JP2829412B2 - Method for manufacturing adhesive members - Google Patents
Method for manufacturing adhesive membersInfo
- Publication number
- JP2829412B2 JP2829412B2 JP63080996A JP8099688A JP2829412B2 JP 2829412 B2 JP2829412 B2 JP 2829412B2 JP 63080996 A JP63080996 A JP 63080996A JP 8099688 A JP8099688 A JP 8099688A JP 2829412 B2 JP2829412 B2 JP 2829412B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- curing
- acrylic polymer
- parts
- 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
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、エポキシ基含有アクリル系ポリマをスルホ
ニウム塩により硬化せしめて、タックと保持力に優れる
粘着部材を効率よく製造する方法に関する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for curing an epoxy group-containing acrylic polymer with a sulfonium salt to efficiently produce an adhesive member having excellent tack and holding power.
従来の技術及び課題 支持基材にアクリル系粘着剤層を設けてなる粘着部材
の用途は、包装材、マスキング材、電気絶縁材、表面保
護材、防食材、接着材などで代表されるが、その粘着部
材を製造するにあたり、重合形成したアクリル系ポリマ
をそのまま粘着剤に用いたのでは、凝集破壊的ズレを起
こして被着体との接着状態が持続されないという保持力
不足の問題を生じるため、硬化処理しうる組成の粘着剤
とされる。Conventional technology and problems The use of an adhesive member having an acrylic pressure-sensitive adhesive layer provided on a supporting substrate is represented by a packaging material, a masking material, an electrical insulating material, a surface protective material, an anticorrosive material, an adhesive material, and the like. In producing the pressure-sensitive adhesive member, if the polymerization-formed acrylic polymer was used as the pressure-sensitive adhesive as it was, there would be a problem of insufficient holding force that the cohesion and destructive displacement occurred and the bonding state with the adherend was not maintained. And a pressure-sensitive adhesive having a composition that can be cured.
従来、アクリル系粘着剤の硬化方式としては、硫黄に
よる架硫方式、過酸化物、イソシアネート化合物、エポ
キシ系化合物、メラミン系化合物からなる架橋剤による
架橋方式、金属イオンによる架橋方式などの熱硬化方式
が知られていた。しかし、粘着剤層の硬化処理に際して
支持基材が高温下に長時間おかれることとなり、強度低
下や寸法変化を生じる問題があった。また、熱硬化に要
する時間との関係から高速処理を達成するには長い加熱
ゾーンを必要とし、加熱ゾーンの長さが製造ラインのス
ピードを大きく制約したり、アフターキュアに長時間を
要したりして、製造効率に劣る問題もあった。Conventionally, curing methods for acrylic pressure-sensitive adhesives include a sulfur curing method, a thermal curing method such as a crosslinking method using a crosslinking agent composed of peroxide, isocyanate compound, epoxy compound, and melamine compound, and a crosslinking method using metal ions. Was known. However, during the curing treatment of the pressure-sensitive adhesive layer, the supporting substrate is left under a high temperature for a long time, and there is a problem that strength is reduced and dimensional change is caused. Also, in order to achieve high-speed processing in relation to the time required for heat curing, a long heating zone is required, and the length of the heating zone greatly restricts the speed of the production line, or a long time is required for after-curing. As a result, there is a problem that the manufacturing efficiency is inferior.
一方、アクリル系ポリマ中にアクリロイル基等のラジ
カル反応性官能基を導入し、これを紫外線や電子線で処
理して効率的に架橋せしめうるアクリル系粘着剤も知ら
れている。しかしながら、酸素により硬化が阻害され、
その防止のため照射ゾーンを窒素置換する必要があるな
どの硬化性の問題や、アクリル系ポリマ中にラジカル反
応性官能基を導入することが困難で入手性に劣る問題、
さらに硬化による粘着剤層の収縮で支持基材との密着性
が著しく低下する問題などあった。On the other hand, there is also known an acrylic pressure-sensitive adhesive which can introduce a radical-reactive functional group such as an acryloyl group into an acrylic polymer and treat it with an ultraviolet ray or an electron beam to crosslink efficiently. However, curing is inhibited by oxygen,
Curing problems such as the need to replace the irradiation zone with nitrogen to prevent such problems, and difficulties in introducing radically reactive functional groups into acrylic polymers, resulting in poor availability,
Further, there is a problem that the adhesiveness to the supporting substrate is significantly reduced due to shrinkage of the pressure-sensitive adhesive layer due to curing.
課題を解決するための手段 本発明者は上記の課題を克服すべく鋭意研究を重ねた
結果、アクリル系ポリマにエポキシ基を導入し、これを
スルホニウム塩で硬化するようにした粘着剤によりその
目的を達成しうることを見出し、本発明をなすに至っ
た。Means for Solving the Problems The present inventor has conducted intensive studies to overcome the above-described problems, and as a result, introduced an epoxy group into an acrylic polymer, and cured the adhesive with a sulfonium salt. Have been achieved, and the present invention has been accomplished.
すなわち、本発明は、支持基材に粘着剤層を設けてな
る粘着部材を製造するにあたり、炭素数３〜30のアルキ
ル基を有するアクリル酸系アルキルエステル単位の重合
度に基づき１〜10％の割合でエポキシ基を有するアクリ
ル系ポリマと、そのポリマー100重量部あたり0.2〜20重
量部のスルホニウム塩を成分とする粘着剤を用い、これ
を支持基材の片面又は両面に展開付設し、形成された粘
着剤層を被着体に接着する前に紫外線照射又は加熱によ
り硬化処理することを特徴とする粘着部材の製造方法を
提供するものである。That is, in the present invention, when producing a pressure-sensitive adhesive member having a pressure-sensitive adhesive layer provided on a support substrate, 1 to 10% based on the degree of polymerization of acrylic acid alkyl ester units having an alkyl group having 3 to 30 carbon atoms. Acrylic polymer having an epoxy group in a proportion, and an adhesive having a component of 0.2 to 20 parts by weight of a sulfonium salt per 100 parts by weight of the polymer is used. The present invention provides a method for producing a pressure-sensitive adhesive member, which comprises performing a curing treatment by ultraviolet irradiation or heating before bonding the pressure-sensitive adhesive layer to an adherend.
作用 上記のように、アクリル系ポリマにエポキシ基を導入
し、これをスルホニウム塩を用いて硬化するようにした
粘着剤を用い、紫外線照射又は加熱により硬化処理する
方式とすることにより、所期の目的が達成される。すな
わち、アクリル系ポリマ中へのエポキシ基の導入は容易
であるためその入手性に優れ、酸素による硬化阻害をう
けにくいので硬化処理ゾーンを窒素置換する必要がな
く、硬化処理に要する時間も短い。また、加熱硬化の場
合には低温処理が可能であり、長時間にわたるアフター
キュアを必要としない。Action As described above, an epoxy group is introduced into an acrylic polymer, and the adhesive is cured using a sulfonium salt. Objective is achieved. That is, it is easy to introduce an epoxy group into the acrylic polymer, so that it is excellent in availability and hard to be inhibited from curing by oxygen. Therefore, it is not necessary to replace the curing treatment zone with nitrogen, and the time required for the curing treatment is short. Further, in the case of heat curing, low-temperature treatment is possible, and long after-curing is not required.
加えて、前記の硬化反応はスルホニウム塩を反応開始
触媒とするエポキシ基含有アクリル系ポリマのカチオン
反応機構によるエポキシ基の開環反応であるので、従来
のラジカル反応性官能基に基づく硬化反応の場合に比
べ、硬化収縮が少なく、粘着剤層と支持基材との密着維
持力に優れる。In addition, since the above-mentioned curing reaction is a ring-opening reaction of an epoxy group by a cation reaction mechanism of an epoxy group-containing acrylic polymer using a sulfonium salt as a reaction initiation catalyst, a curing reaction based on a conventional radically reactive functional group is performed. As compared with the above, it has less curing shrinkage and is excellent in maintaining the adhesion between the pressure-sensitive adhesive layer and the supporting substrate.
発明の構成要素の例示 本発明において用いられる粘着剤は、エポキシ基を有
するアクリル系ポリマを成分とするものである。エポキ
シ基は、アクリル系ポリマの分子鎖内にあってもよい
し、分子鎖の側鎖や末端などにあってもよく、その存在
形態や導入方式について特に限定はない。Illustrative Components of the Invention The pressure-sensitive adhesive used in the present invention comprises an acrylic polymer having an epoxy group as a component. The epoxy group may be present in the molecular chain of the acrylic polymer, or may be present on the side chain or terminal of the molecular chain, and there is no particular limitation on the form and method of introduction.
エポキシ基を有するアクリル系ポリマの代表的な調製
法としては、アクリル酸系アルキルエステルと、グリシ
ジルメタクリレートや3,4−エポキシシクロヘキシルメ
チル−３′−アクリロイル−４′−ヒドロキシシクロヘ
キサンカルボキシレートなどのエポキシ基含有共重合性
モノマを、ラジカル重合開始剤などを用いて溶液重合方
式、塊状重合方式、乳化重合方式、懸濁重合方式など公
知の重合方式で共重合処理して、エポキシ成分を分子鎖
内に有するアクリル系ポリマとする方法、あるいは予め
アクリル酸系アルキルエステルを主モノマ成分とするポ
リマを調製し、これに付加反応や変性反応により適宜な
エポキシ基含有化合物を導入して分子鎖の側鎖や末端な
どにエポキシ成分を有するものとする方法などがあげら
れる。重合に際するモノマ濃度、連鎖移動剤の種類や添
加量、重合温度、溶剤などの処理条件について特に限定
はなく、ポリマの所望分子量などにより適宜に決定する
ことができる。A typical method for preparing an acrylic polymer having an epoxy group includes an acrylic acid alkyl ester and an epoxy group such as glycidyl methacrylate or 3,4-epoxycyclohexylmethyl-3'-acryloyl-4'-hydroxycyclohexanecarboxylate. The containing copolymerizable monomer is copolymerized by a known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method using a radical polymerization initiator or the like, and the epoxy component is converted into a molecular chain. A method of preparing an acrylic polymer having, or a polymer having an acrylic acid alkyl ester as a main monomer component is prepared in advance, and an appropriate epoxy group-containing compound is introduced into the polymer by an addition reaction or a modification reaction, and a side chain of a molecular chain is prepared. Examples of the method include a method having an epoxy component at a terminal or the like. There are no particular limitations on the processing conditions such as the monomer concentration, the type and amount of the chain transfer agent, the polymerization temperature, and the solvent used in the polymerization, and can be appropriately determined according to the desired molecular weight of the polymer.
アクリル系ポリマにおけるエポキシ基の含有割合は、
得られる粘着剤におけるタックと凝集力のバランスなど
の点よりアクリル系ポリマ中におけるアクリル酸系アル
キルエステル単位の重合度に基づき１〜10％の割合が適
当である。The content of epoxy groups in the acrylic polymer is
From the viewpoint of the balance between tack and cohesive force in the obtained pressure-sensitive adhesive, a ratio of 1 to 10% is appropriate based on the degree of polymerization of the acrylic acid alkyl ester unit in the acrylic polymer.
なお、必要に応じ改質モノマを共重合させたアクリル
系ポリマとしたものなどであってもよい。An acrylic polymer obtained by copolymerizing a modified monomer as necessary may be used.
アクリル系ポリマの重量平均分子量としては、1,000
〜5,000,000が一般であり、好ましくは2,000〜3,000,00
0である。重量平均分子量が小さくて常温流動性を有す
るものは無溶剤塗工が可能な粘着剤を調製しうる利点が
ある。なお、流動性に劣るものは通例の如く、有機溶剤
を用いた溶液タイプや、水等に分散させたタイプなどと
して用いればよい。The weight average molecular weight of the acrylic polymer is 1,000
~ 5,000,000 is common, preferably 2,000 ~ 3,000,00
It is 0. Those having a small weight average molecular weight and fluidity at room temperature have the advantage that a pressure-sensitive adhesive that can be applied without solvent can be prepared. In general, those having poor fluidity may be used as a solution type using an organic solvent or a type dispersed in water or the like.
前記したアクリル系ポリマの調製に用いられるアクリ
ル酸系アルキルエステルとしては、例えばｎ−プロピル
基、ｎ−ブチル基、ｎ−アミル基、ｎ−ヘキシル基、２
−エチルヘキシル基、ｎ−オクチル基、イソオクチル
基、ｎ−ノニル基、イソノニル基、ｎ−デシル基などで
代表される炭素数が３〜30のアルキル基を有するアクリ
ル酸やメタクリル酸などのエステルがあげられる。Examples of the acrylic acid alkyl ester used for preparing the acrylic polymer include an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group,
Esters such as acrylic acid and methacrylic acid having an alkyl group having 3 to 30 carbon atoms represented by -ethylhexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group and the like. Can be
また、必要に応じ用いられる改質モノマの代表例とし
てはアクリル酸、メタクリル酸、酢酸ビニル、アクリル
酸２−ヒドロキシエチル、メタクリル酸メチル、アクリ
ル酸エチル、アクリロニトリルなどがあげられる。改質
モノマの使用量は前記アクリル酸系アルキルエステル10
0重量部あたり30重量部以下が一般であるが、これに限
定されない。Typical examples of the modified monomer used as needed include acrylic acid, methacrylic acid, vinyl acetate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl acrylate, acrylonitrile, and the like. The amount of the modified monomer used is the above-mentioned acrylic acid-based alkyl ester 10
The amount is generally 30 parts by weight or less per 0 parts by weight, but is not limited thereto.
本発明において用いられる粘着剤は、スルホニウム塩
が配合されたものである。配合量はアクリル系ポリマ10
0重量部あたり0.2〜20重量部が適当であり、0.5〜10重
量部が好ましい。その配合量が0.2重量部未満では架橋
不足となり、20重量部を超えるとタック等に乏しくなっ
て粘着特性上好ましくない。The pressure-sensitive adhesive used in the present invention contains a sulfonium salt. Amount is acrylic polymer 10
0.2 to 20 parts by weight per 0 parts by weight is suitable, and 0.5 to 10 parts by weight is preferred. If the amount is less than 0.2 parts by weight, crosslinking will be insufficient, and if it exceeds 20 parts by weight, tackiness will be poor, which is not preferable in terms of adhesive properties.
スルホニウム塩としては、例えば一般式:R3S+X-（た
だし、Ｒはアルキル基又はアリール基、X-はBF4 -、P
F5 -、AsF6 -、SbF6 -、SbCl6 -、HSO- 4、ClO- 4等の陰イオ
ンである。）で表されるものなどの如く、紫外線照射又
は加熱によりエポキシ基の開環反応を起こしうるものが
用いられる。ジアゾニウム塩やヨードニウム塩などの、
スルホニウム塩以外のオニウム塩系化合物を用いた場合
には、例えばジアゾニウム塩のガス発生による粘着剤層
の多孔化などの如く、発現する接着強度等に乏しくて本
発明の目的が達成されない。The sulfonium salts, for example the general formula: R 3 S + X - (wherein, R is an alkyl group or an aryl group, X - is BF 4 -, P
F 5 -, AsF 6 -, SbF 6 -, SbCl 6 -, HSO - a 4 such anion - 4, ClO. And the like, which can cause a ring-opening reaction of the epoxy group by ultraviolet irradiation or heating, such as those represented by the formula (1). Such as diazonium salts and iodonium salts,
When an onium salt-based compound other than the sulfonium salt is used, the object of the present invention cannot be achieved because of poor adhesive strength or the like, for example, the pressure-sensitive adhesive layer is made porous by gas generation of a diazonium salt.
本発明において用いられる粘着剤は、架橋効率をあげ
るために必要に応じ、分子中にエポキシ基を１個又は２
個以上有するエポキシ基官能性架橋剤が配合されていて
もよい。その配合量はアクリル系ポリマ100重量部あた
り200重量部以下が適当である。エポキシ基官能性架橋
剤の例としては、ビニルシクロヘキセンジオキサイド、
リモネンジオキサイド、3,4−エポキシシクロヘキシル
メチル−３′,4′−エポキシシクロヘキサンカルボキシ
レート、ビス−（６−メチル−3,4−エポキシシクロヘ
キシル）アジペート、エチレングリコールジグリシジル
エーテルなどがあげられる。The pressure-sensitive adhesive used in the present invention may have one or two epoxy groups in the molecule, if necessary, to increase the crosslinking efficiency.
An epoxy group-functional crosslinking agent having at least one epoxy group-functional crosslinking agent may be blended. The compounding amount is suitably 200 parts by weight or less per 100 parts by weight of the acrylic polymer. Examples of epoxy-functional crosslinkers include vinylcyclohexene dioxide,
Limonenedioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, ethylene glycol diglycidyl ether and the like.
さらに、本発明で用いる粘着剤は必要に応じ、エポキ
シ基を含有しない公知のアクリル系ポリマのほか、タッ
キファイヤ、軟化剤、酸化防止剤、充填剤、顔料、増量
剤などの通例配合されることのある添加剤を含有してい
てもよい。また、イソシアネート化合物などで代表され
る接着性改良剤を含有していてもよい。接着性改良剤は
被着体あるいは支持基材との密着性ないし接着性を改善
するためのものである。Further, the pressure-sensitive adhesive used in the present invention may be, if necessary, commonly used in addition to a known acrylic polymer containing no epoxy group, a tackifier, a softener, an antioxidant, a filler, a pigment, a filler, and the like. May be contained. Further, it may contain an adhesion improver represented by an isocyanate compound or the like. The adhesion improver is for improving the adhesion or adhesion to an adherend or a supporting substrate.
本発明の方法は、エポキシ基を有するアクリル系ポリ
マとスルホニウム塩を成分とする粘着剤を支持基材の片
面又は両面に展開付設し、形成された粘着剤層を被着体
に接着する前に紫外線照射又は加熱により硬化処理し
て、粘着テープや粘着シート等の粘着部材とするもので
ある。粘着テープは、例えば表面保護材のように支持基
材を粘着剤層と一体的に被着体に貼着するようにしたも
のである。粘着シートは、支持基材をセパレータとして
用いて粘着剤層を支持基材より容易に剥がせるように
し、粘着剤をシート状物として利用できるようにしたも
のである。In the method of the present invention, an adhesive comprising an acrylic polymer having an epoxy group and a sulfonium salt is spread and provided on one or both surfaces of a support substrate, and before the formed adhesive layer is bonded to an adherend, It is cured by ultraviolet irradiation or heating to form an adhesive member such as an adhesive tape or an adhesive sheet. The pressure-sensitive adhesive tape is such that a support base material such as a surface protective material is adhered to an adherend integrally with a pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet is such that the pressure-sensitive adhesive layer can be easily peeled off from the support substrate by using the support substrate as a separator, and the pressure-sensitive adhesive can be used as a sheet-like material.
支持基材に粘着剤も塗布するに際しては、無溶剤塗工
が可能な場合にあっても必要に応じ、溶剤や水などから
なる媒体で溶液や分散液としてよい。その場合には、必
要に応じて塗布後乾燥処理する。粘着剤の塗布量は用途
により異なるが一般には固形分で２〜2000g/m2が適当で
ある。When the pressure-sensitive adhesive is also applied to the supporting base material, a solution or a dispersion may be formed with a medium such as a solvent or water, as necessary, even when solventless coating is possible. In that case, if necessary, a drying treatment is performed after the application. The amount of the adhesive to be applied varies depending on the application, but generally, a solid content of 2 to 2000 g / m 2 is appropriate.
支持基材としては、紙、プラスチックラミネート紙、
布、プラスチックラミネート布、プラスチックフィル
ム、金属箔などからなる厚さが通常１〜500μｍの薄葉
体や、厚さが10μｍ〜10cmの発泡シールなどが一般に用
いられる。なお、粘着剤層を容易に剥がせるようにする
ための支持基材（セパレータ）としては、前記の薄葉体
の片面又は両面をシリコーン系化合物や長鎖アルキル系
化合物などからなる剥離剤で表面処理したものや、粘着
剤との接着力に乏しい薄葉体などが用いられる。Paper, plastic laminated paper,
A thin leaf having a thickness of usually 1 to 500 μm, such as a cloth, a plastic laminate cloth, a plastic film, or a metal foil, and a foam seal having a thickness of 10 μm to 10 cm are generally used. In addition, as a supporting base material (separator) for easily peeling off the pressure-sensitive adhesive layer, one or both surfaces of the thin leaf are surface-treated with a release agent composed of a silicone-based compound or a long-chain alkyl-based compound. What is used is a thin leaf having poor adhesion to an adhesive.
紫外線照射による粘着剤層の硬化処理は、水銀ランプ
やメタルハライドランプなどの紫外線照射装置を用いて
行うことができる。紫外線の照射量は、被着体に対する
必要接着力などの所望の粘着特性に応じ適宜に決定して
よい。The curing treatment of the pressure-sensitive adhesive layer by ultraviolet irradiation can be performed using an ultraviolet irradiation device such as a mercury lamp or a metal halide lamp. The irradiation amount of the ultraviolet ray may be appropriately determined according to desired adhesive properties such as a necessary adhesive strength to an adherend.
加熱による粘着剤層の硬化処理は、熱オーブン、赤外
線ヒータ、遠赤外線ヒータ、加熱炉等の適宜な加熱装置
を用いて行うことができる。加熱条件は所望の粘着特性
に応じ適宜に決定してよい。一般には80〜200℃で0.1〜
30分間の加熱条件である。The curing treatment of the pressure-sensitive adhesive layer by heating can be performed using an appropriate heating device such as a heat oven, an infrared heater, a far-infrared heater, and a heating furnace. The heating conditions may be appropriately determined according to the desired adhesive properties. Generally 0.1 ~ at 80 ~ 200 ℃
Heating conditions for 30 minutes.
発明の効果 本発明によれば、入手容易なエポキシ基含有アクリル
系ポリマをスルホニウム基の存在下、紫外線照射又は加
熱により硬化せしめるようにしたので、酸素制御する必
要なく、かつ短時間に硬化処理することができ、しかも
長時間のアフターキュアも必要としないことからその製
造効率に優れている。また、得られた粘着部材は硬化に
よる収縮量が少なくて粘着剤層と支持基材との密着維持
力に優れ、タックと保持力にも優れている。Effect of the Invention According to the present invention, an epoxy group-containing acrylic polymer that is easily available is cured by ultraviolet irradiation or heating in the presence of a sulfonium group, so that it is not necessary to control oxygen, and the curing treatment is performed in a short time. It is excellent in manufacturing efficiency because it does not require long after-curing. Further, the obtained pressure-sensitive adhesive member has a small amount of shrinkage due to curing, has excellent adhesion maintaining force between the pressure-sensitive adhesive layer and the supporting substrate, and has excellent tack and holding power.
実施例 参考例 撹拌羽根、温度計、冷却管、ガス導入管を取り付けた
四ツ口フラスコを用いて窒素置換下、アクリル酸２−エ
チルヘキシル100部（重量部、以下同じ）、アクリル酸
３部及びグリシジルメタクリレート３部を、アゾビスイ
ソブチロニトリル0.6部の存在下に酢酸エチル106部を溶
媒として内浴温度を70℃に調節しながら８時間撹拌下に
重合処理したのち酢酸エチル53部を追加してエポキシ基
含有アクリル系ポリマの溶液を得た。ゲルパーミエーシ
ョンクロマトグラフィーによるポリスチレン換算に基づ
く前記エポキシ基含有アクリル系ポリマの数平均分子量
は48,000、重量平均分子量は380,000であった。EXAMPLES Reference Example Using a four-necked flask equipped with a stirring blade, a thermometer, a cooling pipe, and a gas introduction pipe, under nitrogen replacement, 100 parts of 2-ethylhexyl acrylate (parts by weight, the same applies hereinafter), 3 parts of acrylic acid and 3 parts of glycidyl methacrylate are polymerized in the presence of 0.6 parts of azobisisobutyronitrile with 106 parts of ethyl acetate as a solvent while controlling the internal bath temperature at 70 ° C. for 8 hours with stirring, and then 53 parts of ethyl acetate are added. Thus, a solution of an epoxy group-containing acrylic polymer was obtained. The epoxy group-containing acrylic polymer had a number average molecular weight of 48,000 and a weight average molecular weight of 380,000 based on polystyrene by gel permeation chromatography.
実施例１ 参考例で得たエポキシ基含有アクリル系ポリマー100
部（固形分）にスルホニウム塩系紫外線硬化触媒２部を
配合したのち、これを厚さ38μｍのポリエステルフィル
ム上に塗布した。塗布量は固形分で40g/m2である。つい
で、塗布物を50℃の加熱オーブン中に10分間入れて酢酸
エチルを蒸発乾燥させたのち、その粘着剤層に高圧水銀
ランプを用いて300mJ/cm2の紫外線を照射して硬化処理
し、粘着テープを得た。Example 1 Epoxy group-containing acrylic polymer 100 obtained in Reference Example
After blending 2 parts of a sulfonium salt-based ultraviolet curing catalyst in 1 part (solid content), this was coated on a 38 μm thick polyester film. The coating amount is 40 g / m 2 in solid content. Then, the coating was placed in a heating oven at 50 ° C. for 10 minutes to evaporate and dry the ethyl acetate, and then the adhesive layer was irradiated with ultraviolet rays of 300 mJ / cm 2 using a high-pressure mercury lamp to be cured. An adhesive tape was obtained.
実施例２ 参考例で得たエポキシ基含有アクリル系ポリマー100
部（固形分）にスルホニウム塩系紫外線硬化触媒２部を
配合したのち、これを厚さ38μｍのポリエステルフィル
ム上に塗布した。塗布量は固形分で40g/m2である。つい
で、塗布物を50℃の加熱オーブン中に10分間入れて酢酸
エチルを蒸発乾燥させたのち、110℃の加熱オーブン中
に２分間入れて硬化処理し、粘着テープを得た。Example 2 Epoxy group-containing acrylic polymer 100 obtained in Reference Example
After blending 2 parts of a sulfonium salt-based ultraviolet curing catalyst in 1 part (solid content), this was coated on a 38 μm thick polyester film. The coating amount is 40 g / m 2 in solid content. Then, the coated material was placed in a heating oven at 50 ° C. for 10 minutes to evaporate and dry the ethyl acetate, and then placed in a heating oven at 110 ° C. for 2 minutes to perform a curing treatment to obtain an adhesive tape.
比較例１ スルホニウム塩系紫外線硬化触媒を配合しない粘着剤
を用いたほかは実施例１に準じて粘着テープを得た。Comparative Example 1 An adhesive tape was obtained in the same manner as in Example 1 except that an adhesive not containing a sulfonium salt-based ultraviolet curing catalyst was used.
比較例２ スルホニウム塩系熱硬化触媒に代えて、ジフェニルメ
タンジイソシアネートを配合した粘着剤を用いたほかは
実施例２に準じて粘着テープを得た。Comparative Example 2 An adhesive tape was obtained in the same manner as in Example 2 except that an adhesive containing diphenylmethane diisocyanate was used instead of the sulfonium salt-based thermosetting catalyst.
評価試験 実施例、比較例で得た粘着テープより20mm幅のテープ
片を切り出し、下記の試験に供した。なお、試験は粘着
剤層の硬化処理後２時間以内に開始した。Evaluation Test A piece of tape having a width of 20 mm was cut out from the pressure-sensitive adhesive tape obtained in each of Examples and Comparative Examples, and subjected to the following tests. The test was started within 2 hours after the curing treatment of the pressure-sensitive adhesive layer.
［保持力］ 23℃、65％R.H.下、テープ片をステンレス板（SUS30
4）に長さ15mmで貼着したのち重さ2kgのゴムローラを一
往復させて圧着し、40℃下に20分間放置後テープ片の自
由端に1kgの荷重を負荷して垂下し、テープ片が剥がれ
落ちるまでの時間を測定した。[Holding power] At 23 ° C and 65% RH, a piece of tape was placed on a stainless steel plate (SUS30
4) After sticking 15mm in length, a 2kg rubber roller is reciprocated one time and press-bonded, left at 40 ° C for 20 minutes, and a 1kg load is applied to the free end of the tape piece to hang down. The time until the sample came off was measured.
［タック］ PSTC−６（米国Pressure Sensitive Tape Council−
６）に準じ、23℃、65％R.H.下、テープ片の粘着剤面に
おけるボールのころがり距離を測定した。[Tack] PSTC-6 (US Pressure Sensitive Tape Council-
According to 6), the ball rolling distance on the adhesive surface of the tape piece was measured at 23 ° C. and 65% RH.
結果を表に示した。なお、数値は４測定値の平均値で
ある。The results are shown in the table. The numerical values are average values of four measured values.
表より、本発明の粘着部材は、短時間の硬化処理で優
れた初期タックと高い保持力を示すことがわかる。 From the table, it can be seen that the pressure-sensitive adhesive member of the present invention exhibits excellent initial tack and high holding power in a short curing treatment.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−14574（ＪＰ，Ａ) 特開 昭60−110720（ＪＰ，Ａ) 特表 昭56−500889（ＪＰ，Ａ) 新保正樹編「エポキシ樹脂ハンドブッ ク」昭和62年12月25日 日刊工業新聞社 発行 ｐ．218−220，225−233 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-14574 (JP, A) JP-A-60-110720 (JP, A) Special table Sho-56-500889 (JP, A) Masaki Shinbo “Epoxy” Resin Handbook, published December 25, 1987 by Nikkan Kogyo Shimbun p. 218−220, 225−233
Claims (1)
を製造するにあたり、炭素数３〜30のアルキル基を有す
るアクリル酸系アルキルエステル単位の重合度に基づき
１〜10％の割合でエポキシ基を有するアクリル系ポリマ
と、そのポリマ100重量部あたり0.2〜20重量部のスルホ
ニウム塩を成分とする粘着剤を用い、これを支持基材の
片面又は両面に展開付設し、形成された粘着剤層を被着
体に接着する前に紫外線照射又は加熱により硬化処理す
ることを特徴とする粘着部材の製造方法。In producing a pressure-sensitive adhesive member having a pressure-sensitive adhesive layer provided on a supporting substrate, a ratio of 1 to 10% based on the degree of polymerization of an acrylic acid alkyl ester unit having an alkyl group having 3 to 30 carbon atoms. An acrylic polymer having an epoxy group, and a pressure-sensitive adhesive containing a sulfonium salt in an amount of 0.2 to 20 parts by weight per 100 parts by weight of the polymer, which was spread and provided on one side or both sides of a supporting substrate, and formed. A method for producing a pressure-sensitive adhesive member, comprising performing a curing treatment by ultraviolet irradiation or heating before bonding the pressure-sensitive adhesive layer to an adherend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63080996A JP2829412B2 (en) | 1988-04-01 | 1988-04-01 | Method for manufacturing adhesive members |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63080996A JP2829412B2 (en) | 1988-04-01 | 1988-04-01 | Method for manufacturing adhesive members |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01252682A JPH01252682A (en) | 1989-10-09 |
| JP2829412B2 true JP2829412B2 (en) | 1998-11-25 |
Family
ID=13734101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63080996A Expired - Lifetime JP2829412B2 (en) | 1988-04-01 | 1988-04-01 | Method for manufacturing adhesive members |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2829412B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1180681A (en) * | 1997-09-09 | 1999-03-26 | Sekisui Chem Co Ltd | Foam-based pressure sensitive adhesive tape |
| US6235850B1 (en) | 1998-12-11 | 2001-05-22 | 3M Immovative Properties Company | Epoxy/acrylic terpolymer self-fixturing adhesive |
| JP2001003031A (en) * | 1999-06-22 | 2001-01-09 | Bridgestone Corp | Pressure-sensitive adhesive composition, film coated with pressure-sensitive adhesive, and method for sticking film coated with pressure-sensitive adhesive |
| ATE512177T1 (en) * | 2000-04-17 | 2011-06-15 | Kraton Polymers Res Bv | METHOD FOR PRODUCING STYRENE BLOCK COPOLYMERS BY COUPLING LIVING POLYMER BLOCKS |
| JP5196894B2 (en) * | 2006-07-18 | 2013-05-15 | 日本合成化学工業株式会社 | Resin composition, temporary surface protecting pressure-sensitive adhesive, pressure-sensitive adhesive sheet, method of using pressure-sensitive adhesive sheet, and method of manufacturing pressure-sensitive adhesive sheet |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5614574A (en) * | 1979-07-16 | 1981-02-12 | Hitachi Chem Co Ltd | Self-adhesive or adhesive tape |
| US4286047A (en) * | 1979-07-25 | 1981-08-25 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive susceptible to ultraviolet light-induced detackification |
| US4482679A (en) * | 1982-09-18 | 1984-11-13 | Ciba-Geigy Corporation | Heat-curable epoxy compositions containing diaryliodosyl salts |
-
1988
- 1988-04-01 JP JP63080996A patent/JP2829412B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 新保正樹編「エポキシ樹脂ハンドブック」昭和６２年１２月２５日 日刊工業新聞社発行 ｐ．２１８−２２０，２２５−２３３ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01252682A (en) | 1989-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4776272B2 (en) | Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film | |
| JP6479856B2 (en) | Pressure-sensitive adhesive sheet, method for producing the same, and method for producing an optical member using the same | |
| JP3819661B2 (en) | Fixing method of pressure-sensitive adhesive sheets and functional films | |
| JP4383531B2 (en) | Pressure-sensitive adhesive sheets and methods for producing the same | |
| JP3281490B2 (en) | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or sheet using the composition | |
| JP5518675B2 (en) | Adhesive composition | |
| JP5436394B2 (en) | Adhesive composition | |
| US20100104864A1 (en) | Thermally crosslinking polyacrylates and method for producing the same | |
| JP2016153504A (en) | Acrylic adhesive tape and method for producing the same | |
| JPH0819391B2 (en) | Pressure-sensitive adhesives and their adhesive sheets | |
| JP2007084632A (en) | Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protecting film, and surface protecting film | |
| JP2002047468A (en) | Self-adhesive-coated polarizing plate and self-adhesive composition used for the same | |
| WO2019065817A1 (en) | Adhesive sheet | |
| JP2829412B2 (en) | Method for manufacturing adhesive members | |
| JP2608713B2 (en) | Acrylic foam adhesive layer | |
| JP4516632B2 (en) | Acrylic pressure-sensitive adhesive composition and its adhesive sheets | |
| JP2663129B2 (en) | Adhesive structure | |
| EP3666806A1 (en) | Ultraviolet-curable acrylic polymer, production method therefor, and ultraviolet-curable hot-melt adhesive | |
| CN114891447A (en) | Acrylate/polyisobutylene rubber hybrid pressure-sensitive adhesive composition | |
| JP2608743B2 (en) | Adhesive structure of adhesive thin layer development | |
| JPH0623344B2 (en) | UV curable adhesive tape or sheet | |
| JPH07100784B2 (en) | Adhesive composition and adhesive tape or sheet using the same | |
| JPS63260978A (en) | Sticking structure of pressure-sensitive adhesive tape | |
| JP2002012841A (en) | Acrylic thermoset adhesive composition and adhesive sheets | |
| JP2000303046A (en) | Pressure-sensitive acrylic adhesive composition and adhesive tape, or the like, coated therewith |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080925 Year of fee payment: 10 |