JPH0354150B2 - - Google Patents
Info
- Publication number
- JPH0354150B2 JPH0354150B2 JP59196283A JP19628384A JPH0354150B2 JP H0354150 B2 JPH0354150 B2 JP H0354150B2 JP 59196283 A JP59196283 A JP 59196283A JP 19628384 A JP19628384 A JP 19628384A JP H0354150 B2 JPH0354150 B2 JP H0354150B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- emulsion
- adhesive
- polyvinyl alcohol
- mol
- 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 58
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- 238000007127 saponification reaction Methods 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 description 54
- 230000001070 adhesive effect Effects 0.000 description 54
- 238000011156 evaluation Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000010030 laminating Methods 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- -1 maleic acid Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
（産業上の利用分野）
本発明は紙工用接着剤に関し、詳しくは高速貼
合機に用いても優れた塗工適性を示すエチレン・
酢酸ビニル系共重合体エマルジヨン型の紙工用接
着剤に関するものである。
（従来の技術）
従来より紙、アルミ箱、プラスチツク等の基材
と紙とを接着せしめる紙工用接着剤として、ポリ
ビニルアルコールを保護コロイドとして製造した
エチレン・酢酸ビニル共重合体エマルジヨンを使
用することは良く知られている。
例えば特公昭49−26504号公報には完全ケン化
ポリビニルアルコールと部分ケン化ポリビニルア
ルコールとを用いて製造したエチレン・酢酸ビニ
ル共重体エマルジヨンであつて、Ｂ型粘度計の60
回転の測定値に対する６回転の測定値の比率が
1.8以下（TIが0.255以下に相当）である接着剤が
提案されている。
また特公昭49−26513号公報にはケン化度90〜
97モル％のポリビニルアルコールを用い製造した
エチレン・酢酸ビニル系共重合体エマルジヨンで
あつてTIが0.4以下の接着剤が示唆されている。
（発明が解決しようとする問題点）
近年、生産性を向上すべく接着ラインの高速化
が強く要望されている。この要望に呼応して加工
機は著しく進歩して例えばラインスピード200
ｍ／min以上の高速貼合機が開発された。ところ
が、前記公知接着剤はかかる高速貼合機に使用し
た場合は、運転開始約１〜２時間後にいわゆるガ
ムアツプ現象が起るため、その都度、運転を中断
して塗工機を清掃した後再運転せねばならず、生
産性の低下につながる場合があつた。
このように従来の接着剤は、高速貼合機に対し
て、塗工適性の点で充分ではなく、改良品の開発
が望まれていた。
（問題点を解決するための手段）
本発明者らは上記のような現状に鑑み、前記の
ような高速貼合機に用いてもガムアツプ現象が起
らず、優れた途工適性を示すエチレン・酢酸ビニ
ル系共重合体エマルジヨン型の接着剤を見い出す
べく鋭意検討を重ねた結果、ベースエマルジヨン
として特定のエチレン・酢酸ビニル系共重合体エ
マルジヨンを用い、該ベースエマルジヨンに特定
のポリビニルアルコールを特定量添加して得ら
れ、特定範囲の物性を有する接着剤が前記の目的
にもかなつた極めて優れた塗工適性を示し、しか
も速いセツトスピードを有することを見い出し本
発明に至つた。
すなわち本発明は、
ベースエマルジヨンとして、
平均重合度200〜3000、平均ケン化度80〜96モ
ル％のポリビニルアルコールが保護コロイドとし
て酢酸ビニルに対し２〜10重量％使用され、かつ
共重合体中のエチレン含量が５〜40重量％であ
るエチレン・酢酸ビニル系共重合体エマルジヨン
を用い、該エマルジヨンに、平均ケン化度80〜93
モル％の部分ケン化ポリビニルアルコールを該エ
マルジヨンの固形分100重量部に対し1.6〜40重量
部添加して得られ、かつ
そのBH型粘度計の20回転での粘度が1000〜
20000CpS、および
下式で算出されるチキソトロピーインデツクス
（TI）が0.3以下であることを特徴とする紙工用接
着剤を提供するものである。
TI＝log10（２回転での粘度／20回転での粘度）
本発明に用いられるベースエマルジヨンとして
のエチレン・酢酸ビニル系共重合体エマルジヨン
は、保護コロイドとして平均重合度200〜3000、
平均ケン化度80〜96モル％のポリビニルアルコー
ルが酢酸ビニルに対し２〜10重量％使用されてて
製造され、かつ共重合体中のエチレン含量が５〜
40重量％である。
ここでポリビニルアルコールが上記範囲外であ
る場合、例えば平均重合度が200未満の場合は、
接着剤として必要な粘度を有さずしかもエマルジ
ヨン自信の安定性が劣り、一方平均重合度が3000
を越えた場合はエマルジヨンの粘度が極端に増大
するため、エマルジヨンの製造時、使用時等にお
いて作業性が著しく低下する。また平均ケン化度
が80モル％未満、または96モル％を越える場合
は、いずれもエマルジヨンの安定性が劣る。また
ポリビニルアルコールの使用量が酢酸ビニルに対
して２重量％未満の場合はエマルジヨンの安定性
が劣り、逆に10重量％を越えた場合は、重合系内
においてエマルジヨン粒子へのポリビニルアルコ
ールの吸着状態が極めて複雑になるためか、一方
粘度のエマルジヨンが安定的に得られない。
また共重合体のエチレン含量が５重量％未満で
ある場合は、最低造膜温度が５℃以上となるた
め、冬場においては充分な接着力が得られず、逆
にエチレン含量が40重量％を越える場合は、接着
剤の凝集力が低下するため、接着面に力が加わる
ような場合、例えば反発力の強い基材を使用した
場合は、剥離トラブルを引き起すこともあり好ま
しくない。
本発明の接着剤はエチレン・酢酸ビニル系共重
合体エマルジヨンをベースエマルジヨンとするも
のであるが、上記した特定の共重合体エマルジヨ
ンであれば、その製法自体は特に限定されるもの
ではなく、またエチレン、酢酸ビニルの他にプロ
ピオン酸ビニル、酪酸ビニル、ラウリン酸ビニ
ル、第三級高級脂肪酸ビニルなどの酢酸ビニル以
外のビニルエステル、塩化ビニル、およびアクリ
ル酸、メタアクリル酸、クロトン酸、イタコン
酸、マレイン酸などの不飽和カルボン酸、ならび
に該不飽和カルボン酸のエステル類、無水物など
の１種または２種以上を酢酸ビニルに対し20重量
％以下の範囲で共重合せしめた共重体エマルジヨ
ンを使用することもできる。
本発明の接着剤は上記した特定の共重合体エマ
ルジヨンに、平均ケン化度80〜93モル％のポリビ
ニルアルコールをベースエマルジヨンの固形分
100重量部に対し1.6〜40重量部後添加して得られ
るものであつて、Ｂ型回転粘度計の20回転での粘
度（以下BH−20と略記する）が1000〜20000CpS
の範囲内にあり、かつTIが0.3以下のものに限定
される。
ここで、後添加用のポリビニルアルコールとし
て平均ケン化度80モル％未満のものを使用した場
合はガムアツプが殆ど防止されず、一方ケン化度
が93モル％を越えるポリビニルアルコールを使用
した場合は、TIが0.30を越えるため流動特性が接
着剤として不適当となるのみならず、ガムアツプ
が殆んど防止されずいずれの場合でも高速貼合機
に対しては塗工適性が著しく劣つた結果となる。
また後添加されるポリビニルアルコールは溶解
し易さ等から通常30重量％以下の水溶液の状態で
添加されるが、そのポリビニルアルコールとして
の添加量がベースエマルジヨン固形分100重量部
に対し1.6重量部未満の場合はガムアツプが防止
できず、一方40重量部を越える場合は、ポリビニ
ルアルコール水溶液の添加により接着剤中の水分
量が増大するため、接着剤のセツト性が劣る。
またBH−20が1000CpS未満の場合は、粘度が
低すぎるため、コーターで接着剤を基材（紙）へ
塗工する際のロールへののり（付着）が悪く充分
な塗工ができず、また20000CpSを越える場合は、
流動性が著しく低下し、作業性が著しく低下す
る。
またTIが0.3を越えると、コーターのシエアー
のかかる部分で接着剤がもり上るというチキソト
ロピー性に帰因した現象が起り、表層部が乾燥し
ガムアツプするようになるという問題の他に、坪
量の小さい（密度の小さい）紙材を高速貼合する
際、高速コーターで貼合時、接着剤の粘度が大幅
に低下するため紙材へ接着剤が浸透してしまい、
充分な接着性能が発現しなくなる。
上記のように、本発明の接着剤は特定のベース
エマルジヨンに特定のポリビニルアルコールを特
定量添加せしめて得られるが、必要に応じ、その
乾燥性、セツト性、粘度等を調整するために、ト
ルンエン、パークレン、トリクレン、ジクロルベ
ンゼン、トリクロルベンゼンなどの各種有機溶
剤、ヒドロキシエチルセルロース、メチルセルロ
ース、ポリアクリル酸ソーダなどの各種増粘剤、
炭酸カルシウム、タルク、クレー、酸化チタンな
どの無機フイラーなど、さらには消泡剤、分散
剤、凍結防止剤などの各種添加剤を添加すること
もできる。
（発明の効果）
かくして得られる本発明の接着剤は高速貼合機
に使用した場合でも、ガムアツプ現象が起らず極
めて優れた塗工適性を示し著しい生産性の向上を
もたらす。
（実施例）
以下実施例により、本発明を具体的に説明する
が、本発明はこれらに限定されるものではない。
実施例 １
保護コロイドとして、平均重合度500、平均ケ
ン化度88モル％のポリビニルアルコールおよび平
均重合度1700、平均ケン化度88モル％のポリビニ
ルアルコールをそれぞれ酢酸ビニルに対し４およ
び１重量％用いてエチレン・酢酸ビニル共重合体
エマルジヨンを製造した、固形分；55重量％、
BH−20：1950CpS、TI；0.42、共重合体中のエ
チレン含有量；20重量％であつた。
該エマルジヨンをベースエマルジヨンとし該エ
マルジヨンの固形分100重量部に対して、平均ケ
ン化度88モル％、平均重合度500の部分ケン化ポ
リビニルアルコール20重量部を30重量％水溶液に
してベースエマルジヨンに添加し接着剤を調合し
た。
該接着剤は固形分が48重量％であり、BH−
20；1430CpS、TI；0.11の物性を有するものであ
つた。次いで下記の方法により接着剤としての性
能評価試験を行いその結果を表１に示した。
フイルム再乳化性
接着剤をガラス板上で皮膜化したのち、水中に
浸漬して１時間後にフイルム状態を観察した。フ
イルム形態が崩れたものを再乳化性有りとし、○
印で示し白化現象があつてもフイルム形態が崩れ
ないものを再乳化性なしとし、×印で示した。
セツトタイム
クラフト紙にWet6milsで接着剤をコートし、
ただちに、約半分を短冊状に切つたクラフト紙を
コート面に重ね、貼り合せた後、３秒毎に短冊部
分の剥離を行い、紙材破に至るまでの時間を測定
した。
ロール適性
堀江(株)製ニユーサツクマシンＮ−SSM−1500
型貼合機を用いてダンボール製小箱を貼合せた。
ラインスピード450ｍ／minで６時間連続運転
を行いガムアツプが起らない接着剤を合格とし
た。
実施例 ２
実施例１と同一のベースエマルジヨンに、該エ
マルジヨンの固形分100重量部に対し、平均ケン
化度88モル％平均重合度1700の部分ケン化ポリビ
ニルアルコール3.5重量部を20重量％の水溶液に
して添加し接着剤を調合した。
該接着剤は固形分が52重量％であり、BH−
20；2940CpS、TI；0.23の物性を有していた。次
いで実施１と同様に性能評価試験を行い、その結
果を表１に示した。
実施例 ３
増粘および乾燥性向上を目的として、実施例１
と全く同様の操を行つて得られた接着剤100重量
部に対してパークレン10重量部を添加した接着剤
を調合した。該接着剤は固形分が44重量％であ
り、BH−20；2090CpS、TI；0.27の物性値を有
していた。
次いで実施例１と同様に性能評価試験を行い、
その結果を表１に示した。
実施例 ４
実施例１と全く同様に操作して得られた接着剤
100重量部に対してトルエン10重量部および炭酸
カルシウム10重量部を添加して接着剤を調合し
た。該接着剤は固形分49重量％であり、BH−
20；4970CpS、TI；0.17の物性を有していた。
次いで実施例１と同様に性能評価試験を行い、
その結果を表１に示した。
実施例 ５
保護コロイドとして平均重合度1700、平均ケン
化度88モル％のポリビニルアルコールおよび平均
重合度1800、平均ケン化度96モル％のポリビニル
アルコールをそれぞれ酢酸ビニルに対し、２およ
び３重量％用いて固形分55重量％、BH−20；
3200OpS、TI；0.23、共重合体中のエチレン含
量；15重量％のエチレン・酢酸ビニル系共重合体
エマルジヨンを製造した。
該エマルジヨンをベースエマルジヨンとし、該
エマルジヨンの固形分100重量部に対して、平均
ケン化度88モル％、平均重合度1700の部分ケン化
ポリビニルアルコールを２重量部を20重量％の水
溶液にしてベースエマルジヨンに添加して接着剤
を調合した。該接着剤は固形分が53重量％であ
り、BH−20；3980CpS、TI；0.17の物性値を有
していた。次いで実施例１と同様に性能評価試験
を行い、その結果を表１に示した。
比較例 １
実施例１と同一のベースエマルジヨンをそのま
ま接着剤として使用した。性能評価結果を表１に
示した。
比較例 ２
実施例１と同一のベースエマルジヨンに、該エ
マルジヨンの固形分100重量部に対して平均ケン
化度96モル％、平均重合度1400の完全ケン化タイ
プのポリビニルアルコール3.5部を15重量％の水
溶液にして添加し接着剤を調合した。該接着剤は
固形分が50重量％であり、BH−20；
2600CpSTI；0.52の物性値を有していた。次いで
実施例１と同様の性能評価試験を行いその結果を
表１に示した。
比較例 ３
実施例１と同一のベースエマルジヨンに、該エ
マルジヨンの固形分100重量部に対し平均ケン化
度88モル％、平均重合度1700の部分ケン化ポリビ
ニルアルコール1.2重量部を20重量％の水溶液に
して添加して接着剤を調合した。該接着剤は固形
分が54重量％であり、BH−20；2140CpS、TI；
0.40の物性値を有するものであつた。
次いで、実施例１と同様に性能評価試験を行
い、その結果を表１に示した。
比較例 ４
実施例１と同一のベースエマルジヨンに、該エ
マルジヨンの固形分100重量部に対し平均ケン化
度88モル％、平均重合度1700のポリビニルアルコ
ール45重量部を20重量％の水溶液にして添加して
接着剤を調合した。該接着剤は固形分が36重量％
であり、BH−20；14080CpS、TI；0.09の物性値
を有していた。次いで、実施例１と同様に性能評
価試験を行い、その結果を表１に示した。
比較例 ５
実施例５と同一のベースエマルジヨンをそのま
ま接着剤として使用した。その性能評価結果を表
１に示した。
比較例 ６
保護コロイドとして平均重合度500、平均ケン
化度88モル％のポリビニルアルコールおよび平均
重合度1700、平均ケン化度88モル％のポリビニル
アルコールをそれぞれ酢酸ビニルに対して４およ
び4.4重量％を用いて、固形分52重量％、BH−
20；3300CpS、TI；0.49、共重合体中のエチレン
含量；20重量％のエチレン・酢酸ビニル共重合体
エマルジヨンを製造した。
次いで該エマルジヨンをそのまま接着剤として
使用し性能評価試験を行つた。その結果を表１に
示した。
尚、この接着剤は、実施例２の接着剤とは使用
したポリビニルアルコールの種類およびその使用
量自体は同一であるが、ポリビニルアルコールの
全量を重合時に使用した点で異なる。かかる相違
によつて、この接着剤はTIが著しく増大し、性
能評価結果結果もロール適性が不良となつてい
る。
比較例 ７
保護コロイドとして平均重合度500、平均ケン
化度88モル％のポリビニルアルコールおよび平均
重合度1800、平均ケン化度96モル％のポリビニル
アルコールを酢酸ビニルに対してそれぞれ3.5お
よび4.5重量％用いて固形分；55重量％、BH−
20；3300CpS、TI；0.25、共重体中のエチレン含
量；20重量％のエチレン・酢酸ビニル共重合体エ
マルジヨンを製造した。
次いで該エマルジヨンをそのまま接着剤として
使用し性能評価試験を行つた。その結果を表１に
示した。
(Industrial Application Field) The present invention relates to adhesives for paper processing, and more specifically to ethylene adhesives that exhibit excellent coating suitability even when used in high-speed laminating machines.
This invention relates to a vinyl acetate copolymer emulsion type paper adhesive. (Prior art) Ethylene-vinyl acetate copolymer emulsion produced using polyvinyl alcohol as a protective colloid has not been used as a paper adhesive for bonding paper to base materials such as paper, aluminum boxes, and plastics. well known. For example, Japanese Patent Publication No. 49-26504 discloses an ethylene-vinyl acetate copolymer emulsion produced using fully saponified polyvinyl alcohol and partially saponified polyvinyl alcohol,
The ratio of the measured value of 6 rotations to the measured value of rotation is
Adhesives with a TI of 1.8 or less (corresponding to a TI of 0.255 or less) have been proposed. Also, in Japanese Patent Publication No. 49-26513, the degree of saponification is 90~
An adhesive is suggested that is an ethylene/vinyl acetate copolymer emulsion prepared using 97 mol% polyvinyl alcohol and has a TI of 0.4 or less. (Problems to be Solved by the Invention) In recent years, there has been a strong demand for faster bonding lines in order to improve productivity. In response to this demand, processing machines have significantly improved, for example, line speeds up to 200
A high-speed laminating machine with a speed of more than m/min has been developed. However, when the above-mentioned known adhesive is used in such a high-speed laminating machine, a so-called gum-up phenomenon occurs approximately 1 to 2 hours after the start of operation, so the operation must be interrupted each time, the coating machine must be cleaned, and then the coating machine must be restarted. This sometimes led to a decrease in productivity. As described above, conventional adhesives do not have sufficient coating suitability for high-speed laminating machines, and the development of improved products has been desired. (Means for Solving the Problems) In view of the above-mentioned current situation, the present inventors have developed an ethylene film that does not cause the gum-up phenomenon even when used in the above-mentioned high-speed laminating machine and exhibits excellent processing suitability.・As a result of intensive research to find a vinyl acetate copolymer emulsion type adhesive, we used a specific ethylene/vinyl acetate copolymer emulsion as the base emulsion, and added a specific polyvinyl alcohol to the base emulsion. The present inventors have discovered that an adhesive obtained by adding a specific amount and having physical properties in a specific range exhibits extremely excellent coating suitability that meets the above objectives, and also has a fast setting speed, leading to the present invention. That is, in the present invention, as a base emulsion, polyvinyl alcohol having an average degree of polymerization of 200 to 3000 and an average saponification degree of 80 to 96 mol% is used as a protective colloid in an amount of 2 to 10% by weight based on vinyl acetate, and in the copolymer. An ethylene/vinyl acetate copolymer emulsion having an ethylene content of 5 to 40% by weight is used, and the emulsion has an average saponification degree of 80 to 93.
It is obtained by adding 1.6 to 40 parts by weight of partially saponified polyvinyl alcohol at mol % to 100 parts by weight of the solid content of the emulsion, and the viscosity at 20 revolutions on a BH viscometer is 1000 to 1000.
20,000CpS and a thixotropy index (TI) calculated by the following formula of 0.3 or less. TI=log 10 (viscosity at 2 revolutions/viscosity at 20 revolutions) The ethylene/vinyl acetate copolymer emulsion as the base emulsion used in the present invention has an average degree of polymerization of 200 to 3000 as a protective colloid,
Polyvinyl alcohol with an average saponification degree of 80-96 mol% is used in an amount of 2-10% by weight based on vinyl acetate, and the ethylene content in the copolymer is 5-10% by weight.
It is 40% by weight. If the polyvinyl alcohol is outside the above range, for example, if the average degree of polymerization is less than 200,
It does not have the viscosity required as an adhesive, and the stability of the emulsion itself is poor, while the average degree of polymerization is 3000.
If it exceeds 100%, the viscosity of the emulsion will increase dramatically, resulting in a significant decrease in workability during production, use, etc. of the emulsion. Furthermore, if the average degree of saponification is less than 80 mol% or more than 96 mol%, the stability of the emulsion will be poor. Furthermore, if the amount of polyvinyl alcohol used is less than 2% by weight based on vinyl acetate, the stability of the emulsion will be poor, and if it exceeds 10% by weight, the adsorption state of polyvinyl alcohol on the emulsion particles in the polymerization system will deteriorate. On the other hand, an emulsion with a stable viscosity cannot be obtained, probably because the process becomes extremely complicated. Furthermore, if the ethylene content of the copolymer is less than 5% by weight, the minimum film forming temperature will be 5°C or higher, making it difficult to obtain sufficient adhesion in winter; If it exceeds the range, the cohesive force of the adhesive will decrease, so if force is applied to the adhesive surface, for example, if a base material with strong repulsive force is used, it may cause peeling troubles, which is not preferable. Although the adhesive of the present invention uses an ethylene/vinyl acetate copolymer emulsion as a base emulsion, the manufacturing method itself is not particularly limited as long as the above-mentioned specific copolymer emulsion is used. In addition to ethylene and vinyl acetate, vinyl esters other than vinyl acetate such as vinyl propionate, vinyl butyrate, vinyl laurate, and vinyl tertiary higher fatty acids, vinyl chloride, and acrylic acid, methacrylic acid, crotonic acid, and itaconic acid A copolymer emulsion prepared by copolymerizing one or more of unsaturated carboxylic acids such as maleic acid, and esters and anhydrides of the unsaturated carboxylic acids in an amount of 20% by weight or less based on vinyl acetate. You can also use The adhesive of the present invention is based on the specific copolymer emulsion mentioned above, and polyvinyl alcohol with an average saponification degree of 80 to 93 mol% based on the solid content of the emulsion.
It is obtained by adding 1.6 to 40 parts by weight to 100 parts by weight, and the viscosity at 20 rotations on a B-type rotational viscometer (hereinafter abbreviated as BH-20) is 1000 to 20000 CpS.
is within the range and has a TI of 0.3 or less. Here, if a polyvinyl alcohol with an average saponification degree of less than 80 mol% is used as the polyvinyl alcohol for post-addition, gum up will hardly be prevented, whereas if a polyvinyl alcohol with a saponification degree of more than 93 mol% is used, Since the TI exceeds 0.30, not only is the fluidity property unsuitable as an adhesive, but gum build-up is hardly prevented, resulting in extremely poor coating suitability for high-speed laminating machines in any case. . Polyvinyl alcohol, which is added later, is usually added in the form of an aqueous solution of 30% by weight or less due to ease of dissolution, but the amount added as polyvinyl alcohol is 1.6 parts by weight per 100 parts by weight of the solid content of the base emulsion. If the amount is less than 40 parts by weight, the amount of water in the adhesive increases due to the addition of the aqueous polyvinyl alcohol solution, resulting in poor adhesive setting properties. In addition, if BH-20 is less than 1000CpS, the viscosity is too low, so when applying the adhesive to the base material (paper) with a coater, it will not stick (adhere) to the roll and will not be able to be applied sufficiently. Also, if it exceeds 20000CpS,
Fluidity and workability are significantly reduced. In addition, if the TI exceeds 0.3, a phenomenon caused by thixotropy occurs in which the adhesive swells up in the areas where the coater applies shear, and in addition to the problem that the surface layer dries and gums up, the basis weight also increases. When laminating small (low density) paper materials at high speed, the viscosity of the adhesive decreases significantly when laminating with a high-speed coater, causing the adhesive to penetrate into the paper material.
Sufficient adhesive performance will not be developed. As mentioned above, the adhesive of the present invention is obtained by adding a specific amount of a specific polyvinyl alcohol to a specific base emulsion. Various organic solvents such as toluene, perchlorene, trichlorobenzene, dichlorobenzene, trichlorobenzene, various thickeners such as hydroxyethylcellulose, methylcellulose, and sodium polyacrylate,
Inorganic fillers such as calcium carbonate, talc, clay, and titanium oxide, and various additives such as antifoaming agents, dispersants, and antifreeze agents can also be added. (Effects of the Invention) Even when the adhesive of the present invention thus obtained is used in a high-speed laminating machine, it does not cause the gum-up phenomenon and exhibits extremely excellent coating suitability, resulting in a remarkable improvement in productivity. (Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Example 1 As protective colloids, polyvinyl alcohol with an average degree of polymerization of 500 and an average degree of saponification of 88 mol% and polyvinyl alcohol with an average degree of polymerization of 1700 and an average saponification degree of 88 mol% were used in an amount of 4 and 1% by weight, respectively, based on vinyl acetate. The ethylene/vinyl acetate copolymer emulsion was produced using
BH-20: 1950CpS, TI: 0.42, ethylene content in the copolymer: 20% by weight. The emulsion is used as a base emulsion, and 20 parts by weight of partially saponified polyvinyl alcohol having an average degree of saponification of 88 mol% and an average degree of polymerization of 500 is added to a 30% by weight aqueous solution to 100 parts by weight of the solid content of the emulsion to form a base emulsion. was added to prepare an adhesive. The adhesive has a solids content of 48% by weight and has a BH-
It had physical properties of 20: 1430CpS and TI: 0.11. Next, a performance evaluation test as an adhesive was conducted using the method described below, and the results are shown in Table 1. Film re-emulsification property After the adhesive was formed into a film on a glass plate, it was immersed in water and the state of the film was observed one hour later. If the film shape has collapsed, it is considered to be re-emulsifiable, and ○
Films whose film shape did not collapse even when a whitening phenomenon occurred, as indicated by a mark, were considered to have no re-emulsifying property, and were marked with an x mark. Set time Coat adhesive with Wet6mils on kraft paper,
Immediately, a piece of kraft paper cut into strips about half of it was layered on the coated surface and bonded together, then the strips were peeled off every 3 seconds and the time until the paper material broke was measured. Roll suitability: Horie Co., Ltd. New Sack Machine N-SSM-1500
A small cardboard box was pasted using a mold pasting machine. Adhesives that did not cause gum up after continuous operation for 6 hours at a line speed of 450 m/min were deemed to have passed the test. Example 2 To the same base emulsion as in Example 1, 20% by weight of 3.5 parts by weight of partially saponified polyvinyl alcohol with an average degree of saponification of 88 mol% and an average degree of polymerization of 1700 was added to 100 parts by weight of the solid content of the emulsion. An adhesive was prepared by adding it as an aqueous solution. The adhesive has a solids content of 52% by weight and has a BH-
It had physical properties of 20:2940CpS and TI:0.23. Next, a performance evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Example 3 For the purpose of thickening and improving drying properties, Example 1
An adhesive was prepared by adding 10 parts by weight of percrene to 100 parts by weight of the adhesive obtained by carrying out exactly the same procedure as above. The adhesive had a solid content of 44% by weight and physical properties of BH-20: 2090CpS, TI: 0.27. Next, a performance evaluation test was conducted in the same manner as in Example 1,
The results are shown in Table 1. Example 4 Adhesive obtained by operating in exactly the same manner as Example 1
An adhesive was prepared by adding 10 parts by weight of toluene and 10 parts by weight of calcium carbonate to 100 parts by weight. The adhesive has a solids content of 49% by weight and has a BH-
It had physical properties of 20:4970CpS and TI:0.17. Next, a performance evaluation test was conducted in the same manner as in Example 1,
The results are shown in Table 1. Example 5 As protective colloids, polyvinyl alcohol with an average degree of polymerization of 1700 and an average saponification degree of 88 mol% and polyvinyl alcohol with an average degree of polymerization of 1800 and an average saponification degree of 96 mol% were used at 2 and 3% by weight, respectively, based on vinyl acetate. solid content 55% by weight, BH-20;
An ethylene/vinyl acetate copolymer emulsion was produced with 3200 OpS, TI: 0.23, and ethylene content in the copolymer: 15% by weight. This emulsion is used as a base emulsion, and 2 parts by weight of partially saponified polyvinyl alcohol having an average degree of saponification of 88 mol% and an average degree of polymerization of 1700 is made into a 20% by weight aqueous solution based on 100 parts by weight of the solid content of the emulsion. The adhesive was formulated by adding it to the base emulsion. The adhesive had a solid content of 53% by weight and physical properties of BH-20: 3980CpS, TI: 0.17. Next, a performance evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 1 The same base emulsion as in Example 1 was used as an adhesive as is. The performance evaluation results are shown in Table 1. Comparative Example 2 To the same base emulsion as in Example 1, 15 parts by weight of completely saponified polyvinyl alcohol with an average saponification degree of 96 mol% and an average polymerization degree of 1400 was added to 100 parts by weight of solid content of the emulsion. % aqueous solution and added to prepare an adhesive. The adhesive has a solids content of 50% by weight and is BH-20;
2600CpSTI: It had a physical property value of 0.52. Next, a performance evaluation test similar to that in Example 1 was conducted, and the results are shown in Table 1. Comparative Example 3 To the same base emulsion as in Example 1, 1.2 parts by weight of partially saponified polyvinyl alcohol having an average degree of saponification of 88 mol% and an average degree of polymerization of 1700 was added to 20 parts by weight of the solid content of the emulsion, based on 100 parts by weight of the emulsion. An adhesive was prepared by adding it as an aqueous solution. The adhesive has a solids content of 54% by weight, BH-20; 2140CpS, TI;
It had a physical property value of 0.40. Next, a performance evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 4 To the same base emulsion as in Example 1, 45 parts by weight of polyvinyl alcohol having an average degree of saponification of 88 mol% and an average degree of polymerization of 1700 was made into a 20% by weight aqueous solution based on 100 parts by weight of the solid content of the emulsion. The adhesive was prepared by adding: The adhesive has a solids content of 36% by weight.
It had physical property values of BH-20: 14080CpS and TI: 0.09. Next, a performance evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 5 The same base emulsion as in Example 5 was used as is as an adhesive. The performance evaluation results are shown in Table 1. Comparative Example 6 As protective colloids, polyvinyl alcohol with an average degree of polymerization of 500 and an average degree of saponification of 88 mol% and polyvinyl alcohol with an average degree of polymerization of 1700 and an average saponification degree of 88 mol% were used in amounts of 4 and 4.4% by weight, respectively, based on vinyl acetate. Solid content: 52% by weight, BH-
An ethylene/vinyl acetate copolymer emulsion was produced with 20:3300CpS, TI: 0.49, and ethylene content in the copolymer: 20% by weight. Next, a performance evaluation test was conducted using the emulsion as it was as an adhesive. The results are shown in Table 1. This adhesive is the same as the adhesive of Example 2 in the type and amount of polyvinyl alcohol used, but differs in that the entire amount of polyvinyl alcohol was used during polymerization. Due to this difference, the TI of this adhesive increases significantly, and the performance evaluation results show that the roll suitability is poor. Comparative Example 7 As protective colloids, polyvinyl alcohol with an average degree of polymerization of 500 and an average saponification degree of 88 mol% and polyvinyl alcohol with an average degree of polymerization of 1800 and an average saponification degree of 96 mol% were used at 3.5 and 4.5% by weight, respectively, based on vinyl acetate. Solid content; 55% by weight, BH-
An ethylene/vinyl acetate copolymer emulsion with 20:3300CpS, TI: 0.25, and ethylene content in the copolymer: 20% by weight was produced. Next, a performance evaluation test was conducted using the emulsion as it was as an adhesive. The results are shown in Table 1.
【表】【table】
Claims (1)
〜3000平均ケン化度80〜96モル％のポリビニルア
ルコールが保護コロイドとして酢酸ビニルに対し
２〜10重量％使用され、かつ共重合体中のエチレ
ン含量が５〜40重量％であるエチレン・酢酸ビニ
ル系共重合体エマルジヨンを用い、該エマルジヨ
ンに、平均ケン化度80〜93モル％の部分ケン化ポ
リビニルアルコールを該エマルジヨンの固形分
100重量部に対し、1.6〜40重量部添加して得ら
れ、かつそのBH型粘度計の20回転での粘度が、
1000〜20000CpS、および下式で算出されるチキ
ソトロピーインデツクス（TI）が0.3以下である
ことを特徴とする紙工用接着剤。 TI＝log10（２回転での粘度／20回転での粘度）[Claims] 1. As a base emulsion, an average degree of polymerization of 200
~3000 Ethylene/vinyl acetate in which polyvinyl alcohol with an average saponification degree of 80 to 96 mol% is used as a protective colloid in an amount of 2 to 10% by weight based on vinyl acetate, and the ethylene content in the copolymer is 5 to 40% by weight. Using a copolymer emulsion, partially saponified polyvinyl alcohol with an average degree of saponification of 80 to 93 mol% is added to the emulsion based on the solid content of the emulsion.
It is obtained by adding 1.6 to 40 parts by weight to 100 parts by weight, and the viscosity at 20 revolutions on a BH type viscometer is:
1,000 to 20,000 CpS, and a thixotropy index (TI) calculated by the following formula of 0.3 or less. TI=log 10 (viscosity at 2 revolutions/viscosity at 20 revolutions)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19628384A JPS6173779A (en) | 1984-09-19 | 1984-09-19 | Paper adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19628384A JPS6173779A (en) | 1984-09-19 | 1984-09-19 | Paper adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6173779A JPS6173779A (en) | 1986-04-15 |
| JPH0354150B2 true JPH0354150B2 (en) | 1991-08-19 |
Family
ID=16355223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19628384A Granted JPS6173779A (en) | 1984-09-19 | 1984-09-19 | Paper adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6173779A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625328B2 (en) * | 1986-05-30 | 1994-04-06 | オキツモ株式会社 | Instant adhesive for paper |
| JPS63297407A (en) * | 1987-05-12 | 1988-12-05 | 大蓮化学工業股ふん有限公司 | Manufacture of emulsion |
| JP3839557B2 (en) * | 1997-06-30 | 2006-11-01 | 株式会社クラレ | adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111888A (en) * | 1974-07-19 | 1976-01-30 | Showa Highpolymer | BINIRUESUTERUUECHIRENKEIKYOJUGOTAISUISEINYUDAKUEKINO SEIZOHOHO |
| JPS5614558A (en) * | 1979-07-12 | 1981-02-12 | Nippon Synthetic Chem Ind Co Ltd:The | Thixotropic aqueous resin composition |
-
1984
- 1984-09-19 JP JP19628384A patent/JPS6173779A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111888A (en) * | 1974-07-19 | 1976-01-30 | Showa Highpolymer | BINIRUESUTERUUECHIRENKEIKYOJUGOTAISUISEINYUDAKUEKINO SEIZOHOHO |
| JPS5614558A (en) * | 1979-07-12 | 1981-02-12 | Nippon Synthetic Chem Ind Co Ltd:The | Thixotropic aqueous resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6173779A (en) | 1986-04-15 |
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