JP2599589C - - Google Patents
Info
- Publication number
- JP2599589C JP2599589C JP2599589C JP 2599589 C JP2599589 C JP 2599589C JP 2599589 C JP2599589 C JP 2599589C
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- parts
- resin
- sensitive adhesive
- pressure
- 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 - Lifetime
Links
- 239000000839 emulsion Substances 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- -1 acrylate ester Chemical class 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 150000002989 phenols Chemical class 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 230000001070 adhesive Effects 0.000 description 11
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000001804 emulsifying Effects 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QUOZWMJFTQUXON-UXXRCYHCSA-N Androsin Natural products COC1=CC(C(C)=O)=CC=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QUOZWMJFTQUXON-UXXRCYHCSA-N 0.000 description 2
- 239000004698 Polyethylene (PE) Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000005429 turbidity Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 230000001771 impaired Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003097 polyterpenes Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、ポリオレフインに対する密着性及び透明性に優れた新規な水性粘着
剤組成物に関する。
従来の技術及びその問題点
粘着剤は、通常、紙、プラスチツクフイルム等に塗布され、テープ、シート、
ラベル等に適用されるものである。水性エマルジヨン型粘着剤は、有機溶剤型粘
着剤に比べて、大気汚染がないこと、安全衛生に優れていること及び省資源に適
すること等の種々の利点を有するため、近年急速に有機溶剤型から水性エマルジ
ヨン型に転換される傾向にある。こうして、水性エマルジヨン型粘着剤の用途が
拡大するにつれて、求められる性能もより高度になり、かかる要求性能の一つに
ポリプロピレン、ポリエチレン等のポリオレフイン基材特にその曲面に対する密
着性、即ち耐フラツギング性が重視されている。ここで耐フラツギング性とはテ
ープ又はラベル等の経日的な剥離が起きないことをいう。このような性能が要求
される用途としては、たとえば食品、化粧品等の高級美麗ラベル、電気機器等の
品質表示ラベル、スーパーマーケツトのプライスラベル、事務用コンピユーター
ラベル、粘着シート、粘着テープ等があげられる。さらに、透明フイルムに使用
する場合には耐フラツギング性の問題に加えて粘着シートの透明性が求められる
。
従来、アクリル系重合体エマルジヨンに不均化ロジンのグリセリンエステル等
の粘着付与剤樹脂のエマルジヨンを配合することによりポリオレフイン基材に対
する密着性を改善することが行なわれているが、この場合密着性をいくぶんかは
改良できるもののフラツギング性の問題に関しては未だ改良されていない。また
、ある程度フラツギング性の問題を改良できたものでも、粘着シートが濁るため
透明フイルム等の透明性が必要な用途には使用できない場合がある。すなわち、
水性エマルジヨン粘着剤で該要求性能を満足させるものは未だ得られていない。
問題点を解決するための手段
本発明者らは、既存のアクリル系エマルジヨンに粘着付与剤樹脂エマルジヨン
を配合してなる水性粘着剤組成物の有する上記問題点に鑑み、水性粘着剤組成物
のポリオレフイン基材特にその曲面に対する密着性即ち耐フラツギング性の問題
及び粘着シートの透明性を改良すべく鋭意研究を重ねた結果、粘着付与剤樹脂と
して特定の高軟化点粘着付与剤樹脂エマルジヨンを使用した場合にはポリオレフ
イン平面に対する接着性はもとよりポリオレフイン曲面に対する密着性及び粘着
シートの透明性を同時に付与できることを見出し、本発明を完成するに至った。
即ち本発明は、(1)アクリル酸エステル及び/又はメタクリル酸エステルを主
成分とするアクリル系重合体エマルジヨンと
(2)ロジン変性フエノール樹脂である粘着付与剤樹脂で、かつその軟化点が11
0〜150℃である樹脂エマルジヨン
とからなることを特徴とする水性粘着剤組成物に係る。
本発明において用いるアクリル系重合体エマルジヨンとは、一般に各種のアク
リル系粘着剤に用いられているエマルジヨンが使用できる。該アクリル系重合体
エマルジヨンは、通常アクリル酸エステル及び/又はメタクリル酸エステルを乳
化重合の方法として行なわれる一括仕込み重合法、モノマー逐次添加重合法、乳
化モノマー逐次添加重合法、シード重合法等に付すことにより容易に製造するこ
とができる。
ここで、使用されるアクリル酸エステル、メタクリル酸エステル(以下、(メ
タ)アクリル酸エステルとする)モノマーとしては(メタ)アクリル酸メチルエ
ステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸ブチルエステ
ル、(メタ)アクリル酸2−エチルヘキシルエステル、(メタ)アクリル酸グリ
シジルエステル、(メタ)アクリル酸2−ヒドロキシエチルエステル等を挙げる
ことができ、これらを単独あるいは二種以上を混合して用いる。また、得られる
樹脂エマルジヨンの安定性を付与するため前記(メタ)アクリル酸エステルの一
部に換えて(メタ)アクリル酸を少量使用するのがよい。さらに所望により(メ
タ)アクリル酸エステル重合体の接着特性を損なわない程度において共重合可能
なモノマー、たとえば、酢酸ビニル、スチレン等を併用できる。これらアクリル
酸エステル、メタクリル酸エステルを主成分とする重合体のガラス転移温度は−
70〜0℃、好ましくは−60〜−10℃である。0℃を越える場合にはタツク
が著しく低下し好ましくない。アクリル系エマルジヨンに用いられる乳化剤には
アニオン系乳化剤、部分ケン化ポリビニルアルコール等が使用でき、その使用量
は重合体100重量部に対して0.1〜5重量部程度、好ましくは0.5〜3重
量部である。
他方、本発明組成物中の一成分たる高軟化点粘着付与剤樹脂エマルジヨンに用
いる高軟化点粘着付与剤樹脂としては、ロジン変性フエノール樹脂でなければな
らない。すなわち上記粘着付与剤樹脂を用いることにより本発明の目的が達成さ
れるのである。
ロジン変性フエノール樹脂は、プロトン酸、ルイス酸等の酸性触媒の存在下に
トール油ロジン、ウツドロジン及びガムロジンのいずれか少くとも一種100重
量部に対してフエノール75〜150重量部を付加反応させた後、水酸化カルシ
ウム等のアルカリにより中和、ろ過し、さらに250〜300℃の条件下に熱重
合させることにより得られる。このようにして得られた粘着付与剤樹脂の軟化点
は110〜150℃であるのが好ましく、特に110〜130℃が好ましい。軟
化点が110℃に満たない場合には、耐フラツギング性が劣る。150℃を越え
る場合にはタツクが著しく低下し、また相溶性が悪く濁りが生じる。
上記樹脂をエマルジヨン化するのに使用する乳化剤としてはα−オレフインス
ルホン化物、アルキルサルフエート、アルキルフエニルサルフエート、ポリオキ
シエチレンアルキルフエニルエーテルサルフエート、ポリオキシエチレンアラル
キルフエニルエーテルのスルホコハク酸のハーフエステル塩、ロジン石鹸等のア
ニオン系乳化剤、ポリオキシエチレンアルキルフエニルエーテル等のノニオン系
乳化剤を例示できる。また、乳化剤量は特に限定されないが樹脂100重量部に
対し、通常は固形分換算で1〜10重量部程度、好ましくは1〜5重量部である
。10重量部を越える場合には得られる粘着剤の耐水性が低下する。1重量部に
満たない場合には乳化時の樹脂エマルジヨンの安定性が悪くなる。
高軟化点粘着付与剤樹脂エマルジヨンは前記高軟化点粘着付与剤樹脂をベンゼ
ン、トルエン等の溶剤に溶解したのち前記乳化剤と軟水を添加し、高圧乳化機を
用いてエマルジヨン化した後減圧下に溶剤を除去する方法、または、樹脂の軟化
点が約90℃以下となるよう少量のベンゼン、トルエン等の溶剤を混合し、つづ
いて乳化剤を練り込み、さらに熱水を徐々に添加してゆき転相乳化させてエマル
ジヨンを得た後溶剤を減圧下に除去またはそのまま使用する方法、あるいはオー
トクレーブ中にて樹脂の軟化点以上に昇温して乳化剤を練り込み熱水を徐々に添
加してゆき転相乳化させてエマルジヨン化する方法等により得ることができ、い
ずれの方法によってもよい。
本発明の水性粘着剤組成物はアクリル系エマルジヨンの固形分換算量100重
量部に対して高軟化点粘着付与剤樹脂エマルジヨンの固形分換算量が5〜30重
量部程度の範囲で配合使用するのが好ましい。特に好ましいのは7〜15重量部
である。高軟化点粘着付与剤樹脂エマルジヨンの添加量が5重量部に満たない場
合には十分な密着性を付与することが困難となり、30重量部を越える場合には
密着性の低下のみならず粘着剤が固くなりタツクも低下するため好ましくない。
本発明の水性粘着剤組成物は必要に応じて消泡剤、増粘剤、充填剤、酸化防止
剤、耐水化剤、造膜助剤等を若干使用してもよい。
発明の効果
本発明の水性粘着剤組成物は、従来のアクリル系粘着剤の使用されていた種々
の用途に極めて好適に使用できる。殊にポリオレフイン基材特にその曲面に対す
る密着性が要求される分野において卓効を生じ、従来問題とされていたフラツギ
ングの現象が生ぜず、さらに透明性にも優れるため商品価値は高いものとなる。
実施例
以下、製造例、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明
はこれら各例に限定されるものではない。尚、各例中、部及び%は特記しない限
りすべて重量基準である。
製造例
(1) 水 44.46 部
(2) アニオン系乳化剤(「ハイテノールS」、 0.90 部
固形分50%、第一工業製薬(株)製)
(3) ブチルアクリレート 43.90 部
アクリル酸 1.36 部
(4) 触媒(過硫酸カリウム) 0.23 部
pH調整剤(重ソウ) 0.11 部
水 9.04 部
攪拌装置、冷却管、滴下ロート及び窒素導入管を備えた四つ口フラスコ中、7
0℃の窒素ガス気流下で上記(1)、(2)を溶解した後、攪拌下に(3)、(4)の1/10量
を添加し70℃で窒素ガス気流下にて30分間予備反応を行い、その後、(3)、(
4)の9/10量を2時間かけて滴下し、滴下重合を行なった。(3)、(4)の全量を滴下
し終わった後、1時間完結反応を70℃で行ない室温に冷却後100メツシユ金
網ろ過を行ないながら取出し、固形分45.7%のアクリルエマルジヨンを得た
。
実施例 1
軟化点147℃のロジン変性フエノール樹脂100部をトルエン60部に10
0℃にて約1時間溶解した後、80℃まで冷却してアニオン系乳化剤(ドデシル
ベンゼンスルホン酸ナトリウム)を固形分換算で3部及び水160部を添加し7
5℃にて1時間強攪拌し予備乳化を行なった、得られた予備乳化物を高圧乳化機
(マントンガウリン社製)により300kg/cm2の圧力で高圧乳化して乳化物を
得た。次いで、減圧蒸留装置に前記乳化物200部を仕込み50℃、100mmHg
の条件下に6時間減圧蒸留を行ない固形分50%のロジン変性フエノール樹脂エ
マルジヨンを得た。このようにして得たロジン変性フエノール樹脂エマルジヨン
10部(固形分換算)と前記製造例で得られたアクリルエマルジヨン90部(固
形分換算)を混合し、さらに、アクリル系の増粘剤として「プライマルASE−
60」(日本アクリル社製)0.5部(固形分換算)を添加しアンモニア水にて
増
粘させて水性粘着剤組成物を得た。 比
較例 1
実施例1において、ロジン変性フエノール樹脂に換えて脂肪族系石油樹脂(軟
化点100℃、「クイントンA−100」、日本ゼオン(株)製)を用いた他は
実施例1と全く同様の操作を行ないエマルジヨンを得た。また、同様の配合によ
り水性粘着剤組成物を得た。
比較例 2
実施例1において、ロジン変性フエノール樹脂に換えて芳香族系石油樹脂(軟
化点120℃、「ペトロジン120」、三井石油化学(株)製)を用いた他は実
施例1と全く同様の操作を行ないエマルジヨンを得た。また、同様の配合により
水性粘着剤組成物を得た。
比較例 3
実施例1において、ロジン変性フエノール樹脂に換えて不均化ロジンのグリセ
リンエステル(軟化点100℃、「スーパーエステルA−100」、荒川化学工
業(株)製)を用いた他は実施例1と全く同様の操作を行ないエマルジヨンを得
た。また、同様の配合により水性粘着剤組成物を得た。
比較例 4
実施例1において、ロジン変性フエノール樹脂に換えてマレイン化ロジンのグ
リセリンエステル(軟化点150℃、「マルキードNo.5」、荒川化学工業(株
)製)を用いた他は実施例1と全く同様の操作を行ないエマルジヨンを得た。ま
た、同様の配合により水性粘着剤組成物を得た。
比較例 5
実施例1において、ロジン変性フエノール樹脂に換えてポリテルペン樹脂(軟
化点115℃、「YX−レジンPx#1150」安原油脂化学工業(株)製)を
用いた他は実施例1と全く同様の操作を行ないエマルジヨンを得た。また、同様
の配合により水性粘着剤組成物を得た。
各実施例及び比較例にて調製した水性粘着剤組成物を乾燥後の糊厚が30μm
となるように厚さ40μmのポリエステルフイルムに塗布し、105℃の循風乾
燥器中にて3分間乾燥し、粘着シートを作成して各種試験を行なった結果を第1
表に示す。
各種試験は以下の方法による。
1.接着力:測定温度20℃、引張速度300mm/minで、180°剥離により
、接着力(g/cm)を測定した。被着体は、ステンレス板(SS)、ポリエチレ
ン板(PE)及びポリプロピレン板(PP)である。
2.タツク:JIS Z 0237に記載されたJ.Dow法により、傾斜度30
°、測定温度20℃で測定した。第1表中の数値はBall No.を示す。
3.凝集力:JIS C 2107により、貼付面積25×25mm2、荷重1kg
で、ステンレス板に対する40℃での1時間後のずれ(mm)を測定した。
4.フラツギング性:φ16mmのPP曲面に20×20mm2の粘着シートを貼り
付け30日後の耐フラツギング性を保持率((フラツギングを起こしていない個
数/全個数)×100%)で示す。
5.シートの濁り:乾燥後の粘着シートを目視で判定した。濁りのあるものは×
、濁りのないものは○で表示した。
Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aqueous pressure-sensitive adhesive composition having excellent adhesion to polyolefin and excellent transparency. Conventional technology and its problems Adhesives are usually applied to paper, plastic film, etc., and tapes, sheets,
This is applied to labels and the like. Aqueous emulsion-type pressure-sensitive adhesives have various advantages compared to organic solvent-type pressure-sensitive adhesives, such as no air pollution, excellent safety and health, and suitability for resource saving. From water to an aqueous emulsion type. Thus, as the application of the aqueous emulsion type adhesive expands, the required performance also becomes higher, and one of such required performances is adhesion to polyolefin base materials such as polypropylene and polyethylene, particularly to the curved surface, that is, anti-flagging properties. It is valued. Here, the anti-flagging property means that a tape or a label does not peel off over time. Applications requiring such performance include, for example, high-quality beautiful labels for foods and cosmetics, quality indication labels for electric appliances, etc., supermarket price labels, office computer labels, adhesive sheets, adhesive tapes, and the like. . Further, when used for a transparent film, transparency of the pressure-sensitive adhesive sheet is required in addition to the problem of anti-flagging. Conventionally, it has been carried out to improve the adhesion to a polyolefin substrate by blending an emulsion of a tackifier resin such as a glycerin ester of disproportionated rosin into an acrylic polymer emulsion, but in this case, the adhesion is improved. Some improvements can be made, but the flagging problem has not yet been improved. Further, even if the problem of the flagging property can be improved to some extent, the adhesive sheet may become turbid and cannot be used for applications requiring transparency such as a transparent film. That is,
Aqueous emulsion adhesives satisfying the required performance have not yet been obtained. Means for Solving the Problems In view of the above problems of the aqueous pressure-sensitive adhesive composition obtained by blending the tackifier resin emulsion with the existing acrylic emulsion, the present inventors have proposed a water-based pressure-sensitive adhesive polyolefin. In the case of using a specific high softening point tackifier resin emulsion as a tackifier resin, as a result of intensive studies to improve the adhesiveness of the substrate, particularly its curved surface, that is, the problem of flagging resistance, and to improve the transparency of the pressure-sensitive adhesive sheet. It has been found that not only adhesiveness to a polyolefin plane but also adhesiveness to a polyolefin curved surface and transparency of a pressure-sensitive adhesive sheet can be imparted at the same time, and the present invention has been completed. That is, the present invention relates to (1) an acrylic polymer emulsion containing acrylic acid ester and / or methacrylic acid ester as a main component and (2) a tackifier resin which is a rosin-modified phenol resin , and has a softening point of 11
A water-based pressure-sensitive adhesive composition comprising a resin emulsion at 0 to 150 ° C. As the acrylic polymer emulsion used in the present invention, emulsions generally used for various acrylic pressure-sensitive adhesives can be used. The acrylic polymer emulsion is usually subjected to a batch charge polymerization method, a monomer sequential addition polymerization method, an emulsion monomer sequential addition polymerization method, a seed polymerization method, etc., which are usually performed as an emulsion polymerization method of an acrylic ester and / or a methacrylic ester. Thus, it can be easily manufactured. Here, the acrylic acid ester and methacrylic acid ester (hereinafter, referred to as (meth) acrylic acid ester) monomers used are (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid butyl ester. Examples thereof include esters, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and these may be used alone or in combination of two or more. Further, it is preferable to use a small amount of (meth) acrylic acid instead of a part of the (meth) acrylic ester in order to impart stability to the obtained resin emulsion. If desired, a copolymerizable monomer such as vinyl acetate or styrene can be used in combination to the extent that the adhesive properties of the (meth) acrylate polymer are not impaired. The glass transition temperature of these acrylic acid and methacrylic acid ester-based polymers is −
The temperature is 70 to 0C, preferably -60 to -10C. If the temperature exceeds 0 ° C., the tack is remarkably reduced, which is not preferable. As the emulsifier used for the acrylic emulsion, an anionic emulsifier, partially saponified polyvinyl alcohol, or the like can be used, and the amount of the emulsifier is about 0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer. 3 parts by weight. On the other hand, as the high softening point tackifier resin used in the one component serving high softening point tackifier resin Emarujiyon in the composition of the present invention must be a rosin-modified phenolic resins. That is, the object of the present invention is achieved by using the above tackifier resin. The rosin-modified phenolic resin is obtained by adding 75 to 150 parts by weight of phenol to at least 100 parts by weight of at least one of tall oil rosin, utsdrozine and gum rosin in the presence of an acidic catalyst such as protonic acid and Lewis acid. , neutralized with an alkali such as calcium hydroxide, filtered, it can be obtained by further thermal polymerization under the conditions of 250 to 300 ° C.. The softening point of the tackifier resin obtained as this is preferably a 110 to 150 ° C., in particular 110-130 ° C. are preferred. When the softening point is less than 110 ° C., the anti-flagging property is poor. When the temperature exceeds 150 ° C., the tack is remarkably reduced, and the compatibility is poor and turbidity occurs. Examples of the emulsifier used for emulsifying the above resin include α-olefin sulfonate, alkyl sulfate, alkyl phenyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, and polyoxyethylene aralkyl phenyl ether sulfosuccinic acid. Examples include anionic emulsifiers such as half ester salts and rosin soaps, and nonionic emulsifiers such as polyoxyethylene alkyl phenyl ether. The amount of the emulsifier is not particularly limited, but is usually about 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin. When the amount exceeds 10 parts by weight, the water resistance of the obtained pressure-sensitive adhesive decreases. If the amount is less than 1 part by weight, the stability of the resin emulsion at the time of emulsification becomes poor. The high softening point tackifier resin emulsion is obtained by dissolving the high softening point tackifier resin in a solvent such as benzene and toluene, adding the emulsifier and soft water, emulsifying the mixture using a high-pressure emulsifier, and then removing the solvent under reduced pressure. Alternatively, a small amount of a solvent such as benzene or toluene is mixed so that the softening point of the resin is about 90 ° C. or less, then the emulsifier is kneaded, and hot water is gradually added, and phase inversion is continued. After emulsifying to obtain an emulsion, the solvent is removed under reduced pressure or used as it is, or in an autoclave, the temperature is raised above the softening point of the resin, the emulsifier is kneaded, and hot water is gradually added, followed by phase inversion. It can be obtained by a method of emulsifying and emulsifying, or any other method. The aqueous pressure-sensitive adhesive composition of the present invention is blended and used in a range of about 5 to 30 parts by weight of a high softening point tackifier resin emulsion based on 100 parts by weight of the solid content of the acrylic emulsion. Is preferred. Particularly preferred is 7 to 15 parts by weight. When the amount of the high softening point tackifier resin emulsion is less than 5 parts by weight, it is difficult to impart sufficient adhesiveness. Is not preferred because the hardness becomes high and the tack decreases. The aqueous pressure-sensitive adhesive composition of the present invention may optionally contain a small amount of an antifoaming agent, a thickener, a filler, an antioxidant, a water-proofing agent, a film-forming aid, and the like. Effect of the Invention The water-based pressure-sensitive adhesive composition of the present invention can be used very suitably for various uses in which conventional acrylic pressure-sensitive adhesives have been used. Particularly, a polyolefin base material, particularly in the field where its adhesiveness to a curved surface is required, has an excellent effect, does not cause the phenomenon of flagging, which has been conventionally regarded as a problem, and is excellent in transparency, so that its commercial value is high. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to each of these examples. In each example, all parts and percentages are by weight unless otherwise specified. Production Example (1) 44.46 parts of water (2) Anionic emulsifier (“HITENOL S”, 0.90 part, solid content 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (3) Butyl acrylate 43.90 parts Acrylic acid 1.36 parts (4 ) Catalyst (potassium persulfate) 0.23 parts pH adjuster (heavy sodium) 0.11 parts Water 9.04 parts In a four-necked flask equipped with a stirrer, cooling tube, dropping funnel and nitrogen inlet tube, 7 parts
After dissolving the above (1) and (2) under a nitrogen gas stream at 0 ° C., add 1/10 amount of (3) and (4) under stirring, and at 70 ° C. under a nitrogen gas stream for 30 minutes Preliminary reaction was performed, and then (3), (
9/10 amount of 4) was added dropwise over 2 hours to carry out dropwise polymerization. After the dropwise addition of all of (3) and (4), the reaction was completed at 70 ° C. for 1 hour, cooled to room temperature, and then taken out while performing 100 mesh wire mesh filtration to obtain an acrylic emulsion having a solid content of 45.7%. Was. Example 1 100 parts of a rosin-modified phenol resin having a softening point of 147 ° C. was added to 60 parts of toluene by 10 parts.
After dissolving at 0 ° C. for about 1 hour, the mixture was cooled to 80 ° C., and 3 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) in terms of solid content and 160 parts of water were added.
Preliminary emulsification was carried out by vigorous stirring at 5 ° C. for 1 hour. The resulting preliminarily emulsified product was emulsified at a pressure of 300 kg / cm 2 by a high pressure emulsifier (manufactured by Manton Gaulin) to obtain an emulsified product. Next, 200 parts of the emulsion was charged into a vacuum distillation apparatus at 50 ° C. and 100 mmHg.
The mixture was distilled under reduced pressure for 6 hours to obtain a rosin-modified phenol resin emulsion having a solid content of 50%. 10 parts (in terms of solid content) of the rosin-modified phenolic resin emulsion thus obtained and 90 parts (in terms of solid content) of the acrylic emulsion obtained in the above Production Example were mixed, and further, as an acrylic thickener, Primal ASE-
60 "(manufactured by Nippon Acrylic Co., Ltd.) in an amount of 0.5 part (in terms of solid content), and the mixture was thickened with aqueous ammonia to obtain an aqueous pressure-sensitive adhesive composition . In the specific Comparative Examples 1 Example 1, instead of the rosin-modified phenolic resin aliphatic petroleum resin (softening point 100 ° C., "Quinton A-100", Nippon Zeon Co., Ltd.) was used in Example 1 The same operation was performed to obtain an emulsion. Further, an aqueous pressure-sensitive adhesive composition was obtained by the same blending. Comparative Example 2 The same as Example 1 except that an aromatic petroleum resin (softening point: 120 ° C., “Petrogin 120”, manufactured by Mitsui Petrochemical Co., Ltd.) was used instead of the rosin-modified phenol resin. Was carried out to obtain an emulsion. Further, an aqueous pressure-sensitive adhesive composition was obtained by the same blending. Comparative Example 3 In Example 1, glycerin ester of disproportionated rosin (softening point: 100 ° C., “Superester A-100”, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of the rosin-modified phenol resin. The same operation as in Example 1 was performed to obtain an emulsion. Further, an aqueous pressure-sensitive adhesive composition was obtained by the same blending. Comparative Example 4 The procedure of Example 1 was repeated, except that the rosin-modified phenolic resin was replaced with a glycerin ester of maleated rosin (softening point 150 ° C., “Marquid No. 5”, manufactured by Arakawa Chemical Industries, Ltd.). The same operation was performed to obtain an emulsion. Further, an aqueous pressure-sensitive adhesive composition was obtained by the same blending. Comparative Example 5 In Example 1, a polyterpene resin (softening point 115 ° C., “YX-Resin Px # 1150” manufactured by Yasuhara Yushi Kagaku Kogyo Co., Ltd.) was used in place of the rosin-modified phenol resin. The same operation was performed to obtain an emulsion. Further, an aqueous pressure-sensitive adhesive composition was obtained by the same blending. The adhesive thickness after drying of the aqueous pressure-sensitive adhesive composition prepared in each of Examples and Comparative Examples is 30 μm
It was applied to a polyester film having a thickness of 40 μm so as to obtain an adhesive sheet and dried in a circulating drier at 105 ° C. for 3 minutes to prepare a pressure-sensitive adhesive sheet and subjected to various tests. Various tests are performed according to the following methods. 1. Adhesive force: Adhesive force (g / cm) was measured by 180 ° peeling at a measuring temperature of 20 ° C. and a tensile speed of 300 mm / min. The adherend is a stainless steel plate (SS), a polyethylene plate (PE) and a polypropylene plate (PP). 2. Tack: J. described in JIS Z 0237. According to the Dow method, the inclination is 30
° and a measurement temperature of 20 ° C. The numerical values in Table 1 indicate Ball No. 3. Cohesive force: According to JIS C 2107, application area 25 × 25 mm 2 , load 1 kg
Then, the deviation (mm) after 1 hour at 40 ° C. with respect to the stainless steel plate was measured. 4. Flanging property: Fragging resistance after 30 days after sticking a 20 × 20 mm 2 pressure-sensitive adhesive sheet to a φ16 mm PP curved surface is indicated by a retention rate ((number of non-flagging / total number) × 100%). 5. Sheet turbidity: The dried adhesive sheet was visually judged. Those with cloudiness are ×
And those without cloudiness were indicated by ○.
Claims (1)
リル系重合体エマルジヨンと (2) ロジン変性フエノール樹脂である粘着付与剤樹脂で、かつその軟化点が1
10〜150℃である樹脂エマルジヨン とからなることを特徴とする水性粘着剤組成物。 アクリル系重合体エマルジヨン100重量部(固形分換算)に対して粘着付
与剤樹脂の樹脂エマルジヨンを5〜30重量部(固形分換算)配合してなる特許
請求の範囲第1項記載の水性粘着剤組成物。Claims: (1) An acrylic polymer emulsion mainly composed of an acrylate ester and / or a methacrylate ester, and (2) a tackifier resin which is a rosin-modified phenol resin having a softening point of 1
An aqueous pressure-sensitive adhesive composition comprising: a resin emulsion having a temperature of 10 to 150 ° C. 2. The aqueous pressure-sensitive adhesive according to claim 1, wherein the resin emulsion of the tackifier resin is blended in an amount of 5 to 30 parts by weight (solid content) with respect to 100 parts by weight (solid content) of the acrylic polymer emulsion. Composition.
Family
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