JP7382937B2 - 強化された接着剤及びそれを用いた接着方法 - Google Patents
強化された接着剤及びそれを用いた接着方法 Download PDFInfo
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- JP7382937B2 JP7382937B2 JP2020534511A JP2020534511A JP7382937B2 JP 7382937 B2 JP7382937 B2 JP 7382937B2 JP 2020534511 A JP2020534511 A JP 2020534511A JP 2020534511 A JP2020534511 A JP 2020534511A JP 7382937 B2 JP7382937 B2 JP 7382937B2
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- fibers
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- polyamide
- polymer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Description
一実施形態では、ベールのポリマーバインダーは、75°F~500°F(24℃~260℃)、好ましくは100°F~400°F(37.7℃~204.4℃)、又は150°F~350°F(65.5℃~176.7℃)の範囲の温度で、流体相への少なくとも部分的な相転移をすることができる。一般的に、ポリマーバインダーの相転移は、室温と、硬化性接着剤組成物のゲル化及び/又は合一の実質的な開始温度との間で生じるはずである。接着剤組成物が硬化すると、ポリマーバインダーは溶解し、接着剤層の熱硬化性マトリックスの中に流れ込む。いくつかの実施形態では、ポリマーバインダーは、熱硬化性マトリックスの中に完全に溶解する。
上述したバインダー含有ベールは、1種以上の熱硬化性樹脂、硬化剤、及び/又は触媒、並びに任意選択的な強化剤、導電性添加剤、改質剤、及び充填剤を含有する熱硬化性接着剤組成物に埋め込まれる。熱硬化性樹脂としては、限定するものではないが、エポキシ樹脂、不飽和ポリエステル樹脂、ビスマレイミド、ポリイミド、シアン酸エステル、フェノールなどが挙げられる。
本開示の接着方法は、上述した硬化性接着剤層を使用して2つの基材を接合し、その後硬化することを含む。接着剤層は、接合された基材の間に挟まれる。一緒に接着される基材は、金属対金属、金属対複合材料、複合材料対複合材料、複合材料対ハニカム構造体であってよい。この文脈における複合基材とは、マトリックス材料を含浸した又は染み込ませた強化繊維から構成された繊維強化ポリマー複合材料を指す。
接着される複合基材としては、プリプレグ又はプリプレグレイアップ(航空宇宙複合構造体の製造のために使用されるものなど)が挙げられる。本明細書で使用される「プリプレグ」という用語は、硬化性マトリックス樹脂で含浸された強化繊維の層を指す。用語「含浸」は、繊維を樹脂で部分的に又は完全に封入するために硬化性マトリックス樹脂材料を強化繊維に導入することを意味する。複合基材中のマトリックス樹脂は、未硬化又は部分的に硬化の状態であってもよい。本明細書で使用される「プリプレグレイアップ」という用語は、積み重ね構成でレイアップされた複数のプリプレグプライを指す。一例として、レイアップのプリプレグプライの数は、2~100プライ、又は10~50プライであってもよい。プリプレグプライのレイアップは、手作業行ってもよく、或いは自動テープ積層(ATL)などの自動プロセスで行ってもよい。
本開示における、本明細書で使用される「硬化する(cure)」及び「硬化(curing)」という用語には、ベース成分の混合、高温での加熱、紫外線及び放射への暴露によって引き起こされるモノマー又はオリゴマーの重合及び/又は架橋が包含される。本明細書で使用される「完全に硬化した」は、100%の硬化度を意味する。本明細書で使用される「部分的に硬化した」は、100%未満の硬化度を意味する。
エポキシを主体とするフィルム接着剤は、予め分散されているナノサイズのビスフェノールA 25重量部を含むビスフェノールAのジグリシジルエーテル125重量部と、ポリエーテルスルホン6.5重量部と、トリフェニルホスフィン0.1重量部と、アミン末端PES-PEESコポリマー5重量部と、シアノグアニジン4重量部と、メチレンジフェニルビス(ジメチル尿素)2重量部と含有する樹脂配合物を調製することによって形成した。
バインダー含有ポリアミドベールを含む接着剤フィルムを、実施例1に開示の通りに作製した。CYCOM 5320-1テーププリプレグを、80psiで2時間、3°F/分で350°Fまで加熱することにより、ポリエステル剥離層と共に予備硬化した。硬化したプリプレグを2枚のパネルに切断して接着した。剥離層を取り除いて、粗い接着可能な表面を得た。2枚のプリプレグパネルを接着剤フィルムを使用して一体に接着し、実施例1に記載の通りに硬化を行った。得られた接着されたラミネートを「ラミネートA」と名付けた。
Claims (20)
- (a)基材間の硬化性接着剤層を用いて第1の基材を第2の基材に接合すること;及び
(b)前記接着剤層を25℃より高い温度で硬化して接着された構造体を形成すること;
を含む接着方法であって、
前記接着剤層が硬化性マトリックス樹脂の中に埋め込まれた繊維ベールを含み、前記硬化性マトリックス樹脂が、1種以上の熱硬化性樹脂と少なくとも1種の硬化剤を含み、前記繊維ベールが、室温(20℃~25℃)で固相であるポリマーバインダーを含み、前記ポリマーバインダーが、ポリアミド11(「PA11」)とポリアミド12(「PA12」)とのコポリマーであり、前記ポリマーバインダーが硬化中に前記マトリックス樹脂の中に溶解する、接着方法。 - 前記ポリマーバインダーが前記繊維ベール全体に分散されている粒子の形態である、請求項1に記載の接着方法。
- PA11対PA12の比が20:80~80:20である、請求項1又は2に記載の接着方法。
- 前記繊維ベールが、主に交絡されたランダムに配向しているポリマー繊維を含む、請求項1~3のいずれか1項に記載の接着方法。
- 前記繊維ベールが織布又は編マットである、請求項1~3のいずれか1項に記載の接着方法。
- 前記繊維ベールが、約2~約150gsmの目付を有する、請求項1~5のいずれか1項に記載の接着方法。
- 前記繊維ベールがポリマー繊維又はガラス繊維を含む、請求項1~6のいずれか1項に記載の接着方法。
- 前記ポリマー繊維が、ポリアミド繊維、ポリエステル繊維、ポリイミド繊維、及びそれらの組み合わせから選択される、請求項7に記載の接着方法。
- 前記ベールの前記繊維が、0.1~100ミクロン、又は1.0~50ミクロンの範囲の直径を有する、請求項1~8のいずれか1項に記載の接着方法。
- 硬化が、100°F~400°F(38℃~204℃)、又は250°F~350°F(121℃~177℃)の範囲の温度で行われる、請求項1~9のいずれか1項に記載の接着方法。
- 前記接着剤層の前記硬化性マトリックス樹脂が、1種以上のエポキシ樹脂と少なくとも1種のアミン硬化剤とを含む、請求項1~10のいずれか1項に記載の接着方法。
- 前記硬化性マトリックス樹脂が、熱可塑性及びエラストマー系ポリマー、コアシェルゴム(CSR)粒子などのポリマー粒子、並びにそれらの組み合わせから選択される強化材料を更に含む、請求項11に記載の接着方法。
- 前記第1の基材が、金属基材、複合基材、及びハニカム構造体から選択され、前記第2の基材が、金属基材、複合基材、及びハニカム構造体から選択される、請求項1~12のいずれか1項に記載の接着方法。
- (a)の前記第1及び第2の基材が、硬化性マトリックス樹脂の中に埋め込まれた強化繊維を含む複合基材である、請求項13に記載の接着方法。
- 前記複合基材が、プリプレグ、又は積み重ね構成に配置された複数のプリプレグを含むプリプレグレイアップであり、各プリプレグが、熱硬化性樹脂組成物で含浸した連続的な一方向繊維を含む、請求項13に記載の接着方法。
- 硬化性マトリックス樹脂の中に埋め込まれた繊維ベールを含む接着剤フィルムであって、
前記硬化性マトリックス樹脂が1種以上のエポキシ樹脂と少なくとも1種の硬化剤とを含み、
前記繊維ベールが、ランダムに配置されたポリマー繊維又はガラス繊維を含み、
前記繊維ベールがポリマーバインダーを担持し、前記ポリマーバインダーが室温(20℃~25℃)で固相であり、
前記ポリマーバインダーが、ポリアミド11(「PA11」)とポリアミド12(「PA12」)とのコポリマーであり且つ動的機械分析により決定される350°F未満(<177℃)又は250°F未満(<121℃)のガラス転移温度を有する、
接着剤フィルム。 - 前記硬化性マトリックス樹脂が、1種以上のポリエポキシドと、アミン硬化剤と、反応性官能基を有する又は有さないポリアリールスルホン;コアシェルゴム(CSR)粒子;エラストマー系ポリマー(カルボキシル末端ブタジエンニトリルポリマー(CTBN)、及びアミン末端ブタジエンアクリロニトリル(ATBN)エラストマーを含む);及びそれらの組み合わせから選択される強化材料と、を含む、請求項16に記載の接着剤フィルム。
- 前記硬化性マトリックス樹脂が、1種以上のポリエポキシドと、アミン硬化剤と、触媒の存在下でエポキシ樹脂とビスフェノールAを反応させることにより形成される予備反応生成物と、コアシェルゴム(CSR)粒子と、ポリアリールスルホンとを含む、請求項16に記載の接着剤フィルム。
- 互いに接合された2つの基材と、前記基材間に挟まれている接着剤フィルムとを含む接着された構造体であって、
前記基材のうちの少なくとも1つが金属基材であり、
接着剤層が、1種以上の熱硬化性樹脂と少なくとも1種の硬化剤とを含む硬化性マトリックス樹脂の中に埋め込まれている繊維ベールを含み、
前記繊維ベールが、交絡されたランダムに配向しているポリマー繊維又はガラス繊維を含み、
前記繊維ベールがポリマーバインダーを担持し、前記ポリマーバインダーが、室温(20℃~25℃)で固相であり、ポリアミド11(「PA11」)とポリアミド12(「PA12」)とのコポリマーであり、且つ動的機械分析により決定される350°F未満(<177℃)又は250°F未満(<121℃)のガラス転移温度を有する、
接着された構造体。 - 前記2つの基材が金属基材である、請求項19に記載の接着された構造体。
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WO2017083631A1 (en) | 2015-11-12 | 2017-05-18 | Cytec Industries Inc. | Hybrid veil as interlayer in composite materials |
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JP2021508747A (ja) | 2021-03-11 |
US11377530B2 (en) | 2022-07-05 |
US20200308358A1 (en) | 2020-10-01 |
EP4289889A3 (en) | 2024-03-13 |
EP4289889A2 (en) | 2023-12-13 |
CN111511815B (zh) | 2024-01-23 |
AU2018390818A1 (en) | 2020-05-28 |
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