JP6475434B2 - 感圧接着剤 - Google Patents
感圧接着剤 Download PDFInfo
- Publication number
- JP6475434B2 JP6475434B2 JP2014153792A JP2014153792A JP6475434B2 JP 6475434 B2 JP6475434 B2 JP 6475434B2 JP 2014153792 A JP2014153792 A JP 2014153792A JP 2014153792 A JP2014153792 A JP 2014153792A JP 6475434 B2 JP6475434 B2 JP 6475434B2
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- JP
- Japan
- Prior art keywords
- acrylate
- synthetic rubber
- meth
- poly
- compatible
- 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.)
- Expired - Fee Related
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- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Description
a)接着剤の総質量に対して30〜65質量%の少なくとも1種のポリ(メタ)アクリラートと、
b)接着剤の総質量に対して5〜20質量%の少なくとも1種の合成ゴムと、
c)ポリ(メタ)アクリラートと相溶性の少なくとも1種の粘着付与剤と、
d)合成ゴムと相溶性の少なくとも1種の炭化水素樹脂と
を含む感圧接着剤を提供する。この種類のPSAは、例えば自動車両の仕上げなどの非極性基材に対しても高い結合強度を示し、対応する試験によって示されている通り、著しく高いせん断強度を示す。
a)次式のアクリル酸エステルおよび/またはメタクリル酸エステル
CH2=C(RI)(COORII)
[式中、RI=HまたはCH3であり、RIIは、4〜14個のC原子を有するアルキル基である]、
b)エポキシド基との反応性が既に定義されている種類の官能基を有するオレフィン性不飽和モノマー、
c)場合によっては、成分(a)と共重合可能な、さらなるアクリラートおよび/またはメタクリラートおよび/またはオレフィン性不飽和モノマー。
ここで、
−ブロックAは、互いに独立に、少なくとも1種のビニル芳香族化合物の重合によって形成されたポリマーであり、
−ブロックBは、互いに独立に、4〜18個のC原子を有する共役ジエンおよび/またはイソブチレンの重合によって形成されたポリマーであるか、またはこのようなポリマーの部分的もしくは完全に水素化された誘導体であり、
−Xは、カップリング試薬または開始剤の残基であり、
−nは、2以上の整数である。
a)PSAの総質量に対して35〜55質量%の少なくとも1種のポリ(メタ)アクリラートと、
b)PSAの総質量に対して7.5〜15質量%の少なくとも1種の合成ゴムと、
c)10〜25質量%の、ポリ(メタ)アクリラートと相溶性の少なくとも1種の粘着付与剤と、
d)PSAの総質量に対して10〜25質量%の、合成ゴムと相溶性の少なくとも1種の炭化水素樹脂と
を含む。
試験方法
試験1:90°結合強度
鋼および試験用ワニス(BASF製の製品FF99−0778)に対する結合強度を、温度23℃+/−1℃および相対湿度50%+/−5%の試験条件下で求めた。被験物を幅20mmに切り出し、鋼プレートに接着させた。測定の前に、試験用プレートを清浄にし、調整した。この処理は、まず、鋼プレートをアセトン(鋼)またはイソプロパノール(ワニス)で拭き取り、その後5分間(鋼)または2時間(ワニス)かけて空気中に静置して、溶媒を蒸発させることによって行った。次に、試験用基材に面していない単層接着テープの片面を、エッチング処理した36μmのPETフィルムで裏打ちし、それによって測定中に被験物が延伸しないようにした。この後、試験用被験物を、鋼基材またはワニスにローラーで適用した。この目的では、4kgのローラーを、ロール速度10m/分でテープ上に5回往復させた。このローラー適用の20分後に、被験物を角度90°で垂直上方に向かって剥離できる特別な架台に、鋼またはワニスプレートを挿入した。結合強度を、Zwick引張試験機を使用して測定した。測定結果を、3回の個々の測定の平均としてN/cmで記録する。
端部の長さが25mmの正方形の接着剤転写テープを、清浄にした2つの鋼プレートの間に結合させた。結合部を、0.9kNで1分間プレスした。その集合体を24時間保存した後、ZWICK製の引張試験機により、23℃および相対湿度50%において、50mm/分で2つの鋼プレートを角度180°で引き剥がすことによって分離した。最大限の力をN/cm2で求めた。その結果は、3回の個々の測定の平均とする。
2つのT字形の形状のアルミニウム(25mm×25mm×25mm)をアセトンで清浄にし、その後、溶媒を10分間かけて蒸発させた。接着テープ被験物を、端部の長さが25mmの正方形に切り出した。次に、先の形状のアルミニウムを、両面接着テープ被験物を使用して結合させ、110Nで15秒間プレスした。その後、試験系を、23℃および相対湿度50%で24時間かけて平衡状態にした。次に、それをZWICK製の引張試験機に固定し、その後、2つのTブロックを300mm/分で引き離した。記録した結果は、5回の別個の測定の平均(N/cm2)である。
ラジカル重合で通常使用される反応器に、2−エチルヘキシルアクリラート72.0kg、メチルアクリラート20.0kg、アクリル酸8.0kg、およびアセトン/イソプロパノール(94:6)66.6kgを入れた。撹拌しながら窒素ガスを45分間通気した後、反応器を58℃に加熱し、AIBN50gのアセトン500g溶液を添加した。次に、外部加熱によって浴を75℃に加熱し、この外部温度において一定速度で反応させた。1時間後に、さらなるAIBN50gのアセトン500g溶液を添加し、4時間後に、バッチをアセトン/イソプロパノール混合物(94:6)10kgで希釈した。
4つの混合帯域を備えた遊星形ローラー押出機で、顆粒形態の合成ゴムKraton D1102および炭化水素樹脂Piccolyte A115を、2つの固体用の計量設備を介して取込み領域に導入し、第1の混合帯域で混合して、均質な組成物を得た。単軸押出機で予熱しておいたポリアクリラートベースポリマーを、次の帯域に供給した。その後、テルペン−フェノール樹脂Dertophen T105を、樹脂を溶融することにより計量して入れた。混合物を二軸押出機に移し、そこで架橋剤(Polypox R16、Rheofos RDP中20%)および促進剤(Rheofos RDP中20%Epicure 925)の溶液と混合した。この後、マイクロバルーンペースト(Ethomeen C25中50%Expancel 051DU40)を添加した。ダブルロールカレンダーを使用して、溶融物を2つの放出フィルム(シリコン処理したPETフィルム)の間にコーティングした。これによって、層の厚さ1000μmおよび密度700kg/m3の単層接着テープを得た。その組成は、42%ポリアクリラート、10%Kraton D1102、25%Dertophen T105、15%Piccolyte A115、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
例1の手順を反復した。これによって、層の厚さ1000μmおよび密度630kg/m3の単層接着テープを得た。その組成は、44%ポリアクリラート、12%Kraton D1102、14%Dertophen T105、22%Piccolyte A115、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
例1の手順を反復した。これによって、層の厚さ1000μmおよび密度500kg/m3の単層接着テープを得た。その組成は、50%ポリアクリラート、8%Kraton D1102、16%Dertophen T105、18%Piccolyte A115、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
遊星形ローラー押出機に合成ゴムも炭化水素樹脂も添加しなかったことを除き、例1の手順を反復した。これによって、層の厚さ1000μmおよび密度700kg/m3の単層接着テープを得た。その組成は、63%ポリアクリラート、29%Dertophen T105、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
炭化水素樹脂を使用しなかったことを除き、例1の手順を反復した。これによって、層の厚さ1000μmおよび密度620kg/m3の単層接着テープを得た。その組成は、47%ポリアクリラート、15%Kraton D1102、30%Dertophen T105、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
ポリ(メタ)アクリラートと相溶性の粘着付与剤を使用しなかったことを除き、例1の手順を反復した。これによって、層の厚さ1000μmおよび密度600kg/m3の単層接着テープを得た。その組成は、55%ポリアクリラート、9%Kraton D1102、28%Piccolyte A115、2%架橋剤/促進剤溶液(架橋剤:促進剤=1:1)、および6%マイクロバルーンペーストであった(数値は質量%)。
(1)a)接着剤の総質量に対して30〜65質量%の少なくとも1種のポリ(メタ)アクリラートと、
b)接着剤の総質量に対して5〜20質量%の少なくとも1種の合成ゴムと、
c)ポリ(メタ)アクリラートと相溶性の少なくとも1種の粘着付与剤と、
d)合成ゴムと相溶性の少なくとも1種の炭化水素樹脂と
を含む、感圧接着剤。
(2)(合成ゴムと相溶性の炭化水素樹脂)対合成ゴムの質量比が、1:1〜4:1であることを特徴とする、前記(1)に記載の感圧接着剤。
(3)(ポリ(メタ)アクリラートと相溶性の粘着付与剤)対合成ゴムの質量比が、0.5:1〜4:1であることを特徴とする、前記(1)または(2)に記載の感圧接着剤。
(4)ポリ(メタ)アクリラートと相溶性の粘着付与剤、および合成ゴムと相溶性の炭化水素樹脂の総量が、接着剤の総質量に対して25〜50質量%であることを特徴とする、前記(1)〜(3)のいずれか一つに記載の感圧接着剤。
(5)合成ゴムが、A−B、A−B−A、(A−B) n 、(A−B) n Xまたは(A−B−A) n Xの構造を有するブロックコポリマーであることを特徴とし、
−ブロックAが、互いに独立に、少なくとも1種のビニル芳香族化合物の重合によって形成されたポリマーであり、
−ブロックBが、互いに独立に、4〜18個のC原子を有する共役ジエンおよび/もしくはイソブチレンの重合によって形成されたポリマーであるか、またはこのようなポリマーの部分的もしくは完全に水素化された誘導体であり、
−Xが、カップリング試薬または開始剤の残基であり、
−nが、2以上の整数である
前記(1)〜(4)のいずれか一つに記載の感圧接着剤。
(6)接着剤中に存在するすべてのブロックコポリマーに対するブロックAの質量分率が、10〜40質量%であることを特徴とする、前記(5)に記載の感圧接着剤。
(7)ポリ(メタ)アクリラートと相溶性の粘着付与剤が、テルペン−フェノール樹脂またはロジン誘導体であることを特徴とする、前記(1)〜(6)のいずれか一つに記載の感圧接着剤。
(8)合成ゴムと相溶性の炭化水素樹脂が、ジシクロペンタジエンの水素化ポリマー;C5−、C5/C9またはC9モノマーをベースとする、水素化されていないか、または部分的、選択的もしくは完全に水素化されている炭化水素樹脂;ならびにα−ピネンおよび/またはβ−ピネンおよび/またはδ−リモネンをベースとするポリテルペン樹脂;ならびに先の炭化水素樹脂の混合物からなる群から選択されることを特徴とする、前記(1)〜(7)のいずれか一つに記載の感圧接着剤。
(9)発泡していることを特徴とする、前記(1)〜(8)のいずれか一つに記載の感圧接着剤。
(10)前記(1)〜(9)のいずれか一つに記載の感圧接着剤の少なくとも1つの層を含む、接着テープ。
(11)層の厚さが100μm〜5000μmであることを特徴とする、前記(10)に記載の接着テープ。
(12)前記(1)から(9)のいずれか一つに記載の感圧接着剤の層からなることを特徴とする、前記(10)または(11)に記載の接着テープ。
Claims (10)
- a)接着剤の総質量に対して30〜65質量%の少なくとも1種のポリ(メタ)アクリラートと、
b)接着剤の総質量に対して5〜20質量%の少なくとも1種の合成ゴムと、
c)ポリ(メタ)アクリラートと相溶性の少なくとも1種の粘着付与剤と、
d)合成ゴムと相溶性の少なくとも1種の炭化水素樹脂と
を含み、
上記合成ゴムが、A−B、A−B−A、(A−B) n 、(A−B) n Xまたは(A−B−A) n Xの構造を有するブロックコポリマーであることを特徴とし、
−ブロックAが、互いに独立に、少なくとも1種のビニル芳香族化合物の重合によって形成されたポリマーであり、
−ブロックBが、互いに独立に、4〜18個のC原子を有する共役ジエンおよび/もしくはイソブチレンの重合によって形成されたポリマーであるか、またはこのようなポリマーの部分的もしくは完全に水素化された誘導体であり、
−Xが、カップリング試薬または開始剤の残基であり、
−nが、2以上の整数である;
そして
接着剤中に存在するすべてのブロックコポリマーに対するブロックAの質量分率が、10〜40質量%である、
感圧接着剤。 - (合成ゴムと相溶性の炭化水素樹脂)対合成ゴムの質量比が、1:1〜4:1であることを特徴とする、請求項1に記載の感圧接着剤。
- (ポリ(メタ)アクリラートと相溶性の粘着付与剤)対合成ゴムの質量比が、0.5:1〜4:1であることを特徴とする、請求項1または2に記載の感圧接着剤。
- ポリ(メタ)アクリラートと相溶性の粘着付与剤、および合成ゴムと相溶性の炭化水素樹脂の総量が、接着剤の総質量に対して25〜50質量%であることを特徴とする、請求項1〜3のいずれか一つに記載の感圧接着剤。
- ポリ(メタ)アクリラートと相溶性の粘着付与剤が、テルペン−フェノール樹脂またはロジン誘導体であることを特徴とする、請求項1〜4のいずれか一つに記載の感圧接着剤。
- 合成ゴムと相溶性の炭化水素樹脂が、ジシクロペンタジエンの水素化ポリマー;C5−、C5/C9またはC9モノマーをベースとする、水素化されていないか、または部分的、選択的もしくは完全に水素化されている炭化水素樹脂;ならびにα−ピネンおよび/またはβ−ピネンおよび/またはδ−リモネンをベースとするポリテルペン樹脂;ならびに先の炭化水素樹脂の混合物からなる群から選択されることを特徴とする、請求項1〜5のいずれか一つに記載の感圧接着剤。
- 発泡していることを特徴とする、請求項1〜6のいずれか一つに記載の感圧接着剤。
- 請求項1〜7のいずれか一つに記載の感圧接着剤の少なくとも1つの層を含む、接着テープ。
- 層の厚さが100μm〜5000μmであることを特徴とする、請求項8に記載の接着テープ。
- 請求項1から7のいずれか一つに記載の感圧接着剤の層からなることを特徴とする、請求項8または9に記載の接着テープ。
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US20150037559A1 (en) | 2015-02-05 |
EP2883926B1 (de) | 2016-09-28 |
TWI639666B (zh) | 2018-11-01 |
TW201510140A (zh) | 2015-03-16 |
ES2605882T3 (es) | 2017-03-16 |
CA2858031A1 (en) | 2015-02-02 |
CN104342056A (zh) | 2015-02-11 |
PL2883926T3 (pl) | 2017-02-28 |
MX2014009171A (es) | 2015-03-04 |
KR102230244B1 (ko) | 2021-03-18 |
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