TWI623600B - Adhesive sheet, laminate and their production method - Google Patents

Adhesive sheet, laminate and their production method Download PDF

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TWI623600B
TWI623600B TW103114888A TW103114888A TWI623600B TW I623600 B TWI623600 B TW I623600B TW 103114888 A TW103114888 A TW 103114888A TW 103114888 A TW103114888 A TW 103114888A TW I623600 B TWI623600 B TW I623600B
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monomer
adhesive
adhesive sheet
acrylate
solvent
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TW201444932A (en
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鹽田隼介
緒方孝德
山本真之
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王子控股股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer

Abstract

本發明之黏著片材容易確保凹凸追隨性,並且可防止膜之變形、應變,且可以低成本製造,其含有包含藉由加熱使如下黏著組合物半硬化而成之黏著劑之黏著劑層(X),該黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 The adhesive sheet of the present invention is easy to ensure unevenness and follow-up, and can prevent deformation and strain of the film, and can be produced at low cost, and contains an adhesive layer containing an adhesive which is semi-hardened by heating the following adhesive composition ( X), the adhesive composition comprises: a base polymer (A) comprising a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; a body (B) having at least one polymerizable unsaturated group; a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; and a polymerization initiator (D) which is active The polymerization of the above monomer (B) is started by irradiation of an energy ray; and the solvent (E).

Description

黏著片材及積層體與其製造方法 Adhesive sheet and laminated body and manufacturing method thereof

本發明係關於一種適於使具有凹凸之一對光學構件彼此接著之黏著片材及積層體與其製造方法。 The present invention relates to an adhesive sheet and a laminate which are suitable for adhering one of the concavities and convexities to the optical members, and a method of manufacturing the same.

近年,於各種領域,逐漸廣泛使用液晶顯示器(LCD,liquid crystal display)等顯示裝置、或觸控面板等與顯示裝置組合而使用之輸入裝置。於該等顯示裝置或輸入裝置之製造等中,於貼合光學構件之用途中使用透明之雙面黏著片材,顯示裝置與輸入裝置之貼合亦使用透明之雙面黏著片材(例如,專利文獻1~3)。 In recent years, display devices such as liquid crystal displays (LCDs) or display devices that are used in combination with display devices have been widely used in various fields. In the manufacture of such display devices or input devices, a transparent double-sided adhesive sheet is used for the purpose of bonding optical members, and a transparent double-sided adhesive sheet is also used for bonding the display device to the input device (for example, Patent Documents 1 to 3).

上述觸控面板或液晶顯示器等中存在包含具有由印刷等引起之階差(凹凸)之構成構件者。例如,行動電話中使用包含實施有框狀之印刷部分之構件的觸控面板。於該用途中,對黏著片材同時要求將構件貼合固定之性能及填埋印刷階差之性能、即優異之凹凸追隨性(階差吸收性)(例如,專利文獻4)。 The touch panel, the liquid crystal display, or the like includes a component including a step (concavity and convexity) caused by printing or the like. For example, a touch panel including a member that implements a frame-shaped printed portion is used in a mobile phone. In this application, the adhesive sheet is required to have a property of bonding and fixing the member and a performance of the landfill printing step, that is, excellent unevenness followability (step difference absorbability) (for example, Patent Document 4).

於專利文獻4中揭示有吸收印刷階差之組合物,其係將同為玻璃基板之液晶面板與覆蓋面板貼合之黏著劑組合物。此外,於觸控面板或液晶顯示器之構成構件中,除如玻璃之板狀基板以外,亦包含膜型者,膜與玻璃基板之貼合亦使用雙面黏著片材。印刷階差存在設置於膜上之情形,亦存在設置於板狀基板上之情形。例如,多使用用以賦 予設計性或裝飾性之具有印刷階差(凹凸)之加飾膜。加飾膜與如塗裝之方法相比,步驟較少,生產性較高,另一方面,由於近年裝飾之多樣化而實施有多層之油墨印刷或鏡面印刷等加飾印刷,僅印刷層之厚度即達數十μm。若以凹凸追隨性較高之雙面黏著片材將此種加飾膜與板狀基板貼合,則存在如下問題:為了追隨凹凸,黏著劑層較柔軟,無法將加飾膜保持為平坦之狀態,加飾膜產生變形、應變。即,凹凸追隨性與加飾膜之變形/應變防止存在取捨之關係,難以同時實現。 Patent Document 4 discloses a composition for absorbing a printing step which is an adhesive composition in which a liquid crystal panel which is a glass substrate is bonded to a cover panel. Further, in the constituent members of the touch panel or the liquid crystal display, in addition to the plate-shaped substrate such as glass, the film type is also included, and the double-sided adhesive sheet is also used for bonding the film to the glass substrate. There is a case where the printing step is disposed on the film, and there is also a case where it is disposed on the plate substrate. For example, use more to assign A decorative film with a print step (concavity and convexity) designed or decorative. Compared with the method of coating, the decorative film has fewer steps and higher productivity. On the other hand, due to the diversification of decoration in recent years, multi-layer printing such as ink printing or mirror printing is performed, and only the printed layer is printed. The thickness is several tens of μm. When such a decorative film is bonded to a plate-shaped substrate by a double-sided adhesive sheet having a high degree of followability, there is a problem that the adhesive layer is soft to follow the unevenness, and the decorative film cannot be kept flat. In the state, the decorative film is deformed and strained. That is, the relationship between the unevenness followability and the deformation/strain prevention of the decorative film is trade-off, and it is difficult to achieve at the same time.

為了解決該等情況,例如有預先以透明樹脂填埋階差部分而使其變得平坦後以雙面黏著片材貼合之方法,但製造步驟增加,成本變高,且存在隨著時間推移而產生透明樹脂之黃變、霧值上升等問題。 In order to solve such a problem, for example, there is a method in which a stepped portion is filled with a transparent resin in advance, and the sheet is bonded to the double-sided sheet, but the manufacturing steps are increased, the cost becomes high, and there is a change with time. However, problems such as yellowing of the transparent resin and an increase in the fog value occur.

又,作為用於此種用途之雙面黏著片材,通常為無基材之無載體型。通常,此種無載體雙面黏著片材係藉由於重剝離隔片(separator)上形成黏著劑層後貼合輕剝離隔片而製造。 Further, as a double-sided adhesive sheet for such use, it is usually a carrierless type without a substrate. Typically, such unsupported double-sided adhesive sheets are manufactured by laminating a light release liner after forming an adhesive layer on a heavy release separator.

先前,上述黏著劑層之形成係使用含有基礎聚合物之活性能量線硬化性或熱硬化性之黏著劑組合物。作為基礎聚合物,就透明性等優異之方面而言,使用含有(甲基)丙烯酸烷基酯、(甲基)丙烯酸胺基甲酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯等丙烯酸系單體單元之丙烯酸系之基礎聚合物。 Previously, the above adhesive layer was formed by using an active energy ray-curable or thermosetting adhesive composition containing a base polymer. As the base polymer, an alkyl (meth)acrylate, a (meth)acrylic acid amide, an epoxy (meth) acrylate, a polyester (A) is used in terms of excellent transparency and the like. An acrylic base polymer of an acrylic monomer unit such as an acrylate or a polyether (meth) acrylate.

作為活性能量線硬化性之黏著劑組合物,通常為無溶劑型。然而,由於將不含溶劑且表面張力較大之黏著劑組合物塗佈於表面張力較小之剝離膜上,故而容易產生厚壁端部(亦稱為成框(framing)、厚邊(fat edge))等製造上之問題。 As the active energy ray-curable adhesive composition, it is usually a solventless type. However, since an adhesive composition containing no solvent and having a large surface tension is applied to a release film having a small surface tension, thick end portions (also referred to as framing, thick edges (fat) are easily generated. Edge)) and other manufacturing issues.

作為熱硬化性之黏著劑組合物,通常使用含有稀釋基礎聚合物之溶劑者。熱硬化性之黏著劑組合物通常具有藉由熱交聯而提高凝聚力,且保持力或耐熱性提昇之優點。然而,存在容易產生乾燥步驟中 之隆起(亦稱為溶劑泡(solvent popping))等塗佈缺陷之問題。於用於顯示器等中時,塗佈缺陷成為圖像變形之原因,故而欠佳。 As the thermosetting adhesive composition, a solvent containing a diluted base polymer is usually used. The thermosetting adhesive composition generally has an advantage of improving cohesive force by thermal crosslinking and improving retention or heat resistance. However, there are easy to produce drying steps The problem of coating defects such as bulging (also known as solvent popping). When used in a display or the like, coating defects are a cause of image distortion, which is not preferable.

黏著劑層越厚膜化越容易產生此種厚壁端部或隆起等製造上之問題,難以於不產生如上所述之製造上之問題的情況下製造例如150μm以上之厚膜之黏著劑層。 The thicker the adhesive layer is, the more likely it is to cause manufacturing problems such as thick end portions or bumps, and it is difficult to produce an adhesive layer of, for example, a thick film of 150 μm or more without causing the above-mentioned manufacturing problems. .

因此,業界要求塗佈適應性優異、可製造表面平滑之黏著劑層、且亦可實現厚膜化之丙烯酸系之黏著劑組合物,尤其是即便含有溶劑亦可形成厚壁端部或隆起等塗佈缺陷較少之黏著劑層的丙烯酸系之黏著劑組合物。 Therefore, the industry requires an adhesive composition which is excellent in coating suitability, can produce a smooth surface layer, and can also be thickened, and can form a thick-walled end or a bulge even if a solvent is contained. An acrylic adhesive composition that coats an adhesive layer having less defects.

於專利文獻5中,揭示有如下光聚合性黏著劑組合物、及對其進行光照射而得之厚度0.1~5mm之黏著片材,該光聚合性黏著劑組合物作為即便為了提高緩衝性而加厚黏著劑層,亦可不損壞、污染被黏著體而容易地再剝離,且即便於高溫高濕條件下亦不產生白濁者,係於由特定之結構式所表示之單體、丙烯酸烷基酯及含羧基之單體而得之含有聚合物與單體之丙烯酸系漿液中分別以特定之比率調配具有2個以上聚合性不飽和基之單體、交聯劑、及光聚合起始劑而成。 Patent Document 5 discloses a photopolymerizable adhesive composition and an adhesive sheet having a thickness of 0.1 to 5 mm obtained by light irradiation, and the photopolymerizable adhesive composition is used for improving cushioning properties. The adhesive layer is thickened, and it can be easily peeled off without damaging or contaminating the adherend, and even if it is not turbid under high temperature and high humidity conditions, it is a monomer represented by a specific structural formula, and an alkyl acrylate. a monomer, a crosslinking agent, and a photopolymerization initiator having two or more polymerizable unsaturated groups in a specific ratio in an acrylic slurry containing a polymer and a monomer containing a carboxyl group and a carboxyl group-containing monomer Made.

然而,於專利文獻5中,有如下記載:雖亦可含有有機溶劑等溶劑,但若考慮製作厚膜片材之作業性或對環境之影響,則較佳為不含溶劑之無溶劑型者,並無考慮塗佈缺陷等製造上之問題之溶劑之規定。又,於製造例中,揭示有利用剝離膜夾著液狀之黏著劑組合物,密閉成夾層狀後進行硬化之方法(濕式層壓),於該情形時,由於溶劑之添加會導致後續步驟中之故障,故而為禁忌。 However, Patent Document 5 discloses that a solvent such as an organic solvent may be contained. However, in consideration of the workability of producing a thick film sheet or the influence on the environment, it is preferably a solvent-free type containing no solvent. There is no provision for solvents that deal with manufacturing problems such as coating defects. Further, in the production example, a method in which a liquid adhesive composition is sandwiched between a release film and sealed in a sandwich shape and then cured (wet lamination) is disclosed. In this case, the addition of a solvent causes subsequent The fault in the step is therefore taboo.

於專利文獻6中,作為厚度為100μm以上之紫外線硬化型黏著劑層之製造方法,揭示有依序進行於基材上塗佈紫外線硬化型黏著劑組合物之步驟、加熱之步驟、照射紫外線之步驟之方法。於該方法中,記載有藉由於照射紫外線之前進行加熱,而使塗佈膜之厚度均勻化, 改善由氣泡引起之凹陷。 Patent Document 6 discloses a method for producing an ultraviolet curable adhesive layer having a thickness of 100 μm or more, a step of sequentially applying an ultraviolet curable adhesive composition to a substrate, a step of heating, and irradiation with ultraviolet rays. The method of the steps. In this method, it is described that the thickness of the coating film is made uniform by heating before irradiation with ultraviolet rays. Improve the depression caused by air bubbles.

然而,該方法之特徵在於將聚合性單體用作稀釋劑,實質上不含有機溶劑,從而無法應用於含有溶劑之黏著劑。又,實際上僅評價了胺基甲酸酯系之黏著劑。 However, this method is characterized in that a polymerizable monomer is used as a diluent and is substantially free of an organic solvent, so that it cannot be applied to a solvent-containing adhesive. Further, only the urethane-based adhesive was actually evaluated.

此外,作為用於如上所述之用途之雙面黏著片材,提出有包含以下黏著劑層者,該黏著劑層係將具備熱硬化性及活性能量線硬化性兩者之黏著劑組合物(以下有時稱為「雙硬化型黏著劑組合物」)塗佈於基材上並進行熱硬化或活性能量線硬化而成。此種黏著劑層於為熱硬化物之情形時具有活性能量線硬化性,於為活性能量線硬化物之情形時具有熱硬化性。因此,認為其係兼具初始黏著力與保持力者,於與被黏著體接合時具有黏著性而可暫時接著,其後,藉由進而利用活性能量線或加熱使之硬化,可牢固地接著於被黏著體上。 Further, as a double-sided adhesive sheet for use as described above, there has been proposed an adhesive composition comprising an adhesive composition having both thermosetting properties and active energy ray curability ( Hereinafter, the "double-curing adhesive composition" may be applied to a substrate and subjected to thermal curing or active energy ray hardening. Such an adhesive layer has active energy ray hardenability in the case of a thermosetting material and thermosetting property in the case of an active energy ray hardened material. Therefore, it is considered that the system has both initial adhesion and retention, and can be temporarily adhered when it is bonded to the adherend, and then can be firmly cured by further using an active energy ray or heating. On the body.

先前,作為此種黏著片材所使用之雙硬化型黏著劑組合物,提出有於基礎聚合物中調配作為賦予熱硬化性之成分之交聯劑、作為賦予活性能量線硬化之成分之單體及光起始劑而成者。 Conventionally, as a bis-curing adhesive composition for use in such an adhesive sheet, a crosslinking agent which is a component which imparts thermosetting property in a base polymer, and a monomer which is a component which imparts an active energy ray hardening property has been proposed. And the light starter is the original.

例如,於專利文獻7中,揭示有如下所述之黏著劑及黏著體,其藉由將可進行紫外線交聯之光交聯劑與可進行加熱交聯之潛在型硬化劑兩者調配於基礎聚合物中而製成兼具紫外線交聯與加熱交聯兩種交聯方式之黏著劑,先利用任一交聯方式進行交聯而貼附被黏著體後,利用剩餘之交聯方式進行後交聯,可使用含有多官能單體與光起始劑者作為光交聯劑。 For example, Patent Document 7 discloses an adhesive and an adherend which are prepared by blending a photocrosslinking agent capable of ultraviolet crosslinking with a latent hardener which can be thermally crosslinked. In the polymer, an adhesive having both cross-linking modes of ultraviolet crosslinking and heating cross-linking is prepared, and the cross-linking method is used to cross-link and adhere the adherend, and the remaining cross-linking method is used. For crosslinking, a person having a polyfunctional monomer and a photoinitiator can be used as a photocrosslinking agent.

於專利文獻8中,揭示有含有具有順丁烯二醯亞胺基之聚合物之活性能量線硬化型黏接著劑組合物,記載有該組合物可進而含有有機溶劑、分子中具有1個以上乙烯性不飽和基之化合物、光聚合起始劑、熱硬化型交聯劑等。 Patent Document 8 discloses an active energy ray-curable adhesive composition containing a polymer having a maleimide group, and the composition may further contain an organic solvent and have one or more molecules. A compound of an ethylenically unsaturated group, a photopolymerization initiator, a thermosetting crosslinking agent, and the like.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2003-238915號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-238915

[專利文獻2]日本專利特開2003-342542號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-342542

[專利文獻3]日本專利特開2004-231723號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-231723

[專利文獻4]日本專利特開2010-90204號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-90204

[專利文獻5]日本專利特開2007-161908號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-161908

[專利文獻6]日本專利特開2010-085578號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-085578

[專利文獻7]日本專利特開2006-335840號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2006-335840

[專利文獻8]日本專利特開2010-261029號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2010-261029

然而,藉由本發明者等人之研究可知,於使用如上所述之雙硬化型黏著劑組合物之黏著片材中,無法充分獲得其凹凸追隨性。又,於含有溶劑之情形時,與上述熱硬化性黏著劑組合物同樣地,於進行塗佈、熱硬化時容易產生厚壁端部或隆起等塗佈缺陷,存在膜產生變形、應變之情形。 However, as a result of investigation by the inventors of the present invention, it has been found that in the adhesive sheet using the double-curing type adhesive composition as described above, the unevenness followability cannot be sufficiently obtained. In the case of containing a solvent, in the same manner as the above-mentioned thermosetting adhesive composition, coating defects such as thick end portions or bulges are likely to occur during coating and thermal curing, and the film may be deformed or strained. .

因此,本發明之目的在於提供一種容易確保凹凸追隨性,並且可防止膜之變形、應變,而且成本較低之黏著片材及其使用方法以及積層體。 Accordingly, an object of the present invention is to provide an adhesive sheet which is easy to secure unevenness and which can prevent deformation and strain of a film, and which is low in cost, a method for using the same, and a laminated body.

即,本發明包括以下態樣。 That is, the present invention includes the following aspects.

[1]一種黏著片材,其含有包含藉由加熱使如下所述之黏著組合物半硬化而成之黏著劑之黏著劑層(X),上述黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始 劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 [1] An adhesive sheet comprising an adhesive layer (X) comprising an adhesive obtained by semi-hardening an adhesive composition as described below by heating, the adhesive composition comprising: a base polymer (A), a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; and a monomer (B) having at least one polymerizable unsaturated group; a crosslinking agent (C) which reacts with the above base polymer (A) by heat; polymerization initiation The agent (D), which starts the polymerization reaction of the above monomer (B) by irradiation with an active energy ray; and the solvent (E).

[2]如上述[1]之黏著片材,其中上述單體(B)具有鏈長原子數為10以上之烷基。 [2] The adhesive sheet according to the above [1], wherein the monomer (B) has an alkyl group having a chain length of 10 or more.

[3]如上述[2]之黏著片材,其中上述烷基之鏈長原子數為15~22。 [3] The adhesive sheet according to [2] above, wherein the alkyl group has a chain length of from 15 to 22.

[4]一種黏著片材,其含有包含加熱如下所述之黏著組合物而成之黏著劑之黏著劑層(X),上述黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基與鏈長原子數為15~22之烷基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 [4] An adhesive sheet comprising an adhesive layer (X) comprising an adhesive which heats an adhesive composition as described below, the adhesive composition comprising: a base polymer (A) containing non-crosslinking a (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; and a monomer (B) having at least one polymerizable unsaturated group and a chain length atomic number a 15 to 22 alkyl group; a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; and a polymerization initiator (D) which is irradiated with an active energy ray to cause the monomer The polymerization reaction of (B) is started; and the solvent (E).

[5]如上述[1]至[4]中任一項之黏著片材,其中上述單體(B)為丙烯酸異硬脂酯。 [5] The adhesive sheet according to any one of the above [1] to [4] wherein the above monomer (B) is isostearyl acrylate.

[6]如上述[1]至[5]中任一項之黏著片材,其中上述單體(B)於25℃下之蒸氣壓為300Pa以下, 上述溶劑(E)於25℃下之表面張力為20mN/m以上且未達40mN/m。 [6] The adhesive sheet according to any one of [1] to [5] wherein the monomer (B) has a vapor pressure of 300 Pa or less at 25 ° C, The solvent (E) has a surface tension at 25 ° C of 20 mN/m or more and less than 40 mN/m.

[7]如上述[1]至[6]中任一項之黏著片材,其中上述單體(B)含有熔點為25℃以下之具有1個聚合性不飽和基之單官能單體(B1)及具有2個以上聚合性不飽和基之多官能單體(B2)中之至少一者。 [7] The adhesive sheet according to any one of [1] to [6] wherein the monomer (B) contains a monofunctional monomer having a melting point of 25 ° C or less and having one polymerizable unsaturated group (B1) And at least one of the polyfunctional monomer (B2) having two or more polymerizable unsaturated groups.

[8]如上述[1]至[7]中任一項之黏著片材,其中上述單體(B)具有多環結構。 [8] The adhesive sheet according to any one of the above [1] to [7] wherein the above monomer (B) has a polycyclic structure.

[9]如上述[8]之黏著片材,其中上述單體(B)係具有雙環或三環之丙烯酸酯。 [9] The adhesive sheet according to [8] above, wherein the monomer (B) has a bicyclic or tricyclic acrylate.

[10]如上述[1]至[9]中任一項之黏著片材,其中上述溶劑(E)不具有聚合性不飽和基,且於25℃下之蒸氣壓大於上述單體(B)。 [10] The adhesive sheet according to any one of [1] to [9] wherein the solvent (E) does not have a polymerizable unsaturated group, and the vapor pressure at 25 ° C is greater than the above monomer (B) .

[11]如上述[1]至[10]中任一項之黏著片材,其中上述溶劑(E)包含與上述單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內之溶劑。 [11] The adhesive sheet according to any one of the above [1] to [10] wherein the solvent (E) contains a difference of 2 [(cal/cm 3 ) from the solubility parameter of the above monomer (B). Solvents within 1/2 ].

[12]如上述[1]至[11]中任一項之黏著片材,其於藉由壓接於SUS板上並照射活性能量線而硬化後依據JIS Z0237測得之保持力為360分鐘以上。 [12] The adhesive sheet according to any one of the above [1] to [11], which is cured by crimping on a SUS plate and irradiated with an active energy ray, and has a holding force of 360 minutes measured in accordance with JIS Z0237. the above.

[13]如上述[1]至[12]中任一項之黏著片材,其係雙面黏著片材。 [13] The adhesive sheet according to any one of [1] to [12] above which is a double-sided adhesive sheet.

[14]一種積層體之製造方法,其包括使如上述[1]至[13]中任一項之黏著片材之黏著劑層(X)與被黏著體表面接觸,並於該狀態下照射活性能量線使上述黏著劑層(X)完全硬化。 [14] A method of producing a laminate comprising contacting the adhesive layer (X) of the adhesive sheet according to any one of the above [1] to [13] with the surface of the adherend, and irradiating in this state. The active energy ray completely hardens the above-mentioned adhesive layer (X).

[15]一種積層體,其係經由如上述[1]至[13]中任一項之黏著片材而貼合一對光學構件,並於該狀態下照射活性能量線使上述黏著劑層(X)完全硬化而成。 [15] A laminated body which is bonded to a pair of optical members via an adhesive sheet according to any one of the above [1] to [13], and irradiated with an active energy ray in this state to cause the above-mentioned adhesive layer ( X) Completely hardened.

本發明提供一種於貼合一對光學構件時容易確保對印刷階差(凹凸)之凹凸追隨性,並且可防止膜之變形、應變,而且成本較低之黏著片材及其使用方法以及積層體。 The present invention provides an adhesive sheet which is easy to ensure the unevenness of the printing step (concavity and convexity) when the pair of optical members are bonded, and which can prevent deformation and strain of the film, and which is low in cost, and a method of using the same and a laminated body .

1‧‧‧黏著片材(附剝離片材) 1‧‧‧Adhesive sheet (with release sheet)

2‧‧‧觸控面板模組 2‧‧‧Touch panel module

11、21‧‧‧黏著劑層 11, 21‧‧‧ adhesive layer

12a、12b‧‧‧剝離片材 12a, 12b‧‧‧ peeling sheet

22‧‧‧加飾膜 22‧‧‧Adding film

22a‧‧‧加飾膜之與黏著劑層之接著面 22a‧‧‧ Adhesive film and adhesive layer

23a、23b、23c、23d‧‧‧印刷階差(凹凸) 23a, 23b, 23c, 23d‧‧‧Printing step (bump)

24‧‧‧板狀基板(ITO玻璃基板) 24‧‧‧ Plate substrate (ITO glass substrate)

24a‧‧‧板狀基板(ITO玻璃基板)之與黏著劑層之接著面 24a‧‧‧ the surface of the plate substrate (ITO glass substrate) and the adhesive layer

圖1係本發明之黏著片材。 Figure 1 is an adhesive sheet of the present invention.

圖2係表示作為本發明之實施形態之觸控面板模組之一部分的剖面圖。 Fig. 2 is a cross-sectional view showing a part of a touch panel module as an embodiment of the present invention.

以下,對本發明進行詳細說明。以下所記載之構成要件之說明存在基於代表性之實施形態或具體例而完成之情況,本發明並不限定於此種實施形態。再者,本說明書中使用「~」所表示之數值範圍意 指包含「~」前後所記載之數值作為下限值及上限值之範圍。 Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on representative embodiments or specific examples, and the present invention is not limited to such an embodiment. Furthermore, the numerical range expressed by "~" is used in this specification. The range including the numerical values described before and after "~" is the lower limit and upper limit.

對本發明之黏著片材之實施形態進行說明。 An embodiment of the adhesive sheet of the present invention will be described.

本發明之黏著片材含有包含藉由加熱使如下所述之黏著組合物半硬化而成之黏著劑之黏著劑層(X),上述黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 The adhesive sheet of the present invention contains an adhesive layer (X) comprising an adhesive which is obtained by heat-hardening an adhesive composition as described below, and the adhesive composition contains a base polymer (A) which contains a non- a crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; a monomer (B) having at least one polymerizable unsaturated group; a crosslinking agent (C), which is reacted with the above base polymer (A) by heat; a polymerization initiator (D) which starts the polymerization of the above monomer (B) by irradiation with an active energy ray; and a solvent (E).

圖1係本發明之黏著片材(附剝離片材)。 Figure 1 is an adhesive sheet (with a release sheet) of the present invention.

圖2係藉由本發明之黏著片材而貼合有光學構件之觸控面板模組之構成之一部分。本實施形態之黏著片材1作為雙面黏著片材而發揮功能。黏著片材1係於將加飾膜22與ITO(Indium Tin Oxides,氧化銦錫)玻璃基板24接著時所使用者,於加飾膜22之與黏著劑層之接著面22a上設置有印刷階差(23a、23b)。 2 is a part of a configuration of a touch panel module in which an optical member is bonded by an adhesive sheet of the present invention. The adhesive sheet 1 of the present embodiment functions as a double-sided adhesive sheet. The adhesive sheet 1 is attached to the ITO (Indium Tin Oxide) glass substrate 24, and the printing step is provided on the bonding surface 22a of the decorative film 22 and the adhesive layer. Poor (23a, 23b).

或者亦存在於ITO玻璃基板24之與黏著劑層之接著面24a上設置有印刷階差(23c、23d)之情形。印刷階差23之厚度通常為5~60μm。 Alternatively, the printing step (23c, 23d) may be provided on the contiguous surface 24a of the ITO glass substrate 24 and the adhesive layer. The thickness of the printing step 23 is usually 5 to 60 μm.

(黏著劑層) (adhesive layer)

本發明之黏著片材1之黏著劑層11係包含藉由加熱使如下所述之黏著組合物半硬化而成之黏著劑者,且呈柔軟之半硬化狀態,上述黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。本發明中之所謂半硬化,係指凝膠分率未達20%,凝膠分率較佳為未達15%,進而較佳為未達10%。並 且於將加飾膜22與ITO玻璃基板24貼合後,藉由照射活性能量線而使黏著劑層完全硬化。 The adhesive layer 11 of the adhesive sheet 1 of the present invention comprises an adhesive which is obtained by semi-hardening an adhesive composition as described below by heating, and is in a soft semi-hardened state, and the adhesive composition contains: a base polymerization (A) comprising a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; and a monomer (B) having at least one polymerization a non-saturated group; a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; and a polymerization initiator (D) which is irradiated with an active energy ray to cause the above monomer (B) The polymerization begins; and the solvent (E). The term "semi-hardening" as used in the present invention means that the gel fraction is less than 20%, and the gel fraction is preferably less than 15%, and more preferably less than 10%. and After the decorative film 22 is bonded to the ITO glass substrate 24, the adhesive layer is completely cured by irradiation of the active energy ray.

即本發明之黏著片材1之特徵在於:其係具有貼合前僅藉由熱而半硬化之黏著劑層11、於貼合後藉由活性能量線而使黏著劑層11完全硬化之二階段硬化之雙面黏著片材。 That is, the adhesive sheet 1 of the present invention is characterized in that it has an adhesive layer 11 which is only semi-hardened by heat before bonding, and the adhesive layer 11 is completely hardened by an active energy ray after bonding. Stage hardened double-sided adhesive sheet.

以下,本說明書中之所謂「半硬化」,係指起初僅藉由熱使黏著劑層硬化,所謂「半硬化狀態」,係指於熱硬化後且照射活性能量線前之柔軟之黏著劑層中,硬化後動態黏彈性成為1.5倍以上之狀態。該動態黏彈性較佳為1.5~1000倍,更佳為2~100倍。於本發明中之半硬化狀態下,上述黏著材層之動態黏彈性較佳為1.0×106Pa以下,進而較佳為8.0×105Pa以下,尤佳為5.0×105Pa以下。所謂「完全硬化」,係指於藉由熱而半硬化後,藉由活性能量線而使黏著劑層硬化。 Hereinafter, the term "semi-hardening" as used in the present specification means that the adhesive layer is initially cured only by heat, and the term "semi-hardened state" refers to a soft adhesive layer after thermal curing and before irradiation of the active energy ray. In the middle, the dynamic viscoelasticity after hardening is 1.5 times or more. The dynamic viscoelasticity is preferably from 1.5 to 1000 times, more preferably from 2 to 100 times. In the semi-hardened state of the present invention, the dynamic viscoelasticity of the adhesive layer is preferably 1.0 × 10 6 Pa or less, more preferably 8.0 × 10 5 Pa or less, still more preferably 5.0 × 10 5 Pa or less. The term "completely hardened" means that the adhesive layer is hardened by an active energy ray after being semi-hardened by heat.

作為形成黏著劑層11之基礎聚合物,較佳為具有不降低顯示裝置之視認性之程度之透明性者。於上述基礎聚合物中含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2)。 As the base polymer forming the adhesive layer 11, it is preferred to have transparency to the extent that the visibility of the display device is not lowered. The base polymer contains a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group.

形成黏著劑層11之黏著劑組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 The adhesive composition forming the adhesive layer 11 contains: a base polymer (A) containing a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit having a crosslinkable functional group (a2) a monomer (B) having at least one polymerizable unsaturated group; a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; a polymerization initiator (D), The polymerization of the above monomer (B) is started by irradiation with an active energy ray; and the solvent (E).

<黏著劑組合物> <Adhesive Composition>

上述黏著劑組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照 射而使上述單體(B)之聚合反應開始;及溶劑(E)。 The above adhesive composition contains: a base polymer (A) containing a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; B) having at least one polymerizable unsaturated group; a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; and a polymerization initiator (D) which is supported by an active energy ray Photo The polymerization of the above monomer (B) is started by spraying; and the solvent (E).

又,上述黏著劑組合物含有於25℃下之蒸氣壓為300Pa以下之單體(B),並且可將溶劑(E)於25℃下之表面張力設為20mN/m以上且未達40mN/m。藉此,塗佈適應性提高,於進行塗佈、熱硬化時,可形成表面平滑之黏著劑層。 Further, the above-mentioned adhesive composition contains the monomer (B) having a vapor pressure of 300 Pa or less at 25 ° C, and the surface tension of the solvent (E) at 25 ° C is 20 mN/m or more and less than 40 mN / m. Thereby, the coating suitability is improved, and when the coating or heat curing is performed, an adhesive layer having a smooth surface can be formed.

認為其理由如下。首先,藉由含有溶劑(E),而於塗佈時不易產生厚壁端部之問題。又,藉由含有與溶劑(E)同樣地作為使塗材低黏度化之液狀介質而發揮功能之單體(B),可將容易導致隆起之溶劑(E)之濃度抑制為較低。又,於進行加熱時溶劑(E)選擇性地蒸發,但藉由含有不易揮發之單體(B),可抑制塗膜之表面張力之急遽增加,進而,藉由溶劑(E)之選擇性蒸發,隨著黏著劑層之濃度上升而黏度上升,可抑制黏著劑層內之物質之流動。認為藉由該等協同作用,可抑制厚壁端部或隆起等製造上之問題,可形成表面平滑之黏著劑層。 The reason is considered as follows. First, by containing the solvent (E), it is difficult to produce a thick-walled end portion at the time of coating. In addition, the monomer (B) which functions as a liquid medium which makes the coating material low-viscosity similarly to the solvent (E) can suppress the concentration of the solvent (E) which is likely to cause swelling to be low. Further, the solvent (E) is selectively evaporated during heating, but by containing the monomer (B) which is not volatile, it is possible to suppress an increase in the surface tension of the coating film, and further, the selectivity by the solvent (E) Evaporation increases the viscosity of the adhesive layer as the concentration of the adhesive layer increases, thereby suppressing the flow of the substance in the adhesive layer. It is considered that by such synergistic action, manufacturing problems such as thick end portions or bulges can be suppressed, and an adhesive layer having a smooth surface can be formed.

進而,於滿足下述條件(1)、(2)之至少1者、較佳為全部滿足之情形時,上述效果尤其優異。 Further, the above effects are particularly excellent when at least one of the following conditions (1) and (2) is satisfied, and it is preferable that all of them satisfy the above conditions.

(1)單體(B)之熔點為25℃以下。 (1) The melting point of the monomer (B) is 25 ° C or lower.

(2)溶劑(E)不具有聚合性不飽和基,且於25℃下之蒸氣壓大於單體(B)。 (2) The solvent (E) does not have a polymerizable unsaturated group, and the vapor pressure at 25 ° C is higher than that of the monomer (B).

再者,於上述專利文獻7~8中並未特別考慮此種單體之蒸氣壓或熔點、溶劑之蒸氣壓或表面張力。 Further, in the above Patent Documents 7 to 8, the vapor pressure or melting point of the monomer, the vapor pressure of the solvent, or the surface tension are not particularly considered.

於上述黏著劑組合物中,溶劑(E)較佳為設為溶劑(E)與單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內者。藉此,塗佈適應性提高,於進行塗佈、熱硬化時,可形成表面平滑之黏著劑層。 In the above adhesive composition, the solvent (E) is preferably such that the difference between the solubility parameters of the solvent (E) and the monomer (B) is 2 [(cal/cm 3 ) 1/2 ]. Thereby, the coating suitability is improved, and when the coating or heat curing is performed, an adhesive layer having a smooth surface can be formed.

認為其理由如下。首先,藉由含有溶劑(E),於塗佈時不易產生厚壁端部之塗佈缺陷之問題。又,藉由溶劑(E)含有與單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內之溶劑,而於進行熱硬化時,可抑制 由過大之氣液平衡之失衡導致之溶劑(E)之急遽蒸發,故而不易產生橘皮(Orange Peel)之塗佈缺陷之問題。又,藉由含有與溶劑(E)同樣地作為使塗材低黏度化之液狀介質而發揮功能之單體(B),可將容易導致塗佈缺陷之溶劑(E)之濃度抑制為較低。又,於進行加熱時,藉由溶劑(E)之蒸發,隨著黏著劑層之濃度上升而黏度上升,可抑制黏著劑層內之物質之流動。認為藉由該等協同作用,可抑制厚壁端部、塗佈缺陷等製造上之問題,可形成表面平滑之黏著劑層。 The reason is considered as follows. First, by containing the solvent (E), the problem of coating defects at the end portions of the thick walls is less likely to occur at the time of coating. Further, when the solvent (E) contains a solvent having a difference in solubility parameter with the monomer (B) of 2 [(cal/cm 3 ) 1/2 ], when it is thermally cured, it can be suppressed from being excessively large. The imbalance of the gas-liquid equilibrium causes the solvent (E) to evaporate rapidly, so that the problem of coating defects of Orange Peel is not easily generated. In addition, by containing the monomer (B) which functions as a liquid medium which makes the coating material low-viscosity similarly to the solvent (E), the concentration of the solvent (E) which is likely to cause coating defects can be suppressed. low. Further, when heating is performed, the viscosity of the adhesive layer rises as the concentration of the adhesive layer rises by evaporation of the solvent (E), and the flow of the substance in the adhesive layer can be suppressed. It is considered that by such synergistic action, manufacturing problems such as thick end portions and coating defects can be suppressed, and an adhesive layer having a smooth surface can be formed.

於溶劑(E)含有與單體(B)之溶解性參數之差超過2[(cal/cm3)1/2]之溶劑之情形時,因過大之氣液平衡失衡導致溶劑(E)急遽蒸發,容易引起橘皮(Orange Peel)等塗佈缺陷,有難以獲得表面平滑之黏著劑層之傾向。 In the case where the solvent (E) contains a solvent which differs from the solubility parameter of the monomer (B) by more than 2 [(cal/cm 3 ) 1/2 ], the solvent (E) is impatient due to excessive gas-liquid equilibrium imbalance. Evaporation tends to cause coating defects such as Orange Peel, and it is difficult to obtain an adhesive layer having a smooth surface.

進而於溶劑(E)不具有聚合性不飽和基,且於25℃下之表面張力為20mN/m以上且未達40mN/m之情形時,上述效果尤其優異。即,於黏著劑組合物中,較佳為單體(B)於25℃下之蒸氣壓為300Pa以下,溶劑(E)於25℃下之表面張力為20mN/m以上且未達40mN/m,進而溶劑(E)含有與單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內之溶劑。再者,於上述專利文獻7~8中並未特別考慮此種溶劑與單體之溶解性參數之差或溶劑之表面張力。 Further, when the solvent (E) does not have a polymerizable unsaturated group and the surface tension at 25 ° C is 20 mN/m or more and less than 40 mN/m, the above effects are particularly excellent. That is, in the adhesive composition, it is preferred that the vapor pressure of the monomer (B) at 25 ° C is 300 Pa or less, and the surface tension of the solvent (E) at 25 ° C is 20 mN/m or more and less than 40 mN/m. Further, the solvent (E) contains a solvent having a difference from the solubility parameter of the monomer (B) of 2 [(cal/cm 3 ) 1/2 ]. Further, in the above Patent Documents 7 to 8, the difference between the solubility parameter of the solvent and the monomer or the surface tension of the solvent is not particularly considered.

[基礎聚合物(A)] [Base Polymer (A)]

黏著劑層含有非交聯性之(甲基)丙烯酸酯單元(a1)與具有交聯性官能基之丙烯酸系單體單元(a2)作為基礎聚合物(A)。 The adhesive layer contains a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group as a base polymer (A).

於本說明書及申請專利範圍中,「單元」係構成聚合物之重複單元(單體單元)。 In the present specification and the scope of the patent application, "unit" is a repeating unit (monomer unit) constituting a polymer.

非交聯性之(甲基)丙烯酸酯單元(a1)係源自(甲基)丙烯酸烷基酯者。 The non-crosslinkable (meth) acrylate unit (a1) is derived from an alkyl (meth) acrylate.

作為(甲基)丙烯酸烷基酯,可列舉:(甲基)丙烯酸甲酯、(甲基) 丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯等。該等可單獨使用1種,亦可併用2種以上。 Examples of the alkyl (meth)acrylate include methyl (meth)acrylate and (methyl). Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( Methyl) n-amyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (methyl) N-decyl acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, (meth) acrylate Dodecyl ester, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Benzyl acrylate and the like. These may be used alone or in combination of two or more.

於上述(甲基)丙烯酸烷基酯中,就黏著性變高之方面而言,較佳為選自(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯中之至少1種。 In the above alkyl (meth)acrylate, it is preferably selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid 2 in terms of high adhesion. At least one of -ethylhexyl ester.

再者,於本發明中,所謂「(甲基)丙烯酸酯」,意指包含「丙烯酸酯」及「甲基丙烯酸酯」兩者,所謂「(甲基)丙烯酸」,意指包含「丙烯酸」及「甲基丙烯酸」兩者。 In the present invention, the term "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid". And "methacrylic acid".

作為具有交聯性官能基之丙烯酸系單體單元(a2),可列舉:含羥基之單體單元、含胺基之單體單元、含縮水甘油基之單體單元、含羧基之單體單元。其中,較佳為含羥基之單體單元、含胺基之單體單元,尤佳為含羥基之單體單元。 Examples of the acrylic monomer unit (a2) having a crosslinkable functional group include a hydroxyl group-containing monomer unit, an amine group-containing monomer unit, a glycidyl group-containing monomer unit, and a carboxyl group-containing monomer unit. . Among them, a hydroxyl group-containing monomer unit, an amine group-containing monomer unit, and preferably a hydroxyl group-containing monomer unit are preferable.

再者,該等單體單元可為1種,亦可為2種以上。其中,丙烯酸系單體單元(a2)所含之含羧基之單體單元之比率相對於丙烯酸系單體單元(a2)之總質量,較佳為1%以下,更佳為0.1%以下,尤佳為0%。藉由將丙烯酸系單體單元(a2)所含之含羧基之單體單元之比率設為上述範圍內,可抑制對設置於被黏著體之表面之金屬配線之腐蝕性。 Further, the monomer units may be one type or two or more types. The ratio of the carboxyl group-containing monomer unit contained in the acrylic monomer unit (a2) is preferably 1% or less, more preferably 0.1% or less, more preferably 0.1% or less, based on the total mass of the acrylic monomer unit (a2). Good is 0%. When the ratio of the carboxyl group-containing monomer unit contained in the acrylic monomer unit (a2) is within the above range, the corrosiveness to the metal wiring provided on the surface of the adherend can be suppressed.

含羥基之單體單元係源自含羥基之單體者。作為含羥基之單體,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁 酯、(甲基)丙烯酸2-羥基丙酯等(甲基)丙烯酸羥基烷基酯;單(二乙二醇)(甲基)丙烯酸酯等[(單、二或聚)伸烷基二醇](甲基)丙烯酸酯;(甲基)丙烯酸單己內酯等(甲基)丙烯酸內酯。 The hydroxyl group-containing monomer unit is derived from a monomer having a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. a hydroxyalkyl (meth) acrylate such as an ester or a 2-hydroxypropyl (meth)acrylate; a mono(diethylene glycol) (meth) acrylate or the like [(mono, di or poly) alkylene glycol (Meth) acrylate; (meth) acrylate lactone such as monocaprolactone (meth) acrylate.

含胺基之單體單元例如可列舉源自(甲基)丙烯醯胺、烯丙胺等含胺基之單體者。 Examples of the monomer unit containing an amine group include those derived from an amine group-containing monomer such as (meth) acrylamide or allylamine.

含縮水甘油基之單體單元可列舉源自(甲基)丙烯酸縮水甘油酯等含縮水甘油基之單體者。 Examples of the monomer unit containing a glycidyl group include those derived from a glycidyl group-containing monomer such as glycidyl (meth)acrylate.

含羧基之單體單元可列舉丙烯酸、甲基丙烯酸。 Examples of the carboxyl group-containing monomer unit include acrylic acid and methacrylic acid.

基礎聚合物(A)中之交聯性丙烯酸系單體單元(a2)之含量較佳為0.01~20質量%,更佳為0.5~15質量%,進而較佳為0.5~10質量%。若交聯性丙烯酸系單體單元(a2)之含量為上述範圍之下限值以上,則充分具有維持半硬化狀態所需之交聯性,若為上述範圍之上限值以下,則可維持必需之黏著物性。 The content of the crosslinkable acrylic monomer unit (a2) in the base polymer (A) is preferably from 0.01 to 20% by mass, more preferably from 0.5 to 15% by mass, still more preferably from 0.5 to 10% by mass. When the content of the crosslinkable acrylic monomer unit (a2) is at least the lower limit of the above range, the crosslinkability required to maintain the semi-cured state is sufficiently maintained, and if it is at most the upper limit of the above range, it can be maintained. The necessary adhesive properties.

基礎聚合物(A)亦可視需要而具有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2)以外之其他單體單元。作為該其他單體,只要為可與非交聯性(甲基)丙烯酸酯及具有交聯性官能基之丙烯酸系單體共聚合者即可,例如可列舉(甲基)丙烯腈、乙酸乙烯酯、苯乙烯、氯乙烯、乙烯基吡咯啶酮、乙烯基吡啶等。 The base polymer (A) may optionally have a non-crosslinkable (meth) acrylate unit (a1) and a monomer unit other than the acrylic monomer unit (a2) having a crosslinkable functional group. The other monomer may be a copolymerizable with a non-crosslinkable (meth) acrylate and an acrylic monomer having a crosslinkable functional group, and examples thereof include (meth)acrylonitrile and vinyl acetate. Ester, styrene, vinyl chloride, vinyl pyrrolidone, vinyl pyridine, and the like.

基礎聚合物(A)中之任意單體單元之含量較佳為0~20質量%,更佳為0~15質量%。 The content of any monomer unit in the base polymer (A) is preferably from 0 to 20% by mass, more preferably from 0 to 15% by mass.

基礎聚合物(A)之重量平均分子量較佳為10萬~200萬,更佳為30萬~150萬。若重量平均分子量為上述下限值以上,則可維持半硬化狀態,若不超過上述上限值,則可確保充分之凹凸追隨性。再者,基礎聚合物(A)之重量平均分子量係利用交聯劑進行交聯之前之值。該重量平均分子量係藉由尺寸排除層析法(SEC,Size Exclusion Chromatography)測定,以聚苯乙烯基準求出之值。作為基礎聚合物(A),可使用市售者,亦可使用藉由公知之方法合成者。 The weight average molecular weight of the base polymer (A) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1.5 million. When the weight average molecular weight is at least the above lower limit value, the semi-hardened state can be maintained, and if it does not exceed the above upper limit value, sufficient unevenness followability can be ensured. Further, the weight average molecular weight of the base polymer (A) is a value before crosslinking by a crosslinking agent. The weight average molecular weight is determined by size exclusion chromatography (SEC, Size Exclusion) Chromatography) Determination of the value obtained on a polystyrene basis. As the base polymer (A), those which are commercially available or which are synthesized by a known method can also be used.

[單體(B)] [monomer (B)]

單體(B)較佳為含有具有至少1個聚合性不飽和基之單官能單體(B1)及具有2個以上聚合性不飽和基之多官能單體(B2)之至少一者。單體(B)較佳為含有單官能單體(B1)或多官能單體(B2)之任一者,亦可含有單官能單體(B1)及多官能單體(B2)兩者。 The monomer (B) is preferably at least one of a monofunctional monomer (B1) having at least one polymerizable unsaturated group and a polyfunctional monomer (B2) having two or more polymerizable unsaturated groups. The monomer (B) preferably contains either a monofunctional monomer (B1) or a polyfunctional monomer (B2), and may contain both a monofunctional monomer (B1) and a polyfunctional monomer (B2).

藉由含有單體(B),可於使上述黏著劑組合物熱硬化時,熱硬化物之黏著劑層為半硬化狀態,且具有活性能量線硬化性。 When the above-mentioned adhesive composition is thermally cured by containing the monomer (B), the adhesive layer of the thermosetting material is in a semi-hardened state and has active energy ray hardenability.

作為聚合性不飽和基,較佳為含有乙烯性雙鍵之基,例如可列舉(甲基)丙烯醯基、乙烯基等。其中尤佳為(甲基)丙烯醯基。 The polymerizable unsaturated group is preferably a group containing an ethylenic double bond, and examples thereof include a (meth)acryl fluorenyl group and a vinyl group. Of these, it is especially preferred to be a (meth) acrylonitrile group.

作為單體(B),較佳為於25℃下之蒸氣壓為300Pa以下者。藉此,塗佈適應性提高,於進行塗佈、熱硬化時,可使溶劑選擇性蒸發,並且形成厚壁端部或隆起等塗佈缺陷較少之黏著劑層。 As the monomer (B), the vapor pressure at 25 ° C is preferably 300 Pa or less. Thereby, the coating suitability is improved, and when the coating or thermal curing is performed, the solvent can be selectively evaporated, and an adhesive layer having less coating defects such as thick end portions or ridges can be formed.

單體(B)於25℃下之蒸氣壓更佳為200Pa以下,進而較佳為100Pa以下。就塗佈適應性之方面而言,該蒸氣壓之下限並無特別限定。單體(B)之蒸氣壓可藉由JIS-K2258「原油及燃料油-蒸氣壓試驗方法-雷德法(Reid Method)」等測定,又,例如可藉由http://www.chemspider.com/等網站或ACD/PhysChem Suite等軟體求出預測值。 The vapor pressure of the monomer (B) at 25 ° C is more preferably 200 Pa or less, further preferably 100 Pa or less. The lower limit of the vapor pressure is not particularly limited in terms of coating suitability. The vapor pressure of the monomer (B) can be measured by JIS-K2258 "Crude oil and fuel oil-vapor pressure test method - Reid Method", and the like, for example, by http://www.chemspider. Software such as com/ or ACD/PhysChem Suite can obtain predicted values.

單體(B)進而較佳為熔點為25℃以下。藉此,所形成之黏著劑層之透明性(霧度等)等提高。又,單體(B)之熔點更佳為20℃以下,進而較佳為15℃以下。該熔點之下限並無特別限定。單體(B)之熔點可藉由JIS K 0064:1992「化學製品之熔點及熔融範圍測定方法」等而測定。 The monomer (B) further preferably has a melting point of 25 ° C or lower. Thereby, the transparency (haze, etc.) etc. of the adhesive layer formed are improved. Further, the melting point of the monomer (B) is more preferably 20 ° C or lower, further preferably 15 ° C or lower. The lower limit of the melting point is not particularly limited. The melting point of the monomer (B) can be measured by JIS K 0064: 1992 "Method for measuring melting point and melting range of chemical products".

作為單體(B),若使用具有鏈長原子數為10以上之烷基之單體、 或具有多環結構之單體,則於硬化後可發揮更優異之保持力。 When the monomer (B) is a monomer having an alkyl group having a chain length of 10 or more, Or a monomer having a polycyclic structure can exhibit more excellent retention after hardening.

通常,為了使單體以更高分子量體之形式聚合,鏈長原子數越短越佳,單體彼此越容易結合,而產生更加優異之硬化。然而,認為本發明中藉由使用如上所述之單體,單體與基礎聚合物交聯,藉此易於硬化,可發揮優異之保持力。 In general, in order to polymerize a monomer in the form of a higher molecular weight body, the shorter the number of chain length atoms, the more easily the monomers are bonded to each other, resulting in more excellent hardening. However, it is considered that in the present invention, by using the monomer as described above, the monomer is crosslinked with the base polymer, whereby it is easily hardened, and excellent retention can be exerted.

作為具有鏈長原子數為10以上之烷基之單體,可列舉具有鏈長原子數為10以上之烷基之丙烯酸烷基酯。若烷基之鏈長原子數為10以上,則亦可具有側鏈或取代基。作為此種側鏈或取代基,可列舉烷基。烷基之較佳之鏈長原子數為10~27,更佳為10~25,進而較佳為15~22。就保持力之方面而言,作為尤佳之丙烯酸烷基酯,可列舉丙烯酸異硬脂酯。 Examples of the monomer having an alkyl group having a chain length of 10 or more include an alkyl acrylate having an alkyl group having a chain length of 10 or more. When the alkyl group has a chain length of 10 or more, it may have a side chain or a substituent. As such a side chain or a substituent, an alkyl group is mentioned. The preferred chain length of the alkyl group is from 10 to 27, more preferably from 10 to 25, still more preferably from 15 to 22. In terms of retention, as a particularly preferred alkyl acrylate, isostearyl acrylate is exemplified.

具有多環結構之單體可為多環脂肪族單體,亦可為多環芳香族單體,較佳為多環脂肪族單體。多環結構中,較佳為雙環結構與三環結構。可於該等多環結構上鍵結烷基等取代基。作為多環結構之具體例,可例示降烯環、金剛烷環等。 The monomer having a polycyclic structure may be a polycyclic aliphatic monomer or a polycyclic aromatic monomer, preferably a polycyclic aliphatic monomer. Among the polycyclic structures, a bicyclic structure and a tricyclic structure are preferred. Substituents such as an alkyl group may be bonded to the polycyclic structures. As a specific example of the multi-ring structure, a drop can be exemplified An olefin ring, an adamantane ring, and the like.

作為本發明可使用之單官能單體(B1)之具體例,較佳為選自(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸2-乙基己酯等中之至少1種。 Specific examples of the monofunctional monomer (B1) which can be used in the present invention are preferably selected from amyl (meth)acrylate, hexyl (meth)acrylate, and (h) (meth)acrylate. N-octyl acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, N-undecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylic acid At least one of a base ester and 2-ethylhexyl (meth)acrylate.

該等中,尤佳為選自熔點為25℃以下之(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十一烷基酯、(甲 基)丙烯酸月桂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸2-乙基己酯中之至少1種。 In these, it is especially preferred to select amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, (a) having a melting point of 25 ° C or less. Isooctyl acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Monoalkyl ester, lauryl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylic acid At least one of a base ester and 2-ethylhexyl (meth)acrylate.

作為多官能單體(B2),例如可列舉:乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,6-己二醇二丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等多元醇之(甲基)丙烯酸酯類;甲基丙烯酸乙烯酯等。 Examples of the polyfunctional monomer (B2) include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and 1,3-butylene glycol di(meth)acrylate. , 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol diacrylate, polytetramethylene glycol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trishydroxyl (meth)acrylates of polyhydric alcohols such as methyl propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.; vinyl methacrylate.

再者,單體(B)較佳為不具有表現出與丙烯酸系單體單元(a2)所具有之官能基之反應性之官能基者。例如,單體(B)較佳為具有與丙烯酸系單體單元(a2)相同之官能基(例如,羥基)者,或為不具有官能基者。 Further, the monomer (B) is preferably one which does not have a functional group which exhibits reactivity with a functional group of the acrylic monomer unit (a2). For example, the monomer (B) is preferably one having the same functional group (for example, a hydroxyl group) as the acrylic monomer unit (a2), or a member having no functional group.

單體(B)可單獨使用單官能單體(B1)或多官能單體(B2)中之任1種,或者可併用單官能單體(B1)及/或多官能單體(B2)之2種以上。 Any one of the monofunctional monomer (B1) or the polyfunctional monomer (B2) may be used alone as the monomer (B), or a monofunctional monomer (B1) and/or a polyfunctional monomer (B2) may be used in combination. 2 or more types.

上述黏著劑組合物中,單體(B)之含量可根據基礎聚合物(A)之組成或分子量、交聯密度等而適當選擇,並無特別限定,相對於基礎聚合物(A)100質量份,較佳為5~150質量份,更佳為10~120質量份,進而較佳為15~90質量份。若單體(B)之含量為上述範圍之下限值以上,則凹凸追隨性之變形/應變防止性能優異,若為上述範圍之上限值以下,則加工性優異。 In the above adhesive composition, the content of the monomer (B) can be appropriately selected depending on the composition or molecular weight of the base polymer (A), the crosslinking density, and the like, and is not particularly limited, and is 100% by mass based on the base polymer (A). The portion is preferably 5 to 150 parts by mass, more preferably 10 to 120 parts by mass, still more preferably 15 to 90 parts by mass. When the content of the monomer (B) is at least the lower limit of the above range, the deformation/strain prevention performance of the unevenness followability is excellent, and when it is at most the upper limit of the above range, the workability is excellent.

又,單體(B)之含量相對於黏著劑組合物之總質量,較佳為1~60質量%,更佳為2~50質量%,進而較佳為5~35質量%。 Further, the content of the monomer (B) is preferably from 1 to 60% by mass, more preferably from 2 to 50% by mass, even more preferably from 5 to 35% by mass, based on the total mass of the adhesive composition.

尤其是於單體(B)含有單官能單體(B1)與多官能單體(B2)兩者之情形時,可根據聚合物(A)之組成或分子量、交聯密度等而適當選 擇,並無特別限定,相對於基礎聚合物(A)100質量份,單官能單體(B1)較佳為4~120質量份,更佳為8~100質量份,進而較佳為12~80質量份,多官能單體(B2)較佳為1~30質量份,更佳為2~20質量份,進而較佳為3~10質量份。又,單官能單體(B1)與多官能單體(B2)之含有質量比為2:1,較佳為3:1,更佳為5:1。 In particular, when the monomer (B) contains both the monofunctional monomer (B1) and the polyfunctional monomer (B2), it can be appropriately selected depending on the composition or molecular weight of the polymer (A), the crosslinking density, and the like. The monofunctional monomer (B1) is preferably 4 to 120 parts by mass, more preferably 8 to 100 parts by mass, even more preferably 12 to 10 parts by mass based on 100 parts by mass of the base polymer (A). The polyfunctional monomer (B2) is preferably from 1 to 30 parts by mass, more preferably from 2 to 20 parts by mass, even more preferably from 3 to 10 parts by mass, per 100 parts by mass. Further, the mass ratio of the monofunctional monomer (B1) to the polyfunctional monomer (B2) is 2:1, preferably 3:1, more preferably 5:1.

[交聯劑(C)] [Crosslinking agent (C)]

作為交聯劑(C),並無特別限定,可考慮與基礎聚合物(A)所具有之交聯性官能基之反應性而自例如異氰酸酯化合物、環氧化合物、唑啉化合物、氮丙啶化合物、金屬螯合物化合物、丁基化三聚氰胺化合物等公知之交聯劑中適當選擇。例如於含有羥基作為交聯性官能基之情形時,就羥基之反應性而言,較佳為使用異氰酸酯化合物。 The crosslinking agent (C) is not particularly limited, and can be considered from, for example, an isocyanate compound or an epoxy compound, depending on the reactivity with the crosslinking functional group of the base polymer (A). A known crosslinking agent such as an oxazoline compound, an aziridine compound, a metal chelate compound or a butylated melamine compound is appropriately selected. For example, in the case where a hydroxyl group is contained as a crosslinkable functional group, an isocyanate compound is preferably used in terms of reactivity of a hydroxyl group.

該等中,就可容易地交聯具有交聯性官能基之丙烯酸系單體單元(a2)而言,較佳為異氰酸酯化合物、環氧化合物。 Among these, an acrylic monomer unit (a2) having a crosslinkable functional group can be easily crosslinked, and an isocyanate compound or an epoxy compound is preferred.

作為異氰酸酯化合物,例如可列舉:甲苯二異氰酸酯、二甲苯二異氰酸酯、六亞甲基二異氰酸酯、異佛酮二異氰酸酯等。 Examples of the isocyanate compound include toluene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

作為環氧化合物,例如可列舉:乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、甘油二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、四縮水甘油基苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、三羥甲基丙烷聚縮水甘油醚、二甘油聚縮水甘油醚、聚甘油聚縮水甘油醚、山梨糖醇聚縮水甘油醚等。 Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and neopentyl glycol. Glycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidyl xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trihydroxyl Methylpropane polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like.

作為交聯劑(C),可單獨使用1種,亦可併用2種以上。 One type of the crosslinking agent (C) may be used alone or two or more types may be used in combination.

黏著劑組合物中,交聯劑(C)之含量可根據所需之黏著物性等而適當選擇,並無特別限定,相對於基礎聚合物(A)100質量份,較佳為0.01~5質量份,更佳為0.03~3質量份。若交聯劑(C)之含量為上述下限值以上,則加工性或基材密接性優異,若為上述上限值以下,則凹 凸追隨性與膜之變形/應變防止性能優異。 In the adhesive composition, the content of the crosslinking agent (C) can be appropriately selected depending on the desired adhesive properties and the like, and is not particularly limited, and is preferably 0.01 to 5 by mass based on 100 parts by mass of the base polymer (A). More preferably, it is 0.03 to 3 parts by mass. When the content of the crosslinking agent (C) is at least the above lower limit value, workability or substrate adhesion is excellent, and if it is at most the above upper limit value, it is concave. The convex follow-up property and the deformation/strain prevention performance of the film are excellent.

又,交聯劑(C)之含量相對於黏著劑組合物之總質量,較佳為0.01~5.0質量%,更佳為0.02~2.0質量%。 Further, the content of the crosslinking agent (C) is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 2.0% by mass based on the total mass of the adhesive composition.

[聚合起始劑(D)] [Polymerization initiator (D)]

作為聚合起始劑(D),只要為可藉由照射活性能量線而使單體(B)之聚合反應開始者即可,作為光聚合起始劑等,可利用公知者。 As the polymerization initiator (D), a polymerization reaction of the monomer (B) can be started by irradiation with an active energy ray, and a known one can be used as a photopolymerization initiator or the like.

此處,所謂「活性能量線」,意指電磁波或帶電粒子束中具有能量量子者,可列舉紫外線、電子束、可見光線、X射線、離子束等。其中,就通用性之方面而言,較佳為紫外線或電子束,尤佳為紫外線。 Here, the "active energy ray" means an electromagnetic wave or a charged quantum beam having energy quantum, and examples thereof include ultraviolet rays, electron beams, visible rays, X-rays, and ion beams. Among them, in terms of versatility, it is preferably ultraviolet light or electron beam, and particularly preferably ultraviolet light.

作為聚合起始劑(D),例如可列舉苯乙酮系起始劑、安息香醚系起始劑、二苯甲酮系起始劑、羥基烷基苯酮系起始劑、9-氧硫系起始劑、胺系起始劑等。該等中,作為苯乙酮系起始劑,具體而言,可列舉二乙氧基苯乙酮、苯偶醯二甲基縮酮等。作為安息香醚系起始劑,具體而言,可列舉安息香、安息香甲醚等。作為二苯甲酮系起始劑,具體而言,可列舉二苯甲酮、鄰苯甲醯基苯甲酸甲酯等。作為羥基烷基苯酮系起始劑,具體而言,可列舉1-羥基-環己基-苯基-酮等。作為9-氧硫系起始劑,具體而言,可列舉2-異丙基-9-氧硫、2,4-二甲基-9-氧硫等。作為胺系起始劑,具體而言,可列舉三乙醇胺、4-二甲基苯甲酸乙酯等。 Examples of the polymerization initiator (D) include an acetophenone-based initiator, a benzoin ether-based initiator, a benzophenone-based initiator, a hydroxyalkylphenone-based initiator, and 9-oxosulfuric acid. It is an initiator, an amine initiator, and the like. In particular, examples of the acetophenone-based initiator include diethoxyacetophenone and benzoindimethylketal. Specific examples of the benzoin ether-based initiator include benzoin, benzoin methyl ether and the like. Specific examples of the benzophenone-based initiator include benzophenone and methyl benzylidenebenzoate. Specific examples of the hydroxyalkylphenone-based initiator include 1-hydroxy-cyclohexyl-phenyl-ketone. 9-oxosulfur The initiator, specifically, 2-isopropyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur Wait. Specific examples of the amine-based initiator include triethanolamine and ethyl 4-dimethylbenzoate.

作為聚合起始劑(D),可單獨使用1種,亦可併用2種以上。 One type of the polymerization initiator (D) may be used alone or two or more types may be used in combination.

黏著劑組合物中,聚合起始劑(D)之含量可根據單體(B)之含量或完全硬化時之活性能量線之照射量等而適當選擇,並無特別限定,相對於單體(B)之總質量,較佳為0.05~10質量%,更佳為0.1~5.0質量%。若為上述下限值以上,則可使完全硬化時之聚合反應容易地開始,若為上述上限值以下,則不易引起由完全硬化時之聚合反應熱之 影響導致之基材之損傷。 In the adhesive composition, the content of the polymerization initiator (D) can be appropriately selected depending on the content of the monomer (B) or the irradiation amount of the active energy ray at the time of complete hardening, and the like, and is not particularly limited, and is relative to the monomer ( The total mass of B) is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 5.0% by mass. When it is at least the above lower limit value, the polymerization reaction at the time of complete curing can be easily started, and if it is at most the above upper limit value, the heat of polymerization reaction at the time of complete curing is less likely to occur. Affect the damage caused by the substrate.

又,聚合起始劑(D)之含量相對於基礎聚合物(A)100質量份,較佳為0.1~10質量份,更佳為1~5質量份。 Further, the content of the polymerization initiator (D) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the base polymer (A).

[溶劑(E)] [solvent (E)]

溶劑(E)係用以提高黏著劑組合物之塗佈適應性。 The solvent (E) is used to improve the coating suitability of the adhesive composition.

作為此種溶劑(E),例如可列舉:己烷、庚烷、辛烷、甲苯、二甲苯、乙基苯、環己烷、甲基環己烷等烴類;二氯甲烷、三氯乙烷、三氯乙烯、四氯乙烯、二氯丙烷等鹵化烴類;甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、二丙酮醇等醇類;二乙醚、二異丙醚、二烷、四氫呋喃等醚類;丙酮、甲基乙基酮、甲基異丁基酮、異佛酮、環己酮等酮類;乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、丁酸乙酯等酯類;乙二醇單甲醚、乙二醇單乙醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚、丙二醇單乙醚、丙二醇單甲醚乙酸酯等多元醇及其衍生物。 Examples of such a solvent (E) include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; dichloromethane and trichloroethane; Halogenated hydrocarbons such as alkane, trichloroethylene, tetrachloroethylene, dichloropropane; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and diacetone; diethyl ether and diisopropyl ether ,two Ethers such as alkane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, Esters such as amyl acetate and ethyl butyrate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Polyols such as esters and derivatives thereof.

作為溶劑(E),尤佳為不具有聚合性不飽和基且於25℃下之蒸氣壓高於單體(B)之溶劑。 As the solvent (E), a solvent having no polymerizable unsaturated group and having a vapor pressure higher than that of the monomer (B) at 25 ° C is particularly preferable.

由於單體(B)與溶劑(E)之蒸氣壓之差越大,塗佈缺陷越少,越容易製造,故而溶劑(E)之蒸氣壓較佳為2000Pa以上,尤佳為5000Pa以上。上限並無特別限定,實用上較佳為50000Pa以下。 The larger the difference in vapor pressure between the monomer (B) and the solvent (E), the smaller the coating defect and the easier the production. Therefore, the vapor pressure of the solvent (E) is preferably 2,000 Pa or more, and more preferably 5,000 Pa or more. The upper limit is not particularly limited, but is preferably 50,000 Pa or less in practical use.

溶劑(E)之蒸氣壓可藉由JIS-K2258-2「原油及石油製品-蒸氣壓之求法-第2部:3次膨脹法」等測定,又,例如可藉由http://www.chemspider.com/等網站或ACD/PhysChem Suite等軟體預測。 The vapor pressure of the solvent (E) can be measured by JIS-K2258-2 "Calculation of crude oil and petroleum products - vapor pressure - Part 2: 3 expansion method", and, for example, by http://www. Software predictions such as chemspider.com/ or ACD/PhysChem Suite.

作為不具有聚合性不飽和基且於25℃下之蒸氣壓高於單體(B)之溶劑,亦根據單體(B)而有所不同,可列舉:己烷、庚烷、環己烷、苯、甲苯、乙醇、異丙醇、二異丙醚、四氫呋喃、丙酮、甲基乙基 酮、甲基異丁基酮、乙酸乙酯等。 The solvent which does not have a polymerizable unsaturated group and has a vapor pressure higher than the monomer (B) at 25 ° C varies depending on the monomer (B), and examples thereof include hexane, heptane, and cyclohexane. , benzene, toluene, ethanol, isopropanol, diisopropyl ether, tetrahydrofuran, acetone, methyl ethyl Ketone, methyl isobutyl ketone, ethyl acetate, and the like.

又,溶劑(E)於25℃下之表面張力較佳為20mN/m以上且未達40mN/m,更佳為22mN/m以上且未達36mN/m。若表面張力為上述範圍之下限值以上,則不易產生橘皮(Orange Peel)等塗佈缺陷,若未達上述範圍之上限值,則不易產生厚壁端部(成框)等塗佈缺陷。 Further, the surface tension of the solvent (E) at 25 ° C is preferably 20 mN / m or more and less than 40 mN / m, more preferably 22 mN / m or more and less than 36 mN / m. When the surface tension is at least the lower limit of the above range, coating defects such as orange peel are less likely to occur, and if the upper limit of the above range is not reached, coating of thick end portions (frame formation) is less likely to occur. defect.

溶劑(E)可使用與單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內、較佳為1.5[(cal/cm3)1/2]以內之溶劑。藉此,不易產生由異常地促進溶劑(E)之蒸發所導致之橘皮(Orange Peel)等塗佈缺陷。 The difference between the solvent (E) and the solubility parameter of the monomer (B) is 2 [(cal/cm 3 ) 1/2 ], preferably 1.5 [(cal/cm 3 ) 1/2 ]. Solvent. Thereby, coating defects such as orange peel which is caused by abnormally promoting evaporation of the solvent (E) are less likely to occur.

溶解性參數係溶解之指標,具有下式之含義。 The solubility parameter is an indicator of dissolution and has the meaning of the following formula.

δ=(ΔE/V)1/2 δ=(ΔE/V) 1/2

此處,δ為溶解性參數,ΔE為莫耳蒸發能量(cal/mol),V為莫耳體積(cm3/mol)。溶解性參數δ之值相近者彼此充分溶解。符合相似者彼此充分溶解之經驗規則。溶解性參數可藉由各種方法求出,藉由Fedors之方法而根據化學組成進行計算之方法較為簡便。 Here, δ is a solubility parameter, ΔE is a molar evaporation energy (cal/mol), and V is a molar volume (cm 3 /mol). The values of the solubility parameters δ are close to each other and are sufficiently dissolved. Meet the rules of experience that similar people dissolve fully with each other. The solubility parameter can be determined by various methods, and the method of calculating the chemical composition by the method of Fedors is relatively simple.

溶劑(E)可單獨使用1種,亦可併用2種以上。 The solvent (E) may be used alone or in combination of two or more.

上述黏著劑組合物中,溶劑(E)之含量並無特別限定,相對於基礎聚合物(A)100質量份,較佳為25~500質量份,更佳為30~400質量份。若溶劑(E)之含量為上述範圍之下限值以上,則不易產生厚壁端部等塗佈缺陷,塗佈適應性優異,若為上述範圍之上限值以下,則不易於塗厚時產生隆起(溶劑泡)等塗佈缺陷,塗佈適應性優異。 The content of the solvent (E) in the above-mentioned adhesive composition is not particularly limited, and is preferably 25 to 500 parts by mass, more preferably 30 to 400 parts by mass, per 100 parts by mass of the base polymer (A). When the content of the solvent (E) is at least the lower limit of the above range, coating defects such as thick end portions are less likely to occur, and the coating suitability is excellent. When the content is at most the upper limit of the above range, it is not easy to apply thickness. Coating defects such as bulges (solvent bubbles) are generated, and coating suitability is excellent.

又,溶劑(E)之含量相對於黏著劑組合物之總質量,較佳為10~90質量%,更佳為20~80質量%。 Further, the content of the solvent (E) is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass based on the total mass of the adhesive composition.

[塑化劑] [Plasticizer]

為了進一步提高凹凸追隨性,本發明之黏著片材1亦可於黏著劑組合物中含有塑化劑。於含有塑化劑之情形時,塑化劑相對於各黏著劑組合物中所含之基礎聚合物(A)100質量份,較佳為含有50質量份以 下,更佳為含有30質量份以下,進而較佳為含有10質量份以下。 In order to further improve the unevenness followability, the adhesive sheet 1 of the present invention may contain a plasticizer in the adhesive composition. In the case of containing a plasticizer, the plasticizer is preferably contained in an amount of 50 parts by mass based on 100 parts by mass of the base polymer (A) contained in each of the adhesive compositions. More preferably, it is contained in an amount of 30 parts by mass or less, and more preferably 10 parts by mass or less.

作為塑化劑,尤佳為無官能性丙烯酸系聚合物。所謂無官能基丙烯酸系聚合物,意指僅由不具有丙烯酸酯基以外之官能基之丙烯酸系單體單元所構成之聚合物、或包含不具有丙烯酸酯基以外之官能基之丙烯酸系單體單元與不具有官能基之非丙烯酸系單體單元之聚合物。由於該無官能性丙烯酸系聚合物不與基礎聚合物(A)交聯,故而可不對黏著物性造成影響而提高凹凸追隨性。 As the plasticizer, a non-functional acrylic polymer is particularly preferred. The non-functional acrylic polymer means a polymer composed only of an acrylic monomer unit having no functional group other than the acrylate group, or an acrylic monomer containing a functional group other than the acrylate group. A polymer of a unit and a non-acrylic monomer unit having no functional group. Since the non-functional acrylic polymer is not crosslinked with the base polymer (A), the adhesion followability can be improved without affecting the adhesive properties.

作為不具有丙烯酸酯基以外之官能基之丙烯酸系單體單元,例如可列舉與上述非交聯性(甲基)丙烯酸酯單元(a1)相同者。 Examples of the acrylic monomer unit having no functional group other than the acrylate group include the same as those of the non-crosslinkable (meth) acrylate unit (a1).

作為不具有官能基之非丙烯酸系單體單元,例如可列舉如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、己酸乙烯酯、辛酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、環己烷甲酸乙烯酯、苯甲酸乙烯酯之羧酸乙烯酯類或苯乙烯等。 Examples of the non-acrylic monomer unit having no functional group include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl phthalate, vinyl laurate, Vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl carboxylate of vinyl benzoate or styrene.

[任意成分] [arbitrary ingredients]

黏著劑組合物亦可於無損本發明之效果之範圍內任意地含有除上述以外之其他成分。作為該其他成分,可視需要自作為黏著劑用添加劑而公知之成分,例如抗氧化劑、金屬防腐蝕劑、黏著賦予劑、矽烷偶合劑、紫外線吸收劑、受阻胺系化合物等光穩定劑等中選擇。 The adhesive composition may optionally contain other components than the above without departing from the effects of the present invention. As such other components, a component known as an additive for an adhesive, such as an antioxidant, a metal corrosion inhibitor, an adhesion-imparting agent, a decane coupling agent, a UV absorber, a light stabilizer such as a hindered amine compound, or the like may be selected as needed.

作為抗氧化劑,可列舉:酚系抗氧化劑、胺系抗氧化劑、內酯系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑等。該等抗氧化劑可單獨使用1種,亦可併用2種以上。 Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. These antioxidants may be used alone or in combination of two or more.

作為金屬防腐蝕劑,就黏著劑之相溶性或效果高低而言,較佳為苯并三唑系樹脂。 As the metal anticorrosive agent, a benzotriazole resin is preferred in terms of compatibility or effect of the adhesive.

作為黏著賦予劑,例如可列舉:松香系樹脂、萜烯系樹脂、萜酚系樹脂、薰草咔茚系樹脂、苯乙烯系樹脂、二甲苯系樹脂、酚系樹 脂、石油樹脂等。 Examples of the adhesion-imparting agent include a rosin-based resin, a terpene-based resin, a phenol-based resin, a chlorinated resin, a styrene resin, a xylene-based resin, and a phenol-based tree. Fat, petroleum resin, etc.

作為矽烷偶合劑,例如可列舉:巰基烷氧基矽烷化合物(例如,巰基取代烷氧基低聚物等)等。 Examples of the decane coupling agent include a mercapto alkoxydecane compound (for example, a mercapto-substituted alkoxy oligomer).

作為紫外線吸收劑,例如可列舉:苯并三唑系化合物、二苯甲酮系化合物等。然而,於完全硬化時之活性能量線使用紫外線之情形時,需於不阻礙聚合反應之範圍內進行添加。 Examples of the ultraviolet absorber include a benzotriazole-based compound and a benzophenone-based compound. However, in the case where ultraviolet rays are used for the active energy ray at the time of complete hardening, it is necessary to carry out the addition without hindering the polymerization reaction.

(附剝離片材之黏著片材) (Adhesive sheet with peeling sheet)

本發明之黏著片材1係藉由加熱使上述黏著劑層11半硬化而成,為以未反應之狀態含有上述單體(B)及上述聚合起始劑(D)之至少一部分者。 In the adhesive sheet 1 of the present invention, the pressure-sensitive adhesive layer 11 is semi-hardened by heating, and at least a part of the monomer (B) and the polymerization initiator (D) are contained in an unreacted state.

本發明之黏著片材1例如可藉由於剝離片材12上塗佈黏著劑組合物而形成塗膜,並加熱該塗膜製成硬化物而得。藉由加熱塗膜而進行基礎聚合物(A)及交聯劑(C)之反應,形成硬化物(黏著劑層11)。即,於加熱時,於塗膜中不進行由聚合起始劑(D)引起之單體(B)之聚合反應,或者即便進行亦為微量,故而於所得之硬化物(黏著劑層11)中殘留有黏著劑組合物所含之單體(B)及聚合起始劑(D)。因此本發明之黏著片材1具有活性能量線硬化性。為了使上述黏著組合物成為半硬化狀態,較佳為於塗佈後除去溶劑,然後於一定溫度下實施將黏著片材靜置一定時間之熟化處理。上述熟化處理例如可於23℃下靜置7天而進行。 The adhesive sheet 1 of the present invention can be obtained, for example, by applying a pressure-sensitive adhesive composition to the release sheet 12 to form a coating film, and heating the coating film to obtain a cured product. The base polymer (A) and the crosslinking agent (C) are reacted by heating the coating film to form a cured product (adhesive layer 11). That is, at the time of heating, the polymerization reaction of the monomer (B) by the polymerization initiator (D) is not carried out in the coating film, or even if it is carried out, the obtained cured product (adhesive layer 11) The monomer (B) and the polymerization initiator (D) contained in the adhesive composition remain. Therefore, the adhesive sheet 1 of the present invention has active energy ray hardenability. In order to make the adhesive composition semi-hardened, it is preferred to remove the solvent after coating, and then carry out the aging treatment of leaving the adhesive sheet at a constant temperature for a certain period of time. The aging treatment can be carried out, for example, by allowing to stand at 23 ° C for 7 days.

作為剝離片材12,可列舉具有剝離片材用基材與設置於該剝離片材用基材之單面之剝離劑層的剝離性積層片材、或者作為低極性基材之聚乙烯膜或聚丙烯膜等聚烯烴膜。 Examples of the release sheet 12 include a release laminated sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate, or a polyethylene film as a low polarity substrate or A polyolefin film such as a polypropylene film.

作為剝離性積層片材中之剝離片材用基材,可使用紙類、高分子膜。作為構成剝離劑層之剝離劑,例如可使用通用之加成型或縮合型之矽酮系剝離劑或者含長鏈烷基之化合物。 As the base material for the release sheet in the release laminated sheet, paper or polymer film can be used. As the release agent constituting the release agent layer, for example, a general-purpose addition or condensation type anthrone-based release agent or a compound containing a long-chain alkyl group can be used.

本發明之黏著片材含有包含如下所述之黏著劑之黏著劑層(X),上述黏著劑係藉由加熱而使上述黏著劑組合物硬化(半硬化)而成,且以未反應之狀態含有上述單體(B)及上述聚合起始劑(D)之至少一部分。 The adhesive sheet of the present invention contains an adhesive layer (X) comprising an adhesive which is cured (semi-hardened) by heating and is in an unreacted state by heating. At least a part of the above monomer (B) and the above polymerization initiator (D) are contained.

黏著劑層(X)之厚度可根據用途等而適當設定,並無特別限定,通常為10~500μm之範圍內,尤佳為20~350μm。若該厚度為上述下限值以上,則可充分確保凹凸追隨性。若黏著劑層(X)之厚度為上述上限值以下,則可容易地製造黏著片材。 The thickness of the pressure-sensitive adhesive layer (X) can be appropriately set depending on the use and the like, and is not particularly limited, and is usually in the range of 10 to 500 μm, particularly preferably 20 to 350 μm. When the thickness is at least the above lower limit value, the unevenness followability can be sufficiently ensured. When the thickness of the adhesive layer (X) is at most the above upper limit value, the adhesive sheet can be easily produced.

半硬化後之黏著劑層(X)之楊氏模數較佳為處於0.01~0.30[N/mm2]之範圍內,更佳為處於0.05~0.20[N/mm2]之範圍內。若楊氏模數為上述範圍內,則黏著劑層(X)容易成為所期望之硬度。特別是若為上述下限值以上,則有變得更加不易引起糊劑自黏著劑層(X)溢出或加工適應性之惡化之傾向。又,若楊氏模數為上述上限值以下,則有黏著劑層(X)變得容易表現出更加優異之階差追隨性之傾向。楊氏模數可藉由調整單體之添加量而調整為所需之範圍內。 The Young's modulus of the semi-hardened adhesive layer (X) is preferably in the range of 0.01 to 0.30 [N/mm 2 ], more preferably in the range of 0.05 to 0.20 [N/mm 2 ]. When the Young's modulus is within the above range, the adhesive layer (X) tends to have a desired hardness. In particular, when it is at least the above lower limit value, it tends to be less likely to cause the paste to overflow from the adhesive layer (X) or to deteriorate the processing suitability. In addition, when the Young's modulus is equal to or less than the above upper limit value, the adhesive layer (X) tends to exhibit more excellent step followability. The Young's modulus can be adjusted to a desired range by adjusting the amount of addition of the monomer.

再者,本測定使用島津製作所股份有限公司之Autograph AGS-X,以拉伸速度10[mm/min]進行測定。 In addition, this measurement was performed using the Autograph AGS-X of Shimadzu Corporation, and the tensile speed was 10 [mm / min].

本發明之黏著片材可為僅由黏著劑層(X)所構成者,亦可為包括除黏著劑層(X)以外之其他層(以下稱為層(Y))之積層體。作為層(Y),例如可列舉黏著劑層(X)以外之黏著劑層、支持體、剝離片材等。 The adhesive sheet of the present invention may be composed only of the adhesive layer (X), or may be a laminate including a layer other than the adhesive layer (X) (hereinafter referred to as a layer (Y)). Examples of the layer (Y) include an adhesive layer other than the adhesive layer (X), a support, and a release sheet.

作為支持體,例如可列舉:聚苯乙烯、苯乙烯-丙烯酸系共聚物、丙烯酸系樹脂、聚對苯二甲酸乙二酯、聚碳酸酯、聚醚醚酮、三乙醯纖維素等塑膠膜;抗反射膜、電磁波屏蔽膜等光學膜;等。 Examples of the support include plastic films such as polystyrene, styrene-acrylic copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyether ether ketone, and triacetyl cellulose. An optical film such as an antireflection film or an electromagnetic wave shielding film;

剝離片材係至少單面具有脫模性之片材。作為剝離片材,可列舉具有剝離片材用基材與設置於該剝離片材用基材之單面之剝離劑層的剝離性積層片材、或者作為低極性基材之聚乙烯膜或聚丙烯膜等聚 烯烴膜。 The release sheet is a sheet having a mold release property on at least one side. Examples of the release sheet include a release laminated sheet having a release sheet layer and a release agent layer provided on one surface of the release sheet substrate, or a polyethylene film or a polypolar substrate. Acrylic film Olefin film.

作為剝離性積層片材中之剝離片材用基材,可使用紙類、高分子膜。作為構成剝離劑層之剝離劑,例如可使用通用之加成型或縮合型之矽酮系剝離劑或含長鏈烷基之化合物。尤其是可較佳地使用反應性較高之加成型矽酮系剝離劑。 As the base material for the release sheet in the release laminated sheet, paper or polymer film can be used. As the release agent constituting the release agent layer, for example, a general-purpose addition or condensation type anthrone-based release agent or a long-chain alkyl group-containing compound can be used. In particular, a highly reactive addition ketone ketone release agent can be preferably used.

作為矽酮系剝離劑,具體而言,可列舉:Dow Corning Toray Silicone公司製造之BY24-4527、SD-7220等,或信越化學工業股份有限公司製造之KS-3600、KS-774、X62-2600等。又,較佳為於矽酮系剝離劑中含有作為具有SiO2單元與(CH3)3SiO1/2單元或CH2=CH(CH3)SiO1/2單元之有機矽化合物的矽酮樹脂。作為矽酮樹脂之具體例,可列舉:Dow Corning Toray Silicone公司製造之BY24-843、SD-7292、SHR-1404等,或信越化學工業股份有限公司製造之KS-3800、X92-183等。 Specific examples of the anthrone-based release agent include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicone Co., Ltd., or KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Wait. Further, it is preferable to contain an anthrone as an organic ruthenium compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 =CH(CH 3 )SiO 1/2 unit in an anthrone-based release agent. Resin. Specific examples of the fluorene ketone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Dow Corning Toray Silicone Co., Ltd., or KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

為了容易剝離,剝離片材12較佳為於剝離片材12a與剝離片材12b中剝離性各不相同。即,若自一側之剝離性與自另一側之剝離性不同,則容易僅將剝離性較高一側之剝離片材12先行剝離。於此情形時,根據貼合方法或貼合順序調整剝離片材12a與剝離片材12b之剝離片材12之剝離性即可。 In order to facilitate peeling, the release sheet 12 is preferably different in peelability from the release sheet 12a and the release sheet 12b. In other words, when the peelability from one side is different from the peelability from the other side, it is easy to peel only the release sheet 12 having the higher peeling property. In this case, the peeling property of the peeling sheet 12 of the peeling sheet 12a and the peeling sheet 12b may be adjusted according to the bonding method or the bonding order.

形成黏著劑層11之黏著劑組合物之塗佈可使用公知之塗佈裝置而實施。作為塗佈裝置,例如可列舉:刮刀塗佈機、氣刀塗佈機、輥式塗佈機、棒式塗佈機、凹版塗佈機、微凹版塗佈機、桿式刮刀塗佈機、模唇塗佈機、模具塗佈機、淋幕式塗佈機等。 The application of the adhesive composition forming the adhesive layer 11 can be carried out using a known coating device. Examples of the coating device include a knife coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, and a bar coater. Lip coater, die coater, curtain coater, and the like.

本發明之黏著片材可為單面黏著片材,亦可為雙面黏著片材。 The adhesive sheet of the present invention may be a single-sided adhesive sheet or a double-sided adhesive sheet.

作為單面黏著片材,可列舉於支持體上積層有黏著劑層(X)之多層片材等。可於該多層片材之黏著劑層(X)上進而積層剝離片材。又,亦可於支持體與黏著劑層(X)之間設置其他層。 Examples of the one-side adhesive sheet include a multilayer sheet in which an adhesive layer (X) is laminated on a support. The release sheet can be laminated on the adhesive layer (X) of the multilayer sheet. Further, another layer may be provided between the support and the adhesive layer (X).

作為雙面黏著片材,可列舉:包含黏著劑層(X)之單層片材、積層有複數層黏著劑層(X)之多層片材、積層有黏著劑層(X)與黏著劑層(X)以外之黏著劑層之多層片材、於支持體之雙面積層有黏著劑層(X)之多層片材、於支持體之一面積層有黏著劑層(X)且於另一面積層有黏著劑層(X)以外之黏著劑層之多層片材、於該等單層片材或多層片材之單面或雙面積層有剝離片材之多層片材等。 Examples of the double-sided adhesive sheet include a single-layer sheet comprising an adhesive layer (X), a multilayer sheet in which a plurality of layers of adhesive (X) are laminated, and an adhesive layer (X) and an adhesive layer. a multi-layer sheet of an adhesive layer other than (X), a multi-layer sheet having an adhesive layer (X) in a double-area layer of a support, an adhesive layer (X) on one area of the support, and another area layer A multilayer sheet having an adhesive layer other than the adhesive layer (X), a multilayer sheet having a release sheet or a single-sided or double-area layer of the single-layer sheet or the multilayer sheet.

作為雙面片材,較佳為不具有支持體之無載體型、或使用透明支持體作為支持體者。該雙面黏著片材除了黏著劑層(X)自身之透明性較高以外,作為黏著片材整體之透明性亦優異,故而可較佳地用於光學構件彼此之接著。 As the double-sided sheet, a carrierless type having no support or a support using a transparent support is preferable. In addition to the high transparency of the adhesive layer (X) itself, the double-sided adhesive sheet is excellent in transparency as a whole of the adhesive sheet, and thus can be preferably used for the optical members to be bonded to each other.

上述中,較佳為無載體型,更佳為包含黏著劑層(X)之單層片材、或積層有複數層黏著劑層(X)之多層片材,尤佳為包含黏著劑層(X)之單層片材。 In the above, it is preferably a carrier-free type, more preferably a single-layer sheet comprising the adhesive layer (X), or a multilayer sheet in which a plurality of layers of the adhesive layer (X) are laminated, and particularly preferably an adhesive layer ( Single layer sheet of X).

黏著片材例如可藉由於剝離片材上塗佈黏著劑組合物而形成塗膜,並加熱該塗膜製成硬化物而得。藉由加熱塗膜而進行基礎聚合物(A)及交聯劑(C)之反應,形成硬化物(黏著劑層(X))。 The adhesive sheet can be obtained, for example, by coating a pressure-sensitive adhesive composition on a release sheet to form a coating film, and heating the coating film to obtain a cured product. The base polymer (A) and the crosslinking agent (C) are reacted by heating the coating film to form a cured product (adhesive layer (X)).

於塗佈液中含有溶劑。作為溶劑,例如可使用:甲醇、乙醇、異丙醇、丙酮、甲基乙基酮、甲苯、正己烷、正丁醇、甲基異丁基酮、甲基丁基酮、乙基丁基酮、環己酮、乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙二醇單乙醚、丙二醇單甲醚、N-甲基-2-吡咯啶酮等。該等可單獨使用1種以上,亦可混合2種以上而使用。 A solvent is contained in the coating liquid. As the solvent, for example, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, n-butanol, methyl isobutyl ketone, methyl butyl ketone, ethyl butyl ketone can be used. , cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and the like. These may be used alone or in combination of two or more.

塗膜之加熱可使用加熱爐、紅外線燈等公知之加熱裝置而實施。 The heating of the coating film can be carried out by using a known heating device such as a heating furnace or an infrared lamp.

本發明之黏著片材1之黏著劑層11之厚度較佳為10~500μm,更佳為20~350μm。若黏著片材1之黏著劑層11之厚度為上述下限值以上,則即便於加飾膜22之與黏著劑層11之接著面22a或ITO玻璃基板24 之與黏著劑層11之接觸面24a上形成有印刷階差23,亦可充分確保凹凸追隨性。若黏著片材1之黏著劑層11之厚度為上述上限值以下,則可容易地製造黏著片材1。 The thickness of the adhesive layer 11 of the adhesive sheet 1 of the present invention is preferably from 10 to 500 μm, more preferably from 20 to 350 μm. If the thickness of the adhesive layer 11 of the adhesive sheet 1 is at least the above lower limit value, even if the decorative film 22 and the adhesive layer 11 are adjacent to the surface 22a or the ITO glass substrate 24 A printing step 23 is formed on the contact surface 24a of the adhesive layer 11, and the unevenness followability can be sufficiently ensured. When the thickness of the adhesive layer 11 of the adhesive sheet 1 is less than or equal to the above upper limit value, the adhesive sheet 1 can be easily produced.

作為本發明之黏著片材1之使用方法,較佳為於該雙面黏著片材1之黏著劑層11為半硬化狀態時貼合加飾膜22與ITO玻璃基板24,並照射活性能量線使黏著劑層11完全硬化之方法。 As a method of using the adhesive sheet 1 of the present invention, it is preferable that the adhesive film layer 11 and the ITO glass substrate 24 are attached to the adhesive layer 11 of the double-sided adhesive sheet 1 in a semi-hardened state, and the active energy ray is irradiated. A method of completely hardening the adhesive layer 11.

作為被黏著體,並無特別限定,可應用於先前使用黏著片材進行固定、接著等之任意者。 The adherend is not particularly limited, and can be applied to any of the conventional use of an adhesive sheet for fixation, and the like.

例如單面黏著片材可於各種製品之製造步驟等中用於各種構件之保護、固定等。 For example, a single-sided adhesive sheet can be used for protection, fixation, and the like of various members in various manufacturing steps of products.

活性能量線可自加飾膜側22進行照射,亦可自ITO玻璃基板24側進行照射,較佳為自加飾膜側22進行照射。 The active energy ray may be irradiated from the decorative film side 22, or may be irradiated from the ITO glass substrate 24 side, preferably from the decorative film side 22.

於照射活性能量線之前,由於為半硬化狀態,故而黏著劑層11較柔軟,對具有印刷階差23之與黏著劑層11之接著面而言凹凸追隨性優異。貼合後藉由利用活性能量線使黏著劑層11完全硬化,可提高黏著劑層11之凝聚力,提高被黏著體之保持力,並防止加飾膜22之變形、應變。 Since the adhesive layer 11 is soft before the irradiation of the active energy ray, the adhesive layer 11 is soft, and the adhesion surface having the printing step 23 and the adhesive layer 11 is excellent in unevenness followability. After the bonding, the adhesive layer 11 is completely cured by the active energy ray, whereby the cohesive force of the adhesive layer 11 can be improved, the holding force of the adherend can be improved, and the deformation and strain of the decorative film 22 can be prevented.

作為活性能量線,可列舉紫外線、電子束、可見光線、X射線、離子束等,可根據黏著劑層所含之聚合起始劑(D)而適當選擇。其中,就通用性之方面而言,較佳為紫外線或電子束,尤佳為紫外線。 Examples of the active energy ray include ultraviolet light, electron beam, visible light, X-ray, ion beam, and the like, and can be appropriately selected depending on the polymerization initiator (D) contained in the pressure-sensitive adhesive layer. Among them, in terms of versatility, it is preferably ultraviolet light or electron beam, and particularly preferably ultraviolet light.

作為紫外線之光源,例如可使用:高壓水銀燈、低壓水銀燈、超高壓水銀燈、金屬鹵化物燈、碳弧、氙弧、無電極紫外線燈等。 As the light source of ultraviolet rays, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used.

作為電子束,例如可使用自Cockcroft Walton型、Van de Graaff型、共振變壓型、絕緣芯變壓器型、直線型、高頻高壓型、高頻型等各種電子束加速器釋放之電子束。 As the electron beam, for example, an electron beam released from various electron beam accelerators such as a Cockcroft Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a high frequency high voltage type, and a high frequency type can be used.

(積層體) (layered body)

藉由使用本發明之黏著片材1貼合至少一者為光學膜之一對光學構件,可製作積層體。 A laminate can be produced by bonding at least one of the optical sheets to the optical member using the adhesive sheet 1 of the present invention.

所謂光學構件,係觸控面板或圖像顯示裝置等光學製品中之各構成構件。作為觸控面板之構成構件,例如可列舉:於透明樹脂膜上設置有ITO膜之ITO膜(film)、於玻璃板之表面設置有ITO膜之ITO玻璃、於透明樹脂膜上塗佈有導電性聚合物之透明導電性膜、硬塗膜、耐指紋性膜等。作為圖像顯示裝置之構成構件,例如可列舉:用於液晶顯示裝置之抗反射膜、配向膜、偏光膜、相位差膜、增亮膜等。 The optical member is a constituent member of an optical product such as a touch panel or an image display device. Examples of the constituent members of the touch panel include an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on a surface of the glass plate, and a conductive film coated on the transparent resin film. A transparent conductive film, a hard coat film, a fingerprint-resistant film, or the like of a polymer. Examples of the constituent members of the image display device include an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used in the liquid crystal display device.

作為該等構件所使用之材料,可列舉:玻璃、聚碳酸酯,聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯、環烯烴聚合物,三乙醯纖維素,聚醯亞胺、醯化纖維素等。 Examples of the materials used for the members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, and triethyl hydrazine. Cellulose, polyimine, cellulose, etc.

作為藉由本發明之黏著片材1而貼合之一對光學構件,可列舉:觸控面板之內部之ITO膜彼此之貼合、ITO膜與ITO玻璃之貼合、觸控面板之ITO膜與液晶面板之貼合、覆蓋玻璃與ITO膜之貼合、覆蓋玻璃與加飾膜之貼合等。 As an optical member to be bonded to the adhesive sheet 1 of the present invention, the ITO film inside the touch panel is bonded to each other, the ITO film is bonded to the ITO glass, and the ITO film of the touch panel is The bonding of the liquid crystal panel, the bonding of the cover glass and the ITO film, the bonding of the cover glass and the decorative film, and the like.

於本發明之黏著片材為雙面黏著片材之情形時,可用於2個被黏著體之貼合。例如經由黏著片材貼合一對被黏著體,並於該狀態下照射活性能量線使黏著劑層(X)完全硬化,藉此可製成一對被黏著體經由雙面黏著片材積層而成之積層體。 When the adhesive sheet of the present invention is a double-sided adhesive sheet, it can be used for bonding two adhesive bodies. For example, a pair of adherends are bonded via an adhesive sheet, and the active energy rays are irradiated in this state to completely cure the adhesive layer (X), whereby a pair of adherends can be laminated via a double-sided adhesive sheet. Into the layered body.

於該情形時,作為被黏著體,可較佳地使用光學構件。 In this case, as the adherend, an optical member can be preferably used.

作為藉由雙面黏著片材貼合一對光學構件之例,可列舉:觸控面板之內部之ITO膜彼此之貼合、ITO膜與ITO玻璃之貼合、觸控面板之ITO膜與液晶面板之貼合、覆蓋玻璃與ITO膜之貼合、覆蓋玻璃與加飾膜之貼合等。 An example in which a pair of optical members are bonded to each other by a double-sided adhesive sheet includes an ITO film adhered to each other inside the touch panel, an ITO film and an ITO glass, and an ITO film and a liquid crystal of the touch panel. The bonding of the panel, the bonding of the cover glass to the ITO film, the bonding of the cover glass and the decorative film, and the like.

(作用效果) (Effect)

上述實施形態中之黏著片材1具有貼合前為柔軟之半硬化狀態之 黏著劑層11。藉由於該狀態下貼合至設置有印刷階差23之加飾膜22或ITO玻璃基板24上,而容易確保對印刷階差23之凹凸追隨性。繼而,藉由利用活性能量線之照射使黏著劑層11完全硬化,可提高黏著力及保持力,防止加飾膜22之變形或應變。 The adhesive sheet 1 in the above embodiment has a semi-hardened state before being bonded. Adhesive layer 11. By adhering to the decorative film 22 or the ITO glass substrate 24 provided with the printing step 23 in this state, it is easy to ensure the unevenness of the printing step 23. Then, the adhesive layer 11 is completely cured by irradiation with the active energy ray, whereby the adhesion and the holding force can be improved, and the deformation or strain of the decorative film 22 can be prevented.

進而,僅使用本發明之黏著片材1進行貼合即可確保凹凸追隨性,並且防止加飾膜22之變形、應變,因此步驟得以簡化,成本變低,經濟上亦有用。 Further, by merely bonding the adhesive sheet 1 of the present invention, it is possible to ensure unevenness and followability, and to prevent deformation and strain of the decorative film 22, so that the steps are simplified, the cost is lowered, and it is economically useful.

再者,本發明並不限定於上述實施形態。 Furthermore, the present invention is not limited to the above embodiment.

[實施例] [Examples]

以下列舉實施例與比較例進一步具體地說明本發明之特徵。以下之實施例所示之材料、使用量、比率、處理內容、處理順序等只要不脫離本發明之主旨,則可適當變更。因此,本發明之範圍不應藉由如下所示之具體例而限定性地加以解釋。 The features of the present invention will be further specifically described below by way of examples and comparative examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention should not be construed as being limited by the specific examples shown below.

單體(B)之蒸氣壓、溶劑(E)之蒸氣壓及表面張力均為25℃下之值。 The vapor pressure of the monomer (B), the vapor pressure of the solvent (E), and the surface tension were both values at 25 °C.

(實施例1之黏著片材製作方法) (Method for Producing Adhesive Sheet of Example 1)

交聯性丙烯酸系樹脂係藉由於乙酸乙酯中之溶液聚合而製作。將丙烯酸2-羥基乙酯單體及丙烯酸正丁酯單體以質量比計達到1:3之方式進行調配,將作為自由基聚合起始劑之AIBN(azobisisobutyronitrile,偶氮雙異丁腈)溶解於溶液中。將溶液加熱至60℃而進行無規共聚,獲得丙烯酸酯共聚物。該共聚物之35%溶液於23℃下之溶液黏度為5500mPa‧s。 The crosslinkable acrylic resin is produced by solution polymerization in ethyl acetate. The 2-hydroxyethyl acrylate monomer and the n-butyl acrylate monomer are blended in a mass ratio of 1:3, and the AIBN (azobisisobutyronitrile, azobisisobutyronitrile) as a radical polymerization initiator is dissolved. In solution. The solution was heated to 60 ° C to carry out random copolymerization to obtain an acrylate copolymer. The solution of the 35% solution of the copolymer at 23 ° C had a solution viscosity of 5500 mPa ‧ s.

相對於交聯性丙烯酸系樹脂100質量份,添加作為單體(B)中之單官能單體(B1)之丙烯酸異硬脂酯(大阪有機化學工業股份有限公司製造,ISTA,蒸氣壓:0Pa,熔點:<-50℃)20質量份、作為單體(B)中之多官能單體(B2)之三羥甲基丙烷環氧乙烷改性三丙烯酸酯(東亞合 成股份有限公司製造,Aronix M-360(EOTMPTA,Ethyloxylated trimethylopropane triacrylate))4質量份、作為交聯劑(C)之甲苯二異氰酸酯系化合物(Nippon Polyurethane Industry股份有限公司製造,Coronate L)0.15質量份、作為聚合起始劑(D)之1-羥基-環己基-苯基-酮(BASF Japan股份有限公司,IRGACURE184)1.12質量份,以濃度成為30質量%之方式添加作為溶劑(E)之乙酸乙酯(蒸氣壓:15×103Pa,表面張力23.8mN/m)。由此獲得黏著劑溶液。 Addition of isostearyl acrylate as a monofunctional monomer (B1) in the monomer (B) to 100 parts by mass of the crosslinkable acrylic resin (manufactured by Osaka Organic Chemical Industry Co., Ltd., ISTA, vapor pressure: 0 Pa) , melting point: <-50 ° C) 20 parts by mass of trimethylolpropane ethylene oxide modified triacrylate as a polyfunctional monomer (B2) in the monomer (B) (manufactured by Toagosei Co., Ltd., 4 parts by mass of a toluene diisocyanate compound (Nippon Polyurethane Industry Co., Ltd., Coronate L) as a crosslinking agent (C), which is a polymerization initiator, in an amount of 4 parts by mass, as a cross-linking agent (C), Eronyl M-360 (EOTMPTA, Ethyloxylated trimethylopropane triacrylate) (D) 1-hydroxy-cyclohexyl-phenyl-ketone (BASF Japan Co., Ltd., IRGACURE 184) 1.12 parts by mass, and ethyl acetate as a solvent (E) was added so as to have a concentration of 30% by mass (vapor pressure: 15 × 10 3 Pa, surface tension 23.8 mN / m). Thus, an adhesive solution was obtained.

使用Yoshimitsu Seiki股份有限公司製造之Doctor Blade YD型將上述黏著劑溶液以乾燥後之厚度成為150μm之方式塗佈於第1剝離片材(Teijin Dupont Films股份有限公司製造之經脫模處理之聚對苯二甲酸乙二酯膜)上。其後,利用熱風乾燥機於100℃下乾燥3分鐘而除去溶劑,獲得半硬化狀態之黏著劑層。 The above-mentioned adhesive solution was applied to the first release sheet by a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd., and the thickness of the adhesive solution was 150 μm after drying (a pair of release-treated polyethylene manufactured by Teijin Dupont Films Co., Ltd.) On the ethylene phthalate film). Thereafter, the solvent was removed by drying at 100 ° C for 3 minutes using a hot air dryer to obtain an adhesive layer in a semi-hardened state.

於該黏著劑層之單面上貼合剝離性高於第1剝離片材之經脫模處理之第2剝離片材(Teijin Dupont Films股份有限公司製造),獲得附剝離片材之黏著片材。 A second release sheet (manufactured by Teijin Dupont Films Co., Ltd.) having a release property higher than that of the first release sheet is bonded to one surface of the pressure-sensitive adhesive layer to obtain an adhesive sheet with a release sheet. .

使用所得之黏著片材,以黏著劑層朝向印刷階差側之方式貼合具有40μm之印刷階差之厚度100μm的PET膜與厚度0.5μm之鈉玻璃,實施高壓釜處理(40℃、0.5MPa、30分鐘)後,利用紫外線照射器(Eye Graphic公司製造,ECS-301G1)照射累積光量1000mJ/cm2而獲得積層體。 Using the obtained adhesive sheet, a PET film having a thickness of 100 μm and a soda glass having a thickness of 0.5 μm were attached to the side of the printing step with the adhesive layer facing the printing step side, and autoclaving treatment was carried out (40 ° C, 0.5 MPa). After 30 minutes, a laminated body was obtained by irradiating a cumulative amount of light of 1000 mJ/cm 2 with an ultraviolet ray irradiator (ECS-301G1, manufactured by Eye Graphic Co., Ltd.).

(實施例2) (Example 2)

單體(B)中,不添加單官能單體(B1),將作為多官能單體(B2)之三羥甲基丙烷環氧乙烷改性三丙烯酸酯設為10質量份,將聚合起始劑(D)設為1.1質量份,除此以外,以與實施例1相同之方式獲得黏著片材及積層體。 In the monomer (B), the monofunctional monomer (B1) is not added, and the trimethylolpropane ethylene oxide-modified triacrylate as the polyfunctional monomer (B2) is 10 parts by mass, and the polymerization is started. An adhesive sheet and a laminate were obtained in the same manner as in Example 1 except that the amount of the initiator (D) was 1.1 parts by mass.

(實施例3) (Example 3)

單體(B)中,不添加單官能單體(B1),將作為多官能單體(B2)之三羥甲基丙烷環氧乙烷改性三丙烯酸酯設為30質量份,將聚合起始劑(D)設為1.3質量份,除此以外,以與實施例1相同之方式獲得黏著片材及積層體。 In the monomer (B), the monofunctional monomer (B1) is not added, and the trimethylolpropane ethylene oxide-modified triacrylate as the polyfunctional monomer (B2) is 30 parts by mass, and the polymerization is started. An adhesive sheet and a laminate were obtained in the same manner as in Example 1 except that the amount of the initiator (D) was 1.3 parts by mass.

(比較例1) (Comparative Example 1)

除了不添加單體(B)與聚合起始劑(D)以外,以與實施例1相同之方式獲得黏著片材。又,除了不實施紫外線照射以外,以與實施例1相同之方式獲得積層體。 An adhesive sheet was obtained in the same manner as in Example 1 except that the monomer (B) and the polymerization initiator (D) were not added. Further, a laminate was obtained in the same manner as in Example 1 except that ultraviolet irradiation was not carried out.

(比較例2) (Comparative Example 2)

不添加單體(B)與聚合起始劑(D),將作為塑化劑之ARUFON UP-1000(東亞合成)設為100質量份,將交聯劑(C)設為0.19質量份,除此以外,以與實施例1相同之方式獲得黏著片材。又,除了不實施紫外線照射以外,以與實施例1相同之方式獲得積層體。 The monomer (B) and the polymerization initiator (D) were not added, and ARUFON UP-1000 (East Asia Synthesis) as a plasticizer was set to 100 parts by mass, and the crosslinking agent (C) was set to 0.19 parts by mass. Otherwise, an adhesive sheet was obtained in the same manner as in Example 1. Further, a laminate was obtained in the same manner as in Example 1 except that ultraviolet irradiation was not carried out.

[評價方法] [Evaluation method]

(評價1:黏著力) (Evaluation 1: Adhesion)

關於實施例及比較例所獲得之黏著片材,依照JIS Z0237測定對鈉玻璃之180°剝離黏著力(UV照射前對玻璃之黏著力)。 With respect to the adhesive sheets obtained in the examples and the comparative examples, the 180° peeling adhesion to soda glass (adhesion to glass before UV irradiation) was measured in accordance with JIS Z0237.

進而,將實施例及比較例所獲得之黏著帶之單面貼合於厚度100μm之光學PET膜上,繼而貼合於厚度1mm之鈉玻璃上。進而實施高壓釜處理(40℃、0.5MPa、30分鐘)後,利用紫外線照射器(Eye Graphic公司製造,ECS-301G1)照射累積光量1000mJ/cm2而獲得積層體。關於積層體,依照JIS Z0237測定對鈉玻璃之180°剝離黏著力(UV照射後對玻璃之黏著力)。 Further, the single faces of the adhesive tapes obtained in the examples and the comparative examples were bonded to an optical PET film having a thickness of 100 μm, and then bonded to a soda glass having a thickness of 1 mm. After the autoclave treatment (40° C., 0.5 MPa, and 30 minutes), the cumulative amount of light was 1000 mJ/cm 2 by an ultraviolet ray irradiator (ECS-301G1 manufactured by Eye Graphic Co., Ltd.) to obtain a laminate. Regarding the laminate, the 180° peel adhesion to soda glass (adhesion to glass after UV irradiation) was measured in accordance with JIS Z0237.

(評價2:霧度(haze)) (Evaluation 2: haze)

依照JIS K7136對實施例及比較例所獲得之黏著片材測定霧度(haze)。 The haze of the adhesive sheets obtained in the examples and the comparative examples was measured in accordance with JIS K7136.

試片係藉由以下方法而製作。將所獲得之雙面黏著帶之單面貼合於厚度100μm之光學PET膜上,繼而貼合於厚度1mm之鈉玻璃上。進而實施高壓釜處理(40℃、0.5MPa、30分鐘)後,利用紫外線照射器(Eye Graphic公司製造,ECS-301G1)照射累積光量1000mJ/cm2而獲得試片。 The test piece was produced by the following method. One side of the obtained double-sided adhesive tape was attached to an optical PET film having a thickness of 100 μm, and then attached to a soda glass having a thickness of 1 mm. After the autoclave treatment (40° C., 0.5 MPa, and 30 minutes), the test piece was obtained by irradiating a cumulative light amount of 1000 mJ/cm 2 with an ultraviolet ray irradiator (ECS-301G1 manufactured by Eye Graphic Co., Ltd.).

將霧度(haze)為10%以上者設為不合格,將未達10%者設為合格。藉由該方法,可判斷可否用於液晶顯示器(LCD)等顯示裝置、或觸控面板等與上述顯示裝置組合使用之輸入裝置等中。 If the haze is 10% or more, it is set as a failure, and if it is less than 10%, it is set as a pass. According to this method, it is possible to determine whether or not it can be used in a display device such as a liquid crystal display (LCD) or an input device or the like which is used in combination with the display device, such as a touch panel.

(評價3:凹凸追隨性) (Evaluation 3: bump followability)

以使實施例及比較例所獲得之黏著片材與印刷階差片材之印刷面密接之方式貼合,繼而以與PET膜(厚度100μm)密接之方式貼合,於溫度40℃、壓力0.5MPa下利用高壓釜進行30分鐘之加壓脫法處理,製作PET/黏著片材/印刷階差片材之積層體。利用顯微鏡觀察積層體之印刷階差部,按照以下之基準評價凹凸追隨性。 The adhesive sheet obtained in the examples and the comparative examples was bonded to the printing surface of the printing step sheet, and then adhered to the PET film (thickness: 100 μm) in a manner of a temperature of 40 ° C and a pressure of 0.5. The pressure-release treatment was carried out for 30 minutes in an autoclave at MPa to prepare a laminate of a PET/adhesive sheet/printing step sheet. The printed step portion of the laminate was observed with a microscope, and the bump followability was evaluated according to the following criteria.

◎:完全無氣泡 ◎: completely no bubbles

○:存在數個微小之氣泡 ○: There are several tiny bubbles

Δ:存在氣泡 Δ: there is a bubble

×:存在大量氣泡 ×: There are a lot of bubbles

(評價4:凹凸追隨耐久性) (Evaluation 4: Bump following durability)

將積層體於80℃之環境下靜置24小時,利用顯微鏡觀察有否產生氣泡或剝離,按照以下之基準進行評價。 The laminate was allowed to stand in an environment of 80 ° C for 24 hours, and it was observed by a microscope whether or not bubbles were formed or peeled off, and the evaluation was carried out in accordance with the following criteria.

◎:完全無氣泡 ◎: completely no bubbles

○:存在數個微小之氣泡 ○: There are several tiny bubbles

Δ:存在氣泡 Δ: there is a bubble

×:存在大量氣泡 ×: There are a lot of bubbles

(評價5:膜之變形) (Evaluation 5: Deformation of the film)

‧評價方法 ‧ Evaluation method

自PET膜側觀察PET/黏著片材/印刷階差片材之積層體中印刷階差部與無印刷部分是否有應變,按照以下之基準進行評價。 When there was strain in the printed step portion and the non-printed portion in the laminate of the PET/adhesive sheet/printed step sheet from the PET film side, the evaluation was performed according to the following criteria.

○:完全無應變、變形 ○: Completely unstrained and deformed

Δ:存在若干應變、變形。 Δ: There are several strains and deformations.

×:存在較大之應變、變形 ×: There is a large strain and deformation

如上述結果所示,可知於實施例1~3中,UV照射後之黏著力與照射前之黏著力相比有所提高,藉由UV照射而形成完全硬化狀態之接著劑層。又,UV照射後之黏著力充分高。進而,於實施例1~3中,凹凸追隨性與凹凸追隨耐久性較高,膜中未觀察到應變等變形。 As shown in the above results, in Examples 1 to 3, it was found that the adhesion force after the UV irradiation was improved as compared with the adhesion force before the irradiation, and the adhesive layer in the completely cured state was formed by UV irradiation. Moreover, the adhesion after UV irradiation is sufficiently high. Further, in Examples 1 to 3, the unevenness followability and the unevenness followability were high, and no deformation such as strain was observed in the film.

另一方面,於比較例1中,由於未含有單體(B)與聚合起始劑(D),因此黏著劑層完全硬化,凹凸追隨性與凹凸追隨耐久性顯著惡化。又,膜中產生較大之應變。於比較例2中,由於雖然未含有單體 (B)與聚合起始劑(D),但含有塑化劑,因此雖然獲得凹凸追隨性,但凹凸追隨耐久性顯著惡化。又,黏著力亦降低。 On the other hand, in the comparative example 1, since the monomer (B) and the polymerization initiator (D) were not contained, the adhesive layer was completely cured, and the unevenness followability and the unevenness following durability were remarkably deteriorated. Also, a large strain is generated in the film. In Comparative Example 2, although there is no monomer (B) and the polymerization initiator (D), but containing a plasticizer, the unevenness followability is remarkably deteriorated although the unevenness followability is obtained. Also, the adhesion is also reduced.

(實施例4-1) (Example 4-1)

相對於實施例1之基礎聚合物(A)100質量份,添加作為單體(B)中之單官能單體(B1)之丙烯酸異基酯(共榮社化學股份有限公司製造,Light Acrylate IB-XA)50質量份、作為單體(B)中之多官能單體(B2)之三羥甲基丙烷環氧乙烷改性三丙烯酸酯(東亞合成股份有限公司製造,Aronix M-360,蒸氣壓:0Pa,熔點:<15℃)30質量份、作為交聯劑(C)之甲苯二異氰酸酯系化合物(Nippon Polyurethane Industry股份有限公司製造,Coronate L)0.1質量份、作為聚合起始劑(D)之1-羥基-環己基-苯基-酮(BASF Japan股份有限公司製造,IRGACURE184)2質量份,以濃度成為40質量%之方式添加作為溶劑(E)之乙酸乙酯,獲得黏著劑溶液。 The acrylic acid as the monofunctional monomer (B1) in the monomer (B) is added with respect to 100 parts by mass of the base polymer (A) of Example 1. 50 parts by mass of a base ester (Light Acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd.), trimethylolpropane ethylene oxide modified as a polyfunctional monomer (B2) in the monomer (B) Acrylate (Aronix M-360, vapor pressure: 0 Pa, melting point: <15 ° C) 30 parts by mass, toluene diisocyanate compound as a crosslinking agent (C) (Nippon Polyurethane Industry Co., Ltd.) Produced, Coronate L) 2 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Co., Ltd., IRGACURE 184) as a polymerization initiator (D), and the concentration was 40% by mass. Ethyl acetate as a solvent (E) was added in a manner to obtain an adhesive solution.

使用Yoshimitsu Seiki股份有限公司製造之Doctor Blade YD型將上述黏著劑溶液以乾燥後之厚度達到50μm之方式塗佈於第1剝離片材(Teijin Dupont Films股份有限公司製造之經脫模處理之聚對苯二甲酸乙二酯膜)上。其後,利用熱風乾燥機於100℃下乾燥3分鐘或6分鐘而除去溶劑,獲得半硬化狀態之黏著劑層。 The above-mentioned adhesive solution was applied to the first release sheet by a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. to a thickness of 50 μm after drying (a pair of release-treated polyethylene manufactured by Teijin Dupont Films Co., Ltd.) On the ethylene phthalate film). Thereafter, the solvent was removed by drying at 100 ° C for 3 minutes or 6 minutes using a hot air dryer to obtain an adhesive layer in a semi-hardened state.

於該黏著劑層上貼合對聚對苯二甲酸乙二酯膜之單面實施剝離性高於第1剝離片材之脫模處理之第2剝離片材(Teijin Dupont Films股份有限公司製造),獲得黏著片材。 A second release sheet (available from Teijin Dupont Films Co., Ltd.) having a release property higher than that of the first release sheet on one side of the polyethylene terephthalate film is bonded to the adhesive layer. , get the adhesive sheet.

(實施例4-2) (Example 4-2)

將單體(B)中之單官能單體(B1)設為丙烯酸己酯(東京化成工業股份有限公司製造),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1 except that the monofunctional monomer (B1) in the monomer (B) was hexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

(實施例4-3) (Example 4-3)

將單體(B)中之單官能單體(B1)設為丙烯酸異辛酯(Sigma-Aldrich Japan股份有限公司製造),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1 except that the monofunctional monomer (B1) in the monomer (B) was changed to isooctyl acrylate (manufactured by Sigma-Aldrich Japan Co., Ltd.). .

(實施例4-4) (Example 4-4)

將單體(B)中之單官能單體(B1)設為丙烯酸異癸酯(Sartomer Japan股份有限公司製造,SR395),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1 except that the monofunctional monomer (B1) in the monomer (B) was isodecyl acrylate (SR395, manufactured by Sartomer Japan Co., Ltd.). .

(實施例4-5) (Example 4-5)

將單體(B)中之單官能單體(B1)設為丙烯酸月桂酯(Sartomer Japan股份有限公司製造,SR335),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1 except that the monofunctional monomer (B1) in the monomer (B) was made into lauryl acrylate (SR335, manufactured by Sartomer Japan Co., Ltd.).

(實施例4-6) (Examples 4-6)

將溶劑(E)設為丙酮,除此以外,以與實施例4-3相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-3 except that the solvent (E) was changed to acetone.

[實施例4-7] [Examples 4-7]

將溶劑(E)設為甲苯,除此以外,以與實施例4-3相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-3 except that the solvent (E) was changed to toluene.

(實施例4-8) (Examples 4-8)

將溶劑(E)設為環己酮,除此以外,以與實施例4-3相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-3 except that the solvent (E) was changed to cyclohexanone.

(實施例4-9) (Examples 4-9)

將單體(B)中之單官能單體(B1)設為丙烯酸硬脂酯(和光純藥工業股份有限公司製造),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1 except that the monofunctional monomer (B1) in the monomer (B) was stearyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.). .

(實施例4-10) (Examples 4-10)

將單體(B)中之單官能單體(B1)設為丙烯酸乙酯(東京化成工業股 份有限公司製造),除此以外,以與實施例4-1相同之方式獲得黏著片材。 The monofunctional monomer (B1) in the monomer (B) is used as ethyl acrylate (Tokyo Chemical Industry Co., Ltd.) An adhesive sheet was obtained in the same manner as in Example 4-1 except for the production of Co., Ltd.).

(實施例4-11) (Examples 4-11)

將單體(B)中之單官能單體(B1)設為丙烯酸丁酯(東京化成工業股份有限公司製造),除此以外,以與實施例4-1相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-1, except that the monofunctional monomer (B1) in the monomer (B) was butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

(實施例4-12) (Examples 4-12)

將溶劑(E)設為己烷,除此以外,以與實施例4-3相同之方式獲得黏著片材。 An adhesive sheet was obtained in the same manner as in Example 4-3 except that the solvent (E) was changed to hexane.

將上述之各例所使用之單體(B)中之單官能單體(B1)之蒸氣壓及熔點、溶劑(E)之蒸氣壓及表面張力示於表2。 Table 2 shows the vapor pressure and melting point of the monofunctional monomer (B1) in the monomer (B) used in each of the above examples, and the vapor pressure and surface tension of the solvent (E).

又,對於所得之黏著片材進行以下之評價。將結果示於表3。 Further, the obtained adhesive sheet was subjected to the following evaluation. The results are shown in Table 3.

[評價方法] [Evaluation method]

(評價1:塗佈面之平滑性) (Evaluation 1: Smoothness of coated surface)

以目視觀察貼合第2剝離片材前之半硬化狀態之黏著劑層之表面(塗佈面)之平滑性。將可獲得無橘皮(Orange Peel)或貝納德穴流(Benard Cell)等塗佈缺陷且平滑之塗佈面之水準設為合格。若將不合格品用於顯示器,則會產生圖像產生應變等不良情況。 The smoothness of the surface (coated surface) of the adhesive layer in the semi-hardened state before the second release sheet was bonded was visually observed. The level of the coated surface which is free of coating defects such as Orange Peel or Benard Cell and which is smooth can be obtained. If a defective product is used for the display, problems such as strain on the image may occur.

(評價2:黏著力) (Evaluation 2: Adhesion)

關於所得之黏著片材(塗劑之乾燥時間為3分鐘者與6分鐘者),依照JIS Z0237測定對鈉玻璃之180°剝離黏著力(對玻璃之黏著力)。 Regarding the obtained adhesive sheet (the drying time of the coating agent was 3 minutes and 6 minutes), the 180° peeling adhesion to the soda glass (adhesion to glass) was measured in accordance with JIS Z0237.

試片係以與實施例1相同之方法製作。 The test piece was produced in the same manner as in Example 1.

算出塗劑之乾燥時間為3分鐘之情形時與6分鐘之情形時之對玻璃之黏著力的差量及該等之平均值,求出差量相對於平均值之比率(%)。將該黏著力之差<差量/平均值>為50%以上者設為不合格,將未達50%者設為合格。藉由該方法,可判斷作為重要性能之一之黏著力是否根據季節因素等微妙之乾燥條件之不同而大幅變化並易對製造良率造成影響。 The ratio (%) of the difference to the average value was calculated by calculating the difference between the adhesion to the glass and the average value of the adhesion to the glass at the time of 6 minutes when the drying time of the coating agent was 3 minutes. When the difference of the adhesion force <difference/average value> is 50% or more, it is considered as a failure, and if it is less than 50%, it is regarded as a pass. By this method, it can be judged whether or not the adhesion as one of the important properties largely changes depending on the subtle drying conditions such as seasonal factors and is easy to affect the manufacturing yield.

(評價3:霧度(haze)) (Evaluation 3: haze)

依照JIS K7136,與實施例1同樣地對所得之黏著片材測定霧度(haze)。將霧度(haze)為10%以上者設為不合格,將未達10%者設為合格。 The obtained adhesive sheet was measured for haze in the same manner as in Example 1 in accordance with JIS K7136. If the haze is 10% or more, it is set as a failure, and if it is less than 10%, it is set as a pass.

如上述結果所示,於實施例4-1~4-9中,形成平滑之塗佈面。又,乾燥條件之不同對黏著力造成之影響較小。其中,單體(B)之熔點為25℃以下之實施例4-1~4-8之黏著片材之霧度亦良好。 As shown by the above results, in Examples 4-1 to 4-9, a smooth coated surface was formed. Moreover, the difference in drying conditions has less effect on the adhesion. Among them, the haze of the adhesive sheets of Examples 4-1 to 4-8 in which the melting point of the monomer (B) was 25 ° C or less was also good.

另一方面,使用蒸氣壓較低之單官能單體之實施例4-1~4-9形成相對平滑之塗佈面,又,由乾燥條件之不同引起之黏著力之變動亦較小。 On the other hand, Examples 4-1 to 4-9 using a monofunctional monomer having a low vapor pressure form a relatively smooth coated surface, and the change in adhesion caused by the difference in drying conditions is also small.

與使用表面張力未達20mmN/m之溶劑(E)之實施例4-12相比,其他實施例可形成更平滑之塗佈面。 Other embodiments may result in a smoother coated surface than Examples 4-12 using a solvent (E) having a surface tension of less than 20 mm N/m.

又,實施例4-1~4-12之凹凸追隨性能與膜變形防止性能均良好。 Further, the unevenness following performance and the film deformation preventing performance of Examples 4-1 to 4-12 were good.

(實施例5-1~5-7) (Examples 5-1 to 5-7)

相對於實施例1之基礎聚合物(A)100質量份,添加作為單體(B)中之單官能單體(B1)之丙烯酸異硬脂酯(大阪有機化學股份有限公司製造,ISTA)20質量份、作為單體(B)中之多官能單體(B2)之三羥甲基丙烷三丙烯酸酯(東亞合成股份有限公司製造,Aronix M-321)4質量份、 交聯劑(C)(Nippon Polyurethane Industry股份有限公司製造,Coronate L-55E)0.15質量份、作為聚合起始劑(D)之1-羥基-環己基-苯基-酮(BASF Japan股份有限公司製造,IRGACURE184)0.62質量份,添加矽烷偶合劑(綜研化學股份有限公司製造,C-50)0.15質量份、抗腐蝕劑(綜研化學股份有限公司製造,M)0.0025質量份,進而以濃度達到33質量%之方式添加作為溶劑(E)之乙酸乙酯,獲得黏著劑溶液。 Addition of isostearyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., ISTA) 20 as a monofunctional monomer (B1) in the monomer (B) with respect to 100 parts by mass of the base polymer (A) of Example 1. 4 parts by mass of trimethylolpropane triacrylate (Aronix M-321, manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer (B2) in the monomer (B), Crosslinking agent (C) (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L-55E) 0.15 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone as polymerization initiator (D) (BASF Japan Co., Ltd.) Manufactured, IRGACURE 184) 0.62 parts by mass, 0.15 parts by mass of a decane coupling agent (manufactured by Synthetic Chemical Co., Ltd., C-50), 0.0025 parts by mass of an anticorrosive agent (manufactured by Synthetic Chemical Co., Ltd., M), and then a concentration of 33 parts by mass Ethyl acetate as a solvent (E) was added in a manner of % to obtain an adhesive solution.

使用Yoshimitsu Seiki股份有限公司製造之Doctor Blade YD型將上述黏著劑溶液以乾燥後之厚度達到50μm之方式塗佈於第1剝離片材(Teijin Dupont Films股份有限公司製造之經脫模處理之聚對苯二甲酸乙二酯膜)上。其後,利用熱風乾燥機於100℃下乾燥3分鐘或6分鐘而除去溶劑,獲得半硬化狀態之黏著劑層。 The above-mentioned adhesive solution was applied to the first release sheet by a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. to a thickness of 50 μm after drying (a pair of release-treated polyethylene manufactured by Teijin Dupont Films Co., Ltd.) On the ethylene phthalate film). Thereafter, the solvent was removed by drying at 100 ° C for 3 minutes or 6 minutes using a hot air dryer to obtain an adhesive layer in a semi-hardened state.

於該黏著劑層上貼合對聚對苯二甲酸乙二酯膜之單面實施剝離性高於第1剝離片材之脫模處理之第2剝離片材(Teijin Dupont Films股份有限公司製造),獲得黏著片材。 A second release sheet (available from Teijin Dupont Films Co., Ltd.) having a release property higher than that of the first release sheet on one side of the polyethylene terephthalate film is bonded to the adhesive layer. , get the adhesive sheet.

依照JIS Z0237,對所得之黏著片材進行保持力測定。具體而言,按照以下順序測定保持力。 The obtained adhesive sheet was subjected to retention force measurement in accordance with JIS Z0237. Specifically, the holding power was measured in the following order.

準備25mm×25mm尺寸之黏著片材,將第2剝離片材剝離,將露出之黏著面貼合於PET膜(東洋紡(股)A4300#100)上而製作試片。繼而,將第1剝離片材剝離,將露出之黏著面貼附於SUS板(JIS G 4305、SUS304)上,利用1kg輥進行壓接。其後,利用紫外線照射器(Eye Graphic公司製造,ECS-301G1)以累積光量達到1000mJ/cm2之方式照射紫外線。繼而,以夾片固持試片之一端,使試片垂直垂下,於其下端施加1kg之荷重,置於40℃、相對濕度0~30%之環境下。計測自施加荷重起至試片自SUS板落下為止之時間,對保持力進行評價。將結果示於表4。 An adhesive sheet having a size of 25 mm × 25 mm was prepared, and the second release sheet was peeled off, and the exposed adhesive surface was bonded to a PET film (Toyobo A4300 #100) to prepare a test piece. Then, the first release sheet was peeled off, and the exposed adhesive surface was attached to a SUS plate (JIS G 4305, SUS304), and pressure-bonded by a 1 kg roller. Thereafter, ultraviolet rays were irradiated so as to have a cumulative light amount of 1000 mJ/cm 2 by an ultraviolet ray irradiator (ECS-301G1, manufactured by Eye Graphic Co., Ltd.). Then, one end of the test piece was held by a clip, and the test piece was vertically suspended, and a load of 1 kg was applied to the lower end thereof, and placed in an environment of 40 ° C and a relative humidity of 0 to 30%. The holding force was evaluated from the time when the load was applied until the time when the test piece fell from the SUS plate. The results are shown in Table 4.

如上述結果所示,於實施例5-1、5-2、5-4、5-5、5-7中,保持力更加優異。根據該情況,確認於使用具有鏈長原子數為10以上之烷基之單體(B)、或具有多環結構之單體(B)時,可獲得更加優異之保持力。其中,於使用丙烯酸異硬脂酯作為單體(B)時,可獲得尤其優異之保持力。 As shown in the above results, in Examples 5-1, 5-2, 5-4, 5-5, and 5-7, the holding power was further improved. In this case, it was confirmed that when a monomer (B) having an alkyl group having a chain length of 10 or more or a monomer (B) having a polycyclic structure is used, a more excellent holding power can be obtained. Among them, when isostearyl acrylate is used as the monomer (B), particularly excellent holding power can be obtained.

實施例5-1~5-7之凹凸追隨性能與膜變形防止性能均良好。 The unevenness following performance and the film deformation preventing performance of Examples 5-1 to 5-7 were both good.

藉由上述之全部實施例,紫外線照射後之完全硬化狀態之接著劑層之動態黏彈性均處於照射前之半硬化狀態之動態黏彈性的2~100倍之範圍內。 According to all of the above embodiments, the dynamic viscoelasticity of the adhesive layer in the fully cured state after the ultraviolet irradiation is in the range of 2 to 100 times the dynamic viscoelasticity of the semi-hardened state before the irradiation.

[產業上之可利用性] [Industrial availability]

本發明之黏著片材由於具有凹凸追隨性能與膜變形防止性能,故而對於至少一者為膜之一對光學構件彼此之貼合、例如觸控面板模組之製造而言有用。 Since the adhesive sheet of the present invention has unevenness following performance and film deformation preventing performance, it is useful for at least one of the films to be bonded to each other, for example, a touch panel module.

Claims (13)

一種黏著片材,其含有包含藉由加熱使如下黏著組合物半硬化而成之黏著劑之黏著劑層(X),該黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其具有至少1個聚合性不飽和基;交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E);上述單體(B)含有具有1個聚合性不飽和基之單官能單體(B1)、及具有2個以上聚合性不飽和基之多官能單體(B2),上述單官能單體(B1)進而具有鏈長原子數為10以上之烷基及多環結構中之至少一者;且上述黏著劑層(X)之楊氏模數為0.01~0.30N/mm2An adhesive sheet comprising an adhesive layer (X) comprising an adhesive obtained by semi-hardening an adhesive composition comprising: a base polymer (A) containing non-crosslinking properties a (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; a monomer (B) having at least one polymerizable unsaturated group; and a crosslinking agent (C) And reacting with the base polymer (A) by heat; a polymerization initiator (D) which starts the polymerization of the monomer (B) by irradiation with an active energy ray; and a solvent (E) The monomer (B) contains a monofunctional monomer (B1) having one polymerizable unsaturated group, and a polyfunctional monomer (B2) having two or more polymerizable unsaturated groups, and the above monofunctional monomer ( B1) Further, it has at least one of an alkyl group having a chain length of 10 or more and a polycyclic structure; and the Young's modulus of the above-mentioned adhesive layer (X) is 0.01 to 0.30 N/mm 2 . 如請求項1之黏著片材,其中上述單官能單體(B1)所具有之烷基之鏈長原子數為15~22。 The adhesive sheet of claim 1, wherein the monofunctional monomer (B1) has an alkyl group having a chain length of 15 to 22. 一種黏著片材,其含有包含加熱如下黏著組合物而成之黏著劑之黏著劑層(X),該黏著組合物含有:基礎聚合物(A),其含有非交聯性(甲基)丙烯酸酯單元(a1)及具有交聯性官能基之丙烯酸系單體單元(a2);單體(B),其含有具有1個聚合性不飽和基與鏈長原子數為15~22之烷基之單官能單體(B1)、及具有2個以上聚合性不飽和基之多官能單體(B2);交聯劑(C),其藉由熱而與上述基礎聚合物(A)反應;聚合起始劑(D),其藉由活性能量線之照射而使上述單體(B)之聚合反應開始;及溶劑(E)。 An adhesive sheet comprising an adhesive layer (X) comprising an adhesive obtained by heating an adhesive composition comprising: a base polymer (A) containing non-crosslinkable (meth)acrylic acid An ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group; and a monomer (B) containing an alkyl group having one polymerizable unsaturated group and having a chain length of 15 to 22 a monofunctional monomer (B1), and a polyfunctional monomer (B2) having two or more polymerizable unsaturated groups; and a crosslinking agent (C) which is reacted with the above base polymer (A) by heat; a polymerization initiator (D) which starts the polymerization of the above monomer (B) by irradiation with an active energy ray; and a solvent (E). 如請求項1至3中任一項之黏著片材,其中上述單官能單體(B1)為丙烯酸異硬脂酯。 The adhesive sheet according to any one of claims 1 to 3, wherein the monofunctional monomer (B1) is isostearyl acrylate. 如請求項1至3中任一項之黏著片材,其中上述單官能單體(B1)於25℃下之蒸氣壓為300Pa以下,上述溶劑(E)於25℃下之表面張力為20mN/m以上且未達40mN/m。 The adhesive sheet according to any one of claims 1 to 3, wherein the monofunctional monomer (B1) has a vapor pressure of 300 Pa or less at 25 ° C, and the surface tension of the solvent (E) at 25 ° C is 20 mN / m or more and less than 40 mN/m. 如請求項1至3中任一項之黏著片材,其中上述單體(B)含有熔點為25℃以下之具有1個聚合性不飽和基之單官能單體(B1)、及具有2個以上聚合性不飽和基之多官能單體(B2),上述單官能單體(B1)進而具有鏈長原子數為10以上之烷基及多環結構中之至少一者。 The adhesive sheet according to any one of claims 1 to 3, wherein the monomer (B) contains a monofunctional monomer (B1) having a melting point of 25 ° C or less and having one polymerizable unsaturated group, and has two In the above polyfunctional monomer (B2) which is a polymerizable unsaturated group, the monofunctional monomer (B1) further has at least one of an alkyl group having a chain length of 10 or more and a polycyclic structure. 如請求項1至3中任一項之黏著片材,其中上述單官能單體(B1)係具有雙環或三環之丙烯酸酯。 The adhesive sheet according to any one of claims 1 to 3, wherein the monofunctional monomer (B1) has a bicyclic or tricyclic acrylate. 如請求項1至3中任一項之黏著片材,其中上述溶劑(E)不具有聚合性不飽和基,且於25℃下之蒸氣壓大於上述單官能單體(B1)。 The adhesive sheet according to any one of claims 1 to 3, wherein the solvent (E) does not have a polymerizable unsaturated group, and the vapor pressure at 25 ° C is greater than the above monofunctional monomer (B1). 如請求項1至3中任一項之黏著片材,其中上述溶劑(E)包含與上述單體(B)之溶解性參數之差為2[(cal/cm3)1/2]以內之溶劑。 The adhesive sheet according to any one of claims 1 to 3, wherein the solvent (E) comprises a difference between the solubility parameter of the monomer (B) and the monomer (B) of 2 [(cal/cm 3 ) 1/2 ] Solvent. 如請求項1至3中任一項之黏著片材,其中於藉由壓接於SUS板上並照射活性能量線而硬化後依據JIS Z0237測得之保持力為360分鐘以上。 The adhesive sheet according to any one of claims 1 to 3, wherein the holding force measured according to JIS Z0237 is more than 360 minutes or more after being hardened by being pressed against a SUS plate and irradiated with an active energy ray. 如請求項1至3中任一項之黏著片材,其係雙面黏著片材。 The adhesive sheet according to any one of claims 1 to 3, which is a double-sided adhesive sheet. 一種積層體之製造方法,其包括:使如請求項1至11中任一項之黏著片材之黏著劑層(X)與被黏著體表面接觸,於該狀態下照射活性能量線而使上述黏著劑層(X)完全硬化。 A method for producing a laminate, comprising: contacting an adhesive layer (X) of an adhesive sheet according to any one of claims 1 to 11 with a surface of an adherend, and irradiating an active energy ray in the state to cause the above The adhesive layer (X) is completely hardened. 一種積層體,其係經由如請求項1至11中任一項之黏著片材而貼合一對光學構件,並於該狀態下照射活性能量線使上述黏著劑層(X)完全硬化而成。 A laminated body which is bonded to a pair of optical members via an adhesive sheet according to any one of claims 1 to 11, and irradiated with an active energy ray in this state to completely cure the adhesive layer (X). .
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