。該サンプルのYI値を、分光色差計(日本電色工業(株)製SE−6000)を用いた透過法にて測定し、下記判断基準に基づいて耐熱性能を評価した。
◎:YI値が10以下であり、特に優れた耐熱性を有していた。
〇:YI値が10を超え、15以下であり、優れた耐熱性を有していた。
×:YI値が15を超え、優れた耐熱性を有していなかった。
各実施例及び比較例で得られた発泡成形体の成形性については、下記判断基準に基づいて評価した。
〇:発泡体表面にボイド、突起物、異物及び変色はいずれも見られず、平滑で外観良好であった。
×:発泡体表面にボイド、突起物、異物及び変色の少なくともが一つが存在し、平滑さも外観も悪いものであった。
Claims (6)
- 少なくとも下記の成分(B1)、成分(C)及び成分(D)、
(B1)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)、
(C)脂肪酸亜鉛、及び、
(D)脂肪酸金属塩(ただし、前記(C)成分は除く)
を含み、
前記成分(B1)100質量部あたりの前記成分(C)の含有量が0.1〜15質量部であり、
前記成分(B1)100質量部あたりの前記成分(D)の含有量が1〜35質量部である、発泡スチレン樹脂用難燃剤組成物。 - 前記成分(B1)以外に難燃剤として成分(B2)を含有し、
前記成分(B2)は、含臭素難燃剤である、請求項1に記載の発泡スチレン樹脂用難燃剤組成物。 - 前記成分(B2)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)、トリス(2,3−ジブロモプロピル)イソシアヌレート、トリス(トリブロモフェノキシ)トリアジン、及び、臭素化エポキシオリゴマーからなる群より選択される少なくとも1種を含む、請求項1又は2に記載の発泡スチレン樹脂用難燃剤組成物。
- 前記成分(B1)及び前記成分(B2)の総量に対して、前記成分(B1)の含有割合が10〜99質量%である、請求項2又は3に記載の発泡スチレン樹脂用難燃剤組成物。
- 請求項1〜4のいずれか1項に記載の発泡スチレン樹脂用難燃剤組成物と、成分(A)スチレン系樹脂とを含む、難燃性発泡スチレン系樹脂組成物。
- 請求項5に記載の難燃性発泡スチレン系樹脂組成物の押出発泡成形体。
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JP2021016840A JP6972401B1 (ja) | 2021-02-04 | 2021-02-04 | 発泡スチレン樹脂用難燃剤組成物、難燃性発泡スチレン系樹脂組成物及びその押出発泡成形体 |
TW110148561A TW202242019A (zh) | 2021-02-04 | 2021-12-24 | 發泡苯乙烯樹脂用阻燃劑組成物、阻燃性發泡苯乙烯系樹脂組成物及其擠出發泡成形體 |
EP22749441.6A EP4289896A1 (en) | 2021-02-04 | 2022-01-14 | Flame retardant composition for foamed styrene resin, flame-retardant foamed styrene-based resin composition, and extrusion foam-molded product of same |
PCT/JP2022/001014 WO2022168564A1 (ja) | 2021-02-04 | 2022-01-14 | 発泡スチレン樹脂用難燃剤組成物、難燃性発泡スチレン系樹脂組成物及びその押出発泡成形体 |
CN202280012251.4A CN116829629A (zh) | 2021-02-04 | 2022-01-14 | 发泡苯乙烯树脂用阻燃剂组合物、阻燃性发泡苯乙烯系树脂组合物及其挤出发泡成形体 |
KR1020237025777A KR20230142476A (ko) | 2021-02-04 | 2022-01-14 | 발포 스티렌 수지용 난연제 조성물, 난연성 발포 스티렌계수지 조성물 및 그 압출 발포 성형체 |
US18/274,886 US20240101807A1 (en) | 2021-02-04 | 2022-01-14 | Flame retardant composition for foamed styrene resin, flame-retardant foamed styrene-based resin composition, and extrusion foam-molded product of same |
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