TW202104500A - Optical adhesive composition, and adhesive film, adhesive sheet using the same - Google Patents

Optical adhesive composition, and adhesive film, adhesive sheet using the same Download PDF

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TW202104500A
TW202104500A TW109113290A TW109113290A TW202104500A TW 202104500 A TW202104500 A TW 202104500A TW 109113290 A TW109113290 A TW 109113290A TW 109113290 A TW109113290 A TW 109113290A TW 202104500 A TW202104500 A TW 202104500A
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meth
adhesive
acrylate
group
adhesive layer
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TW109113290A
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TWI840551B (en
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長倉毅
鈴木史恵
塚田高士
大津賀健太郎
吉田弘幸
廣神萌美
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日商藤森工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/13338—Input devices, e.g. touch panels
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • C09J2451/00—Presence of graft polymer
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

An optical adhesive composition, adhesive film and adhesive sheet using the same are provided. The optical adhesive composition can form an adhesive layer excellent in step-conformability to a step (for example, frame printing of an adherend), handleability during rework, and moist heat durability. The optical adhesive composition includes: a copolymer obtained by copolymerizing at least two kinds selected from the compound group of a copolymerizable vinyl monomer and a nitrogen-containing vinyl monomer, wherein the copolymerizable vinyl monomer does not have a carboxyl group as a functional group, but has any of an alkyl group, a hydroxyl group, an alkoxy group, and an aromatic group as a functional group; (F) a (meth)acrylate monomer having a (meth)acryloyl group and an allyl ether group in one molecule, and having two or more ethylenically unsaturated groups; (G) a (meth)acrylate monomer having two or more ethylenically unsaturated groups in one molecule and having an alkylene oxide group; (E) a heat-crosslinking agent; and (H) a photo-crosslinking agent.

Description

光學用黏著劑組合物及使用了該光學用黏著劑組合物的黏著膜、黏著片Optical adhesive composition and adhesive film and adhesive sheet using the optical adhesive composition

本發明涉及一種光學用黏著劑組合物，以及使用了該光學用黏著劑組合物的黏著膜、黏著片。進一步詳細而言，涉及提供一種可形成兼具對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能(易於從被黏物上剝離)及優異的濕熱耐久性的黏著劑層的光學用黏著劑組合物。進一步，涉及提供使用了該光學用黏著劑組合物的黏著膜、黏著片。 此外，使用本發明的光學用黏著劑組合物，並利用熱交聯劑交聯而成的黏著劑層對設置於被黏物表面的框印刷等段差(凹凸)的段差追隨性、及再操作時的處理性能良好。並且，進一步，經基於該熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段而進行交聯後的黏著劑層的濕熱耐久性優異。 此外，本發明的光學用黏著劑組合物、以及使用了該光學用黏著劑組合物的黏著膜、黏著片能夠用於將光學膜貼合於各種顯示器的情況、將光學膜彼此貼合而製作光學膜的積層體的情況、及固定各種安裝於電子設備的光學部件・電子部件的情況等。 另外，在本發明中，黏著劑層的「濕熱耐久性」是指即使將黏著劑層長時間放置於濕熱環境下後，取出至室溫環境(溫度23℃×50%RH)下，也不會發生由水分導致的明顯起泡且可維持透明性的耐久性。The present invention relates to an optical adhesive composition, and an adhesive film and an adhesive sheet using the optical adhesive composition. In more detail, it relates to the provision of an adhesive that can be formed to have both step-following properties for the frame printing of the adherend, handling performance during re-operation (easy to peel from the adherend), and excellent moisture and heat durability. The optical adhesive composition of the layer. Furthermore, it relates to the provision of an adhesive film and an adhesive sheet using this optical adhesive composition. In addition, the optical adhesive composition of the present invention is used and the adhesive layer cross-linked with a thermal cross-linking agent is used to follow the level difference (concave and convex) of the frame printed on the surface of the adherend, and re-operation The processing performance at the time is good. Furthermore, the adhesive layer after crosslinking through the two stages of crosslinking with the thermal crosslinking agent and the subsequent crosslinking with the photocrosslinking agent has excellent wet heat durability. In addition, the optical adhesive composition of the present invention, and the adhesive film and the adhesive sheet using the optical adhesive composition can be used when bonding optical films to various displays, and can be produced by bonding optical films to each other. In the case of laminates of optical films, and in the case of fixing various optical components and electronic components mounted on electronic devices, etc. In addition, in the present invention, the "damp heat durability" of the adhesive layer means that even after the adhesive layer is left in a humid and hot environment for a long time, it will not be removed to a room temperature environment (temperature 23℃×50%RH). Obvious blistering caused by moisture occurs and the durability of transparency can be maintained.

近年來，結合了顯示器(圖像顯示裝置)與作為輸入裝置的觸控面板的電子設備不斷得到普及。作為應用觸控面板的顯示器(圖像顯示裝置)，可列舉出液晶顯示器(LCD)、電致發光顯示器(無機EL、有機EL)等。此外，作為利用觸控面板作為輸入裝置的具體的電子設備，可列舉出液晶電視、無機EL電視、有機EL電視、移動終端、行動電話、電子紙、電子書終端、電腦等。 在這些電子設備中，要求用於貼合構成觸控面板的光學構件的黏著劑層具備段差追隨性、濕熱耐久性等功能。In recent years, electronic devices that combine a display (image display device) and a touch panel as an input device have become popular. Examples of the display (image display device) to which the touch panel is applied include a liquid crystal display (LCD), an electroluminescence display (inorganic EL, organic EL), and the like. In addition, specific electronic devices using a touch panel as an input device include liquid crystal televisions, inorganic EL televisions, organic EL televisions, mobile terminals, mobile phones, electronic paper, e-book terminals, and computers. In these electronic devices, it is required that the adhesive layer used to bond the optical members constituting the touch panel have functions such as step-following properties and wet-heat durability.

在以往，為了得到具有段差追隨性的黏著劑層，提出了各種方案(專利文獻1~3)。此外，還提出了用於得到具有段差追隨性及濕熱耐久性的黏著劑層的方案(專利文獻4)。 專利文獻1中記載了一種當固定透明面板與圖像顯示裝置時，對因設置於透明面板表面或圖像顯示裝置表面的裝飾部而產生的段差的密合性優異，且在高溫環境下可抑制段差部分的起泡及剝落的雙面黏著片。 此外，專利文獻2中記載了一種在形成黏著劑層時，由印刷段差造成的印刷邊緣的氣泡少，且貼合於被黏物時不會產生氣泡的發生，即使施加負荷也不易產生凹陷的帶裝飾印刷層的表面保護膜。 此外，專利文獻3中記載了一種由於耐濕熱穩定性及耐起泡性優異，因此在用於具有由金屬或金屬氧化物構成的導電膜的觸控面板的光聚合性黏著劑中，可抑制白化或起泡，並且不產生氣味或沒有皮膚刺激，進一步對金屬或金屬氧化物沒有腐蝕性的光聚合性黏著劑、使用了該光聚合性黏著劑的黏著片。 此外，專利文獻4中記載了一種用於透明性、黏合性、耐久性、耐腐蝕性、段差追隨性、高介電常數、塗佈性優異的觸控面板用黏著劑組合物的丙烯酸類高分子化合物。 [現有技術文獻] [專利文獻]In the past, in order to obtain an adhesive layer having step-following properties, various proposals have been proposed (Patent Documents 1 to 3). In addition, a proposal for obtaining an adhesive layer having step-following properties and moisture-heat durability has also been proposed (Patent Document 4). Patent Document 1 describes that when a transparent panel and an image display device are fixed, it has excellent adhesion to a step caused by a decorative portion provided on the surface of the transparent panel or the surface of the image display device, and can be used in a high-temperature environment. A double-sided adhesive sheet that suppresses blistering and peeling of the stepped part. In addition, Patent Document 2 describes a method for forming an adhesive layer that has fewer air bubbles at the printing edge caused by printing steps, and does not generate air bubbles when it is attached to an adherend, and it is not easy to produce dents even if a load is applied. Surface protective film with decorative printing layer. In addition, Patent Document 3 describes a photopolymerizable adhesive used in a touch panel having a conductive film made of metal or metal oxide due to its excellent moisture and heat resistance stability and blistering resistance. Whitening or foaming, no smell or skin irritation, and a photopolymerizable adhesive that is not corrosive to metals or metal oxides, and an adhesive sheet using the photopolymerizable adhesive. In addition, Patent Document 4 describes an acrylic-based adhesive composition for a touch panel with excellent transparency, adhesiveness, durability, corrosion resistance, step-following properties, high dielectric constant, and excellent coating properties. Molecular compound. [Prior Art Literature] [Patent Literature]

[專利文獻1]：日本特開2012-211282號公報 [專利文獻2]：日本特開2015-221531號公報 [專利文獻3]：日本特開2013-256552號公報 [專利文獻4]：日本特開2012-041456號公報[Patent Document 1]: JP 2012-211282 A [Patent Document 2]: Japanese Patent Application Publication No. 2015-221531 [Patent Document 3]: JP 2013-256552 A [Patent Document 4]: JP 2012-041456 A

[本發明要解決的技術問題][Technical Problem to be Solved by the Invention]

專利文獻1中記載的雙面黏著片由於黏著劑層的儲存模數的值被抑制在特定的數值範圍內並製成了柔軟的黏著劑層，因此滿足與印刷段差追隨性相關的性能。然而，若提高黏著劑層的黏著力，則當將光學構件貼合於被黏物後，需要重新貼附時，有時會不易剝離，亦所謂再操作時的處理性能(重新貼合的操作性)差。相反，若提高黏著劑層的再操作時的處理性能，則將光學構件貼合於被黏物後的黏著力過低而可能會發生剝落。因此，專利文獻1中記載的雙面黏著片存在難以兼顧黏著劑層的確保再操作時的處理性能、以及提高將光學構件貼合於被黏物後的黏著力的問題。In the double-sided adhesive sheet described in Patent Document 1, the storage modulus of the adhesive layer is suppressed within a specific numerical range and the adhesive layer is made soft, and thus satisfies the performance related to the followability of the printing step. However, if the adhesive force of the adhesive layer is increased, when the optical member needs to be reattached after attaching the optical member to the adherend, it may not be easy to peel off. This is also the so-called handling performance during re-operation (re-attaching operation) Sex) is poor. On the contrary, if the handling performance at the time of the rework of the adhesive layer is improved, the adhesive force after bonding the optical member to the adherend is too low, and peeling may occur. Therefore, the double-sided pressure-sensitive adhesive sheet described in Patent Document 1 has a problem that it is difficult to balance the process performance during re-handling of the pressure-sensitive adhesive layer and the improvement of the adhesive force after bonding the optical member to the adherend.

此外，專利文獻2中公開了，在透明樹脂膜的單面上形成圖形、文字等裝飾印刷層，將包含光聚合引發劑且具有流動性的光固化性樹脂組合物塗佈於未形成該裝飾印刷層的部分的上部、及所述裝飾印刷層的上部後，進行UV照射而形成光固化而成的黏著劑層，得到帶裝飾印刷層的表面保護膜。專利文獻2的帶裝飾印刷層的表面保護膜由於在塗佈包含光聚合引發劑且具有流動性的光固化性樹脂組合物後，進行UV照射而形成光固化而成的黏著劑層，因此無論UV固化後的黏著劑層的柔軟性如何，均能夠包埋印刷段差。然而，由於塗佈液體狀的黏著劑組合物，因此專利文獻2的發明的黏著劑層存在難以形成厚膜的黏著劑層的問題。此外，在印刷段差的部分塗佈液體狀的光固化性樹脂組合物以包埋印刷段差具有操作繁瑣的技術問題。In addition, Patent Document 2 discloses that a decorative printing layer such as graphics and characters is formed on a single side of a transparent resin film, and a photocurable resin composition containing a photopolymerization initiator and having fluidity is applied to the unformed decorative layer. After the upper part of the printed layer and the upper part of the decorative printed layer, UV irradiation is performed to form a photocured adhesive layer, and a surface protective film with a decorative printed layer is obtained. The surface protective film with a decorative printed layer of Patent Document 2 is coated with a photocurable resin composition containing a photopolymerization initiator and having fluidity, and then subjected to UV irradiation to form a photocured adhesive layer. Regardless of the flexibility of the adhesive layer after UV curing, it can bury the printing step. However, since a liquid adhesive composition is applied, the adhesive layer of the invention of Patent Document 2 has a problem that it is difficult to form a thick-film adhesive layer. In addition, applying a liquid photocurable resin composition to the portion of the printing step to embed the printing step has a technical problem that the operation is cumbersome.

此外，專利文獻3中公開了一種光聚合性黏著劑，其含有40~92重量%的(a-1)(甲基)丙烯酸烷基酯、5~20重量%的(a-2)含羥基單體、3~25重量%的(a-3)水溶性N取代丙烯醯胺，且相對於100重量份的基本上不含有含酸性基團單體的單體組(A)(將總單體設為100重量%)或其部分聚合物(A’)，含有0.01~2重量份的異氰酸酯類交聯劑和/或多官能度單體(B)與0.1~2重量份的光聚合引發劑(C)。若為專利文獻3的光聚合性黏著劑，則段差追隨性及再剝離性良好。根據專利文獻3的實施例1~6，將光聚合性黏著劑塗佈於基材而形成厚度為300μm的塗佈膜，將經脫模處理的厚度為25μm的PET膜以脫模處理面與該塗佈膜的表面相接觸的方式設置在該塗佈膜的表面上，在氮氣氛圍下利用UV照射而進行光聚合，製作黏著片。然而，由於所得到的黏著片的黏著力的值為14~25N/25mm的範圍，因此對貼合於被黏物的黏著片進行重新貼附時，很難將黏著片從被黏物上剝離，存在再操作時的處理性能差的問題。In addition, Patent Document 3 discloses a photopolymerizable adhesive containing 40 to 92% by weight of (a-1) alkyl (meth)acrylate and 5 to 20% by weight of (a-2) hydroxyl group-containing Monomer, 3-25% by weight of (a-3) water-soluble N-substituted acrylamide, and relative to 100 parts by weight of monomer group (A) which contains substantially no monomers containing acidic groups (the total single The body is set to 100% by weight) or part of the polymer (A'), containing 0.01 to 2 parts by weight of isocyanate crosslinking agent and/or multifunctional monomer (B) and 0.1 to 2 parts by weight of photopolymerization initiator剂(C). In the case of the photopolymerizable adhesive of Patent Document 3, the step followability and re-peelability are good. According to Examples 1 to 6 of Patent Document 3, a photopolymerizable adhesive is applied to a substrate to form a coating film with a thickness of 300 μm, and a PET film with a thickness of 25 μm after a mold release treatment is applied to the mold release treatment surface. The surface of the coating film is placed on the surface of the coating film in a manner in which the coating film is in contact, and photopolymerization is performed by UV irradiation in a nitrogen atmosphere to produce an adhesive sheet. However, since the value of the adhesive force of the obtained adhesive sheet is in the range of 14~25N/25mm, it is difficult to peel off the adhesive sheet from the adherend when reattaching the adhesive sheet attached to the adherend. , There is a problem of poor processing performance during re-operation.

此外，專利文獻4中公開了一種用於觸控面板用黏著劑組合物的丙烯酸類高分子化合物，該高分子化合物藉由共聚單體成分而得到，該單體成分包含(a)具有碳原子數為1~12的烴基的(甲基)丙烯酸酯類單體、(b)含羥基的(甲基)丙烯酸酯類單體、(c)含有醯胺基的單體及(d)乙烯基酯類單體，所述高分子化合物的樹脂酸值為0.1 mgKOH/g以下，重均分子量為40萬~200萬，Tg為-80~0℃，介電常數為3~6。在專利文獻4的丙烯酸類高分子化合物中，「較佳為含羥基的丙烯酸酯類單體，出於能夠給予高分子化合物成為與交聯劑的反應部位的官能團，進行交聯而得到的交聯產物可賦予作為黏著劑的適當的彈性並提高凝聚力，且同時提高介電常數，進一步有助於提高黏著片的耐濕熱性等理由，特佳為丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯」(引用文獻4的第[0021]段)。 此外，在專利文獻4的黏著片中，「為了提高產品的設計性、謀求差異化，多在保護透明板上設置印刷層。在基材片或膜上多具有該印刷油墨層、用於各種電路的銀膏等的層、FPD部分上產生的段差等10~30μm左右的段差，存在利用黏著片進行貼合時會產生氣泡的問題。這是黏著劑層的段差追隨性的不足所引起的。該段差追隨性與由黏著劑組合物得到的黏著片的黏著特性中的適當的Tg及凝膠分率密切相關。黏著劑的凝膠分率較佳為30~70%左右，更佳為40~65%左右」(引用文獻4的第[0081]段)。 然而，在引用文獻4的實施例1~12的黏著片中，儘管實施例1、2、5、6、8、10的黏著片的黏著劑層的厚度薄至50μm，但由於耐濕熱試驗後的霧度值超過4.0%，因此存在需要進一步提高耐濕熱性的問題。In addition, Patent Document 4 discloses an acrylic polymer compound used in an adhesive composition for a touch panel. The polymer compound is obtained by copolymerizing a monomer component, and the monomer component includes (a) having a carbon atom. (Meth)acrylate monomers with 1-12 hydrocarbon groups, (b) (meth)acrylate monomers containing hydroxyl groups, (c) monomers containing amide groups, and (d) vinyl groups Ester monomers, the polymer compound has a resin acid value of 0.1 mgKOH/g or less, a weight average molecular weight of 400,000 to 2 million, a Tg of -80 to 0°C, and a dielectric constant of 3 to 6. In the acrylic polymer compound of Patent Document 4, "a hydroxyl-containing acrylate monomer is preferable because it can give the polymer compound a functional group that becomes a reactive site with a crosslinking agent and is crosslinked. The co-product can impart appropriate elasticity as an adhesive and improve cohesive force, and at the same time increase the dielectric constant, which further contributes to the improvement of the heat and humidity resistance of the adhesive sheet. Particularly preferred are 2-hydroxyethyl acrylate and 4-hydroxy acrylate. Butyl ester" (paragraph [0021] of Reference 4). In addition, in the adhesive sheet of Patent Document 4, "In order to improve the design of products and achieve differentiation, a printing layer is often provided on a protective transparent plate. The printing ink layer is often provided on a substrate sheet or film, and is used for various The layer of the silver paste of the circuit, the step generated on the FPD part, etc., with a step of about 10 to 30 μm, there is a problem that bubbles are generated when using the adhesive sheet. This is caused by the insufficient step followability of the adhesive layer 。 This step followability is closely related to the appropriate Tg and gel fraction in the adhesive properties of the adhesive sheet obtained from the adhesive composition. The gel fraction of the adhesive is preferably about 30 to 70%, more preferably About 40~65%" (paragraph [0081] of Reference 4). However, in the adhesive sheets of Examples 1 to 12 of Reference 4, although the thickness of the adhesive layer of the adhesive sheets of Examples 1, 2, 5, 6, 8, and 10 is as thin as 50 μm, the thickness of the adhesive layer is as thin as 50 μm. The haze value exceeds 4.0%, so there is a problem that it is necessary to further improve the heat and humidity resistance.

如此，藉由現有技術難以得到可形成對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能良好，且具有優異的濕熱耐久性的黏著劑層的光學用黏著劑組合物，以及使用了該光學用黏著劑組合物的黏著膜、黏著片。As such, it is difficult to obtain an optical adhesive composition that can form an adhesive layer with good processing performance during re-operation and excellent wet-heat durability, such as step-following to the step of the frame printing of the adherend, and the like with the prior art. , And adhesive films and adhesive sheets using the optical adhesive composition.

本發明是鑒於上述問題而完成的，其技術問題在於提供一種可形成兼具對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能及優異的濕熱耐久性的黏著劑層的光學用黏著劑組合物，以及使用了該光學用黏著劑組合物的黏著膜、黏著片。 [解決技術問題的技術手段]The present invention was completed in view of the above-mentioned problems, and its technical problem is to provide an adhesive layer that can form an adhesive layer that has both step-following properties for the frame printing of the adherend, handling performance during re-operation, and excellent wet-heat durability. The optical adhesive composition, and the adhesive film and adhesive sheet using the optical adhesive composition. [Technical means to solve technical problems]

本申請的發明人對上述技術問題進行了認真研究，發現利用熱交聯劑而使光學用黏著劑組合物交聯而成的黏著劑層，且利用光交聯劑進行交聯前的黏著劑層(第一階段)的段差追隨性、再操作時的處理性能優異，進一步，經基於所述熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段而使所述光學用黏著劑組合物交聯而形成的黏著劑層(第二階段)的濕熱耐久性優異，從而完成了本發明，其中該光學用黏著劑組合物含有：丙烯酸類聚合物；在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；具有環氧烷(alkylene oxide)基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；熱交聯劑；及光交聯劑。 本發明的光學用黏著劑組合物具有下述特徵：經基於熱交聯劑的交聯與基於光交聯劑的交聯這兩個階段，使含有丙烯酸類聚合物、在一分子內具有(甲基)丙烯醯基與烯丙基醚基且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、熱交聯劑、及光交聯劑的光學用黏著劑組合物交聯，可經兩個階段形成物性不同的黏著劑層。 即，本發明的技術構思在於提供一種能夠經兩個階段形成物性不同的黏著劑層的光學用黏著劑組合物，以及使用了該光學用黏著劑組合物的黏著膜、黏著片，所述物性不同的黏著劑層包括對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能良好的所述第一階段的黏著劑層，與具有優異的濕熱耐久性的所述第二階段的黏著劑層。The inventor of the present application has conducted serious research on the above technical problems and found that the adhesive layer formed by crosslinking the optical adhesive composition using a thermal crosslinking agent, and the adhesive before crosslinking using a photocrosslinking agent The layer (first stage) has excellent step-following properties and excellent handling performance during re-operation. Furthermore, the two stages of cross-linking based on the thermal cross-linking agent and the subsequent cross-linking based on the photo-crosslinking agent are achieved. The adhesive layer (second stage) formed by cross-linking the optical adhesive composition has excellent wet-heat durability, thus completing the present invention, wherein the optical adhesive composition contains: acrylic polymer; one molecule (Meth)acrylic acid ester monomer with (meth)acrylic acid group and allyl ether group, and two or more ethylenically unsaturated groups; having alkylene oxide (alkylene oxide) group and one A (meth)acrylate monomer having two or more ethylenically unsaturated groups in the molecule; a thermal crosslinking agent; and a photocrosslinking agent. The optical adhesive composition of the present invention has the following characteristics: after two stages of crosslinking based on a thermal crosslinking agent and crosslinking based on a photocrosslinking agent, it contains an acrylic polymer and has ( (Meth)acrylic acid ester monomers having two or more ethylenically unsaturated groups with meth)acrylic acid groups and allyl ether groups, having epoxy alkyl groups and having two or more ethylenic properties in one molecule The optical adhesive composition of unsaturated group (meth)acrylate monomer, thermal crosslinking agent, and photocrosslinking agent is crosslinked to form an adhesive layer with different physical properties in two stages. That is, the technical idea of the present invention is to provide an optical adhesive composition capable of forming an adhesive layer with different physical properties in two stages, and an adhesive film and an adhesive sheet using the optical adhesive composition. The physical properties Different adhesive layers include the first-stage adhesive layer that has good follow-up to the frame printing of the adherend and other steps, and has good handling performance during re-operation, and the second-stage adhesive layer that has excellent moisture and heat durability. Adhesive layer of the stage.

為了解決所述技術問題，本發明提供一種光學用黏著劑組合物，其特徵在於，其含有：使選自共聚性乙烯基單體、及含氮乙烯基單體的化合物組中的至少兩種以上進行共聚而得到的共聚物，所述共聚性乙烯基單體在官能團中不具有羧基，而具有烷基、羥基、烷氧基、芳香基中的任意一種；(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(E)熱交聯劑；及(H)光交聯劑。In order to solve the above technical problems, the present invention provides an optical adhesive composition characterized in that it contains at least two selected from the group of copolymerizable vinyl monomers and nitrogen-containing vinyl monomers. The copolymer obtained by the above copolymerization, wherein the copolymerizable vinyl monomer does not have a carboxyl group in the functional group, but has any one of an alkyl group, a hydroxyl group, an alkoxy group, and an aromatic group; (F) has in one molecule (Meth)acrylic acid group and allyl ether group, and has two or more ethylenically unsaturated groups (meth)acrylate monomer; (G) has epoxy alkyl group and has in one molecule Two or more ethylenically unsaturated group (meth)acrylate monomers; (E) thermal crosslinking agent; and (H) photocrosslinking agent.

此外，較佳：所述共聚物為重均分子量為20萬~100萬的共聚物，其藉由相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上，共聚合計為2.0~10重量份的(B)含氮乙烯基單體或含烷氧基的(甲基)丙烯酸烷基酯單體中的至少一種以上、合計為1.0~10重量份的(C)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上、合計為0.5~10重量份的(D)具有羥基的共聚性乙烯基單體中的至少一種以上而成；相對於100重量份的所述(A)，所述光學用黏著劑組合物以0.01~5重量份的比例含有所述(E)熱交聯劑、以0.1~10重量份的比例含有所述(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、以0.1~10重量份的比例含有所述(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、以0.01~5重量份的比例含有所述(H)光交聯劑。In addition, it is preferable that the copolymer is a copolymer having a weight average molecular weight of 200,000 to 1 million, and the (A) alkyl group has a carbon number of C1 to C18 (methyl group) with respect to 100 parts by weight of the (A) alkyl group. ) At least one of the alkyl acrylate monomers, copolymerized into at least 2.0 to 10 parts by weight of (B) nitrogen-containing vinyl monomers or alkoxy-containing alkyl (meth)acrylate monomers One or more (C) polyalkylene glycol mono(meth)acrylate monomers totaling 1.0 to 10 parts by weight, totaling 0.5 to 10 parts by weight (D) copolymerization with hydroxyl group The adhesive composition for optics contains the (E) thermally crosslinked in a ratio of 0.01 to 5 parts by weight relative to 100 parts by weight of the (A). Agent, in a ratio of 0.1 to 10 parts by weight containing the (F) having a (meth)acrylic acid group and an allyl ether group in one molecule, and having two or more ethylenically unsaturated groups (methyl ) Monomers of acrylate, containing the (G) (meth)acrylate monomer having an alkylene oxide group and having two or more ethylenically unsaturated groups in one molecule in a ratio of 0.1 to 10 parts by weight The body contains the (H) photocrosslinking agent in a ratio of 0.01 to 5 parts by weight.

此外，較佳：經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成的厚度為250μm的黏著劑層的總透光率為90%以上，且霧度值為1.0%以下。In addition, it is preferable to perform the optical adhesive composition through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent The total light transmittance of the 250 μm-thick adhesive layer formed by crosslinking is 90% or more, and the haze value is 1.0% or less.

此外，較佳：經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成厚度為250μm的黏著劑層在溫度60℃×90%RH的氣氛下放置240小時後，取出至室溫環境(溫度23℃×50%RH)時的霧度值為4.0%以下。In addition, it is preferable to perform the optical adhesive composition through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent After being cross-linked to form an adhesive layer with a thickness of 250μm, the haze value is 4.0% or less when placed in an atmosphere of 60℃×90%RH for 240 hours and taken out to a room temperature environment (temperature 23℃×50%RH) .

此外，較佳在合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上中，所述共聚物以50重量份以上的比例含有烷基的碳原子數為C8~C18的(甲基)丙烯酸烷基酯。In addition, it is preferable that in the total of 100 parts by weight of (A) at least one of the alkyl (meth)acrylate monomers having C1 to C18 carbon atoms, the copolymer is 50 parts by weight The above ratio contains alkyl (meth)acrylates with C8 to C18 carbon atoms in the alkyl group.

此外，較佳：所述共聚物由(C)聚伸烷基二醇單(甲基)丙烯酸酯單體共聚而成，所述光學用黏著劑組合物含有(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體，所述(C)及所述(G)的環氧烷的平均重複數為4~14。In addition, preferably: the copolymer is formed by copolymerizing (C) a polyalkylene glycol mono(meth)acrylate monomer, and the optical adhesive composition contains (G) having an epoxy group and In a (meth)acrylate monomer having two or more ethylenically unsaturated groups in one molecule, the average repeating number of the alkylene oxides of the (C) and the (G) is 4-14.

此外，本發明提供一種黏著膜，其特徵在於，其藉由將黏著劑層積層在基材的單面上而成，所述黏著劑層藉由使用上述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成，或者藉由使用上述的光學用黏著劑組合物，並經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段交聯而成，利用所述(E)熱交聯劑交聯後的所述黏著劑層對鈉鈣玻璃的黏著力為10N/25mm以下，進一步，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段進行交聯後的所述黏著劑層對鈉鈣玻璃的黏著力為25N/25mm以上。In addition, the present invention provides an adhesive film characterized in that it is formed by laminating an adhesive on a single side of a substrate, and the adhesive layer is formed by using the above-mentioned optical adhesive composition and using The (E) thermal crosslinking agent is cross-linked, or by using the above-mentioned optical adhesive composition, and the crosslinking based on the (E) thermal crosslinking agent is followed by the (H) ) It is formed by cross-linking in two stages of cross-linking of the photo-crosslinking agent, and the adhesive layer after cross-linking with the (E) thermal cross-linking agent has an adhesive force of 10N/25mm or less to the soda lime glass, further , After the two stages of cross-linking based on the (E) thermal cross-linking agent and the subsequent cross-linking based on the (H) photo-crosslinking agent, the adhesive layer has an effect on the soda lime glass Adhesive force is above 25N/25mm.

此外，本發明提供一種黏著膜，其特徵在於，其藉由將黏著劑層積層在厚度為188μm的聚鄰苯二甲酸乙二醇酯(polyethylene phthalate)樹脂膜的單面上而成，所述黏著劑層藉由使用上述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成，將所述黏著膜介由厚度為100μm的所述黏著劑層而貼合於具有厚度為42μm的印刷層的印刷段差的玻璃時，對所述印刷段差的追隨性良好，在所述印刷段差的周圍完全沒有起泡。In addition, the present invention provides an adhesive film characterized in that it is formed by laminating an adhesive on one side of a polyethylene phthalate resin film having a thickness of 188 μm. The adhesive layer is formed by using the above-mentioned optical adhesive composition and cross-linking with the (E) thermal cross-linking agent, and the adhesive film is bonded via the adhesive layer having a thickness of 100 μm In the case of a glass with a printing step difference of a printing layer having a thickness of 42 μm, the followability to the printing step difference is good, and there is no blistering at all around the printing step difference.

此外，本發明提供一種使用了上述黏著膜的觸控面板用膜。In addition, the present invention provides a film for a touch panel using the above-mentioned adhesive film.

此外，本發明提供一種黏著片，其藉由將使用上述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成的黏著劑層積層於兩片經脫模處理的脫模膜之間而成。In addition, the present invention provides an adhesive sheet by laminating an adhesive formed by using the above-mentioned optical adhesive composition and crosslinking with the (E) thermal crosslinking agent on two sheets and subjected to a mold release treatment Between the release film.

此外，本發明提供一種帶黏著劑層的光學膜，其藉由黏著劑層積層於光學膜的至少一個面而成，所述黏著劑層藉由使用上述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成，或者藉由使用上述的光學用黏著劑組合物，並經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段交聯而成。 [發明效果]In addition, the present invention provides an optical film with an adhesive layer, which is formed by laminating an adhesive on at least one surface of the optical film, and the adhesive layer uses the above-mentioned optical adhesive composition and uses The (E) thermal crosslinking agent is cross-linked, or by using the above-mentioned optical adhesive composition, and the crosslinking based on the (E) thermal crosslinking agent is followed by the (H) ) It is formed by cross-linking in two stages of cross-linking of photo-crosslinking agent. [Effects of the invention]

本發明的光學用黏著劑組合物為含有丙烯酸類聚合物、在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、熱交聯劑、及光交聯劑的光學用黏著劑組合物。此處，由於利用光交聯劑而使在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體進行光交聯而形成環狀化合物，因此經基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段進行交聯後的黏著劑層具備優異的濕熱耐久性。The optical adhesive composition of the present invention contains an acrylic polymer, has a (meth)acrylic acid group and an allyl ether group in one molecule, and has two or more ethylenically unsaturated groups (methyl) ) The optical of acrylate monomers, (meth)acrylate monomers having epoxy alkyl groups and two or more ethylenically unsaturated groups in one molecule, thermal crosslinking agents, and photocrosslinking agents Use adhesive composition. Here, due to the use of a photocrosslinking agent, the monomer of (meth)acrylate having a (meth)acrylic acid group and an allyl ether group in one molecule, and having two or more ethylenically unsaturated groups The body undergoes photocrosslinking to form a cyclic compound. Therefore, the adhesive layer after crosslinking through two stages of crosslinking based on a thermal crosslinking agent and subsequent crosslinking based on a photocrosslinking agent has excellent wet heat durability .

此外，本發明的黏著膜及黏著片中形成有使用光學用黏著劑組合物交聯而成的黏著劑層，所述光學用黏著劑組合物含有丙烯酸類聚合物、在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、熱交聯劑、及光交聯劑。該黏著劑層為利用熱交聯劑交聯而成的黏著劑層、能夠經基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段進行交聯的黏著劑層，或者為已經藉由基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段進行了交聯的黏著劑層。 因此，根據本發明，可提供一種兼具對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能及優異的濕熱耐久性的黏著膜、及黏著片。In addition, the adhesive film and the adhesive sheet of the present invention are formed with an adhesive layer cross-linked using an optical adhesive composition that contains an acrylic polymer and has (former) in one molecule. (Meth)acrylic acid ester monomer with two or more ethylenically unsaturated groups, acryloyl group and allyl ether group, having epoxy alkyl group and having two or more ethylenic properties in one molecule Unsaturated group (meth)acrylate monomer, thermal crosslinking agent, and photocrosslinking agent. The adhesive layer is an adhesive layer cross-linked with a thermal cross-linking agent, and an adhesive that can be cross-linked through two stages of cross-linking based on the thermal cross-linking agent and subsequent cross-linking based on the photo-cross-linking agent A layer, or an adhesive layer that has been cross-linked through two stages of cross-linking based on a thermal cross-linking agent and subsequent cross-linking based on a photo-crosslinking agent. Therefore, according to the present invention, it is possible to provide an adhesive film and an adhesive sheet that have both step-following properties to the step of the frame printing of the adherend, handling performance during re-operation, and excellent moisture and heat durability.

以下，基於適宜的實施方式，對本發明進行說明。Hereinafter, the present invention will be described based on suitable embodiments.

本實施方式的光學用黏著劑組合物的特徵在於含有：使選自共聚性乙烯基單體、及含氮乙烯基單體的化合物組中的至少兩種以上進行共聚而得到的共聚物，所述共聚性乙烯基單體在官能團中不具有羧基，而具有烷基、羥基、烷氧基、芳香基中的任意一種；(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(E)熱交聯劑；及(H)光交聯劑。The optical adhesive composition of this embodiment is characterized by containing a copolymer obtained by copolymerizing at least two or more selected from the group of copolymerizable vinyl monomers and nitrogen-containing vinyl monomers. The copolymerizable vinyl monomer does not have a carboxyl group in the functional group, but has any one of an alkyl group, a hydroxyl group, an alkoxy group, and an aromatic group; (F) has a (meth)acryloyl group and an allyl group in one molecule Monomers of (meth)acrylates having two or more ethylenically unsaturated groups; (G) those having an epoxy group and two or more ethylenically unsaturated groups in one molecule (Meth) acrylate monomer; (E) thermal crosslinking agent; and (H) photocrosslinking agent.

在本說明書中，(甲基)丙烯酸酯為丙烯酸酯及甲基丙烯酸酯的總稱。此外，(甲基)丙烯醯基為丙烯醯基及甲基丙烯醯基的總稱。本實施方式的光學用黏著劑組合物的共聚物例如為由(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上、(B)含氮乙烯基單體或含烷氧基的(甲基)丙烯酸烷基酯單體中的至少一種以上、(C)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上、及(D)具有羥基的共聚性乙烯基單體中的至少一種以上共聚而成的共聚物。In this specification, (meth)acrylate is a general term for acrylate and methacrylate. In addition, (meth)acryloyl group is a general term for acrylic group and methacryloyl group. The copolymer of the optical adhesive composition of the present embodiment is composed of, for example, at least one of (A) alkyl (C1 to C18) alkyl (meth)acrylate monomers, (B) containing At least one of nitrogen vinyl monomers or alkoxy-containing alkyl (meth)acrylate monomers, and at least one of (C) polyalkylene glycol mono(meth)acrylate monomers And (D) a copolymer in which at least one or more of the copolymerizable vinyl monomers having a hydroxyl group are copolymerized.

作為所述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體，可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯等中的至少一種以上。(甲基)丙烯酸烷基酯單體的烷基可以為直鏈狀、支鏈狀、環狀中的任意一種。關於屬於碳原子數為C3以上的直鏈狀的(甲基)丙烯酸烷基酯單體的具體的化合物，在未指定存在支鏈的情況下，有時將(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯等簡稱作(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。Examples of the (A) alkyl (meth)acrylic acid alkyl ester monomers having C1 to C18 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl) ) Propyl acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid Nonyl ester, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, ten (meth)acrylate Tetraalkyl esters, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, etc. At least one of them. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, and cyclic. Regarding specific compounds belonging to linear alkyl (meth)acrylate monomers with carbon atoms of C3 or more, when the presence of a branch is not specified, n-propyl (meth)acrylate, The n-butyl (meth)acrylate and the like are abbreviated as propyl (meth)acrylate, butyl (meth)acrylate and the like.

在所述(A)中，作為支鏈狀的丙烯酸烷基酯單體(含支鏈結構烷基的單體)，可列舉出(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸異十一烷基酯、(甲基)丙烯酸異十二烷基酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸異十四烷基酯、(甲基)丙烯酸異十五烷基酯、(甲基)丙烯酸異十六烷基酯、(甲基)丙烯酸異十七烷基酯、(甲基)丙烯酸異十八烷基酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸異硬脂酸酯等中的至少一種以上。含支鏈結構烷基的單體也可以具有像三級丁基這樣的、烷基為2個以上的支鏈結構(例如在主鏈上具有2個以上的側鏈)。In (A), examples of branched alkyl acrylate monomers (monomers containing a branched structure alkyl group) include isopropyl (meth)acrylate and isobutyl (meth)acrylate. Ester, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, isononyl (meth)acrylate, isodecyl (meth)acrylate, isundecyl (meth)acrylate, isododecyl (meth)acrylate, isodecyl (meth)acrylate Tridecyl ester, isotetradecyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isohexadecyl (meth)acrylate At least one or more of alkyl ester, isostearyl (meth)acrylate, isomyristyl (meth)acrylate, isostearate (meth)acrylate, and the like. The branched structure alkyl group-containing monomer may also have a branched structure with two or more alkyl groups such as a tertiary butyl group (for example, having two or more side chains in the main chain).

在所述(A)中，作為環狀的丙烯酸烷基酯單體(含脂環族單體)，可列舉出(甲基)丙烯酸環戊基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環庚基酯、(甲基)丙烯酸二環辛基酯、(甲基)丙烯酸二甲基二環庚基酯、(甲基)丙烯酸二環戊基酯等中的至少一種以上。In (A), examples of cyclic alkyl acrylate monomers (alicyclic monomers) include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicycloheptyl (meth)acrylate, dicyclooctyl (meth)acrylate, dimethyl dicycloheptyl (meth)acrylate, dicycloheptyl (meth)acrylate At least one of cyclopentyl esters and the like.

在合計為100重量份的所述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上中，較佳烷基的碳原子數為C8~C18的(甲基)丙烯酸烷基酯的比例為50重量份以上。在烷基的碳原子數為C8~C18的(甲基)丙烯酸烷基酯中，較佳(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯等含支鏈結構烷基的單體。In the total of 100 parts by weight of at least one of the (A) alkyl (meth)acrylic acid alkyl ester monomers having C1 to C18 carbon atoms, the alkyl group preferably has C8 carbon atoms. The ratio of ~C18 alkyl (meth)acrylate is 50 parts by weight or more. Among the alkyl (meth)acrylates with C8~C18 carbon atoms in the alkyl group, isooctyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred.基的monomers.

作為所述(B)中的含氮乙烯基單體，可列舉出含有醯胺鍵的乙烯基單體、含有胺基的乙烯基單體、具有含氮的雜環式結構的乙烯基單體等中的至少一種以上。作為含氮乙烯基單體，較佳不含有羥基的含氮乙烯基單體，更佳不含有羥基及羧基的含氮乙烯基單體。作為這種單體，較佳為上文中例示出的單體，例如含有N,N-二烷基取代胺基或N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基-2-吡咯烷酮、N-乙烯基己內醯胺、N-乙烯基-2-哌啶酮等N-乙烯基取代內醯胺類；N-(甲基)丙烯醯基嗎啉或N-(甲基)丙烯醯基吡咯烷等N-(甲基)丙烯醯基取代環狀胺類。Examples of the nitrogen-containing vinyl monomer in (B) include vinyl monomers containing amide bonds, vinyl monomers containing amine groups, and vinyl monomers having a nitrogen-containing heterocyclic structure. At least one or more of the above. As the nitrogen-containing vinyl monomer, a nitrogen-containing vinyl monomer that does not contain a hydroxyl group is preferable, and a nitrogen-containing vinyl monomer that does not contain a hydroxyl group and a carboxyl group is more preferable. Such monomers are preferably those exemplified above, such as acrylic monomers containing N,N-dialkyl substituted amine groups or N,N-dialkyl substituted amide groups; N-ethylene N-vinyl-substituted lactoamines such as methyl-2-pyrrolidone, N-vinylcaprolactone, N-vinyl-2-piperidone, etc.; N-(meth)acryloylmorpholine or N- N-(meth)acryloyl substituted cyclic amines such as (meth)acryloylpyrrolidine.

作為含有N,N-二烷基取代胺基的丙烯酸類單體，可列舉出二甲基胺基甲基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、二甲基胺基丙基(甲基)丙烯酸酯、二甲基胺基異丙基(甲基)丙烯酸酯、二甲基胺基丁基(甲基)丙烯酸酯、二乙基胺基甲基(甲基)丙烯酸酯、二乙基胺基乙基(甲基)丙烯酸酯、N-乙基-N-甲基胺基乙基(甲基)丙烯酸酯、N-甲基-N-丙基胺基乙基(甲基)丙烯酸酯、N-甲基-N-異丙基胺基乙基(甲基)丙烯酸酯、二丁基胺基乙基(甲基)丙烯酸酯等二烷基胺基(甲基)丙烯酸酯；二甲基胺基丙基(甲基)丙烯醯胺、二乙基胺基丙基(甲基)丙烯醯胺、二丙基胺基丙基(甲基)丙烯醯胺、二異丙基胺基丙基(甲基)丙烯醯胺、N-乙基-N-甲基胺基丙基(甲基)丙烯醯胺、N-甲基-N-丙基胺基丙基(甲基)丙烯醯胺、N-甲基-N-異丙基胺基丙基(甲基)丙烯醯胺等含有N,N-二烷基取代胺基烷基的(甲基)丙烯醯胺等。Examples of acrylic monomers containing N,N-dialkyl substituted amino groups include dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and dialkylaminoethyl (meth)acrylate. Methylaminopropyl (meth)acrylate, dimethylaminoisopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminomethyl ( Meth) acrylate, diethylaminoethyl (meth)acrylate, N-ethyl-N-methylaminoethyl (meth)acrylate, N-methyl-N-propylamine Dialkylamino groups such as ethyl (meth)acrylate, N-methyl-N-isopropylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, etc. (Meth) acrylate; dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dipropylaminopropyl (meth)acrylamide Amine, diisopropylaminopropyl(meth)acrylamide, N-ethyl-N-methylaminopropyl(meth)acrylamide, N-methyl-N-propylamino Propyl (meth)acrylamide, N-methyl-N-isopropylaminopropyl (meth)acrylamide, etc. (methyl) containing N,N-dialkyl substituted aminoalkyl Acrylic amide and so on.

作為含有N,N-二烷基取代醯胺基的丙烯酸類單體，可列舉出二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、二丙基丙烯醯胺、二異丙基(甲基)丙烯醯胺、二丁基(甲基)丙烯醯胺、N-乙基-N-甲基(甲基)丙烯醯胺、N-甲基-N-丙基(甲基)丙烯醯胺、N-甲基-N-異丙基(甲基)丙烯醯胺等二烷基取代(甲基)丙烯醯胺等。Examples of acrylic monomers containing N,N-dialkyl substituted amide groups include dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and dipropylacrylamide , Diisopropyl (meth)acrylamide, dibutyl (meth)acrylamide, N-ethyl-N-methyl (meth)acrylamide, N-methyl-N-propyl Dialkyl substituted (meth)acrylamides such as (meth)acrylamide and N-methyl-N-isopropyl(meth)acrylamide, etc.

作為N-乙烯基取代內醯胺類，可列舉出N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己內醯胺、N-乙烯基十二內醯胺(N-vinyl lauryl lactam)等。 作為N-乙烯基取代的雜環式乙烯基化合物，可列舉出N-乙烯基吡啶、N-乙烯基嘧啶、N-乙烯基哌嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基㗁唑、N-乙烯基嗎啉等。 作為N-(甲基)丙烯醯基取代環狀胺類，可列舉出N-(甲基)丙烯醯基嗎啉、N-(甲基)丙烯醯基哌嗪、N-(甲基)丙烯醯基氮丙啶、N-(甲基)丙烯醯基吖呾、N-(甲基)丙烯醯基吡咯烷、N-(甲基)丙烯醯哌啶、N-(甲基)丙烯醯基氮雜環庚烷(N-(meth)acryloyl azepan)、N-(甲基)丙烯醯基氮雜環辛烷(N-(meth)acryloyl azocan)等。Examples of N-vinyl-substituted lactamines include N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactone, and N-vinyldodecanolide N-vinyl lauryl lactam and so on. Examples of N-vinyl substituted heterocyclic vinyl compounds include N-vinylpyridine, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N -Vinyl imidazole, N-vinyl azole, N-vinyl morpholine, etc. Examples of N-(meth)acryloyl substituted cyclic amines include N-(meth)acryloylmorpholine, N-(meth)acryloylpiperazine, and N-(meth)propylene Acrylaziridine, N-(meth)acrylic acridine, N-(meth)acrylic pyrrolidine, N-(meth)acrylic piperidine, N-(meth)acrylic acid N-(meth)acryloyl azepan, N-(meth)acryloyl azocan, etc.

作為其他的含氮乙烯基單體，可列舉出N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基-N-甲基乙醯胺等N-乙烯基羧酸醯胺類；無取代的(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-三級丁基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-乙氧基乙基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、二丙酮丙烯醯胺、N,N-亞甲基雙(甲基)丙烯醯胺等(甲基)丙烯醯胺類；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等不飽和羧酸醯亞胺類；(甲基)丙烯腈等不飽和羧酸腈等。較佳所述含氮乙烯基單體不含有異氰酸酯基。此外，較佳所述含氮乙烯基單體不含有四級銨鹽等四級陽離子結構。所述含氮乙烯基單體也可以以不成為酸性的程度含有被N,N-二烷基取代胺基中和的三級陽離子結構。Examples of other nitrogen-containing vinyl monomers include N-vinyl carboxamides such as N-vinylformamide, N-vinylacetamide, and N-vinyl-N-methylacetamide. Class; unsubstituted (meth)acrylamide, N-methyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tertiary butyl (meth)acrylamide Amine, N-methoxymethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone propylene (Meth)acrylamides such as amide, N,N-methylenebis(meth)acrylamide; N-cyclohexylmaleimide, N-phenylmaleimide, etc. unsaturated Carboxylic imines; (meth)acrylonitrile and other unsaturated carboxylic acid nitriles. Preferably, the nitrogen-containing vinyl monomer does not contain an isocyanate group. In addition, it is preferable that the nitrogen-containing vinyl monomer does not contain a quaternary cation structure such as a quaternary ammonium salt. The nitrogen-containing vinyl monomer may contain a tertiary cationic structure neutralized by an N,N-dialkyl substituted amine group to the extent that it does not become acidic.

作為所述(B)中的含烷氧基的(甲基)丙烯酸烷基酯單體，可列舉出2-甲氧基乙基(甲基)丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、2-丙氧基乙基(甲基)丙烯酸酯、2-異丙氧基乙基(甲基)丙烯酸酯、2-丁氧基乙基(甲基)丙烯酸酯、2-甲氧基丙基(甲基)丙烯酸酯、2-乙氧基丙基(甲基)丙烯酸酯、2-丙氧基丙基(甲基)丙烯酸酯、2-異丙氧基丙基(甲基)丙烯酸酯、2-丁氧基丙基(甲基)丙烯酸酯、3-甲氧基丙基(甲基)丙烯酸、3-乙氧基丙基(甲基)丙烯酸酯、3-丙氧基丙基(甲基)丙烯酸酯、3-異丙氧基丙基(甲基)丙烯酸酯、3-丁氧基丙基(甲基)丙烯酸酯、4-甲氧基丁基(甲基)丙烯酸酯、4-乙氧基丁基(甲基)丙烯酸酯、4-丙氧基丁基(甲基)丙烯酸酯、4-異丙氧基丁基(甲基)丙烯酸酯、4-丁氧基丁基(甲基)丙烯酸酯等中的至少一種以上。這些含烷氧基的(甲基)丙烯酸烷基酯單體具有(甲基)丙烯酸烷基酯中的烷基的原子被烷氧基取代的結構。Examples of the alkoxy group-containing (meth)acrylate alkyl ester monomer in (B) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth) Base) acrylate, 2-propoxyethyl (meth)acrylate, 2-isopropoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2- Methoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 2-propoxypropyl (meth)acrylate, 2-isopropoxypropyl (meth)acrylate Base) acrylate, 2-butoxypropyl (meth)acrylate, 3-methoxypropyl (meth)acrylic acid, 3-ethoxypropyl (meth)acrylate, 3-propoxy Propyl (meth)acrylate, 3-isopropoxypropyl (meth)acrylate, 3-butoxypropyl (meth)acrylate, 4-methoxybutyl (meth) Acrylate, 4-ethoxybutyl (meth)acrylate, 4-propoxybutyl (meth)acrylate, 4-isopropoxybutyl (meth)acrylate, 4-butoxy At least one or more of butyl (meth)acrylate and the like. These alkoxy-containing alkyl (meth)acrylate monomers have a structure in which the alkyl group atoms in the alkyl (meth)acrylate are substituted with alkoxy groups.

所述共聚物中，相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上，較佳以合計為2.0~10重量份的比例共聚、更佳以合計為2.0~9重量份的比例共聚、特佳以合計為2.5~9重量份的比例共聚(B)含氮乙烯基單體或含烷氧基的(甲基)丙烯酸烷基酯單體中的至少一種以上。能夠分別使用一種或同時使用兩種以上的含氮乙烯基單體及含烷氧基的(甲基)丙烯酸烷基酯單體。In the copolymer, at least one of C1-C18 alkyl (meth)acrylate monomers with respect to a total of 100 parts by weight of the alkyl group (A) is preferably 2.0 in total. Copolymerization at a ratio of ~10 parts by weight, more preferably at a ratio of 2.0-9 parts by weight in total, particularly preferably at a ratio of 2.5-9 parts by weight in total (B) Nitrogen-containing vinyl monomer or alkoxy-containing At least one or more of alkyl (meth)acrylate monomers. The nitrogen-containing vinyl monomers and the alkoxy-containing alkyl (meth)acrylate monomers can be used separately or simultaneously.

所述(C)聚伸烷基二醇單(甲基)丙烯酸酯單體只要為具有聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，且為聚伸烷基二醇所具有的多個羥基中的一個羥基被酯化成(甲基)丙烯酸酯的化合物即可。由於(甲基)丙烯酸酯基為聚合性基團，因此能夠與所述共聚物共聚。其他羥基可以仍是OH，也可以成為甲基醚或乙基醚等烷基醚、或者醋酸酯等飽和羧酸酯等。The (C) polyalkylene glycol mono(meth)acrylate monomer should be a mono(meth)acrylate monomer having a polyalkylene glycol chain and be a polyalkylene glycol mono(meth)acrylate monomer. What is necessary is just a compound in which one of the multiple hydroxyl groups is esterified into a (meth)acrylate. Since the (meth)acrylate group is a polymerizable group, it can be copolymerized with the copolymer. Other hydroxyl groups may remain OH, or may be alkyl ethers such as methyl ether or ethyl ether, or saturated carboxylic acid esters such as acetate.

在所述(C)中，作為聚伸烷基二醇所具有的伸烷基，可列舉出伸乙基、伸丙基、伸丁基等，但並不限定於此。聚伸烷基二醇可以為聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇等在一分子中具有2種以上伸烷基的聚伸烷基二醇。 此外，在所述(C)中，構成聚伸烷基二醇鏈的環氧烷的平均重複數較佳為4~14。此處，「環氧烷的平均重複數」是指在「聚伸烷基二醇鏈」的部分中，環氧烷單元重複的平均數。In (C), examples of the alkylene group possessed by the polyalkylene glycol include ethylene group, propylene group, and butylene group, but are not limited to these. The polyalkylene glycol can be polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, etc., having two or more alkylene groups in one molecule. Glycol. In addition, in the above (C), the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain is preferably 4-14. Here, "the average repeating number of alkylene oxide" refers to the average number of repeating alkylene oxide units in the part of the "polyalkylene glycol chain".

作為所述(C)，較佳選自聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯中的至少一種以上。更具體而言，可列舉出聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚丁二醇單(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、甲氧基聚丁二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丁二醇(甲基)丙烯酸酯等。 所述共聚物中，相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上，較佳以合計為1.0~10重量份的比例共聚、更佳以合計為1.5~9重量份的比例共聚、特佳以合計為2.0~9重量份的比例共聚(C)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上。As said (C), it is preferably selected from polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene glycol (meth)acrylate, ethoxy polyalkylene glycol At least one or more of (meth)acrylates. More specifically, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, methoxy polyethylene glycol (meth) Meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polybutylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, ethoxy poly Propylene glycol (meth)acrylate, ethoxy polybutylene glycol (meth)acrylate, etc. In the copolymer, at least one of the alkyl (meth)acrylate monomers having C1 to C18 carbon atoms with respect to 100 parts by weight of the (A) alkyl group in total is preferably 1.0 in total. Copolymerization at a ratio of ~10 parts by weight, more preferably copolymerization at a ratio of 1.5-9 parts by weight in total, particularly preferably copolymerization at a ratio of 2.0-9 parts by weight in total (C) Polyalkylene glycol mono(meth)acrylic acid At least one or more of ester monomers.

作為所述(D)具有羥基的共聚性乙烯基單體，可列舉出(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯等含羥基的(甲基)丙烯酸烷基酯類、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等含羥基的(甲基)丙烯醯胺類等中的至少一種以上。 所述共聚物中，相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上，較佳以合計為0.5~10重量份的比例共聚、更佳以合計為0.8~9重量份的比例共聚、特佳以合計為0.8~8重量份的比例共聚(D)具有羥基的共聚性乙烯基單體中的至少一種以上。當所述(C)可以具有羥基時，較佳所述(D)不具有聚伸烷基二醇鏈。Examples of the (D) copolymerizable vinyl monomer having a hydroxyl group include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Hydroxy-containing alkyl (meth)acrylates such as esters, 2-hydroxyethyl (meth)acrylate, etc., N-hydroxy(meth)acrylamide, N-methylol(meth)acrylamide, At least one or more of hydroxyl group-containing (meth)acrylamides, such as N-hydroxyethyl (meth)acrylamide. In the copolymer, at least one of the alkyl (meth)acrylate monomers having C1 to C18 carbon atoms with respect to 100 parts by weight of the (A) alkyl group in total is preferably 0.5 in total. It is copolymerized at a ratio of ~10 parts by weight, more preferably at a ratio of 0.8 to 9 parts by weight in total, and particularly preferably at a ratio of 0.8 to 8 parts by weight in total. (D) At least one of the copolymerizable vinyl monomers having hydroxyl groups More than one kind. When the (C) may have a hydroxyl group, it is preferable that the (D) does not have a polyalkylene glycol chain.

在所述共聚物中，除了所述(A)~(D)中的至少一種以上以外，也可以共聚有具有芳香基的共聚性乙烯基單體。作為具有芳香基的共聚性乙烯基單體，可列舉出(甲基)丙烯酸苄酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基丁酯、2-(1-萘氧基)乙基(甲基)丙烯酸酯、2-(2-萘氧基)乙基(甲基)丙烯酸酯、6-(1-萘氧基)己基(甲基)丙烯酸酯、6-(2-萘氧基)己基(甲基)丙烯酸酯、8-(1-萘氧基)辛基(甲基)丙烯酸酯、8-(2-萘氧基)辛基(甲基)丙烯酸酯等具有芳香基的(甲基)丙烯酸酯單體、苯乙烯、甲基苯乙烯等苯乙烯類單體等中的至少一種以上。所述(A)~(D)也可以為不具有芳香基的共聚性乙烯基單體。In the copolymer, in addition to at least one of (A) to (D), a copolymerizable vinyl monomer having an aromatic group may be copolymerized. Examples of copolymerizable vinyl monomers having aromatic groups include benzyl (meth)acrylate, naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxy (meth)acrylate. Butyl ester, 2-(1-naphthyloxy) ethyl (meth) acrylate, 2-(2-naphthyloxy) ethyl (meth) acrylate, 6-(1-naphthyloxy) hexyl ( Meth)acrylate, 6-(2-naphthyloxy)hexyl(meth)acrylate, 8-(1-naphthyloxy)octyl(meth)acrylate, 8-(2-naphthyloxy) At least one or more of (meth)acrylate monomers having aromatic groups such as octyl (meth)acrylate, styrene monomers such as styrene and methylstyrene, and the like. The (A) to (D) may be copolymerizable vinyl monomers that do not have an aromatic group.

所述共聚物的聚合方法沒有特別限定，可使用溶液聚合法、乳液聚合法等適宜且公知的聚合方法。較佳所述共聚物為含有50~100重量%的(甲基)丙烯酸酯單體等丙烯酸類單體的丙烯酸類聚合物。較佳所述共聚物為重均分子量為20萬~100萬的共聚物。較佳所述共聚物為不使具有羧基的共聚性的乙烯基單體共聚的共聚物。此外，從抑制透明導電性膜的ITO表面等對容易被腐蝕的被黏物的腐蝕性的角度出發，較佳製成不使具有羧基的共聚性乙烯基單體共聚的共聚物，由此將所述共聚物的酸值設為1.0以下。The polymerization method of the copolymer is not particularly limited, and suitable and well-known polymerization methods such as a solution polymerization method and an emulsion polymerization method can be used. Preferably, the copolymer is an acrylic polymer containing 50 to 100% by weight of acrylic monomers such as (meth)acrylate monomers. Preferably, the copolymer is a copolymer with a weight average molecular weight of 200,000 to 1 million. Preferably, the copolymer is a copolymer in which a copolymerizable vinyl monomer having a carboxyl group is not copolymerized. In addition, from the viewpoint of suppressing the corrosiveness of the ITO surface of the transparent conductive film to easily corroded adherends, it is preferable to form a copolymer that does not copolymerize a copolymerizable vinyl monomer having a carboxyl group. The acid value of the copolymer is set to 1.0 or less.

作為所述(E)熱交聯劑，可列舉出異氰酸酯類交聯劑、環氧類交聯劑、鋁螯合物類交聯劑等中的至少一種以上。 作為異氰酸酯類交聯劑，可列舉出六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)、二苯甲烷二異氰酸酯(MDI)、甲苯二異氰酸酯(TDI)、苯二亞甲基二異氰酸酯(XDI)等雙官能度異氰酸酯(二異氰酸酯化合物)、或它們的縮二脲改性體、異氰脲酸酯改性體、加合物等三官能度以上的多異氰酸酯(polyisocyanate)化合物。此處，三官能度以上的加合物可列舉出二異氰酸酯化合物與三羥甲基丙烷、甘油等三元以上的多元醇的加合物。作為所述(E)熱交聯劑，也可以僅使用異氰酸酯化合物。 所述共聚物較佳具有羥基作為可與所述(E)熱交聯劑反應的官能團，特佳共聚有所述(D)。 此外，相對於100重量份的所述(A)，所述光學用黏著劑組合物較佳以0.01~5重量份的比例含有所述(E)熱交聯劑。As said (E) thermal crosslinking agent, at least 1 or more types of isocyanate type crosslinking agent, epoxy type crosslinking agent, aluminum chelate type crosslinking agent, etc. are mentioned. Examples of isocyanate-based crosslinking agents include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and xylylene diisocyanate Diisocyanate (XDI) and other bifunctional isocyanates (diisocyanate compounds), or their biuret-modified products, isocyanurate-modified products, adducts, and other polyisocyanates with tri-functionality or higher (polyisocyanate) Compound. Here, the adduct having a trifunctionality or higher may include an adduct of a diisocyanate compound and a trivalent or higher polyol such as trimethylolpropane and glycerin. As the (E) thermal crosslinking agent, only an isocyanate compound may be used. The copolymer preferably has a hydroxyl group as a functional group capable of reacting with the (E) thermal crosslinking agent, and the (D) is particularly preferably copolymerized. In addition, the optical adhesive composition preferably contains the (E) thermal crosslinking agent in a ratio of 0.01 to 5 parts by weight relative to 100 parts by weight of the (A).

作為所述(F)，可列舉出在一分子內具有(甲基)丙烯醯基與烯丙基醚基的(甲基)丙烯酸酯的單體中的至少一種以上。由於(甲基)丙烯醯基及烯丙基醚基分別具有乙烯性不飽和基團，因此所述(F)具有兩個以上的乙烯性不飽和基團。所述(F)在一分子內所具有的(甲基)丙烯醯基的個數為1或2個以上，所述(F)在一分子內所具有的烯丙基醚基的個數為1或2個以上。所述(F)在一分子內所具有的(甲基)丙烯醯基的個數與烯丙基醚基的個數可以不同，但較佳為相同的數目。As said (F), at least one or more of the monomers of the (meth)acrylate which has a (meth)acrylic acid group and an allyl ether group in one molecule are mentioned. Since the (meth)acrylic acid group and the allyl ether group each have an ethylenically unsaturated group, the (F) has two or more ethylenically unsaturated groups. The number of (meth)acrylic acid groups in one molecule of (F) is 1 or 2 or more, and the number of allyl ether groups in one molecule of (F) is 1 or 2 or more. The number of (meth)acrylic acid groups and the number of allyl ether groups in one molecule of (F) may be different, but are preferably the same number.

此外，在本實施方式的光學用黏著劑組合物中，所述(F)具有顯著地提高黏著劑層的濕熱耐久性的功能。使光學用黏著劑組合物包含所述(F)時，黏著劑層的濕熱耐久性得以顯著提高的理由尚不明確，但認為其理由之一可能如下所述。 其理由在於，利用所述(H)光交聯劑而使所述(F)進行交聯時，(甲基)丙烯醯基與烯丙基醚基形成環狀結構。並且推測，當利用所述(H)光交聯劑而使所述(F)進行交聯時，形成具有由(甲基)丙烯醯基與烯丙基醚基形成的環狀結構的聚合物，和/或，該環狀結構與所述丙烯酸類聚合物的共聚物進行交聯等，由此在長時間放置於濕熱環境下的黏著劑層中，濕熱環境下的水分被封閉在該環狀結構的內部，即使在此後將黏著劑層取出至室溫環境(溫度23℃×50%RH)下，水分的自由移動也被阻止且水分聚集所引起的起泡也受到抑制。 認為出於上述理由，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段而進行交聯後的黏著劑層具備優異的濕熱耐久性。利用所述(H)光交聯劑而使所述(F)交聯從而形成黏著劑層時，為了形成環狀結構，較佳利用所述(E)熱交聯劑交聯而成的黏著劑層含有所述(F)，且所述(F)維持兩個以上的乙烯性不飽和基團的反應性。因此，利用所述(E)熱交聯劑進行交聯時，較佳所述光學用黏著劑組合物不含有熱聚合引發劑。In addition, in the optical adhesive composition of the present embodiment, the (F) has a function of remarkably improving the wet heat durability of the adhesive layer. When the optical adhesive composition contains the above (F), the reason why the wet heat durability of the adhesive layer is significantly improved is not yet clear, but one of the reasons is thought to be as follows. The reason is that when the (F) is crosslinked by the (H) photocrosslinking agent, the (meth)acrylic acid group and the allyl ether group form a cyclic structure. It is also speculated that when the (F) is crosslinked by the (H) photocrosslinking agent, a polymer having a cyclic structure formed of a (meth)acrylic acid group and an allyl ether group is formed , And/or, the cyclic structure and the copolymer of the acrylic polymer are cross-linked, etc., so that in the adhesive layer placed in a humid and hot environment for a long time, the moisture in the humid and hot environment is enclosed in the ring Even if the adhesive layer is taken out in a room temperature environment (temperature 23°C×50%RH) afterwards, the free movement of water is prevented and the blistering caused by the accumulation of water is also suppressed. It is considered that for the above reasons, the adhesive layer after crosslinking through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent has Excellent damp and heat durability. When the (H) photocrosslinking agent is used to crosslink the (F) to form an adhesive layer, in order to form a cyclic structure, it is preferable to use the (E) thermal crosslinking agent to crosslink the adhesive The agent layer contains the (F), and the (F) maintains the reactivity of two or more ethylenically unsaturated groups. Therefore, when the (E) thermal crosslinking agent is used for crosslinking, it is preferable that the optical adhesive composition does not contain a thermal polymerization initiator.

此外，作為所述(F)，可列舉出含烯丙基醚基的(甲基)丙烯酸烷基酯[CH2 =C(R1 )COO-R2 -OCH2 CH=CH2 ；此處，R1 為氫原子或甲基、R2 為伸烷基等二價基團]、2-(烯丙氧基甲基)丙烯酸烷基酯[CH2 =CHCH2 OCH2 C(=CH2 )COOR；此處，R為烷基]等。作為環狀結構，特佳能夠形成穩定性高的五元環或六元環。 作為所述(F)的具體例，可列舉出烯丙氧基乙基(甲基)丙烯酸酯、烯丙氧基丙基(甲基)丙烯酸酯、2-(烯丙氧基甲基)丙烯酸甲酯、2-(烯丙氧基甲基)丙烯酸乙酯、2-(烯丙氧基甲基)丙烯酸丙酯、2-(烯丙氧基甲基)丙烯酸丁酯、2-(烯丙氧基甲基)丙烯酸戊酯、2-(烯丙氧基甲基)丙烯酸己酯等。 此外，相對於100重量份的所述(A)，所述光學用黏著劑組合物較佳以0.1~10重量份的比例含有所述(F)。In addition, as the (F), an allyl ether group-containing alkyl (meth)acrylate [CH 2 =C(R 1 )COO-R 2 -OCH 2 CH=CH 2 ; here , R 1 is a hydrogen atom or a methyl group, R 2 is a divalent group such as an alkylene group], 2-(allyloxymethyl) acrylate alkyl ester [CH 2 =CHCH 2 OCH 2 C(=CH 2 ) COOR; here, R is an alkyl group] and so on. As a cyclic structure, it is particularly preferable to form a five-membered ring or a six-membered ring with high stability. As specific examples of (F), allyloxyethyl (meth)acrylate, allyloxypropyl (meth)acrylate, 2-(allyloxymeth)acrylic acid Methyl ester, ethyl 2-(allyloxymeth)acrylate, propyl 2-(allyloxymeth)acrylate, butyl 2-(allyloxymeth)acrylate, 2-(allyloxymethyl) Pentyl oxymeth)acrylate, hexyl 2-(allyloxymeth)acrylate and the like. In addition, the optical adhesive composition preferably contains the (F) in a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of the (A).

作為所述(G)，可列舉出具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體中的至少一種以上。 此外，所述(G)例如只要為將伸烷基二醇(alkylene glycol)、聚伸烷基二醇等所具有的多個羥基中的兩個以上的羥基酯化成(甲基)丙烯酸酯的化合物即可。 此外，在所述(G)中，構成聚伸烷基二醇鏈的環氧烷的平均重複數較佳為4~14。此處，「環氧烷的平均重複數」是指在「聚伸烷基二醇鏈」的部分中，環氧烷單元重複的平均數。所述(G)的環氧烷的平均重複數可以與所述(C)的環氧烷的平均重複數相同，也可以不同。As said (G), at least one or more of the monomers of the (meth)acrylate which has an alkylene oxide group and two or more ethylenic unsaturated groups in one molecule is mentioned. In addition, the (G) may be, for example, those obtained by esterifying two or more of the multiple hydroxyl groups possessed by alkylene glycol and polyalkylene glycol into (meth)acrylate. Compound is sufficient. In addition, in the above (G), the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain is preferably 4-14. Here, "the average repeating number of alkylene oxide" refers to the average number of repeating alkylene oxide units in the part of the "polyalkylene glycol chain". The average repeating number of the alkylene oxide of (G) may be the same as or different from the average repeating number of the alkylene oxide of (C).

在所述(G)中，作為所述環氧烷基，可列舉出環氧乙烷(ethylene oxide)基、環氧丙烷(propylene oxide)基、環氧丁烷(butylene oxide)基等中的至少一種以上。所述(G)所具有的環氧烷基可以與所述(C)所具有的環氧烷基相同，也可以不同。作為所述(G)的具體例，可列舉出聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯等。 此外，相對於100重量份的所述(A)，所述光學用黏著劑組合物較佳以0.1~10重量份的比例含有所述(G)。In (G), examples of the alkylene oxide group include ethylene oxide group, propylene oxide group, butylene oxide group, etc. At least one or more. The alkylene oxide group that the (G) has may be the same as or different from the alkylene oxide group that the (C) has. Specific examples of (G) include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and the like. In addition, the optical adhesive composition preferably contains the (G) in a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of the (A).

作為所述(H)光交聯劑，例如可列舉出光自由基引發劑等光引發劑。為了利用所述(E)熱交聯劑而使所述光學用黏著劑組合物交聯後，利用所述(H)光交聯劑而使其交聯從而形成黏著劑層，較佳所述(H)光交聯劑即使在利用所述(E)熱交聯劑進行交聯後的階段也維持反應性。作為這種(H)光交聯劑，例如可列舉出苯乙酮類光交聯劑、苯偶姻類光交聯劑、二苯甲酮類光交聯劑、噻噸酮類光交聯劑、醯基氧化膦類光交聯劑等。 此外，相對於100重量份的所述(A)，所述光學用黏著劑組合物較佳以0.01~5重量份的比例含有所述(H)光交聯劑。As said (H) photocrosslinking agent, photoinitiators, such as a photoradical initiator, are mentioned, for example. In order to use the (E) thermal crosslinking agent to crosslink the optical adhesive composition, then use the (H) photocrosslinking agent to crosslink to form an adhesive layer, preferably the (H) The photocrosslinking agent maintains reactivity even in the stage after crosslinking with the (E) thermal crosslinking agent. Examples of such (H) photocrosslinking agents include acetophenone-based photocrosslinking agents, benzoin-based photocrosslinking agents, benzophenone-based photocrosslinking agents, and thioxanthone-based photocrosslinking agents. Agent, phosphine oxide-based photo-crosslinking agent, etc. In addition, the optical adhesive composition preferably contains the (H) photocrosslinking agent in a ratio of 0.01 to 5 parts by weight relative to 100 parts by weight of the (A).

作為苯乙酮類光交聯劑，可列舉出苯乙酮、對(三級丁基)1’,1’,1’-三氯苯乙酮、氯苯乙酮、2’,2’-二乙氧基苯乙酮、羥基苯乙酮、2,2-二甲氧基-2’-苯基苯乙酮、2-胺基苯乙酮、二烷基胺基苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮等。 作為苯偶姻類光交聯劑，可列舉出二苯乙二酮(benzil)、苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻異丁醚、1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、芐基二甲基縮酮(benzyl dimethyl ketal)、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等。 作為二苯甲酮類光交聯劑，可列舉出二苯甲酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、甲基鄰苯甲醯基苯甲酸酯、4-苯基二苯甲酮、羥基二苯甲酮、羥基丙基二苯甲酮、丙烯酸二苯甲酮、4,4’-雙(二甲基胺基)二苯甲酮等。 作為噻噸酮類光交聯劑，可列舉出噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、二乙基噻噸酮、二甲基噻噸酮等。 作為醯基氧化膦類光交聯劑，可列舉出(2,4,6-三甲基苯甲醯基)二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等。 作為其他光交聯劑，可列舉出α-醯基肟酯(acyl oxime ester)、苄基-(鄰乙氧基羰基)-α-單肟、苯甲醯甲酸酯、3-香豆素酮、2-乙基蒽醌、樟腦醌(camphorquinone)、硫化四甲基秋蘭姆、偶氮雙異丁腈、過氧化苯甲醯、二烷基過氧化物、過氧化異丁酸三級丁酯(tert-butyl peroxypivalate)等。As the acetophenone-based photocrosslinking agent, acetophenone, p-(tertiary butyl) 1',1',1'-trichloroacetophenone, chloroacetophenone, 2',2'- Diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2'-phenylacetophenone, 2-aminoacetophenone, dialkylaminoacetophenone, 2- Hydroxy-2-methyl-1-phenyl-propan-1-one and so on. As the benzoin-based photocrosslinking agent, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be cited. , 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropane-1-one, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. As the benzophenone-based photocrosslinking agent, benzophenone, benzoic acid, methyl benzoic acid, methyl benzoic acid ester, 4-benzene Base benzophenone, hydroxybenzophenone, hydroxypropyl benzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, etc. As the thioxanthone-based photocrosslinking agent, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, etc. may be mentioned. As the phosphine oxide-based photocrosslinking agent, (2,4,6-trimethylbenzyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) ) Phenyl phosphine oxide and the like. Other photocrosslinking agents include α-acyl oxime ester, benzyl-(o-ethoxycarbonyl)-α-monooxime, benzyl carboxylate, 3-coumarin Ketone, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, and isobutyric acid peroxide Butyl (tert-butyl peroxypivalate) and so on.

所述光學用黏著劑組合物中可適當地摻合抗氧化劑、表面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、固化延遲劑、加工助劑、抗老化劑等公知的添加劑作為任意的成分。這些添加劑能夠單獨使用，或同時使用兩種以上。The optical adhesive composition can be appropriately blended with antioxidants, surfactants, curing accelerators, plasticizers, fillers, cross-linking catalysts, cross-linking retarders, curing retarders, processing aids, and antioxidants. Known additives such as ageing agents are used as optional components. These additives can be used singly, or two or more of them can be used at the same time.

本實施方式的黏著劑層能夠藉由將所述光學用黏著劑組合物塗佈於基材或脫模膜，然後藉由基於所述(E)熱交聯劑的交聯與基於所述(H)光交聯劑的交聯而使所述光學用黏著劑組合物進行交聯而製作。對於本實施方式的黏著劑層，利用所述(E)熱交聯劑進行交聯後、利用所述(H)光交聯劑進行交聯之前的黏著劑層(第一階段)的段差追隨性、再操作時的處理性能優異。進一步，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段交聯而成的黏著劑層(第二階段)的濕熱耐久性優異。對於本實施方式的黏著劑層，可根據用途、目的等，將第一階段的黏著劑層貼合於被黏物，也可以將第二階段的黏著劑層貼合於被黏物。 第一階段的黏著劑層含有所述(H)光交聯劑，可利用所述(H)光交聯劑進行交聯。將第一階段的黏著劑層貼合於被黏物時，也可以利用所述(H)光交聯劑而使處在貼合於被黏物的狀態的黏著劑層進行交聯。 作為利用所述(H)光交聯劑進行交聯時所照射的能量射線，可列舉出紫外線、電子束，視情況可列舉出可見光等，就簡便性這一點而言，適宜使用紫外線。然而，在本發明中，並不限定於紫外線。進行能量射線的照射時，可以使黏著劑層露出，但若積層於黏著劑層的脫模膜或被黏物對能量射線具有透射性，則較佳隔著脫模膜或被黏物對黏著劑層進行能量射線的照射。The adhesive layer of this embodiment can be achieved by applying the optical adhesive composition to a substrate or a release film, and then by crosslinking based on the (E) thermal crosslinking agent and based on the ( H) Crosslinking of a photocrosslinking agent to crosslink the optical adhesive composition to produce. For the adhesive layer of the present embodiment, after cross-linking with the (E) thermal cross-linking agent and before cross-linking with the (H) photo-cross-linking agent, the step of the adhesive layer (first stage) follows Excellent processing performance during re-operation. Further, the adhesive layer (the second stage) formed by the two stages of crosslinking based on the (E) thermal crosslinking agent and the subsequent crosslinking based on the (H) photocrosslinking agent Excellent damp heat durability. Regarding the adhesive layer of this embodiment, the adhesive layer of the first stage may be attached to the adherend according to use, purpose, etc., or the adhesive layer of the second stage may be attached to the adherend. The adhesive layer of the first stage contains the (H) photocrosslinking agent, and can be crosslinked with the (H) photocrosslinking agent. When bonding the adhesive layer of the first stage to the adherend, the (H) photocrosslinking agent may be used to crosslink the adhesive layer in a state of being bonded to the adherend. Examples of the energy rays irradiated when crosslinking with the (H) photocrosslinking agent include ultraviolet rays, electron beams, and visible light as appropriate. In terms of simplicity, ultraviolet rays are suitably used. However, in the present invention, it is not limited to ultraviolet rays. When the energy ray is irradiated, the adhesive layer can be exposed, but if the release film or adherend layered on the adhesive layer is transmissive to energy rays, it is better to adhere to the adhesive through the release film or adherend. The agent layer is irradiated with energy rays.

較佳將本實施方式的光學用黏著劑組合物製成黏著劑層時的光學特性優異。所述光學用黏著劑組合物較佳是透明的。較佳所述添加劑的功能或分量等不損害所述黏著劑層的透明性(非著色性)。此外，較佳由所述光學用黏著劑組合物製作的黏著劑層(第一階段的黏著劑層或第二階段的黏著劑層)是透明的。 具體而言，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成的厚度為250μm的黏著劑層的總透光率較佳為90%以上，總透光率更佳為91%以上。 此外，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成的厚度為250μm的黏著劑層的霧度值較佳為1.0%以下，霧度值更佳為0.6%以下。 此外，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成厚度為250μm的黏著劑層在溫度60℃×相對濕度90%RH的氣氛下放置240小時後，取出至室溫環境(溫度23℃×50%RH)時的霧度值較佳為4.0%以下，霧度值更佳為3.5%以下。It is preferable that the optical adhesive composition of this embodiment is excellent in optical characteristics when it is made into an adhesive layer. The optical adhesive composition is preferably transparent. It is preferable that the function or amount of the additive does not impair the transparency (non-coloring) of the adhesive layer. In addition, it is preferable that the adhesive layer (the first-stage adhesive layer or the second-stage adhesive layer) made of the optical adhesive composition is transparent. Specifically, the optical adhesive composition is cross-linked through two stages of cross-linking based on the (E) thermal cross-linking agent and subsequent cross-linking based on the (H) photo-crosslinking agent. The total light transmittance of the adhesive layer with a thickness of 250 μm formed by coupling is preferably 90% or more, and the total light transmittance is more preferably 91% or more. In addition, the optical adhesive composition is crosslinked through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent. The formed adhesive layer with a thickness of 250 μm preferably has a haze value of 1.0% or less, and more preferably has a haze value of 0.6% or less. In addition, the optical adhesive composition is crosslinked through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent. The formed adhesive layer with a thickness of 250μm is placed in an atmosphere of 60℃×90%RH for 240 hours, and then taken out to room temperature environment (temperature 23℃×50%RH), the haze value is preferably 4.0% Below, the haze value is more preferably 3.5% or less.

利用所述(E)熱交聯劑進行交聯後(利用所述(H)光交聯劑進行交聯之前)的所述黏著劑層對鈉鈣玻璃的黏著力較佳為10N/25mm以下。由此，能夠提高黏著劑層的再操作時的處理性能。 進一步，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段而交聯的黏著劑層對鈉鈣玻璃的黏著力較佳為25N/25mm以上。將第一階段的黏著劑層貼合於被黏物後再利用所述(H)光交聯劑進行交聯時，也能夠與製作第二階段的黏著劑層後再貼合於被黏物的情況相同地，得到高黏著力。 對於將黏著劑層積層在厚度為188μm的聚鄰苯二甲酸乙二醇酯樹脂膜的單面上而成的黏著膜，將所述黏著膜介由厚度為100μm的所述黏著劑層而貼合於具有厚度為42μm的印刷層的印刷段差的玻璃時，較佳對所述印刷段差的追隨性良好，且在所述印刷段差的周圍完全沒有起泡。所述黏著劑層藉由使用所述光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成。The adhesive force of the adhesive layer after crosslinking with the (E) thermal crosslinking agent (before crosslinking with the (H) photocrosslinking agent) to the soda lime glass is preferably 10N/25mm or less . Thereby, it is possible to improve the handling performance during the rework of the adhesive layer. Further, the adhesion of the adhesive layer crosslinked to soda lime glass through two stages of crosslinking based on the (E) thermal crosslinking agent and subsequent crosslinking based on the (H) photocrosslinking agent Preferably it is 25N/25mm or more. When the first-stage adhesive layer is bonded to the adherend and then cross-linked with the (H) photocrosslinking agent, it can also be bonded to the adherend after the second-stage adhesive layer is made In the same way, high adhesion is obtained. For an adhesive film formed by laminating an adhesive on one side of a polyethylene phthalate resin film with a thickness of 188 μm, the adhesive film is pasted via the adhesive layer with a thickness of 100 μm When it is applied to a glass having a printing step with a printing layer having a thickness of 42 μm, it is preferable that the followability to the printing step is good, and there is no blistering at all around the printing step. The adhesive layer is formed by using the optical adhesive composition and crosslinking with the (E) thermal crosslinking agent.

本實施方式的黏著膜及黏著片能夠藉由在基材或脫模膜的單面上形成所述黏著劑層而製造。另外，在JIS Z0109(黏著膠帶·黏著片術語)的2015年版中，將「黏著片」定義為「在基材的單面或雙面上設有黏著劑層的、板狀的且貼合有剝離襯墊的物品的總稱」，與定義為「在基材的單面或雙面上設有黏著劑層，並捲繞成輥狀的物品的總稱」的「黏著膠帶」有所區分，但本實施方式的黏著膜及黏著片並不限定於此。所述黏著膜及黏著片中的黏著劑層的厚度沒有特別限定，例如較佳為10~3000μm，更佳為50~2000μm。The adhesive film and the adhesive sheet of this embodiment can be manufactured by forming the said adhesive layer on the single side|surface of a base material or a release film. In addition, in the 2015 edition of JIS Z0109 (Adhesive Tape and Adhesive Sheet Terminology), "adhesive sheet" is defined as "a sheet with an adhesive layer on one or both sides of a substrate, plate-like and laminated with The general term of the release liner article is distinguished from the “adhesive tape” which is defined as “the general term for the article that has an adhesive layer on one or both sides of the substrate and is wound into a roll”, but The adhesive film and adhesive sheet of this embodiment are not limited to this. The thickness of the adhesive layer in the adhesive film and the adhesive sheet is not particularly limited. For example, it is preferably 10 to 3000 μm, more preferably 50 to 2000 μm.

作為用於所述黏著劑層的形成的基材膜或保護黏著面的脫模膜(分離膜)，能夠使用聚酯膜等樹脂膜等。 在基材膜中，能夠對樹脂膜的與形成有黏著劑層的一側相反的面實施利用矽酮類、氟類脫模劑或塗佈劑、二氧化矽微粒等的防汙處理，基於抗靜電劑的塗佈或捏合等的抗靜電處理。 在脫模膜中，可利用矽酮類、氟類脫模劑等對與黏著劑層的黏著面進行貼合的一側的面實施脫模處理。藉由將脫模膜的實施了脫模處理的面分別貼合於一個黏著劑層的雙面，也能夠製成具有「脫模膜/黏著劑層/脫模膜」的構成的黏著片。此時，藉由依次或同時剝離兩側的脫模膜而使黏著面露出，可將光學膜等光學構件貼合於玻璃等被黏物。作為光學膜，可列舉出偏振膜、相位差膜、抗反射膜、防眩(anti-glare)膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜等。As the base film used for the formation of the adhesive layer or the release film (separation film) for protecting the adhesive surface, a resin film such as a polyester film or the like can be used. In the base film, the surface of the resin film opposite to the side on which the adhesive layer is formed can be treated with antifouling treatment using silicones, fluorine-based mold release agents or coating agents, silica particles, etc., based on Antistatic treatment such as coating or kneading of antistatic agent. In the release film, the surface on the side to be bonded to the adhesive surface of the adhesive layer can be subjected to a release treatment with a silicone-based, fluorine-based release agent, or the like. By sticking the release-treated surface of the release film on both sides of one adhesive layer, it is also possible to form an adhesive sheet having a configuration of "release film/adhesive layer/release film". At this time, by peeling the release films on both sides sequentially or at the same time to expose the adhesive surfaces, optical members such as optical films can be bonded to adherends such as glass. As an optical film, a polarizing film, a retardation film, an anti-reflection film, an anti-glare film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, a brightness improvement film, etc. are mentioned.

由於所述黏著劑層即使在蓋板玻璃(cover glass)與感測器玻璃(sensor glass)這樣的玻璃與玻璃的貼合中也可得到良好的段差追隨性，因此能夠在貼合觸控面板的蓋板玻璃與感測器玻璃時適宜地進行使用。此外，當貼合膜構件與玻璃構件時，將所述黏著劑層積層於膜構件的單面而得到的所述黏著膜也能夠貼合於蓋板玻璃、感測器玻璃等玻璃構件上。所述黏著劑層及黏著膜適宜作為觸控面板用黏著劑層及觸控面板用黏著膜。作為使用了所述黏著膜的觸控面板用膜，除了觸控面板用黏著膜以外，可列舉出後述的觸控面板用的各種光學膜等。Since the adhesive layer can obtain good step followability even in the bonding of glass and glass such as cover glass and sensor glass, it can be used in bonding touch panels. The cover glass and the sensor glass are used appropriately. In addition, when bonding a film member and a glass member, the adhesive film obtained by laminating the adhesive on one side of the film member can also be bonded to glass members such as cover glass and sensor glass. The adhesive layer and adhesive film are suitable as an adhesive layer for touch panels and an adhesive film for touch panels. As the film for touch panels using the said adhesive film, in addition to the adhesive film for touch panels, various optical films for touch panels mentioned later, etc. are mentioned.

所述黏著膜及所述黏著片能夠用於貼合以偏振片為主的液晶顯示裝置的周圍構件用的各種光學膜、觸控面板用的各種光學膜、電子紙用的各種光學膜、有機EL用的各種光學膜等。 此外，能夠製成在這些光學膜的至少一個面上積層有所述黏著劑層的帶黏著劑層的光學膜。具體而言，可列舉出「光學膜/黏著劑層/光學膜」、「光學膜/黏著劑層/脫模膜」、「光學膜/黏著劑層」、「光學膜/黏著劑層/光學膜/黏著劑層/光學膜」、「光學膜/黏著劑層/光學膜/黏著劑層/脫模膜」、「脫模膜/黏著劑層/光學膜/黏著劑層/脫模膜」等構成。 例如，當如「光學膜/黏著劑層/脫模膜」這樣，具有被脫模膜保護的黏著劑層時，藉由剝離脫模膜，以「光學膜/黏著劑層」的形式使黏著劑層露出，並與其他光學膜貼合，可得到黏著劑層被用於層間貼合的「光學膜/黏著劑層/光學膜」這種構成。The adhesive film and the adhesive sheet can be used to bond various optical films for peripheral components of liquid crystal display devices, mainly polarizers, various optical films for touch panels, various optical films for electronic paper, and organic Various optical films for EL. Moreover, it can be set as the optical film with an adhesive layer in which the said adhesive layer was laminated|stacked on at least one surface of these optical films. Specifically, "optical film/adhesive layer/optical film", "optical film/adhesive layer/release film", "optical film/adhesive layer", "optical film/adhesive layer/optical Film/adhesive layer/optical film", "optical film/adhesive layer/optical film/adhesive layer/release film", "release film/adhesive layer/optical film/adhesive layer/release film" And other composition. For example, when there is an adhesive layer protected by a release film like "optical film/adhesive layer/release film", by peeling off the release film, it will be adhered in the form of "optical film/adhesive layer" The agent layer is exposed and bonded with other optical films to obtain a structure of "optical film/adhesive layer/optical film" in which the adhesive layer is used for interlayer bonding.

所述黏著膜及黏著片適宜用於貼合偏振片與顯示器面板。作為顯示器面板，例如可列舉出液晶面板或有機EL面板。所述黏著膜及黏著片能夠適宜地用作帶黏著劑層的偏振片的黏著劑層。作為偏振片的構成材料，也可以使用具有λ/4或λ/2的相位差的相位差膜。貼合相位差膜與偏振片時，能夠使用所述黏著劑層。根據所述黏著膜及黏著片，由於黏著劑層的介電常數低，因此在彩色濾光片與偏振片之間設置有觸控感測器的On-cell方式的顯示裝置中，能夠適宜地用於偏振片與背光單元之間的光學構件的貼合。此外，當固定安裝於各種電子設備的光學部件及電子部件時，能夠使用所述黏著膜及黏著片。 [實施例]The adhesive film and the adhesive sheet are suitable for bonding a polarizer and a display panel. As the display panel, for example, a liquid crystal panel or an organic EL panel can be cited. The adhesive film and the adhesive sheet can be suitably used as an adhesive layer of a polarizing plate with an adhesive layer. As a constituent material of the polarizing plate, a retardation film having a retardation of λ/4 or λ/2 can also be used. When bonding a retardation film and a polarizing plate, the said adhesive layer can be used. According to the adhesive film and the adhesive sheet, since the dielectric constant of the adhesive layer is low, the on-cell display device in which the touch sensor is provided between the color filter and the polarizer can be suitably used Used for bonding of the optical member between the polarizing plate and the backlight unit. In addition, the adhesive film and adhesive sheet can be used when fixing optical components and electronic components mounted on various electronic devices. [Example]

以下，利用實施例對本發明進行具體說明。Hereinafter, the present invention will be specifically explained using examples.

＜丙烯酸類聚合物的製備＞ [實施例1] 向具備攪拌器、溫度計、回流冷凝器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換反應裝置內的空氣。然後，向反應裝置中加入70重量份的丙烯酸2-乙基己酯、10重量份的丙烯酸乙酯、20重量份的丙烯酸異冰片酯、5重量份的N-乙烯基吡咯烷酮、4重量份的聚丙二醇單丙烯酸酯(環氧烷的平均重複數n=12)、3.0重量份的丙烯酸6-羥基己酯及60重量份的溶劑(乙酸乙酯)。然後，經2小時滴加0.1重量份的作為聚合引發劑的偶氮雙異丁腈，於65℃反應6小時，得到實施例1中使用的丙烯酸類聚合物溶液。 [實施例2~5及比較例1~3] 除了使單體的組成分別如表1的(A)組~(D)組的記載所示以外，以與上述實施例1中使用的丙烯酸類聚合物溶液相同的方式，得到實施例2~5及比較例1~3中使用的丙烯酸類聚合物溶液。＜Preparation of acrylic polymer＞ [Example 1] Nitrogen was introduced into the reaction device equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe, and the air in the reaction device was replaced with nitrogen. Then, 70 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of ethyl acrylate, 20 parts by weight of isobornyl acrylate, 5 parts by weight of N-vinylpyrrolidone, 4 parts by weight of Polypropylene glycol monoacrylate (average number of repeating alkylene oxide n=12), 3.0 parts by weight of 6-hydroxyhexyl acrylate, and 60 parts by weight of solvent (ethyl acetate). Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65°C for 6 hours to obtain the acrylic polymer solution used in Example 1. [Examples 2 to 5 and Comparative Examples 1 to 3] Except that the composition of the monomers is as shown in the description of the (A) group to the (D) group in Table 1, in the same manner as the acrylic polymer solution used in the above-mentioned Example 1, Examples 2 to 5 were obtained. And the acrylic polymer solution used in Comparative Examples 1 to 3.

＜黏著劑組合物、黏著劑層及黏著片的製備＞ [實施例1] 向以上述方式製備的實施例1的丙烯酸類聚合物溶液中加入0.5重量份的CORONATE HX、5重量份的2-(烯丙氧基甲基)丙烯酸甲酯、5重量份的聚乙二醇二丙烯酸酯(環氧烷的平均重複數n=4)、0.5重量份的光交聯劑(Omnirad(註冊商標)184)，並攪拌混合，得到實施例1的黏著劑組合物。將該黏著劑組合物以乾燥後的黏著劑層的厚度成為規定值的方式塗佈在脫模膜(1)(塗佈有作為脫模劑層的矽酮樹脂、且基材的厚度為100μm的聚對苯二甲酸乙二醇酯(PET)膜)上後，藉由於90℃進行乾燥而去除溶劑，然後，在23℃、50%RH的氣氛下熟化7天，從而利用熱交聯劑使黏著劑組合物進行交聯而形成黏著劑層。進一步，將具有比所述脫模膜(1)更輕的剝離力的脫模劑層、且基材的厚度為75μm的脫模膜(2)貼合於所述黏著劑層的表面，得到由脫模膜(1)/黏著劑層/脫模膜(2)構成的實施例1的黏著片A(形成第一階段的黏著劑層)。對利用該熱交聯劑進行交聯後的黏著劑層進一步照射紫外線(UV)，並利用光交聯劑使其交聯。由此，得到黏著劑層被兩片脫模膜夾持的實施例1的黏著片B(形成第二階段的黏著劑層)，所述黏著劑層藉由實施基於熱交聯的交聯與基於光交聯的交聯這兩個階段而成。 [實施例2~5及比較例1~3] 除了使添加劑的組成分別如表1的(E)組~(H)組的記載所示以外，以與上述實施例1的黏著片A~B相同的方式，得到實施例2~5及比較例1~3的黏著片A~B。<Preparation of adhesive composition, adhesive layer and adhesive sheet> [Example 1] To the acrylic polymer solution of Example 1 prepared in the above manner, 0.5 parts by weight of CORONATE HX, 5 parts by weight of methyl 2-(allyloxymeth)acrylate, and 5 parts by weight of polyethylene glycol were added Diacrylate (the average repeating number of alkylene oxide n=4), 0.5 parts by weight of a photocrosslinking agent (Omnirad (registered trademark) 184) were stirred and mixed, and the adhesive composition of Example 1 was obtained. The adhesive composition is coated on the release film (1) (coated with silicone resin as the release agent layer, and the thickness of the substrate is 100μm) so that the thickness of the adhesive layer after drying becomes a predetermined value After the polyethylene terephthalate (PET) film) is applied, the solvent is removed by drying at 90°C, and then cured for 7 days under an atmosphere of 23°C and 50% RH to use a thermal crosslinking agent The adhesive composition is crosslinked to form an adhesive layer. Furthermore, a release film (2) having a release agent layer having a lighter peeling force than the release film (1) and a base material having a thickness of 75 μm was attached to the surface of the adhesive layer to obtain The adhesive sheet A of Example 1 (formed the first-stage adhesive layer) composed of a release film (1)/adhesive layer/release film (2). The adhesive layer crosslinked by the thermal crosslinking agent is further irradiated with ultraviolet (UV), and the photocrosslinking agent is used to crosslink the adhesive layer. Thus, the adhesive sheet B of Example 1 in which the adhesive layer was sandwiched by two release films (forming the second-stage adhesive layer) was obtained, and the adhesive layer was cross-linked and cross-linked by thermal cross-linking. Based on the two stages of photocrosslinking and crosslinking. [Examples 2 to 5 and Comparative Examples 1 to 3] Except that the composition of the additives is as shown in the description of the (E) group to the (H) group in Table 1, in the same manner as the adhesive sheets A to B of the above-mentioned Example 1, Examples 2 to 5 and Comparative Examples are obtained Adhesive sheets A~B of 1~3.

[表1]   (A) (B) (C) (D) (E) (F) (G) (H) 實施例1 2EHA 70 EA 10 IBOA 20 NVP 5 C-1 4 6HHA 3.0 HX 0.5 F-1 5 G-1 5 H-1 0.5 實施例2 IOA 80 ISTA 10 IDA 10 DEAA 6 C-2 5 4HBA 3.5 HL 1.5 F-2 8 G-2 3 H-1 0.4 實施例3 IOA 70 BA 5 IBOA 5 IDA 20 DMAA 4 C-3 3 HEA 4.0 L-45 1.0 F-3 3 G-2 8 H-2 0.3 實施例4 2EHA 50 IOA 20 IBOA 20 IDA 10 MTA 6 C-3 8 HEAA 2.0 24A 1.0 F-4 3 G-1 5 H-1 0.1 H-3 0.1 實施例5 2EHA 60 BA 10 IBOA 10 IDA 20 ETA 5 C-2 6 4HBA 4.5 HL 1.0 F-1 4 G-2 4 H-1 0.25 比較例1 2EHA 100 - C-4 12 HEA 4.0 L-45 1.0 F-1 12 - H-1 0.2 比較例2 2EHA 30 BA 40 EA 20 IBOA 10 ETA 1 - 4HBA 3.5 HX 5.5 - G-3 5 H-2 0.5 比較例3 2EHA 90 BA 10 DEAA 15 C-1 4 HEA 2.0 HL 1.0 F-2 8 G-1 15 H-1 0.2 [Table 1] (A) (B) (C) (D) (E) (F) (G) (H) Example 1 2EHA 70 EA 10 IBOA 20 NVP 5 C-1 4 6HHA 3.0 HX 0.5 F-1 5 G-1 5 H-1 0.5 Example 2 IOA 80 ISTA 10 IDA 10 DEAA 6 C-2 5 4HBA 3.5 HL 1.5 F-2 8 G-2 3 H-1 0.4 Example 3 IOA 70 BA 5 IBOA 5 IDA 20 DMAA 4 C-3 3 HEA 4.0 L-45 1.0 F-3 3 G-2 8 H-2 0.3 Example 4 2EHA 50 IOA 20 IBOA 20 IDA 10 MTA 6 C-3 8 HEAA 2.0 24A 1.0 F-4 3 G-1 5 H-1 0.1 H-3 0.1 Example 5 2EHA 60 BA 10 IBOA 10 IDA 20 ETA 5 C-2 6 4HBA 4.5 HL 1.0 F-1 4 G-2 4 H-1 0.25 Comparative example 1 2EHA 100 - C-4 12 HEA 4.0 L-45 1.0 F-1 12 - H-1 0.2 Comparative example 2 2EHA 30 BA 40 EA 20 IBOA 10 ETA 1 - 4HBA 3.5 HX 5.5 - G-3 5 H-2 0.5 Comparative example 3 2EHA 90 BA 10 DEAA 15 C-1 4 HEA 2.0 HL 1.0 F-2 8 G-1 15 H-1 0.2

表1中示出了將(A)組的合計設為100重量份而求得的重量份的數值。此外，表2中示出了表1中使用的各成分的縮寫符號的化合物名稱。另外，CORONATE(註冊商標)為TOSOH股份有限公司的商品名稱，Duranate(註冊商標)為Asahi Kasei股份有限公司的商品名稱，Omnirad(註冊商標)為IGM公司的商品名稱。Omnirad 184為以1-羥基環己基苯基酮為主要成分的光交聯劑。Omnirad 651為以2,2-二甲氧基-2-苯基苯乙酮為主要成分的光交聯劑。Omnirad TPO為以(2,4,6-三甲基苯甲醯基)二苯基氧化膦為主要成分的光交聯劑。Table 1 shows the numerical values of parts by weight obtained by setting the total of the group (A) to 100 parts by weight. In addition, in Table 2, the compound name of the abbreviation of each component used in Table 1 is shown. In addition, CORONATE (registered trademark) is a product name of TOSOH Co., Ltd., Duranate (registered trademark) is a product name of Asahi Kasei Co., Ltd., and Omnirad (registered trademark) is a product name of IGM. Omnirad 184 is a photocrosslinking agent based on 1-hydroxycyclohexyl phenyl ketone. Omnirad 651 is a photocrosslinking agent with 2,2-dimethoxy-2-phenylacetophenone as the main component. Omnirad TPO is a photocrosslinking agent with (2,4,6-trimethylbenzyl) diphenyl phosphine oxide as the main component.

[表2] 組 縮寫符號 化合物名稱 (A) 2EHA 丙烯酸2-乙基己酯 IOA 丙烯酸異辛酯 BA 丙烯酸丁酯 EA 丙烯酸乙酯 IBOA 丙烯酸異冰片酯 ISTA 丙烯酸異硬脂酸酯 IDA 丙烯酸異癸酯 (B) NVP N-乙烯基吡咯烷酮 DEAA 二乙基丙烯醯胺 DMAA 二甲基丙烯醯胺 MTA 丙烯酸甲氧基乙酯 ETA 丙烯酸乙氧基乙酯 (C) C-1 聚丙二醇單丙烯酸酯(n=12) C-2 甲氧基聚乙二醇丙烯酸酯(n=8) C-3 甲氧基聚乙二醇甲基丙烯酸酯(n=9) C-4 甲氧基聚乙二醇甲基丙烯酸酯(n=23) (D) 6HHA 丙烯酸6-羥基己酯 4HBA 丙烯酸4-羥基丁酯 HEA 丙烯酸2-羥基乙酯 HEAA N-羥乙基丙烯醯胺 (E) HX CORONATE HX(HDI異氰脲酸酯體) HL CORONATE HL(HDI加合物) L-45 CORONATE L-45(TDI加合物) 24A Duranate 24A-100(HDI縮二脲體) (F) F-1 2-(烯丙氧基甲基)丙烯酸甲酯 F-2 2-(烯丙氧基甲基)丙烯酸乙酯 F-3 2-(烯丙氧基甲基)丙烯酸丁酯 F-4 2-(烯丙氧基甲基)丙烯酸己酯 (G) G-1 聚乙二醇二丙烯酸酯(n=4) G-2 聚乙二醇二丙烯酸酯(n=9) G-3 聚乙二醇二丙烯酸酯(n=23) (H) H-1 Omnirad 184 H-2 Omnirad 651 H-3 Omnirad TPO [Table 2] group Abbreviation Compound name (A) 2EHA 2-ethylhexyl acrylate IOA Isooctyl acrylate BA Butyl acrylate EA Ethyl acrylate IBOA Isobornyl acrylate ISTA Acrylic Isostearate IDA Isodecyl acrylate (B) NVP N-vinylpyrrolidone DEAA Diethyl acrylamide DMAA Dimethacrylamide MTA Methoxyethyl acrylate ETA Ethoxy ethyl acrylate (C) C-1 Polypropylene glycol monoacrylate (n=12) C-2 Methoxy polyethylene glycol acrylate (n=8) C-3 Methoxy polyethylene glycol methacrylate (n=9) C-4 Methoxy polyethylene glycol methacrylate (n=23) (D) 6HHA 6-hydroxyhexyl acrylate 4HBA 4-hydroxybutyl acrylate HEA 2-hydroxyethyl acrylate HEAA N-Hydroxyethyl allylamide (E) HX CORONATE HX (HDI isocyanurate body) HL CORONATE HL (HDI adduct) L-45 CORONATE L-45 (TDI adduct) 24A Duranate 24A-100 (HDI Biuret) (F) F-1 Methyl 2-(allyloxymeth)acrylate F-2 Ethyl 2-(allyloxymeth)acrylate F-3 2-(allyloxy meth) butyl acrylate F-4 2-(allyloxymeth)hexyl acrylate (G) G-1 Polyethylene glycol diacrylate (n=4) G-2 Polyethylene glycol diacrylate (n=9) G-3 Polyethylene glycol diacrylate (n=23) (H) H-1 Omnirad 184 H-2 Omnirad 651 H-3 Omnirad TPO

＜試驗方法及評價＞ 根據需要，從實施例1~5及比較例1~3中的黏著片A~B上剝離脫模膜(1)~(2)，使黏著劑層露出，並利用下述試驗方法及測定方法進行評價。 另外，關於實施例1~5及比較例1~3中的黏著片A~B，為了符合下述測定方法及試驗方法，準備了黏著劑層的厚度不同，進一步，形成有第一階段的黏著劑層的多種黏著片A、或形成有第二階段的黏著劑層的多種黏著片B。對第一階段的黏著劑層進行試驗時，使用黏著片A。此外，對第二階段的黏著劑層進行試驗時，使用黏著片B。＜Test method and evaluation＞ If necessary, peel off the release films (1) to (2) from the adhesive sheets A to B in Examples 1 to 5 and Comparative Examples 1 to 3 to expose the adhesive layer, and use the following test methods and measurement methods Make an evaluation. In addition, regarding the adhesive sheets A to B in Examples 1 to 5 and Comparative Examples 1 to 3, in order to comply with the following measurement methods and test methods, the thickness of the adhesive layer is different, and further, the first-stage adhesive is formed Multiple types of adhesive sheets A of the agent layer, or multiple types of adhesive sheets B formed with the second-stage adhesive layer. When testing the first-stage adhesive layer, adhesive sheet A was used. In addition, when testing the second-stage adhesive layer, adhesive sheet B was used.

＜總透光率的測定方法＞ 透光率的測定方法：藉由JIS K7105、「塑膠的光學特性試驗方法」，測定厚度為250μm的黏著劑層(第二階段的黏著劑層)的總透光率(%)，記作表3的「總透光率」。＜Measuring method of total light transmittance＞ Method for measuring light transmittance: Measure the total light transmittance (%) of an adhesive layer with a thickness of 250μm (adhesive layer in the second stage) according to JIS K7105, "Test Methods for Optical Properties of Plastics", and record it as a table 3 "total light transmittance".

＜霧度值的測定方法＞ 霧度值的測定方法：藉由JIS K7136、「塑膠-透明材料的霧度的確定方法」，測定厚度為250μm的黏著劑層(第二階段的黏著劑層)的霧度值(%)，記作表3的「初期的霧度值」。進一步，在溫度60℃×90%RH的氣氛下放置240小時後，取出至室溫環境(23℃、50%RH)。取出五分鐘後，在用所述剝離膜(1)~(2)覆蓋黏著劑層的雙面的狀態下測定霧度值(%)，記作表3的「濕熱後的霧度值」。＜Measuring method of haze value＞ How to measure the haze value: Measure the haze value (%) of an adhesive layer with a thickness of 250μm (the second-stage adhesive layer) according to JIS K7136, "Method for determining the haze of plastic-transparent materials", It is recorded as the "initial haze value" in Table 3. Furthermore, after standing for 240 hours in an atmosphere of a temperature of 60° C.×90% RH, it was taken out to a room temperature environment (23° C., 50% RH). Five minutes after taking it out, the haze value (%) was measured in a state where both sides of the adhesive layer were covered with the release films (1) to (2), and the haze value (%) was recorded as the "haze value after heat and humidity" in Table 3.

＜濕熱耐久性的評價＞ 使用利用上述的霧度值的測定方法測定的「濕熱後的霧度值」評價形成在實施例1~5及比較例1~3中的黏著片B上的黏著劑層的濕熱耐久性。另外，將濕熱耐久性的判定基準設定如下，將其評價結果記作表3的「濕熱耐久性」。 ○：「濕熱後的霧度值」為4.0%以下。 △：「濕熱後的霧度值」超過4.0%且為6.0%以下。 ╳：「濕熱後的霧度值」超過6.0%。＜Evaluation of damp heat durability＞ The wet-heat durability of the adhesive layer formed on the adhesive sheet B in Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated using the "haze value after heat and humidity" measured by the above-mentioned haze value measurement method. In addition, the criteria for judging the damp heat durability are set as follows, and the evaluation results are described as "damp heat durability" in Table 3. ○: The "haze value after heat and humidity" is 4.0% or less. △: The "haze value after heat and humidity" exceeds 4.0% and is 6.0% or less. ╳: "Haze value after heat and humidity" exceeds 6.0%.

＜黏著力的測定方法＞ 將厚度為175μm的黏著劑層(第一階段的黏著劑層或第二階段的黏著劑層)從黏著片A~B上轉印至厚度為50μm的聚酯膜的單面上，得到作為試樣的黏著膜(帶黏著劑層的光學膜)。用壓輥分別將所得到的黏著膜貼合於用丙酮進行了洗滌的無鹼玻璃的非錫面上，以50℃、0.5MPa×20分鐘的條件進行壓熱處理後，恢復至23℃×50%RH的空氣氣氛下，並經過1小時。利用拉伸試驗機，以JIS Z0237「黏著膠帶·黏著片試驗方法」為基準測定之後的黏著膜的剝離強度，並測定沿180°方向以300mm/分鐘的速度進行剝離時的剝離強度，作為各個黏著劑層的黏著力(N/25mm)。表3中，將使用第一階段的黏著劑層測定的黏著力記作「熱交聯後的黏著力」，將使用第二階段的黏著劑層測定的黏著力記作「光交聯後的黏著力」。＜Measurement method of adhesive force＞ The adhesive layer (the first-stage adhesive layer or the second-stage adhesive layer) with a thickness of 175μm is transferred from the adhesive sheets A to B to a single side of a polyester film with a thickness of 50μm. Such an adhesive film (optical film with adhesive layer). The obtained adhesive film was attached to the non-tin surface of the alkali-free glass washed with acetone with a pressure roller, and then autoclaved at 50°C, 0.5MPa×20 minutes, and then restored to 23°C×50 Under an air atmosphere of %RH, and after 1 hour. Using a tensile testing machine, the peel strength of the subsequent adhesive film was measured based on JIS Z0237 "Adhesive Tape and Adhesive Sheet Test Method", and the peel strength when peeled off at a speed of 300 mm/min in the 180° direction was measured as each Adhesion of the adhesive layer (N/25mm). In Table 3, the adhesive force measured using the adhesive layer of the first stage is recorded as "adhesive force after thermal crosslinking", and the adhesive force measured using the adhesive layer of the second stage is recorded as "photocrosslinked adhesive force". Adhesion".

＜段差追隨性的試驗方法＞ 將利用熱交聯劑交聯而成的厚度為100μm的黏著劑層(第一階段的黏著劑層)從黏著片A上轉印至厚度為188μm的聚鄰苯二甲酸乙二醇酯樹脂膜的單面上並進行貼合，得到作為試樣的黏著膜。然後，在壓力為80kPa、真空度為-100kPa的條件下，利用真空貼合裝置，從所述黏著劑層(第一階段的黏著劑層)的上方將具有厚度為42μm的印刷層的印刷段差的厚度為1.1mm的蓋板玻璃貼合在所述黏著劑層上。進一步，用肉眼確認以溫度為60℃、6個大氣壓、30分鐘的條件進行壓熱處理後的段差追隨性。將肉眼確認的判定基準設定如下，將其評價結果記作表3的「段差追隨性」。 ○：追隨印刷段差、印刷段差周圍完全沒有起泡。 △：印刷段差周圍有少量起泡。 ╳：印刷段差周圍有起泡。＜Test method of step followability＞ A 100μm thick adhesive layer (the first stage adhesive layer) crosslinked with a thermal crosslinking agent is transferred from the adhesive sheet A to a polyethylene phthalate resin film with a thickness of 188μm The adhesive film is obtained by bonding on one side of the sample. Then, under the conditions of a pressure of 80kPa and a vacuum of -100kPa, using a vacuum laminating device, from above the adhesive layer (the first stage of the adhesive layer), the printing step with a thickness of 42μm A cover glass with a thickness of 1.1mm is attached to the adhesive layer. Furthermore, it was visually confirmed that the step followability after autoclaving at a temperature of 60°C, 6 atmospheres, and 30 minutes was performed. The judgment criteria for visual confirmation were set as follows, and the evaluation results were recorded as the "step followability" in Table 3. ○: Following the printing step, there is no blistering around the printing step. △: There is a small amount of blistering around the printing step. ╳: There is blistering around the printing step.

表3中示出了實施例1~5的黏著片A~B及比較例1~3的黏著片A~B的評價結果。Table 3 shows the evaluation results of the adhesive sheets A to B of Examples 1 to 5 and the adhesive sheets A to B of Comparative Examples 1 to 3.

[表3]   總透 光率 [%] 初期的 霧度值 [%] 濕熱後的 霧度值 [%] 濕熱 耐久性 熱交聯後的黏著力 [N/25mm] 光交聯後的黏著力 [N/25mm] 段差 追隨性 實施例1 95 0.20 2.5 ○ 6.8 30.0 ○ 實施例2 93 0.30 2.5 ○ 4.5 28.5 ○ 實施例3 92 0.20 1.5 ○ 3.0 32.5 ○ 實施例4 94 0.25 1.5 ○ 6.5 29.0 ○ 實施例5 95 0.20 1.8 ○ 4.0 30.5 ○ 比較例1 95 0.30 2.5 ○ 23.0 27.5 ╳ 比較例2 94 0.20 8.5 ╳ 1.5 3.5 ╳ 比較例3 92 0.40 2.5 ○ 2.5 18.5 ╳ [table 3] Total light transmittance [%] Initial haze value [%] Haze value after heat and humidity [%] Humidity and heat durability Adhesion after thermal crosslinking [N/25mm] Adhesion after photocrosslinking [N/25mm] Gap followability Example 1 95 0.20 2.5 ○ 6.8 30.0 ○ Example 2 93 0.30 2.5 ○ 4.5 28.5 ○ Example 3 92 0.20 1.5 ○ 3.0 32.5 ○ Example 4 94 0.25 1.5 ○ 6.5 29.0 ○ Example 5 95 0.20 1.8 ○ 4.0 30.5 ○ Comparative example 1 95 0.30 2.5 ○ 23.0 27.5 ╳ Comparative example 2 94 0.20 8.5 ╳ 1.5 3.5 ╳ Comparative example 3 92 0.40 2.5 ○ 2.5 18.5 ╳

對於本發明的實施例1~5的黏著片B，經基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段而進行交聯後的厚度為250μm的黏著劑層的總透光率為90%以上，且「初期的霧度值」為1.0%以下，且「濕熱後的霧度值」為4.0%以下，即使將黏著劑層長時間放置於濕熱環境下後，取出至室溫環境(溫度23℃×50%RH)下，由於光學特性優異，因此濕熱耐久性也優異。 此外，對於使用本發明的實施例1~5的黏著片A~B而製作的黏著膜，其對鈉鈣玻璃的黏著力在利用熱交聯劑進行交聯後為10N/25mm以下，進一步經基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段而進行交聯後為25N/25mm以上。因此，利用熱交聯劑進行交聯後的黏著劑層的再操作時的處理性能(易於從被黏物上剝離)優異，經基於熱交聯劑的交聯與後續的基於光交聯劑的交聯這兩個階段而進行交聯後的黏著劑層具有高黏著力。 此外，對於使用本發明的實施例1~5的黏著片A而製作的黏著膜，形成有厚度為100μm的黏著劑層(第一階段的黏著劑層)時，所述段差追隨性的試驗的結果為追隨厚度為42μm的印刷段差，所述印刷段差周圍完全沒有起泡，段差追隨性優異。 即，根據本發明的實施例1~5的黏著片A~B、及使用它們而製作的黏著膜，可實現作為本發明的技術問題的、對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能良好且具有優異的濕熱耐久性的黏著劑層。For the adhesive sheet B of Examples 1 to 5 of the present invention, an adhesive with a thickness of 250 μm after being cross-linked through two stages of cross-linking based on a thermal cross-linking agent and subsequent cross-linking based on a photo-crosslinking agent The total light transmittance of the layer is more than 90%, and the "initial haze value" is 1.0% or less, and the "haze value after heat and humidity" is 4.0% or less, even if the adhesive layer is placed in a humid and hot environment for a long time After that, it was taken out under a room temperature environment (temperature 23° C.×50% RH). Since it has excellent optical properties, it also has excellent wet heat durability. In addition, for the adhesive films produced using the adhesive sheets A to B of Examples 1 to 5 of the present invention, the adhesive force to soda lime glass after crosslinking with a thermal crosslinking agent is 10N/25mm or less, and further It is 25N/25mm or more after crosslinking in two stages of crosslinking by a thermal crosslinking agent and subsequent crosslinking by a photocrosslinking agent. Therefore, the adhesive layer after crosslinking by the thermal crosslinking agent has excellent handling performance (easy to peel from the adherend) during the re-operation. The crosslinking based on the thermal crosslinking agent and the subsequent photocrosslinking agent The adhesive layer after cross-linking has high adhesive force after the two stages of cross-linking. In addition, when the adhesive film produced using the adhesive sheet A of Examples 1 to 5 of the present invention is formed with an adhesive layer with a thickness of 100 μm (adhesive layer of the first stage), the test of the step followability As a result, it follows a printing step with a thickness of 42 μm, and there is no blistering around the printing step, and the step followability is excellent. That is, according to the adhesive sheets A to B of Examples 1 to 5 of the present invention, and the adhesive films produced using them, the technical problem of the present invention can be achieved with respect to the level difference such as the frame printing of the adherend. , Adhesive layer with good handling performance and excellent wet-heat durability during re-operation.

另一方面，對於形成在比較例1的黏著片A~B上的黏著劑層，其藉由使由兩種以上的單體共聚而得到的共聚物，以含有(F)組的單體而不含有(G)組的單體的方式進行交聯而得到，比較例1的黏著片B的「濕熱後的霧度值」低，透明性高，因此濕熱耐久性優異。此外，使用比較例1的黏著片A而製作的黏著膜的「熱交聯後的黏著力」高，再操作性差，印刷段差周圍有起泡，段差追隨性差。 此外，對於形成在比較例2的黏著片A~B上的黏著劑層，其藉由使由兩種以上的單體共聚而得到的共聚物，以不含有(F)組的單體而含有(G)組的單體的方式進行交聯而得到，比較例2的黏著片B的「濕熱後的霧度值」高，透明性低，因此濕熱耐久性差。此外，使用比較例2的黏著片B而製作的黏著膜的「光交聯後的黏著力」非常低。此外，使用比較例2的黏著片A而製作的黏著膜的印刷段差周圍有起泡，段差追隨性差。 此外，對於形成在比較例3的黏著片A~B上的黏著劑層，其藉由使由兩種以上的單體共聚而得到的共聚物，以含有(F)組及(G)組的單體的方式進行交聯而得到，比較例3的黏著片B的「濕熱後的霧度值」低，透明性高，因此濕熱耐久性優異。此外，使用比較例3的黏著片B而製作的黏著膜的「光交聯後的黏著力」略低。此外，使用比較例3的黏著片A而製作的黏著膜的印刷段差周圍有起泡，段差追隨性差。 如此，比較例1~3的黏著片A~B、及使用它們製作的黏著膜未能實現作為本發明的技術問題的、對被黏物的框印刷等段差的段差追隨性、再操作時的處理性能良好且具有優異的濕熱耐久性的黏著劑層。On the other hand, for the adhesive layers formed on the adhesive sheets A to B of Comparative Example 1, the copolymer obtained by copolymerizing two or more monomers contains monomers of group (F). It is obtained by crosslinking without containing the monomer of the group (G). The adhesive sheet B of Comparative Example 1 has a low "haze value after heat and humidity" and high transparency, so it is excellent in heat and humidity durability. In addition, the adhesive film produced using the adhesive sheet A of Comparative Example 1 had high "adhesive strength after thermal crosslinking", poor reworkability, blistering around the printing step, and poor step followability. In addition, the adhesive layer formed on the adhesive sheets A to B of Comparative Example 2 contains a copolymer obtained by copolymerizing two or more monomers without containing the monomers of the (F) group It is obtained by crosslinking the monomers of the group (G). The pressure-sensitive adhesive sheet B of Comparative Example 2 has a high "haze value after heat and humidity" and low transparency, so the heat and humidity durability is poor. In addition, the "adhesive force after photocrosslinking" of the adhesive film produced using the adhesive sheet B of Comparative Example 2 was very low. In addition, the adhesive film produced using the adhesive sheet A of Comparative Example 2 had blisters around the printing step, and the step followability was poor. In addition, for the adhesive layers formed on the adhesive sheets A to B of Comparative Example 3, a copolymer obtained by copolymerizing two or more monomers to contain (F) group and (G) group The adhesive sheet B of Comparative Example 3 is obtained by cross-linking in a monomeric manner. The adhesive sheet B of Comparative Example 3 has a low "haze value after heat and humidity" and high transparency, so it is excellent in heat and humidity durability. In addition, the "adhesive force after photocrosslinking" of the adhesive film produced using the adhesive sheet B of Comparative Example 3 was slightly low. In addition, the adhesive film produced using the adhesive sheet A of Comparative Example 3 had blisters around the printing step, and the step followability was poor. In this way, the adhesive sheets A to B of Comparative Examples 1 to 3 and the adhesive films produced using them failed to achieve the level difference followability of the level difference such as the frame printing of the adherend, which is the technical problem of the present invention, and the re-operation. Adhesive layer with good handling properties and excellent damp heat durability.

在上述比較例1~3的黏著片B中，使由兩種以上的單體共聚而得到的共聚物，以含有(F)組的單體的方式進行交聯而得到的比較例1及比較例3的黏著片B的「濕熱後的霧度值」低，黏著劑層的濕熱耐久性優異。然而，使由兩種以上的單體共聚而得到的共聚物，以不含有(F)組的單體的方式進行交聯而得到的比較例2的黏著片B的「濕熱後的霧度值」高，黏著劑層的濕熱耐久性差。因此，證實了在本發明的光學用黏著劑組合物中，用於得到具備優異的濕熱耐久性的黏著劑層的有用成分為(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體。In the pressure-sensitive adhesive sheet B of Comparative Examples 1 to 3, a copolymer obtained by copolymerizing two or more monomers was cross-linked to contain monomers of group (F). Comparative Example 1 and comparison The pressure-sensitive adhesive sheet B of Example 3 has a low "haze value after heat and humidity", and the pressure-sensitive adhesive layer has excellent heat and humidity durability. However, a copolymer obtained by copolymerizing two or more monomers was cross-linked so as not to contain monomers of the (F) group. The adhesive sheet B of Comparative Example 2 showed the "haze value after heat and humidity" "High, poor wet and heat durability of the adhesive layer. Therefore, it was confirmed that in the optical adhesive composition of the present invention, the useful component for obtaining an adhesive layer with excellent wet-heat durability is (F) having a (meth)acryloyl group and alkene in one molecule. A propyl ether group and a (meth)acrylate monomer having two or more ethylenically unsaturated groups.

無。no.

無。no.

Claims (11)

一種光學用黏著劑組合物，其特徵在於，其含有：使選自共聚性乙烯基單體、及含氮乙烯基單體的化合物組中的至少兩種以上進行共聚而得到的共聚物，所述共聚性乙烯基單體在官能團中不具有羧基，而具有烷基、羥基、烷氧基、芳香基中的任意一種；(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體；(E)熱交聯劑；及(H)光交聯劑。An adhesive composition for optics, characterized in that it contains a copolymer obtained by copolymerizing at least two or more selected from the group of copolymerizable vinyl monomers and nitrogen-containing vinyl monomers, and The copolymerizable vinyl monomer does not have a carboxyl group in the functional group, but has any one of an alkyl group, a hydroxyl group, an alkoxy group, and an aromatic group; (F) has a (meth)acryloyl group and an allyl group in one molecule Monomers of (meth)acrylates having two or more ethylenically unsaturated groups; (G) those having an epoxy group and two or more ethylenically unsaturated groups in one molecule (Meth) acrylate monomer; (E) thermal crosslinking agent; and (H) photocrosslinking agent. 如請求項1所述的光學用黏著劑組合物，其中， 所述共聚物為相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上， 使合計為2.0~10重量份的(B)含氮乙烯基單體或含烷氧基的(甲基)丙烯酸烷基酯單體中的至少一種以上、合計為1.0~10重量份的(C)聚伸烷基二醇單(甲基)丙烯酸酯單體中的至少一種以上、及合計為0.5~10重量份的(D)具有羥基的共聚性乙烯基單體中的至少一種以上共聚而成的重均分子量為20萬~100萬的共聚物， 相對於100重量份的所述(A)，所述光學用黏著劑組合物以0.01~5重量份的比例含有所述(E)熱交聯劑、以0.1~10重量份的比例含有所述(F)在一分子內具有(甲基)丙烯醯基與烯丙基醚基，且具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、以0.1~10重量份的比例含有所述(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體、以0.01~5重量份的比例含有所述(H)光交聯劑。The optical adhesive composition according to claim 1, wherein The copolymer is at least one or more of alkyl (meth)acrylate monomers having C1 to C18 carbon atoms with respect to 100 parts by weight of the (A) alkyl group in total, Make a total of 2.0-10 parts by weight of (B) nitrogen-containing vinyl monomers or alkoxy-containing alkyl (meth)acrylate monomers at least one or more, and a total of 1.0-10 parts by weight (C ) At least one or more of the polyalkylene glycol mono(meth)acrylate monomers and at least one or more of the (D) copolymerizable vinyl monomers having a hydroxyl group in a total of 0.5 to 10 parts by weight are copolymerized and Into a copolymer with a weight average molecular weight of 200,000 to 1 million, With respect to 100 parts by weight of the (A), the optical adhesive composition contains the (E) thermal crosslinking agent in a ratio of 0.01 to 5 parts by weight, and contains the (E) thermal crosslinking agent in a ratio of 0.1 to 10 parts by weight. (F) A monomer of (meth)acrylate having a (meth)acrylic acid group and an allyl ether group in one molecule, and having two or more ethylenically unsaturated groups, in an amount of 0.1-10 parts by weight The monomer containing the (G) (meth)acrylate having an alkylene oxide group and two or more ethylenically unsaturated groups in one molecule is contained in the ratio of 0.01 to 5 parts by weight. (H) Photocrosslinking agent. 如請求項1或2所述的光學用黏著劑組合物，其中，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成的厚度為250μm的黏著劑層的總透光率為90%以上，且霧度值為1.0%以下。The optical adhesive composition according to claim 1 or 2, wherein both the crosslinking based on the (E) thermal crosslinking agent and the subsequent crosslinking based on the (H) photocrosslinking agent In each stage, the adhesive layer with a thickness of 250 μm formed by crosslinking the optical adhesive composition has a total light transmittance of 90% or more and a haze value of 1.0% or less. 如請求項1或2所述的光學用黏著劑組合物，其中，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段，使所述光學用黏著劑組合物進行交聯而形成厚度為250μm的黏著劑層在溫度60℃×90%RH的氣氛下放置240小時後，取出至室溫環境(溫度23℃×50%RH)時的霧度值為4.0%以下。The optical adhesive composition according to claim 1 or 2, wherein both the crosslinking based on the (E) thermal crosslinking agent and the subsequent crosslinking based on the (H) photocrosslinking agent In each stage, the optical adhesive composition was cross-linked to form an adhesive layer with a thickness of 250 μm. After being placed in an atmosphere at a temperature of 60° C. × 90% RH for 240 hours, it was taken out to a room temperature environment (temperature of 23° C. × The haze value at 50%RH) is 4.0% or less. 如請求項1或2所述的光學用黏著劑組合物，其中，在合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸烷基酯單體中的至少一種以上中，所述共聚物以50重量份以上的比例含有烷基的碳原子數為C8~C18的(甲基)丙烯酸烷基酯。The optical adhesive composition according to claim 1 or 2, wherein the (A) alkyl group has C1-C18 alkyl (meth)acrylate monomers in total in 100 parts by weight In at least one or more of the above, the copolymer contains an alkyl (meth)acrylate having C8 to C18 carbon atoms in an alkyl group in a ratio of 50 parts by weight or more. 如請求項1或2所述的光學用黏著劑組合物，其中，所述共聚物由(C)聚伸烷基二醇單(甲基)丙烯酸酯單體共聚而成，所述光學用黏著劑組合物含有(G)具有環氧烷基且在一分子內具有兩個以上乙烯性不飽和基團的(甲基)丙烯酸酯的單體，所述(C)及所述(G)的環氧烷的平均重複數為4~14。The optical adhesive composition according to claim 1 or 2, wherein the copolymer is formed by copolymerizing (C) a polyalkylene glycol mono(meth)acrylate monomer, and the optical adhesive The agent composition contains (G) a (meth)acrylate monomer having an epoxy group and two or more ethylenically unsaturated groups in one molecule, the (C) and the (G) The average repeating number of alkylene oxide is 4-14. 一種黏著膜，其特徵在於，其為藉由將黏著劑層積層在基材的單面上而成之黏著膜，所述黏著劑層是藉由使用如請求項1~6中任一項所述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成、或者經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段交聯而成， 利用所述(E)熱交聯劑進行交聯後的所述黏著劑層對鈉鈣玻璃的黏著力為10N/25mm以下，進一步，經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段進行交聯後的所述黏著劑層對鈉鈣玻璃的黏著力為25N/25mm以上。An adhesive film characterized in that it is an adhesive film formed by laminating an adhesive layer on a single side of a substrate, and the adhesive layer is formed by using any one of claims 1 to 6 The optical adhesive composition is cross-linked by the (E) thermal cross-linking agent, or is cross-linked based on the (E) thermal cross-linking agent and subsequently based on the (H) light The cross-linking of the cross-linking agent is cross-linked in two stages, The adhesive layer after crosslinking with the (E) thermal crosslinking agent has an adhesive force of 10N/25mm or less to the soda lime glass, and further, after crosslinking with the (E) thermal crosslinking agent The adhesion of the adhesive layer to the soda lime glass after the subsequent two stages of cross-linking based on the (H) photo-crosslinking agent is 25N/25mm or more. 一種黏著膜，其特徵在於，其為藉由將黏著劑層積層在厚度為188μm的聚鄰苯二甲酸乙二醇酯樹脂膜的單面上而成之黏著膜，所述黏著劑層是使用如請求項1~6中任一項所述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成，將所述黏著膜介由厚度為100μm的所述黏著劑層而貼合於具有厚度為42μm的印刷層的印刷段差的玻璃時，對所述印刷段差的追隨性良好，在所述印刷段差的周圍完全沒有起泡。An adhesive film characterized in that it is an adhesive film formed by laminating an adhesive layer on one side of a polyethylene phthalate resin film with a thickness of 188 μm, and the adhesive layer is used The optical adhesive composition according to any one of claims 1 to 6, which is cross-linked with the (E) thermal cross-linking agent, and the adhesive film is interposed with the adhesive having a thickness of 100 μm When the agent layer is bonded to a glass having a printing step with a printing layer having a thickness of 42 μm, the followability to the printing step is good, and there is no blistering around the printing step. 一種使用如請求項7或8所述的黏著膜的觸控面板用膜。A film for a touch panel using the adhesive film according to claim 7 or 8. 一種黏著片，其藉由將使用如請求項1~6中任一項所述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成的黏著劑層積層於兩片經脫模處理的脫模膜之間而成。An adhesive sheet by laminating an adhesive formed by using the optical adhesive composition as described in any one of claims 1 to 6 and crosslinking with the (E) thermal crosslinking agent It is formed between two release films that have undergone release treatment. 一種帶黏著劑層的光學膜，其藉由將黏著劑層積層於光學膜的至少一個面而成，所述黏著劑層是藉由使用如請求項1~6中任一項所述的光學用黏著劑組合物，並利用所述(E)熱交聯劑交聯而成、或者經基於所述(E)熱交聯劑的交聯與後續的基於所述(H)光交聯劑的交聯這兩個階段交聯而成。An optical film with an adhesive layer, which is formed by laminating an adhesive layer on at least one surface of the optical film, and the adhesive layer is formed by using the optical film described in any one of claims 1 to 6 The adhesive composition is cross-linked with the (E) thermal cross-linking agent, or is cross-linked based on the (E) thermal cross-linking agent and the subsequent (H) photo-crosslinking agent The cross-linking is formed by cross-linking in these two stages.
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