JPS6223794B2 - - Google Patents
Info
- Publication number
- JPS6223794B2 JPS6223794B2 JP4636378A JP4636378A JPS6223794B2 JP S6223794 B2 JPS6223794 B2 JP S6223794B2 JP 4636378 A JP4636378 A JP 4636378A JP 4636378 A JP4636378 A JP 4636378A JP S6223794 B2 JPS6223794 B2 JP S6223794B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- mol
- sulfonic acid
- adhesive according
- containing monomer
- 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
Links
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- -1 olefin sulfonic acid alkali salt Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical group FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000123 paper Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000007757 hot melt coating Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229940049920 malate Drugs 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- JAXRXOLOMNDJGH-UHFFFAOYSA-M sodium;propane-1-sulfonate;prop-2-enamide Chemical compound [Na+].NC(=O)C=C.CCCS([O-])(=O)=O JAXRXOLOMNDJGH-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は基材がなかんずく紙である場合に特徴
を発揮する水溶性で、かつホツトメルト性を有す
る感圧粘着剤に関するものである。
感圧粘着剤は、包装用テープの裏のり、各種紙
袋の封緘用のり、各種ラベルの裏のり、シールテ
ープ用裏のり、ワツペンの裏のりなどに広く用い
られている。
従来上記用途に用いられている感圧粘着剤とし
ては、天然ゴム類を有機溶剤に溶解したもの、ア
クリル系樹脂を有機溶剤に溶解したものなどがあ
るが、これらはいずれも有機溶剤に可溶化したの
ち、基材上にコーテングし、乾燥により溶剤を除
しなければならず、かかる工程が経済的不利を招
くものであり、さらに水不溶性のものであるか
ら、ラベルなどを剥離したあとの樹脂が取り除き
がたい、さらに基材が紙の場合古紙回収に際し
て、樹脂がガムアツプして過工程に於いてフイ
ルターの目詰りを引き起こしたり、また製品に混
入して斑点となり、不良品を多発せしめるなどの
欠点を有している。
本発明者らは、かかる従来技術の問題の解決の
ために鋭意検討を加えた結果、酢酸ビニルと共重
合可能なオレフインスルホン酸、オレフインスル
ホン酸アルカリ塩、カルボキシル基含有単量体、
アミド基含有単量体、Ｎ−ビニルピロリドン単独
又は２種以上の混合物と酢酸ビニルとを特定の比
率で共重合した共重合体のケン化物は、従来の天
然ゴム類、アクリル系樹脂が水不溶性であるのに
対して水溶性であるばかりでなく、ポリビニルア
ルコールよりも水溶性が向上すること、さらに粘
着附与剤を配合することによつて、より粘着接着
性が優れたものとなることを見い出し、本発明を
完成するにいたつたのである。
本発明によれば、以下の如き顕著なる効果を奏
することが出来るものである。
１ ホツトメルトコーテイング工程が採用出来る
ため、従来の溶剤型のような乾燥、溶剤回収工
程が不要となり、生産性が向上し、コストダウ
ンが図られる。
２ 水溶性であるため古紙回収の妨害とならな
い。
３ 水溶性であるためラベルなどを剥離後樹脂の
除去が容易に且つ完全に出来て、被接着体を汚
染しない。
４ 加熱圧着せずとも、常温にて少しの加圧によ
つて接着が可能である。
５ 水溶性であることによつて、被接着体が濡れ
たものであつても容易に接着できる。
しかして本発明に用いられる共重合体は酢酸ビ
ニル成分が80〜99.9モル％、前記特定の共重合性
単量体成分が20〜0.1モル％の共重合体でなけれ
ばならず、共重合性単量体の比率が0.1モル％未
満では極度に水分散性ないし水溶解性が低下し使
用に耐えない。これら共重合体の重合度は30〜
1500の範囲のものが望ましく、特に好ましくは
150〜600である。30未満では接着性が低下し、
1500を越える場合は溶融粘度が高すぎて作業性が
低下する傾向があり好ましくない。
またかかる共重合体中の酢酸ビニル成分の100
モル％以下、好ましくは80モル％以下、特に好ま
しくは30〜60モル％をケン化したケン化物は、溶
融流動性と水分散性ないし水溶解性とのバランス
がとれたものとなる、などの点で未ケン化物より
も一段優れている。
本発明に於いては、前記共重合性単量体を１種
のみならず、２種以上併用してもよく、また得ら
れた共重合体ケン化物は１種のみならず、２種以
上併用してもよい。さらに水溶性可塑剤を配合す
ることが、溶融流動性などをおぎなう点で望まし
い。
本発明で用いられるオレフインスルホン酸とし
ては、アリルスルホン酸、メタアリルスルホン
酸、エチレンスルホン酸、スルホン酸マレートな
どがあげられ、オレフインスルホン酸アルカリ塩
としては、アリルスルホン酸ソーダ、メタアリル
スルホン酸ソーダ、エチレンスルホン酸ソーダ、
スルホン酸ソーダ（メタ）アクリレート、スルホ
ン酸ソーダ（モノアルキル）マレート、ジスルホ
ン酸ソーダアルキルマレートなどがあげられる。
該単量体による変性度は0.1〜20.0モル％の範囲
である。
本発明に用いられるカルボキシル基含有単量体
としては、マレイン酸、無水マレイン酸、クロト
ン酸、アクリル酸、メタクリル酸、マレイン酸の
半エステルなどがあげられる。該単量体による変
性度は0.1〜20.0モル％の範囲である。
本発明に用いられるアミド基含有単量体として
は、Ｎ−メチロールアクリルアミド、アクリルア
ミド、アクリルアミドアルキルスルホン酸アルカ
リ塩、例えばアクリルアミドプロピルスルホン酸
ソーダ、２−アクリルアミド−２−メチルプロパ
ンスルホン酸ソーダなどがあげられ、該単量体に
よる変性度は0.1〜20.0モル％の範囲である。
本発明に用いられる他の単量体としては、Ｎ−
ビニルピロリドン、Ｎ−ビニルピロリドン誘導体
などがあげられ、さらに（メタ）アクリル酸エス
テルも使用出来る。該単量体による変性度は0.1
〜10.0モル％の範囲である。
本発明に用いられる水溶性可塑剤としては、エ
チレングリコール、ヘキサメチルグリコール、プ
ロピレングリコール、ポリエチレングリコール、
グリセリン、ジグリセリン、トリメチロールプロ
パン、ペンタエリスリトール、キシリツト、アラ
ビツト、アドニツト、マンニツト、ソルビツト、
ダルシツトなどの多価アルコール類またはこれら
の高級脂肪酸エステル類、及びこれらにエチレン
オキサイド又はプロピレンオキサイドを附加した
附加物、エチレン尿素などの尿素誘導体、フタル
酸エステル類など樹脂と相溶性のよいものがあげ
られ、該可塑剤の添加量としては樹脂100重量部
に対して１重量部〜100重量部であり好ましくは
５重量部〜30重量部である。
本発明に用いられる粘着附与剤とれては、ロジ
ン類、ロジンエステル化物、ピネン系ポリマー、
水添石油樹脂、炭化水素樹脂、及びソルビタン脂
肪酸エステル、ポリオキシエチレンソルビタン脂
肪酸エステル、３−メチルペンタン−1.3.5−ト
リオールなどがあげられ、該粘着附与剤の添加量
としては、樹脂100重量部に対して１〜100重量
部、好ましくは10〜60重量部である。
本発明によつて得られた粘着剤を用いて粘着シ
ート、フイルムを製造する場合は、温度100℃〜
250℃にて樹脂を溶解し、樹脂に添加剤などを加
えて粘度500〜10000センチポイズとし、ロールコ
ーター、ドクターコーターなどによつて基材にコ
ーテイング又はスプレーすることによつて、容易
に得られる。得られた粘着テープ、フイルムは、
加熱圧着する必要は全くなく、常温で、指圧程度
の圧力を加えることによつて、被着体、例えば
紙、木材、ガラス、金属、布、プラスチツクス、
果物などの表面に接着することができるものであ
る。また基材は紙の場合特に好ましいが、これに
限定されることがなく、ホツトメルトコーテング
時の温度に耐えうるもの、即ちホツトメルトコー
テング時に、変形したり、溶融したりするもの以
外のものは、すべて用いることが出来る。
次に実施例によつて本発明を具体的に説明す
る。
実施例 １
アリルスルホン酸ソーダで2.0モル変性された
重合度250ケン化度50モル％の変性PVA100部
（重量部、以下同様）、３−メチルペンタン−
1.3.5−トリオール50部を170℃で混合機により溶
融混合して感圧粘着剤を調製した。得られた粘着
剤は粘着力注(1)が20℃、65％RHでNO25、20℃、
98％RHでNO23、水溶解性注(2)は５分で完溶しホ
ツトメルト作業性、粘着力、水溶解性のいずれも
優れた性質を示した。
実施例 ２〜12
実施例２ではアリルスルホン酸で3.0モル％変
性された変性PVAを用い、実施例３ではマレイ
ン酸で、10.0モル％変性された変性PVAを用い、
実施例４では無水マレイン酸で5.0モル％変性さ
れた変性PVAを用い、実施例５ではクロトン酸
で10.0モル％変性されたPVAを用い、実施例６で
はアクリル酸で5.0モル％変性された変性PVAを
用い、実施例７ではメタクリル酸で7.0モル％変
性された変性PVAを用い、実施例８ではアクリ
ルアミドで15.0モル％変性された変性PVAを用
い、実施例９ではアクリルアミドプロピルスルホ
ン酸ソーダで5.0モル％変性された変性PVAを用
い、実施例10ではＮ−ビニルピロリドンで5.0モ
ル％変性された変性PVAを用い、さらに実施例
11ではＮ−ビニルピロリドンで2.0モル％、マレ
イン酸3.0モル％変性されれ変性PVAを用い、実
施例12ではアリルスルホン酸ソーダで2.0モル％
変性された変性PVA50部とマレイン酸で3.0モル
％変性された変性PVA50部との混合物を用い
て、実施例１と同様に接着力、水溶解性を測定
し、表−１に示した。
対照例
天然ゴムをｎ−ヘキサンに溶解した溶液を実施
例１の変性PVAに代えて用いた。得られた粘着
剤は粘着力が20℃、65％RHでNO6、20℃、98％
RHでNO3で非常に弱く、水溶解性は水に浸漬す
るとただちにガムアツプして凝集し溶解は全くな
かつた。
注(1)粘着力
ポリエステルフイルム100mm×100mmの面積で粘
着剤を塗布量120ｇ／m2の割合で塗布し、T.Dow
式ボールタツク測定機で測定角度30゜に設定し、
助走距離100mm、粘着測定距離100mmで鋼球が静止
した時のボールで粘着力を測定し、測定鋼球のボ
ールHOで粘着力を表わした。
注(2)粘着剤の水溶解性
粘着剤を塗布量120ｇ／m2で塗布したポリエス
テルフイルム片（20mm×20mm×0.1mm）を30℃の
水に浸漬した時の粘着剤の経時変化を観察した。
The present invention relates to a pressure-sensitive adhesive that is water-soluble and has hot-melt properties, particularly when the base material is paper. Pressure-sensitive adhesives are widely used as adhesives on the backs of packaging tapes, adhesives for sealing various paper bags, adhesives on the backs of various labels, adhesives on the backs of sealing tapes, adhesives on the backs of badges, etc. Pressure-sensitive adhesives conventionally used for the above applications include those made by dissolving natural rubbers in organic solvents, and those made by dissolving acrylic resins in organic solvents; After that, the resin must be coated on the substrate and the solvent must be removed by drying, which is an economically disadvantageous process.Furthermore, since the resin is water-insoluble, the resin after peeling off the label, etc. Furthermore, when the base material is paper, when collecting used paper, the resin may gum up and cause filter clogging during over-processing, or it may get mixed into the product and cause spots, resulting in a large number of defective products. It has drawbacks. As a result of intensive studies to solve the problems of the prior art, the present inventors discovered that olefin sulfonic acid copolymerizable with vinyl acetate, an alkali salt of olefin sulfonic acid, a carboxyl group-containing monomer,
A saponified copolymer made by copolymerizing an amide group-containing monomer, N-vinylpyrrolidone alone or a mixture of two or more and vinyl acetate at a specific ratio, is water-insoluble compared to conventional natural rubbers and acrylic resins. However, it is not only water-soluble, but also has improved water solubility than polyvinyl alcohol, and by adding an adhesion agent, it has even better adhesive properties. This led to the completion of the present invention. According to the present invention, the following remarkable effects can be achieved. 1. Since a hot melt coating process can be adopted, the drying and solvent recovery processes required for conventional solvent-based coatings are not required, improving productivity and reducing costs. 2 Since it is water soluble, it does not interfere with waste paper collection. 3. Because it is water-soluble, the resin can be easily and completely removed after peeling off labels, etc., and does not contaminate the adhered object. 4. Bonding is possible with a slight pressure at room temperature without heat-pressing. 5. Because it is water-soluble, it can be easily bonded even if the object to be bonded is wet. Therefore, the copolymer used in the present invention must have a vinyl acetate component of 80 to 99.9 mol% and a copolymerizable monomer component of 20 to 0.1 mol%. If the monomer ratio is less than 0.1 mol%, the water dispersibility or water solubility will be extremely low and it will not be usable. The degree of polymerization of these copolymers is 30~
1500 range is desirable, particularly preferably
It is 150-600. If it is less than 30, the adhesion will decrease,
If it exceeds 1500, the melt viscosity is too high and workability tends to decrease, which is not preferable. Also, 100% of the vinyl acetate component in such copolymers.
A saponified product saponified in mol% or less, preferably 80 mol% or less, particularly preferably 30 to 60 mol%, has a well-balanced melt fluidity and water dispersibility or water solubility. In this respect, it is much better than unsaponified products. In the present invention, the above copolymerizable monomers may be used not only alone, but also in combination of two or more types, and the resulting saponified copolymer may be used not only in one type but also in combination of two or more types. You may. Furthermore, it is desirable to incorporate a water-soluble plasticizer in order to improve melt fluidity. Examples of the olefin sulfonic acid used in the present invention include allyl sulfonic acid, meta-allyl sulfonic acid, ethylene sulfonic acid, and sulfonic acid malate, and examples of the alkali salts of olefin sulfonate include sodium allyl sulfonate and sodium meta-allyl sulfonate. , sodium ethylene sulfonate,
Examples include sodium sulfonate (meth)acrylate, sodium sulfonate (monoalkyl)malate, and sodium disulfonate alkyl maleate.
The degree of modification by the monomer is in the range of 0.1 to 20.0 mol%. Examples of the carboxyl group-containing monomer used in the present invention include maleic acid, maleic anhydride, crotonic acid, acrylic acid, methacrylic acid, and half esters of maleic acid. The degree of modification by the monomer is in the range of 0.1 to 20.0 mol%. Examples of the amide group-containing monomer used in the present invention include N-methylol acrylamide, acrylamide, alkali salts of acrylamide alkyl sulfonate, such as sodium acrylamide propyl sulfonate, sodium 2-acrylamide-2-methylpropanesulfonate, and the like. , the degree of modification by the monomer is in the range of 0.1 to 20.0 mol%. Other monomers used in the present invention include N-
Examples include vinylpyrrolidone and N-vinylpyrrolidone derivatives, and (meth)acrylic acid esters can also be used. The degree of modification by this monomer is 0.1
It is in the range of ~10.0 mol%. Examples of water-soluble plasticizers used in the present invention include ethylene glycol, hexamethyl glycol, propylene glycol, polyethylene glycol,
Glycerin, diglycerin, trimethylolpropane, pentaerythritol, xylitol, arabite, adonite, mannite, sorbitol,
Examples include polyhydric alcohols such as dulcite, higher fatty acid esters thereof, additives of these with ethylene oxide or propylene oxide, urea derivatives such as ethylene urea, and phthalate esters that are compatible with resins. The amount of the plasticizer added is 1 part by weight to 100 parts by weight, preferably 5 parts by weight to 30 parts by weight, per 100 parts by weight of the resin. The tackifying agents used in the present invention include rosins, rosin esters, pinene polymers,
Examples include hydrogenated petroleum resins, hydrocarbon resins, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, 3-methylpentane-1.3.5-triol, etc. The amount of the tackifier added is based on 100% of the weight of the resin. 1 to 100 parts by weight, preferably 10 to 60 parts by weight. When producing adhesive sheets and films using the adhesive obtained by the present invention, the temperature is 100°C to
It can be easily obtained by melting the resin at 250°C, adding additives, etc. to the resin to give a viscosity of 500 to 10,000 centipoise, and coating or spraying it on a substrate using a roll coater, doctor coater, etc. The obtained adhesive tape and film are
There is no need to heat and press, and by applying pressure similar to finger pressure at room temperature, the adherend can be bonded, such as paper, wood, glass, metal, cloth, plastics, etc.
It can be attached to surfaces such as fruits. In addition, the base material is particularly preferably paper, but is not limited to this, and materials that can withstand the temperature during hot melt coating, that is, those that do not deform or melt during hot melt coating, are recommended. , all can be used. Next, the present invention will be specifically explained with reference to Examples. Example 1 100 parts (parts by weight, same hereinafter) of modified PVA with a degree of polymerization of 250 and a degree of saponification of 50 mol% modified with 2.0 mol of sodium allylsulfonate, 3-methylpentane-
A pressure-sensitive adhesive was prepared by melt-mixing 50 parts of 1.3.5-triol using a mixer at 170°C. The obtained adhesive has an adhesive strength (1) of NO25 at 20℃ and 65%RH, 20℃,
At 98% RH, NO23 and water solubility Note (2) were completely dissolved in 5 minutes and exhibited excellent properties in terms of hot melt workability, adhesive strength, and water solubility. Examples 2 to 12 In Example 2, modified PVA modified with 3.0 mol% of allyl sulfonic acid was used, and in Example 3, modified PVA modified with 10.0 mol% of maleic acid was used.
Example 4 uses modified PVA modified with 5.0 mol% maleic anhydride, Example 5 uses PVA modified with 10.0 mol% crotonic acid, and Example 6 uses modified PVA modified with 5.0 mol% acrylic acid. In Example 7, modified PVA modified with 7.0 mol% of methacrylic acid was used, in Example 8, modified PVA modified with 15.0 mol% of acrylamide was used, and in Example 9, modified PVA modified with 7.0 mol% of methacrylic acid was used, and in Example 9, modified PVA was modified with 5.0 mol% of sodium acrylamide propylsulfonate. In Example 10, modified PVA modified with 5.0 mole % of N-vinylpyrrolidone was used, and in Example
In Example 11, modified PVA was modified with 2.0 mol% of N-vinylpyrrolidone and 3.0 mol% of maleic acid, and in Example 12, 2.0 mol% of sodium allylsulfonate was used.
Using a mixture of 50 parts of modified PVA and 50 parts of modified PVA modified with 3.0 mol % maleic acid, the adhesive strength and water solubility were measured in the same manner as in Example 1, and the results are shown in Table 1. Control Example A solution of natural rubber dissolved in n-hexane was used in place of the modified PVA in Example 1. The adhesive strength obtained is NO6 at 20℃, 65%RH, 98% at 20℃
It was very weak at RH and NO3, and its water solubility immediately gummed up and agglomerated when immersed in water, and there was no dissolution at all. Note (1) Adhesive strength Apply adhesive at a rate of 120 g/m 2 to a polyester film 100 mm x 100 mm, and apply T.Dow
Set the measurement angle to 30° with a ball-tack measuring machine,
The adhesion force was measured with the steel ball at rest at a run-up distance of 100 mm and an adhesion measurement distance of 100 mm, and the adhesion force was expressed by the ball HO of the measured steel ball. Note (2) Water solubility of adhesive A piece of polyester film (20 mm x 20 mm x 0.1 mm) coated with adhesive at a coating amount of 120 g/m 2 was immersed in water at 30°C and the change in adhesive over time was observed. did.
【表】【table】
Claims (1)
ン酸、オレフインスルホン酸アルカリ塩、カルボ
キシル基含有単量体、アミド基含有単量体、Ｎ−
ビニルピロリドンからなる群より選ばれた１種又
は２種以上の単量体0.1〜20モル％と酢酸ビニル
99.9〜80モル％との共重合体ケン化物に粘着附与
剤を配合してなる感圧粘着剤。 ２ オレフインスルホン酸がアリルスルホン酸、
ビニルスルホン酸である特許請求の範囲第１項記
載の粘着剤。 ３ オレフインスルホン酸アルカリ塩がアリルス
ルホン酸ソーダ、ビニルスルホン酸ソーダである
特許請求の範囲第１項記載の粘着剤。 ４ カルボキシル基含有単量体が、マレイン酸、
無水マレイン酸、クロトン酸、アクリル酸、メタ
クリル酸、マレイン酸半エステルである特許請求
の範囲第１項記載の粘着剤。 ５ アミド基含有単量体が、Ｎ−メチロールアク
リルアミド、アクリルアミド、アクリルアミドア
ルキルスルホン酸アルカリ塩である特許請求の範
囲第１項記載の粘着剤。 ６ 粘着附与剤がロジン類、ロジンエステル化合
物、水添石油樹脂、ピネン系ポリマー、炭化水素
樹脂、３−メチルペンタン−１，３，５−トリオ
ールである特許請求の範囲第１項記載の粘着剤。[Claims] 1. Olefin sulfonic acid copolymerizable with vinyl acetate, olefin sulfonic acid alkali salt, carboxyl group-containing monomer, amide group-containing monomer, N-
0.1 to 20 mol% of one or more monomers selected from the group consisting of vinylpyrrolidone and vinyl acetate
A pressure-sensitive adhesive comprising a saponified copolymer of 99.9 to 80 mol% and a tackifying agent. 2 Olefin sulfonic acid is allyl sulfonic acid,
The adhesive according to claim 1, which is vinylsulfonic acid. 3. The adhesive according to claim 1, wherein the alkali salt of olefin sulfonate is sodium allylsulfonate or sodium vinylsulfonate. 4 The carboxyl group-containing monomer is maleic acid,
The adhesive according to claim 1, which is maleic anhydride, crotonic acid, acrylic acid, methacrylic acid, or maleic acid half ester. 5. The pressure-sensitive adhesive according to claim 1, wherein the amide group-containing monomer is N-methylol acrylamide, acrylamide, or acrylamide alkyl sulfonic acid alkali salt. 6. The adhesive according to claim 1, wherein the tackifier is a rosin, a rosin ester compound, a hydrogenated petroleum resin, a pinene polymer, a hydrocarbon resin, or 3-methylpentane-1,3,5-triol. agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4636378A JPS54138035A (en) | 1978-04-18 | 1978-04-18 | Pressure sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4636378A JPS54138035A (en) | 1978-04-18 | 1978-04-18 | Pressure sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54138035A JPS54138035A (en) | 1979-10-26 |
| JPS6223794B2 true JPS6223794B2 (en) | 1987-05-25 |
Family
ID=12745062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4636378A Granted JPS54138035A (en) | 1978-04-18 | 1978-04-18 | Pressure sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54138035A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6144940A (en) * | 1984-08-09 | 1986-03-04 | Kuraray Co Ltd | Polyvinyl alcohol film |
| JPH06256740A (en) * | 1993-03-05 | 1994-09-13 | Nippon Synthetic Chem Ind Co Ltd:The | Water soluble hot melt adhesive |
-
1978
- 1978-04-18 JP JP4636378A patent/JPS54138035A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54138035A (en) | 1979-10-26 |
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