JP6921063B2 - 多糖類を含む熱膨張性組成物 - Google Patents
多糖類を含む熱膨張性組成物 Download PDFInfo
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- JP6921063B2 JP6921063B2 JP2018516037A JP2018516037A JP6921063B2 JP 6921063 B2 JP6921063 B2 JP 6921063B2 JP 2018516037 A JP2018516037 A JP 2018516037A JP 2018516037 A JP2018516037 A JP 2018516037A JP 6921063 B2 JP6921063 B2 JP 6921063B2
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Description
a)少なくとも1種の過酸化物架橋性ポリマー、
b)少なくとも1種の過酸化物、
c)少なくとも1種のデンプン、及び
d)少なくとも1種の吸熱性化学発泡剤
を含む熱膨張性組成物により達成される。
a)少なくとも1種の過酸化物架橋性ポリマー、
b)少なくとも1種の過酸化物、
c)少なくとも1種の多糖類、及び
d)少なくとも1種の吸熱性化学発泡剤
を含む熱膨張性組成物である。
R1−NH−C(=X)−NR2R3 (I)、
[式(I)中、XはO又はSを表し、R1、R2及びR3は、各々独立に、H、置換若しくは非置換アルキル、置換若しくは非置換ヘテロアルキル、置換若しくは非置換シクロアルキル、置換若しくは非置換アリール又は−C(O)−R4を表す(R4は、H又は置換若しくは非置換アルキルを表す)]
の尿素誘導体である。
H2C(フェニル−NH−C(=X)−NR2R3)2 (II)
[式(II)中、X、R2及びR3は上と同義である。好ましくは、この種の化合物において全てのR2は同じであり、全てのR3は同じである]
のビス尿素誘導体が生成されるよう選択される。
a)30〜90重量%の少なくとも1種過酸化物架橋ポリマー、
b)0.05〜4重量%の少なくとも1種の過酸化物、
c)0.5〜15重量%の少なくとも1種の多糖類、好ましくは少なくとも1種のデンプン及び/又は少なくとも1種のセルロース、特に少なくとも1種のデンプン、及び
d)0.1〜40重量%の少なくとも1種の吸熱性化学発泡剤を含み、
好ましくは5〜35重量%の量の少なくとも1種のカルボン酸、特に少なくとも1種の固体の任意に官能化されたポリカルボン酸又はその塩、好ましくは1〜10重量%の量の更に少なくとも1種の炭酸塩、及び/又は好ましくは0.02〜6重量%の量の少なくとも1種の式(I)の尿素誘導体を、各場合において膨張前の熱膨張性調製物の総重量を基準として少なくとも1種の吸熱性化学発泡剤として含有する熱膨張性組成物である。
a)30〜90重量%、特に40〜85重量%、好ましくは50〜80重量%の少なくとも1種の過酸化物架橋性ポリマー、
b)0.05〜4重量%、好ましくは0.05〜2重量%、特に0.1〜1重量%の少なくとも1種の過酸化物、
c)0.5〜15重量%、好ましくは1〜10重量%、特に2〜5重量%の少なくとも1種の多糖類、好ましくは少なくとも1種のデンプン及び/又は少なくとも1種のセルロース、特に少なくとも1種のデンプン、及び
d)0.1〜40重量%、好ましくは1〜35重量%、より好ましくは5〜35重量%、特に好ましくは10〜30重量%、非常に特に好ましくは15〜25重量%の少なくとも1種の吸熱性化学発泡剤を含み、
該吸熱性化学発泡剤は、好ましくは5〜35重量%の量で、より好ましくは10〜25重量%の量で、非常に好ましくは15〜22重量%の量の好ましくは少なくとも1種のカルボン酸、特に少なくとも1種の固体の任意に官能化されたポリカルボン酸又はその塩、及び好ましくは0.02〜6重量%の量で、より好ましくは0.02〜2重量%の量で、更に好ましくは0.1〜1.5重量%の量の少なくとも1種の式(I)の尿素誘導体を、各場合において膨張前の熱膨張性調製物の総重量を基準として含有する熱膨張性組成物である。
a)30〜85重量%、特に40〜75重量%、好ましくは50〜70重量%の少なくとも1種のエチレン−ビニルアセテートコポリマー、及び2〜40重量%、特に5〜30重量%、好ましくは7.5〜22.5重量%の共重合形態においてモノマーとしてグリシジル(メタ)アクリレートを含有する少なくとも1種の過酸化物架橋性ポリマー、
b)0.05〜4重量%、好ましくは0.05〜2重量%、特に0.1〜1重量%の少なくとも1種の過酸化物、
c)0.5〜15重量%、好ましくは1〜10重量%、特に2〜5重量%の少なくとも1種の多糖類、好ましくは少なくとも1種のデンプン及び/又は少なくとも1種のセルロース、特に少なくとも1種のデンプン、及び
d)0.1〜40重量%、好ましくは1〜35重量%、より好ましくは5〜35重量%、特に好ましくは10〜30重量%、非常に特に好ましくは15〜25重量%の少なくとも1種の吸熱性化学発泡剤を含み、
該吸熱性発泡剤は、好ましくは5〜35重量%の量で、より好ましくは10〜25重量%の量で、非常に好ましくは15〜22重量%の量の好ましくは少なくとも1種のカルボン酸、特に少なくとも1種の固体の任意に官能化されたポリカルボン酸又はその塩を含む、及び好ましくは0.02〜6重量%の量で、より好ましくは0.02〜2重量%の量で、更に好ましくは0.1〜1.5重量%の量の少なくとも1種の式(I)の尿素誘導体を、各場合において膨張前の熱膨張性調製物の総重量を基準として含有する熱膨張性組成物である。
<一般的な実験的手順/調製物の調製>
本発明の熱膨張性調製物を調製するために、含有ポリマーを、必要に応じて150℃までに加熱しながら、ニーダー中で室温でフィラーと共に加工して均一な生地を形成した。存在する場合、フィラー、カーボンブラック、安定剤、及び可塑剤のような非反応性成分を、順次添加し、調製物が滑らかになるまで混練した。次いで、促進剤、過酸化物、活性化剤及び触媒のような全ての反応性成分、並びに発泡剤を70℃未満で添加し、接着剤が均一に混合されるまでゆっくりと折り重ねられた。発泡剤を、マスターバッチとして部品に挿入した。
膨張を測定するために、約20mm×20mm×3mmの寸法を有する試験片を実施例調製物の完成シートから切断し、対流オーブンに入れ、これを表に示す温度(加熱時間 約7〜10分)に加熱し、試験片をこの温度で表に示す期間(加熱時間を含む)、放置した。175℃での膨張は、車両構造物における硬化中に得られる理想的な条件に対応する。160℃での膨張は、下地条件をシミュレートし、200℃での膨張は過剰べーク条件をシミュレートする。
粘着性を測定するために、試験片(膨張を決定するのと同じ方法で作製した)を対流オーブン中に亜鉛メッキしたシート上で160℃で20分間加熱した。発泡形成体の粘着性を試験するために、前記成形体を対流オーブンから取り出した後、室温で24時間貯蔵する。次いで、発泡体形成体を機械的に金属表面から引き剥がす。金属表面上の成形体の残りの残渣を評価し、ぬれた表面(%cf)に関して定量する。
本発明の好ましい態様は、以下を包含する。
〔1〕 (a)少なくとも1種の過酸化物架橋性ポリマー、
(b)少なくとも1種の過酸化物、
(c)少なくとも1種の多糖類、及び
(d)少なくとも1種の吸熱性化学発泡剤
を含む熱膨張性組成物。
〔2〕 少なくとも1種の過酸化物架橋性ポリマーa)は、スチレン−ブタジエンブロックコポリマー、スチレン−イソプレンブロックコポリマー、エチレン−ビニルアセテートコポリマー、官能化エチレン−ビニルアセテートコポリマー、官能化エチレン−ブチルアクリレートコポリマー、エチレン−プロピレン−ジエンコポリマー、エチレン−メチルアクリレートコポリマー、エチレン−エチルアクリレートコポリマー、エチレン−ブチルアクリレートコポリマー、エチレン−(メタ)アクリル酸コポリマー、エチレン−2−エチルヘキシルアクリレートコポリマー、エチレン−アクリルエステルコポリマー及びポリオレフィンから選択され、特にエチレンビニルアセテートコポリマー及び官能化エチレン−ビニルアセテートコポリマーから選択されることを特徴とする、〔1〕に記載の熱膨張性組成物。
〔3〕 前記少なくとも1種の多糖類は、デンプン及び/又はセルロース、特にデンプンであることを特徴とする、〔1〕又は〔2〕に記載の熱膨張性組成物。
〔4〕 前記発泡剤は、少なくとも1種のカルボン酸、特に固体の任意に官能化したポリカルボン酸又はその塩、特に固体の有機ヒドロキシ−官能化又は不飽和ジ、トリ、テトラ、又はポリカルボン酸又はそれらの塩、好ましくはクエン酸、酒石酸、リンゴ酸、フマル酸、マレイン酸及びそれらの塩、特にクエン酸及びそれらの塩から選択される少なくとも1種を含むことを特徴とする、〔1〕〜〔3〕のいずれかに記載の熱膨張性組成物。
〔5〕 前記発泡剤は、少なくとも1種の重炭酸塩、特に炭酸水素ナトリウム及び/又は炭酸水素カリウム、好ましくは炭酸水素ナトリウムを含むことを特徴する、〔1〕〜〔4〕のいずれかに記載の熱膨張性組成物。
〔6〕 前記発泡剤は、式(I)
R1−NH−C(=X)−NR2R3 (I)、
[式中、Xは、O又はSを表し、R1、R2及びR3は、各々独立に、H、置換若しくは非置換のアルキル、置換若しくは非置換のヘテロアルキル、置換若しくは非置換のシクロアルキル、置換若しくは非置換のアリール、又は−C(O)−R4を表す(R4は、H、置換又は非置換のアルキルを表す)]
の少なくとも1種の尿素誘導体を含み、該尿素誘導体は、特に尿素、N,N−ジメチル尿素、N,N−ジエチル尿素、N,N’−ジメチル尿素、N,N’−ジエチル尿素、4−クロロフェニル−N,N−ジメチル尿素、4,4’−メチレンビス(フェニルジメチル尿素)、1,1−ジメチル−3−(4−クロロフェニル)尿素、1,1−ジメチル−3−(3,4−ジクロロフェニル)尿素、イソホロンビス(ジメチル尿素)、1,1−ジメチル−3−フェニル尿素、1,1−ジメチル−3−(4−エトキシフェニル)尿素、1,1’−(4−フェニレン)−ビス−(3,3−ジメチル尿素)、1,1−ジメチル−3−(2−ヒドロキシフェニル)尿素及び1,1−ジメチル−3−(3−クロロ−4−メチルフェニル)尿素から選択され、特に尿素、N,N−ジメチル尿素、N,N−ジエチル尿素、N,N’−ジメチル尿素及びN,N’−ジエチル尿素から選択されることを特徴とする、〔1〕〜〔5〕のいずれかに記載の熱膨張性組成物。
〔7〕 〔1〕〜〔6〕のいずれかに記載の熱膨張性組成物を有することを特徴とする、成形体。
〔8〕 〔1〕〜〔6〕のいずれかに記載の熱膨張性組成物又は〔7〕に記載の成形体を使用する部材において空洞を封止又は充填するための、部材、特に中空部材を強化又は補強させるための、及び可動部材を接合するための、方法。
〔9〕 〔7〕に記載の成形体を、部材、特に部材の空洞へ導入し、次いで110℃を超える温度に加熱し、熱膨張性組成物を膨張させ、前記部材を封止、充填、強化又は補強させることを特徴とする、部材の空洞を封止又は充填するための、及び部材を強化又は補強させるための、〔8〕に記載の方法。
〔10〕 部材の空洞を音響的に封止するための、及び/又は、水及び/又は湿気から部材の空洞を封止するための、又は部材、特に中空の部材を強化又は補強させるための、〔7〕に記載の成形体の使用。
Claims (10)
- (a)少なくとも1種の過酸化物架橋性ポリマー、
(b)少なくとも1種の過酸化物、
(c)少なくとも1種の多糖類、及び
(d)少なくとも1種の吸熱性化学発泡剤
を含み、前記発泡剤は、少なくとも1種のカルボン酸と少なくとも1種の尿素誘導体との混合物である、熱膨張性組成物。 - 少なくとも1種の過酸化物架橋性ポリマーa)は、スチレン−ブタジエンブロックコポリマー、スチレン−イソプレンブロックコポリマー、エチレン−ビニルアセテートコポリマー、官能化エチレン−ビニルアセテートコポリマー、官能化エチレン−ブチルアクリレートコポリマー、エチレン−プロピレン−ジエンコポリマー、エチレン−メチルアクリレートコポリマー、エチレン−エチルアクリレートコポリマー、エチレン−ブチルアクリレートコポリマー、エチレン−(メタ)アクリル酸コポリマー、エチレン−2−エチルヘキシルアクリレートコポリマー、エチレン−アクリルエステルコポリマー及びポリオレフィンから選択されることを特徴とする、請求項1に記載の熱膨張性組成物。
- 前記少なくとも1種の多糖類は、デンプン及び/又はセルロースであることを特徴とする、請求項1又は2に記載の熱膨張性組成物。
- 前記少なくとも1種のカルボン酸は、固体の任意に官能化したポリカルボン酸又はその塩から選択されることを特徴とする、請求項1〜3のいずれかに記載の熱膨張性組成物。
- 前記発泡剤は、少なくとも1種の重炭酸塩を含むことを特徴する、請求項1〜4のいずれかに記載の熱膨張性組成物。
- 前記少なくとも1種の尿素誘導体は、式(I)
R1−NH−C(=X)−NR2R3 (I)、
[式中、Xは、O又はSを表し、R1、R2及びR3は、各々独立に、H、置換若しくは非置換のアルキル、置換若しくは非置換のヘテロアルキル、置換若しくは非置換のシクロアルキル、置換若しくは非置換のアリール、又は−C(O)−R4を表す(R4は、H、置換又は非置換のアルキルを表す)]
の尿素誘導体から選択されることを特徴とする、請求項1〜5のいずれかに記載の熱膨張性組成物。 - 請求項1〜6のいずれかに記載の熱膨張性組成物を有することを特徴とする、成形体。
- 請求項1〜6のいずれかに記載の熱膨張性組成物又は請求項7に記載の成形体を使用して、部材において空洞を封止又は充填するための、部材を強化又は補強させるための、及び可動部材を接合するための、方法。
- 請求項7に記載の成形体を、部材へ導入し、次いで110℃を超える温度に加熱し、熱膨張性組成物を膨張させ、前記部材を封止、充填、強化又は補強させることを特徴とする、部材の空洞を封止又は充填するための、及び部材を強化又は補強させるための、請求項8に記載の方法。
- 部材の空洞を音響的に封止するための、及び/又は、水及び/又は湿気から部材の空洞を封止するための、又は部材を強化又は補強させるための、請求項7に記載の成形体の使用。
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EP3778734A1 (en) * | 2019-08-15 | 2021-02-17 | Sika Technology Ag | Thermally expandable compositions comprising a chemical blowing agent |
EP3778737A1 (en) * | 2019-08-15 | 2021-02-17 | Sika Technology Ag | Thermally expandable compositions comprising an endothermic blowing agent |
EP3789461A1 (de) * | 2019-09-06 | 2021-03-10 | Henkel AG & Co. KGaA | Thermisch expandierbare zubereitung |
EP4116363A1 (de) | 2021-07-06 | 2023-01-11 | Henkel AG & Co. KGaA | Thermisch expandierbare zusammensetzungen umfassend wachs |
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WO2024080233A1 (ja) * | 2022-10-14 | 2024-04-18 | ソニーグループ株式会社 | 梱包材及び梱包材の製造方法 |
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