JP5680051B2 - ポリマー系から作られた接着剤 - Google Patents
ポリマー系から作られた接着剤 Download PDFInfo
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- JP5680051B2 JP5680051B2 JP2012501319A JP2012501319A JP5680051B2 JP 5680051 B2 JP5680051 B2 JP 5680051B2 JP 2012501319 A JP2012501319 A JP 2012501319A JP 2012501319 A JP2012501319 A JP 2012501319A JP 5680051 B2 JP5680051 B2 JP 5680051B2
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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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
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
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- C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
Description
a)エラストマーゴム、またはエチレン−プロピレンゴムおよびエチレン−プロピレン−ジエンモノマーターポリマーゴムからなる群より選択されるエラストマーゴムのブレンド、および
b)半結晶性オレフィンポリマーまたは半結晶性オレフィンポリマーのブレンド
を含む。
a)エラストマーゴム、またはエチレン−プロピレンゴムおよびエチレン−プロピレン−ジエンモノマーターポリマーゴムからなる群より選択されるエラストマーゴムのブレンド、および
b)半結晶性オレフィンポリマーまたは半結晶性オレフィンポリマーのブレンド
からなる。
a)エラストマーゴム、または、エチレン−プロピレンゴムおよびエチレン−プロピレン−ジエンモノマーターポリマーゴムからなる群より選択されるエラストマーゴムのブレンド、および、半結晶性オレフィンポリマーまたは半結晶性オレフィンポリマーのブレンドを含むか、またはそれからなる少なくとも1つのポリマーブレンド出発物質を提供する工程;
b)前記ポリマーブレンド出発物質を少なくとも1つのラジカル供与体で、該ポリマーブレンド出発物質の軟化点を超えた温度で、剪断応力下で、処理することによって、少なくとも1つのポリマーブレンド出発物質の溶融粘度を低下させる工程;
を含むプロセスによって得ることができる。
1. C5/C6テルペン樹脂、スチレンテルペン、α-メチルスチレンテルペン樹脂、C9テルペン樹脂、芳香族変性C5/C6、芳香族変性環状樹脂、芳香族変性ジシクロペンタジエン系樹脂またはその混合物のような樹脂。一般的には、これらの樹脂は以下のモノマー:(1-3ペンタジエン、イソプレン等のような)C5ジオレフィン;(2-メチルブテン、シクロペンテン等のような)C5オレフィン;(ヘキセンのような)C6オレフィン、(スチレン、α-メチルスチレン、ビニルトルエン、インデン、メチルインデン等のような)C9ビニル芳香族;(ジシクロペンタジエン、メチルジシクロペンタジエン等のような)環状体;および/または(リモネン、カレン等のような)テルペンの1つ以上を含有する組成物のカチオン重合から得られる。
2. ジシクロペンタジエンの熱重合、および/または、シクロペンタジエンおよび/またはメチルシクロペンタジエンのダイマーまたはオリゴマーと、任意に、(スチレン、αメチルスチレン、ビニルトルエン、インデン、メチルインデンのような)ビニル芳香族との熱重合によって得られる樹脂。
a)本発明の少なくとも1つのポリマー系、20〜80重量%;
b)少なくとも1つの粘着付与剤、5〜80重量%;
c)少なくとも1つのワックス、0〜50重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー系、20〜80重量%;
b)少なくとも1つの粘着付与剤、5〜80重量%;
c)少なくとも1つのワックス、0〜50重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含み、ここで、成分c)およびd)の総和は、前記接着剤の、0.1〜50重量%、好ましくは1〜30重量%、より好ましくは5〜15重量%を含む。
a)本発明の少なくとも1つのポリマー系、15〜80重量%;
b)少なくとも1つの粘着付与剤、10〜70重量%;
c)少なくとも1つのワックス、0〜40重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー系、30〜50重量%;
b)少なくとも1つの粘着付与剤、20〜45重量%;
c)少なくとも1つのワックス、5〜30重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー系15〜80重量%;
b)の少なくとも1つの粘着付与剤、10〜70重量%;
c)少なくとも1つのワックス、0〜5重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー、20〜60重量%;
b)少なくとも1つの粘着付与剤、30〜65重量%;
c)少なくとも1つのワックス、0〜5重量%;および
d)少なくとも1つの添加剤、0〜25重量%
を含む。
ラミネート製品は、適当なバインダーで互いに結合した層またはラミナからなる。ラミナは、通常、紙または不織布のような連続シート形態で、容易に入手可能な材料である。バインダーは、主にフェノール樹脂である合成樹脂であり、ベースラミナに溶媒被覆させるかまたは含浸させる。乾燥後、いくつかのラミナを積層し、全体を熱および圧力下で固定させて、その機械的、電気的、化学的または美的品質のために用いる剛性シートまたはパネルを形成する。産業において、ラミナは、その電気的特性、衝撃強度、着用品質、または化学的抵抗性のために用いられる。ラミナはエレクトロニクス用途、電気スイッチ、ギア等で用いられる。機能的には極めて重要であるが、それらはめったに顕著ではない。
a)本発明の少なくとも1つのポリマー系、20〜80重量%;
b)少なくとも1つの粘着付与剤、10〜50重量%;
c)少なくとも1つのワックス、0〜20重量%;および
d)少なくとも1つの添加剤、0〜50重量%
を含む。
a)本発明の少なくとも1つのポリマー系、50〜70重量%;
b)少なくとも1つの粘着付与剤、20〜40重量%;
c)少なくとも1つのワックス、0〜15重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー系、20〜80重量%;
b)少なくとも1つの粘着付与剤、10〜70重量%;
c)少なくとも1つのワックス、0〜20重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む。
a)本発明の少なくとも1つのポリマー系、20〜40重量%;
b)少なくとも1つの粘着付与剤、30〜65重量%;
c)少なくとも1つのワックス、5〜15重量%;および
d)少なくとも1つの添加剤、5〜30重量%
を含む。
特記しない限り、以下の方法を用いて、本発明のポリマーを特徴付ける。
mPasで表される粘度は、200℃の温度にて(Brookfield Engineering Laboratories, Inc. Stoughton, Mass.USAから入手可能な)Brookfield Thermosell RVT粘度計で測定した。100.000mPasまでの粘度については、スピンドル27を用い、より高い粘度はスピンドル29で測定した。
DSC測定は、以下の条件下でTA Instruments Q2000 MDSCを用いて行った:約6〜10mgのポリマーの小さな試料を、アルミニウム試料パン中に封入し、室温で機器に投入し、−90℃まで冷却した。この温度で20分間の平衡後、10℃/分の加熱速度で、この試料を200℃まで加熱した(第一の加熱サイクル)。次いで、試料を、この温度で10分間保持して、その熱履歴を破壊した。次いで、5℃/分の冷却速度で、試料を−90℃まで冷却した。この冷却相を、以後、復帰相という。試料を−90℃にて10分間維持し、続いて、第二の加熱相において10℃/分にて250℃まで加熱した(第二の加熱サイクル)。3つの相の間で起こった全ての熱効果(例えば、ガラス転移、ピーク融点(Tm)、融解熱(ΔHm))を、続いて、実験データファイルからソフトウェアによって評価した。融解温度は、特記しない限り、第二の熱からのピーク融点である。多数のピークを呈するポリマーでは、より高い融解ピーク温度を報告した。曲線下面積を用いて、融解熱(ΔHm)を決定した。ピークの積分の結果を、試料の重量について正規化し、J/gで報告した。
ゲル浸透クロマトグラフィシステムは、屈折率検出器を備えたPolymer Laboratories Model PL-220機器からなるものであった。カラム区画およびカルーセル区画を150℃で操作した。3つの直線状カラム(Polymer Laboratories, Typ “Olexis”;300×8mm)を用いた。溶媒は1,2,4-トリクロロベンゼンであった。試料は、200ppmのブチル化ヒドロキシトルエン(BHT)を含有する1.0mg/mlの濃度にて調製した。流速は1.0ml/分であった。GPCカラムセットのキャリブレーションは、狭い分子量分布のポリスチレン標準で行った。
引張特性はZwick引張試験機(モデルZMART.PRO)で、EN ISO 527-3-3に従って測定した。全ての試料を、10mm/分の速度で測定した。試験検体を、試験の24時間前に、23℃および50パーセントの相対湿度でコンディショニングした。
軟化点は、Ring and Ball法を用い、ASTM E-28に従って測定した。
〔ポリマーブレンド出発物質〕
Adflex T100F:高含量のEPRゴムを有するポリプロピレンコポリマー、LyondellBasell製
Softel CA02:高含量のEPRゴムを有するポリプロピレンコポリマー、LyondellBasell製。このポリマーブレンド出発物質は、200℃で68000Pasの粘度、EN ISO 527-3で500%より大きい破断点伸び、およびEN ISO 527-3で10MPaの破断点引張り強さを有する。
NERSM 1:ポリプロピレン/エチレンランダムコポリマー。このポリマーは、200℃で1600Pasの粘度、EN ISO 527-3で500%の破断点伸び、およびEN ISO 527−3で25MPaの破断点引張り強さを有する。
NERSM 2:ポリプロピレン/エチレン/ブテンランダムターポリマー。このポリマーは200℃で5000Pasの粘度、EN ISO 527-3で500%より大きい破断点伸び、およびEN ISO 527−3で35MPaの破断点引張り強さを有する。
Regalite S1100:水素化スチレン/メチルスチレン/インデンコポリマー、Eastman製
Trigonox 145-E85:2,5-ジメチル−2,5-ジ(tert−ブチルペルオキシ)ヘキシン-3、AkzoNobel製
ポリマー系1を、以下のプロセスで得た:
13500Pasの溶融粘度(200℃)を有するポリマーブレンド出発物質Adflex T100Fに、Adflex T100Fの全量に基づいて1.2重量%のTrigonox 145-E85を加えた。200℃で、25mm二軸スクリュー押出機(ZSK 25/40D;Werner & Pfleiderer)中で、得られた混合物を処理することにより、25Pasの溶融粘度(200℃)を示す本発明のポリマー系を得た。
ポリマー系2を、以下のプロセスで得た。
68000Pasの溶融粘度(200℃)を有するポリマーブレンド出発物質Softel CA02に、Softel CA02の全量に基づいて2.0重量%のTrigonox 145-E85を加えた。200℃で、25mm二軸スクリュー押出機(ZSK 25/40D;Werner & Pfleiderer)中で、得られた混合物を処理することにより、107Pasの溶融粘度(200℃)を示す本発明のポリマー系を得た。
ポリマー1を含有する分解した非エラストマーゴム(DNERP 1)を、以下のプロセスで得た。
1600Pasの溶融粘度(200℃)を有するNERSM 1に、NERSM 1の全量に基づいて、2.0重量%のTrigonox 145-E85を加えた。200℃で、25mm二軸スクリュー押出機(ZSK 25/40D;Werner & Pfleiderer)中で、得られた混合物を処理することによって、9Pasの溶融粘度(200℃)を示す、ポリマーを含有する分解した非エラストマーゴムDNERP 1を得た。
ポリマー2を含有する分解した非エラストマーゴム(DNERP 2)を、以下のプロセスで得た。
5000Pasの溶融粘度(200℃)を有するNERSM 2に、NERSM 2の全量に基づいて、2.0重量%のTrigonox 145-E85を加えた。200℃で、25mm二軸スクリュー押出機(ZSK 25/40D;Werner & Pfleiderer)中で、得られた混合物を処理することによって、4.5Pasの溶融粘度(200℃)を示す、ポリマーを含有する分解した非エラストマーゴムDNERP 2を得た。
ホットメルト製剤を200℃で調製した。この温度において、KRAFTLINER段ボール板(5×5cm)の2つのストリップを、表2に示したホットメルト製剤0.9〜1.1グラムをスパチュラで適用して、互いに結合させ、続いて、手でプレスした。検体を室温(23℃)で少なくとも1日貯蔵した後、検体を手で引き離した。検体の繊維破断の程度を用いて、製剤の接着剤特性を評価した。
接着の失敗:接着剤スポット上に残存する繊維が0〜30%:−
部分的な繊維破断:接着剤スポット上に残存する繊維が30〜60%:−+
繊維破断:接着剤スポット上に残存する繊維が60〜90%:+
激しい繊維破断:接着剤スポット上に残存する繊維が90%より多い:++
Claims (19)
- 少なくとも1つのポリマー系を含む接着剤であって、該ポリマー系は、少なくとも1つのポリマーブレンド出発物質の溶融粘度を低下させるプロセスによって得られ、該プロセスは、少なくとも1つのポリマーブレンド出発物質を、少なくとも1つのラジカル供与体で、該ポリマーブレンド出発物質の軟化点を超える温度で、剪断応力下で、処理する工程を含み、該ポリマーブレンド出発物質は、:
a)エラストマーゴム、またはエチレン−プロピレンゴムおよびエチレン−プロピレン−ジエンモノマーターポリマーゴムからなる群より選択されるエラストマーゴムのブレンド、および
b)半結晶性オレフィンポリマーまたは半結晶性オレフィンポリマーのブレンド
からなる、接着剤であって、少なくとも1つのポリマーブレンド出発物質の溶融粘度を、得られたポリマー系の(200℃における)溶融粘度がポリマーブレンド出発物質の(200℃における)初期溶融粘度の50%未満となるまで低下させる、
ここで、該ポリマーブレンド出発物質が、200℃で、少なくとも300,000mPasの初期溶融粘度を有し、
該ポリマー系が、200℃で、3,000〜1,000,000mPasの溶融粘度、および、ゲル浸透クロマトグラフィで測定して、1.5〜5.0の分子量分布Mw/Mnを有する、接着剤。 - ラジカル供与体が、アゾ化合物、ジアゾ化合物および/または過酸化物から選択される、請求項1に記載のポリマー系。
- ポリマー系が、EN ISO 527-3に従い測定して、少なくとも50%の破断点伸びを有する、請求項1または2記載のポリマー系。
- ポリマー系が、EN ISO 527-3に従い測定して、少なくとも2.5MPaの破断点引張り強さを有する、請求項1〜3のいずれかに記載のポリマー系。
- ポリマー系が、DSCで測定して、5〜−65℃のガラス転移温度を有する、請求項1〜4のいずれかに記載のポリマー系。
- ポリマー系が、DSCで測定して、30〜90J/gの融解熱を有する、請求項1〜5のいずれかに記載のポリマー系。
- ポリマー系が、DSCで測定して、125℃〜165℃の間に含まれるピーク融点(Tm)を有する、請求項1〜6のいずれかに記載のポリマー系。
- エラストマーゴムが、少なくとも40重量%のエチレンを含有するエチレンおよびプロピレンのコポリマーを含む、請求項1〜7のいずれかに記載のポリマー系。
- エラストマーゴムが、15〜50重量%のプロピレンを含有するエチレンおよびプロピレンのコポリマーを含む、請求項1〜8のいずれかに記載のポリマー系。
- エラストマーゴムが、カルボン酸基、無水物基、ヒドロキシル基、エーテル基、第一級アミン基、第二級アミン基、第三級アミン基およびエステル基から選択される官能性モノマーで変性させたエチレンおよびプロピレンのコポリマーを含む、請求項1〜9のいずれかに記載のポリマー系。
- エラストマーゴムが、40〜80重量%のエチレン、15〜50重量%のプロピレン、および2〜15重量%のジエンのターポリマーを含む、請求項1〜10のいずれかに記載のポリマー系。
- ターポリマーが、20〜45重量%のプロピレンを含有する、請求項11に記載のポリマー系。
- ジエンが、1,4-ヘキサジエン、ノルボルナジエン、エチリデン−ノルボルネン、ジシクロペンタジエン、ブタジエンおよびイソプレンからなる群より選択される、請求項11または12に記載のポリマー系。
- エラストマーゴムが、35重量%未満のエチレンを含有するエチレンおよびプロピレンのコポリマーを含む、請求項1〜7のいずれかに記載のポリマー系。
- 半結晶性オレフィンポリマーが、1〜35重量%で存在するエチレンおよび65〜99重量%で存在するC3-C20のα−オレフィンからなる群より選択される少なくとも1つのコモノマーのコポリマーである、請求項1〜14のいずれかに記載のポリマー系。
- 接着剤が、15〜95重量%の量で少なくとも1つのポリマー系を含む、請求項1〜15のいずれかに記載の接着剤。
- 接着剤が、さらに、1つ以上の粘着付与剤、および/または1つ以上のワックス、および/または可塑剤、充填剤、油、安定化剤、抗酸化剤、顔料、染料、ポリマー添加剤、脱泡剤、防腐剤、増粘剤、レオロジー変性剤、保湿剤、マスターバッチおよび水から選択される1つ以上の添加剤を含む、請求項1〜16のいずれかに記載の接着剤。
- a)少なくとも1つのポリマー系、20〜80重量%;
b)少なくとも1つの粘着付与剤、5〜80重量%;
c)少なくとも1つのワックス、0〜50重量%;および
d)少なくとも1つの添加剤、0〜30重量%
を含む、請求項1〜17のいずれかに記載の接着剤。 - 少なくとも30重量%の少なくとも1つのポリマー系を含む接着剤であって、該接着剤が100〜500,000mPasの粘度を有し、ここで、該粘度は該接着剤の適用温度で測定される、請求項1〜18のいずれかに記載の接着剤。
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