JP2010018689A - 水性粘着剤組成物及びこれを用いた粘着シート - Google Patents
水性粘着剤組成物及びこれを用いた粘着シート Download PDFInfo
- Publication number
- JP2010018689A JP2010018689A JP2008179637A JP2008179637A JP2010018689A JP 2010018689 A JP2010018689 A JP 2010018689A JP 2008179637 A JP2008179637 A JP 2008179637A JP 2008179637 A JP2008179637 A JP 2008179637A JP 2010018689 A JP2010018689 A JP 2010018689A
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- Prior art keywords
- sensitive adhesive
- adhesive composition
- parts
- aqueous
- pressure
- Prior art date
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- Granted
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 239000000853 adhesive Substances 0.000 title claims abstract description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 66
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 14
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- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
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- 239000000758 substrate Substances 0.000 abstract description 17
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
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- 239000004814 polyurethane Substances 0.000 description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 239000004094 surface-active agent Substances 0.000 description 3
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- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000013032 Hydrocarbon resin Substances 0.000 description 2
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- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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Abstract
本発明は、ウレタンフォームのような表面に凹凸を有する基材(発泡体)への密着性、接着性、初期粘着性、保持力に優れるとともに、耐水性にも優れ、且つVOCの発生を極めて少なくすることのできる水性粘着剤組成物、及びこれを用いた粘着シートに関する。
【解決手段】
本発明は、カルボニル基含有エチレン性不飽和単量体を含むエチレン性不飽和単量体成分を乳化重合して得られるポリマーエマルジョン(A)、石油系樹脂からなる粘着付与剤(B)及び分子中に少なくとも2つのヒドラジノ基を有する化合物(C)からなる水性粘着剤組成物に関する。また、本発明は、前記水性粘着剤組成物からなる発泡体用水性粘着剤組成物に関する。さらには、本発明は、シートの少なくとも一方の面に、前記水性粘着剤組成物から形成される粘着剤層が積層された粘着シートに関する。
【選択図】 なし
Description
A1901法(小形チャンバー法)で測定した総揮発性有機化合物が3,000μg/m3以下である水性粘着剤(特許文献10参照)や、ホルムアルデヒドの放散量が3μg/m3未満で、且つトルエンの放散量が10μg/g以下である粘着シート(特許文献11参照)が開示されている。しかし、いずれの場合も、発泡体への基材密着性、接着性、初期粘着性、保持力、耐水性は十分なものであるとはいえなかった。
(式中、pは2又は3である)で表される化合物、式(7):
還流冷却器、攪拌機、温度計窒素導入管、原料投入口を具備する容積2Lの4つ口フラスコ(以下、反応容器という)に、イオン交換水189部、乳化剤アクアロンKH−10(第一工業製薬株式会社製)1部を入れ、内温を78℃まで加温した。一方、単量体として、n−ブチルアクリレート213.5部、2−エチルヘキシルアクリレート213.5部、メチルメタクリレート72部、2−ヒドロキシエチルメタクリレート4.29部、アクリル酸12.86部、ダイアセトンアクリルアマイド0.85部、連鎖移動剤として2−エチルヘキシルチオグリコレート0.86部、乳化剤としてアクアロンKH−10(第一工業製薬株式会社製)4.3部及びイオン交換水200部の混合物をホモミキサーで乳化し、単量体エマルジョンを作製した。上記の反応容器中に、単量体エマルジョンの3%を添加し、同時に過硫酸カリウム(以下、KPSという)0.31部を添加して乳化重合を開始した。次いで、反応容器中にKPSを添加してから20分後に、単量体エマルジョンの残り97%と、KPS1.08部をイオン交換水16部で溶解した溶液をそれぞれ3.5時間かけて滴下した。この間、反応容器内は80℃に保った。滴下終了後、1時間、80℃に保ち、熟成を行った。その後、65℃まで冷却し、t−ブチルヒドロパーオキシド1部、重亜硫酸ナトリウム1部及びイオン交換水10部部を添加し、未反応の単量体を反応させた。65℃のまま、3時間保持した後、35%アンモニア水6部を添加し、冷却を開始した。得られたポリマーエマルジョン(i)は固形分53.1%(測定方法:105℃において1時間乾燥に測定。)、pH8、粘度3000mPa・s(測定方法:23℃において、BL型粘度計でNo.4ローターを用い、10rpmにて測定。以下の実施例及び比較例において同様の方法にて測定する)、平均粒子径150nm(日機装株式会社製、マイクロトラックUPA型粒度分布測定装置にて平均粒子径(体積基準での50%メジアン径)を測定。以下の実験例において、同様の方法にて測定する)であった。
重合に使用する単量体中のアクリル酸を6.43部、連鎖移動剤の2−エチルヘキシルチオグリコレートを0.43部とし、反応終了後に添加するアンモニア水を4部とした以外は、ポリマーエマルジョン(i)の製造と同様の操作を行い、ポリマーエマルジョン(B)を得た。ポリマーエマルジョン(ii)は固形分53.1%、pH8、粘度3000mPa・s、平均粒子径150nmであった。
得られたポリマーエマルジョン(i)100部に対し、エマルジョン型石油樹脂系粘着付与樹脂(荒川化学工業株式会社製、アルコンM−100(前記式(2)の構造式からなる骨格を有する石油系樹脂の水素化物、芳香環水素化率56%、数平均分子量800、固形分濃度50%、軟化点100℃)66部、アジピン酸ジヒドラジド0.2部、水3.8部、消泡剤(商品名:アデカネートB−940、株式会社ADEKA製)0.1部、防腐剤(商品名:ネオシントールBC−60、住化エンビロサイエンス株式会社製)0.05部、濡れ剤(商品名:サーフィノールSE−F、エアプロダクツジャパン株式会社製)0.1部を加え、さらに増粘剤(商品名:プライマルASE−60、ローム・アンド・ハース・ジャパン株式会社製)0.9部、デナコールEX810(ナガセケムテックス株式会社製、前記式(1)で表されるエポキシ基を有する化合物)0.1部を添加し、粘度が15000mPa・sの水性粘着剤組成物を得た。
ポリマーエマルジョン(i)100部の代わりに、ポリマーエマルジョン(ii)100部を用いた以外は実施例1と同様の操作を行い、粘度が15000mPa・sの水性粘着剤組成物を得た。
ポリマーエマルジョン(i)100部の代わりに、ポリマーエマルジョン(ii)100部を用い、デナコールEX810を添加しなかったこと以外は実施例1と同様の操作を行い、粘度が15000mPa・sの水性粘着剤組成物を得た。
エマルジョン型石油樹脂系粘着付与樹脂の代わりに、スーパーエステルE−865NT(荒川化学工業株式会社製、ロジン系粘着付与樹脂、固形分50%)66部を用いた以外は実施例1と同様の操作を行い、粘度が15000mPa・sの水性粘着剤組成物を得た。
デナコールEX810を添加しなかったこと以外は実施例1と同様の操作を行い、粘度が15000mPa・sの水性粘着剤組成物を得た。
デナコールEX810の代わりに、アクアネートAQ−200(日本ポリウレタン工業株式会社製、イソシアネート系架橋剤)0.25部を用いた以外は実施例1と同様の操作を行い、粘度が15000mPa・sの水性粘着剤組成物を得た。
基材密着性:得られた試験片の粘着剤層面に指を押し当て、ゆっくりと引き剥がした際の粘着剤層、ウレタン発泡体の破壊状態を目視にて評価した。
○;粘着剤層の指への転着は無く、試験片は原型を保持した。或いはウレタン発泡体が破壊し、粘着剤層がウレタン発泡体と密着したまま指に転着した。
×;粘着剤層がウレタン発泡体から離れ、指に転着し、粘着剤層が破壊した。或いは粘着剤層の指への転着は無かったが、粘着剤層がウレタン発泡体から分離した。
Claims (10)
- カルボニル基含有エチレン性不飽和単量体を含むエチレン性不飽和単量体成分を乳化重合して得られるポリマーエマルジョン(A)、石油系樹脂からなる粘着付与剤(B)及び分子中に少なくとも2つのヒドラジノ基を有する化合物(C)からなる水性粘着剤組成物。
- さらに、分子中に少なくとも2つのエポキシ基を有する架橋剤(D)を含有する請求項1記載の水性粘着剤組成物。
- ポリマーエマルジョン(A)の固形分100質量部に対し、分子中に少なくとも2つのエポキシ基を有する架橋剤(D)0.1〜10質量部を含有する請求項2又は3記載の水性粘着剤組成物。
- カルボニル基含有エチレン性不飽和単量体が、エチレン性不飽和単量体成分に対し、0.1〜5質量%である請求項1、2、3又は4のいずれかに記載の水性粘着剤組成物。
- ポリマーエマルジョン(A)の固形分100質量部に対し、石油系樹脂からなる粘着付与剤(B)1〜15質量部を含有する請求項1、2、3、4又は5記載の水性粘着剤組成物。
- ポリマーエマルジョン(A)の固形分100質量部に対し、分子中に少なくとも2つのヒドラジノ基を有する化合物(C)0.1〜5質量部を含有する請求項1、2、3、4、5又は6記載の水性粘着剤組成物。
- 請求項1、2、3、4、5、6又は7のいずれかに記載の水性粘着剤組成物からなる発泡体用水性粘着剤組成物。
- シートの少なくとも一方の面に、請求項1、2、3、4、5、6又は7のいずれかに記載の水性粘着剤組成物から形成される粘着剤層が積層された粘着シート。
- シートが発泡体である請求項9記載の粘着シート。
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Cited By (5)
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JP2012097234A (ja) * | 2010-11-04 | 2012-05-24 | Nitto Denko Corp | 粘着シート |
WO2012120920A1 (ja) | 2011-03-09 | 2012-09-13 | 日東電工株式会社 | 水分散型粘着剤組成物および粘着シート |
WO2012120921A1 (ja) | 2011-03-09 | 2012-09-13 | 日東電工株式会社 | 水分散型粘着剤組成物および粘着シート |
JP2014185310A (ja) * | 2013-02-21 | 2014-10-02 | Dic Corp | 粘着テープ |
JP2014196457A (ja) * | 2013-03-08 | 2014-10-16 | Dic株式会社 | 粘着テープ |
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JPH06287534A (ja) * | 1993-04-07 | 1994-10-11 | Mitsubishi Yuka Badische Co Ltd | 水性粘接着剤組成物 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2012097234A (ja) * | 2010-11-04 | 2012-05-24 | Nitto Denko Corp | 粘着シート |
WO2012120920A1 (ja) | 2011-03-09 | 2012-09-13 | 日東電工株式会社 | 水分散型粘着剤組成物および粘着シート |
WO2012120921A1 (ja) | 2011-03-09 | 2012-09-13 | 日東電工株式会社 | 水分散型粘着剤組成物および粘着シート |
JP2014185310A (ja) * | 2013-02-21 | 2014-10-02 | Dic Corp | 粘着テープ |
JP2014196457A (ja) * | 2013-03-08 | 2014-10-16 | Dic株式会社 | 粘着テープ |
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