JPH0959580A - Pressure-sensitive adhesive - Google Patents
Pressure-sensitive adhesiveInfo
- Publication number
- JPH0959580A JPH0959580A JP16662896A JP16662896A JPH0959580A JP H0959580 A JPH0959580 A JP H0959580A JP 16662896 A JP16662896 A JP 16662896A JP 16662896 A JP16662896 A JP 16662896A JP H0959580 A JPH0959580 A JP H0959580A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- polymerizable monomer
- acrylic resin
- weight
- 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.)
- Granted
Links
Landscapes
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、セルロース系フィルム
を保護層に持つ偏光フィルムまたは位相差フィルムと液
晶セルとを接着させる等の光学用に特に有用な粘着剤に
関する。更に詳しくは高温、高湿条件下での耐久性に優
れた感圧接着型偏光板および感圧接着型位相差板等の光
学用シート用の粘着剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive which is particularly useful for optical purposes such as bonding a polarizing film or a retardation film having a cellulosic film as a protective layer to a liquid crystal cell. More specifically, the present invention relates to a pressure-sensitive adhesive for an optical sheet such as a pressure-sensitive adhesive type polarizing plate and a pressure-sensitive adhesive type retardation plate which have excellent durability under high temperature and high humidity conditions.
【０００２】[0002]
【従来の技術】偏光板は液晶表示体の普及により工業的
に大量に生産され、使用される様になって来た。ウオッ
チ、電卓等の小物の表示体から出発した液晶表示体もパ
ソコン、ワ−ドプロセッサ−等のＯＡ機器、液晶テレ
ビ、液晶プロジェクタ−、車載用インスツルメントパネ
ル、車載用ナビゲ−ションシステム等、高価格機器や高
耐久機器に適用されるようになるにしたがい、益々その
高い信頼性が要求される様になって来た。液晶表示体の
信頼性の中で、従来より最も改善が望まれている部品の
１つが偏光板である。この液晶用偏光板は、組立上の簡
便さ及び表面での反射ロスを軽減させる為に製品形態の
大部分は感圧性接着剤層を有する感圧性接着型偏光板で
あり、その偏光子自身の耐久性向上の他に実用上最も重
要なポイントは偏光板に使用される感圧接着剤層の耐久
性向上である。2. Description of the Related Art Polarizing plates have been industrially produced and used in large quantities due to the spread of liquid crystal displays. Liquid crystal displays starting from small displays such as watches and calculators can also be used for personal computers, office automation equipment such as word processors, liquid crystal televisions, liquid crystal projectors, in-vehicle instrument panels, in-vehicle navigation systems, etc. As it has been applied to high-priced equipment and highly durable equipment, its high reliability has been required more and more. Among the reliability of the liquid crystal display, one of the components most desired to be improved is a polarizing plate. Most of the product forms of this polarizing plate for liquid crystal are pressure-sensitive adhesive type polarizing plates having a pressure-sensitive adhesive layer in order to simplify assembly and reduce reflection loss on the surface. Besides the improvement of durability, the most important point for practical use is the improvement of durability of the pressure-sensitive adhesive layer used for the polarizing plate.
【０００３】一般に感圧接着型偏光板は、ヨウ素または
二色性染料を偏光子として配向させた延伸ポリビニルア
ルコ−ル（以下ＰＶＡと略す）フィルムの両面をトリア
セチルセルロ−ス（以下ＴＡＣと略す）フィルムで積層
接着し、さらにＴＡＣ表面に感圧性接着剤層を設けるこ
とにより製造される。実際の製造に際してはこの感圧接
着型偏光板を液晶セルのガラス板表面に感圧性接着剤層
を介して貼り合わされる。この様にして作られた一般の
偏光板付き液晶セルを高温、高湿の条件下に長時間暴露
すると、偏光板のＴＡＣの白濁、変色、物理的破壊へと
劣化が進み、最終的には全く偏光板としての機能を消失
するに至ることがある。In general, a pressure-sensitive adhesive type polarizing plate has a triacetyl cellulose (hereinafter abbreviated as TAC) on both sides of a stretched polyvinyl alcohol (hereinafter abbreviated as PVA) film in which iodine or a dichroic dye is used as a polarizer. ) A film is laminated and adhered, and a pressure-sensitive adhesive layer is further provided on the surface of the TAC to manufacture. In the actual production, the pressure-sensitive adhesive type polarizing plate is attached to the surface of the glass plate of the liquid crystal cell via a pressure-sensitive adhesive layer. If a general liquid crystal cell with a polarizing plate made in this way is exposed to high temperature and high humidity conditions for a long time, the TAC of the polarizing plate deteriorates to white turbidity, discoloration, and physical destruction, and finally In some cases, the function as a polarizing plate may be lost.
【０００４】一方、ＳＴＮ方式の液晶表示体による白黒
表示法の一つとして、液晶セルと偏光板の間に位相差板
を設ける方法が普及している。位相差板の一種であるＰ
ＶＡ位相差板は、延伸されたＰＶＡフィルムの片面また
は両面をＴＡＣフィルムで支持し、その表面に感圧性接
着剤層を設けることにより製造される。この一層または
複数層の位相差板を、感圧性接着剤層を介して、ＳＴＮ
セルに貼り合わせ、最外層に偏光板を貼り合わせること
により、液晶表示体を構成するものであるが、この場合
も偏光板単体を貼り合わせた場合と同様、高温、高湿条
件下に長時間暴露されると白濁、物理的破壊へと至りそ
う長くない時間で全く機能を消失してしまうことがあ
る。On the other hand, a method of providing a retardation plate between a liquid crystal cell and a polarizing plate has become widespread as one of black and white display methods by an STN type liquid crystal display. P which is a kind of retarder
The VA retardation plate is produced by supporting one or both sides of a stretched PVA film with a TAC film and providing a pressure-sensitive adhesive layer on the surface. This single-layer or multi-layer retardation plate is used to form an STN via a pressure-sensitive adhesive layer.
A liquid crystal display is constructed by laminating it to the cell and laminating the polarizing plate to the outermost layer. In this case as well, the same as when laminating the polarizing plate alone, it is necessary to keep it under high temperature and high humidity conditions for a long time. When exposed, it may become cloudy and physical destruction may completely disappear in a short time.
【０００５】上記ＴＡＣの劣化を防止する手段として、
特開昭５９−１１１１１４では感圧性接着剤のアクリル
酸含量を少なくする方法が、また特開平４−２５４８０
３では３級アミンを添加する方法などが提案されてい
る。しかしながら上記手段ではＴＡＣの劣化防止には効
果があるものの、ガラスとの密着性が低下することによ
り高温高湿下で剥離等を生じ耐久性が低下する傾向にあ
る。As a means for preventing the deterioration of the TAC,
Japanese Patent Laid-Open No. 59-111114 discloses a method of reducing the acrylic acid content of a pressure-sensitive adhesive.
3 proposes a method of adding a tertiary amine. However, although the above-mentioned means is effective in preventing the deterioration of TAC, the adhesion with the glass tends to deteriorate, so that peeling or the like occurs under high temperature and high humidity and the durability tends to decrease.
【０００６】[0006]
【発明が解決しようとする課題】本発明は高温高湿の条
件下で長時間暴露してもＴＡＣの劣化のない高耐久の感
圧接着型偏光板、感圧接着型位相差板等の感圧接着型光
学用シート用の粘着剤を提供するものである。DISCLOSURE OF THE INVENTION The present invention relates to a pressure-sensitive adhesive type polarizing plate, a pressure-sensitive adhesive type retardation plate or the like having high durability, which does not deteriorate TAC even when exposed to a high temperature and high humidity for a long time. The present invention provides a pressure-sensitive adhesive for a pressure-adhesive optical sheet.
【０００７】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討し、これらの原因を鋭意究明したと
ころ、感圧性接着剤の共重合成分の一つであるアクリル
酸の酸性により高温、高湿条件下接触しているＴＡＣの
アセチル基を加水分解させ、その酢酸がさらに別のアセ
チル基を次々と加水分解させ、急激に破壊、劣化させる
ものであることを突きとめた。そして、その対策とし
て、偏光板、位相差板等の光学素子に設けられる感圧性
接着剤層を形成する樹脂共重合体系粘着剤において、共
重合体の１成分として分子中にカルボキシル基を有する
重合性モノマ−、分子中に水酸基を有する重合性モノマ
ー及び分子中にアミド基を有する重合性モノマーを使用
することにより、従来の欠点が改善されることを見い出
した。すなわち本発明は、（１）アクリル樹脂共重合体
系粘着剤において、重合成分としてアクリル酸系アルキ
ルエステル、分子中にカルボキシル基を有する重合性モ
ノマー、分子中に水酸基を有する重合性モノマー、及び
分子中にアミド基を有する重合性モノマーを必須成分と
するアクリル樹脂共重合体を含有することを特徴とする
粘着剤、（２）アクリル樹脂共重合体中のカルボキシル
基とアミド基の比率がカルボキシル基１個に対しアミド
基が３〜５個である（１）の粘着剤、（３）アクリル樹
脂共重合体の重量平均分子量が１，０００，０００〜
２，０００，０００である（１）または（２）の粘着
剤、（４）上記（１）ないし（３）の粘着剤の層を有す
る光学用シート、（５）光学用シートが偏光板又は位相
差板である（４）の光学用シート、に関するものであ
る。[Means for Solving the Problems] The inventors of the present invention have made extensive studies to solve the above problems, and have made thorough investigations into their causes. As a result, the acidity of acrylic acid, which is one of the copolymerization components of pressure-sensitive adhesives, has been investigated. It was found that the acetyl group of TAC that is contacted under high temperature and high humidity is hydrolyzed, and the acetic acid hydrolyzes further acetyl groups one after another, causing rapid destruction and deterioration. Then, as a countermeasure, in a resin-copolymer-based pressure-sensitive adhesive forming a pressure-sensitive adhesive layer provided on an optical element such as a polarizing plate or a retardation plate, a polymer having a carboxyl group in the molecule as one component of the copolymer. It has been found that the conventional defects can be improved by using a polymerizable monomer, a polymerizable monomer having a hydroxyl group in the molecule and a polymerizable monomer having an amide group in the molecule. That is, the present invention provides (1) an acrylic resin copolymer-based pressure-sensitive adhesive, which comprises an acrylic acid-based alkyl ester as a polymerization component, a polymerizable monomer having a carboxyl group in the molecule, a polymerizable monomer having a hydroxyl group in the molecule, and A pressure-sensitive adhesive containing an acrylic resin copolymer containing a polymerizable monomer having an amide group as an essential component, and (2) the ratio of carboxyl groups to amide groups in the acrylic resin copolymer is 1 The weight average molecular weight of the (1) pressure-sensitive adhesive having 3 to 5 amide groups and (3) acrylic resin copolymer per 1,000,000
The pressure-sensitive adhesive according to (1) or (2), which is 2,000,000, (4) an optical sheet having a layer of the pressure-sensitive adhesive according to (1) to (3) above, and (5) the optical sheet is a polarizing plate or The present invention relates to the optical sheet (4) which is a retardation plate.
【０００８】[0008]
【発明の実施の形態】本発明で使用するアクリル樹脂共
重合体は、重合成分としてアクリル酸系アルキルエステ
ル、分子中にカルボキシル基を有する重合性モノマ−、
分子中に水酸基を有する重合性モノマー及び分子中にア
ミド基を有する重合性モノマーを必須の成分としたもの
で、必要に応じてコモノマー等のその他のモノマー成分
を使用する。アクリル酸系アルキルエステルとしては、
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）アクリル酸イソプロピル、（メタ）
アクリル酸ｎ−プロピル、（メタ）アクリル酸イソブチ
ル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル
酸ｔ−ブチル、（メタ）アクリル酸ドデシル等の（メ
タ）アクリル酸（炭素数１〜１２）アルキルエステルが
挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The acrylic resin copolymer used in the present invention comprises an acrylic acid alkyl ester as a polymerization component, a polymerizable monomer having a carboxyl group in the molecule,
A polymerizable monomer having a hydroxyl group in the molecule and a polymerizable monomer having an amide group in the molecule are used as essential components, and other monomer components such as comonomers are used as necessary. As acrylic acid type alkyl ester,
For example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
(Meth) acrylic acid (having 1 to 12 carbon atoms) such as n-propyl acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and dodecyl (meth) acrylate. ) Alkyl esters are mentioned.
【０００９】分子中にカルボキシル基を有する重合性モ
ノマ−としては、例えばアクリル酸、メタクリル酸、マ
レイン酸、イタコン酸などが挙げられる。分子中に水酸
基を有する重合性モノマーとしては、例えば２−ヒドロ
キシエチルアクリレート、２−ヒドロキシエチルメタク
リレート、２−ヒドロキシプロピルアクリレート、２−
ヒドロキシプロピルメタクリレート、３−クロロ−２−
ヒドロキシプロピルアクリレート、３−クロロ−２−ヒ
ドロキシプロピルメタクリレート等のヒドロキシ（炭素
数１〜５）アルキル（メタ）アクリレート、ジエチレン
グリコールモノアクリレート、ジエチレングリコールモ
ノメタクリレート等のジエチレングリコール（メタ）ア
クリレートなどが挙げられ、さらにグリシジルメタクリ
レート、アリルグリシジルエーテルなどが挙げられる。
分子中にアミド基を有する重合性モノマーとしては、例
えばＮ，Ｎ−ジメチルアミノプロピルアクリルアミド、
Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルア
クリルアミド、アクリロイルモルホリン、Ｎ−イソプロ
ピルアクリルアミド、Ｎ−メチロールアクリルアミド、
アクリルアミドなどのアクリルアミド系モノマーが挙げ
られる。コモノマー等のその他のモノマーとしては、例
えば酢酸ビニル、アクリロニトリル、スチレンなどが挙
げられる。Examples of the polymerizable monomer having a carboxyl group in the molecule include acrylic acid, methacrylic acid, maleic acid and itaconic acid. Examples of the polymerizable monomer having a hydroxyl group in the molecule include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-
Hydroxypropyl methacrylate, 3-chloro-2-
Examples thereof include hydroxy (C 1-5) alkyl (meth) acrylates such as hydroxypropyl acrylate and 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol (meth) acrylates such as diethylene glycol monoacrylate and diethylene glycol monomethacrylate, and glycidyl. Examples thereof include methacrylate and allyl glycidyl ether.
Examples of the polymerizable monomer having an amide group in the molecule include N, N-dimethylaminopropylacrylamide,
N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, N-methylolacrylamide,
Examples thereof include acrylamide-based monomers such as acrylamide. Examples of other monomers such as comonomers include vinyl acetate, acrylonitrile, and styrene.
【００１０】これらのモノマーの使用割合は、アクリル
酸系アルキルエステルが５０〜９８重量％、好ましくは
７０〜９５重量％、分子中にカルボキシル基を有する重
合性モノマーが０．５〜１０重量％、好ましくは１〜７
重量％、分子中に水酸基を有する重合性モノマーが０．
１〜１０重量％、好ましくは０．５〜５重量％、分子中
にアミド基を有する重合性モノマーが１〜２０重量％、
好ましくは３〜１５重量％、官能基不含有のモノマーが
０〜２０重量％、好ましくは０〜１０重量％である。
又、分子中にアミド基を有する重合性モノマー成分のア
ミド基の数は、高温高湿での耐久性や粘着力を考慮する
と、アクリル樹脂共重合体全体のカルボキシル基の数の
３〜５倍が好ましい。The proportion of these monomers used is 50 to 98% by weight, preferably 70 to 95% by weight of acrylic acid type alkyl ester, and 0.5 to 10% by weight of the polymerizable monomer having a carboxyl group in the molecule. Preferably 1-7
% By weight of the polymerizable monomer having a hydroxyl group in the molecule.
1 to 10% by weight, preferably 0.5 to 5% by weight, 1 to 20% by weight of the polymerizable monomer having an amide group in the molecule,
It is preferably 3 to 15% by weight, and the functional group-free monomer is 0 to 20% by weight, preferably 0 to 10% by weight.
In addition, the number of amide groups of the polymerizable monomer component having an amide group in the molecule is 3 to 5 times the number of carboxyl groups of the entire acrylic resin copolymer, considering durability and adhesive strength at high temperature and high humidity. Is preferred.
【００１１】本発明に用いられるアクリル樹脂共重合体
は、使用するモノマーを有機溶剤に溶解し、周知方法に
より有機溶剤中でラジカル共重合させることにより容易
に製造することができる。前記重合に用いられる有機溶
剤としては、トルエン、キシレン等の芳香族炭化水素
類、酢酸エチル、酢酸ブチル等のエステル類、ｎ−プロ
ピルアルコール、イソプロピルアルコール等の脂肪族ア
ルコール類、メチルエチルケトン、メチルイソブチルケ
トン等のケトン類等が挙げられる。前記ラジカル重合に
使用される重合触媒としては、通常の重合触媒であるア
ゾビスイソブチロニトリル、ベンゾイルパーオキサイ
ド、ジ−ｔ−ブチルパーオキサイド、クメンハイドロパ
ーオキサイド等が挙げられる。The acrylic resin copolymer used in the present invention can be easily produced by dissolving the monomer to be used in an organic solvent and radically copolymerizing it in the organic solvent by a known method. As the organic solvent used in the polymerization, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol, methyl ethyl ketone and methyl isobutyl ketone. And the like. Examples of the polymerization catalyst used for the radical polymerization include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like which are common polymerization catalysts.
【００１２】かくして得られるアクリル樹脂共重合体
は、無色透明で、ガラス転移温度（以下、Ｔｇと略記す
る）が−２０℃以下、好ましくは−３０℃〜−６０℃で
あり、又重量平均分子量は５００，０００以上、好まし
くは７００，０００〜２，５００，０００、さらに好ま
しくは１，０００，０００〜２，０００，０００程度で
ある。Ｔｇが−２０℃をこえると粘着力に乏しく、耐久
性が劣る。又、平均分子量は５００，０００以下である
と耐熱性が不足する可能性があり、２，５００，０００
をこえると密着性が不足してくる傾向にあり、剥離等を
起こし易くなる。又、該共重合体中のカルボキシル基と
アミド基の比率はカルボキシル基１個に対しアミド基が
３〜５個が好ましい。更に、このアクリル樹脂共重合体
は、プレッシャークッカーテストにおける１０５℃／１
００時間後の抽出水のｐＨが７以上であるものが好まし
く、より好ましくはｐＨ７〜１０、更に好ましくはｐＨ
７〜９程度のものが好ましい。The acrylic resin copolymer thus obtained is colorless and transparent, has a glass transition temperature (hereinafter abbreviated as Tg) of -20 ° C or lower, preferably -30 ° C to -60 ° C, and has a weight average molecular weight. Is 500,000 or more, preferably 700,000 to 2,500,000, and more preferably about 1,000,000 to 2,000,000. If the Tg exceeds -20 ° C, the adhesive strength is poor and the durability is poor. If the average molecular weight is 500,000 or less, heat resistance may be insufficient,
If it exceeds, the adhesiveness tends to be insufficient and peeling or the like is likely to occur. Further, the ratio of carboxyl group to amide group in the copolymer is preferably 3 to 5 amide groups per one carboxyl group. Furthermore, this acrylic resin copolymer has a pressure cooker test of 105 ° C./1.
The pH of the extracted water after 00 hours is preferably 7 or more, more preferably pH 7 to 10, still more preferably pH.
It is preferably about 7-9.
【００１３】本発明に用いられるアクリル樹脂共重合体
は、単独でも光学用粘着剤として勿論使用可能である
が、必要に応じて架橋剤を配合して架橋しうる組成で光
学用粘着剤として用いてもよい。架橋剤には適宜なもの
を用いてよい。一般には例えば、脂肪族ジイソシアネー
ト、芳香族ジイソシアネートの如きポリイソシアネート
化合物、ブチルエーテル化スチロールメラミン、トリメ
チロールメラミンの如きメラミン化合物、ジアミン系化
合物、エポキシ樹脂系化合物、尿素樹脂系化合物、金属
塩等が用いられる。架橋剤を配合する場合、その配合量
はアクリル樹脂共重合体１００重量部あたり０．００１
〜１０重量部、好ましくは０．００５〜５重量部、さら
に好ましくは０．０１〜５重量部である。又、シランカ
ップリング剤を配合してもよい。シランカップリング剤
を配合する場合、その配合量はアクリル樹脂共重合体１
００重量部あたり０．００１〜１０重量部、好ましくは
０．００５〜５重量部、さらに好ましくは０．０１〜５
重量部である。The acrylic resin copolymer used in the present invention can of course be used alone as an optical pressure-sensitive adhesive, but if necessary, it may be used as an optical pressure-sensitive adhesive in a composition which can be crosslinked by incorporating a crosslinking agent. May be. A suitable crosslinking agent may be used. Generally, for example, aliphatic diisocyanates, polyisocyanate compounds such as aromatic diisocyanates, butyl etherified styrene melamine, melamine compounds such as trimethylol melamine, diamine compounds, epoxy resin compounds, urea resin compounds, metal salts and the like are used. . When the cross-linking agent is blended, the blending amount is 0.001 per 100 parts by weight of the acrylic resin copolymer.
10 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 5 parts by weight. Moreover, you may mix | blend a silane coupling agent. When the silane coupling agent is blended, the blending amount is the acrylic resin copolymer 1
0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 5 parts by weight per 00 parts by weight.
Parts by weight.
【００１４】本発明の粘着剤を製造するには、例えば上
記の各成分を均一に混合すればよい。又、本発明の粘着
剤は、上記の各成分をメチルエチルケトン、トルエン、
酢酸エチル等の有機溶剤に溶解して粘着剤溶液とした
後、アクリル樹脂共重合体の濃度が１０〜３０重量％に
なるように希釈して使用される。尚、本発明の粘着剤
は、プレッシャークッカーテストにおける１０５℃／１
００時間後の抽出水のｐＨが７以上であるものが好まし
く、より好ましくはｐＨ７〜１０、更に好ましくはｐＨ
７〜９程度のものが好ましい。To produce the pressure-sensitive adhesive of the present invention, for example, the above-mentioned components may be uniformly mixed. Further, the pressure-sensitive adhesive of the present invention contains the above-mentioned components in the form of methyl ethyl ketone, toluene,
It is dissolved in an organic solvent such as ethyl acetate to give a pressure-sensitive adhesive solution, which is then diluted to a concentration of the acrylic resin copolymer of 10 to 30% by weight before use. The pressure-sensitive adhesive of the present invention has a pressure cooker test of 105 ° C./1.
The pH of the extracted water after 00 hours is preferably 7 or more, more preferably pH 7 to 10, still more preferably pH.
It is preferably about 7-9.
【００１５】本発明の光学用シートとしては、例えば偏
光板、位相差板があげられる。この偏光板、位相差板は
偏光フィルム、位相差フィルムの片面又は両面が通常セ
ルロ−ス系保護層で被覆されてなるものである。上記偏
光性フィルムとしては通常ポリビニルアルコ−ル、ポリ
ビニルホルマ−ル、ポリビニルアセタ−ル、エチレン−
酢酸ビニル共重合体ケン化物等のポリビニルアルコ−ル
系樹脂から製せられたフィルムにヨウ素、二色性染料等
の偏光素子を含浸させ延伸させることにより偏光性が付
与されたものが好適に用いられるが、その他の種類のも
のであってもよい。又上記位相差フィルムとしては通常
ポリビニルアルコール、ポリビニルホルマール、ポリビ
ニルアセタール、エチレン−酢酸ビニル共重合体ケン化
物等のポリビニルアルコール系樹脂から製せられたフィ
ルムを延伸させることにより位相差性が付与された物が
好適に用いられるが、その他の種類であってもよい。上
記偏光性フィルム、位相差性フィルムを被覆するセルロ
−ス系保護層としては、例えば三酢酸セルロ−スやその
他の透明なセルロ−ス系フィルムが用いられる。Examples of the optical sheet of the present invention include a polarizing plate and a retardation plate. The polarizing plate and the retardation plate are usually obtained by coating one side or both sides of the polarizing film or the retardation film with a cellulosic protective layer. The above-mentioned polarizing film is usually polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, ethylene-
A film made of a polyvinyl alcohol-based resin such as a saponified product of vinyl acetate copolymer is preferably impregnated with a polarizing element such as iodine or a dichroic dye to give a polarizing property by stretching the film. However, other types may be used. Further, the retardation film is usually retarded by stretching a film made of polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl alcohol resin such as saponified ethylene-vinyl acetate copolymer. However, other types may be used. As the cellulose-based protective layer that covers the polarizing film and the retardation film, for example, triacetate cellulose or other transparent cellulose-based film is used.
【００１６】本発明の上記粘着剤は、光学用シートの片
面又は両面、特に偏光板、位相差板のセルロース系保護
層に塗布されるが、塗布方法としては、一般に剥離フィ
ルムにコーターで乾燥後の膜厚が２０〜３０μｍになる
ように塗布、乾燥され、ついで光学用シートの片面また
は両面に転写する方法がとられる。The above-mentioned pressure-sensitive adhesive of the present invention is applied to one side or both sides of an optical sheet, especially to a cellulose-based protective layer of a polarizing plate or a retardation plate. The coating method is generally after drying a release film with a coater. Is applied and dried to a film thickness of 20 to 30 μm, and then transferred onto one side or both sides of the optical sheet.
【００１７】本発明の粘着剤は、光学用の粘着剤とし
て、特にセルロース系保護層で被覆された偏光フィルム
または位相差フィルムと液晶セルのガラス基板とを接着
させる粘着剤として有用である。かかる粘着剤は、高温
高湿の状態で長時間放置しても発泡、剥離、劣化等の外
観異常をおこさない。かかる特性を利用して液晶表示体
の用途に用いられ、特に車両用途、各種工業計器類、家
庭用電化製品の表示等に有用である。The pressure-sensitive adhesive of the present invention is useful as an optical pressure-sensitive adhesive, particularly as a pressure-sensitive adhesive for adhering a polarizing film or a retardation film coated with a cellulosic protective layer and a glass substrate of a liquid crystal cell. Such a pressure-sensitive adhesive does not cause abnormal appearance such as foaming, peeling or deterioration even if it is left in a high temperature and high humidity state for a long time. Utilizing such characteristics, it is used for a liquid crystal display, and is particularly useful for a vehicle, various industrial instruments, display of household electric appliances, and the like.
【００１８】[0018]
【実施例】以下、実施例、比較例を挙げて本発明を更に
具体的に説明する。 実施例１ アクリル酸ｎ−ブチル８０ｇ、２−ヒドロキシエチルア
クリレート１ｇ、アクリル酸３ｇ、Ｎ，Ｎ−ジメチルア
クリルアミド１６ｇを酢酸エチル１８５ｇに溶解し、ア
ゾビスイソブチロニトリル０．０５ｇを添加して、７０
℃で５時間重合してアクリル樹脂共重合体（平均分子
量：１，２００，０００、Ｔｇ：−３７℃）を得た。さ
らに酢酸エチルで樹脂分が２０重量％になるように調製
した該アクリル樹脂共重合体溶液（粘度２，０００ｃｐ
ｓ／２５℃）１００重量部にトリレンジイソシアネート
（３モル）のトリメチロールプロパン（１モル）付加物
０．５重量部、γ−グリシドキシプロピルメトキシシラ
ン０．５重量部を配合して本発明の粘着剤を得た。EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. Example 1 80 g of n-butyl acrylate, 1 g of 2-hydroxyethyl acrylate, 3 g of acrylic acid, 16 g of N, N-dimethylacrylamide were dissolved in 185 g of ethyl acetate, and 0.05 g of azobisisobutyronitrile was added, 70
Polymerization was performed at 5 ° C for 5 hours to obtain an acrylic resin copolymer (average molecular weight: 1,200,000, Tg: -37 ° C). Further, the acrylic resin copolymer solution (viscosity of 2,000 cp) was prepared with ethyl acetate to a resin content of 20% by weight.
s / 25 ° C.) 0.5 parts by weight of trimethylolpropane (1 mol) adduct of tolylene diisocyanate (3 mols) and 0.5 parts by weight of γ-glycidoxypropylmethoxysilane were blended with 100 parts by weight of s / 25 ° C. An adhesive of the invention was obtained.
【００１９】実施例２ 実施例１の方法により得られた本発明の粘着剤を剥離フ
ィルム上に乾燥後の膜厚が２０〜３０μｍになるように
塗布し乾燥後、三酢酸セルロースフィルムを保護層とす
るポリビニルアルコール系偏光板（ポリビニルアルコー
ル系偏光性フィルムの平均重合度１７００、平均ケン化
度９９．５モル％、５倍延伸）の三酢酸セルロースフィ
ルム側に積層し、ローラーで押圧して本発明の偏光板を
作成した。かかる偏光板をガラス板に貼り合わせ耐久性
試験（８０℃／９０％ＲＨ１０００時間放置）を行い、
発泡状態、剥離状態、劣化状態を観察した。結果を表１
に示す。Example 2 The pressure-sensitive adhesive of the present invention obtained by the method of Example 1 was applied on a release film so that the film thickness after drying was 20 to 30 μm, and after drying, a cellulose triacetate film was used as a protective layer. To be laminated on the cellulose triacetate film side of a polyvinyl alcohol-based polarizing plate (average degree of polymerization of polyvinyl alcohol-based polarizing film: 1700, average saponification degree: 99.5 mol%, 5 times stretched) and pressed with a roller to form a book. A polarizing plate of the invention was prepared. A durability test (80 ° C./90% RH 1000 hours left) is performed by laminating such a polarizing plate on a glass plate,
The foaming state, peeling state, and deterioration state were observed. Table 1 shows the results
Shown in
【００２０】比較例１ アクリル樹脂共重合体のモノマー組成をアクリル酸ｎ−
ブチル／２−ヒドロキシエチルアクリレート／アクリル
酸＝９６／１／３（ｇ）に変更した以外は実施例１に準
じて粘着剤組成物を製造し、実施例２に準じて実験を行
った。結果を表１に示す。Comparative Example 1 The monomer composition of the acrylic resin copolymer was changed to acrylic acid n-
A pressure-sensitive adhesive composition was produced according to Example 1 except that butyl / 2-hydroxyethyl acrylate / acrylic acid was changed to 96/1/3 (g), and an experiment was performed according to Example 2. The results are shown in Table 1.
【００２１】[0021]
【表１】 表１ 実施例２ 比較例１ 発泡状態 ◎ 偏光板のＴＡＣがボロボロに破壊されて観察できず 剥離状態 ◎ 偏光板のＴＡＣがボロボロに破壊されて観察できず 劣化状態 ◎ 偏光板のＴＡＣがボロボロに破壊 [Table 1] Table 1 Example 2 Comparative Example 1 Foamed state ◎ The TAC of the polarizing plate was broken into pieces and could not be observed. Peeling state ◎ The TAC of the polarizing plate was broken into pieces and could not be observed. TAC is destroyed
【００２２】 発泡状態 ◎：偏光板とガラス板の間に発泡が認められない 剥離状態 ◎：偏光板とガラス板の間に剥離が認められない 劣化状態 ◎：偏光板に変化が認められない Foamed state ◎: No foaming observed between the polarizing plate and the glass plate Peeling state ◎: No peeling observed between the polarizing plate and the glass plate ◎: No change observed in the polarizing plate
【００２３】実施例３ 実施例１の方法により得られた本発明の粘着剤を剥離フ
ィルム上に乾燥後の膜厚が２０〜３０μｍになるように
塗布し乾燥後、三酢酸セルロースフィルムを保護層とす
るポリビニルアルコール系位相差板（ポリビニルアルコ
ール系位相差フィルムの平均重合度１７００、平均ケン
化度９９．５モル％、１．１倍延伸）の三酢酸セルロー
スフィルム側に積層し、ローラーで押圧して本発明の位
相差板を作成した。Example 3 The pressure-sensitive adhesive of the present invention obtained by the method of Example 1 was coated on a release film so that the film thickness after drying was 20 to 30 μm, and after drying, a cellulose triacetate film was used as a protective layer. And a polyvinyl alcohol-based retardation plate (average polymerization degree of polyvinyl alcohol-based retardation film: 1700, average saponification degree: 99.5 mol%, stretched 1.1 times) laminated on the cellulose triacetate film side and pressed with a roller. Then, the retardation plate of the present invention was prepared.
【００２４】実施例４ モノマー組成（重量部）がアクリル酸ｎ−ブチル／２−
ヒドロキシエチルアクリレート／アクリル酸／Ｎ，Ｎ−
ジメチルアクリルアミド＝８１／１／２／１１である混
合物を共重合させてなるアクリル樹脂共重合体（平均分
子量１，２００，０００）の２０重量％酢酸エチル溶液
（粘度２，０００ｃｐｓ／２５℃）１００重量部にトリ
レンジイソシアネート（３モル）のトリメチロールプロ
パン（１モル）付加物０．５重量部、γ−グリシドキシ
プロピルメトキシシラン０．５重量部を配合して、均一
に溶解し、本発明の粘着剤の溶液を得た。この粘着剤の
溶液を剥離フィルム上に乾燥後の膜厚が２０〜３０μｍ
になるように塗布し乾燥後、三酢酸セルロースフィルム
を保護層とするポリビニルアルコール偏光フィルム（平
均重合度１７００、平均ケン化度９９．５モル％、５倍
延伸）の三酢酸セルロースフィルム側に積層し、ローラ
ーで押圧して偏光板を作成した。かかる偏光板をガラス
板に貼り合わせ耐久性試験（８０℃／９０％ＲＨ、１０
００時間放置）を行い、粘着剤の発泡状態、偏光板の剥
離状態、劣化状態を観察したところ、いずれも◎であっ
た。一方、上記アクリル樹脂共重合体５ｇと純水５０ｇ
をテフロン製密閉式耐圧容器に入れ、１０５℃の恒温試
験機中に１００時間放置するプレッシャークッカーテス
トを行った後、テフロン製密閉式耐圧容器中の抽出水の
ｐＨをｐＨメーター（ＨＭ−１０Ｋ：東亜電波工業
（株）製）で測定したところｐＨは７．８２であった。
尚、純水は蒸留水をイオン交換樹脂に通し、抵抗値１０
Ｍオーム以上のものを使用した。Example 4 Monomer composition (parts by weight) was n-butyl acrylate / 2-
Hydroxyethyl acrylate / acrylic acid / N, N-
20% by weight ethyl acetate solution of acrylic resin copolymer (average molecular weight 1,200,000) obtained by copolymerizing a mixture of dimethylacrylamide = 81/1/2/11 (viscosity 2,000 cps / 25 ° C.) 100 0.5 parts by weight of a trimethylolpropane (1 mol) adduct of tolylene diisocyanate (3 mols) and 0.5 parts by weight of γ-glycidoxypropylmethoxysilane were added to 1 part by weight and uniformly dissolved. A solution of the adhesive of the invention was obtained. A film thickness after drying this adhesive solution on a release film is 20 to 30 μm.
And then dried, and laminated on the side of the cellulose triacetate film of a polyvinyl alcohol polarizing film (average degree of polymerization 1700, average degree of saponification 99.5 mol%, 5 times stretched) having a cellulose triacetate film as a protective layer. Then, it was pressed with a roller to prepare a polarizing plate. A durability test (80 ° C / 90% RH, 10%
After leaving it to stand for 00 hours) and observing the foaming state of the pressure-sensitive adhesive, the peeling state of the polarizing plate, and the deterioration state, all were ◎. On the other hand, 5 g of the acrylic resin copolymer and 50 g of pure water
Was placed in a Teflon sealed pressure-resistant container and subjected to a pressure cooker test in which it was left in a thermostatic tester at 105 ° C. for 100 hours. When measured by Toa Denpa Kogyo Co., Ltd., pH was 7.82.
For pure water, distilled water is passed through an ion exchange resin to obtain a resistance value of 10
The thing of M ohm or more was used.
【００２５】[0025]
【発明の効果】本発明の接着剤を使用することにより、
高温高湿条件下での耐久性に優れた感圧接着型偏光板や
感圧接着型位相差板等の光学用シートを得ることができ
る。By using the adhesive of the present invention,
It is possible to obtain an optical sheet such as a pressure-sensitive adhesive type polarizing plate or a pressure-sensitive adhesive type retardation plate having excellent durability under high temperature and high humidity conditions.
Claims (5)
重合成分としてアクリル酸系アルキルエステル、分子中
にカルボキシル基を有する重合性モノマー、分子中に水
酸基を有する重合性モノマー、及び分子中にアミド基を
有する重合性モノマーを必須成分とするアクリル樹脂共
重合体を含有することを特徴とする粘着剤。1. In an acrylic resin copolymer-based pressure-sensitive adhesive,
Acrylic resin copolymer containing acrylic acid alkyl ester as a polymerization component, a polymerizable monomer having a carboxyl group in the molecule, a polymerizable monomer having a hydroxyl group in the molecule, and a polymerizable monomer having an amide group in the molecule as essential components A pressure-sensitive adhesive comprising a coalesced product.
とアミド基の比率がカルボキシル基１個に対しアミド基
が３〜５個である請求項１の粘着剤。2. The pressure-sensitive adhesive according to claim 1, wherein the ratio of carboxyl groups to amide groups in the acrylic resin copolymer is 3 to 5 amide groups per one carboxyl group.
１，０００，０００〜２，０００，０００である請求項
１または２の粘着剤。3. The pressure-sensitive adhesive according to claim 1, wherein the acrylic resin copolymer has a weight average molecular weight of 1,000,000 to 2,000,000.
の層を有する光学用シート。4. An optical sheet having a layer of the pressure-sensitive adhesive according to any one of claims 1 to 3.
請求項４の光学用シート。5. The optical sheet according to claim 4, wherein the optical sheet is a polarizing plate or a retardation plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16662896A JP3827364B2 (en) | 1995-06-16 | 1996-06-07 | Adhesive |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-172980 | 1995-06-16 | ||
| JP17298095 | 1995-06-16 | ||
| JP16662896A JP3827364B2 (en) | 1995-06-16 | 1996-06-07 | Adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0959580A true JPH0959580A (en) | 1997-03-04 |
| JP3827364B2 JP3827364B2 (en) | 2006-09-27 |
Family
ID=26490919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16662896A Expired - Fee Related JP3827364B2 (en) | 1995-06-16 | 1996-06-07 | Adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3827364B2 (en) |
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|---|---|---|---|---|
| JP2005097451A (en) * | 2003-09-26 | 2005-04-14 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
| KR100737653B1 (en) * | 2003-04-30 | 2007-07-09 | 도요 잉키 세이조 가부시끼가이샤 | Adhesive agent, and an optical part using the same |
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| JP2008050459A (en) * | 2006-08-24 | 2008-03-06 | Riken Technos Corp | Adhesive composition and adhesive sheet member using the same |
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| JP2010196065A (en) * | 2010-04-14 | 2010-09-09 | Nitto Denko Corp | Pressure-sensitive adhesive composition for conductive film, pressure-sensitive adhesive sheet, and conductive film |
| JP2010196064A (en) * | 2010-04-14 | 2010-09-09 | Nitto Denko Corp | Pressure-sensitive adhesive composition for sticking/fixing of optical film to liquid crystal panel, pressure-sensitive adhesive sheet, and optical film |
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1996
- 1996-06-07 JP JP16662896A patent/JP3827364B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100737653B1 (en) * | 2003-04-30 | 2007-07-09 | 도요 잉키 세이조 가부시끼가이샤 | Adhesive agent, and an optical part using the same |
| JP2005097451A (en) * | 2003-09-26 | 2005-04-14 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
| JP4498711B2 (en) * | 2003-09-26 | 2010-07-07 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
| EP2006715A2 (en) * | 2006-03-15 | 2008-12-24 | Nitto Denko Corporation | Adhesive optical film, multilayer optical film and image display |
| US8932710B2 (en) | 2006-03-15 | 2015-01-13 | Nitto Denko Corporation | Adhesive optical film, multilayer optical film and image display |
| EP2006715A4 (en) * | 2006-03-15 | 2013-04-17 | Nitto Denko Corp | Adhesive optical film, multilayer optical film and image display |
| JP2007264092A (en) * | 2006-03-27 | 2007-10-11 | Nitto Denko Corp | Optical adhesive, optical film with binder and image display device |
| US9321942B2 (en) | 2006-03-27 | 2016-04-26 | Nitto Denko Corporation | Optical pressure-sensitive adhesive, pressure-sensitive adhesive attached optical film, and image display |
| JP2008050459A (en) * | 2006-08-24 | 2008-03-06 | Riken Technos Corp | Adhesive composition and adhesive sheet member using the same |
| WO2011111575A1 (en) * | 2010-03-10 | 2011-09-15 | 日東電工株式会社 | Adhesive sheet for optical use |
| WO2011111576A1 (en) * | 2010-03-10 | 2011-09-15 | 日東電工株式会社 | Adhesive sheet for optical use |
| US8945710B2 (en) | 2010-03-10 | 2015-02-03 | Nitto Denko Corporation | Optical pressure-sensitive adhesive sheet |
| JP2010196064A (en) * | 2010-04-14 | 2010-09-09 | Nitto Denko Corp | Pressure-sensitive adhesive composition for sticking/fixing of optical film to liquid crystal panel, pressure-sensitive adhesive sheet, and optical film |
| JP2010196065A (en) * | 2010-04-14 | 2010-09-09 | Nitto Denko Corp | Pressure-sensitive adhesive composition for conductive film, pressure-sensitive adhesive sheet, and conductive film |
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| JP3827364B2 (en) | 2006-09-27 |
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