JP2642479B2 - Release paper and method for producing the same - Google Patents
Release paper and method for producing the sameInfo
- Publication number
- JP2642479B2 JP2642479B2 JP1129576A JP12957689A JP2642479B2 JP 2642479 B2 JP2642479 B2 JP 2642479B2 JP 1129576 A JP1129576 A JP 1129576A JP 12957689 A JP12957689 A JP 12957689A JP 2642479 B2 JP2642479 B2 JP 2642479B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- paper
- undercoat layer
- release
- aqueous copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は剥離紙に関し、特にカールの発生がなく、通
紙適性、複写適性等に優れた粘着紙を構成することがで
きる剥離紙及びその製造方法に関するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release paper, and more particularly, to a release paper capable of forming an adhesive paper having no curl and excellent in sheet-passing suitability, copy suitability, and the like. It relates to a manufacturing method.
「従来の技術」 粘着紙は商業用、事務用、家庭用等非常に広範囲な用
途にラベル、シール、ステッカー、ワッペン等として使
用されている。この粘着紙の一般的構成は、表面基材と
剥離紙との間に粘着剤をサンドイッチにした状態のもの
であり、表面基材には紙、合成紙、フィルム、金属フォ
イル等が用いられ、剥離紙としてはグラシン紙のような
高密度原紙、クレーコート紙、ポリラミ原紙、下塗り層
を設けた剥離原紙等にシリコーン化合物や弗素化合物の
如き剥離剤を塗布したものが使用される。また粘着剤と
しては、溶剤型粘着剤、エマルジョン型粘着剤、ホット
メルト型粘着剤等が使用される。[Background Art] Adhesive paper is used as a label, a sticker, a sticker, an emblem and the like for a very wide range of uses such as commercial use, office use, and home use. The general configuration of this adhesive paper is a state in which an adhesive is sandwiched between the surface base material and the release paper, and the surface base material is paper, synthetic paper, film, metal foil, or the like, As the release paper, a high-density base paper such as glassine paper, a clay-coated paper, a polylamine base paper, a release base paper provided with an undercoat layer, or the like, to which a release agent such as a silicone compound or a fluorine compound is applied is used. As the pressure-sensitive adhesive, a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, or the like is used.
「発明が解決しようとする課題」 かかる粘着紙では、剥離紙に起因するカールが発生し
易い。即ち、粘着紙の一般的な製造工程では剥離原紙に
剥離剤を塗布乾燥し、この剥離剤塗布面に粘着剤を塗布
乾燥したのち表面基材と貼合わされるため、剥離原紙は
剥離剤と粘着剤の塗布工程において二度乾燥されて収縮
しており、水分に対する反応性が極めて高くなってい
る。そのため外部環境の変化等で偏った吸湿、吸水作用
が起こると、直ちにカールが発生してしまう。特に、原
紙としてグラシン紙のような高叩解、高密度の紙を使用
した場合には、乾燥時に普通の紙以上に収縮しているた
め、吸湿、吸水によって起こる繊維の膨潤を吸収すべき
空隙が極めて少なく、結果的にカールの発生がとりわけ
著しい。"Problems to be Solved by the Invention" In such adhesive paper, curling due to release paper is likely to occur. That is, in the general production process of adhesive paper, a release agent is applied to the release base paper and dried, and then the adhesive is applied to the release agent application surface and then dried and bonded to the surface substrate. It is dried and shrunk twice in the application step of the agent, and has extremely high reactivity to moisture. For this reason, if uneven moisture absorption or water absorption occurs due to a change in the external environment or the like, curling occurs immediately. In particular, when high-beaten, high-density paper such as glassine paper is used as the base paper, it shrinks more than ordinary paper during drying, so there is a gap to absorb the swelling of the fiber caused by moisture absorption and water absorption. Extremely low, and consequently the occurrence of curling is particularly remarkable.
このように剥離紙が原因で発生する粘着紙のカール
は、例えば粘着紙に印刷、ダイカット（打ち抜き）、シ
ートカット等の処理を施してラベルやシール等に加工す
る段階で給紙不良、紙不揃い、印刷ずれ等のトラブルを
起こし、また複写機で複写する際には通紙不良や転写不
良を起こすため、作業適性及び品質面において極めて重
大な障害となる。The curl of the adhesive paper caused by the release paper as described above may be caused, for example, by a process such as printing, die cutting (punching), or sheet cutting on the adhesive paper, and processing into a label or a sticker. This causes troubles such as print misregistration, and also causes poor paper passing and poor transfer when copying with a copying machine, which is a very serious obstacle in workability and quality.
粘着紙のカールを矯正するために、粘着紙をカール方
向とは逆の方向に鋭角的に曲げるカールブレーカーの使
用、エアーコンディショナーの付設やスチームダンピン
グを行う方法等が提案されているが、工程の複雑さが伴
う上に効果の点でも不充分であり、必ずしも満足すべき
結果が得られていないのが現状である。In order to correct the curl of the adhesive paper, use of a curl breaker that sharply bends the adhesive paper in a direction opposite to the curl direction, a method of attaching an air conditioner and performing steam damping, etc. have been proposed. In addition to the complexity, the effect is insufficient, and satisfactory results have not always been obtained.
かかる現状に鑑み、本発明者等は剥離紙に起因する粘
着紙のカールを防止する方法について、下塗り層塗液の
組成、配合比、濃度、粘度、塗工方法等を詳細に検討し
た結果、剥離紙用基紙に特定の乳化剤を特定量含有する
特定組成の単量体を乳化共重合し、且つ特定のガラス転
移温度となる水性共重合体を主成分とする下塗り層を形
成し、しかる後に剥離剤層を設けると、上記の如き難点
が極めて効率良く解消されることを見出し本発明を完成
するに至った。In view of this situation, the present inventors have studied in detail the method of preventing the curl of the pressure-sensitive adhesive paper caused by the release paper, the composition of the undercoat layer coating solution, the mixing ratio, the concentration, the viscosity, the coating method and the like, Emulsion-copolymerizing a monomer having a specific composition containing a specific amount of a specific emulsifier into a base paper for release paper, and forming an undercoat layer mainly composed of an aqueous copolymer having a specific glass transition temperature, The inventors have found that if a release agent layer is provided later, the above-described difficulties can be solved very efficiently, and the present invention has been completed.
「課題を解決するための手段」 本発明は、基紙の少なくとも片面に下塗り層を介して
剥離剤層を設けてなる剥離紙において、該下塗り層の主
成分が、分子量が1000〜10000の乳化剤を２〜10重量％
含有する下記組成の単量体を乳化共重合し、且つガラス
転移温度が−60〜０℃である水性共重合体〔Ｉ〕 （ａ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｂ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:40〜90重量％ （ｃ） これらの単量体と共重合可能な他の単量体:0〜
40重量％ と、分子量が1000〜10000の乳化剤を２〜10重量％含有
する下記組成の単量体を乳化共重合し、且つガラス転移
温度が45〜100℃である水性共重合体〔II〕 （ｄ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｅ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:5〜40重量％ （ｆ） これらの単量体と共重合可能な他の単量体:50
〜90重量％ との混合物であることを特徴とする剥離紙、及び基紙の
少なくとも片面に上記特定の下塗り層を形成し、該下塗
り層上に剥離剤層を形成することを特徴とする剥離紙の
製造方法である。`` Means for Solving the Problems '' The present invention relates to a release paper comprising a base paper and a release agent layer provided on at least one side of the base paper via an undercoat layer, wherein the main component of the undercoat layer has an emulsifier having a molecular weight of 1,000 to 10,000. 2-10% by weight
Aqueous copolymer [I] (a) having an ethylenically unsaturated carboxylic acid-containing monomer obtained by emulsion-copolymerizing a monomer having the following composition and having a glass transition temperature of -60 to 0 ° C: 1 to 20
(B) C4-18 alkyl ester monomer of (meth) acrylic acid: 40-90% by weight (c) Other monomers copolymerizable with these monomers: 0-
An aqueous copolymer [II] in which 40% by weight and a monomer having the following composition containing 2 to 10% by weight of an emulsifier having a molecular weight of 1,000 to 10,000 are emulsion-copolymerized and have a glass transition temperature of 45 to 100 ° C. (D) Ethylenically unsaturated carboxylic acid-containing monomer: 1 to 20
(E) C4-18 alkyl ester monomer of (meth) acrylic acid: 5 to 40% by weight (f) Other monomers copolymerizable with these monomers: 50
And a release paper characterized in that the specific undercoat layer is formed on at least one surface of a base paper and a release agent layer is formed on the undercoat layer. This is a method for producing paper.
「作用」 本発明においては、カール防止効果の面から、下塗り
層を形成する水性共重合体のガラス転移温度が非常に重
要である。即ち、水性共重合体のガラス転移温度が低い
ほどカールは発生しにくいが、皮膜の粘着性が強くなっ
てくるため実用性に乏しくなる。したがって、単量体組
成を調節することにより本発明の所望の効果が発現され
るように水性共重合体のガラス転移温度が調節される。[Function] In the present invention, the glass transition temperature of the aqueous copolymer forming the undercoat layer is very important from the viewpoint of the curl prevention effect. That is, as the glass transition temperature of the aqueous copolymer is lower, curling is less likely to occur, but the tackiness of the film becomes stronger and the practicality becomes poor. Therefore, by adjusting the monomer composition, the glass transition temperature of the aqueous copolymer is adjusted so that the desired effect of the present invention is exhibited.
本発明において用いられる上記特定の水性共重合体を
構成するエチレン性不飽和カルボン酸含有単量体として
は、例えばアクリル酸、メタクリル酸、クロトン酸、マ
レイ酸、イタコン酸、フマル酸、モノアルキルマレイン
酸、モノアルキルイタコン酸、モノアルキルフマル酸等
が挙げられる。Examples of the ethylenically unsaturated carboxylic acid-containing monomer constituting the specific aqueous copolymer used in the present invention include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, monoalkyl maleic acid Acid, monoalkyl itaconic acid, monoalkyl fumaric acid and the like.
共重合体中に占めるこれらのエチレン性不飽和カルボ
ン酸含有単量体の割合が全単量体の１重量％未満になる
と、得られた共重合体の分散安定性が不充分となり、逆
に20重量％を越えると、乾燥性が不充分となりカールの
改良効果も低下してしまう恐れもある為、これらのエチ
レン性不飽和カルボン酸含有単量体は水性共重合体
〔Ｉ〕、〔II〕共に、１〜20重量％の範囲で共重合する
必要がある。When the proportion of these ethylenically unsaturated carboxylic acid-containing monomers in the copolymer is less than 1% by weight of all monomers, the dispersion stability of the obtained copolymer becomes insufficient, and conversely, If the content exceeds 20% by weight, the drying property becomes insufficient and the curl improving effect may be reduced. Therefore, these ethylenically unsaturated carboxylic acid-containing monomers are used in aqueous copolymers [I] and [II]. ] Need to be copolymerized in the range of 1 to 20% by weight.
一方、本発明で用いられる水性共重合体を構成する
（メタ）アクリル酸のＣ４〜18アルキルエステル単量体
としては、例えば（メタ）アクリル酸ブチル、（メタ）
アクリル酸ヘキシル、（メタ）アクリル酸オクチル、
（メタ）アクリル酸−２−エチルヘキシル、（メタ）ア
クリル酸ラウリル、（メタ）アクリル酸ステアリル等が
挙げられる。On the other hand, examples of the C 4-18 alkyl ester monomer of (meth) acrylic acid constituting the aqueous copolymer used in the present invention include butyl (meth) acrylate and (meth) acrylate.
Hexyl acrylate, octyl (meth) acrylate,
Examples thereof include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
共重合体中に占めるこれらの（メタ）アクリル酸のＣ
４〜18アルキルエステル単量体の割合は、水性共重合体
〔Ｉ〕では全単量体の40〜90重量％、水性共重合体〔I
I〕では全単量体の５〜40重量％の範囲で調節される。The C of these (meth) acrylic acids in the copolymer
In the aqueous copolymer [I], the proportion of the 4-18 alkyl ester monomer is 40-90% by weight of the total monomer, and the aqueous copolymer [I
In [I], the content is adjusted in the range of 5 to 40% by weight of the total monomers.
本発明においては、これらの（メタ）アクリル酸のＣ
４〜18アルキルエステル単量体の中でも、特にアクリル
酸ブチル、アクリル酸−２−エチルヘキシルが共重合
性、ガラス転移温度等の面から好ましく用いられる。In the present invention, these (meth) acrylic acid C
Among the 4 to 18 alkyl ester monomers, butyl acrylate and 2-ethylhexyl acrylate are particularly preferably used in view of copolymerizability, glass transition temperature and the like.
また、本発明で用いられる水性共重合体を構成する上
記の如き単量体と共重合可能な他の単量体としては、例
えば（メタ）アクリル酸メチル、（メタ）アクリル酸エ
チル、（メタ）アクリル酸プロピル、酢酸ビニル、塩化
ビニル、塩化ビニリデン、（メタ）アクリロニトリル、
スチレン、エチレン、ジ（メタ）アクリル酸エチレング
リコール、ジ（メタ）アクリル酸ジエチレングリコー
ル、ジ（メタ）アクリル酸トリエチレングリコール、ジ
（メタ）アクリル酸（ポリ）エチレングリコール、ジ
（メタ）アクリル酸プロピレングリコール、ジ（メタ）
アクリル酸ジプロピレングリコール、ジ（メタ）アクリ
ル酸トリプロピレングリコール、ジ（メタ）アクリル酸
（ポリ）プロピレングリコール、ジ（メタ）アクリル酸
−1,3−ブチレングリコール、トリ（メタ）アクリル酸
トリメチロールプロパン、テトラ（メタ）アクリル酸テ
トラメチロールメタン、ジビニルベンゼン、ジ（メタ）
アクリル酸−1,4−ブタンジオール、ジ（メタ）アクリ
ル酸−1,6−ヘキサンジオール、（メタ）アクリル酸グ
リシジル、（メタ）アクリル酸メチルグリシジル、（メ
タ）アクリルアミド、Ｎ−メチロール（メタ）アクリル
アミド、Ｎ−メトキシメチル（メタ）アクリルアミド、
Ｎ−ブトキシメチル（メタ）アクリルアミド、N,N′−
メチレンビス（メタ）アクリルアミド等が挙げられる。Other monomers copolymerizable with the above-mentioned monomers constituting the aqueous copolymer used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate. ) Propyl acrylate, vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylonitrile,
Styrene, ethylene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, propylene di (meth) acrylate Glycol, di (meth)
Dipropylene glycol acrylate, tripropylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylol tri (meth) acrylate Propane, tetramethylolmethane tetra (meth) acrylate, divinylbenzene, di (meth)
Acrylic acid-1,4-butanediol, di (meth) acrylic acid-1,6-hexanediol, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) Acrylamide, N-methoxymethyl (meth) acrylamide,
N-butoxymethyl (meth) acrylamide, N, N'-
Methylene bis (meth) acrylamide and the like can be mentioned.
共重合体中に占めるこれらの共重合可能な他の単量体
の割合は、水性共重合体〔Ｉ〕では全単量体の０〜40重
量％、水性共重合体〔II〕では全単量体の50〜90重量％
の範囲で調節される。The proportion of these other copolymerizable monomers in the copolymer is 0 to 40% by weight of the total monomers in the aqueous copolymer [I], and is all in the aqueous copolymer [II]. 50-90% by weight of monomer
Is adjusted in the range.
本発明においては、これらの共重合可能な他の単量体
の中でも、特に（メタ）アクリル酸メチル、（メタ）ア
クリロニトリル、（メタ）アクリルアミド等がガラス転
移温度、耐溶剤性、耐熱性等の面から好ましく用いられ
る。In the present invention, among these other copolymerizable monomers, in particular, (meth) methyl acrylate, (meth) acrylonitrile, (meth) acrylamide and the like have glass transition temperatures, solvent resistance, heat resistance and the like. It is preferably used in terms of surface.
本発明の水性共重合体は、上記の如き各単量体を乳化
剤、連鎖移動剤、重合開始剤等の存在下水系で乳化共重
合する方法で製造されるが、特に乳化剤の種類及び使用
量は重要である。即ち、本発明では分子量が1000〜1000
0の乳化剤を選択的に使用するものであるが、分子量が1
000より小さくなると水性共重合体〔Ｉ〕と〔II〕を混
合した際に凝集物が発生し易くなり、10000より大きく
なると乳化力が非常に低下し実用性に乏しくなってしま
う。このような乳化剤のうちでも、特に、１分子中にノ
ニオン性とアニオン性を兼備した界面活性剤が好まし
い。その具体例としては、例えば、ポリオキシエチレン
アルキルエーテル硫酸エステル塩、ポリオキシエチレン
アルキルフェニルエーテル硫酸エステル塩等が挙げられ
る。また、乳化剤の使用量は、共重合体を構成する単量
体の全量に対して２〜10重量％の範囲で含有せしめられ
る。使用量が２重量％を下回ると、得られるエマルジョ
ンの安定性が不充分となり、重合体の粒子径が大きくな
ってしまう。また、10重量％を越える程多量に使用する
と、下塗り層と剥離剤層との密着性が低下する。The aqueous copolymer of the present invention is produced by a method of emulsifying and copolymerizing each monomer as described above in an aqueous system in the presence of an emulsifier, a chain transfer agent, a polymerization initiator, and the like. Is important. That is, in the present invention, the molecular weight is 1000 to 1000
0 emulsifier is selectively used, but the molecular weight is 1
If it is smaller than 000, agglomerates are apt to be generated when the aqueous copolymers [I] and [II] are mixed, and if it is larger than 10,000, the emulsifying power is extremely reduced and practicality is poor. Among such emulsifiers, a surfactant having both nonionic and anionic properties in one molecule is particularly preferable. Specific examples thereof include polyoxyethylene alkyl ether sulfates and polyoxyethylene alkyl phenyl ether sulfates. The amount of the emulsifier used is in the range of 2 to 10% by weight based on the total amount of the monomers constituting the copolymer. If the amount used is less than 2% by weight, the stability of the resulting emulsion will be insufficient, and the particle size of the polymer will increase. On the other hand, if used in a large amount exceeding 10% by weight, the adhesion between the undercoat layer and the release agent layer is reduced.
また、連鎖移動剤としては、例えばチオグリセロー
ル、エチレンチオグリコール、チオグリコール酸、ｎ−
ドデシルメルカプタン等が例示され、重合開始剤として
は、例えば過酸化水素、過硫酸カリウム、過硫酸アンモ
ニウム又はそれらと亜硫酸ソーダ、酸性亜硫酸ソーダ等
の還元剤との組み合わせから成る所謂レドックス系の重
合開始剤等が挙げられる。Examples of the chain transfer agent include thioglycerol, ethylene thioglycol, thioglycolic acid, and n-glycol.
Examples of the polymerization initiator include, for example, hydrogen peroxide, potassium persulfate, ammonium persulfate, and a so-called redox-based polymerization initiator comprising a combination thereof with a reducing agent such as sodium sulfite and sodium acid sulfite. Is mentioned.
本発明では、かくして得られるガラス転移温度が−60
〜０℃である水性共重合体〔Ｉ〕とガラス転移温度が45
〜100℃である水性共重合体〔II〕が混合して使用され
る。この混合比率は水性共重合体〔Ｉ〕100重量部に対
して水性共重合体〔II〕が５〜80重量部である。因み
に、水性共重合体〔II〕の混合比率が５重量部より低く
なると、カールはよいが皮膜の粘着性が強くなり過ぎ
（皮膜のガラス転移温度が低くなり過ぎる）てブロッキ
ングを起こす問題があり、逆に80重量部より高くなる
と、得られる皮膜が硬くなり過ぎ（皮膜のガラス転移温
度が高くなり過ぎる）て下塗り層塗布面にカールを起こ
すという問題がある。In the present invention, the glass transition temperature thus obtained is -60.
Aqueous copolymer [I] having a glass transition temperature of 45.degree.
The aqueous copolymer [II] having a temperature of 100100 ° C. is used as a mixture. The mixing ratio is such that the aqueous copolymer [II] is 5 to 80 parts by weight based on 100 parts by weight of the aqueous copolymer [I]. By the way, when the mixing ratio of the aqueous copolymer [II] is lower than 5 parts by weight, the curl is good, but the tackiness of the film becomes too strong (the glass transition temperature of the film becomes too low) and there is a problem that blocking occurs. Conversely, if the amount is more than 80 parts by weight, the resulting film becomes too hard (the glass transition temperature of the film becomes too high), and there is a problem that the undercoat layer-coated surface is curled.
なお、共重合体のガラス転移温度〔Tg〕は本発明にお
いては下記一般式（１）に基づいて推定される。In the present invention, the glass transition temperature [Tg] of the copolymer is estimated based on the following general formula (1).
Tg :共重合体のガラス転移温度 Tgi:第ｉ単量体ホモポリマーのガラス転移温度 Wi:第ｉ単量体の重量分率 上記の如き特定の水性共重合体は、共重合体中のカル
ボキシル基を例えば水酸化ナトリウム、水酸化カリウ
ム、アンモニア、各種の第１級、第２級、第３級アミン
等の適当なアルカリ性物質で中和することによって安定
化し、濃度20〜60重量％、好ましくは30〜50重量％程度
に調節して使用される。 Tg: glass transition temperature of the copolymer Tg i : glass transition temperature of the i-th monomer homopolymer W i : weight fraction of the i-th monomer The specific aqueous copolymer as described above is contained in the copolymer. Is stabilized by neutralization with a suitable alkaline substance such as, for example, sodium hydroxide, potassium hydroxide, ammonia, various primary, secondary, and tertiary amines, and a concentration of 20 to 60% by weight. , Preferably adjusted to about 30 to 50% by weight.
本発明の剥離紙は、上記の如き特定のガラス転移温度
を有する水性共重合体を主成分とする下塗り層を形成す
ることによって極めて顕著なカール防止効果が達成され
るものである。The release paper of the present invention achieves a very remarkable curl prevention effect by forming an undercoat layer containing an aqueous copolymer having a specific glass transition temperature as a main component as described above.
本発明において、下塗り層塗液の剥離紙基紙への塗布
は、例えば、ブレードコーター、エアーナイフコータ
ー、ロールコーター、グラビアコーター、バーコータ
ー、サイズプレスコーター等の各種装置が適宜使用され
るが、特に、本発明のような比較的高分子量の乳化剤を
用いて乳化共重合した水性共重合体は高濃度化が可能と
なるため、ブレードコーターが好ましく用いられる。而
して、ブレード塗工に適した塗液を得るためには、増粘
剤を添加することが望ましい。塗液用の増粘剤として
は、例えば、アルギン酸ナトリウム、カルボキシメチル
セルロース、メチルセルロース等が知られているが、塗
液の分散安定性、腐敗性等に問題があるため、ポリオキ
シエチレンエーテル誘導体型増粘剤を添加することは好
ましい実施態様の一つである。加えて、通常の増粘剤に
比較してポリオキシエチレンエーテル誘導体型増粘剤
は、塗液の保水性を改良する効果に優れているため、効
率良く高濃度ブレード塗工に適した塗液を調製すること
ができる。In the present invention, the application of the undercoat layer coating liquid to the release paper base paper, for example, various devices such as a blade coater, an air knife coater, a roll coater, a gravure coater, a bar coater, a size press coater are appropriately used, In particular, a blade coater is preferably used because an aqueous copolymer emulsified and copolymerized with a relatively high molecular weight emulsifier as in the present invention can be made to have a high concentration. In order to obtain a coating liquid suitable for blade coating, it is desirable to add a thickener. As a thickener for a coating solution, for example, sodium alginate, carboxymethylcellulose, methylcellulose, etc. are known, but there are problems with the dispersion stability of the coating solution, spoilage, etc. Adding a thickening agent is one of the preferred embodiments. In addition, compared to ordinary thickeners, polyoxyethylene ether derivative-type thickeners are more effective in improving the water retention of coating liquids, so coating liquids suitable for high-density blade coating efficiently Can be prepared.
増粘剤の使用量は、全水性共重合体100重量部に対し
て0.01〜５重量部の範囲で含有せしめられる。使用量が
0.01重量部を下回ると、所望の効果が得られず、５重量
部をを越えると、粘度が高くなり過ぎ、ブレード塗工に
は不適切である。因みに、ブレード塗工に適する塗液の
粘度は、300〜2000cps程度である。The amount of the thickener used is in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total aqueous copolymer. Consumption
If the amount is less than 0.01 part by weight, the desired effect cannot be obtained. If the amount exceeds 5 parts by weight, the viscosity becomes too high, which is unsuitable for blade coating. Incidentally, the viscosity of a coating liquid suitable for blade coating is about 300 to 2000 cps.
ブレード塗工法としては、ベベルタイプやベンドタイ
プのブレードを使用した塗工法に限られず、ロッドブレ
ード等を使用した塗工法も包含される。上記の如き特定
の塗液を基紙にブレード塗工することによって得られる
下塗り層は、バーやエアーナイフ塗工等とは異なり極め
て優れた表面平滑性を有しており、過度のキャレンダー
処理等を必要としないため空隙率も高く結果的にカール
の発生がない剥離紙の製造に大きく貢献するものであ
る。しかも、塗布層の乾燥速度が早く、乾燥に要する設
備、エネルギー等の経費を大幅に節減できる効果も付随
する。The blade coating method is not limited to a coating method using a bevel type or bend type blade, but also includes a coating method using a rod blade or the like. The undercoat layer obtained by applying the specific coating solution as described above to the base paper with a blade has extremely excellent surface smoothness, unlike bar or air knife coating, and excessive calendering treatment. Since no porosity is required, the porosity is high and consequently greatly contributes to the production of release paper free from curling. In addition, there is an effect that the drying speed of the coating layer is high and the cost of equipment and energy required for drying can be largely reduced.
かかる下塗り層水性塗液中には、本発明の所望の効果
を阻害しない範囲で、例えばエチレングリコール、グリ
セリン、トリメチロールプロパン、ジエチレングリコー
ル等の多価アルコール類、ポリエチレングリコール、ポ
リプロピレングリコール等のポリアルキレングリコール
類等の水溶性可塑剤；尿素・ホルムアルデヒド樹脂、メ
ラミン・ホルムアルデヒド樹脂、ポリアミド・ポリアミ
ン・エピクロルヒドリン樹脂、エポキシ樹脂等の架橋
剤；ポリビニルアルコール、スチレン・無水マレイン酸
共重合体塩、エチレン・アクリル酸共重合体塩等のバイ
ンダー樹脂；さらには滑剤；充填剤；消泡剤；濡れ剤；
レベリング剤；硬化剤；皮膜形成助剤等を適宜添加する
ことができる。これらの添加剤の量は、全水性共重合体
100重量部に対して０〜20重量部程度である。In such an undercoat layer aqueous coating solution, a polyhydric alcohol such as ethylene glycol, glycerin, trimethylolpropane, diethylene glycol, polyethylene glycol, or a polyalkylene glycol such as polypropylene glycol is contained within a range that does not inhibit the desired effect of the present invention. Water-soluble plasticizers such as urea / formaldehyde resin, melamine / formaldehyde resin, polyamide / polyamine / epichlorohydrin resin, epoxy resin, etc .; polyvinyl alcohol, styrene / maleic anhydride copolymer salt, ethylene / acrylic acid copolymer Binder resins such as polymer salts; further lubricants; fillers; defoamers; wetting agents;
A leveling agent, a curing agent, a film-forming auxiliary, and the like can be appropriately added. The amount of these additives depends on the total aqueous copolymer
It is about 0 to 20 parts by weight based on 100 parts by weight.
下塗り層塗液の剥離紙基紙への塗工は、オフマシンコ
ーターに限られず抄紙機上に設置したオンマシンコータ
ーで塗布してもよい。特に基紙が上質紙の場合にはオン
マシンブレードコーターでの塗工は、塗工直前の紙面温
度等の影響で塗布量が付け易く乾燥性も良好なため好ま
しい実施態様の一つである。The application of the undercoat layer coating liquid to the release paper base paper is not limited to an off-machine coater, and may be applied by an on-machine coater installed on a paper machine. In particular, when the base paper is high-quality paper, coating with an on-machine blade coater is one of the preferred embodiments because the coating amount is easy to apply and the drying property is good due to the influence of the paper surface temperature immediately before coating.
本発明において、下塗り層塗液の塗布量は、乾燥重量
で0.1〜20g/m2程度の範囲で調節するのが好ましく、特
に１〜10g/m2程度が望ましい。In the present invention, the coating amount of the undercoat layer coating liquid is preferably adjusted in a range of about 0.1 to 20 g / m 2 by dry weight, and particularly preferably about 1 to 10 g / m 2 .
本発明の剥離紙において、基紙としては通常の坪量30
〜300g/m2程度、厚さ30〜300μｍ程度の各種繊維シート
類が使用される。In the release paper of the present invention, the base paper has a normal basis weight of 30.
Various fiber sheets having a thickness of about 300 g / m 2 and a thickness of about 30 to 300 μm are used.
下塗り層の上に塗布される剥離剤については、特に限
定されず、各種のシリコーン化合物や弗素化合物等が常
法に従って塗布される。The release agent applied on the undercoat layer is not particularly limited, and various silicone compounds, fluorine compounds and the like are applied according to a conventional method.
かくして得られる本発明の剥離紙は基紙に特定のガラ
ス転移温度を有する水性共重合体を主成分とする下塗り
層が形成されているため、特にカールの発生が効果的に
防止され、通紙適性や複写適性等に優れた粘着紙を構成
することができるものである。The thus obtained release paper of the present invention has an undercoat layer containing an aqueous copolymer having a specific glass transition temperature as a main component formed on a base paper. It is capable of forming an adhesive paper excellent in suitability, copy suitability and the like.
なお、本発明の剥離紙を使用して粘着紙を構成する方
法については、格別の限定はなく、常法に従って例えば
溶剤型粘着剤、エマルジョン型粘着剤、ホットメルト型
粘着剤等を使用して塗布、乾燥、調湿等を行って適宜粘
着紙に仕上げられる。The method for forming the pressure-sensitive adhesive paper using the release paper of the present invention is not particularly limited, for example, using a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, and the like according to a conventional method. The adhesive paper is appropriately finished by performing application, drying, humidity control and the like.
「実施例」 以下に実施例を挙げて本発明をより具体的に説明する
が、勿論これらに限定されるものではない。なお、例中
の塗布量、部数、混合割合などは全て固形分で示した。"Examples" Hereinafter, the present invention will be described more specifically with reference to examples, but is not limited thereto. In addition, the coating amount, the number of copies, the mixing ratio, and the like in the examples are all represented by solid contents.
実施例１ アクリル酸ブチル270g、アクリル酸16g、アクリロニ
トリル114g、ポリオキシエチレンノニルフェニルエーテ
ル硫酸ナトリウム系乳化剤10g（花王（株）製 商品名
「ラテムル Ｅ−975」）（分子量:3622）、イオン交換
水170gから成る乳化単量体混合液〔Ａ〕を調製した。Example 1 270 g of butyl acrylate, 16 g of acrylic acid, 114 g of acrylonitrile, 10 g of sodium polyoxyethylene nonylphenyl ether sulfate emulsifier (trade name "Latemul E-975" manufactured by Kao Corporation) (molecular weight: 3622), ion-exchanged water An emulsion monomer mixture [A] consisting of 170 g was prepared.
次に、攪拌機、クーラー、滴下ロート、チッ素吸込
管、温度計を付帯した２の四つ口フラスコにイオン交
換水240gと上記乳化剤2g、過硫酸カリウム0.8gを仕込
み、チッ素置換しながら70℃まで昇温した後、上記乳化
単量体混合液〔Ａ〕の1/6を滴下した。反応率が90％に
達した時点で残りの乳化単量体混合液〔Ａ〕を２時間か
けて滴下して重合させた。滴下終了後70℃で２時間熟成
して反応を完結させた。Next, 240 g of ion-exchanged water, 2 g of the above-described emulsifier, and 0.8 g of potassium persulfate were charged into a two-necked two-necked flask equipped with a stirrer, a cooler, a dropping funnel, a nitrogen suction tube, and a thermometer. After the temperature was raised to ℃, 1/6 of the above-mentioned emulsified monomer mixture [A] was added dropwise. When the reaction rate reached 90%, the remaining emulsified monomer mixture [A] was added dropwise over 2 hours to polymerize. After completion of the dropwise addition, the mixture was aged at 70 ° C. for 2 hours to complete the reaction.
熟成終了後、フラスコ内容物を40℃に冷却し、水酸化
ナトリウム水溶液を添加して中和反応を行い、反応終了
後に強攪拌して本発明で使用する水性共重合体〔Ｉ〕を
得た。得られた水性共重合体〔Ｉ〕のガラス転移温度は
−21℃であった。（乳化剤量:3.0重量％） 次に、アクリル酸ブチル80g、アクリル酸8g、アクリ
ロニトリル240g、メタクリル酸メチル72g、上記乳化剤1
0g、イオン交換水170gから成る乳化単量体混合液〔Ｂ〕
を調製し、水性共重合体〔Ｉ〕と同様にして重合・熟成
を行った。After completion of aging, the contents of the flask were cooled to 40 ° C., an aqueous sodium hydroxide solution was added to carry out a neutralization reaction, and after completion of the reaction, the mixture was vigorously stirred to obtain an aqueous copolymer [I] used in the present invention. . The glass transition temperature of the obtained aqueous copolymer [I] was -21 ° C. (Emulsifier amount: 3.0% by weight) Next, 80 g of butyl acrylate, 8 g of acrylic acid, 240 g of acrylonitrile, 72 g of methyl methacrylate, and the above emulsifier 1
0 g, 170 g of ion-exchanged water emulsified monomer mixture [B]
Was prepared and polymerized and aged in the same manner as in the aqueous copolymer [I].
熟成終了後、フラスコ内容物を40℃に冷却し、水酸化
ナトリウム水溶液を添加して中和反応を行い、反応終了
後に強攪拌して本発明で使用する水性共重合体〔II〕を
得た。得られた水性共重合体〔II〕のガラス転移温度は
56℃であった。（乳化剤量:3.0重量％） 上記水性共重合体〔Ｉ〕100重量部に水性共重合体〔I
I〕20重量部を添加し、さらにコロイダルシリカ（日産
化学工業（株）製 商品名「スノーテックス30」）を１
重量部、グリセリン１重量部を添加して濃度35重量％の
下塗り層水性塗液を調製した。（粘度:400cps） 坪量40g/m2、厚さ55μｍの上質紙に上記下塗り層水性
塗液をブレードコーターで乾燥重量が5g/m2となるよう
に塗布、乾燥して剥離基紙を得た。After completion of aging, the contents of the flask were cooled to 40 ° C., and a neutralization reaction was performed by adding an aqueous sodium hydroxide solution. After the completion of the reaction, the mixture was vigorously stirred to obtain an aqueous copolymer [II] used in the present invention. . The glass transition temperature of the obtained aqueous copolymer [II] is
56 ° C. (Amount of emulsifier: 3.0% by weight) The aqueous copolymer [I] was added to 100 parts by weight of the aqueous copolymer [I].
I] 20 parts by weight of colloidal silica (trade name “Snowtex 30” manufactured by Nissan Chemical Industries, Ltd.)
In addition, 1 part by weight of glycerin and 1 part by weight of glycerin were added to prepare a 35% by weight aqueous solution of an undercoat layer. (Viscosity: 400 cps) The above undercoat layer aqueous coating solution is applied to a high-quality paper having a basis weight of 40 g / m 2 and a thickness of 55 μm using a blade coater so as to have a dry weight of 5 g / m 2 and dried to obtain a release base paper. Was.
この剥離基紙表面に、市販のシリコーン剥離剤を塗
布、乾燥して本発明の剥離紙を得た。A commercially available silicone release agent was applied to the surface of the release base paper and dried to obtain a release paper of the present invention.
なお、この剥離基紙の対剥離剤塗工液バリヤー性は極
めて良好であり、均一な軽剥離性剥離紙が得られた。ま
た、この剥離紙を用いて粘着紙を製造したところ、カー
ルの発生がなく、複写機での通紙適性、複写適性の極め
て良好な粘着紙が得られた。In addition, the barrier properties of the release base paper with respect to the release agent coating liquid were extremely good, and a uniform light release release paper was obtained. Further, when an adhesive paper was produced using this release paper, no curl occurred, and an adhesive paper having extremely good paper-passing and copying suitability in a copying machine was obtained.
実施例２ アクリル酸−２−エチルヘキシル190g、メタクリル酸
メチル60g、アクリロニトリル120g、アクリル酸30g、ポ
リオキシエチレンラウリルエーテル硫酸ナトリウム系乳
化剤16g（花王（株）製 商品名「ラテムル Ｅ−15
0」）（分子量:2488）、イオン交換水170gから成る乳化
単量体混合液〔Ｃ〕を調製した。Example 2 190 g of 2-ethylhexyl acrylate, 60 g of methyl methacrylate, 120 g of acrylonitrile, 30 g of acrylic acid, 16 g of sodium polyoxyethylene lauryl ether sulfate emulsifier (trade name "Latemul E-15" manufactured by Kao Corporation)
0 ") (molecular weight: 2488) and an emulsified monomer mixture [C] comprising 170 g of ion-exchanged water was prepared.
得られた乳化単量体混合液〔Ｃ〕を使用した以外は実
施例１と同様にして重合し、70℃で２時間熟成して反応
を完結させた。Polymerization was carried out in the same manner as in Example 1 except that the obtained emulsified monomer mixture [C] was used, followed by aging at 70 ° C. for 2 hours to complete the reaction.
熟成終了後、フラスコ内容物を40℃に冷却し、水酸化
カリウム水溶液を添加して中和反応を行い、反応終了後
に強攪拌して本発明で使用する水性共重合体〔Ｉ〕を得
た。なお、得られた水性共重合体〔Ｉ〕のガラス転移温
度は−６℃であった。（乳化剤量:4.5重量％） 次に、アクリル酸−２−エチルヘキシル50g、メタク
リル酸メチル100g、アクリロニトリル200g、アクリル酸
50g、上記乳化剤20g、イオン交換水170gから成る乳化単
量体混合液〔Ｄ〕を調製し、以下実施例１と同様にして
重合・熟成を行った。After completion of the aging, the contents of the flask were cooled to 40 ° C., an aqueous potassium hydroxide solution was added to carry out a neutralization reaction, and after completion of the reaction, the mixture was vigorously stirred to obtain an aqueous copolymer [I] used in the present invention. . In addition, the glass transition temperature of the obtained aqueous copolymer [I] was -6 degreeC. (Amount of emulsifier: 4.5% by weight) Next, 50 g of 2-ethylhexyl acrylate, 100 g of methyl methacrylate, 200 g of acrylonitrile, acrylic acid
An emulsified monomer mixture [D] comprising 50 g, the above-mentioned emulsifier 20 g, and ion-exchanged water 170 g was prepared, and polymerization and aging were carried out in the same manner as in Example 1.
熟成終了後、フラスコ内容物を40℃に冷却し、水酸化
カリウム水溶液を添加して中和反応を行い、反応終了後
に強攪拌して本発明で使用する水性共重合体〔II〕を得
た。なお、得られた水性共重合体〔II〕のガラス転移温
度は69℃であった。（乳化剤量:5.5重量％） 水性共重合体〔Ｉ〕100重量部に水性共重合体〔II〕
を40重量部添加して濃度40重量％の下塗り層水性塗液を
調製した。（粘度:500cps） 得られた下塗り層塗液を抄紙機上で坪量50g/m2、厚さ
65μｍの上質紙にブレードコーターで乾燥重量が4g/m2
となるように塗布、乾燥して剥離基紙を得た。After completion of aging, the contents of the flask were cooled to 40 ° C., a neutralization reaction was performed by adding an aqueous solution of potassium hydroxide, and after completion of the reaction, vigorous stirring was performed to obtain an aqueous copolymer [II] used in the present invention. . The glass transition temperature of the obtained aqueous copolymer [II] was 69 ° C. (Amount of emulsifier: 5.5% by weight) Aqueous copolymer [II] was added to 100 parts by weight of aqueous copolymer [I].
Was added to prepare an aqueous undercoat layer coating solution having a concentration of 40% by weight. (Viscosity: 500 cps) The obtained undercoat layer coating liquid was applied on a paper machine at a basis weight of 50 g / m 2 and a thickness of 50 g / m 2 .
Dry weight of 4 g / m 2 on blade paper with 65 μm high quality paper
And dried to obtain a release base paper.
この剥離基紙に市販のシリコーン剥離剤を塗布、乾燥
して本発明の剥離紙を得た。なお、この剥離基紙の対剥
離剤塗工液バリヤー性は極めて良好であり、均一な軽剥
離性剥離紙が得られた。また、この剥離紙を用いて粘着
紙を製造したところ、カールの発生がなく、複写機での
通紙適性、複写適性の極めて良好な粘着紙が得られた。A commercially available silicone release agent was applied to the release base paper and dried to obtain a release paper of the present invention. In addition, the barrier properties of the release base paper with respect to the release agent coating liquid were extremely good, and a uniform light release release paper was obtained. Further, when an adhesive paper was produced using this release paper, no curl occurred, and an adhesive paper having extremely good paper-passing and copying suitability in a copying machine was obtained.
実施例３ アクリル酸ブチル300g、アクリル酸80g、アクリロニ
トリル12g、アクリルアミド8gの単量体混合物を使用し
た以外は実施例１と同様に乳化共重合し、水酸化ナトリ
ウムによる中和反応等を行い水性共重合体〔Ｉ〕を得
た。この水性共重合体〔Ｉ〕のガラス転移温度は−41℃
であった。（乳化剤量:3.0重量％） この水性共重合体100重量部に実施例２の水性共重合
体〔II〕50重量部とポリエチレングリコール５重量部及
びエポキシ化合物（ナガセ化成工業（株）製 商品名
「デナコールEX−851」）５重量部を添加して濃度35重
量％の下塗り層水性塗液を調製した。（粘度:350cps） 坪量64g/m2、厚さ70μｍの上質紙に上記下塗り層水性
塗液をブレードコーターで乾燥重量が7g/m2となるよう
に塗布、乾燥して剥離基紙を得た。Example 3 Emulsion copolymerization was carried out in the same manner as in Example 1 except that a monomer mixture of 300 g of butyl acrylate, 80 g of acrylic acid, 12 g of acrylonitrile, and 8 g of acrylamide was used. A polymer [I] was obtained. The glass transition temperature of this aqueous copolymer [I] is -41 ° C.
Met. (Amount of emulsifier: 3.0% by weight) To 100 parts by weight of this aqueous copolymer, 50 parts by weight of the aqueous copolymer [II] of Example 2, 5 parts by weight of polyethylene glycol, and an epoxy compound (trade name, manufactured by Nagase Kasei Kogyo Co., Ltd.) "Denacol EX-851") was added in an amount of 5 parts by weight to prepare a 35% by weight aqueous solution of an undercoat layer. (Viscosity: 350 cps) The above undercoat layer aqueous coating liquid is applied to a high-quality paper having a basis weight of 64 g / m 2 and a thickness of 70 μm with a blade coater so as to have a dry weight of 7 g / m 2 and dried to obtain a release base paper. Was.
この剥離基紙表面に、市販のシリコーン剥離剤を塗
布、乾燥して本発明の剥離紙を得た。なお、この剥離基
紙の対剥離剤塗工液バリヤー性も極めて良好であり、均
一な軽剥離性剥離紙が得られた。また、この剥離紙を用
いて粘着紙を製造したところ、カールの発生がなく、複
写機での通紙適性、複写適性の極めて良好な粘着紙が得
られた。A commercially available silicone release agent was applied to the surface of the release base paper and dried to obtain a release paper of the present invention. In addition, the barrier properties of this release base paper with respect to the release agent coating liquid were extremely good, and a uniform light release release paper was obtained. Further, when an adhesive paper was produced using this release paper, no curl occurred, and an adhesive paper having extremely good paper-passing and copying suitability in a copying machine was obtained.
実施例４ 分子量2500の乳化剤を２重量％含有するアクリル酸ブ
チル−アクリロニトリル−アクリル酸３元共重合体（中
央理化工業（株）製 商品名「リカボンドET−Ｌ−924
−１」）（ガラス転移温度：−14℃）100重量部と分子
量2500の乳化剤を２重量％含有するアクリル酸ブチル−
アクリロニトリル−メタクリル酸メチル−アクリル酸４
元共重合体（中央理化工業（株）製 商品名「リカボン
ドET−Ｌ−924−２」）（ガラス転移温度:48℃）20重量
部を混合した水性共重合体に、ポリビニルアルコール10
重量部、グリセリン１重量部、コロイダルシリカ２重量
部、消泡剤0.1重量部を添加して濃度40重量％の下塗り
層水性塗液を調製した。（粘度:400cps） この下塗り水性塗液を坪量40g/m2、厚さ55μｍの上質
紙にロッドブレードコーターで乾燥重量が5g/m2となる
ように塗布、乾燥して剥離基紙を得た。Example 4 A butyl acrylate-acrylonitrile-acrylic acid terpolymer containing 2% by weight of an emulsifier having a molecular weight of 2500 (trade name "Licabond ET-L-924, manufactured by Chuo Rika Kogyo Co., Ltd.)
-1 ") (Glass transition temperature: -14 ° C) Butyl acrylate containing 100 parts by weight and 2% by weight of an emulsifier having a molecular weight of 2500
Acrylonitrile-methyl methacrylate-acrylic acid 4
Polyvinyl alcohol 10 was added to an aqueous copolymer obtained by mixing 20 parts by weight of a base copolymer (trade name “Licabond ET-L-924-2” manufactured by Chuo Rika Kogyo KK) (glass transition temperature: 48 ° C.).
By weight, 1 part by weight of glycerin, 2 parts by weight of colloidal silica, and 0.1 part by weight of an antifoaming agent were added to prepare an aqueous undercoat layer coating solution having a concentration of 40% by weight. (Viscosity: 400 cps) This undercoat aqueous coating liquid is applied to a high-quality paper having a basis weight of 40 g / m 2 and a thickness of 55 μm with a rod blade coater so as to have a dry weight of 5 g / m 2 and dried to obtain a release base paper. Was.
この剥離基紙表面に市販のシリコーン剥離剤を塗布、
乾燥して本発明の剥離紙を得た。なお、この剥離基紙の
対剥離剤塗工液バリヤー性も極めて良好であり、均一な
軽剥離性剥離紙が得られた。また、この剥離紙を用いて
粘着紙を製造したところ、カールの発生がなく、複写機
での通紙適性、複写適性の極めて良好な粘着紙が得られ
た。A commercially available silicone release agent is applied to the surface of the release base paper,
After drying, a release paper of the present invention was obtained. In addition, the barrier properties of this release base paper with respect to the release agent coating liquid were extremely good, and a uniform light release release paper was obtained. Further, when an adhesive paper was produced using this release paper, no curl occurred, and an adhesive paper having extremely good paper-passing and copying suitability in a copying machine was obtained.
実施例５ 実施例４の水性共重合体混合物100重量部に、ポリオ
キシエチレンエーテル誘導体型増粘剤（花王（株）製
商品名「ビスサーフＳ」）0.5重量部、ポリビニルアル
コール８重量部、グリセリン１重量部、コロイダルシリ
カ２重量部、消泡剤0.1重量部を添加して濃度40重量％
の下塗り層水性塗液を調製した。（粘度:800cps） 得られた下塗り層水性塗液を抄紙機上で、坪量40g/
m2、厚さ55μｍの上質紙にブレードコーターで乾燥重量
が5g/m2となるように塗布、乾燥して剥離基紙を得た。Example 5 A polyoxyethylene ether derivative type thickener (manufactured by Kao Corporation) was added to 100 parts by weight of the aqueous copolymer mixture of Example 4.
Brand name "Bissurf S") 0.5 part by weight, 8 parts by weight of polyvinyl alcohol, 1 part by weight of glycerin, 2 parts by weight of colloidal silica, 0.1 part by weight of antifoaming agent, concentration 40% by weight
The undercoat layer aqueous coating liquid was prepared. (Viscosity: 800 cps) The obtained undercoat layer aqueous coating liquid was applied on a paper machine at a basis weight of 40 g /
m 2, dry weight at a blade coater on a high-quality paper having a thickness of 55μm was obtained coated to a 5 g / m 2, dried to a release base paper.
この剥離基紙表面に市販のシリコーン剥離剤を塗布、
乾燥して本発明の剥離紙を得た。なお、この剥離基紙の
対剥離剤塗工液バリヤー性も極めて良好であり、均一な
軽剥離性剥離紙が得られた。また、この剥離紙を用いて
粘着紙を製造したところ、カールの発生がなく、複写機
での通紙適性、複写適性の極めて良好な粘着紙が得られ
た。A commercially available silicone release agent is applied to the surface of the release base paper,
After drying, a release paper of the present invention was obtained. In addition, the barrier properties of this release base paper with respect to the release agent coating liquid were extremely good, and a uniform light release release paper was obtained. Further, when an adhesive paper was produced using this release paper, no curl occurred, and an adhesive paper having extremely good paper-passing and copying suitability in a copying machine was obtained.
実施例６ 乳化剤としてポリオキシエチレンアルキルエーテル硫
酸ナトリウム（花王（株）製 商品名「レベノールW
Z」）（分子量:1200）を用いた以外は実施例１と同様に
して水性共重合体〔Ｉ〕、〔II〕を製造し、濃度30重量
％の下塗り層水性塗液を調製した。（粘度:100cps） 坪量64g/m2、厚さ70μｍの上質紙に上記下塗り層水性
塗液をバーコーターで乾燥重量が7g/m2となるように塗
布、乾燥して剥離基紙を得た。Example 6 Sodium polyoxyethylene alkyl ether sulfate (trade name "Levenol W" manufactured by Kao Corporation) as an emulsifier
Z ") (molecular weight: 1200), except that aqueous copolymers [I] and [II] were produced in the same manner as in Example 1 to prepare a 30% by weight aqueous solution of an undercoat layer. (Viscosity: 100 cps) The above undercoat layer aqueous coating liquid is applied to a high quality paper having a basis weight of 64 g / m 2 and a thickness of 70 μm with a bar coater so as to have a dry weight of 7 g / m 2 and dried to obtain a release base paper. Was.
この剥離基紙表面に、市販のシリコーン剥離剤を塗
布、乾燥して本発明の剥離紙を得た。なお、この剥離基
紙の対剥離剤塗工液バリヤー性も極めて良好であり、均
一な軽剥離性剥離紙が得られたまた、この剥離紙を用い
て粘着紙を製造したところ、カールの発生がなく、複写
機での通紙適性、複写適性の極めて良好な粘着紙が得ら
れた。A commercially available silicone release agent was applied to the surface of the release base paper and dried to obtain a release paper of the present invention. The release base paper had extremely good barrier properties with respect to the release agent coating liquid, and a uniform light release paper was obtained. In addition, when this release paper was used to produce an adhesive paper, curling occurred. As a result, an adhesive paper having very good suitability for paper passing and copying in a copying machine was obtained.
比較例１ 坪量50g/m2、厚さ65μｍの上質紙に、下塗り層水溶液
としてスチレン・マレイン酸共重合体（モンサント
（株）製 商品名「スクリプトセット520」）をバーコ
ーターで乾燥重量が5g/m2となるように塗布、乾燥して
剥離基紙を得た。Comparative Example 1 A styrene / maleic acid copolymer (product name “Script Set 520” manufactured by Monsanto Co., Ltd.) was used as an undercoat aqueous solution on a high-quality paper having a basis weight of 50 g / m 2 and a thickness of 65 μm using a bar coater. Coating and drying were carried out at 5 g / m 2 to obtain a release base paper.
なお、この下塗り層水溶液は濃度12重量％であり、ガ
ラス転移温度は156℃であった。The undercoat layer aqueous solution had a concentration of 12% by weight and a glass transition temperature of 156 ° C.
この剥離基紙に市販のシリコーン剥離剤を塗布乾燥し
て剥離紙を得た。剥離基紙の対剥離剤塗工液バリヤー性
は良好であったが、得られた剥離紙を用いて粘着紙を製
造したところ、カールの発生が著しく、複写機での通紙
適性、複写適性の極めて悪い粘着紙しか得られなかっ
た。A commercially available silicone release agent was applied to the release base paper and dried to obtain a release paper. Although the release base paper had good barrier properties with respect to the release agent coating liquid, adhesive paper was manufactured using the obtained release paper. Only extremely poor adhesive paper was obtained.
比較例２ 攪拌機、クーラー、滴下ロート、チッ素吸込管、温度
計を付帯する１の四つ口フラスコにイソプロピルアル
コール120gと水56gを仕込み、チッ素気流、攪拌下、還
流温度まで昇温する。滴下ロートにアクリル酸ブチル60
g、アクリル酸30g、アクリロニトリル10g、2,2′−アゾ
ビスイソブチロニトリル0.5gを仕込み、この均一溶液を
２時間要して滴下し、滴下後２時間熟成をおこなった。
なお、重合及び熟成は還流温度で行い、熟成終了後にフ
ラスコ内容物を40℃に冷却し、水酸化ナトリウム水溶液
を添加して中和反応を行った。中和反応終了後、昇温し
てイソプロピルアルコールを水との共沸によって系から
除去し、冷却後に濃度を30重量％に希釈して水溶液共重
合体を得た。得られた水溶液共重合体のガラス転移温度
は−11℃であった。Comparative Example 2 120 g of isopropyl alcohol and 56 g of water were charged into a four-necked flask equipped with a stirrer, a cooler, a dropping funnel, a nitrogen suction tube, and a thermometer, and heated to a reflux temperature under a nitrogen gas flow and stirring. Butyl acrylate 60 in dropping funnel
g, 30 g of acrylic acid, 10 g of acrylonitrile, and 0.5 g of 2,2'-azobisisobutyronitrile were charged, and this homogeneous solution was added dropwise over 2 hours, and aging was performed for 2 hours after the addition.
The polymerization and the aging were carried out at a reflux temperature. After the completion of the aging, the contents of the flask were cooled to 40 ° C., and a neutralization reaction was carried out by adding an aqueous sodium hydroxide solution. After completion of the neutralization reaction, the temperature was raised to remove isopropyl alcohol from the system by azeotropic distillation with water. After cooling, the concentration was diluted to 30% by weight to obtain an aqueous solution copolymer. The glass transition temperature of the resulting aqueous solution copolymer was -11 ° C.
この水溶性共重合体80重量部に酸化澱粉（王子コーン
・スターチ（株）製 商品名「エースＣ」）水溶液を18
重量部添加し、さらにコロイダルシリカを２重量部添加
して濃度24重量％の下塗り水溶液を調製した。An aqueous solution of oxidized starch (Ace C, trade name, manufactured by Oji Corn Starch Co., Ltd.) was added to 18 parts by weight of the water-soluble copolymer.
2 parts by weight of colloidal silica was further added to prepare an undercoat aqueous solution having a concentration of 24% by weight.
坪量50g/m2、厚さ65μｍの上質紙に上記下塗り層水溶
液をバーコーターで乾燥重量が7g/m2となるように塗
布、乾燥して剥離基紙を得た。なお、この下塗り水溶液
は乾燥性が悪く、紙切れが頻発して生産性が著しく悪か
った。The aqueous solution of the undercoat layer was applied to a high-quality paper having a basis weight of 50 g / m 2 and a thickness of 65 μm using a bar coater to a dry weight of 7 g / m 2 and dried to obtain a release base paper. In addition, the undercoat aqueous solution had poor drying properties, and paper breakage frequently occurred, resulting in extremely poor productivity.
この剥離基紙に市販のシリコーン剥離剤を塗布乾燥し
て剥離紙を得た。剥離基紙の対剥離剤塗工液バリヤー性
は良好であったが、得られた剥離紙を用いて製造した粘
着紙は複写機での通紙適性が不充分であった。A commercially available silicone release agent was applied to the release base paper and dried to obtain a release paper. Although the release base paper had good barrier properties with respect to the release agent coating liquid, the pressure-sensitive adhesive paper produced by using the obtained release paper had insufficient paper-passing suitability in a copying machine.
比較例３ アニオン系乳化剤（ラウリル硫酸ナトリウム）（分子
量:272）0.2g、過硫酸アンモニウム0.5g、水125gを反応
器に入れ、攪拌しつつ加熱して75℃に保ち、アクリル酸
ブチル85g、メタクリル酸メチル7g、アクリル酸5g、メ
タクリル酸−β−ヒドロキシエチル3gよりなる混合物を
連続的に３時間で添加した。添加終了後75℃で３時間保
持して反応を完結した。得られたエマルジョンのガラス
転移温度は−45℃であった。（乳化剤量:0.2重量％） このエマルジョン75重量部に酸化澱粉（王子コーン・
スターチ（株）製 商品名「エースＡ」）水溶液を25重
量部添加し、濃度25重量％の下塗り水性塗液を調製し
た。この水性塗液は安定性が悪く、澱粉が沈降する傾向
が認められた。Comparative Example 3 0.2 g of an anionic emulsifier (sodium lauryl sulfate) (molecular weight: 272), 0.5 g of ammonium persulfate, and 125 g of water were placed in a reactor, heated with stirring and maintained at 75 ° C., and 85 g of butyl acrylate and methacrylic acid. A mixture consisting of 7 g of methyl, 5 g of acrylic acid and 3 g of β-hydroxyethyl methacrylate was added continuously over 3 hours. After completion of the addition, the reaction was maintained at 75 ° C. for 3 hours to complete the reaction. The glass transition temperature of the obtained emulsion was -45 ° C. (Amount of emulsifier: 0.2% by weight) 75 parts by weight of this emulsion was oxidized starch (Oji corn,
An aqueous solution of an undercoat was prepared by adding 25 parts by weight of an aqueous solution (trade name “Ace A” manufactured by Starch Co., Ltd.) to a concentration of 25% by weight. This aqueous coating liquid had poor stability, and a tendency for starch to settle was observed.
坪量50g/m2、厚さ65μｍの上質紙に上記下塗り水性塗
液をバーコーターで乾燥重量が5g/m2となるように塗
布、乾燥して剥離基紙を得たが、剥離基紙表面にはスト
リークの発生が認められた。The above undercoat aqueous coating solution was applied to a high-quality paper having a basis weight of 50 g / m 2 and a thickness of 65 μm with a bar coater so that the dry weight was 5 g / m 2, and dried to obtain a release base paper. Streaks were observed on the surface.
この剥離基紙に市販のシリコーン剥離剤を塗布乾燥し
て剥離紙を得たが、剥離基紙の対剥離剤塗工液バリヤー
性が不充分であり、この剥離紙を用いて製造した粘着紙
は剥離不良を起こした。A commercially available silicone release agent was applied to this release base paper and dried to obtain a release paper. However, the barrier properties of the release base paper with respect to the release agent coating liquid were insufficient, and the adhesive paper produced using this release paper was used. Caused poor peeling.
比較例４ アクリル酸−２−エチルヘキシル190g、メタクリル酸
メチル60g、アクリロニトリル120g、アクリル酸30g、分
子量1000以下のアニオン系乳化剤、例えば、ドデシルベ
ンゼンスルホン酸ナトリウム（分子量:348）8g、ジオク
チルスルホコハク酸ナトリウム（分子量:444）8g、イオ
ン交換水170gから成る乳化単量体混合液〔Ｅ〕を調製し
た。Comparative Example 4 190 g of 2-ethylhexyl acrylate, 60 g of methyl methacrylate, 120 g of acrylonitrile, 30 g of acrylic acid, 8 g of an anionic emulsifier having a molecular weight of 1,000 or less, for example, 8 g of sodium dodecylbenzenesulfonate (molecular weight: 348), 8 g of sodium dioctyl sulfosuccinate ( Emulsion monomer mixture [E] consisting of 8 g of molecular weight: 444) and 170 g of ion-exchanged water was prepared.
得られた乳化単量体混合液〔Ｅ〕を使用した以外は実
施例１と同様にして重合し、水酸化ナトリウムによる中
和反応等を行い水性共重合体〔Ｉ〕を得た。この水性共
重合体〔Ｉ〕のガラス転移温度は−６℃であった。（乳
化剤量:4.5重量％） 次に、アクリル酸ブチル100g、メタクリル酸メチル25
0g、アクリル酸50g、上記乳化剤10g、イオン交換水170g
から成る乳化単量体混合液〔Ｆ〕を調製した。Polymerization was carried out in the same manner as in Example 1 except that the obtained emulsion monomer mixture [E] was used, and a neutralization reaction with sodium hydroxide and the like were performed to obtain an aqueous copolymer [I]. The glass transition temperature of this aqueous copolymer [I] was -6 ° C. (Emulsifier amount: 4.5% by weight) Next, 100 g of butyl acrylate and 25 g of methyl methacrylate
0 g, acrylic acid 50 g, the above emulsifier 10 g, ion exchange water 170 g
(F) was prepared.
得られた乳化単量体混合液〔Ｆ〕を使用した以外は実
施例１と同様にして重合し、水酸化ナトリウムによる中
和反応等を行い水性共重合体〔II〕を得た。この水性共
重合体〔II〕のガラス転移温度は42℃であった。（乳化
剤量:3.0重量％） 水性共重合体〔Ｉ〕100重量部に水性共重合体〔II〕4
0重量部添加して濃度35重量％の下塗り層塗液を調整し
た。（粘度:300cps） この下塗り層塗液は混合安定性が悪く、少量の凝集物
の発生が認められた。Polymerization was carried out in the same manner as in Example 1 except that the obtained emulsified monomer mixture [F] was used, and a neutralization reaction with sodium hydroxide and the like were performed to obtain an aqueous copolymer [II]. The glass transition temperature of this aqueous copolymer [II] was 42 ° C. (Emulsifier amount: 3.0% by weight) Aqueous copolymer [II] 4 was added to 100 parts by weight of aqueous copolymer [I].
By adding 0 parts by weight, an undercoat layer coating solution having a concentration of 35% by weight was prepared. (Viscosity: 300 cps) This undercoat layer coating liquid had poor mixing stability, and generation of a small amount of aggregates was observed.
坪量50g/m2、厚さ65μｍの上質紙に上記下塗り水性塗
液をブレードコーターで乾燥重量が4g/m2となるように
塗布、乾燥して剥離基紙を得たが、剥離基紙表面にはス
トリークの発生が認められた。The undercoat aqueous coating liquid was applied to a high-quality paper having a basis weight of 50 g / m 2 and a thickness of 65 μm with a blade coater so that the dry weight was 4 g / m 2, and dried to obtain a release base paper. Streaks were observed on the surface.
この剥離基紙に市販のシリコーン剥離剤を塗布乾燥し
て剥離紙を得たが、剥離基紙の対剥離剤塗工液バリヤー
性が不充分であり、この剥離紙を用いて製造した粘着紙
は剥離不良を起こした。A commercially available silicone release agent was applied to this release base paper and dried to obtain a release paper. However, the barrier properties of the release base paper with respect to the release agent coating liquid were insufficient, and the adhesive paper produced using this release paper was used. Caused poor peeling.
「効果」 本発明の剥離紙は、カールの発生が効果的に防止さ
れ、通紙適性や複写適性に優れた粘着紙を構成すること
ができるものであった。[Effect] The release paper of the present invention was capable of effectively preventing the occurrence of curling, and was able to constitute an adhesive paper excellent in paper passage suitability and copy suitability.
Claims (10)
剥離剤層を設けてなる剥離紙において、該下塗り層の主
成分が、分子量が1000〜10000の乳化剤を２〜10重量％
含有する下記組成の単量体を乳化共重合し、且つガラス
転移温度が−60〜０℃である水性共重合体〔Ｉ〕 （ａ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｂ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:40〜90重量％ （ｃ） これらの単量体と共重合可能な他の単量体:0〜
40重量％ と、分子量が1000〜10000の乳化剤を２〜10重量％含有
する下記組成の単量体を乳化共重合し、且つガラス転移
温度が45〜100℃である水性共重合体〔II〕 （ｄ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｅ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:5〜40重量％ （ｆ） これらの単量体と共重合可能な他の単量体:50
〜90重量％ との混合物であることを特徴とする剥離紙。1. A release paper comprising a base paper and a release agent layer provided on at least one side of the base paper via an undercoat layer, wherein the main component of the undercoat layer is 2 to 10% by weight of an emulsifier having a molecular weight of 1,000 to 10,000.
Aqueous copolymer [I] (a) having an ethylenically unsaturated carboxylic acid-containing monomer obtained by emulsion-copolymerizing a monomer having the following composition and having a glass transition temperature of -60 to 0 ° C: 1 to 20
(B) C4-18 alkyl ester monomer of (meth) acrylic acid: 40-90% by weight (c) Other monomers copolymerizable with these monomers: 0-
An aqueous copolymer [II] in which 40% by weight and a monomer having the following composition containing 2 to 10% by weight of an emulsifier having a molecular weight of 1,000 to 10,000 are emulsion-copolymerized and have a glass transition temperature of 45 to 100 ° C. (D) Ethylenically unsaturated carboxylic acid-containing monomer: 1 to 20
(E) C4-18 alkyl ester monomer of (meth) acrylic acid: 5 to 40% by weight (f) Other monomers copolymerizable with these monomers: 50
Release paper characterized in that it is a mixture of about 90% by weight.
に対して水性共重合体〔II〕を５〜80重量部含有する請
求項（１）記載の剥離紙。2. The release paper according to claim 1, wherein the undercoat layer contains 5-80 parts by weight of the aqueous copolymer [II] based on 100 parts by weight of the aqueous copolymer [I].
た界面活性剤である請求項（１）〜（２）記載の剥離
紙。3. The release paper according to claim 1, wherein the emulsifier is a surfactant having both nonionic and anionic properties.
してポリオキシエチレンエーテル誘導体型増粘剤を0.01
〜５重量部含有する請求項（１）〜（３）記載の剥離
紙。4. An undercoat layer comprising a polyoxyethylene ether derivative-type thickener in an amount of 0.01 part by weight based on 100 parts by weight of the total aqueous copolymer.
The release paper according to any one of Claims (1) to (3), wherein the release paper contains from 5 to 5 parts by weight.
10000の乳化剤を２〜10重量％含有する下記組成の単量
体を乳化共重合し、且つガラス転移温度が−60〜０℃で
ある水性共重合体〔Ｉ〕 （ａ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｂ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:40〜90重量％ （ｃ） これらの単量体と共重合可能な他の単量体:0〜
40重量％ と、分子量が1000〜10000の乳化剤を２〜10重量％含有
する下記組成の単量体を乳化共重合し、且つガラス転移
温度が45〜100℃である水性共重合体〔II〕 （ｄ） エチレン性不飽和カルボン酸含有単量体:1〜20
重量％ （ｅ） （メタ）アクリル酸のＣ４〜18アルキルエステ
ル単量体:5〜40重量％ （ｆ） これらの単量体と共重合可能な他の単量体:50
〜90重量％ との混合物を主成分とする塗液を塗工して下塗り層を形
成し、該下塗り層上に剥離剤層を形成することを特徴と
する剥離紙の製造方法。5. A base paper having a molecular weight of at least 1,000 on at least one side.
Aqueous copolymer [I] having a glass transition temperature of -60 to 0 ° C by emulsion-copolymerizing a monomer having the following composition containing 2 to 10% by weight of 10,000 emulsifiers (a) ethylenically unsaturated carboxylic acid Acid-containing monomer: 1-20
(B) C4-18 alkyl ester monomer of (meth) acrylic acid: 40-90% by weight (c) Other monomers copolymerizable with these monomers: 0-
An aqueous copolymer [II] in which 40% by weight and a monomer having the following composition containing 2 to 10% by weight of an emulsifier having a molecular weight of 1,000 to 10,000 are emulsion-copolymerized and have a glass transition temperature of 45 to 100 ° C. (D) Ethylenically unsaturated carboxylic acid-containing monomer: 1 to 20
(E) C4-18 alkyl ester monomer of (meth) acrylic acid: 5 to 40% by weight (f) Other monomers copolymerizable with these monomers: 50
To 90% by weight of a coating liquid containing a mixture of the above as a main component, forming an undercoat layer, and forming a release agent layer on the undercoat layer.
に対して水性共重合体〔II〕を５〜80重量部含有する請
求項（５）記載の製造方法。6. The method according to claim 5, wherein the undercoat layer contains 5-80 parts by weight of the aqueous copolymer [II] based on 100 parts by weight of the aqueous copolymer [I].
界面活性剤である請求項（５）〜（６）記載の製造方
法。7. The method according to claim 5, wherein the emulsifier has both nonionic and anionic properties and is a surfactant.
塗り層を形成する請求項（５）〜（７）記載の製造方
法。8. The method according to claim 5, wherein an undercoat layer is formed on at least one side of the base paper by blade coating.
してポリオキシエチレンエーテル誘導体型増粘剤を0.01
〜５重量部含有する請求項（５）〜（８）記載の製造方
法。9. An undercoat layer comprising a polyoxyethylene ether derivative type thickener in an amount of 0.01 to 100 parts by weight of the total aqueous copolymer.
The production method according to any one of claims (5) to (8), wherein the content is from 5 to 5 parts by weight.
工で下塗り層を形成する請求項（５）〜（９）記載の製
造方法。10. The method according to claim 5, wherein the undercoat layer is formed on one side of the base paper by on-machine blade coating.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1129576A JP2642479B2 (en) | 1989-05-22 | 1989-05-22 | Release paper and method for producing the same |
| US07/514,430 US5064717A (en) | 1989-04-28 | 1990-04-25 | Adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1129576A JP2642479B2 (en) | 1989-05-22 | 1989-05-22 | Release paper and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02308881A JPH02308881A (en) | 1990-12-21 |
| JP2642479B2 true JP2642479B2 (en) | 1997-08-20 |
Family
ID=15012881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1129576A Expired - Fee Related JP2642479B2 (en) | 1989-04-28 | 1989-05-22 | Release paper and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2642479B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2888083B2 (en) * | 1993-03-23 | 1999-05-10 | 王子製紙株式会社 | Adhesive sheet |
| JP4678913B2 (en) * | 1999-04-19 | 2011-04-27 | 旭化成ケミカルズ株式会社 | Latex for release paper undercoat |
| JP6384307B2 (en) * | 2014-12-17 | 2018-09-05 | 日本製紙パピリア株式会社 | Release paper base |
| JP7298648B2 (en) * | 2021-05-28 | 2023-06-27 | 王子ホールディングス株式会社 | water resistant paper |
-
1989
- 1989-05-22 JP JP1129576A patent/JP2642479B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02308881A (en) | 1990-12-21 |
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