JP5095926B2 - Adhesive and adhesive using the same - Google Patents
Adhesive and adhesive using the same Download PDFInfo
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- JP5095926B2 JP5095926B2 JP2005160914A JP2005160914A JP5095926B2 JP 5095926 B2 JP5095926 B2 JP 5095926B2 JP 2005160914 A JP2005160914 A JP 2005160914A JP 2005160914 A JP2005160914 A JP 2005160914A JP 5095926 B2 JP5095926 B2 JP 5095926B2
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本発明は、コンデンサー素子止め用、部品結束用、ディスプレイパネル等の固定用、合わせガラス中間膜用、或いはその他の用途に利用可能なアクリル系粘着剤及び粘着体に関する。 The present invention relates to an acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive body that can be used for fixing capacitor elements, for binding components, for fixing display panels, for laminated glass interlayer films, and for other applications.
粘着シートなどの粘着体を利用すると、例えば光学製品や電子部品の製造や、家電製品、情報電子機器、ディスプレイ材等の組立加工などにおいて、接着剤の塗布工程を省略できる上、連続加工が可能となるため、近年、接着剤の代わりに粘着体を利用するケースが増えてきている。例えば光学製品や電子部品の製造・組立工程においては、レンズ等の光学部品や半導体ウエハ等の半導体製品、或いは電子部品などを粘着体に貼着した状態で精密加工することが行われている。また、ガラスやセラミックス等の硬質で脆い材料を切断する際、被切断物を粘着剤を用いて硬質材料上に固定した上で切断することが行われている。また、液晶表示装置（ＬＣＤ）の液晶セルに偏光板や保護シートを貼り合わせる際に用いる中間膜としても利用されている。 By using an adhesive such as an adhesive sheet, the adhesive coating process can be omitted and the continuous processing is possible, for example, in the manufacture of optical products and electronic components, as well as assembly processing of household electrical appliances, information electronic equipment, display materials, etc. Therefore, in recent years, an increasing number of cases using an adhesive instead of an adhesive. For example, in manufacturing and assembling processes of optical products and electronic parts, precision processing is performed in a state where optical parts such as lenses, semiconductor products such as semiconductor wafers, or electronic parts are attached to an adhesive body. Moreover, when cutting hard and brittle materials such as glass and ceramics, cutting is performed after fixing an object to be cut on a hard material using an adhesive. It is also used as an intermediate film used when a polarizing plate or a protective sheet is bonded to a liquid crystal cell of a liquid crystal display device (LCD).
この種の粘着体としては、従来、例えば特許文献１において、高温・多湿環境や温水浸漬あるいは煮沸等の条件下に長時間保持されても白化を抑制できる粘着シートとして、アクリル系粘着剤の主剤１００質量部に対して、親水性シリカ超微粒子１０質量部を１５０℃の加圧ニーダーで均一に溶融攪拌させた後、金属化合物の架橋剤としてアセチルアセトン亜鉛塩２．０質量部を溶融攪拌させ、直ちに離型フィルム間に厚み０．５ｍｍのシート状に成形することによって、アクリル系粘着剤の主剤に超微粒子を含有させるようにしてなる透明粘着シートが開示されている。 As this type of pressure-sensitive adhesive, for example, in Patent Document 1, as a pressure-sensitive adhesive sheet that can suppress whitening even if kept for a long time under conditions such as high-temperature and high-humidity environment, hot water immersion or boiling, the main component of an acrylic pressure-sensitive adhesive To 100 parts by mass, after 10 parts by mass of hydrophilic silica ultrafine particles were uniformly melted and stirred with a pressure kneader at 150 ° C., 2.0 parts by mass of acetylacetone zinc salt as a metal compound crosslinking agent was melted and stirred. A transparent pressure-sensitive adhesive sheet is disclosed in which ultrafine particles are contained in a main component of an acrylic pressure-sensitive adhesive by immediately forming a sheet having a thickness of 0.5 mm between release films.
また、特許文献２には、オートクレーブによる高温・高圧処理を必要とすることなく、室温でかつ良好な外観品質を得ることができる粘着シートとして、α，β不飽和カルボン酸を含有した（メタ）アクリル酸エステル系共重合体に前記不飽和カルボン酸と反応する有機官能基含有（メタ）アクリレートモノマー及び光開始剤を配合してなる透明粘着剤を、厚さ０．０５〜２ｍｍのシート状に成形し、紫外線を照射して架橋させてなる透明粘着シートが開示されている。 Further, Patent Document 2 contains an α, β unsaturated carboxylic acid as a pressure-sensitive adhesive sheet capable of obtaining good appearance quality at room temperature without requiring high-temperature and high-pressure treatment by an autoclave (meta). A transparent pressure-sensitive adhesive prepared by blending an acrylic ester copolymer with an organic functional group-containing (meth) acrylate monomer that reacts with the unsaturated carboxylic acid and a photoinitiator into a sheet having a thickness of 0.05 to 2 mm. A transparent pressure-sensitive adhesive sheet that has been molded and then crosslinked by irradiation with ultraviolet rays is disclosed.
さらに特許文献３には、オートクレーブによる高温・高圧処理を必要とすることなく室温で積層体の製造が可能で、さらには板ズレを生じ難い透明粘着シートとして、（メタ）アクリル酸エステル系共重合体に対して、光ラジカル開始剤の少なくとも水素引き抜きタイプ光ラジカル開始剤を０．０１〜１．０質量％配合してなるホットメルト型紫外線架橋透明粘着剤を、ホットメルト成形した後に紫外線照射させて架橋させてなる粘着シートが開示されている。 Furthermore, in Patent Document 3, a laminate can be produced at room temperature without requiring high-temperature and high-pressure treatment by an autoclave, and further, a (meth) acrylic acid ester-based copolymer is used as a transparent pressure-sensitive adhesive sheet that is less prone to plate displacement. A hot-melt type UV-crosslinked transparent adhesive comprising 0.01 to 1.0% by mass of at least a hydrogen abstraction type photo-radical initiator as a photo-radical initiator is subjected to UV irradiation after hot-melt molding. A pressure-sensitive adhesive sheet obtained by cross-linking is disclosed.
一般的に粘着剤は、初期粘着性があり、それでいて剥離可能に貼着できるというメリットを備えている反面、接着剤に比べると永久接着力に劣るため、長期耐久性や接着信頼性の要求される用途には不向きであった。 In general, pressure-sensitive adhesives have the advantage that they have initial stickiness and can be applied in a peelable manner. On the other hand, they are inferior in permanent adhesive strength compared to adhesives, so long-term durability and adhesive reliability are required. It was unsuitable for use.
例えばここで、アルミ電解コンデンサーなどの製造において粘着テープを使用することを想定してみる。すなわち、アルミ箔と絶縁紙を多重に巻いて素子を形成し、この際、巻き緩みが生じないように粘着テープを素子に対して１．５周巻いて巻き止めて巻き端末を接着した後、この巻き止めした素子を電解液に浸漬させて絶縁紙に電解液を含浸させ、アルミキャップ内に挿入し封止することを想定すると、この粘着テープには次の性能が要求される。 For example, assume that an adhesive tape is used in the manufacture of an aluminum electrolytic capacitor or the like. In other words, multiple elements of aluminum foil and insulating paper are wound to form an element. At this time, an adhesive tape is wound around the element for 1.5 turns to prevent winding looseness, and then the winding terminal is bonded, Assuming that the wound element is immersed in an electrolytic solution and impregnated with an electrolytic solution in an insulating paper and inserted into an aluminum cap and sealed, this adhesive tape is required to have the following performance.
（１）素子巻きから巻き止めの生産速度が１分間に１００個以上の高速であるため、巻き止めした素子が緩まないような初期粘着力が必要である。
（２）巻き止めして直ぐに電解液に浸漬されても巻き緩まず、巻き端末が剥がれない永久接着力が必要である。
（３）家電・電気機器等の部品として、高温（１００〜１２０℃）環境下での長期使用に耐える高凝集力が必要である。
(1) Since the production speed from element winding to unwinding is as high as 100 or more per minute, it is necessary to have an initial adhesive force that does not loosen the wound elements.
(2) Even if it is immediately wound and immersed in an electrolytic solution, it does not loosen and a permanent adhesive force that prevents the winding terminal from peeling off is required.
(3) A high cohesive force that can withstand long-term use in a high-temperature (100 to 120 ° C.) environment is required as a component for home appliances and electrical devices.
ところが、従来の粘着テープ（粘着剤製品）は、初期粘着力を上げると凝集力が低下して長期接着耐久性が低下し、逆に凝集力を上げると初期粘着性が低下するのが一般的であったため、両性質を兼ね備えることが困難であった。 However, conventional adhesive tapes (adhesive products) generally have a lower cohesive force and lower long-term adhesion durability when the initial adhesive force is increased, and conversely, initial cohesiveness decreases when the cohesive force is increased. Therefore, it was difficult to combine both properties.
そこで本発明の目的は、初期粘着力を低下させることなく、高凝集力が得られるアクリル系粘着剤を提供することにある。 Accordingly, an object of the present invention is to provide an acrylic pressure-sensitive adhesive capable of obtaining a high cohesive force without reducing the initial adhesive force.
かかる課題解決のため、本発明は、２種類の架橋方式を兼ね備えた粘着剤を設計することにより、先にどちらか一方の架橋方式で架橋させて被着体を貼着した後、残った架橋方式で後架橋させることにより、初期粘着力を低下させることなく、高凝集力を得ることに成功した。 In order to solve this problem, the present invention is designed by designing a pressure-sensitive adhesive having two types of cross-linking methods, and after cross-linking with either one of the cross-linking methods and pasting the adherend, By post-crosslinking by the method, it succeeded in obtaining a high cohesion force without reducing the initial adhesive force.
すなわち、本発明のアクリル系粘着剤は、紫外線架橋可能な光架橋剤と加熱架橋可能な潜在型硬化剤の両方をベースポリマーに配合してなる組成を特徴とするものである。 That is, the acrylic pressure-sensitive adhesive of the present invention is characterized by a composition comprising both a photo-crosslinking agent capable of UV crosslinking and a latent curing agent capable of crosslinking by heating in a base polymer.
本発明のアクリル系粘着剤は、テープ状、フィルム状またはシート状に成形し、これに紫外線を照射して架橋させることにより、熱硬化性を潜在させた粘着体とすることができる。また、テープ状、フィルム状またはシート状に成形し、これを加熱して架橋させることにより、紫外線硬化性を潜在させた粘着体とすることもできる。よって、熱硬化性を潜在させた粘着体については、被着体を貼合せた後に加熱することにより後硬化させて高凝集力を得て長期接着耐久性を高めることができ、他方の紫外線硬化性を潜在させた粘着体については、被着体を貼合せた後に紫外線を照射することにより後硬化させて高凝集力を得て長期接着耐久性を高めることができる。 The acrylic pressure-sensitive adhesive of the present invention can be formed into a pressure-sensitive adhesive having a thermosetting property by forming it into a tape shape, a film shape or a sheet shape and irradiating it with ultraviolet rays to crosslink. Moreover, it can also be set as the adhesive body which made ultraviolet curing latent by shape | molding in tape shape, a film form, or a sheet form, and heating and bridge | crosslinking this. Therefore, the pressure-sensitive adhesive with latent thermosetting property can be post-cured by heating after laminating the adherend to obtain a high cohesive force and increase the long-term adhesion durability. The pressure-sensitive adhesive having latent properties can be post-cured by irradiating ultraviolet rays after the adherends are bonded together to obtain a high cohesive force and enhance long-term adhesion durability.
なお、本発明において、「熱硬化性を潜在させた粘着体」とは、被着体を貼合せた後であっても、加熱して後硬化させることができる性質を備えた粘着体の意であり、「紫外線硬化性を潜在させた粘着体」とは、被着体を貼合せた後であっても、紫外線を照射することにより後硬化させることができる性質を備えた粘着体の意である。
また、本発明において「主剤」又は「主成分」と表現した場合には、特に記載しない限り、当該主剤成分又は主成分の機能を妨げない範囲で他の成分を含有することを許容する意を包含するものである。特に当該主剤成分又は主成分の含有割合を特定するものではないが、その成分（２成分以上が主成分である場合には、これらの合計量）が組成物中で５０質量％以上、特に７０質量％以上、中でも特に９０質量％以上（１００％を含む）を占めるのが一般的である。
また一般的に「シート」とは、ＪＩＳにおける定義上、薄く、一般にその厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう（日本工業規格ＪＩＳＫ６９００）が、テープ、シート、フィルムの境界は定かでないため、本発明ではこれらを厳密に区別するものではない。よって、「テープ」と表現してもシートやフィルムも含み、「シート」と表現してもテープやフィルムを含み、「フィルム」と表現してもシートやテープを含むものとする。
また、本明細書において、「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と記載した場合、特にことわらない限り「Ｘ以上Ｙ以下」の意である。
In the present invention, the “adhesive with latent thermosetting property” means an adhesive having the property that it can be heated and post-cured even after the adherend has been bonded. The term “adhesive with latent UV curing” means an adhesive having the property that it can be post-cured by irradiating it with ultraviolet rays even after the adherend has been bonded. It is.
In addition, when expressed as “main agent” or “main component” in the present invention, unless otherwise specified, the intention to allow other components to be contained within a range that does not hinder the function of the main agent component or main component. It is included. In particular, the content ratio of the main ingredient component or the main component is not specified, but the component (when two or more components are main components, the total amount thereof) is 50% by mass or more, particularly 70% in the composition. Generally, it accounts for 90% by mass or more (including 100%) in particular.
In general, "sheet" is a thin product as defined by JIS, and generally its thickness is small and flat instead of length and width, and "film" is generally compared to length and width. A thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, which is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900), but the boundary between tape, sheet and film is Since it is not certain, the present invention does not strictly distinguish them. Accordingly, the expression “tape” includes a sheet or film, the expression “sheet” includes a tape or film, and the expression “film” includes a sheet or tape.
Further, in this specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “X or more and Y or less” unless otherwise specified.
本実施形態に係るアクリル系粘着剤は、紫外線架橋した後であっても加熱架橋可能であるか、或いは加熱架橋した後であっても紫外線架橋可能であるように、ベースポリマーに、紫外線架橋可能な光架橋剤と加熱架橋可能な潜在型硬化剤の両方を配合してなる組成を特徴として備えたアクリル系粘着剤である。 The acrylic pressure-sensitive adhesive according to this embodiment can be cross-linked to the base polymer so that it can be heat-crosslinked even after UV-crosslinking, or can be UV-crosslinked even after heat-crosslinking. It is an acrylic pressure-sensitive adhesive characterized by a composition comprising both a photocrosslinking agent and a latent curing agent that can be heat-crosslinked.
＜ベースポリマー＞
ベースポリマーとしては、光学的透明性、耐候性、耐熱性に優れるアクリル系重合体、その中でも(メタ)アクリル酸エステル系重合体が好ましい。その組成は、アルキル基としてのｎ−オクチル、イソオクチル、２−エチルヘキシル、ｎ−ブチル、イソブチル、メチル、エチル、イソプロピル等のアルキル基の中から選択された１種又はこれらから選ばれた２種以上の組み合わせからなるアルキル基を有するアルキルアクリレート或いはアルキルメタクリレートと、カルボキシル基、水酸基、グリシジル基、無水マレイン酸基等の中から選択された１種又はこれらから選ばれた２種以上の組み合わせからなる有機官能基を有するアクリレート或いはメタクリレートとがランダム共重合してなるものを挙げることができる。例えば、前記アルキル（メタ）アクリレート成分と前記有機官能基を有する（メタ）アクリレート成分とを適宜に選択的に組み合わせたモノマー成分を出発原料として加熱重合して得られる(メタ)アクリル酸エステル系共重合体を好ましい例として挙げることができる。
<Base polymer>
As the base polymer, an acrylic polymer excellent in optical transparency, weather resistance, and heat resistance, and a (meth) acrylic acid ester polymer is preferable among them. The composition is one or more selected from alkyl groups such as n-octyl, isooctyl, 2-ethylhexyl, n-butyl, isobutyl, methyl, ethyl, isopropyl and the like as an alkyl group. An organic compound comprising an alkyl acrylate or alkyl methacrylate having an alkyl group consisting of a combination of the above, one selected from a carboxyl group, a hydroxyl group, a glycidyl group, a maleic anhydride group, or a combination of two or more selected from these. The thing formed by random copolymerization with the acrylate or methacrylate which has a functional group can be mentioned. For example, a (meth) acrylic acid ester copolymer obtained by heat polymerization using a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material. A polymer can be mentioned as a preferred example.
＜紫外線架橋可能な光架橋剤＞
光架橋剤としては、多官能モノマー（すなわち、官能基を２以上有するモノマー）と光開始剤とを含み、光架橋によって三次元架橋ポリマーを形成し得るものであればよい。
<Photocrosslinking agent capable of UV crosslinking>
Any photocrosslinking agent may be used as long as it contains a polyfunctional monomer (that is, a monomer having two or more functional groups) and a photoinitiator and can form a three-dimensional crosslinked polymer by photocrosslinking.
多官能モノマーとしては、多官能アクリレートモノマー、その中でも、架橋密度を高めて歪復元率や剥離強度を所定範囲に調整することができるという観点から、２官能又は３官能アクリレートモノマー、例えば１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレート、トリメチロールプロパントリアクリレートなどが好ましい。
多官能モノマーの配合量は、ベースポリマー１００質量部に対して０．０１〜１０．０質量部、中でも０．０３〜５．０質量部とするのが好ましい。
As the polyfunctional monomer, a polyfunctional acrylate monomer, among them, a bifunctional or trifunctional acrylate monomer, for example, 1, 4 from the viewpoint that the crosslink density can be increased and the strain recovery rate and peel strength can be adjusted within a predetermined range. -Butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate and the like are preferable.
The compounding quantity of a polyfunctional monomer is 0.01-10.0 mass part with respect to 100 mass parts of base polymers, It is preferable to set it as 0.03-5.0 mass part especially.
光開始剤としては、光の照射を受けて架橋反応を促す光開始剤であればよく、高圧水銀ランプやメタルハライドランプの紫外線で反応する光開始剤であれば、光ラジカルタイプの光開始剤であっても、光カチオンタイプの光開始剤であってもよい。
中でも、４つ以上の官能基を有する開裂型光開始剤であるか、或いは水素引き抜き型光開始剤を用いるのが好ましい。その中でもベンゾフェノン誘導体、ヒドロキシ−シクロヘキシル−フェニルケトン或いはこれらの二種類以上の組合わせからなる混合成分は特に好ましい。
The photoinitiator may be any photoinitiator that promotes a crosslinking reaction upon receiving light irradiation, and a photoinitiator that reacts with ultraviolet light of a high-pressure mercury lamp or a metal halide lamp may be a photoradical type photoinitiator. It may be a photocation type photoinitiator.
Among them, it is preferable to use a cleavage type photoinitiator having four or more functional groups or a hydrogen abstraction type photoinitiator. Among them, a benzophenone derivative, hydroxy-cyclohexyl-phenyl ketone, or a mixed component composed of a combination of two or more of these is particularly preferable.
光開始剤の添加量は、適宜調整すればよいが、例えばベースポリマー１００質量部に対して０．０５〜３．０質量部、中でも０．１〜２．０質量部配合するのが好ましい。 Although the addition amount of a photoinitiator should just be adjusted suitably, it is preferable to mix | blend 0.05-3.0 mass parts with respect to 100 mass parts of base polymers, for example, and 0.1-2.0 mass parts especially.
＜加熱架橋可能な潜在型硬化剤＞
加熱架橋可能な潜在型硬化剤の主剤としては、加熱すると活性化してベースポリマー（例えばアクリル酸エステル共重合体）の有機官能基と反応し、粘着剤を硬化させるものであればよい。
中でも、紫外線を吸収する熱硬化型樹脂ではなく、紫外線を照射しても安定である点で、芳香環を有しない樹脂、中でも脂肪族系の樹脂、その中でも脂肪族イソシアネートを主剤とする多官能イソシアネート硬化剤が好ましい。
<Heat-crosslinkable latent curing agent>
The main component of the latent curing agent capable of being heat-crosslinked may be any one that is activated when heated and reacts with the organic functional group of the base polymer (for example, acrylic ester copolymer) to cure the adhesive.
Among them, it is not a thermosetting resin that absorbs ultraviolet rays, but is stable even when irradiated with ultraviolet rays, and is a polyfunctional resin that does not have an aromatic ring, especially an aliphatic resin, especially an aliphatic isocyanate. Isocyanate curing agents are preferred.
ところで、本実施形態のアクリル系粘着剤は、紫外線架橋可能な光架橋剤と加熱架橋可能な潜在型硬化剤の２種類の架橋剤を１液にしてベースポリマーに配合することができるが、この際、一方の架橋手段（硬化手段）を実行する際に他方の架橋手段による架橋剤（硬化剤）は安定であるのが好ましい。すなわち、紫外線架橋可能な光架橋剤は、加熱環境下で安定（固まった状態を確保可能）であり、他方の加熱架橋可能な潜在型硬化剤は、紫外線照射環境下で安定（固まった状態を確保可能）であるのが好ましい。
この点から、特に熱硬化性を潜在させた粘着体については、室温環境はもちろん、好ましくは紫外線照射した際に上昇する温度環境下においても安定であるように、加熱架橋可能な潜在型硬化剤は、メチルエチルケトン（ＭＥＫ）オキシムやフェノール等を反応させることにより、所定温度（例えば１００℃〜２００℃、好ましくは１５０℃〜２００℃）に到達するまで反応を開始しないようにした（これを本発明では「マスキング」と称する）潜在型硬化剤を用いるのが好ましい。これらは、所定温度に到達するとマスキングが外れて熱硬化反応を開始するように設計することができる。
なお、３級或いは４級アンモニウム塩を配合させることにより、マスキングを外れ易くすることができるから、反応開始温度をさらに調整することができる。
By the way, the acrylic pressure-sensitive adhesive of the present embodiment can be blended into the base polymer by combining two types of crosslinking agents, that is, a UV-crosslinkable photocrosslinking agent and a heat-crosslinkable latent curing agent. At this time, it is preferable that the crosslinking agent (curing agent) by the other crosslinking means is stable when one crosslinking means (curing means) is executed. That is, the UV-crosslinkable photocrosslinking agent is stable in a heating environment (can ensure a solidified state), and the other heat-crosslinkable latent curing agent is stable (in a solidified state in an ultraviolet irradiation environment). It is preferable that it can be secured).
From this point, the latent curing agent capable of being heat-crosslinked, particularly for a pressure-sensitive adhesive having a latent thermosetting property, is stable not only in a room temperature environment but also in a temperature environment that preferably rises when irradiated with ultraviolet rays. In the present invention, methyl ethyl ketone (MEK) oxime, phenol and the like are reacted so that the reaction is not started until a predetermined temperature (for example, 100 ° C. to 200 ° C., preferably 150 ° C. to 200 ° C.) is reached (this invention It is preferable to use a latent curing agent (hereinafter referred to as “masking”). They can be designed such that when a predetermined temperature is reached, the masking is removed and the thermosetting reaction is initiated.
In addition, since it can make it easy to remove | eliminate masking by mix | blending tertiary or quaternary ammonium salt, reaction start temperature can further be adjusted.
また、加熱架橋可能な潜在型硬化剤の主剤として、メラミン系樹脂を用いることも可能である。この場合には、反応開始温度が１５０℃以上であるから、上記の如くマスキングする必要がない。 Moreover, it is also possible to use a melamine resin as the main component of the latent curing agent capable of being heat-crosslinked. In this case, since the reaction start temperature is 150 ° C. or higher, it is not necessary to mask as described above.
（他の成分）
本実施形態に係るアクリル系粘着剤は、前記紫外線架橋性能及び加熱架橋性能を妨げない範囲であれば、必要に応じて、ベースポリマー、紫外線架橋可能な光架橋剤及び加熱架橋可能な潜在型硬化剤以外の成分（添加成分）を含んでもよい。
(Other ingredients)
If necessary, the acrylic pressure-sensitive adhesive according to the present embodiment is a base polymer, a photo-crosslinking agent capable of being UV-crosslinkable, and a latent-type curing capable of being heat-crosslinked as long as it does not interfere with the UV-crosslinking performance and the heat-crosslinking performance. Components (additive components) other than the agent may be included.
（用途）
上記本実施形態のアクリル系粘着剤は、例えば離型シート間に挟んで、テープ状、フィルム状またはシート状（これらをまとめて「フィルム状等」という。）に成形した後、紫外線を照射して架橋してフィルム状等の粘着体とすることができる。この場合、先に紫外線で架橋することにより、 “熱硬化性を潜在させた粘着体”とすることができ、この場合には、該粘着体を被着体に貼合した後に加熱して硬化させることにより、凝集力を高めて強力な接着力を得ることができる。つまり、“熱硬化性を潜在させた粘着体”は、紫外線を照射できない使用環境下であっても、加熱によって凝集力を高めて接着力を向上させることができる。
(Use)
The acrylic pressure-sensitive adhesive of the present embodiment is, for example, sandwiched between release sheets and formed into a tape shape, a film shape, or a sheet shape (collectively referred to as “film shape”), and then irradiated with ultraviolet rays. To form a pressure-sensitive adhesive such as a film. In this case, it is possible to obtain an “adhesive with latent thermosetting property” by crosslinking with ultraviolet rays in advance, and in this case, the adhesive is bonded to the adherend and then heated and cured. By doing so, it is possible to increase the cohesive force and obtain a strong adhesive force. In other words, the “adhesive with latent thermosetting property” can increase the cohesive force by heating and improve the adhesive force even in a use environment where ultraviolet rays cannot be irradiated.
他方、上記本実施形態のアクリル系粘着剤を、例えば離型シート間に挟んでフィルム状等に成形した後、熱を加えて架橋してフィルム状等の粘着体とすることができる。この場合、先に熱を加えて架橋することにより、 “紫外線硬化性を潜在させた粘着体”とすることができ、この場合には、該粘着体を被着体に貼合した後に紫外線を照射して硬化させることにより、凝集力を高めて強力な接着力を得ることができる。つまり、“紫外線硬化性を潜在させた粘着体”は、加熱できない使用環境下であっても、紫外線照射によって凝集力を高めて接着力を向上させることができる。 On the other hand, after the acrylic pressure-sensitive adhesive of the present embodiment is sandwiched between release sheets and formed into a film or the like, for example, it can be crosslinked by applying heat to form a film-like pressure-sensitive adhesive. In this case, it is possible to obtain an “adhesive with latent ultraviolet curable properties” by crosslinking by applying heat first. In this case, after the adhesive is bonded to the adherend, ultraviolet rays are applied. By irradiating and curing, the cohesive force can be increased and a strong adhesive force can be obtained. In other words, the “pressure-sensitive adhesive having latent ultraviolet curable properties” can improve the cohesive force by increasing the cohesive force by irradiation with ultraviolet rays even in a use environment where heating cannot be performed.
なお、粘着フィルム等の厚さは、特に限定するものではないが、２０μｍ〜２０００μｍ、特に５０μｍ〜１０００μｍであるのが好ましい。 The thickness of the adhesive film or the like is not particularly limited, but is preferably 20 μm to 2000 μm, particularly 50 μm to 1000 μm.
以下、実施例について説明するが、本発明はこれに限定されるものではない。 Hereinafter, although an example is described, the present invention is not limited to this.
（実施例１）
２−エチルヘキシルアクリレートモノマー、ｎ−ブチルアクリレートモノマー及びアクリル酸モノマーを４８．５：４８．５：３．０の質量割合で配合し、これらの総モノマー（前記モノマーの合計量）が３５質量％となるように酢酸エチルに仕込んだ後、ＡＩＢＮ(アゾビスイソブチロニトリル)重合触媒を溶解し、６０℃に加熱してランダム共重合させてアクリル酸エステル共重合体溶液を得、このアクリル酸エステル共重合体溶液をベースポリマーとして用いた。この共重合体溶液の２３℃での溶液粘度は５５０ｍＰａ・ｓであった。
Example 1
2-ethylhexyl acrylate monomer, n-butyl acrylate monomer and acrylic acid monomer were blended in a mass ratio of 48.5: 48.5: 3.0, and these total monomers (total amount of the monomers) were 35% by mass. After being charged into ethyl acetate, the AIBN (azobisisobutyronitrile) polymerization catalyst was dissolved and heated to 60 ° C. for random copolymerization to obtain an acrylate copolymer solution. This acrylate ester A copolymer solution was used as the base polymer. The solution viscosity at 23 ° C. of this copolymer solution was 550 mPa · s.
このアクリル酸エステル共重合体溶液１００質量部に、紫外線架橋可能な光架橋剤としてのベンゾフェノンを０．３５質量部、多官能モノマーとしてのトリメチロールプロパントリアクリレートを０．３５質量部、加熱架橋可能な潜在型硬化剤としてのマスクドイソシアネート（イソホロンジイソシアネート３量体のＭＥＫオキシムマスキング品）を１．０質量部配合し、攪拌してアクリル系粘着剤溶液を得た。 100 parts by mass of this acrylate copolymer solution can be thermally crosslinked by 0.35 parts by mass of benzophenone as a photocrosslinkable photocrosslinker and 0.35 parts by mass of trimethylolpropane triacrylate as a polyfunctional monomer. 1.0 parts by mass of masked isocyanate (MEK oxime masking product of isophorone diisocyanate trimer) as a latent curing agent was mixed and stirred to obtain an acrylic pressure-sensitive adhesive solution.
そして、厚さ３０μｍの２軸延伸ポリプロピレン（ＯＰＰ）フィルムの片面に、前記アクリル系粘着剤溶液をドライ厚さが１５μｍとなるように塗布して積層し、８０℃×３分間加熱して酢酸エチルを乾燥させ、その後ＯＰＰフィルムの背面から高圧水銀ランプで積算光量が１５００ｍＪ／ｃｍ2になるように紫外線を照射することにより、熱硬化性を潜在させた粘着テープを得た。 Then, the acrylic pressure-sensitive adhesive solution was applied and laminated on one side of a 30 μm thick biaxially oriented polypropylene (OPP) film so as to have a dry thickness of 15 μm, and heated at 80 ° C. for 3 minutes to obtain ethyl acetate. Was then dried, and ultraviolet rays were irradiated from the back of the OPP film with a high-pressure mercury lamp so that the integrated light quantity was 1500 mJ / cm 2 , thereby obtaining a pressure-sensitive adhesive tape having latent thermosetting properties.
（実施例２）
厚さ３０μｍの２軸延伸ポリプロピレン（ＯＰＰ）フィルムの片面に、実施例１と同様のアクリル系粘着溶液をドライ厚さが１５μｍとなるように塗布して積層し、１２０℃×３分間加熱して酢酸エチルを乾燥させると共にＭＥＫオキシムを同時に解離・揮発させ、その後４０℃を２日間保持するように熟成させて紫外線硬化性を潜在させた粘着テープを得た。
(Example 2)
On one side of a 30 μm thick biaxially oriented polypropylene (OPP) film, the same acrylic adhesive solution as in Example 1 was applied and laminated so that the dry thickness was 15 μm, and heated at 120 ° C. for 3 minutes. Ethyl acetate was dried and MEK oxime was simultaneously dissociated and volatilized, and then aged such that the temperature was kept at 40 ° C. for 2 days to obtain a pressure-sensitive adhesive tape having latent ultraviolet curability.
（比較例１）
実施例１で重合して得たアクリル酸エステル共重合体溶液１００質量部に、紫外線架橋可能な光架橋剤としてのベンゾフェノンを０．３５質量部、多官能モノマーとしてのトリメチロールプロパントリアクリレートを０．３５質量部配合し、攪拌してアクリル系粘着剤溶液を得た。
厚さ３０μｍのＯＰＰフィルムの片面に、前記アクリル系粘着剤溶液をドライ厚さが１５μｍになるように塗布して積層し、８０℃×３分間加熱して酢酸エチルを乾燥させた後、ＯＰＰフィルムの背面から高圧水銀ランプで積算光量が１５００ｍＪ／ｃｍ2になるように紫外線を照射して粘着テープを得た。
(Comparative Example 1)
To 100 parts by mass of the acrylate copolymer solution obtained by polymerization in Example 1, 0.35 part by mass of benzophenone as a photocrosslinking agent capable of UV crosslinking, 0 of trimethylolpropane triacrylate as a polyfunctional monomer .35 parts by mass was mixed and stirred to obtain an acrylic pressure-sensitive adhesive solution.
The acrylic pressure-sensitive adhesive solution was applied and laminated on one side of a 30 μm thick OPP film so that the dry thickness was 15 μm, and heated at 80 ° C. for 3 minutes to dry ethyl acetate, and then the OPP film A pressure-sensitive adhesive tape was obtained by irradiating ultraviolet rays with a high-pressure mercury lamp from the back surface of the substrate so that the accumulated light amount was 1500 mJ / cm 2 .
（比較例２）
実施例１で重合して得たアクリル酸エステル共重合体溶液１００質量部に、加熱架橋可能な潜在型硬化剤としてのマスクドイソシアネート（イソホロンジイソシアネート３量体のＭＥＫオキシムマスキング品）を１．０質量部配合し、攪拌してアクリル系粘着剤溶液を得た。
厚さ３０μｍのＯＰＰフィルムの片面に、前記アクリル系粘着剤溶液をドライ厚さが１５μｍになるように塗布して積層し、１２０℃×３分間加熱して酢酸エチルを乾燥させると共にＭＥＫオキシムを同時に解離・揮発させ、その後４０℃を２日間保持するように熟成させて粘着テープを得た。
(Comparative Example 2)
To 100 parts by mass of the acrylic ester copolymer solution obtained by polymerization in Example 1, 1.0 mass of masked isocyanate (MEK oxime masking product of isophorone diisocyanate trimer) as a latent curing agent capable of being heat-crosslinked. Partly mixed and stirred to obtain an acrylic pressure-sensitive adhesive solution.
The acrylic pressure-sensitive adhesive solution is applied and laminated on one side of a 30 μm-thick OPP film so that the dry thickness is 15 μm, and heated at 120 ° C. for 3 minutes to dry ethyl acetate and simultaneously with MEK oxime. Dissociation and volatilization were performed, followed by aging so as to maintain 40 ° C. for 2 days to obtain an adhesive tape.
＜試験＞
実施例１、２および比較例１、２で得た粘着テープをそれぞれ、巾５ｍｍ×長さ２３．６ｍｍに切断し、コンデンサー素子の代用として直径φ５ｍｍ×長さ５０ｍｍのアルミ棒に１．５周巻き付けて、室温で約６０分放置後、それぞれ次のように処理した。
<Test>
Each of the adhesive tapes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was cut into a width of 5 mm × a length of 23.6 mm, and 1.5 times on an aluminum rod having a diameter of φ5 mm × a length of 50 mm as a substitute for the capacitor element. The sample was wound and allowed to stand at room temperature for about 60 minutes, and then treated as follows.
実施例１：アルミ棒に巻いた状態で、電解液代用のガンマブチロラクトンに浸漬した。
実施例２：アルミ棒に巻いた状態で、高圧水銀ランプを用いて積算光量が１５００ｍＪ／ｃｍ2になるように紫外線照射後、電解液代用のガンマブチロラクトンに浸漬した。
比較例１：アルミ棒に巻いた状態で、電解液代用のガンマブチロラクトンに浸漬した。
比較例２：アルミ棒に巻いた状態で、電解液代用のガンマブチロラクトンに浸漬した。
Example 1: The sample was immersed in gamma-butyrolactone instead of an electrolyte while wound on an aluminum rod.
Example 2: In a state of being wound around an aluminum rod, after irradiating with ultraviolet rays so that the integrated light amount was 1500 mJ / cm 2 using a high-pressure mercury lamp, it was immersed in gamma-butyrolactone as a substitute for an electrolyte.
Comparative Example 1: The sample was immersed in gamma-butyrolactone as a substitute for an electrolyte while wound on an aluminum rod.
Comparative Example 2: The sample was immersed in gamma-butyrolactone as a substitute for an electrolyte while wound on an aluminum rod.
ガンマブチロラクトンにそれぞれ浸漬したまま、ガンマブチロラクトンを２時間かけて１２０℃まで昇温し１００時間放置した後、アルミ棒を取り出して粘着テープ末端の剥がれ具合を、次の基準で評価し、評価結果を下記表１に示した。
（○）：粘着テープの末端部の剥がれが８ｍｍ未満の状態。
（×）：粘着テープの末端部が８ｍｍ以上にわたり剥がれていた状態。
With each gamma-butyrolactone immersed in gamma-butyrolactone, the temperature of gamma-butyrolactone was raised to 120 ° C. over 2 hours and allowed to stand for 100 hours. The results are shown in Table 1 below.
(◯): State in which the peeling of the end portion of the adhesive tape is less than 8 mm.
(X): The state where the end portion of the adhesive tape was peeled over 8 mm or more.
以上の結果より、実施例１，２の粘着テープは試験後の端末剥がれが８ｍｍ未満であったのに対し、比較例１，２は端末剥がれが８ｍｍ以上に達しており、この結果より単一架橋方式の粘着テープに比べ、紫外線および加熱架橋方式を併用した粘着テープの方が高温の電解液中でも剥がれない高凝集力を備えていることが判明した。
From the above results, the adhesive tapes of Examples 1 and 2 had a terminal peeling after the test of less than 8 mm, whereas Comparative Examples 1 and 2 had a terminal peeling of 8 mm or more. It was found that the pressure-sensitive adhesive tape combined with the ultraviolet ray and the heat-crosslinking method has a higher cohesive force that does not peel off even in a high-temperature electrolyte solution, compared with the cross-linked pressure-sensitive adhesive tape.
Claims (7)
加熱架橋可能な潜在型硬化剤は、メチルエチルケトン（ＭＥＫ）オキシム或いはフェノールを反応させてマスキングされたものであることを特徴とする粘着剤。 A pressure-sensitive adhesive characterized in that a (meth) acrylic acid ester copolymer is used as a base polymer, and both a photo-crosslinking agent capable of UV crosslinking and a latent curing agent capable of heat crosslinking are blended with the base polymer. And
A pressure-sensitive adhesive, wherein the heat-crosslinkable latent curing agent is masked by reaction with methyl ethyl ketone (MEK) oxime or phenol.
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| JP5221040B2 (en) * | 2007-01-10 | 2013-06-26 | 三菱樹脂株式会社 | Near-infrared absorbing transparent adhesive sheet |
| KR101047922B1 (en) | 2007-02-07 | 2011-07-08 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for polarizing plate |
| JP5004633B2 (en) * | 2007-03-30 | 2012-08-22 | 三菱樹脂株式会社 | Active energy ray-curable adhesive composition |
| JP4991421B2 (en) * | 2007-07-13 | 2012-08-01 | リンテック株式会社 | Adhesive, adhesive sheet and optical film with adhesive |
| KR100983026B1 (en) * | 2008-12-18 | 2010-09-17 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, polarizer and liquid crystal display |
| KR101928727B1 (en) * | 2011-10-24 | 2018-12-13 | 오지 홀딩스 가부시키가이샤 | Pressure-sensitive adhesive sheet, method for using same, and laminate |
| JP6180161B2 (en) * | 2012-04-10 | 2017-08-16 | 日本合成化学工業株式会社 | Pressure-sensitive adhesive sheet, method for producing laminate with pressure-sensitive adhesive layer, and use thereof |
| JP5567619B2 (en) * | 2012-05-07 | 2014-08-06 | リンテック株式会社 | Adhesive, adhesive sheet and optical film with adhesive |
| JP6274206B2 (en) | 2013-04-24 | 2018-02-07 | 王子ホールディングス株式会社 | Adhesive sheet, laminate and method for producing the same |
| JP2013156666A (en) * | 2013-05-23 | 2013-08-15 | Sumitomo Chemical Co Ltd | Polarizing plate, method for manufacturing the same, and laminated optical member using the same |
| JP5858347B2 (en) * | 2014-02-05 | 2016-02-10 | 大日本印刷株式会社 | Adhesive composition and adhesive film using the same |
| DE102015217131A1 (en) * | 2015-09-08 | 2017-03-09 | Tesa Se | Adhesive resin-modified pressure-sensitive adhesive |
| KR20200012568A (en) * | 2018-07-27 | 2020-02-05 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Adhesive composition, adhesive film, laminate and preparation method thereof |
| JP6743855B2 (en) * | 2018-09-05 | 2020-08-19 | 王子ホールディングス株式会社 | Method for producing pressure-sensitive adhesive sheet for laminating optical member and laminate |
| JP6642752B2 (en) * | 2019-02-21 | 2020-02-12 | 大日本印刷株式会社 | sticker |
| WO2021193681A1 (en) * | 2020-03-27 | 2021-09-30 | 三井化学株式会社 | Pellicle, and production method therefor |
| TW202336198A (en) * | 2021-12-06 | 2023-09-16 | 日商日絆股份有限公司 | Adhesive composition, adhesive tape and capacitor element |
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| JPH04353582A (en) * | 1991-05-31 | 1992-12-08 | Nitto Denko Corp | Pressure-sensitive adhesive |
| JPH06108031A (en) * | 1992-09-28 | 1994-04-19 | Nippon Synthetic Chem Ind Co Ltd:The | Self-adhesive composition for polarizing plate |
| JP3506519B2 (en) * | 1995-03-06 | 2004-03-15 | リンテック株式会社 | Adhesive tape and method of using the same |
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