TW201542752A - Adhesive sheet and laminate - Google Patents

Adhesive sheet and laminate Download PDF

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Publication number
TW201542752A
TW201542752A TW104108037A TW104108037A TW201542752A TW 201542752 A TW201542752 A TW 201542752A TW 104108037 A TW104108037 A TW 104108037A TW 104108037 A TW104108037 A TW 104108037A TW 201542752 A TW201542752 A TW 201542752A
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Taiwan
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adhesive
meth
adhesive layer
mass
layer
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TW104108037A
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Chinese (zh)
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TWI666289B (en
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Yuki Ozawa
Takayuki Arai
Satoru Shoshi
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Lintec Corp
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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Abstract

An adhesive sheet (1) that comprises an adhesive layer (11) having a thickness of 10 to 400 [mu]m formed by crosslinking an adhesive composition including a (meth)acrylic acid ester copolymer (A) which has a weight-average molecular weight of 200,000 to 900,000, and includes 15 to 30 mass% of a monomer having a hydroxyl group and does not include a monomer having a carboxyl group as a monomer unit that constitutes the polymer, a polyisocyanate compound (B), and a chelate compound (C). The adhesive sheet (1) has excellent step conformability as well as excellent resistance to blisters and resistance to moisture, heat and whitening, and can suppress corrosion of transparent conductive films and metal lines and changes in resistance values of the transparent conductive films.

Description

黏著片及積層體 Adhesive sheet and laminate

本發明係有關一種能夠在觸摸面板等中使用之黏著片、以及使用該黏著片的黏著劑層而得到之積層體者。 The present invention relates to an adhesive sheet which can be used in a touch panel or the like, and a laminated body obtained by using an adhesive layer of the adhesive sheet.

近年來，行動電話和平板電腦等各種移動電子設備包括使用具有液晶元件、發光二極體(LED元件)、有機電致發光(有機EL)元件等之顯示體模組之顯示器，該種顯示器成為觸摸面板之情況亦逐漸增加。 In recent years, various mobile electronic devices such as mobile phones and tablet computers include displays using a display body module having a liquid crystal element, a light emitting diode (LED element), and an organic electroluminescence (organic EL) element, and the display has become The situation with the touch panel has also gradually increased.

在如上顯示器中，通常在顯示體模組的表面側設有保護面板。隨著電子設備的薄型化、輕量化，上述保護面板逐漸由習知的玻璃板變更為丙烯酸板和聚碳酸酯板等塑膠板。 In the above display, a protective panel is usually provided on the surface side of the display body module. As the electronic device is thinner and lighter, the protective panel is gradually changed from a conventional glass plate to a plastic plate such as an acrylic plate or a polycarbonate plate.

在此，在保護面板與顯示體模組之間設有空隙，以使在保護面板藉由外力而變形時，變形之保護面板亦不會碰撞到顯示體模組。 Here, a gap is provided between the protective panel and the display body module so that when the protective panel is deformed by an external force, the deformed protective panel does not collide with the display body module.

然而，若存在如上空隙亦即空氣層，則由保護面板與空氣層的折射率差、以及空氣層與顯示體模組的折射率差引起之光的反射損失增大，存在顯示器的畫質下降之問題。 However, if there is an air layer as described above, the difference in refractive index between the protective panel and the air layer and the reflection loss of light caused by the difference in refractive index between the air layer and the display module increase, and the image quality of the display decreases. The problem.

因此，提出了藉由用黏著劑層填補保護面板與顯示體模組之間的空隙來提高顯示器的畫質。但是，有時邊框狀的印刷層在保護面板的顯示體模組側以段差形態存在。若黏著 劑層不追隨該段差，則黏著劑層會在段差附近翹起，藉此產生光的反射損失。因此，對上述黏著劑層要求段差追隨性。 Therefore, it has been proposed to improve the image quality of the display by filling the gap between the protective panel and the display body module with an adhesive layer. However, sometimes the border-shaped printed layer may be in the form of a step on the display body module side of the protective panel. If sticking If the agent layer does not follow the step, the adhesive layer will lift up near the step, thereby causing a reflection loss of light. Therefore, step adhesion follow-up is required for the above adhesive layer.

為了解決上述課題，專利文獻1中，作為填補保護面板與顯示體模組之間的空隙之黏著劑層，公開有一種在25℃、1Hz下的剪切儲存彈性模量(G’)為1.0×105Pa以下，且凝膠率為40%以上之黏著劑層。 In order to solve the above problem, Patent Document 1 discloses a shear storage elastic modulus (G') of 1.0 at 25 ° C and 1 Hz as an adhesive layer filling a gap between a protective panel and a display module. An adhesive layer of ×10 5 Pa or less and a gel fraction of 40% or more.

專利文獻1中，藉由降低黏著劑層中之常溫時的儲存彈性模量來提高段差追隨性。然而，若如上降低常溫時的儲存彈性模量，則高溫時的儲存彈性模量過度下降，在耐久條件下會發生問題。例如，施加高溫高濕條件時，在段差附近產生氣泡或者從作為保護面板之塑膠板產生漏氣而產生氣泡、翹起、剝落等膨脹，或者在高溫高濕條件後恢復為常溫常濕時，發生黏著劑層白化(濕熱白化)之問題。並且，若為了提高抗起泡性而使黏著劑層變硬，則段差追隨性下降。 In Patent Document 1, the stepwise followability is improved by reducing the storage elastic modulus at the normal temperature in the adhesive layer. However, if the storage elastic modulus at the normal temperature is lowered as described above, the storage elastic modulus at a high temperature is excessively lowered, and a problem occurs under endurance conditions. For example, when a high-temperature and high-humidity condition is applied, bubbles are generated in the vicinity of the step, or air bubbles are generated from the plastic sheet as a protective panel to cause air bubbles, lift, peeling, or the like, or return to normal temperature and humidity after high-temperature and high-humidity conditions. The problem of whitening of the adhesive layer (wet heat whitening) occurs. Further, if the adhesive layer is hardened in order to improve the anti-foaming property, the step followability is lowered.

另一方面，如上黏著劑層有時貼附於透明導電膜和金屬配線等。此時，若黏著劑中含有羧酸，具體而言，若黏著主劑中含有羧基，則產生透明導電膜和金屬配線腐蝕或者透明導電膜的電阻值發生變化之問題。因而，要求以該種用途使用之黏著劑為上述黏著主劑中不具有羧基之(不含羧酸之)黏著劑。然而，不含羧酸之黏著劑通常難以確保所希望的黏著力，更難以得到充份的耐久性。 On the other hand, the above adhesive layer may be attached to a transparent conductive film, a metal wiring or the like. In this case, when the carboxylic acid is contained in the adhesive, specifically, when the carboxyl group is contained in the adhesive main component, the transparent conductive film and the metal wiring are corroded or the resistance value of the transparent conductive film is changed. Therefore, an adhesive which is required to be used for such a use is an adhesive (having no carboxylic acid) which does not have a carboxyl group in the above-mentioned adhesive main component. However, carboxylic acid-free adhesives are often difficult to ensure a desired adhesive force, and it is more difficult to obtain sufficient durability.

例如，專利文獻2中，以非腐蝕性為課題，並且，黏著劑組成物的丙烯酸系聚合物含有0.05~0.5重量%的含羧基單體來確保所希望的黏著力。然而，根據透明導電膜的種 類，有即使是該量的羧酸亦會發生劣化者。 For example, in Patent Document 2, the non-corrosive property is a problem, and the acrylic polymer of the adhesive composition contains 0.05 to 0.5% by weight of a carboxyl group-containing monomer to secure a desired adhesive force. However, according to the species of the transparent conductive film There are cases in which even a certain amount of carboxylic acid may deteriorate.

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

【專利文獻1】日本特開2010-97070號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-97070

【專利文獻2】日本特開2012-136660號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-136660

本發明係鑑於如上實際情況而完成者，其目的為提供一種具有使用不含有羧基之黏著主劑而段差追隨性優異並且抗起泡性及耐濕熱白化性亦優異之黏著劑層之黏著片及積層體。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive sheet having an adhesive layer which is excellent in step followability and excellent in anti-foaming property and wet heat whitening resistance, using an adhesive main component containing no carboxyl group. Laminated body.

為了實現上述目的，第一、本發明提供一種黏著片，其中，前述黏著片具有使黏著性組成物交聯而成之厚度10~400μm的黏著劑層，前述黏著性組成物中含有：(甲基)丙烯酸酯共聚物(A)，其重量平均分子量為20萬~90萬，作為構成聚合物之單體單位，含有15~30質量%的具有羥基之單體，且不含有具有羧基之單體；聚異氰酸酯化合物(B)；及螯合化合物(C)(發明1)。 In order to achieve the above object, the present invention provides an adhesive sheet, wherein the adhesive sheet has an adhesive layer having a thickness of 10 to 400 μm which is obtained by crosslinking an adhesive composition, and the adhesive composition contains: The acrylate copolymer (A) has a weight average molecular weight of 200,000 to 900,000, and contains, as a monomer unit constituting the polymer, 15 to 30% by mass of a monomer having a hydroxyl group, and does not contain a monomer having a carboxyl group. a polyisocyanate compound (B); and a chelate compound (C) (Invention 1).

上述發明(發明1)之黏著片的黏著劑層中，針對不含有羧基之上述(甲基)丙烯酸酯共聚物(A)同時使用聚異氰酸酯化合物(B)及螯合化合物(C)這兩者，藉此成為貼附時的段差追隨性優異，並且即使在耐久條件下段差追隨性、 抗起泡性及耐濕熱白化性亦優異者。並且，還能夠抑制對透明導電膜和金屬配線帶來由羧酸引起之不良影響。 In the adhesive layer of the adhesive sheet of the invention (Invention 1), both the polyisocyanate compound (B) and the chelate compound (C) are used together for the (meth) acrylate copolymer (A) containing no carboxyl group. In order to achieve excellent step followability at the time of attachment, and even in the case of endurance conditions, step followability, It is also excellent in anti-foaming property and moist heat whitening resistance. Further, it is also possible to suppress the adverse effect caused by the carboxylic acid on the transparent conductive film and the metal wiring.

上述發明(發明1)中，前述黏著性組成物中之前述聚異氰酸酯化合物(B)的含量相對於前述(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份為較佳(發明2)。 In the above invention (Invention 1), the content of the polyisocyanate compound (B) in the adhesive composition is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer (A). (Invention 2).

上述發明(發明1、2)中，前述黏著性組成物中之前述螯合化合物(C)的含量相對於前述(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份為較佳(發明3)。 In the above invention (Inventions 1 and 2), the content of the chelating compound (C) in the adhesive composition is 0.001 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer (A). Preferably (Invention 3).

上述發明(發明1~3)中，前述螯合化合物(C)為鋁螯合化合物為較佳(發明4)。 In the above invention (Inventions 1 to 3), it is preferred that the chelate compound (C) is an aluminum chelate compound (Invention 4).

上述發明(發明1~4)中，前述螯合化合物(C)為乙醯丙酮錯合物為較佳(發明5)。 In the above invention (Inventions 1 to 4), it is preferred that the chelate compound (C) is an acetamidineacetate complex (Invention 5).

上述發明(發明1~5)中，前述黏著片包括兩片剝離片，前述黏著劑層以與前述兩片剝離片的剝離面接觸之方式被前述剝離片夾持為較佳(發明6)。 In the above invention (Inventions 1 to 5), the pressure-sensitive adhesive sheet includes two release sheets, and the pressure-sensitive adhesive layer is preferably sandwiched between the release sheets in contact with the release surfaces of the two release sheets (Invention 6).

第二、本發明提供一種積層體，其包括：兩片硬質板；及黏著劑層，其被前述兩片硬質板夾持，其中，前述黏著劑層為前述黏著片(發明1~6)的黏著劑層(發明7)。 Secondly, the present invention provides a laminated body comprising: two sheets of hard plates; and an adhesive layer sandwiched by the two sheets of hard plates, wherein the adhesive layer is the aforementioned adhesive sheet (Inventions 1 to 6) Adhesive layer (Invention 7).

上述發明(發明7)中，前述硬質板中的至少一個可以在前述黏著劑層側的表面具有段差(發明8)。 In the above invention (Invention 7), at least one of the hard plates may have a step on the surface on the side of the adhesive layer (Invention 8).

上述發明(發明8)中，前述段差為由印刷層的有無產生之段差為較佳(發明9)。 In the above invention (Invention 8), it is preferable that the step is a step caused by the presence or absence of the printed layer (Invention 9).

上述發明(發明7~9)中，前述硬質板中的至少一個包含塑膠板為較佳(發明10)。 In the above invention (Inventions 7 to 9), it is preferable that at least one of the hard plates includes a plastic plate (Invention 10).

上述發明(發明7~10)中，前述兩片硬質板中的一個為顯示體模組或其一部份，前述兩片硬質板中的另一個為在前述黏著劑層側的表面具有邊框狀的段差之保護板為較佳(發明11)。 In the above invention (Inventions 7 to 10), one of the two rigid plates is a display body module or a part thereof, and the other of the two hard plates has a frame shape on a surface on the side of the adhesive layer. The protection plate of the step is preferred (Invention 11).

本發明之黏著片的黏著劑層的段差追隨性優異，並且抗起泡性及耐濕熱白化性亦優異。在使用該種黏著片而得到之積層體中，即使在黏著劑層側存在段差，黏著劑層亦會追隨該段差，因此成為在段差附近沒有翹起和氣泡等者。並且，上述積層體中之黏著劑層即使在耐久條件下，段差追隨性、抗起泡性及耐濕熱白化性亦優異。另外，即使在將上述黏著劑層貼附於透明導電膜和金屬配線等之情況下，亦能夠抑制透明導電膜和金屬配線腐蝕或者透明導電膜的電阻值發生變化。 The adhesive layer of the adhesive sheet of the present invention is excellent in step followability and excellent in anti-foaming property and moist heat whitening resistance. In the laminated body obtained by using such an adhesive sheet, even if there is a step on the side of the adhesive layer, the adhesive layer follows the step, and therefore, there is no lifting or bubbles in the vicinity of the step. Further, the adhesive layer in the laminate is excellent in step followability, anti-foaming property, and moist heat whitening resistance even under endurance conditions. In addition, even when the adhesive layer is attached to the transparent conductive film, the metal wiring, or the like, it is possible to suppress corrosion of the transparent conductive film and the metal wiring or change the resistance value of the transparent conductive film.

1‧‧‧黏著片 1‧‧‧Adhesive film

11‧‧‧黏著劑層 11‧‧‧Adhesive layer

12a、12b‧‧‧剝離片 12a, 12b‧‧‧ peeling film

2‧‧‧積層體 2‧‧‧Laminated body

21‧‧‧第1硬質板 21‧‧‧1st hard board

22‧‧‧第2硬質板 22‧‧‧2nd hard board

3‧‧‧印刷層 3‧‧‧Printing layer

第1圖係本發明的一實施形態之黏著片的剖面圖。 Fig. 1 is a cross-sectional view showing an adhesive sheet according to an embodiment of the present invention.

第2圖係本發明的一實施形態之積層體的剖面圖。 Fig. 2 is a cross-sectional view showing a laminated body according to an embodiment of the present invention.

以下，對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.

〔黏著片〕 [adhesive sheet]

如第1圖所示，本實施形態之黏著片1由兩片剝離片12a、12b和以與該兩片剝離片12a、12b的剝離面接觸之方式被該兩片剝離片12a、12b夾持之黏著劑層11構成。另外，本說明書中之剝離片的剝離面係指在剝離片中具有剝離性之表面，係包 含實施剝離處理之表面及即使未實施剝離處理亦顯示剝離性之表面中的任意一個者。 As shown in Fig. 1, the adhesive sheet 1 of the present embodiment is sandwiched between the two release sheets 12a and 12b by the two release sheets 12a and 12b and the release surfaces of the release sheets 12a and 12b. The adhesive layer 11 is formed. In addition, the peeling surface of the peeling sheet in this specification means the surface which has peeling in a peeling sheet, Any one of the surface on which the release treatment was performed and the surface which showed peelability even if the release treatment was not performed.

1．黏著劑層 1. Adhesive layer

上述黏著劑層11由使黏著性組成物(以下有時稱為“黏著性組成物P”)交聯而成之黏著劑構成，前述黏著性組成物中含有：(甲基)丙烯酸酯共聚物(A)，其重量平均分子量為20萬~90萬，作為構成聚合物之單體單位，含有15~30質量%的具有羥基之單體(含羥基單體)，且不含有具有羧基之單體(含羧基單體)；聚異氰酸酯化合物(B)；及螯合化合物(C)。另外，本說明書中，(甲基)丙烯酸係指丙烯酸及甲基丙烯酸這兩者。其他類似術語亦相同。 The pressure-sensitive adhesive layer 11 is composed of an adhesive obtained by crosslinking an adhesive composition (hereinafter sometimes referred to as "adhesive composition P"), and the adhesive composition contains: (meth) acrylate copolymer (A), which has a weight average molecular weight of 200,000 to 900,000, and contains, as a monomer unit constituting the polymer, 15 to 30% by mass of a monomer having a hydroxyl group (hydroxyl-containing monomer), and does not contain a single monomer having a carboxyl group. a body (carboxyl-containing monomer); a polyisocyanate compound (B); and a chelate compound (C). In the present specification, (meth)acrylic acid means both of acrylic acid and methacrylic acid. Other similar terms are also the same.

在使黏著性組成物P交聯而成之黏著劑中，(甲基)丙烯酸酯共聚物(A)主要藉由聚異氰酸酯化合物(B)而成為交聯之狀態。螯合化合物(C)由於與羧基之反應性較高，因此通常在羧基的存在下進行使用，但本實施形態中，特意在羧基的不存在下使用螯合化合物(C)。本實施形態中，認為螯合化合物(C)係藉由氫鍵以較弱的力與(甲基)丙烯酸酯共聚物(A)的交聯體鍵合者。本實施形態中，針對具有上述結構之(甲基)丙烯酸酯共聚物(A)同時使用聚異氰酸酯化合物(B)及螯合化合物(C)這兩者，藉由該等的相互作用，黏著劑層11成為段差追隨性優異，並且即使在耐久條件下段差追隨性、抗起泡性及耐濕熱白化性亦優異者，能夠兼備通常處於權衡關係之段差追隨性和抗起泡性。 In the adhesive obtained by crosslinking the adhesive composition P, the (meth) acrylate copolymer (A) is mainly crosslinked by the polyisocyanate compound (B). Since the chelate compound (C) has high reactivity with a carboxyl group, it is usually used in the presence of a carboxyl group. However, in the present embodiment, the chelate compound (C) is intentionally used in the absence of a carboxyl group. In the present embodiment, it is considered that the chelating compound (C) is bonded to the crosslinked body of the (meth) acrylate copolymer (A) by a weak bond with a hydrogen bond. In the present embodiment, the (meth) acrylate copolymer (A) having the above-described structure is used together with both the polyisocyanate compound (B) and the chelating compound (C), and the adhesion is achieved by the interaction. The layer 11 is excellent in step followability, and is excellent in step followability, anti-foaming property, and wet heat whitening resistance even under endurance conditions, and can have both step-span followability and anti-foaming property which are usually in a trade-off relationship.

(1)(甲基)丙烯酸酯共聚物(A) (1) (meth) acrylate copolymer (A)

(甲基)丙烯酸酯共聚物(A)為黏著性組成物P中之黏著主劑。(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，含有15~30質量%的含羥基單體，含有17~28質量%為較佳，含有20~25質量%尤為佳。藉由含羥基單體的含量在上述範圍內，藉由(甲基)丙烯酸酯共聚物(A)和聚異氰酸酯化合物(B)形成之交聯結構成為良好者，黏著劑層11成為具有適當的耐久性者。另外，由含有含羥基單體的含量在上述範圍內之(甲基)丙烯酸酯共聚物(A)之黏著性組成物P得到之黏著劑層11在施加高溫高濕條件(例如，在85℃、85%RH的條件下72小時)之後，恢復為常溫常濕時的白化得到抑制，亦即成為耐濕熱白化性優異者。若(甲基)丙烯酸酯共聚物(A)以上述量含有含羥基單體作為單體單位，則在所得到之黏著劑中會殘留既定量的羥基。羥基為親水性基團，若該種親水性基團以既定量存在於黏著劑中，則即使在黏著劑置於高溫高濕條件下之情況下，與在該高溫高濕條件下浸入黏著劑中之水分之相溶性亦良好，其結果，黏著劑的白化得到抑制。 The (meth) acrylate copolymer (A) is an adhesive main component in the adhesive composition P. The (meth) acrylate copolymer (A) contains 15 to 30% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the polymer, and preferably contains 17 to 28% by mass, preferably 20 to 25% by mass. % is especially good. When the content of the hydroxyl group-containing monomer is within the above range, the crosslinked structure formed by the (meth) acrylate copolymer (A) and the polyisocyanate compound (B) becomes good, and the adhesive layer 11 becomes suitable. Durable. Further, the adhesive layer 11 obtained from the adhesive composition P of the (meth) acrylate copolymer (A) having a content of the hydroxyl group-containing monomer in the above range is subjected to high temperature and high humidity conditions (for example, at 85 ° C). After 72 hours under conditions of 85% RH, whitening at the time of returning to normal temperature and normal humidity was suppressed, that is, it was excellent in wet heat and whitening resistance. When the (meth) acrylate copolymer (A) contains a hydroxyl group-containing monomer as a monomer unit in the above amount, a predetermined amount of a hydroxyl group remains in the obtained adhesive. The hydroxyl group is a hydrophilic group, and if the hydrophilic group is present in the adhesive in a quantitative amount, the adhesive is immersed in the high temperature and high humidity condition even under the condition of the high temperature and high humidity. The compatibility of the water in the water is also good, and as a result, the whitening of the adhesive is suppressed.

若作為(甲基)丙烯酸酯共聚物(A)中之單體單位之含羥基單體的含量小於15質量%，則黏著劑層11會成為尤其耐濕熱白化性較差者。另一方面，若含羥基單體的含量超過30質量%，則黏著性組成物P的塗佈性惡化。 When the content of the hydroxyl group-containing monomer as the monomer unit in the (meth) acrylate copolymer (A) is less than 15% by mass, the adhesive layer 11 is particularly inferior in moisture and heat whitening resistance. On the other hand, when the content of the hydroxyl group-containing monomer exceeds 30% by mass, the coatability of the adhesive composition P is deteriorated.

作為含有羥基之單體，可例舉出例如(甲基)丙烯酸2-羥基乙酯，(甲基)丙烯酸2-羥基丙酯，(甲基)丙烯酸3-羥基丙酯，(甲基)丙烯酸2-羥基丁酯，(甲基)丙烯酸3-羥基丁酯，(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥烷 基酯等。其中，從所獲得之(甲基)丙烯酸酯共聚物(A)中之與聚異氰酸酯化合物(B)的反應性以及與其他單體的共聚合性方面考慮，(甲基)丙烯酸2-羥基乙酯為較佳。該些物質可單獨使用，亦可組合使用兩種以上。 The hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or (meth)acrylic acid. 2-hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Base ester and the like. Among them, 2-hydroxyethyl (meth)acrylate is considered from the viewpoint of reactivity with the polyisocyanate compound (B) and copolymerization with other monomers in the obtained (meth) acrylate copolymer (A). Esters are preferred. These may be used singly or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，不含有含羧基單體。藉此，即使在所得到之黏著劑因酸而產生不良情況，例如貼附於透明導電膜和金屬配線等之情況下，亦能夠抑制由酸引起之該等的不良情況。例如，能夠抑制透明導電膜和金屬配線腐蝕或者透明導電膜的電阻值發生變化。 In the (meth) acrylate copolymer (A), the monomer unit constituting the polymer does not contain a carboxyl group-containing monomer. As a result, even when the obtained adhesive is inferior due to acid, for example, when it is attached to a transparent conductive film or a metal wiring, it is possible to suppress such problems caused by acid. For example, it is possible to suppress corrosion of the transparent conductive film and the metal wiring or change the resistance value of the transparent conductive film.

在此，“不含有具有羧基之單體”係指基本上不含有具有羧基之單體，除了完全不含有含羧基單體以外，還容許以不產生由羧基引起之透明導電膜和金屬配線等的腐蝕之程度含有含羧基單體。具體而言，在(甲基)丙烯酸酯共聚物(A)中，作為單體單位，容許以0.01質量%以下的量含有含羧基單體，以0.001質量%以下的量含有為較佳。 Here, the phrase "the monomer having no carboxyl group" means that the monomer having a carboxyl group is substantially not contained, and the transparent conductive film and the metal wiring which are not caused by the carboxyl group are allowed to be contained, except that the carboxyl group-containing monomer is not contained at all. The degree of corrosion contains carboxyl-containing monomers. Specifically, in the (meth) acrylate copolymer (A), the carboxyl group-containing monomer is contained in an amount of 0.01% by mass or less as the monomer unit, and it is preferably contained in an amount of 0.001% by mass or less.

(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，含有烷基的碳數為1~20的(甲基)丙烯酸烷基酯為較佳，作為主成份而含有尤為佳。藉此，所得到之黏著劑能夠顯現出較佳的黏著性。另外，後述的硬單體從該(甲基)丙烯酸烷基酯中除去。 In the (meth) acrylate copolymer (A), as the monomer unit constituting the polymer, an alkyl (meth) acrylate having an alkyl group and having 1 to 20 carbon atoms is preferable as a main component. It is especially good. Thereby, the obtained adhesive can exhibit better adhesion. Further, the hard monomer described later is removed from the alkyl (meth)acrylate.

作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如可例舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙 烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯等。其中，從進一步提高黏著性之觀點考慮，烷基的碳原子數為1~8的(甲基)丙烯酸酯為較佳，(甲基)丙烯酸正丁酯以及(甲基)丙烯酸2-乙基己酯尤為佳。另外，該些物質可單獨使用，亦可組合使用兩種以上。 The alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate or propyl (meth)acrylate, ( N-butyl acrylate, (meth) propyl N-amyl enoate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylic acid Dodecyl ester, tetradecyl (meth)acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, and the like. Among them, from the viewpoint of further improving the adhesion, a (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferred, n-butyl (meth)acrylate and 2-ethyl (meth)acrylate. Hexyl ester is especially preferred. Further, these materials may be used singly or in combination of two or more.

於(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯30~85質量%為較佳，含有40~75質量%尤為佳，含有50~65質量%為進一步較佳。 In the (meth) acrylate copolymer (A), as a monomer unit constituting the polymer, the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is 30 to 85% by mass. Preferably, it is preferably 40 to 75% by mass, more preferably 50 to 65% by mass.

並且，(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，含有丙烯酸酯系的硬單體為較佳。在此，硬單體係指僅使該硬單體聚合而得到之作為均聚物之玻璃化轉變溫度(Tg)為70℃以上、75~200℃為較佳、80~180℃尤為佳的單體。藉由含有上述硬單體作為構成(甲基)丙烯酸酯共聚物(A)之單體單位，所得到之黏著劑成為耐久性及抗起泡性更加優異者。 Further, in the (meth) acrylate copolymer (A), an acrylate-based hard monomer is preferable as a monomer unit constituting the polymer. Here, the hard single system means that the glass transition temperature (Tg) of the homopolymer obtained by polymerizing only the hard monomer is 70° C. or more, preferably 75 to 200° C., and preferably 80 to 180° C. monomer. By containing the above hard monomer as a monomer unit constituting the (meth) acrylate copolymer (A), the obtained adhesive is more excellent in durability and anti-foaming property.

作為上述硬單體，例如可以舉出甲基丙烯酸甲酯(Tg105℃)、丙烯酸異冰片酯(Tg94℃)、甲基丙烯酸異冰片酯(Tg180℃)、丙烯醯嗎啉(Tg145℃)、丙烯酸金剛烷酯(Tg115℃)、甲基丙烯酸金剛烷酯(Tg141℃)、二甲基丙烯醯胺(Tg89℃)、丙烯醯胺(Tg165℃)等。該等可以單獨使用，亦可以組 合使用兩種以上。 Examples of the hard monomer include methyl methacrylate (Tg 105 ° C), isobornyl acrylate (Tg 94 ° C), isobornyl methacrylate (Tg 180 ° C), propylene morpholine (Tg 145 ° C), and acrylic acid. Adamantyl ester (Tg 115 ° C), adamantyl methacrylate (Tg 141 ° C), dimethyl methacrylate (Tg 89 ° C), acrylamide (Tg 165 ° C) and the like. These can be used alone or in groups Use two or more.

上述硬單體中，從防止對黏著性和透明性等其他特性之不良影響的同時進一步發揮硬單體的性能之觀點考慮，甲基丙烯酸甲酯、丙烯酸異冰片酯及丙烯醯嗎啉更為佳，甲基丙烯酸甲酯尤為佳。 Among the above hard monomers, methyl methacrylate, isobornyl acrylate and propylene morpholine are more preferable from the viewpoint of preventing adverse effects on other properties such as adhesion and transparency while further exerting the performance of the hard monomer. Preferably, methyl methacrylate is particularly preferred.

(甲基)丙烯酸酯共聚物(A)中，作為構成該聚合物之單體單位，含有10~45質量%的上述硬單體為較佳，含有15~30質量%尤為佳。藉由含有10質量%以上的上述硬單體，能夠預料基於該單體單位之耐久性或抗起泡性的改善效果。另一方面，藉由將上述硬單體設為45質量%以下的含量，防止(甲基)丙烯酸酯共聚物(A)中除此以外的單體單位的相對不足，能夠使所得到之黏著劑成為黏著性、段差追隨性及耐濕熱白化性優異者。 In the (meth) acrylate copolymer (A), the hard monomer is preferably from 10 to 45% by mass, particularly preferably from 15 to 30% by mass, based on the monomer unit constituting the polymer. By containing 10% by mass or more of the above hard monomer, it is possible to predict the effect of improving the durability or the anti-foaming property based on the monomer unit. On the other hand, by setting the hard monomer to a content of 45% by mass or less, the relative shortage of the other monomer units in the (meth) acrylate copolymer (A) can be prevented, and the obtained adhesion can be obtained. The agent is excellent in adhesion, step followability, and resistance to moist heat whitening.

(甲基)丙烯酸酯共聚物(A)根據需要亦可含有作為構成該聚合物之單體單位的其他單體。作為其他單體，為了不損害含羥基單體的作用而不含有具有反應性之官能基的單體為較佳。作為所述其他單體，例如可例舉(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸乙氧乙酯等(甲基)丙烯酸烷氧基烷基酯，(甲基)丙烯酸環己基酯等具有脂肪族環之(甲基)丙烯酸酯，(甲基)丙烯酸-N，N-二甲氨基乙酯、(甲基)丙烯酸-N，N-二甲氨基丙酯等具有非交聯性叔氨基之(甲基)丙烯酸酯，乙酸乙烯酯、苯乙烯等。該些物質可單獨使用，亦可組合使用兩種以上。 The (meth) acrylate copolymer (A) may contain other monomers as a monomer unit constituting the polymer, as needed. As the other monomer, a monomer which does not contain a reactive functional group without impairing the action of the hydroxyl group-containing monomer is preferred. The other monomer may, for example, be an alkoxyalkyl (meth)acrylate such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate or a cyclohexyl (meth)acrylate. (meth)acrylate having an aliphatic ring such as an ester, N-N-dimethylaminoethyl (meth)acrylate, N-N-dimethylaminopropyl (meth)acrylate, etc. having non-crosslinking A tertiary amino (meth) acrylate, vinyl acetate, styrene, and the like. These may be used singly or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)的聚合態樣可為無 規共聚物，亦可為嵌段共聚物。 The polymerization state of the (meth) acrylate copolymer (A) may be none The copolymer may also be a block copolymer.

(甲基)丙烯酸酯共聚物(A)的重量平均分子量為20萬~90萬，25萬~80萬為較佳，45萬~65萬尤為佳。另外，本說明書中之重量平均分子量係藉由凝膠滲透色譜(GPC)法測定之聚苯乙烯換算的值。 The (meth) acrylate copolymer (A) has a weight average molecular weight of 200,000 to 900,000, preferably 250,000 to 800,000, and particularly preferably 450,000 to 650,000. Further, the weight average molecular weight in the present specification is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

藉由黏著性組成物P的黏著主劑亦即(甲基)丙烯酸酯共聚物(A)的重量平均分子量在上述範圍內，能夠實現兼備段差追隨性及抗起泡性。若(甲基)丙烯酸酯共聚物(A)的重量平均分子量小於20萬，則黏著劑的內聚力不足而成為抗起泡性較差者。另一方面，若(甲基)丙烯酸酯共聚物(A)的重量平均分子量超過90萬，則成為段差追隨性較差者。 The weight average molecular weight of the (meth) acrylate copolymer (A), which is an adhesive main component of the adhesive composition P, is within the above range, and it is possible to achieve both step followability and anti-foaming property. When the weight average molecular weight of the (meth) acrylate copolymer (A) is less than 200,000, the cohesive force of the adhesive is insufficient and the antifoaming property is inferior. On the other hand, when the weight average molecular weight of the (meth) acrylate copolymer (A) exceeds 900,000, the step-following property is inferior.

另外，黏著性組合物P中，(甲基)丙烯酸酯共聚物(A)可單獨使用一種，亦可組合使用兩種以上。 Further, in the adhesive composition P, the (meth) acrylate copolymer (A) may be used alone or in combination of two or more.

(2)聚異氰酸酯化合物(B) (2) Polyisocyanate compound (B)

若使黏著性組成物P交聯，則聚異氰酸酯化合物(B)與源自構成(甲基)丙烯酸酯共聚物(A)之含羥基單體之羥基發生反應。藉此，形成(甲基)丙烯酸酯共聚物(A)藉由聚異氰酸酯化合物(B)交聯之結構。 When the adhesive composition P is crosslinked, the polyisocyanate compound (B) reacts with the hydroxyl group derived from the hydroxyl group-containing monomer constituting the (meth) acrylate copolymer (A). Thereby, the structure in which the (meth) acrylate copolymer (A) is crosslinked by the polyisocyanate compound (B) is formed.

作為聚異氰酸酯化合物(B)，例如可以舉出甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、亞二甲苯二異氰酸酯等芳香族聚異氰酸酯、六亞甲基二異氰酸酯等脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯等脂環式聚異氰酸酯等及該等的縮二脲物、異氰脲酸酯物、以及作為與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等含低 分子活性氫化合物之反應物之加成物等，其中，從段差追隨性及抗起泡性方面考慮，三羥甲基丙烷改性芳香族聚異氰酸酯，尤其是三羥甲基丙烷改性甲苯二異氰酸酯為較佳。上述聚異氰酸酯化合物(B)可以單獨使用一種或者組合使用兩種以上。 Examples of the polyisocyanate compound (B) include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone. An alicyclic polyisocyanate such as diisocyanate or hydrogenated diphenylmethane diisocyanate, and the like, and the biuret, isocyanurate, and as ethylene glycol, propylene glycol, neopentyl glycol, and trishydroxyl Base propane, castor oil, etc. An adduct of a reactant of a molecularly active hydrogen compound, etc., wherein trimethylolpropane-modified aromatic polyisocyanate, especially trimethylolpropane-modified toluene, is considered in terms of step followability and anti-foaming property. Isocyanates are preferred. The above polyisocyanate compound (B) may be used alone or in combination of two or more.

黏著性組成物P中之聚異氰酸酯化合物(B)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份為較佳，0.005~2質量份尤為佳，0.01~1質量份為進一步較佳。若聚異氰酸酯化合物(B)的含量為0.001質量份以上，則所得到之黏著劑層11成為段差追隨性、抗起泡性及耐濕熱白化性更加優異者。若聚異氰酸酯化合物(B)的含量超過5質量份，則交聯程度變得過高，所得到之黏著劑的段差追隨性有可能下降。並且，(甲基)丙烯酸酯共聚物(A)的羥基大量與聚異氰酸酯化合物(B)發生反應而殘留於黏著劑中之羥基的量變少，耐濕熱白化性有可能下降。 The content of the polyisocyanate compound (B) in the adhesive composition P is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer (A), and particularly preferably 0.005 to 2 parts by mass, 0.01. ~1 part by mass is further preferred. When the content of the polyisocyanate compound (B) is 0.001 part by mass or more, the obtained adhesive layer 11 is more excellent in step followability, anti-foaming property, and moist heat whitening resistance. When the content of the polyisocyanate compound (B) exceeds 5 parts by mass, the degree of crosslinking becomes too high, and the step followability of the obtained adhesive may be lowered. Further, the hydroxyl group of the (meth) acrylate copolymer (A) reacts with the polyisocyanate compound (B) in a large amount to reduce the amount of the hydroxyl group remaining in the adhesive, and the wet heat whitening resistance may be lowered.

(3)螯合化合物(C) (3) Chelating compound (C)

在使黏著性組成物P交聯而得到之黏著劑中，認為螯合化合物(C)係藉由氫鍵以較弱的力與(甲基)丙烯酸酯共聚物(A)的交聯體鍵合者。藉由螯合化合物(C)及聚異氰酸酯化合物(B)相對於(甲基)丙烯酸酯共聚物(A)之相互作用，黏著劑層11成為段差追隨性優異，並且即使在耐久條件下段差追隨性、抗起泡性及耐濕熱白化性亦優異者。 In the adhesive obtained by crosslinking the adhesive composition P, it is considered that the chelating compound (C) is a crosslinker bond of the (meth) acrylate copolymer (A) with a weak force by hydrogen bonding. Together. By the interaction of the chelate compound (C) and the polyisocyanate compound (B) with respect to the (meth) acrylate copolymer (A), the adhesive layer 11 is excellent in step followability and follows the step even under endurance conditions. Excellent in properties, anti-foaming properties, and resistance to moist heat and whitening.

作為螯合化合物(C)，有金屬原子為鋁、鋯、鈦、鋅、鉄、錫等之金屬螯合化合物，但從性能方面考慮，鋁螯合化合物及鋯螯合化合物為較佳，鋁螯合化合物尤為佳。並且， 該等金屬螯合化合物為乙醯丙酮錯合物為較佳。 As the chelating compound (C), a metal chelate compound having a metal atom of aluminum, zirconium, titanium, zinc, lanthanum, tin or the like is preferable, but aluminum chelate compound and zirconium chelate compound are preferable in terms of performance, aluminum Chelating compounds are especially preferred. and, The metal chelate compound is preferably an acetamidineacetate complex.

作為鋁螯合化合物，例如可以舉出二異丙氧基鋁單乙醯乙酸油酯、單異丙氧基鋁雙乙醯乙酸油酯、單異丙氧基鋁單油酸酯單乙醯乙酸乙酯、二異丙氧基鋁單乙醯乙酸月桂酯、二異丙氧基鋁單乙醯乙酸硬脂酯、二異丙氧基鋁單乙醯乙酸異硬脂酯、單異丙氧基鋁單-N-月桂醯基-β-鋁氧化物單乙醯乙酸月桂酯、三乙醯丙酮鋁、單乙醯丙酮鋁雙(乙醯乙酸異丁酯)螯合物、單乙醯丙酮鋁雙(乙醯乙酸2-乙基己酯)螯合物、單乙醯丙酮鋁雙(乙醯乙酸十二烷酯)螯合物、單乙醯丙酮鋁雙(乙醯乙酸油酯)螯合物等，其中，三乙醯丙酮鋁為較佳。該等可以單獨使用，亦可以組合使用兩種以上。 Examples of the aluminum chelate compound include diisopropoxy aluminum monoacetic acid ethyl ester, monoisopropoxy aluminum bisacetate acetic acid ester, and monoisopropoxy aluminum monooleate monoacetic acid acetic acid. Ethyl ester, lauryl aluminum diisopropoxide, lauryl acetate monoacetate, stearyl diisopropoxide aluminum monoacetate, isostearyl diisopropoxide aluminum monoacetate, monoisopropoxy Aluminum mono-N-lauroyl-β-aluminum oxide monoethyl phthalate lauryl acetate, triethyl acetonide aluminum, monoethyl acetonide aluminum bis(acetic acid isobutyl acrylate) chelate, monoethyl acetonide aluminum Bis(2-ethylhexylacetate) chelate, monoethylammonium acetonate acetoacetate (dodecyl acetate) chelate, monoethylammonium acetone bis(acetamidine acetate) chelate Etc., among them, triethylammonium acetone is preferred. These may be used alone or in combination of two or more.

作為鋯螯合化合物，例如可以舉出四乙醯丙酮鋯、三丁氧基乙醯丙酮鋯、單丁氧基乙醯丙酮鋯雙(乙醯乙酸乙酯)、二丁氧基鋯雙(乙醯乙酸乙酯)等，其中，四乙醯丙酮鋯為較佳。該等可以單獨使用，亦可以組合使用兩種以上。 Examples of the zirconium chelate compound include zirconium tetraethoxide, zirconium tributoxyacetone, zirconium monobutoxyacetazolacetate (acetic acid ethyl acetate), and zirconium dibutoxide (B). Ethyl acetate and the like, among which zirconium tetraacetate acetone is preferred. These may be used alone or in combination of two or more.

黏著性組成物P中之螯合化合物(C)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份為較佳，0.05~2質量份尤為佳，0.01~1質量份為進一步較佳。藉由螯合化合物(C)的含量在上述範圍內，可以進一步發揮前述效果。若螯合化合物(C)的含量過多，則段差追隨性能有可能下降。 The content of the chelating compound (C) in the adhesive composition P is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer (A), and particularly preferably 0.05 to 2 parts by mass, 0.01. ~1 part by mass is further preferred. When the content of the chelate compound (C) is within the above range, the above effects can be further exerted. If the content of the chelate compound (C) is too large, the step following performance may be lowered.

(4)各種添加劑 (4) Various additives

於黏著性組合物P中，根據需要能夠添加通常用作丙烯系黏著劑之各種添加劑，例如，矽烷偶合劑、防靜電劑、增黏劑、 抗氧化劑、紫外線吸收劑、光穩定劑、軟化劑、填充劑、折射率調整劑等。 In the adhesive composition P, various additives generally used as a propylene-based adhesive, such as a decane coupling agent, an antistatic agent, a tackifier, and the like, can be added as needed. Antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, refractive index modifiers, and the like.

尤其從改善耐久性之觀點考慮，在黏著性組成物P中添加矽烷偶合劑作為添加劑為較佳。作為矽烷偶合劑，係在分子內具有至少一個烷氧基矽基之有機矽化合物且與(甲基)丙烯酸酯共聚物(A)之相溶性良好者為較佳。並且，當黏著片1用於光學用途時，具有光透過性之矽烷偶合劑為較佳。 In particular, from the viewpoint of improving durability, it is preferred to add a decane coupling agent as an additive to the adhesive composition P. The decane coupling agent is preferably an organic ruthenium compound having at least one alkoxyfluorenyl group in the molecule and having good compatibility with the (meth) acrylate copolymer (A). Further, when the adhesive sheet 1 is used for optical use, a light transmissive decane coupling agent is preferred.

作為該種矽烷偶合劑(C)，例如可例舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯等含聚合性不飽和基之矽化合物，3-縮水甘油醚丙基三甲氧基矽烷，2-(3，4-環氧環己基)乙基三甲氧基矽烷等環氧構造之矽化合物，3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等含巰基矽化合物，3-氨基丙基三甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷，N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷等含氨基矽化合物，3-氯丙基三甲氧基矽烷，3-異氰酸酯丙基三乙氧基矽烷，或者該些至少一種與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等含烷基矽化合物的縮合物等。該些物質可單獨使用一種，亦可組合使用兩種以上。 Examples of the decane coupling agent (C) include a fluorene compound containing a polymerizable unsaturated group such as vinyl trimethoxy decane, vinyl triethoxy decane or methacryl oxime, and 3-glycidyl ether C. Epoxy-based oxime compound such as trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxy A fluorenyl-containing hydrazine compound such as decane or 3-mercaptopropyldimethoxymethyl decane, 3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane An aminoguanidine-containing compound such as N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, Or at least one condensate of an alkyl group-containing compound such as methyltriethoxydecane, ethyltriethoxydecane, methyltrimethoxydecane or ethyltrimethoxydecane. These may be used alone or in combination of two or more.

矽烷偶合劑的添加量相對於(甲基)丙烯酸酯共聚物(A)100質量份為0.01~1.0質量份為較佳，0.05~0.5質量份尤為佳。 The amount of the decane coupling agent to be added is preferably 0.01 to 1.0 part by mass, more preferably 0.05 to 0.5 part by mass, per 100 parts by mass of the (meth) acrylate copolymer (A).

(5)黏著性組成物的製造 (5) Manufacture of adhesive composition

製造(甲基)丙烯酸酯共聚物(A)並將所得到之(甲基) 丙烯酸酯共聚物(A)、聚異氰酸酯化合物(B)及螯合化合物(C)進行混合，並且根據需要加入添加劑，藉此能夠製造黏著性組成物P。 Manufacturing (meth) acrylate copolymer (A) and obtaining the obtained (meth) The acrylate copolymer (A), the polyisocyanate compound (B), and the chelating compound (C) are mixed, and an additive is added as needed, whereby the adhesive composition P can be produced.

藉由利用通常的自由基聚合法來聚合構成聚合物之單體單位的混合物，從而能夠製造(甲基)丙烯酸酯共聚物(A)。根據需要，使用聚合開始劑並藉由溶液聚合法等能夠進行(甲基)丙烯酸酯共聚物(A)的聚合。作為聚合溶劑，例如可例舉醋酸乙酯、酢酸正丁酯、醋酸正異丁酯、甲苯、丙酮、己烷，甲基乙基酮等，亦可並用兩種以上。 The (meth) acrylate copolymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate copolymer (A) can be carried out by a solution polymerization method or the like using a polymerization initiator as needed. The polymerization solvent may, for example, be ethyl acetate, n-butyl phthalate, n-isobutyl acetate, toluene, acetone, hexane or methyl ethyl ketone. Two or more kinds may be used in combination.

作為聚合開始劑，可例舉偶氮系化合物、有機過氧化物等，亦可並用兩種以上。作為偶氮系化合物，例如，2，2'-偶氮二異丁腈、2，2'-偶氮雙(2-甲基丁腈)、1，1'-偶氮二(環己烷-1-腈)、2，2'-偶氮雙(2，4-二甲基戊腈)、2，2'-偶氮二(2，4-二甲基-4-甲氧基戊腈)、2，2'-偶氮二(2-甲基丙酸酯)、4，4'-偶氮二(4-氰基戊酸)、2，2'-偶氮二(2-羥甲基丙腈)、2，2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。 The polymerization initiator may, for example, be an azo compound or an organic peroxide, or two or more kinds thereof may be used in combination. As the azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane- 1-nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethyl) Propionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and the like.

作為有機過氧化物，例如可例舉過氧化苯甲醯，叔丁基過苯甲酸酯、枯烯過氧化氫、二異丙基過氧二碳酸酯、二-N-丙基過氧二碳酸酯、二(2-乙氧基乙基)過氧二碳酸酯、過氧化新癸酸叔丁酯、過氧化新戊酸叔丁酯、(3，5，5-三甲基己醯基)過氧化物、過氧化二丙醯、過氧化二乙醯等。 The organic peroxide may, for example, be benzoic acid benzoate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate or di-N-propyl peroxydicarboxylate. Carbonate, bis(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxy neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexyl) Peroxide, dipropene peroxide, diethylperoxide peroxide, and the like.

另外，於上述聚合製程中，藉由配合2-巰基乙醇等鏈轉移劑，能調節所獲得之聚合物的重量平均分子量。 Further, in the above polymerization process, the weight average molecular weight of the obtained polymer can be adjusted by blending a chain transfer agent such as 2-mercaptoethanol.

得到(甲基)丙烯酸酯共聚物(A)之後，在(甲 基)丙烯酸酯共聚物(A)的溶液中添加聚異氰酸酯化合物(B)、螯合化合物(C)、以及根據需要添加稀釋溶劑、添加劑並充份混合，藉此得到用溶劑稀釋之黏著性組成物P(塗佈溶液)。 After obtaining the (meth) acrylate copolymer (A), The polyisocyanate compound (B), the chelating compound (C), and, if necessary, a diluent solvent and an additive are added to the solution of the acrylate copolymer (A), and the mixture is mixed and mixed, thereby obtaining an adhesive composition diluted with a solvent. Material P (coating solution).

作為上述稀釋溶劑，可使用例如己烷、庚烷、環己烷等脂肪族碳化氫、甲苯、二甲苯等芳香族碳化氫，二氯甲烷、二氯乙烷等氯化碳化氫，甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇，丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等酮，醋酸乙酯、酢酸丁酯等酯，乙基溶纖劑等溶纖劑系溶劑等。 As the diluent solvent, for example, an aliphatic hydrocarbon such as hexane, heptane or cyclohexane, an aromatic hydrocarbon such as toluene or xylene, or a chlorinated hydrocarbon such as dichloromethane or dichloroethane, methanol or ethanol can be used. , propanol, butanol, 1-methoxy-2-propanol and other alcohols, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl citrate An ester such as an ester or a cellosolve such as an ethyl cellosolve is a solvent.

作為如此製備之塗佈溶液的濃度劑黏度，只要於可塗佈之範圍即可，並無特別的限制，根據狀況能夠適當地進行選定。例如，稀釋成使黏著性組合物P的濃度成為10~40質量%。另外，當獲得塗佈溶液時，稀釋溶劑等的添加並非必要條件，若黏著性組合物P為可塗佈之黏度等，則亦可不添加稀釋溶劑。該情況下，黏著性組合物P成為直接將(甲基)丙烯酸酯共聚合物(A)的聚合溶劑作為稀釋溶劑之塗佈溶液。 The concentration of the concentration of the coating solution thus prepared is not particularly limited as long as it is within the range that can be applied, and can be appropriately selected depending on the situation. For example, it is diluted so that the concentration of the adhesive composition P becomes 10 to 40% by mass. Further, when the coating solution is obtained, the addition of a diluent solvent or the like is not a requirement, and if the adhesive composition P is a coatable viscosity or the like, the diluent solvent may not be added. In this case, the adhesive composition P is a coating solution in which a polymerization solvent of the (meth) acrylate copolymer (A) is directly used as a diluent solvent.

(6)黏著劑層的形成 (6) Formation of adhesive layer

黏著劑層11係使黏著性組成物P交聯而成者。黏著性組成物P的交聯能夠藉由加熱處理來進行。另外，還可以利用使黏著性組成物P的稀釋溶劑等揮發時的乾燥處理來兼作該加熱處理。 The adhesive layer 11 is obtained by crosslinking the adhesive composition P. The crosslinking of the adhesive composition P can be carried out by heat treatment. In addition, the heat treatment may be used as the heat treatment when the dilution solvent or the like of the adhesive composition P is volatilized.

當進行加熱處理時，加熱溫度為50~150℃為較佳，70~120℃尤為佳。並且，加熱時間為30秒~10分鐘為較 佳，50秒~2分鐘尤為佳。加熱處理之後，根據需要，亦可設置成常溫(例如，23℃、50%RH)且1~2周程度的養護期間。當需要該養護期間之情況下，於養護期間經過之後形成黏著劑，而不需要養護期間之情況下，於加熱處理結束後形成黏著劑層11。 When the heat treatment is performed, the heating temperature is preferably from 50 to 150 ° C, and particularly preferably from 70 to 120 ° C. And, the heating time is 30 seconds to 10 minutes. Good, 50 seconds to 2 minutes is especially good. After the heat treatment, if necessary, it may be set to a normal temperature (for example, 23 ° C, 50% RH) and a curing period of about 1 to 2 weeks. When the curing period is required, the adhesive layer 11 is formed after the heat treatment is completed, in the case where the adhesive is formed after the curing period, without the need for the curing period.

藉由上述加熱處理(以及養護)，經由聚異氰酸酯化合物(B)(甲基)丙烯酸酯共聚物(A)被良好地交聯。 The polyisocyanate compound (B) (meth) acrylate copolymer (A) is favorably crosslinked by the above heat treatment (and curing).

所形成之黏著劑層11的厚度(按照JIS K7130測定之值)為10~400μm，20~300μm為較佳，50~250μm尤為佳。另外，黏著劑層11可以以單層形成，亦可以積層複數層而形成。 The thickness of the adhesive layer 11 to be formed (value measured in accordance with JIS K7130) is 10 to 400 μm, preferably 20 to 300 μm, and particularly preferably 50 to 250 μm. Further, the adhesive layer 11 may be formed in a single layer or may be formed by laminating a plurality of layers.

若黏著劑層11的厚度小於10μm，則無法得到充份的段差追隨性，若黏著劑層11的厚度超過400μm，則加工性下降。 When the thickness of the adhesive layer 11 is less than 10 μm, sufficient step followability cannot be obtained, and when the thickness of the adhesive layer 11 exceeds 400 μm, workability is lowered.

2.剝離片 2. Stripping sheet

作為剝離片12a、12b，例如，可使用聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚乙烯萘二甲酸薄膜、聚對苯二甲酸丁二酯薄膜、聚氨酯薄膜、乙烯乙酸乙烯酯薄膜、離聚物樹脂薄膜、乙烯/(甲基)丙烯酸共聚物薄膜、乙烯/(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。並且，亦可使用該些物質的交聯薄膜。另外，該些物質的積層薄膜亦可。 As the release sheets 12a and 12b, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, or a poly pair can be used. Ethylene phthalate film, polyethylene naphthalene diene film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene/(meth)acrylic copolymer film , an ethylene/(meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like. Further, a crosslinked film of these materials can also be used. In addition, a laminated film of these materials may also be used.

上述剝離片12a、12b的剝離面(尤其與黏著劑層11接觸之面)被實施剝離處理為較佳。作為使用於剝離處理之剝離劑，例如，可例舉醇酸系，矽酮系、氟系、不飽和聚酯系、聚烯烴系，蠟系等剝離劑。另外，剝離片12a、12b中，將一方剝離片設為剝離力較大的重剝離型剝離片，將另一方剝離片設為剝離力較小的輕剝離型剝離片為較佳。 The release surface of the release sheets 12a and 12b (particularly the surface in contact with the adhesive layer 11) is preferably subjected to a release treatment. The release agent to be used for the release treatment may, for example, be a release agent such as an alkyd type, an anthrone type, a fluorine type, an unsaturated polyester type, a polyolefin type, or a wax type. In the release sheets 12a and 12b, one of the release sheets is a heavy release type release sheet having a large peeling force, and the other release sheet is preferably a light release type release sheet having a small peeling force.

關於剝離片12a、12b的厚度並無特別限制，通常為20~150μm程度。 The thickness of the release sheets 12a and 12b is not particularly limited, and is usually about 20 to 150 μm.

3.黏著片的製造 3. Manufacture of adhesive sheets

作為黏著片1的一個製造例，於一方剝離片12a(或12b)的剝離面塗佈上述黏著性組合物P的塗佈液，並進行加熱處理以使黏著性組合物P交聯，於形成塗佈層之後，使另一方剝離片12b(或12a)的剝離面重合於該塗佈層。當需要養護期間之情況下，事先設置養護期間，當不需要養護期間之情況下，上述塗佈層直接成為黏著劑層11。籍此，可獲得上述黏著片1。關於加熱處理以及養護的條件如同前述。 As a production example of the adhesive sheet 1, the coating liquid of the above-mentioned adhesive composition P is applied to the peeling surface of one of the release sheets 12a (or 12b), and heat treatment is performed to crosslink the adhesive composition P to form After the coating layer is applied, the peeling surface of the other peeling sheet 12b (or 12a) is superposed on the coating layer. In the case where a curing period is required, the coating layer is directly formed as the adhesive layer 11 when the curing period is not required in advance. Thereby, the above-mentioned adhesive sheet 1 can be obtained. The conditions regarding heat treatment and curing are as described above.

作為黏著片1的其他製造例，於一方剝離片12a的剝離面塗佈上述黏著性組合物P的塗佈液，並進行加熱處理以使黏著性組合物P交聯，形成塗佈層，從而獲得帶塗佈層的剝離片12a。並且，於另一剝離片12b的剝離面塗佈上述黏著性組合物P的塗佈液，並進行加熱處理以使黏著性組合物P交聯，形成塗佈層，從而獲得帶塗佈層的剝離片12b。然後，將帶塗佈層的剝離片12a與帶塗佈層的剝離片12b以兩個塗佈層彼此接觸之方式進行貼合。當需要養護期間之情況下，事先設 置養護期間，當不需要養護期間之情況下，上述積層之塗佈層直接成為黏著劑層11。籍此，可獲得上述黏著片1。依據該製造例，即使於黏著劑層11較厚的情況下亦可穩定地進行製造。 In another example of the production of the adhesive sheet 1, the coating liquid of the adhesive composition P is applied to the release surface of one of the release sheets 12a, and heat treatment is performed to crosslink the adhesive composition P to form a coating layer. A release sheet 12a with a coating layer was obtained. Then, the coating liquid of the adhesive composition P is applied onto the peeling surface of the other release sheet 12b, and heat-treated to crosslink the adhesive composition P to form a coating layer, thereby obtaining a coated layer. The sheet 12b is peeled off. Then, the release sheet 12a with the coating layer and the release sheet 12b with the coating layer are bonded so that the two coating layers are in contact with each other. In case of need for maintenance period, set in advance During the curing period, when the curing period is not required, the above-mentioned laminated coating layer directly becomes the adhesive layer 11. Thereby, the above-mentioned adhesive sheet 1 can be obtained. According to this production example, even when the adhesive layer 11 is thick, it can be stably produced.

作為塗佈上述黏著性組合物P的塗佈液之方法，例如能夠利用棒塗佈法，刮刀塗佈法，輥塗佈法，刮板塗佈法，模具塗佈法，凹版塗佈法等。 As a method of applying the coating liquid of the above-mentioned adhesive composition P, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used. .

4．物性 4. Physical property

(1)凝膠率 (1) Gel fraction

構成本實施形態中之黏著劑層11之黏著劑的凝膠率為15~95%為較佳，40~90%尤為佳，60~85%為進一步較佳。若凝膠率小於15%，則黏著劑的內聚力不足，有時抗起泡性會下降。另一方面，若凝膠率超過95%，則黏著力變得過低而耐久性下降或者段差追隨性能下降。另外，凝膠率的測定方法如後述之試驗例所示。 The adhesive agent constituting the adhesive layer 11 of the present embodiment preferably has a gel fraction of 15 to 95%, particularly preferably 40 to 90%, and more preferably 60 to 85%. When the gel fraction is less than 15%, the cohesive force of the adhesive is insufficient, and the anti-foaming property may be lowered. On the other hand, when the gel fraction exceeds 95%, the adhesive force becomes too low, the durability is lowered, or the step following performance is lowered. Further, the method for measuring the gel fraction is as shown in the test examples described later.

(2)霧度值 (2) Haze value

本實施形態中之黏著劑層11的霧度值(按照JIS K7136：2000測定之值)為1.0%以下為較佳，0.9%以下尤為佳，0.8%以下為進一步較佳。若霧度值為1.0%以下，則透明性非常高，成為適合於光學用途者。另外，黏著劑層11的霧度值在後述之耐濕熱白化性的評價試驗後亦在上述範圍內尤為佳。 The haze value (value measured in accordance with JIS K7136:2000) of the adhesive layer 11 in the present embodiment is preferably 1.0% or less, more preferably 0.9% or less, and still more preferably 0.8% or less. When the haze value is 1.0% or less, the transparency is extremely high, and it is suitable for optical use. Further, the haze value of the pressure-sensitive adhesive layer 11 is particularly preferably within the above range after the evaluation test of the moist heat whitening resistance to be described later.

〔積層體〕 [layered body]

如第2圖所示，本實施形態之積層體2由第1硬質板21、第2硬質板22、以及位於該等之間且被第1硬質板21及第2硬質板22夾持之黏著劑層11構成。並且，本實施形態之積層 體2中，第1硬質板21在黏著劑層11側的表面具有段差，具體而言，具有由印刷層3的有無產生之段差。 As shown in Fig. 2, the laminated body 2 of the present embodiment is bonded by the first hard plate 21, the second hard plate 22, and the first hard plate 21 and the second hard plate 22. The agent layer 11 is composed. Further, the laminate of this embodiment In the body 2, the first hard plate 21 has a step on the surface on the side of the adhesive layer 11, and specifically has a step caused by the presence or absence of the printed layer 3.

第1硬質板21及第2硬質板22只要係能夠接著黏著劑層11者，就沒有特別限定。並且，第1硬質板21及第2硬質板22可以係相同的材料，亦可以係不同的材料。 The first hard plate 21 and the second hard plate 22 are not particularly limited as long as they can adhere to the adhesive layer 11 . Further, the first hard plate 21 and the second hard plate 22 may be the same material or different materials.

作為第1硬質板21及第2硬質板22，例如除玻璃板、塑膠板、金屬板、半導體板等以外，還可以舉出該等的積層體、或顯示體模組、太陽能電池模組等板狀的硬質產品等。第1硬質板21及第2硬質板22中的至少一個包含玻璃板或塑膠板為較佳，包含塑膠板尤為佳。 Examples of the first hard plate 21 and the second hard plate 22 include, for example, a glass plate, a plastic plate, a metal plate, a semiconductor plate, and the like, and a laminate, a display module, a solar cell module, or the like. Plate-shaped hard products, etc. It is preferable that at least one of the first hard plate 21 and the second hard plate 22 includes a glass plate or a plastic plate, and a plastic plate is particularly preferable.

作為上述玻璃板並沒有特別限定，例如可以舉出化學強化玻璃、無鹼性玻璃、石英玻璃、鈉鈣玻璃、含鋇/鍶玻璃、鋁矽酸玻璃、鉛玻璃、硼矽酸玻璃、鋇硼矽酸玻璃等。玻璃板的厚度並沒有特別限定，但通常是0.1~5mm，0.2~2mm為較佳。 The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, bismuth/niobium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, and bismuth boron. Citrate glass, etc. The thickness of the glass plate is not particularly limited, but is usually 0.1 to 5 mm, preferably 0.2 to 2 mm.

作為上述塑膠板並沒有特別限定，例如可以舉出由聚甲基丙烯酸甲酯等構成之丙烯酸板、聚碳酸酯板等。塑膠板的厚度並沒有特別限定，但通常是0.2~5mm，0.4~3mm為較佳。 The plastic plate is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate or the like, a polycarbonate plate, and the like. The thickness of the plastic plate is not particularly limited, but is usually 0.2 to 5 mm, and 0.4 to 3 mm is preferable.

另外，在上述玻璃板或塑膠板的一面或兩面可以設有各種功能層(透明導電膜、金屬層、矽氧層、硬塗層、防眩層等)，亦可以形成有金屬配線，還可以積層有光學構件。本實施形態中之黏著劑層11不含羧酸，因此即使在被黏物上因酸而發生腐蝕等不良情況，亦能夠抑制該不良情況。 In addition, various functional layers (transparent conductive film, metal layer, silicon oxide layer, hard coat layer, anti-glare layer, etc.) may be provided on one or both sides of the glass plate or the plastic plate, and metal wiring may be formed. There are laminated optical members. Since the adhesive layer 11 in the present embodiment does not contain a carboxylic acid, such a problem can be suppressed even if the adhesive is corroded by an acid or the like.

作為上述光學構件，例如可以舉出偏光板(偏光膜)、偏光子、相位差板(相位差膜)、視野角補償膜、輝度提高膜、對比度提高膜、液晶聚合物薄膜、擴散膜、硬塗層薄膜、半透射反射膜等。 Examples of the optical member include a polarizing plate (polarizing film), a polarizer, a retardation film (retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast enhancement film, a liquid crystal polymer film, a diffusion film, and a hard film. Coating film, transflective film, and the like.

並且，作為上述顯示體模組，例如可以舉出液晶(LCD)模組、發光二極體(LED)模組、有機電致發光(有機EL)模組、電子紙等。另外，該等顯示體模組中通常積層有上述玻璃板、塑膠板、光學構件等。例如，LCD模組中積層有偏光板，該偏光板形成LCD模組的一表面。 Further, examples of the display body module include a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper. Further, in the display body modules, the glass plate, the plastic plate, the optical member, and the like are usually laminated. For example, a polarizing plate is laminated in the LCD module, and the polarizing plate forms a surface of the LCD module.

在本實施形態之積層體2中，第1硬質板21及第2硬質板22中的至少一者係具有塑膠板者為較佳。並且，本實施形態之積層體2中之第2硬質板22為顯示體模組或其一部份(例如，偏光板等光學構件)，第1硬質板21係保護板，尤其係由塑膠板構成之保護板為較佳。此時，印刷層3一般在第1硬質板21中之黏著劑層11側形成為邊框狀。 In the laminated body 2 of the present embodiment, it is preferable that at least one of the first hard plate 21 and the second hard plate 22 has a plastic plate. Further, the second hard plate 22 in the laminated body 2 of the present embodiment is a display body module or a part thereof (for example, an optical member such as a polarizing plate), and the first hard plate 21 is a protective plate, particularly a plastic plate. A protective plate is preferably formed. At this time, the printed layer 3 is generally formed in a frame shape on the side of the adhesive layer 11 in the first hard plate 21.

構成印刷層3之材料並沒有特別限定，可以使用印刷用的公知的材料。印刷層3的厚度亦即段差的高度為3~45μm為較佳，5~35μm更為佳，7~25μm尤為佳，7~15μm為進一步較佳。 The material constituting the printed layer 3 is not particularly limited, and a known material for printing can be used. The thickness of the printed layer 3, that is, the height of the step is preferably 3 to 45 μm, more preferably 5 to 35 μm, particularly preferably 7 to 25 μm, and further preferably 7 to 15 μm.

並且，印刷層3的厚度(段差的高度)為黏著劑層11的厚度的3~30%為較佳，3.2~20%尤為佳，3.5~15%為進一步較佳。藉此，黏著劑層11可靠地追隨由印刷層3產生之段差，在段差附近不易產生翹起和氣泡等。 Further, the thickness (the height of the step) of the printed layer 3 is preferably from 3 to 30% of the thickness of the adhesive layer 11, particularly preferably from 3.2 to 20%, and further preferably from 3.5 to 15%. Thereby, the adhesive layer 11 reliably follows the step generated by the printed layer 3, and it is less likely to cause lift, bubbles, and the like in the vicinity of the step.

為了製造上述積層體2，作為一例，首先，剝離黏 著片1的一個剝離片12a(或12b)，將黏著片1的露出之黏著劑層11和第1硬質板21(或第2硬質板22)貼合。接著，從黏著片1的黏著劑層11剝離另一個剝離片12b(或12a)，將黏著片1的露出之黏著劑層11和第2硬質板22(或第1硬質板21)貼合。 In order to manufacture the above-mentioned laminated body 2, as an example, first, peeling and sticking One of the release sheets 12a (or 12b) of the sheet 1 is bonded to the exposed adhesive layer 11 of the adhesive sheet 1 and the first hard sheet 21 (or the second hard sheet 22). Next, the other release sheet 12b (or 12a) is peeled off from the adhesive layer 11 of the adhesive sheet 1, and the exposed adhesive layer 11 of the adhesive sheet 1 and the second hard board 22 (or the first hard board 21) are bonded together.

在上述製程中將黏著劑層11和第1硬質板21貼合時，由於黏著劑層11的段差追隨性優異，因此在由印刷層3產生之段差與黏著劑層11之間不易形成空隙，黏著劑層11能夠填補該段差。 When the pressure-sensitive adhesive layer 11 and the first hard plate 21 are bonded together in the above-described process, since the adhesion layer 11 has excellent step followability, it is difficult to form a gap between the step formed by the printed layer 3 and the adhesive layer 11. The adhesive layer 11 is capable of filling the step.

以上的積層體2中，由於黏著劑層11的段差追隨性優異，因此在由印刷層3產生之段差與黏著劑層11之間不易形成空隙或氣泡。並且，該黏著劑層11即使在施加高溫高濕條件之情況下，亦可以防止在段差附近產生氣泡等，段差追隨性優異。並且，當第1硬質板21或第2硬質板22為塑膠板時，即使在因高溫高濕條件等而從該塑膠板產生漏氣之情況下，氣泡、翹起、剝落等膨脹的產生亦得到抑制，抗起泡性優異。另外，該黏著劑層11在施加高溫高濕條件之後，恢復為常溫時的白化得到抑制，耐濕熱白化性優異。另外，耐濕熱白化性的具體評價方法如後述。 In the laminated body 2 described above, since the adhesion layer 11 has excellent step followability, it is difficult to form voids or bubbles between the step formed by the printed layer 3 and the adhesive layer 11. Further, even when high-temperature and high-humidity conditions are applied, the pressure-sensitive adhesive layer 11 can prevent generation of air bubbles or the like in the vicinity of the step, and is excellent in step followability. Further, when the first hard plate 21 or the second hard plate 22 is a plastic plate, even if air leakage occurs from the plastic plate due to high temperature and high humidity conditions, the occurrence of expansion such as bubbles, lift, and peeling is also caused. It is suppressed and excellent in anti-foaming property. In addition, after the application of the high-temperature and high-humidity conditions, the adhesive layer 11 is suppressed from whitening when it returns to normal temperature, and is excellent in wet heat whitening resistance. Moreover, the specific evaluation method of the wet heat whitening resistance is mentioned later.

以上說明之實施形態係為了容易理解本發明而記載者，並非為限定本發明而記載。從而，上述實施形態中所公開之各要素旨包括屬於本發明的技術範圍之所有設計變更或相等物質。 The embodiments described above are described in order to facilitate the understanding of the present invention, and are not intended to limit the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design changes or equivalents falling within the technical scope of the invention.

例如，可以省略黏著片1中之剝離片12a、12b中 的任意一者。並且，第1硬質板21可以係具有印刷層3以外的段差者，亦可以不具有段差。另外，不僅是第1硬質板21，第2硬質板22亦可以係在黏著劑層11側具有段差者。 For example, the peeling sheets 12a, 12b in the adhesive sheet 1 can be omitted. Any one of them. Further, the first hard plate 21 may have a step other than the printed layer 3, or may have no step. Further, not only the first hard plate 21 but also the second hard plate 22 may have a step on the side of the adhesive layer 11.

【實施例】 [Examples]

以下，藉由實施例等進一步對本發明進行具體的說明，但本發明的範圍並不限定於該些實施例等。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited to the examples and the like.

〔實施例1〕 [Example 1]

1．(甲基)丙烯酸酯共聚物的製備 1. Preparation of (meth) acrylate copolymer

使丙烯酸2-乙基己酯60質量份、甲基丙烯酸甲酯20質量份以及丙烯酸2-羥基乙酯20質量份共聚合，從而製備出(甲基)丙烯酸酯共聚物(A)。以後述方法測定該(甲基)丙烯酸酯共聚物(A)的分子量之結果，重量平均分子量(Mw)為50萬。 60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate, and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized to prepare a (meth) acrylate copolymer (A). The molecular weight of the (meth) acrylate copolymer (A) was measured by the method described later, and the weight average molecular weight (Mw) was 500,000.

2．黏著性組成物的製備 2. Preparation of adhesive composition

將上述製程(1)中得到之(甲基)丙烯酸酯共聚物(A)100質量份(固體含量換算值；以下相同)、作為聚異氰酸酯化合物(B)之三羥甲基丙烷改性甲苯二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製，產品名“CORONATE L”)0.24質量份、作為螯合化合物(C)之三乙醯丙酮鋁(Soken Chemical & Engineering Co.,Ltd.製，商品名“M-5A”)0.05質量份、以及作為矽烷偶合劑之3-縮水甘油醚氧丙基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製，產品名“KBM-403”)0.2質量份進行混合並充份攪拌，並且用甲乙酮稀釋，藉此得到固體含量濃度為35質量%的黏著性組成物的塗佈溶液。 100 parts by mass of the (meth) acrylate copolymer (A) obtained in the above process (1) (converted solid content; the same applies hereinafter), and trimethylolpropane-modified toluene as the polyisocyanate compound (B) Isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "CORONATE L"), 0.24 parts by mass, as a chelating compound (C), aluminum acetoacetate (manufactured by Soken Chemical & Engineering Co., Ltd., trade name) "M-5A") 0.05 parts by mass, and 3-glycidyloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") as a decane coupling agent 0.2 mass The mixture was mixed and stirred thoroughly, and diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition having a solid content concentration of 35% by mass.

在此，將該黏著性組成物的配合示於表1。另外，表1所記載的略號等的詳細內容如下。 Here, the adhesion of the adhesive composition is shown in Table 1. In addition, the details of the outlines and the like described in Table 1 are as follows.

[(甲基)丙烯酸酯共聚物(A)] [(Meth)acrylate copolymer (A)]

2EHA：丙烯酸2MA：丙烯酸甲酯 2EHA: Acrylic 2MA: Methyl acrylate

MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate

HEA：丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate

BA：丙烯酸正丁酯 BA: n-butyl acrylate

[聚異氰酸酯化合物(B)] [Polyisocyanate compound (B)]

CORONATEL：三羥甲基丙烷改性甲苯二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製，產品名“CORONATE L”) CORONATEL: Trimethylolpropane modified toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "CORONATE L")

CORONATE HL：三羥甲基丙烷改性六亞甲基二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製，產品名“CORONATE HL”) CORONATE HL: Trimethylolpropane modified hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "CORONATE HL")

3．黏著片的製造 3. Adhesive sheet manufacturing

以乾燥後的厚度成為25μm之方式，用刮刀塗佈機，將所獲得之黏著性組合物的塗佈溶液塗佈於用矽酮系剝離劑來對聚對苯二甲酸乙二酯薄膜的單面進行剝離處理之重剝離型剝離片(Lintec Corporation製，產品名稱“PET752150”)的剝離處理面之後，於90℃下加熱處理1分鐘，從而形成塗佈層。同樣地，以乾燥後的厚度成為25μm之方式，用刮刀塗佈機，將所獲得之黏著性組合物的塗佈溶液，塗佈於用矽酮系剝離劑來對聚對苯二甲酸乙二酯薄膜的單面進行剝離處理之輕剝離型剝離片(Lintec Corporation製，產品名稱“PET382120”)的剝 離處理面之後，於90℃下加熱處理1分鐘，從而形成塗佈層。 The coating solution of the obtained adhesive composition was applied to the polyethylene terephthalate film with an anthrone-based release agent by a knife coater so that the thickness after drying became 25 μm. The peeling-treated surface of the heavy release type release sheet (product name "PET752150" manufactured by Lintec Corporation) which was subjected to the release treatment was heat-treated at 90 ° C for 1 minute to form a coating layer. Similarly, the coating solution of the obtained adhesive composition was applied to the polyethylene terephthalate using an anthrone-based release agent by a knife coater so that the thickness after drying became 25 μm. Peeling of a light release type release sheet (manufactured by Lintec Corporation, product name "PET382120") on which one side of the ester film is subjected to a release treatment After leaving the treated surface, heat treatment was carried out at 90 ° C for 1 minute to form a coating layer.

其次，將上述所獲得之帶塗佈層的重剝離型剝離片和上述所獲得之帶塗佈層的輕剝離型剝離片，以兩個塗佈層彼此接觸之方式進行貼合，並於23℃、50%RH的條件下養護7天，籍此，製作出由重剝離型剝離片/黏著劑層(厚度：50μm)/輕剝離型剝離片的構成而構成之黏著片。另外，黏著劑層的厚度為以JIS K7130為依據並使用恒壓厚度測定器(TECLOCK Company Inc.製，產品名稱“PG-02”)測定之值。 Next, the heavy-peelable release sheet with the coating layer obtained above and the light-peelable release sheet of the obtained coating layer were bonded together so that the two coating layers contact each other, and 23 After curing for 7 days under the conditions of 50% RH, an adhesive sheet composed of a heavy release type release sheet/adhesive layer (thickness: 50 μm)/light release type release sheet was prepared. In addition, the thickness of the adhesive layer is a value measured by a constant pressure thickness measuring instrument (product name "PG-02" by TECLOCK Company Inc.) based on JIS K7130.

〔實施例2~12、比較例1~10〕 [Examples 2 to 12, Comparative Examples 1 to 10]

如表1所示那樣改變構成(甲基)丙烯酸酯共聚物(A)之各單體的種類及比例、聚異氰酸酯化合物(B)的種類及配合量、以及螯合化合物(C)的種類及配合量，除此以外，與實施例1同樣地製造黏著片。另外，實施例10及11中使用之螯合化合物(C)為三乙醯丙酮鋯(Matsumoto Fine Chemical Co.Ltd.製，商品名“Orgatics ZC-150”)。 The type and ratio of each monomer constituting the (meth) acrylate copolymer (A), the type and amount of the polyisocyanate compound (B), and the type of the chelating compound (C) and the type of the chelating compound (C) are changed as shown in Table 1. An adhesive sheet was produced in the same manner as in Example 1 except for the blending amount. Further, the chelating compound (C) used in Examples 10 and 11 was zirconium triacetate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "Orgatics ZC-150").

在此，前述重量平均分子量(Mw)為利用凝膠滲透色譜(GPC)於以下條件測定(GPC測定)之聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions (GPC measurement).

<測定條件> <Measurement conditions>

‧GPC測定裝置：Tosoh Corporation製，HLC-8020 ‧GPC measuring device: manufactured by Tosoh Corporation, HLC-8020

‧GPC柱(按以下順序通過)：Tosoh Corporation製 ‧GPC column (passed in the following order): manufactured by Tosoh Corporation

TSK guard column HXL-H TSK guard column HXL-H

TSK gel GMHXL(×2) TSK gel GMHXL (×2)

TSK gel G2000HXL TSK gel G2000HXL

‧測定溶劑：四氫呋喃 ‧ Determination of solvent: tetrahydrofuran

‧測定溫度：40℃ ‧Measurement temperature: 40 ° C

〔試驗例1〕(黏著力的測定) [Test Example 1] (Measurement of adhesion)

從實施例及比較例中所得到之黏著片剝下易剝離型剝離片，將露出之黏著劑層貼合於具有易接著層之聚對苯二甲酸乙二酯薄膜(TOYOBO Co.,Ltd.製，PET A4300，厚度：100μm)的易接著層。將該積層體裁剪為寬度25mm、長度100mm，將此作為樣品。從該樣品剝下重剝離型剝離片，將露出之黏著劑層貼附於一面設有由錫摻雜氧化銦(ITO)構成之透明導電膜之聚對苯二甲酸乙二酯薄膜(OIKE & Co.,Ltd.製，ITO薄膜，厚度：125μm)的透明導電膜。 The easily peelable release sheet was peeled off from the adhesive sheets obtained in the examples and the comparative examples, and the exposed adhesive layer was attached to a polyethylene terephthalate film having an easy adhesion layer (TOYOBO Co., Ltd. Easy-to-adhere layer of PET A4300, thickness: 100 μm). This laminated body was cut into a width of 25 mm and a length of 100 mm, and this was taken as a sample. The heavy release type release sheet was peeled off from the sample, and the exposed adhesive layer was attached to a polyethylene terephthalate film provided with a transparent conductive film made of tin-doped indium oxide (ITO) (OIKE & A transparent conductive film made of Co., Ltd., ITO film, thickness: 125 μm).

其後，於常壓、23℃、50%RH的條件下放置24小時之後，利用拉伸試驗機(Orientec Company Inc.製，Tensilon)，以JIS Z0237：2009為基準，於剝離速度300mm/min、剝離角度180°的條件下測定出黏著力(N/25mm)。結果於表2示出。 Thereafter, it was allowed to stand under normal pressure, 23 ° C, and 50% RH for 24 hours, and then subjected to a tensile tester (Tensilon, manufactured by Orientec Company Inc.) to JIS Z0237:2009 at a peeling speed of 300 mm/min. The adhesion (N/25 mm) was measured under the conditions of a peeling angle of 180°. The results are shown in Table 2.

〔試驗例2〕(凝膠率的測定) [Test Example 2] (Measurement of gel fraction)

將實施例及比較例中所得到之黏著片裁剪為80mm×80mm的尺寸，將其黏著劑層包在聚酯製網(網眼尺寸200)中，藉由精密天平秤取其質量，減去上述網單獨的質量，藉此計算黏著劑本身的質量。將此時的質量設為M1。 The adhesive sheets obtained in the examples and the comparative examples were cut into a size of 80 mm × 80 mm, and the adhesive layer was wrapped in a polyester mesh (mesh size 200), and the mass was weighed by a precision balance, minus The quality of the above-mentioned net alone is used to calculate the quality of the adhesive itself. Set the quality at this time to M1.

接著，在室溫下(23℃)，在醋酸乙酯中浸漬24小時包在上述聚酯製網中之黏著劑。其後，取出黏著劑，在溫度23℃、相對濕度50%的環境下風乾24小時，另外，在80℃ 的烘箱中乾燥12小時。乾燥後，藉由精密天平秤取其質量，減去上述網單獨的質量，藉此計算黏著劑本身的質量。將此時的質量設為M2。以(M2/M1)×100表示凝膠率(%)。將結果示於表2。 Next, the adhesive contained in the polyester mesh was immersed in ethyl acetate for 24 hours at room temperature (23 ° C). Thereafter, the adhesive was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50%, and further, at 80 ° C. Dry in an oven for 12 hours. After drying, the quality of the adhesive itself is calculated by weighing the mass by a precision balance and subtracting the individual mass of the above net. Set the quality at this time to M2. The gel fraction (%) is represented by (M2/M1) × 100. The results are shown in Table 2.

〔試驗例3〕(段差追隨性評價) [Test Example 3] (segment difference follow-up evaluation)

(a)評價用樣品的製作 (a) Production of samples for evaluation

在玻璃板(NSG Precision Co,Ltd.製，產品名“Corning glass Eagle XG”，縱90mm×橫50mm×厚度0.5mm)的表面上，以塗佈厚度成為5μm、10μm及15μm中的任意一個之方式，以邊框狀(外形：縱90mm×橫50mm，寬度5mm)網版印刷紫外線硬化型油墨(Teikoku Printing Inks Mfg.Co.,Ltd.製，產品名“POS-911墨”)。接著，照射紫外線(80W/cm2，兩個金屬鹵化物燈，燈高度15cm，帶速10~15m/分鐘)，使印刷之上述紫外線硬化型油墨硬化，製作出具有由印刷產生之段差(段差的高度：5μm、10μm及15μm中的任意一個)之帶段差玻璃板。 In the glass plate (manufactured by NSG Precision Co., Ltd., product name "Corning glass Eagle XG", vertical 90 mm × width 50 mm × thickness 0.5 mm), the coating thickness was set to any of 5 μm, 10 μm, and 15 μm. In the manner of a frame shape (outer shape: vertical 90 mm × width 50 mm, width 5 mm), a UV-curable ink (manufactured by Teikoku Printing Inks Mfg. Co., Ltd., product name "POS-911 ink") was screen-printed. Next, ultraviolet rays (80 W/cm 2 , two metal halide lamps, a lamp height of 15 cm, and a belt speed of 10 to 15 m/min) were irradiated to harden the printed ultraviolet curable ink to produce a step (printing difference) caused by printing. The height of the strip: any one of 5 μm, 10 μm, and 15 μm).

從實施例及比較例中所得到之黏著片剝下易剝離型剝離片，將露出之黏著劑層貼合於具有易接著層之聚對苯二甲酸乙二酯薄膜(TOYOBO Co.,Ltd.製，PET A4300，厚度：100μm)的易接著層。接著，剝下重剝離型剝離片，使黏著劑層露出。並且，使用積層機(FUJIPLA Inc.製，產品名“LPD3214”)，以黏著劑層覆蓋邊框狀的整個印刷面之方式將上述積層體積層於各帶段差玻璃板上，將此作為評價用樣品。 The easily peelable release sheet was peeled off from the adhesive sheets obtained in the examples and the comparative examples, and the exposed adhesive layer was attached to a polyethylene terephthalate film having an easy adhesion layer (TOYOBO Co., Ltd. Easy-to-adhere layer of PET A4300, thickness: 100 μm). Next, the heavy release type release sheet was peeled off to expose the adhesive layer. Further, using a laminator (product name "LPD3214" manufactured by FUJIPLA Inc.), the laminated volume layer was applied to each of the stepped glass plates so that the entire printed surface of the frame was covered with the adhesive layer, and this was used as a sample for evaluation. .

(b)段差追隨性(初期)的評價 (b) Evaluation of segment followability (initial)

在50℃、0.5MPa的條件下對所得到之評價用樣品進行30 分鐘高壓滅菌鍋處理之後，目視確認在黏著劑層(尤其在由印刷層產生之段差附近)是否存在氣泡。其結果，將完全沒有氣泡或空隙者評價為◎，將幾乎沒有氣泡或空隙者評價為○，存在氣泡或空隙者評價為×(初期段差追隨性的評價)。將結果示於表2。 The obtained evaluation sample was subjected to 30 at 50 ° C and 0.5 MPa. After the minute autoclave treatment, it was visually confirmed whether or not bubbles were present in the adhesive layer (especially in the vicinity of the step generated by the printed layer). As a result, those who were completely free of air bubbles or voids were evaluated as ◎, those having almost no bubbles or voids were evaluated as ○, and those having bubbles or voids were evaluated as × (evaluation of initial step difference followability). The results are shown in Table 2.

(c)段差追隨性(耐久後)的評價 (c) Evaluation of paragraph followability (after endurance)

接著，將上述高壓滅菌鍋處理後在常壓、23℃、50%RH下放置24小時之後的評價用樣品，進一步在85℃、85%RH的濕熱條件下保管72小時。其後，目視確認在黏著劑層(尤其在由印刷層產生之段差附近)是否存在氣泡、翹起或剝落。其結果，將完全沒有氣泡、翹起及剝落者評價為◎，將僅產生直徑為0.2mm以下的氣泡者評價為￮，將產生直徑超過0.2mm的氣泡、翹起或剝落者評價為×(耐久後的段差追隨性的評價)。將結果示於表2。 Next, the sample for evaluation after being treated in the autoclave at normal pressure, 23° C., and 50% RH for 24 hours was further stored under humid heat conditions of 85° C. and 85% RH for 72 hours. Thereafter, it was visually confirmed whether or not air bubbles, lift or peeling were present in the adhesive layer (especially in the vicinity of the step generated by the printed layer). As a result, those who did not have any bubbles, lifted, and peeled off were evaluated as ◎, and those who produced only bubbles having a diameter of 0.2 mm or less were evaluated as ○, and those who produced bubbles having a diameter of more than 0.2 mm, which were lifted or peeled off, were evaluated as × ( Evaluation of the step followability after endurance). The results are shown in Table 2.

〔試驗例4〕(抗起泡性評價) [Test Example 4] (anti-foaming evaluation)

用一面設有由錫摻雜氧化銦(ITO)構成之透明導電膜之聚對苯二甲酸乙二酯薄膜(OIKE & Co.,Ltd.製，ITO薄膜，厚度：125μm)的透明導電膜和聚碳酸酯板(Mitsubishi Gas Chemical Company製，iupilon sheet MR58，厚度：1mm)或由聚甲基丙烯酸甲酯構成之丙烯酸板(Mitsubishi Gas Chemical Company製，iupilon sheet MR200，厚度：1mm)夾住實施例及比較例中所得到之黏著片的黏著劑層，從而得到積層體。 a transparent conductive film of a polyethylene terephthalate film (ITO film, thickness: 125 μm, manufactured by Oike & Co., Ltd.) provided with a transparent conductive film made of tin-doped indium oxide (ITO) A polycarbonate plate (manupilon sheet MR58, thickness: 1 mm, manufactured by Mitsubishi Gas Chemical Company) or an acrylic plate (made by Mitsubishi Gas Chemical Company, iupilon sheet MR200, thickness: 1 mm) composed of polymethyl methacrylate was sandwiched with the examples. And the adhesive layer of the adhesive sheet obtained in the comparative example, and the laminated body was obtained.

在50℃、0.5MPa的條件下，對所得到之積層體進 行30分鐘高壓滅菌鍋處理之後，在常壓、23℃、50%RH下放置15小時。接著，在85℃、85%RH的耐久條件下保管72小時。其後，目視確認在黏著劑層是否存在氣泡、翹起或剝落。其結果，將完全沒有氣泡、翹起及剝落者評價為◎，將僅產生直徑為0.1mm以下的氣泡者評價為￮，將產生直徑超過0.1mm的氣泡且其最大氣泡的直徑為0.2mm以下者評價為△，將產生直徑超過0.2mm的氣泡、翹起或剝落者評價為×(抗起泡性的評價)。將結果示於表2。 At 50 ° C, 0.5 MPa, the obtained laminated body After the autoclave treatment for 30 minutes, it was allowed to stand at normal pressure, 23 ° C, 50% RH for 15 hours. Next, it was stored under the endurance conditions of 85 ° C and 85% RH for 72 hours. Thereafter, it was visually confirmed whether or not air bubbles, lift or peeling occurred in the adhesive layer. As a result, those who did not have any bubbles, lifted, and peeled out were evaluated as ◎, and those who produced only bubbles having a diameter of 0.1 mm or less were evaluated as ○, and bubbles having a diameter of more than 0.1 mm were produced, and the diameter of the largest bubbles was 0.2 mm or less. The evaluation was Δ, and it was evaluated that bubbles (lifting or peeling) having a diameter of more than 0.2 mm were evaluated as × (evaluation of anti-foaming property). The results are shown in Table 2.

〔試驗例5〕(耐濕熱白化性評價) [Test Example 5] (Evaluation of moisture and heat whitening resistance)

用兩片厚度1.1mm的無鹼性玻璃夾住實施例或比較例中所得到之黏著片的黏著劑層，將該積層體作為樣品。在85℃、85%RH的條件下保管所得到之樣品72小時。其後，恢復23℃、50%RH(常溫常濕)的氣氛，目視確認白化的有無，藉由以下基準對耐濕熱白化性進行評價，並且測定黏著劑層的霧度值。霧度值係恢復上述常溫常濕的氣氛之後在30分鐘以內，按照JIS K7136：2000，使用霧度測定儀(NIPPON DENSHOKU INDUSTRIES Co.,Ltd.製，產品名“NDH2000”)對樣品進行測定。將結果示於表2。 The adhesive layer of the adhesive sheet obtained in the example or the comparative example was sandwiched between two sheets of non-alkaline glass having a thickness of 1.1 mm, and the laminate was used as a sample. The obtained sample was stored under the conditions of 85 ° C and 85% RH for 72 hours. Thereafter, the atmosphere at 23 ° C and 50% RH (normal temperature and normal humidity) was recovered, and the presence or absence of whitening was visually confirmed. The wet heat whitening resistance was evaluated by the following criteria, and the haze value of the adhesive layer was measured. The haze value was measured by using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd., product name "NDH2000") in accordance with JIS K7136:2000 within 30 minutes after restoring the atmosphere of the above-mentioned normal temperature and normal humidity. The results are shown in Table 2.

◎：剛恢復常溫常濕的氣氛之後，完全未發生白化。 ◎: After the atmosphere of normal temperature and humidity was just returned, whitening did not occur at all.

○：一部份發生白化，但恢復常溫常濕的氣氛之後在2小時以內未發生白化。 ○: Part of the whitening occurred, but no whitening occurred within 2 hours after the atmosphere of normal temperature and humidity was restored.

×：整體發生白化。或者一部份發生白化之後，即使在常溫常濕下保管亦無法恢復原狀態。 ×: The overall whitening occurred. Or after a part of whitening occurs, it cannot be restored to its original state even if it is stored under normal temperature and humidity.

【表2】 【Table 2】

由表2可知，實施例中所得到之黏著片的段差追隨性、抗起泡性及耐濕熱白化性均優異。 As is clear from Table 2, the adhesive sheets obtained in the examples were excellent in step followability, anti-foaming property, and moist heat whitening resistance.

【產業上的可利用性】 [Industrial availability]

本發明的黏著片例如可以適合使用於觸摸面板中之顯示體模組與具有段差之保護板尤其是與塑膠板的貼合。 The adhesive sheet of the present invention can be suitably used, for example, for the display body module in the touch panel and the protective sheet having a step, especially the plastic sheet.

1‧‧‧黏著片 1‧‧‧Adhesive film

11‧‧‧黏著劑層 11‧‧‧Adhesive layer

12a、12b‧‧‧剝離片 12a, 12b‧‧‧ peeling film

Claims (11)

一種黏著片，具有使黏著性組成物交聯而成之厚度10~400μm的黏著劑層，前述黏著性組成物中含有：(甲基)丙烯酸酯共聚物(A)，其重量平均分子量為20萬~90萬，作為構成聚合物之單體單位，含有15~30質量%的具有羥基之單體，且不含有具有羧基之單體；聚異氰酸酯化合物(B)；及螯合化合物(C)。 An adhesive sheet comprising an adhesive layer having a thickness of 10 to 400 μm which is obtained by crosslinking an adhesive composition, wherein the adhesive composition comprises: a (meth) acrylate copolymer (A) having a weight average molecular weight of 20 10,000 to 900,000, as a monomer unit constituting the polymer, containing 15 to 30% by mass of a monomer having a hydroxyl group, and containing no monomer having a carboxyl group; a polyisocyanate compound (B); and a chelate compound (C) . 如申請專利範圍第1項所述之黏著片，其中，前述黏著性組成物中之前述聚異氰酸酯化合物(B)的含量相對於前述(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份。 The adhesive sheet according to the above aspect of the invention, wherein the content of the polyisocyanate compound (B) in the adhesive composition is 0.001 based on 100 parts by mass of the (meth) acrylate copolymer (A). ~5 parts by mass. 如申請專利範圍第1項所述之黏著片，其中，前述黏著性組成物中之前述螯合化合物(C)的含量相對於前述(甲基)丙烯酸酯共聚物(A)100質量份為0.001~5質量份。 The adhesive sheet according to the above aspect of the invention, wherein the content of the chelate compound (C) in the adhesive composition is 0.001 based on 100 parts by mass of the (meth)acrylate copolymer (A). ~5 parts by mass. 如申請專利範圍第1項所述之黏著片，其中，前述螯合化合物(C)為鋁螯合化合物。 The adhesive sheet according to claim 1, wherein the chelate compound (C) is an aluminum chelate compound. 如申請專利範圍第1項所述之黏著片，其中，前述螯合化合物(C)為乙醯丙酮錯合物。 The adhesive sheet according to claim 1, wherein the chelate compound (C) is an acetamidineacetate complex. 如申請專利範圍第1項所述之黏著片，其中，前述黏著片包括兩片剝離片，前述黏著劑層以與前述兩片剝離片的剝離面接觸之方式被前述剝離片夾持。 The adhesive sheet according to claim 1, wherein the adhesive sheet comprises two release sheets, and the adhesive layer is sandwiched by the release sheet so as to be in contact with the release surface of the two release sheets. 一種積層體，包括：兩片硬質板；及黏著劑層，其被前述兩片硬質板夾持，其特徵為：前述黏著劑層為申請專利範圍第1至6項中任一項所述之黏著片的黏著劑層。 A laminate comprising: two sheets of hard sheets; and an adhesive layer sandwiched by the two sheets of hard sheets, wherein the adhesive layer is any one of claims 1 to 6. Adhesive layer of adhesive sheet. 如申請專利範圍第7項所述之積層體，其中，前述硬質板中的至少一個在前述黏著劑層側的表面具有段差。 The laminate according to claim 7, wherein at least one of the hard plates has a step on a surface of the adhesive layer side. 如申請專利範圍第8項所述之積層體，其中，前述段差為由印刷層的有無產生之段差。 The laminate according to claim 8, wherein the step is a step caused by the presence or absence of the printed layer. 如申請專利範圍第7項所述之積層體，其中，前述硬質板中的至少一個包含塑膠板。 The laminate according to claim 7, wherein at least one of the hard plates comprises a plastic plate. 如申請專利範圍第7項所述之積層體，其中，前述兩片硬質板中的一個為顯示體模組或其一部份，前述兩片硬質板中的另一個為在前述黏著劑層側的表面具有邊框狀的段差之保護板。 The laminated body according to claim 7, wherein one of the two rigid plates is a display body module or a part thereof, and the other of the two hard plates is on the side of the adhesive layer The surface has a protective plate with a frame-like step.
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