JP3041733B2 - Manufacturing method of pressure-sensitive adhesive - Google Patents
Manufacturing method of pressure-sensitive adhesiveInfo
- Publication number
- JP3041733B2 JP3041733B2 JP3278289A JP27828991A JP3041733B2 JP 3041733 B2 JP3041733 B2 JP 3041733B2 JP 3278289 A JP3278289 A JP 3278289A JP 27828991 A JP27828991 A JP 27828991A JP 3041733 B2 JP3041733 B2 JP 3041733B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- rubber
- organic polymer
- based organic
- 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
Links
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、柔軟性と高い引張強度
とを併せもつ基材に感圧接着剤層が積層されてなる、高
い接着力(剪断接着力および剥離接着力)を有するテー
プ状〜シート状の感圧接着材の製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tape having a high adhesive strength (shear adhesive strength and peel adhesive strength) comprising a pressure-sensitive adhesive layer laminated on a substrate having both flexibility and high tensile strength. The present invention relates to a method for producing a pressure-sensitive adhesive in the form of a sheet.
【0002】[0002]
【従来の技術】従来より、比較的高い接着力を有するテ
ープ状〜シート状の感圧接着材をうる方法がいくつか知
られている。たとえば比較的高い接着力の感圧接着材を
うる方法として、感圧接着剤層を厚くする方法が知られ
ているが、感圧接着剤層を形成するのに溶剤型やエマル
ジョン型の粘着剤を用いて感圧接着剤層を形成する限り
厚さに限界があるので、接着力についても限界がある。2. Description of the Related Art Conventionally, several methods for obtaining a tape-shaped or sheet-shaped pressure-sensitive adhesive having a relatively high adhesive strength have been known. For example, as a method of obtaining a pressure-sensitive adhesive having a relatively high adhesive strength, a method of thickening a pressure-sensitive adhesive layer is known. As long as the pressure-sensitive adhesive layer is formed by using, there is a limit in the thickness, and thus there is also a limit in the adhesive strength.
【0003】また、基材に厚目のフォームを用いると感
圧接着材の接着性は比較的良好になるが、最も一般的な
ウレタンフォームやポリエチレンフォームなどのばあ
い、比較的高い剪断接着力をえようとすると剥離接着力
が充分でなくなり、比較的高い剥離接着力を有するよう
にすると感圧接着材としての剪断接着力に限界があり、
比較的高い剥離接着力と比較的高い剪断接着力とを併せ
もたせるのが容易でなく、満足いく特性のものがえられ
ていないという問題がある。When a thick foam is used as the base material, the adhesiveness of the pressure-sensitive adhesive becomes relatively good. However, in the case of urethane foam or polyethylene foam, which is the most common, a relatively high shear adhesive strength is obtained. When trying to obtain, the peel adhesive strength is not sufficient, and when having a relatively high peel adhesive strength, there is a limit to the shear adhesive strength as a pressure-sensitive adhesive,
There is a problem that it is not easy to combine a relatively high peel adhesive strength and a relatively high shear adhesive strength, and satisfactory properties are not obtained.
【0004】このような問題を解決するため、特定割合
で特定種の気泡を含む感圧接着膜が製造され、柔軟性お
よび比較的高い接着力のいずれをも有する感圧接着材が
えられている(特開昭58−125776号公報)。し
かし、この感圧接着材は特定種の気泡を特定割合で含む
特殊なものであり、通常の方法とは異なる方法、すなわ
ち重合すると感圧接着性を有する状態になる組成物を泡
立てたのち基材の上にのせ、該起泡物の泡が消えないう
ちに現場で重合させて感圧接着性を有する状態にしなけ
ればならないという、形態的にも製法的にもかなり特殊
なものとなるという欠点がある。In order to solve such a problem, a pressure-sensitive adhesive film containing a specific kind of air bubbles at a specific ratio has been produced, and a pressure-sensitive adhesive having both flexibility and relatively high adhesive strength has been obtained. (JP-A-58-125776). However, this pressure-sensitive adhesive is a special material containing specific types of air bubbles at a specific ratio, and is different from the usual method, that is, after foaming a composition that becomes a pressure-sensitive adhesive state when polymerized, It must be put on a material and polymerized on site before the foam of the foamed material disappears to have a pressure-sensitive adhesive property, it is said that it will be quite special in morphology and manufacturing method There are drawbacks.
【0005】なお前記気泡のかわりにガラス微小バブル
を含有せしめた感圧接着テープなども検討されているが
(特開昭53−141346号公報および同62−34
976号公報)、バブルが混合時にこわれやすく、取扱
いに注意がいるというのが実情である。[0005] A pressure-sensitive adhesive tape containing glass microbubbles instead of the air bubbles has been studied (Japanese Patent Application Laid-Open Nos. 53-141346 and 62-34).
No. 976), the fact is that bubbles are easily broken at the time of mixing, and care is taken in handling.
【0006】[0006]
【発明が解決しようとする課題】本発明の課題は、柔軟
性および比較的高い接着力を有するテープ状〜シート状
の感圧接着材の製法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a tape-shaped or sheet-shaped pressure-sensitive adhesive having flexibility and relatively high adhesive strength.
【0007】[0007]
【課題を解決するための手段】上記課題は以下に示す本
発明によって達成される。 1)常温で液状のゴム系有機重合体を主成分とする組成
物を架橋・硬化させてえられた基材と感圧接着剤層が積
層されてなるテープ状〜シート状の感圧接着材を製造す
るにあたり、 感圧接着剤層に基材層を積層し、 その基剤層側どうしを重ね合せることを特徴とする感
圧接着材の製法。The above object is achieved by the present invention described below. 1) A tape-shaped or sheet-shaped pressure-sensitive adhesive obtained by laminating a pressure-sensitive adhesive layer and a substrate obtained by crosslinking and curing a composition mainly composed of a rubber-based organic polymer that is liquid at room temperature. A method for producing a pressure-sensitive adhesive, comprising: laminating a base material layer on a pressure-sensitive adhesive layer; and laminating the base layer sides.
【0008】2)上記1)記載のゴム系有機重合体を主
成分とする組成物が、(A)ケイ素原子に結合した水酸
基または加水分解性基を有し、シロキサン結合を形成す
ることにより架橋しうるケイ素含有基を分子中に少なく
とも1個有する常温で液状のゴム系有機重合体および (B)硬化触媒 を主成分とする硬化性組成物である請求項1記載のテー
プ状〜シート状の感圧接着材の製法。 3)上記1)記載のゴム系有機重合体を主成分とする組
成物が、(A)ケイ素原子に結合した水酸基または加水
分解性基を有し、シロキサン結合を形成することにより
架橋しうるケイ素含有基を分子中に少なくとも1個有す
る常温で液状のゴム系有機重合体および (B)硬化触媒 を主成分とし、粘着付与樹脂を含有した硬化性組成物で
ある請求項1記載のテープ状〜シート状の感圧接着材の
製法。本発明においては、常温で液状のゴム系有機重合
体(以下、特定のゴム系有機重合体ともいう)を主成分
とする組成物が使用される。2) The composition comprising the rubber-based organic polymer as described in 1) above as a main component has (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is crosslinked by forming a siloxane bond. The tape-shaped or sheet-shaped curable composition according to claim 1, wherein the curable composition is a rubber-based organic polymer which is liquid at room temperature and has at least one silicon-containing group in a molecule, and (B) a curing catalyst. Manufacturing method of pressure sensitive adhesive. 3) The composition comprising, as a main component, the rubber-based organic polymer described in 1) above, (A) silicon having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and capable of being crosslinked by forming a siloxane bond. The curable composition according to claim 1, which is a curable composition containing a rubber-based organic polymer which is liquid at room temperature having at least one containing group in a molecule and (B) a curing catalyst as a main component and a tackifier resin. Manufacturing method of sheet-shaped pressure-sensitive adhesive. In the present invention, a composition containing a rubber-based organic polymer that is liquid at room temperature (hereinafter, also referred to as a specific rubber-based organic polymer) as a main component is used.
【0009】特定のゴム系有機重合体は、その名前のと
おり、硬化などののちもゴム状となり柔軟性を有するも
のであることが必要である。なお本明細書にいう柔軟性
を有するとは、常温でごく僅かな指の力で曲げられるこ
とはもちろんであるが、常温での弾性率が1×108 d
yne/cm2 以下、好ましくは5×107 dyne/
cm2 以下であることを意味する概念である。[0009] As the name implies, the specific rubber-based organic polymer is required to be rubbery after curing or the like and to have flexibility. The term “flexible” as used in the present specification means that the elasticity at room temperature is 1 × 10 8 d, although it can be bent with very little finger force at room temperature.
yne / cm 2 or less, preferably 5 × 10 7 dyne /
cm 2 or less.
【0010】このような観点から特定のゴム系有機重合
体は常温で液状、すなわち5〜35℃程度で流動性を有
する、可塑剤なしで室温で混練が容易であるのごとき性
状を有し、要すれば溶剤などを併用してテープ状〜シー
ト状に形づくりやすいものであることが必要である。ま
たテープ状〜シート状に形づくられたのち基材となるた
め、分子中に少なくとも1個の反応性基を有することが
必要である。さらにゴム系重合体であることが必要であ
る。From this viewpoint, the specific rubber-based organic polymer has properties such as being liquid at ordinary temperature, ie, having fluidity at about 5 to 35 ° C., and being easily kneaded at room temperature without a plasticizer, If necessary, a solvent or the like must be used in combination to be easily formed into a tape shape or a sheet shape. Further, since the base material is formed after being formed into a tape shape or a sheet shape, it is necessary to have at least one reactive group in the molecule. Further, it must be a rubber-based polymer.
【0011】このような特定のゴム系有機重合体として
は、たとえば分子中に少なくとも1個の反応性ケイ素基
を有する常温で液状のゴム系有機重合体(以下、ゴム系
有機重合体(A)ともいう)、また反応性基としてたと
えば水酸基、イソシアネート基、グリシジル基、アクリ
ロイル基、メタクリロイル基、ビニル基、アリル基、ア
ミノ基、アミド基、カルボキシル基、メルカプト基など
を分子中に少なくとも1個有する常温で液状の有機重合
体などがあげられるが、硬化後の基材の柔軟性の点から
ゴム系有機重合体(A)が好ましい。Examples of such a specific rubber-based organic polymer include a rubber-based organic polymer which has at least one reactive silicon group in a molecule and is liquid at room temperature (hereinafter referred to as a rubber-based organic polymer (A)). ), And has at least one hydroxyl group, isocyanate group, glycidyl group, acryloyl group, methacryloyl group, vinyl group, allyl group, amino group, amide group, carboxyl group, mercapto group and the like as a reactive group. An organic polymer which is liquid at room temperature can be mentioned, but a rubber organic polymer (A) is preferable from the viewpoint of the flexibility of the substrate after curing.
【0012】前記特定のゴム系有機重合体の主鎖は硬化
物がゴム状物となる有機重合体であるかぎりとくに限定
はないが、たとえば特願昭62−335798号明細書
などに記載のごとき主鎖が本質的に一般式:−R−O−
(式中、Rは2価の有機基)で示される繰返し単位を有
するポリエーテル;特開昭59−168014号公報な
どに記載のごとき2−エチルヘキシルアクリレート、ブ
チルアクリレートなどのアクリル酸エステルをラジカル
重合させてえられるポリアクリル酸エステルや、2−エ
チルヘキシルアクリレートやブチルアクリートなどのア
クリル酸エステルと酢酸ビニル、アクリロニトリル、メ
チルメタクリレート、スチレンなどとのアクリル酸エス
テル系共重合体、特願昭62−327938号明細書や
特願昭62−330890号明細書などに記載のごとき
イソブチレン系重合体や水添ポリジエン系重合体などの
飽和炭化水素系重合体:プロピレンオキシド、エチレン
オキシド、テトラヒドロフランなどの環状エーテルの重
合によりえられたポリエーテル系重合体中で炭素数1〜
12のアルコールのアクリル酸エステルやメタクリル酸
エステル、酢酸ビニル、アクリロニトリル、スチレンな
どのビニルモノマーを重合させてえられるビニルポリマ
ー変性ポリエーテル系重合体などがあげられる。The main chain of the specific rubber-based organic polymer is not particularly limited as long as the cured product is an organic polymer capable of forming a rubber-like material. The main chain is essentially of the general formula: -RO-
(Where R is a divalent organic group) a polyether having a repeating unit represented by the following formula: Radical polymerization of an acrylate such as 2-ethylhexyl acrylate or butyl acrylate as described in JP-A-59-168014 Japanese Patent Application No. 62-327938, polyacrylates obtained by the above method, and acrylate copolymers of acrylates such as 2-ethylhexyl acrylate and butyl acrylate with vinyl acetate, acrylonitrile, methyl methacrylate and styrene. Saturated hydrocarbon polymers such as isobutylene polymer and hydrogenated polydiene polymer as described in the specification and Japanese Patent Application No. 62-330890: polymerization of cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydrofuran. Was obtained Carbon number 1 in Rieteru based polymer
And a vinyl polymer-modified polyether-based polymer obtained by polymerizing vinyl monomers such as acrylic acid ester and methacrylic acid ester of alcohol No. 12, vinyl acetate, acrylonitrile, and styrene.
【0013】これらのうちでは重合体中、一般式:−R
−O−で示される繰返し単位を50%(重量%、以下同
様)以上、好ましくは70%以上、さらに好ましくは9
0%以上含有するポリエーテル系重合体が好ましく、と
くにポリプロピレンオキシド系重合体が好ましい。ま
た、前記ゴム系有機重合体(A)中に含有されている反
応性ケイ素基はよく知られた基であり、室温においても
架橋しうるという特徴を有している。Of these, a polymer represented by the general formula: -R
The repeating unit represented by -O- is not less than 50% (% by weight, the same applies hereinafter), preferably not less than 70%, more preferably not less than 9%.
A polyether polymer containing 0% or more is preferable, and a polypropylene oxide polymer is particularly preferable. Further, the reactive silicon group contained in the rubber-based organic polymer (A) is a well-known group and has a feature that it can be crosslinked at room temperature.
【0014】このような反応性ケイ素基の例としては
〔化1〕に示す一般式(1)で表わされる基が示され
る。An example of such a reactive silicon group is a group represented by the general formula (1) shown in [Chemical Formula 1].
【0015】[0015]
【化1】 Embedded image
【0016】(式中、Xは水酸基または加水分解性基で
あり、2個以上存在するとき、それらは同じであっても
よく、異なっていてもよい。R1 は炭素数1〜20の1
価の炭化水素基または (R′)3 −SiO− (R′は炭素数1〜20の1価の炭素水素基であり、3
個のR′は同じであってもよく異なっていてもよい)で
示されるトリオルガノシロキシ基であり、R1 が2個以
上存在するとき、それらは同じであってもよく異なって
いてもよい。aは0,1,2または3、bは0,1また
は2、但し1≦a+mb、またm個の〔化2〕で示され
る連結基におけるbは同じである必要はない、mは0ま
たは1〜19)好ましい反応ケイ素基は〔化3〕に示す
一般式(2)で表わされる基である。(In the formula, X is a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. R 1 is 1 to 20 carbon atoms.)
A monovalent hydrocarbon group or (R ′) 3 —SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
R's may be the same or different), and when two or more R 1 are present, they may be the same or different . a is 0, 1, 2 or 3, b is 0, 1 or 2, provided that 1 ≦ a + mb, and b in the m linking groups represented by the formulas need not be the same, and m is 0 or 1 to 19) Preferred reactive silicon groups are groups represented by the general formula (2) shown in [Chemical Formula 3].
【0017】[0017]
【化2】 Embedded image
【0018】[0018]
【化3】 Embedded image
【0019】(式中、Xは上記と同じ、R2 は炭素基1
〜18の1価の炭化水素基、nは1,2または3)前記
基材用組成物を構成する特定のゴム系有機重合体と共重
合体に用いられる成分として硬化触媒(B)がある。硬
化触媒(B)は、本発明に用いられるゴム系有機重合体
に作用して架橋、硬化させ、安定な基材組成物を生成さ
せる。前記ゴム系有機重合体(A)と共に用いる硬化触
媒には特に限定はなく、通常使用されるシラノール縮合
用触媒が用いられる。Wherein X is the same as above, and R 2 is a carbon group 1
To 18 monovalent hydrocarbon groups, n is 1, 2 or 3) A curing catalyst (B) is a component used in the specific rubber-based organic polymer and copolymer constituting the base material composition. . The curing catalyst (B) acts on the rubber-based organic polymer used in the present invention to crosslink and cure, thereby producing a stable base composition. The curing catalyst used together with the rubber-based organic polymer (A) is not particularly limited, and a commonly used silanol condensation catalyst is used.
【0020】このような硬化触媒(B)の具体例として
は、例えば、チタン酸エステル類、錫カルボン酸塩類、
有機ジルコニウム化合物、ジブチル錫オキサイドとフタ
ル酸エステル類との反応物、キレート化合物、オクチル
酸鉛、アミン化合物、酸性燐酸エステル、飽和又は不飽
和の多価カルボン酸またはその無水物、アミン化合物と
酸性燐酸エステルとの反応物、アミン化合物と飽和また
は不飽和の多価カルボン酸またはその無水物との反応
物、その他酸性触媒、塩基性触媒などの公知のシラノー
ル触媒があげられる。Specific examples of such a curing catalyst (B) include, for example, titanates, tin carboxylate salts,
Organic zirconium compounds, reactants of dibutyltin oxide with phthalates, chelate compounds, lead octylate, amine compounds, acidic phosphates, saturated or unsaturated polyvalent carboxylic acids or anhydrides, amine compounds and acidic phosphoric acid Examples thereof include a reaction product with an ester, a reaction product of an amine compound with a saturated or unsaturated polycarboxylic acid or an anhydride thereof, and other known silanol catalysts such as an acidic catalyst and a basic catalyst.
【0021】これら硬化触媒(B)の使用量は、ゴム系
有機重合体(A)100重量部に対して0.1〜10重
量部、さらに0.5〜8重量部が好ましい。該量が0.
1重量部未満では触媒効果が充分でなく、10重量部を
超えると硬化が速すぎて支持体への塗布作業性が悪くな
る。前記基材用組成物を構成する特定のゴム系有機重合
体以外に使用され得る成分として、基材の柔軟性を調節
し、強度を高めるために使用される粘着付与樹脂があ
る。粘着付与樹脂としては、特に限定はなく、通常使用
される粘着付与樹脂であれば使用し得る。The amount of the curing catalyst (B) used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the rubber organic polymer (A). The amount is 0.
If it is less than 1 part by weight, the catalytic effect is not sufficient, and if it exceeds 10 parts by weight, the curing is too fast, and the workability of coating on the support deteriorates. As a component that can be used other than the specific rubber-based organic polymer constituting the composition for a base material, there is a tackifier resin used for adjusting the flexibility of the base material and increasing the strength. There is no particular limitation on the tackifier resin, and any commonly used tackifier resin can be used.
【0022】このような粘着付与樹脂の具体例として
は、例えば、フェノール樹脂、変性フェノール樹脂、テ
ルペン−フェノール樹脂、石油樹脂、ロジンエステル樹
脂、低分子量ポリスチレン樹脂、テルペン樹脂などがあ
げられる。これらは、単独で用いてもよく、2種以上混
合して用いてもよい。これらのなかでは、特にフェノー
ル樹脂系やフェノール含有樹脂系のものが柔軟性、高伸
び及び高強度を発現し易いので好ましい。Specific examples of such tackifier resins include, for example, phenolic resins, modified phenolic resins, terpene-phenolic resins, petroleum resins, rosin ester resins, low molecular weight polystyrene resins, terpene resins and the like. These may be used alone or as a mixture of two or more. Among these, phenol resin-based and phenol-containing resin-based resins are particularly preferred because they easily exhibit flexibility, high elongation and high strength.
【0023】粘着付与樹脂の使用量は、ゴム系有機重合
体(A)と共に用いる場合、ゴム系有機重合体(A)1
00重量部に対して0〜140重量部、さらには5〜8
0重量部が好ましい。該量が140重量部を超えると高
弾性率となり、ゴム的な性質が充分得られなくなるので
好ましくない。これ以外に使用される成分としては、基
材の物性の調整やコストダウンのために用いられるフィ
ラーや基材用組成物の粘度を調整するために溶剤が使用
できる。When the tackifier resin is used together with the rubber organic polymer (A), the amount of the rubber organic polymer (A)
0 to 140 parts by weight, more preferably 5 to 8 parts by weight, per 100 parts by weight
0 parts by weight is preferred. If the amount exceeds 140 parts by weight, a high elastic modulus is obtained, and a rubber-like property cannot be sufficiently obtained. As other components to be used, a filler can be used for adjusting the physical properties of the base material and the viscosity of the base material composition used for cost reduction, and a solvent can be used.
【0024】また、酸化防止剤、紫外線吸収剤、顔料、
界面活性剤などがそれぞれの目的に応じて用いられる
が、これらに限定されるものではない。本発明におい
て、ゴム系有機重合体に他の成分を混合するに当たって
は、バンバリーミキサー、ニーダー、ロール、プラネタ
リミキサーなどの混合機を用いて行えばよく、このうち
粘着付与樹脂を用いる場合は、これを予め1〜100μ
m程度の微粉末状態に粉砕しておくことにより、容易に
混合することができるようになる。粘着付与樹脂の微粉
末は塗工前に必ずしも均一溶解状態である必要はなく、
ゴム系有機重合体に小さな粒子として不均一分散状態で
存在していても構わない。Also, an antioxidant, an ultraviolet absorber, a pigment,
Surfactants and the like are used according to the respective purposes, but are not limited thereto. In the present invention, in mixing the rubber-based organic polymer with other components, a Banbury mixer, a kneader, a roll, a mixer such as a planetary mixer may be used, and when a tackifying resin is used, 1 ~ 100μ
By pulverizing to a fine powder state of about m, mixing becomes easy. The fine powder of the tackifier resin does not necessarily have to be in a homogeneously dissolved state before coating,
It may be present in the rubber-based organic polymer as small particles in a non-uniformly dispersed state.
【0025】前述のように調製された硬化性組成物から
硬化シートを製造するには、通常該組成物がシリコン剥
離紙などへ塗工され、乾燥、硬化させることにより達成
される。前記塗工法には、特に限定はなく、硬化性組成
物を通常のコーターを用いて塗工すればよい。塗工後、
乾燥・硬化工程にはいるが、乾燥硬化条件としては、常
温ないし150℃で0.5〜60分程度行われる。The production of a cured sheet from the curable composition prepared as described above is usually achieved by applying the composition to a silicon release paper or the like, drying and curing. The coating method is not particularly limited, and the curable composition may be applied using a usual coater. After coating,
The drying / curing step is performed. The drying and curing conditions are from room temperature to 150 ° C. for about 0.5 to 60 minutes.
【0026】本発明のテープ状ないしシート状の感圧接
着材は、このようにして得られる硬化シートを基材と
し、これに感圧接着剤層が積層される。感圧接着剤層に
基材が積層される時の感圧接着剤層の状態としてはウェ
ット又はドライどちらでもかまわないが、溶剤型の感圧
接着剤を用いる場合において、溶剤の乾燥の容易さを考
慮すればあらかじめドライ状態にて積層することが好ま
しい。The tape-shaped or sheet-shaped pressure-sensitive adhesive of the present invention comprises a cured sheet obtained as described above as a base material, on which a pressure-sensitive adhesive layer is laminated. The state of the pressure-sensitive adhesive layer when the substrate is laminated on the pressure-sensitive adhesive layer may be either wet or dry, but when a solvent-type pressure-sensitive adhesive is used, the drying of the solvent is easy. In consideration of the above, it is preferable to stack the layers in a dry state in advance.
【0027】感圧接着剤層に基材が積層される時の基材
層の状態としては、未硬化、半硬化、ほぼ完全硬化状態
のいずれでもかまわないが、その後の基材層側どうしの
重ね合せ面の結合強度の大きさを考慮すると反応性基が
少しでも残っている状態が望ましく、一方、完全未硬化
状態は、その後の重ね合せ時の取り扱いがやりにくく、
半硬化〜ほぼ完全硬化状態が好ましい。基材層は基材層
面どうしの重ね合せ後に硬化反応が完了し、基材層とし
て一体のものになる。The state of the base material layer when the base material is laminated on the pressure-sensitive adhesive layer may be uncured, semi-cured, or almost completely cured. Considering the size of the bonding strength of the superposed surface, it is desirable that the reactive group remains even a little, while the completely uncured state is difficult to handle during subsequent superposition,
A semi-cured to almost completely cured state is preferred. The curing reaction of the substrate layer is completed after the surfaces of the substrate layers are overlapped, and the substrate layer becomes an integral substrate layer.
【0028】本発明に用いられる感圧接着剤には特に限
定はなく、例えば、溶剤型、エマルジョン型あるいは無
溶剤型のアクリル酸エステル共重合体系粘着剤、天然ゴ
ムや合成ゴムに粘着付与樹脂を配合して得られる溶剤型
あるいはホットメルト型接着剤、その他の粘着剤が使用
される。このようにして形成される感圧接着剤層の厚さ
には特に限定はないが、通常5μm〜1mm程度、好ま
しくは25〜200μmのものである。The pressure-sensitive adhesive used in the present invention is not particularly limited. For example, a solvent-type, emulsion-type or solvent-free acrylate copolymer-based pressure-sensitive adhesive, or a tackifier resin to natural rubber or synthetic rubber. Solvent-type or hot-melt type adhesives obtained by blending, and other pressure-sensitive adhesives are used. The thickness of the pressure-sensitive adhesive layer thus formed is not particularly limited, but is usually about 5 μm to 1 mm, preferably 25 to 200 μm.
【0029】[0029]
【実施例】以下、実施例によって本発明を詳しく述べる
が、本発明はこれらに限定されるものではない。 実施例1 感圧接着剤層は、次のようにして形成した。即ち、市販
の溶剤型アクリル系粘着剤(一方社油脂株式会社製)を
ドクターブレードを用いシリコン剥離紙(創研化工株式
会社製のEK−130R)の上に乾燥後の糊厚が100
μmになるように塗工し、60℃×3分間乾燥し、10
0℃×2分間硬化させた。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example 1 A pressure-sensitive adhesive layer was formed as follows. That is, a commercially available solvent-type acrylic pressure-sensitive adhesive (manufactured by Yushi Co., Ltd.) is dried on a silicone release paper (EK-130R, manufactured by Souken Kako Co., Ltd.) using a doctor blade to a thickness of 100.
μm, and dried at 60 ° C. for 3 minutes.
Cured at 0 ° C for 2 minutes.
【0030】一方、1分子当たり平均1.0個のジメト
キシシリル基: −Si(CH3 )(OCH3 )2 を有する平均分子量9200のプロピレンオキシドから
なる重合体100重量部(以下、プロピレンオキシド系
重合体(A)という)、ストレート系ノボラックフェノ
ール樹脂(住友ベークライト株式会社製、商品名PR−
50731)の微粉末70重量部、酸化防止剤(ノクラ
ックNS−6)1重量部、紫外線吸収剤(チヌビン32
7)1重量部、シラスバルーン7.5重量部、酸/塩基
系シラノール縮合触媒5.6重量部及びカーボンブラッ
ク0.75重量部を加え均一に混合した。これをドクタ
ーブレードを用いシリコン剥離紙(EK−130R)の
上に厚さが500μmになるように塗工し、120℃で
10分間加熱処理して基材層を得た。この基材層のゲル
分は34%であった。On the other hand, 100 parts by weight of a polymer composed of propylene oxide having an average molecular weight of 9200 and having an average of 1.0 dimethoxysilyl groups per molecule: --Si (CH 3 ) (OCH 3 ) 2 (hereinafter referred to as propylene oxide-based) Polymer (A)), straight novolak phenolic resin (trade name: PR-, manufactured by Sumitomo Bakelite Co., Ltd.)
50731), 1 part by weight of an antioxidant (Nocrack NS-6), and an ultraviolet absorber (Tinuvin 32)
7) 1 part by weight, 7.5 parts by weight of Shirasu balloon, 5.6 parts by weight of an acid / base silanol condensation catalyst, and 0.75 parts by weight of carbon black were added and uniformly mixed. This was applied on a silicon release paper (EK-130R) using a doctor blade so that the thickness became 500 μm, and heat-treated at 120 ° C. for 10 minutes to obtain a base material layer. The gel content of this base material layer was 34%.
【0031】この基材層の片面に上記のアクリル系感圧
接着剤層を重ね合せたものを2枚用意し、この基材層面
どうしを重ね合せして両面にアクリル系感圧接着剤層が
積層されている接着テープを得た。 実施例2 実施例1と同様にアクリル系感圧接着剤層を塗工し、乾
燥・硬化した。Two pieces of the above-mentioned acrylic pressure-sensitive adhesive layer were superposed on one side of the base material layer, and the base material layers were superposed on each other to form an acrylic pressure-sensitive adhesive layer on both sides. The laminated adhesive tape was obtained. Example 2 An acrylic pressure-sensitive adhesive layer was applied, dried and cured in the same manner as in Example 1.
【0032】その後、実施例1で用いた基材配合物を上
記アクリル系感圧接着剤層の上から巾広のドクターブレ
ードを用いて基剤層の厚さが500μmになる様に塗工
し、120℃で10分間加熱処理した。この基材層のゲ
ル分を単離して測定すると32%であった。この積層品
の基材層側どうしを重ね合せ、両面にアクリル系感圧接
着剤層が積層されている接着テープを得た。 比較例1 実施例1において、基材層の厚みを1000μmとした
以外は同様にしてそれぞれアクリル系感圧接着剤層及び
基材層を得た。Thereafter, the base composition used in Example 1 was applied from above the acrylic pressure-sensitive adhesive layer using a wide doctor blade so that the thickness of the base layer was 500 μm. At 120 ° C. for 10 minutes. The gel content of this substrate layer was isolated and measured to be 32%. The base material layer side of this laminate was overlaid to obtain an adhesive tape having an acrylic pressure-sensitive adhesive layer laminated on both sides. Comparative Example 1 An acrylic pressure-sensitive adhesive layer and a substrate layer were obtained in the same manner as in Example 1, except that the thickness of the substrate layer was changed to 1000 μm.
【0033】この基材層の両面にアクリル系感圧接着剤
層を重ね合せて両面接着テープを得た。 比較例2 実施例2において、基材層の厚さが1000μmになる
様に塗工する以外は同様にしてアクリル系粘着剤層の上
に基材層を積層した。An acrylic pressure-sensitive adhesive layer was superposed on both sides of the substrate layer to obtain a double-sided adhesive tape. Comparative Example 2 A substrate layer was laminated on the acrylic pressure-sensitive adhesive layer in the same manner as in Example 2, except that the coating was performed so that the thickness of the substrate layer was 1000 μm.
【0034】この基材層面にさらに実施例1で用いた市
販の溶剤型アクリル系粘着剤を乾燥後の糊厚が100μ
mになる様に注意深く塗工し、実施例1と同条件にて乾
燥・硬化して両面接着テープを得た。得られた両面接着
テープの接着特性を下記の方法で測定した。結果は表1
に示す。The commercially available solvent-type acrylic pressure-sensitive adhesive used in Example 1 was further coated on the substrate layer surface with a paste thickness of 100 μm.
m and dried and cured under the same conditions as in Example 1 to obtain a double-sided adhesive tape. The adhesive properties of the obtained double-sided adhesive tape were measured by the following method. Table 1 shows the results
Shown in
【0035】[0035]
【表1】 [Table 1]
【0036】〔180°剥離強度〕厚さ50μmのポリ
エステルフィルムを裏打ちした幅2.5cmの両面接着
テープ片を作成し、これを塗装鋼板に貼合せた。これを
室温で1日放置した後、島津製オートグラフを用いて2
3℃及び80℃雰囲気下で50mm/分を引張速度で1
80°剥離強度を測定した。 〔剪断接着強度〕厚さ2mm、幅2.5cm、長さ8c
mの塗装鋼板と同サイズの鋼板で裏うちした軟PVC板
被着体の端約3.2cm2 の部分を両面接着テープで貼
合せた。これを室温で1日放置した後、島津製オートグ
ラフを用いて23℃及び80℃雰囲気下で50mm/分
の引張強度で引張剪断接着強度を測定した。[180 ° Peeling Strength] A 2.5 cm wide double-sided adhesive tape piece lined with a polyester film having a thickness of 50 μm was prepared and bonded to a coated steel sheet. After leaving it at room temperature for one day, it was
Under the atmosphere of 3 ° C. and 80 ° C., 50 mm / min.
The 80 ° peel strength was measured. [Shear bond strength] 2mm thick, 2.5cm wide, 8c long
An approximately 3.2 cm 2 end of a soft PVC plate adhered with a steel plate of the same size as a painted steel plate of length m was bonded with a double-sided adhesive tape. After leaving this at room temperature for one day, the tensile shear adhesive strength was measured at 23 ° C. and 80 ° C. atmosphere at a tensile strength of 50 mm / min using an autograph manufactured by Shimadzu.
【0037】表1から、本発明品は比較例1の逐次重ね
合せ法と同様の接着特性を有し、比較例2のような残溶
剤による接着力への悪影響を受けることがない。従って
常温で液状のゴム系有機重合体を主成分とする組成物を
架橋・硬化させてえられた基材と感圧接着剤層が積層さ
れてなるテープ〜シート状感圧接着剤の製法として有用
であることがわかる。From Table 1, it can be seen that the product of the present invention has the same adhesive properties as the sequential laminating method of Comparative Example 1, and does not adversely affect the adhesive strength due to the residual solvent as in Comparative Example 2. Therefore, as a method for producing a tape-sheet-shaped pressure-sensitive adhesive obtained by laminating a pressure-sensitive adhesive layer and a substrate obtained by crosslinking and curing a composition mainly composed of a liquid rubber-based organic polymer at room temperature. It turns out to be useful.
【0038】[0038]
【発明の効果】本発明の製法によって得られた感圧接着
材は、常温での弾性率が1×108 dyn/cm2 以下
であり、特に5×107 dyn/cm2 以下であるとい
う柔軟性と安定した高い剥離接着強度及び剪断接着強度
を有し、かつ外観的にも黒色を含む有色配合が容易であ
り、コスト的にも比較的安価であるので、自動車用製品
(例えば、サイドモール、エンブレムモール、ウェザー
ストリップなどの接着)、電気製品、室内調度品、表示
板、建築材料などの組立、固定などの用途に好適に使用
でき、その工業的価値は非常に高い。The pressure-sensitive adhesive obtained by the method of the present invention has an elastic modulus at room temperature of 1 × 10 8 dyn / cm 2 or less, particularly 5 × 10 7 dyn / cm 2 or less. Since it has flexibility, stable high peel adhesive strength and shear adhesive strength, and is easy to mix in color including black in appearance, and is relatively inexpensive, it can be used for automobile products (for example, side It can be suitably used for applications such as bonding of moldings, emblem moldings, weather strips, etc.), assembling and fixing electric appliances, room furniture, display boards, building materials, and the like, and its industrial value is very high.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C09J 7/02 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 7 , DB name) C09J 7/02
Claims (3)
とする組成物を架橋・硬化させてえられた基材と感圧接
着剤層が積層されてなるテープ状〜シート状の感圧接着
材を製造するにあたり、 1)感圧接着剤層に基材層を積層し、 2)その基剤層側どうしを重ね合せることを特徴とする
感圧接着材の製法。1. A tape-shaped or sheet-shaped sensor comprising a substrate obtained by crosslinking and curing a composition mainly composed of a rubber-based organic polymer which is liquid at normal temperature and a pressure-sensitive adhesive layer laminated thereon. In producing a pressure-sensitive adhesive, a method for producing a pressure-sensitive adhesive, comprising: 1) laminating a base material layer on a pressure-sensitive adhesive layer; and 2) laminating the base layer sides together.
分とする組成物が、 (A)ケイ素原子に結合した水酸基または加水分解性基
を有し、シロキサン結合を形成することにより架橋しう
るケイ素含有基を分子中に少なくとも1個有する常温で
液状のゴム系有機重合体および (B)硬化触媒 を主成分とする硬化性組成物である請求項1記載のテー
プ状〜シート状の感圧接着材の製法。2. A composition comprising the rubber-based organic polymer according to claim 1 as a main component, comprising: (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and crosslinking by forming a siloxane bond. The tape-shaped or sheet-shaped curable composition according to claim 1, wherein the curable composition is a rubber-based organic polymer which is liquid at room temperature and has at least one silicon-containing group in a molecule, and (B) a curing catalyst. Manufacturing method of pressure sensitive adhesive.
分とする組成物が、 (A)ケイ素原子に結合した水酸基または加水分解性基
を有し、シロキサン結合を形成することにより架橋しう
るケイ素含有基を分子中に少なくとも1個有する常温で
液状のゴム系有機重合体および (B)硬化触媒 を主成分とし、粘着付与樹脂を含有した硬化性組成物で
ある請求項1記載のテープ状〜シート状の感圧接着材の
製法。3. A composition comprising the rubber-based organic polymer according to claim 1 as a main component, comprising: (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and crosslinking by forming a siloxane bond. The curable composition according to claim 1, wherein the curable composition contains a rubber-based organic polymer which is liquid at room temperature and has at least one silicon-containing group in the molecule, and (B) a curing catalyst, and a tackifier resin. A method for producing a tape-to-sheet pressure-sensitive adhesive.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3278289A JP3041733B2 (en) | 1991-09-30 | 1991-09-30 | Manufacturing method of pressure-sensitive adhesive |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3278289A JP3041733B2 (en) | 1991-09-30 | 1991-09-30 | Manufacturing method of pressure-sensitive adhesive |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0586339A JPH0586339A (en) | 1993-04-06 |
JP3041733B2 true JP3041733B2 (en) | 2000-05-15 |
Family
ID=17595278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3278289A Expired - Fee Related JP3041733B2 (en) | 1991-09-30 | 1991-09-30 | Manufacturing method of pressure-sensitive adhesive |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3041733B2 (en) |
-
1991
- 1991-09-30 JP JP3278289A patent/JP3041733B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0586339A (en) | 1993-04-06 |
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