TWI753902B - Adhesive composition, adhesive, adhesive sheet and display - Google Patents

Adhesive composition, adhesive, adhesive sheet and display Download PDF

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TWI753902B
TWI753902B TW106113727A TW106113727A TWI753902B TW I753902 B TWI753902 B TW I753902B TW 106113727 A TW106113727 A TW 106113727A TW 106113727 A TW106113727 A TW 106113727A TW I753902 B TWI753902 B TW I753902B
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adhesive
adhesive layer
component
polymerizable component
meth
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TW201829682A (en
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吉延毅朗
荒井隆行
大類知生
所司悟
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • 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
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/005—Presence of polyester in the release coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

本發明的課題係在於提供段差追隨性及耐起泡性的雙方優良的黏接著劑組合物、黏接著劑、黏接著板片及顯示體、以及段差追隨性及耐起泡性的雙方優良的黏接著劑、黏接著板片及顯示體之製造方法。 An object of the present invention is to provide an adhesive composition, an adhesive, an adhesive sheet and a display body excellent in both step followability and foam resistance, and an adhesive composition excellent in both step followability and foam resistance An adhesive, an adhesive sheet and a manufacturing method for a display body.

本發明的解決手段係一種黏接著劑組合物，含有：自由基聚合性成分(A)；離子聚合性成分(B)；可藉由可見光活化的可見光活化自由基聚合起始劑(C)；可藉由紫外線活化的紫外線活化離子聚合起始劑(D)。 The solution of the present invention is an adhesive composition comprising: a radical polymerizable component (A); an ion polymerizable component (B); a visible light-activated radical polymerization initiator (C) that can be activated by visible light; The ionic polymerization initiator (D) can be activated by ultraviolet ray activated ultraviolet rays.

Description

黏接著劑組合物、黏接著劑、黏接著板片以及顯示體 Adhesive composition, adhesive, adhesive sheet and display

本發明係關於適合用於貼合顯示體構成構件的黏接著劑組合物、黏接著劑、黏接著板片及使用該等所製造的顯示體，以及關於黏接著劑、黏接著板片及顯示體之製造方法。 The present invention relates to an adhesive composition, an adhesive, an adhesive sheet, and a display manufactured using the same suitable for bonding a component of a display body, as well as an adhesive, an adhesive sheet, and a display body manufacturing method.

近幾年，智慧型手機、平板終端機等的各種行動電子機器，具備使用液晶元件、發光二極體(LED元件)，有機電致發光(有機EL)元件等的顯示體模組的顯示器，該顯示器成為觸控面板的情形逐漸變多。 In recent years, various mobile electronic devices such as smartphones and tablet terminals are equipped with displays using display modules such as liquid crystal elements, light emitting diodes (LED elements), and organic electroluminescence (organic EL) elements. There are more and more cases where the display becomes a touch panel.

在如上所述的顯示器，通常，在顯示體模組的表面側，設有保護面板。伴隨著電子機器的薄型化‧輕量化，上述保護面板，由先前的玻璃板，逐漸變更為丙烯酸板或聚碳酸酯板等的塑膠板。 In the display as described above, usually, a protective panel is provided on the surface side of the display module. With the reduction in thickness and weight of electronic equipment, the above-mentioned protective panels have been gradually changed from glass plates to plastic plates such as acrylic plates and polycarbonate plates.

在此，在保護面板與顯示體模組之間，設有即使因外力使保護面板變形時，也不會使變形的保護面板撞到顯示體模組的空隙。 Here, between the protection panel and the display module, even if the protection panel is deformed by an external force, a gap is provided so that the deformed protection panel will not collide with the display module.

但是，如上所述的空隙，亦即，空氣層的存在，則起因於保護面板與空氣層的折射率差異，及空氣層與顯示體模組的折射率差異的光反射損失大，而有降低顯示器的畫質的問題。 However, the presence of the above-mentioned voids, that is, the presence of the air layer, reduces the light reflection loss due to the difference in refractive index between the protective panel and the air layer, and the difference in refractive index between the air layer and the display module. The problem with the picture quality of the display.

因此，有藉由將保護面板與顯示模組之間的空隙以黏著劑層填埋，以提升顯示器的畫質的提案。但是，在保護面板的顯示體模組側，存在畫框狀的印刷層的段差。若黏著劑層無法追隨該段差，則黏著劑層在段差附近浮起，因此而發生光反射損失。因此，在上述黏著劑層，要求段差追隨性。 Therefore, there is a proposal to improve the image quality of the display by filling the gap between the protective panel and the display module with an adhesive layer. However, on the display module side of the protective panel, there is a level difference of the picture frame-shaped printed layer. If the adhesive layer cannot follow the step, the adhesive layer floats in the vicinity of the step, and thus a light reflection loss occurs. Therefore, in the above-mentioned adhesive layer, step followability is required.

為解決上述課題，專利文獻1揭示一種黏著劑層，其係作為填埋保護面板與顯示體模組之間的空隙的黏接著層，在25℃、1Hz的剪切儲存彈性模數(G')為1.0×105Pa以下，且凝膠分率為40%以上。 In order to solve the above-mentioned problems, Patent Document 1 discloses an adhesive layer, which serves as an adhesive layer for filling the gap between the protective panel and the display module, and has a shear storage elastic modulus (G ′ at 25° C. and 1 Hz). ) is 1.0×10 5 Pa or less, and the gel fraction is 40% or more.

專利文獻1所揭示的發明，藉由使黏著劑層在常溫時的儲存彈性模數(G')低，以提升段差追隨性。但是，使常溫時的儲存彈性模數(G')如上所述的低，則在高溫時的儲存彈性模數(G')會降低到必要以上，在耐久條件下會發生問題。例如，施以高溫高濕條件時，有在段差附近發生氣泡，或由保護面板的塑膠板發生脫氣而發生氣泡、浮起、剝落等的起泡。另一方面，為提升耐起泡性使黏著劑層變硬，則會降低段差追隨性。 The invention disclosed in Patent Document 1 improves the step followability by making the storage elastic modulus (G ' ) of the adhesive layer at room temperature low. However, if the storage elastic modulus (G ′ ) at normal temperature is made as low as described above, the storage elastic modulus (G ′ ) at high temperature is reduced more than necessary, and a problem occurs under durable conditions. For example, when high temperature and high humidity conditions are applied, air bubbles may be generated near the level difference, or foaming such as air bubbles, floating, peeling, etc. may occur due to degassing of the plastic plate of the protective panel. On the other hand, if the adhesive layer is hardened in order to improve the foaming resistance, the step followability is lowered.

此外，專利文獻2，提案將自由基聚合性組合物和陽離子聚合性組合物混合，藉由紫外線(UV)控制黏著劑的硬化狀態，作為提升段差追隨性的黏著薄膜。具體而言，使用照度1~10mW/cm2的UV燈，藉由自由基聚合性組合物的1次架橋反應維持半硬化狀態，在使用時，則使用照度50~150mW/cm2的UV燈進行藉由陽離子聚合性組合物的2次架橋反應的完全硬化反應。 In addition, Patent Document 2 proposes an adhesive film that improves step followability by mixing a radically polymerizable composition and a cationically polymerizable composition, and controlling the curing state of the adhesive by ultraviolet (UV). Specifically, a UV lamp with an illuminance of 1 to 10 mW/cm 2 is used, and the semi-hardened state is maintained by the primary bridging reaction of the radically polymerizable composition. When in use, a UV lamp with an illuminance of 50 to 150 mW/cm 2 is used. A complete hardening reaction by the secondary bridging reaction of the cationically polymerizable composition proceeds.

[先前技術文獻] [Prior Art 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 No. 2010-97070

[專利文獻2]日本特表2015-515527號公報 [Patent Document 2] Japanese Patent Publication No. 2015-515527

但是，專利文獻2所述的發明，由於1次架橋時的UV照度弱而生產性低，再者不只是自由基聚合性化合物，一部分的陽離子聚合性化合物亦在1次架橋時進行了反應，而有2次架橋無法充分進行之虞。如此，則無法得到充分的耐起泡性。 However, the invention described in Patent Document 2 has low productivity due to weak UV illuminance at the time of primary bridging, and not only the radical polymerizable compound but also some cationically polymerizable compounds react during the primary bridging, However, there is a possibility that the 2nd bridging will not be fully carried out. In this way, sufficient foaming resistance cannot be obtained.

本發明係有鑑於如此的實情所完成，以提供段差追隨性及耐起泡性的雙方優良的黏接著劑組合物、黏接著劑、黏接著板片及顯示體、以及段差追隨性及耐起泡性的雙方優良的黏接著劑、黏接著板片及顯示體之製造方法為目標。 The present invention has been made in view of such a situation, and is intended to provide an adhesive composition, an adhesive, an adhesive sheet and a display body excellent in both step followability and foam resistance, as well as step followability and foam resistance. It is aimed at the production method of an adhesive with excellent foaming properties, an adhesive sheet and a display body.

為達成上述目的，第1，本發明提供一種黏接著劑組合物，其特徵在於，含有：自由基聚合性成分(A)；離子聚合性成分(B)；可藉由可見光活化的可見光活化自由基聚合起始劑(C)；可藉由紫外線活化的紫外線活化離子聚合起始劑(D)(發明1)。 In order to achieve the above objects, firstly, the present invention provides an adhesive composition, characterized by comprising: a radically polymerizable component (A); an ionically polymerizable component (B); Base polymerization initiator (C); UV-activatable ionic polymerization initiator (D) which can be activated by UV (Invention 1).

對關於上述發明(發明1)的黏接著劑組合物的塗膜照射可見光，則可活化可見光活化自由基聚合起始劑(C)產生自由基，而形成自由基聚合性成分(A)的聚合物。此時，離子聚合性成分(B)並不會聚合，故可得半硬化狀態的黏接著劑層。該半硬化狀態的黏接著劑層，初期的段差追隨性優良。此外，經由上述黏接著劑層，將一顯示體構成構件與其他顯示體構成構件貼合後，照射紫外線，則可活化紫外線活化離子聚合起始劑(D)產生離子，形成離子聚合性成分(B)的聚合物而使黏接著劑層硬化，成為硬化後黏接著劑層。該硬化後黏接著劑層在高溫高濕條件下的段差追隨性及耐起泡性優良。 When the coating film of the adhesive composition of the invention (Invention 1) is irradiated with visible light, the visible light-activated radical polymerization initiator (C) can be activated to generate radicals, and the radical polymerizable component (A) can be polymerized thing. At this time, since the ionically polymerizable component (B) does not polymerize, a semi-hardened adhesive layer can be obtained. The adhesive layer in the semi-hardened state is excellent in the initial step followability. In addition, after bonding one display component member and another display component component via the above-mentioned adhesive layer, and then irradiating ultraviolet rays, the ultraviolet activated ion polymerization initiator (D) can be activated to generate ions, and the ion polymerizable components (D) can be formed. The polymer of B) hardens the adhesive layer and becomes the adhesive layer after hardening. The cured adhesive layer is excellent in step followability and foaming resistance under high temperature and high humidity conditions.

在上述發明(發明1)，前述自由基聚合性成分(A)，包含在分子中具有(甲基)丙烯醯基的含(甲基)丙烯醯基單體及分子中具有乙烯基的含乙烯基單體的至少1種為佳(發明2)。 In the above invention (Invention 1), the radically polymerizable component (A) includes a (meth)acryloyl group-containing monomer having a (meth)acryloyl group in the molecule and a vinyl group-containing monomer having a vinyl group in the molecule. At least one of the base monomers is preferred (Invention 2).

在上述發明(發明1、2)，前述自由基聚合性成分(A)，包含具有自由基聚合性基的胺甲酸乙酯寡聚物為佳(發明3)。 In the above inventions (Inventions 1 and 2), the radically polymerizable component (A) preferably contains a urethane oligomer having a radically polymerizable group (Invention 3).

在上述發明(發明1~3)，前述離子聚合性成分(B)，含有具有環氧基或縮水甘油醚基的化合物為佳(發明4)。 In the above inventions (Inventions 1 to 3), the ionically polymerizable component (B) preferably contains a compound having an epoxy group or a glycidyl ether group (Invention 4).

在上述發明(發明1~4)，前述黏接著劑組合物，以無溶劑型黏接著劑組合物為佳(發明5)。 In the above inventions (Inventions 1 to 4), the adhesive composition is preferably a solvent-free adhesive composition (Invention 5).

第2，本發明提供一種黏接著劑之製造方法，其特徵在於，藉由對前述黏接著劑組合物(發明1~5)照射可見光，使前述自由基聚合性成分(A)聚合得到黏接著劑(發明6)。 Second, the present invention provides a method for producing an adhesive, characterized in that by irradiating the adhesive composition (Inventions 1 to 5) with visible light, the radically polymerizable component (A) is polymerized to obtain an adhesive. agent (Invention 6).

第3，本發明提供一種黏接著劑，其特徵在於，含有：來自自由基聚合性成分(A)的聚合物；離子聚合性成分(B)；及可藉由紫外線活化的紫外線活化離子聚合起始劑(D)(發 明7)。 Third, the present invention provides an adhesive comprising: a polymer derived from a radically polymerizable component (A); an ionically polymerizable component (B); Starter (D) (fat Ming 7).

第4，本發明提供一種黏接著板片，其具有由前述黏接著劑(發明7)形成的黏接著劑層(發明8)。 Fourth, the present invention provides an adhesive sheet having an adhesive layer (Invention 8) formed of the adhesive (Invention 7).

在上述發明(發明8)，前述黏接著板片，具備2片剝離板片，前述黏接著劑層，以接於上述2片剝離板片的剝離面的方式被前述剝離板片夾持(發明9)。 In the above invention (Invention 8), the adhesive sheet includes two release sheets, and the adhesive layer is sandwiched between the release sheets so as to be in contact with the release surfaces of the two release sheets (Invention 8). 9).

第5，本發明提供一種黏接著板片之製造方法，其係具有黏接著劑層的黏接著板片之製造方法，其特徵在於，將前述黏接著劑組合物(發明1~5)塗層，藉由對前述黏接著劑組合物的塗膜照射可見光，使前述自由基聚合性成分(A)聚合、作成黏接著劑層(發明10)。 Fifth, the present invention provides a method for producing an adhesive sheet, which is a method for producing an adhesive sheet having an adhesive layer, characterized in that the above-mentioned adhesive composition (Inventions 1 to 5) is coated , by irradiating the coating film of the adhesive composition with visible light to polymerize the radically polymerizable component (A) to form an adhesive layer (Invention 10).

第6，本發明提供一種顯示體，其係具備：一顯示體構成構件；其他顯示體構成構件；將前述一顯示體構成構件與前述其他顯示體構成構件互相接著的硬化後黏接著劑層的顯示體，其特徵在於，前述硬化後黏接著劑層，係由含有：來自自由基聚合性成分(A)的聚合物；及來自離子聚合性成分(B)的聚合物的硬化後黏接著劑組成(發明11)。 Sixthly, the present invention provides a display body comprising: a display body constituting member; another display body constituting member; A display body, characterized in that the adhesive layer after curing is made of a post-curing adhesive containing: a polymer derived from the radically polymerizable component (A); and a polymer derived from the ionically polymerizable component (B) Composition (Invention 11).

第7，本發明提供一種顯示體的製造方法，其特徵在於：製作將一顯示體構成構件與其他顯示體構成構件經由前述黏接著板片(發明8、9)的黏接著劑層貼合而成的層積體，對前述層積體的前述黏接著劑層照射紫外線，使前述離子聚合性成分(B)聚合作成硬化後黏接著劑層(發明12)。 Seventhly, the present invention provides a method for manufacturing a display body, characterized in that: producing a display body by laminating one display body constituent member and another display body constituent member through the adhesive layer of the above-mentioned adhesive sheet (inventions 8 and 9). The resulting laminate is irradiated with ultraviolet rays to the adhesive layer of the laminate to polymerize the ionomerizable component (B) to form a cured adhesive layer (Invention 12).

關於本發明的黏接著劑組合物、黏接著劑、黏接著板片及顯示體，係段差追隨性及耐起泡性的雙方優良。 The adhesive composition, adhesive, adhesive sheet, and display of the present invention are excellent in both step followability and foaming resistance.

1‧‧‧黏接著板片 1‧‧‧Bond bonding

11‧‧‧黏接著劑層 11‧‧‧Adhesive layer

12a、12b‧‧‧剝離板片 12a, 12b‧‧‧Peel off the sheet

2‧‧‧顯示體 2‧‧‧Display

11'‧‧‧硬化後接著劑層 11'‧‧‧Adhesive layer after hardening

21‧‧‧第1顯示體構成構件 21‧‧‧First Display Body Components

22‧‧‧第2顯示體構成構件 22‧‧‧Second display body components

3‧‧‧印刷層 3‧‧‧Printing layer

[圖1]係關於本發明的一實施形態的黏接著板片的剖面圖。 1 is a cross-sectional view of an adhesive sheet according to an embodiment of the present invention.

[圖2]係關於本發明的一實施形態的層積體的剖面圖。 [ Fig. 2] Fig. 2 is a cross-sectional view of a laminate according to an embodiment of the present invention.

以下說明關於本發明的實施形態。 Embodiments of the present invention will be described below.

[黏接著劑組合物] [Adhesive composition]

關於本實施形態的黏接著劑組合物(以下，有時稱為「黏接著劑組合物P」。)，含有：自由基聚合性成分(A)；離子聚合性成分(B)；可藉由可見光活化的可見光活化自由基聚合起始劑(C)；可藉由紫外線活化的紫外線活化離子聚合起始劑(D)。在此，所謂「黏接著劑」，係指在初期狀態顯示黏著性，藉由紫外線照射等的觸發而硬化成顯示堅固的接著性的接著劑。此外，在本說明書的可見光，係指波長在380nm以上，780nm以下的光線，紫外線係指波長在10nm以上，未滿380nm的光線。 The adhesive composition (hereinafter, sometimes referred to as "adhesive composition P") of the present embodiment contains: a radically polymerizable component (A); an ionically polymerizable component (B); Visible-light-activated visible-light-activated radical polymerization initiator (C); UV-activated ionic polymerization initiator (D) that can be activated by ultraviolet rays. Here, the "adhesive" refers to an adhesive that exhibits adhesiveness in an initial state, and is cured to exhibit firm adhesiveness when triggered by ultraviolet irradiation or the like. In addition, visible light in this specification refers to light rays having a wavelength of 380 nm or more and 780 nm or less, and ultraviolet rays refer to light rays having a wavelength of 10 nm or more and less than 380 nm.

對上述黏接著劑組合物P的塗膜照射可見光，則可見光活化自由基聚合起始劑(C)進行活化產生自由基。藉此，自由基聚合性成分(A)進行自由基聚合，在組合物中形成自由基聚合性成分(A)的聚合物。此時，由於離子聚合性成分(B)不會聚合，可得到半硬化狀態的黏接著劑層。該半硬化狀態的黏接著劑層，貼附在具有段差的顯示體構成構件時，容易追隨段差，可抑制在段差附近發生間隙、浮起等。因此，以上述黏接著劑組合物P形成的黏接著劑層，初期的段差追隨性優良。 When visible light is irradiated to the coating film of the above-mentioned adhesive composition P, the visible light-activated radical polymerization initiator (C) is activated to generate radicals. Thereby, the radically polymerizable component (A) undergoes radical polymerization, and the polymer of the radically polymerizable component (A) is formed in the composition. At this time, since the ionically polymerizable component (B) does not polymerize, a semi-hardened adhesive layer can be obtained. When the adhesive layer in the semi-hardened state is attached to a display component having a level difference, it is easy to follow the level difference, and it is possible to suppress generation of gaps, floating, etc. in the vicinity of the level difference. Therefore, the adhesive layer formed with the above-mentioned adhesive composition P is excellent in the initial step followability.

此外，在經由上述黏接著劑層，將一顯示體構成構件與其他顯示體構成構件貼合後，透過一顯示體構成構件或其他顯示體構成構件，對黏接著劑層照射紫外線，則紫外線活化離子聚合起始劑(D)會活化產生離子。藉此，離子聚合性成分(B)進行離子聚合，在黏接著劑中形成離子聚合性成分(B)的聚合物，使黏接著劑層硬化，成為硬化後黏接著劑層。該硬化後黏接著劑層，由於顯示很高的凝聚力及堅固的接著性，故所得層積體(顯示體)，即使放置在高溫高濕條件下，例如85℃、85%RH條件下，72小時，亦可抑制在段差附近發生氣泡、浮起、剝落等。再者，亦可抑制在顯示體構成構件與硬化後黏接著劑層的界面，發生氣泡、浮起、剝落等的起泡。因此，藉由上述黏接著劑組合物P形成的黏接著劑層，進而硬化後黏接著劑層，在高溫高濕條件下的段差追隨性及耐起泡性優良。 In addition, after bonding one display component member and other display component members through the above-mentioned adhesive layer, and irradiating the adhesive layer with ultraviolet rays through one display component member or other display component members, the ultraviolet rays are activated. The ionic polymerization initiator (D) is activated to generate ions. Thereby, the ionically polymerizable component (B) is ionically polymerized, the polymer of the ionically polymerizable component (B) is formed in the adhesive, the adhesive layer is cured, and the cured adhesive layer is obtained. Since the hardened adhesive layer exhibits high cohesion and firm adhesiveness, the obtained laminate (display body), even if placed under high temperature and high humidity conditions, such as 85°C and 85% RH conditions, will be 72 When it is small, generation of bubbles, floating, peeling, etc. in the vicinity of the step can also be suppressed. Furthermore, it is also possible to suppress the occurrence of foaming, such as air bubbles, floating, and peeling, at the interface between the display body constituent member and the adhesive layer after curing. Therefore, the adhesive layer formed by the above-mentioned adhesive composition P, and further the adhesive layer after curing, is excellent in step followability and foaming resistance under high temperature and high humidity conditions.

在此，關於本實施形態的黏接著劑組合物P，可見光活化自由基聚合起始劑(C)與紫外線活化離子聚合起始劑(D)係個別存在。藉此，對黏接著劑組合物P的塗膜照射可見光時，無須降低可見光的照度，且無因可見光照射使離子聚合性成分(B)硬化之虞，故可藉由之後的紫外線照射使離子聚合性成分(B)充分硬化，得到所期望的接著性。因此，根據上述黏接著劑組合物P，能夠高生產性地製造段差追隨性及耐起泡性優良的顯示體。 Here, about the adhesive composition P of this embodiment, a visible light-activated radical polymerization initiator (C) and an ultraviolet-ray activated ion polymerization initiator (D) exist individually. Thereby, when the coating film of the adhesive composition P is irradiated with visible light, it is not necessary to reduce the illuminance of the visible light, and there is no fear of hardening the ionomerizable component (B) by the irradiation of the visible light, so that the ion can be irradiated by the subsequent ultraviolet rays. The polymerizable component (B) is sufficiently cured to obtain the desired adhesiveness. Therefore, according to the said adhesive agent composition P, the display body excellent in step followability and foaming resistance can be manufactured with high productivity.

關於本實施形態的黏接著劑組合物P，以無溶劑型黏接著劑組合物為佳，藉由具有上述組成，能夠作成無溶劑型。無溶劑型黏接著劑組合物，能夠不使用溶劑混合、塗層等，且不需要溶劑的揮發步驟，故可容易地形成厚膜的黏接著劑層。 The adhesive composition P of the present embodiment is preferably a non-solvent type adhesive composition, and by having the above-mentioned composition, it can be made into a non-solvent type. The solvent-free adhesive composition can be mixed, coated, etc. without a solvent, and does not require a solvent volatilization step, so a thick-film adhesive layer can be easily formed.

(1)各成分 (1) Each component

(1-1)自由基聚合性成分(A) (1-1) Radically polymerizable component (A)

在本實施形態的自由基聚合性成分(A)，以能夠藉由可見光活化自由基聚合起始劑(C)所產生的自由基進行自由基聚合，發揮既定的黏接著性的成分為佳。該自由基聚合性成分(A)，含有在分子中具有(甲基)丙烯醯基的含(甲基)丙烯醯基單體及在分子中具有乙烯基的含乙烯基單體的至少1種為佳，此外，包含具有自由基聚合性基的胺甲酸乙酯寡聚物(聚合性胺甲酸乙酯寡聚物)亦佳，以含有含(甲基)丙烯醯基單體及含乙烯基單體的至少1種，與聚合性胺甲酸乙酯寡聚物特別佳。在此，在含乙烯基單體，不包含含(甲基)丙烯醯基單體。再者，在本說明書，(甲基)丙烯醯，係指丙烯醯及甲基丙烯醯的雙方。其他的類似用語亦相同。 The radically polymerizable component (A) of the present embodiment is preferably a component capable of radically polymerizing by the radicals generated by the visible light-activated radical polymerization initiator (C) and exhibiting a predetermined adhesiveness. The radically polymerizable component (A) contains at least one of a (meth)acryloyl group-containing monomer having a (meth)acryloyl group in the molecule and a vinyl group-containing monomer having a vinyl group in the molecule Preferably, in addition, it is also preferable to include a urethane oligomer having a radically polymerizable group (polymerizable urethane oligomer), so as to contain a (meth)acryloyl group-containing monomer and a vinyl group-containing monomer. At least one of the monomers and a polymerizable urethane oligomer are particularly preferred. Here, the vinyl group-containing monomer does not include a (meth)acryloyl group-containing monomer. In addition, in this specification, (meth)acryloyl acid refers to both acryl acid and methacryloyl acid. The same applies to other similar terms.

含(甲基)丙烯醯基單體及含乙烯基單體，由於自由基聚合，可發揮既定的黏著性，故可良好的使用。此外，含(甲基)丙烯醯基單體及含乙烯基單體，由於分子量相對較小，而黏度低，故藉由使用該等，黏接著劑組合物P，能夠無須溶劑而混合、塗層等，故可成為無溶劑型黏接著劑組合物。 The (meth)acryloyl group-containing monomer and the vinyl group-containing monomer can exhibit a predetermined adhesiveness due to radical polymerization, so they can be used well. In addition, the (meth)acryloyl group-containing monomer and the vinyl group-containing monomer have relatively small molecular weights and low viscosity, so by using these, the adhesive composition P can be mixed and applied without a solvent. layer, etc., so it can be a solvent-free adhesive composition.

含(甲基)丙烯醯基單體，可為單官能的含(甲基)丙烯醯基單體，亦可為多官能的含(甲基)丙烯醯基單體。在此，所謂單官能的含(甲基)丙烯醯基單體，係指在分子中具有1個(甲基)丙烯醯基的單體，所謂多官能的含(甲基)丙烯醯基單 體，係指在分子中具有2個以上的(甲基)丙烯醯基的單體。再者，含(甲基)丙烯醯基單體，能夠1種單獨使用，亦可組合2種以上使用。 The (meth)acryloyl group-containing monomer may be a monofunctional (meth)acryloyl group-containing monomer or a polyfunctional (meth)acryloyl group-containing monomer. Here, the monofunctional (meth)acryloyl group-containing monomer refers to a monomer having one (meth)acryloyl group in the molecule, and the so-called polyfunctional (meth)acryloyl group-containing monomer The body refers to a monomer having two or more (meth)acryloyl groups in the molecule. In addition, a (meth)acryloyl group containing monomer may be used individually by 1 type, and may be used in combination of 2 or more types.

單官能的含(甲基)丙烯醯基單體，較佳可列舉出，例如，烷基的碳數為1~20的(甲基)丙烯酸烷基酯。作為烷基的碳數為1~20的(甲基)丙烯酸烷基酯，可列舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕櫚酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯等。其中，以烷基的碳數為1~8的(甲基)丙烯酸烷基酯為佳，特別對各種被著體顯現高黏著力的觀點，以(甲基)丙烯酸2-乙基己酯為佳。 Preferable examples of the monofunctional (meth)acryloyl group-containing monomer include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group. Examples of alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. ) butyl acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, Lauryl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, and the like. Among them, alkyl (meth)acrylates having 1 to 8 carbon atoms in the alkyl group are preferred, and 2-ethylhexyl (meth)acrylate is particularly preferred from the viewpoint of showing high adhesion to various substrates. good.

此外，單官能的含(甲基)丙烯醯基單體，較佳可列舉出，在分子內具有脂環式結構(甲基)丙烯酸酯(含脂環式結構(甲基)丙烯酸酯)。含脂環式結構(甲基)丙烯酸酯，由於脂環式結構的體積大，顯示疏水性，故可增加所得黏接著劑的對樹脂板的密著性，以此提升耐起泡性。 Moreover, the monofunctional (meth)acryloyl group containing monomer preferably has an alicyclic structure (meth)acrylate in a molecule|numerator (alicyclic structure containing (meth)acrylate). The alicyclic structure-containing (meth)acrylate can increase the adhesiveness of the obtained adhesive to the resin board due to the large volume of the alicyclic structure and exhibit hydrophobicity, thereby improving the foaming resistance.

含脂環式結構(甲基)丙烯酸酯，可列舉例如，(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯等。該等之中，由塗層液的黏度調整及自由基聚合性的觀點，以(甲基)丙烯酸異莰酯為佳。 Alicyclic structure-containing (meth)acrylates include, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and isobornyl (meth)acrylate. ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. Among these, from the viewpoint of viscosity adjustment of the coating liquid and radical polymerizability, isobornyl (meth)acrylate is preferable.

單官能的含(甲基)丙烯醯基單體，亦可具有反應性基。該反應性基之例，可列舉羥基、羧基、硫醇基，及1或2級的胺基等。具有如此的反應性基的單官能的含(甲基)丙烯醯基單體，可列舉例如(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-羥基丁酯等的(甲基)丙烯酸羥基烷基酯；N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺等的含羥基丙烯醯胺類；丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、依康酸、檸康酸等的乙烯性不飽和羧酸等。 The monofunctional (meth)acryloyl group-containing monomer may have a reactive group. Examples of the reactive group include a hydroxyl group, a carboxyl group, a thiol group, a primary or secondary amine group, and the like. Examples of the monofunctional (meth)acryloyl group-containing monomer having such a reactive group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylate. Hydroxyalkyl (meth)acrylates such as 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. ;Hydroxy-containing acrylamides such as N-methylol acrylamide, N-methylol methacrylamide, etc.; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, etc. of ethylenically unsaturated carboxylic acids, etc.

上述之中，使用(甲基)丙烯酸羥基烷基酯，則在所得黏接著劑中存在既定量的羥基。羥基係親水基，如此的親水性基以既定量存在於黏接著劑中，則即使黏接著劑被放置在高溫高濕條件下時，與在該高溫高濕條件下浸入黏接著劑的水分的相溶性佳，結果，恢復到常溫常濕時可抑制黏接著劑的白化(耐濕熱白化性優良)。由此觀點，使用(甲基)丙烯酸羥基烷基酯為佳，使用具有碳數1~4的羥基烷基的(甲基)丙烯酸羥基烷基酯特別佳，進一步使用(甲基)丙烯酸2-羥基乙酯為佳。 Among the above, when a hydroxyalkyl (meth)acrylate is used, a predetermined amount of hydroxyl groups are present in the obtained adhesive. Hydroxyl is a hydrophilic group, and if such a hydrophilic group exists in the adhesive in a predetermined amount, even when the adhesive is placed under high temperature and high humidity conditions, the difference between the water and the moisture immersed in the adhesive under the high temperature and high humidity conditions. The compatibility is good, and as a result, the whitening of the adhesive can be suppressed when returning to normal temperature and normal humidity (excellent in wet-heat whitening resistance). From this point of view, it is preferable to use hydroxyalkyl (meth)acrylate, especially hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having 1 to 4 carbon atoms, and further, 2-(meth)acrylate is used. Hydroxyethyl esters are preferred.

單官能的含(甲基)丙烯醯基單體，在上述以外，亦能夠使用例如，(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等的(甲基)丙烯酸烷氧基烷基酯；聚氧烷變性(甲基)丙烯酸酯；丙烯腈、甲基丙烯腈等的腈系單體；丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺等的醯胺系單體；(甲基)丙烯酸N,N-二乙基胺基乙酯、N-(甲基)丙烯醯嗎啉等的含3級胺基單體等。 As the monofunctional (meth)acryloyl group-containing monomer, in addition to the above, for example, (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate can be used. Alkoxyalkyl acrylates; polyoxyalkane-modified (meth)acrylates; nitrile monomers such as acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, N-methacrylamide , N-methylmethacrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide and other amide monomers; (methyl) base) 3-level amine group-containing monomers such as N,N-diethylaminoethyl acrylate, N-(meth)acrylomorpholine, etc.

多官能的含(甲基)丙烯醯基單體，較佳可列舉出在一分子中具有2個以上的(甲基)丙烯醯基單體。如此的單體之例，可舉1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯變性二環戊烯基二(甲基)丙烯酸酯、環氧乙烷變性磷酸二(甲基)丙烯酸酯、二(丙烯醯氧乙基)異氰尿酸酯、烯丙基化環己基二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、丙酸變性二異戊四醇三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、氧化丙烯變性三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧乙基)異氰尿酸酯、二(丙烯醯氧乙基)羥基乙基異氰尿酸酯、異三聚氰酸氧化乙烯變性二丙烯酸酯、異三聚氰酸氧化乙烯變性三丙烯酸酯、ε-己內酯變性三(丙烯醯氧乙基)異氰尿酸酯、二甘油四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、丙酸變性二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯變性二新戊四醇六(甲基)丙烯酸酯等。 Preferable examples of the polyfunctional (meth)acryloyl group-containing monomer include (meth)acryloyl group-containing monomers having two or more in one molecule. Examples of such monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate , polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate (Meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, bis(acrylooxyethyl)isocyanuric acid Esters, allylated cyclohexyl di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipivaloerythritol tri(meth)acrylate, propionic acid-modified diisopentaerythritol Tri(meth)acrylate, neotaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, Di(acrylooxyethyl) hydroxyethyl isocyanurate, isocyanuric ethylene oxide modified diacrylate, isocyanuric ethylene oxide modified triacrylate, ε-caprolactone modified tri(propylene) Acetyloxyethyl) isocyanurate, diglycerol tetra(meth)acrylate, neotaerythritol tetra(meth)acrylate, propionic acid-denatured dipivalerythritol penta(meth)acrylate, di Neopentaerythritol hexa(meth)acrylate, caprolactone-modified dipivalerythritol hexa(meth)acrylate, etc.

含乙烯基單體，可列舉例如，醋酸乙烯酯、丙酸乙烯酯等的乙烯酯類；乙烯、丙烯、異丁烯等的烯烴類；氯乙烯、氯化亞乙烯等的鹵化烯烴類；苯乙烯、α-甲基苯乙烯等的苯乙烯系單體；丁二烯、異戊二烯、氯丁二烯等的二烯系單體；N-乙烯基吡咯啶酮等的醯胺系單體等。該等能夠1種單獨使用，亦可組合2種以上使用。 Examples of vinyl-containing monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene, Styrene-based monomers such as α-methylstyrene; diene-based monomers such as butadiene, isoprene, chloroprene, etc.; amide-based monomers such as N-vinylpyrrolidone, etc. . These can be used alone or in combination of two or more.

聚合性胺甲酸乙酯寡聚物，由於自由基聚合，可發揮既定的黏著性，故可良好地使用。此外，反應性胺甲酸乙酯寡聚物，由於具有能夠將塗層液的黏度調節成能夠厚膜加工的程度的優點，可特別良好地使用。 The polymerizable urethane oligomer exhibits a predetermined adhesiveness due to radical polymerization, so it can be used favorably. In addition, the reactive urethane oligomer has the advantage of being able to adjust the viscosity of the coating liquid to a degree that enables thick film processing, and can be used particularly favorably.

聚合性胺甲酸乙酯寡聚物的重量平均分子量，以3,000以上為佳，以5,000以上特別佳，進一步以8,000以上為佳。此外，重量平均分子量，以100,000以下為佳，以50,000以下更佳，進一步以20,000以下為佳。再者，在本說明書的重量平均分子量，係以凝膠滲透層析(GPC)法測定的標準聚苯乙烯換算值。 The weight average molecular weight of the polymerizable urethane oligomer is preferably 3,000 or more, particularly preferably 5,000 or more, and more preferably 8,000 or more. In addition, the weight average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, and more preferably 20,000 or less. In addition, the weight average molecular weight in this specification is the standard polystyrene conversion value measured by gel permeation chromatography (GPC).

聚合性胺甲酸乙酯寡聚物，以多官能為佳，此外，聚合性胺甲酸乙酯寡聚物所具有的聚合性基，以存在於末端，特別是兩末端為佳。該聚合性基的種類，例如，以(甲基)丙烯醯基、乙烯基等為佳，以(甲基)丙烯醯基特別佳。即，聚合性胺甲酸乙酯寡聚物，以多官能(甲基)丙烯酸酯寡聚物為佳，換言之，以胺甲酸乙酯丙烯酸酯系寡聚物為佳。胺甲酸乙酯丙烯酸酯系寡聚物，以與上述含(甲基)丙烯醯基單體或含乙烯基單體同時自由基聚合，能夠發揮良好的黏著性。 The polymerizable urethane oligomer is preferably multifunctional, and the polymerizable group possessed by the polymerizable urethane oligomer is preferably present at the terminals, especially both terminals. The type of the polymerizable group is preferably, for example, a (meth)acryloyl group, a vinyl group, or the like, and a (meth)acryloyl group is particularly preferable. That is, the polymerizable urethane oligomer is preferably a polyfunctional (meth)acrylate oligomer, in other words, a urethane acrylate-based oligomer. The urethane acrylate-based oligomer is radically polymerized simultaneously with the above-mentioned (meth)acryloyl group-containing monomer or vinyl group-containing monomer, and can exhibit good adhesion.

胺甲酸乙酯丙烯酸酯系寡聚物，可列舉例如，聚烯烴多元醇、聚醚多元醇、聚酯多元醇、具有羥基末端的加氫異戊二烯、具有羥基末端的加氫丁二烯等的化合物，與藉由與聚異氰酸酯的反應所得的聚胺甲酸乙酯寡聚物，以(甲基)丙烯酸或(甲基)丙烯酸衍生物進行酯化而得。 Urethane acrylate-based oligomers include, for example, polyolefin polyols, polyether polyols, polyester polyols, hydroxyl-terminated hydrogenated isoprene, and hydroxyl-terminated hydrogenated butadiene. Compounds such as these are obtained by esterification with a (meth)acrylic acid or a (meth)acrylic acid derivative with a polyurethane oligomer obtained by reacting with a polyisocyanate.

在此，可使用於胺甲酸乙酯丙烯酸酯系寡聚物的製造的聚烯烴多元醇之例，可舉聚丙二醇、聚乙二醇、聚丁二醇、聚己二醇等，使用聚丙二醇特別佳。再者，使所得的胺甲酸乙酯丙烯酸酯系寡聚物的官能基數為3以上時，只要適宜組合甘油、三羥甲基丙烷、三乙醇胺、新戊四醇、乙二胺、二乙三胺、山梨醇、蔗糖等即可。 Here, examples of polyolefin polyols that can be used for the production of urethane acrylate-based oligomers include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and polyethylene glycol, and polypropylene glycol is used. Excellent. Furthermore, when the number of functional groups of the obtained urethane acrylate-based oligomer is 3 or more, glycerin, trimethylolpropane, triethanolamine, neotaerythritol, ethylenediamine, diethylenetriol may be appropriately combined. Amine, sorbitol, sucrose, etc. can be used.

此外，聚異氰酸酯之例，可舉六亞甲基二異氰酸酯、三亞甲基二異氰酸酯等的脂肪族二異氰酸酯；甲伸苯二異氰酸酯、二甲苯撐基二異氰酸酯、二苯基二異氰酸酯等的芳香族二異氰酸酯；二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯等的脂環式二異氰酸酯，該等之中，使用脂環式二異氰酸酯為佳，使用二環己基甲烷二異氰酸酯特別佳。由於脂環式結構體積大，低極性，故藉由使用包含來自脂環式二異氰酸酯的脂環式結構的胺甲酸乙酯丙烯酸酯系寡聚物，可使所得黏接著劑的耐起泡性更優良。此外，藉由使用二環己基甲烷二異氰酸酯，所得胺甲酸乙酯丙烯酸酯系寡聚物的化學結構，可成與後述的作為離子聚合性成分(B)較佳的縮水甘油醚類的化學結構類似，相溶性良好。再者，聚異氰酸酯，並不限於2官能，亦可使用3官能以上之物。 In addition, examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylene diisocyanate; aromatic diisocyanates such as tolylylene diisocyanate, xylylene diisocyanate, and diphenyl diisocyanate. Diisocyanates; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate, among these, alicyclic diisocyanates are preferably used, and dicyclohexylmethane diisocyanate is particularly preferably used. Since the alicyclic structure is bulky and low in polarity, the foaming resistance of the obtained adhesive can be improved by using the urethane acrylate-based oligomer containing the alicyclic structure derived from the alicyclic diisocyanate. better. In addition, by using dicyclohexylmethane diisocyanate, the chemical structure of the obtained urethane acrylate-based oligomer can become the chemical structure of the glycidyl ethers which are preferable as the ionically polymerizable component (B) described later. Similarly, the compatibility is good. In addition, the polyisocyanate is not limited to bifunctional, and trifunctional or more may be used.

此外，作為(甲基)丙烯酸衍生物，丙烯酸2-羥基乙基酯、丙烯酸4-羥基丁酯等的(甲基)丙烯酸羥基烷基酯、丙烯酸2-異氰酸基乙酯，甲基丙烯酸2-異氰酸基乙酯，1,1-雙(丙烯醯氧甲基)乙基異氰酸酯等，以丙烯酸2-異氰酸基乙酯特別佳。 In addition, as (meth)acrylic acid derivatives, 2-hydroxyethyl acrylate, hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl acrylate, 2-isocyanatoethyl acrylate, methacrylic acid 2-Isocyanatoethyl ester, 1,1-bis(acrylooxymethyl)ethyl isocyanate, etc., 2-isocyanatoethyl acrylate is particularly preferred.

胺甲酸乙酯丙烯酸酯系寡聚物的其他之製造方 法，將聚烯烴多元醇、聚醚多元醇、聚酯多元醇、具有羥基末端的加氫異戊二烯、具有羥基末端的加氫丁二烯等的化合物所具有的羥基，與(甲基)丙烯酸異氰酸基烷基酯所具有的-N=C=O部分之間的反應，得到胺甲酸乙酯丙烯酸酯系寡聚物。此時，該(甲基)丙烯酸異氰酸基烷基酯，可使用上述丙烯酸2-異氰酸基乙酯、甲基丙烯酸2-異氰酸基乙酯、1,1-雙(丙烯醯氧甲基)乙基異氰酸酯等。 Another method for producing urethane acrylate-based oligomers is to combine polyolefin polyol, polyether polyol, polyester polyol, hydroxyl-terminated hydrogenated isoprene, and hydroxyl-terminated hydrogenated butylene A urethane acrylate type oligomer is obtained by the reaction between the hydroxyl group which the compound, such as diene, has and the -N=C=O part which the isocyanatoalkyl (meth)acrylate has. In this case, as the isocyanatoalkyl (meth)acrylate, the above-mentioned 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 1,1-bis(acryloyl) can be used. oxymethyl) ethyl isocyanate and the like.

在本實施形態的自由基聚合性成分(A)，亦可包含胺甲酸乙酯丙烯酸酯系寡聚物以外的多官能(甲基)丙烯酸酯寡聚物，用以取代胺甲酸乙酯丙烯酸酯系寡聚物，或與胺甲酸乙酯丙烯酸酯系寡聚物一起。如此的寡聚物之例，可列舉聚酯丙烯酸酯系、環氧丙烯酸酯系、聚醚丙烯酸酯系、聚丁二烯丙烯酸酯系、矽酮丙烯酸酯系等的寡聚物。 The radically polymerizable component (A) of the present embodiment may contain a polyfunctional (meth)acrylate oligomer other than the urethane acrylate-based oligomer in place of the urethane acrylate oligomers, or together with urethane acrylate oligomers. Examples of such oligomers include polyester acrylate-based, epoxy acrylate-based, polyether acrylate-based, polybutadiene acrylate-based, and silicone acrylate-based oligomers.

聚酯丙烯酸酯系寡聚物，例如，能夠將藉由多元羧酸與多元醇的縮合所得到的在兩末端具有羥基的聚酯寡聚物的羥基，以(甲基)丙烯酸進行酯化，或者，將對多元羧酸進行加成伸烷基氧化物而得到的寡聚物的末端的羥基，以(甲基)丙烯酸進行酯化而得。 The polyester acrylate-based oligomer, for example, can be esterified with (meth)acrylic acid by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, Alternatively, the hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid is obtained by esterifying with (meth)acrylic acid.

環氧丙烯酸酯系寡聚物，例如，能夠使分子量相對較低的雙酚型環氧樹脂或酚醛型環氧樹脂的環氧乙烷環，藉由與(甲基)丙烯酸反應進行酯化而得。此外，亦可使用以二鹼性羧酸酐將環氧丙烯酸酯系寡聚物部分地進行變性的羧基變性型的環氧丙烯酸酯系寡聚物。 Epoxy acrylate-based oligomers, for example, can esterify the ethylene oxide ring of a bisphenol-type epoxy resin or a novolac-type epoxy resin with a relatively low molecular weight by reacting with (meth)acrylic acid. have to. In addition, a carboxyl-modified epoxy acrylate-based oligomer in which an epoxy acrylate-based oligomer is partially denatured with a dibasic carboxylic acid anhydride can also be used.

聚醚丙烯酸酯系寡聚物，例如，能夠將聚醚多元 醇的羥基以(甲基)丙烯酸進行酯化而得。 The polyether acrylate-based oligomer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth)acrylic acid.

上述多官能(甲基)丙烯酸酯寡聚物的重量平均分子量，以1,000以上為佳，以5,000以上特別佳。此外，該重量平均分子量，以100,000以下為佳，以50,000以下特別佳。 The weight average molecular weight of the polyfunctional (meth)acrylate oligomer is preferably 1,000 or more, and particularly preferably 5,000 or more. In addition, the weight average molecular weight is preferably 100,000 or less, particularly preferably 50,000 or less.

在本實施形態的自由基聚合性成分(A)，在上述之中，以含有烷基的碳數為1~20的(甲基)丙烯酸烷基酯、含脂環式結構(甲基)丙烯酸酯、具有反應性基的含(甲基)丙烯醯基單體、聚合性胺甲酸乙酯寡聚物為佳，以含有丙烯酸2-乙基己酯、丙烯酸異莰酯、丙烯酸2-羥基乙酯、胺甲酸乙酯丙烯酸酯系寡聚物，由各種材料的相溶性的觀點而言特別佳。 In the radically polymerizable component (A) of the present embodiment, among the above, the alkyl group-containing (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms, the alicyclic structure-containing (meth)acrylic acid Esters, (meth)acryloyl group-containing monomers with reactive groups, and polymerizable urethane oligomers are preferred, and those containing 2-ethylhexyl acrylate, isobornyl acrylate, and 2-hydroxyethyl acrylate are preferred. Esters and urethane acrylate-based oligomers are particularly preferred from the viewpoint of compatibility of various materials.

此時，在自由基聚合性成分(A)中的(甲基)丙烯酸烷基酯(特別是丙烯酸2-乙基己酯)的含量，下限值，以5質量%以上為佳，以10質量%以上更佳，以30質量%以上特別佳。此外，上限值，以70質量%以下為佳，以60質量%以下更佳，以50質量%以下特別佳。 In this case, the lower limit of the content of the alkyl (meth)acrylate (especially 2-ethylhexyl acrylate) in the radically polymerizable component (A) is preferably 5 mass % or more, and 10 More preferably, it is at least 30% by mass, and particularly preferably at least 30% by mass. In addition, the upper limit is preferably 70 mass % or less, more preferably 60 mass % or less, and particularly preferably 50 mass % or less.

在自由基聚合性成分(A)中的含脂環式結構(甲基)丙烯酸酯(特別是丙烯酸異莰酯)的含量，作為下限值，以5質量%以上為佳，以10質量%以上更佳，以15質量%以上特別佳。此外，上限值，以50質量%以下為佳，以40質量%以下更佳，以30質量%以下特別佳。 The lower limit of the content of the alicyclic structure-containing (meth)acrylate (in particular, isobornyl acrylate) in the radically polymerizable component (A) is preferably 5% by mass or more, and 10% by mass More preferably, it is 15 mass % or more. In addition, the upper limit is preferably 50 mass % or less, more preferably 40 mass % or less, and particularly preferably 30 mass % or less.

在自由基聚合性成分(A)中，具有反應性基的含(甲基)丙烯醯基單體(特別是丙烯酸2-羥乙基酯)的含量，下限值以2質量%以上為佳，以5質量%以上更佳，以8質量%以上特別 佳。此外，上限值，以40質量%以下為佳，以30質量%以下更佳，以20質量%以下特別佳。 In the radically polymerizable component (A), the lower limit of the content of the reactive group-containing (meth)acryloyl group-containing monomer (especially, 2-hydroxyethyl acrylate) is preferably 2 mass % or more. , more preferably at least 5 mass %, particularly preferably at least 8 mass %. In addition, the upper limit is preferably 40 mass % or less, more preferably 30 mass % or less, and particularly preferably 20 mass % or less.

在自由基聚合性成分(A)中，聚合性胺甲酸乙酯寡聚物(特別是胺甲酸乙酯丙烯酸酯系寡聚物)的含量，下限值，以5質量%以上為佳，以10質量%以上更佳，以20質量%以上特別佳。此外，上限值，以60質量%以下為佳，以50質量%以下更佳，以40質量%以下特別佳。 In the radically polymerizable component (A), the lower limit of the content of the polymerizable urethane oligomer (especially the urethane acrylate oligomer) is preferably 5% by mass or more, and the lower limit is preferably 5% by mass or more. 10 mass % or more is more preferable, and 20 mass % or more is especially preferable. In addition, the upper limit is preferably 60 mass % or less, more preferably 50 mass % or less, and particularly preferably 40 mass % or less.

在黏接著劑組合物P中的自由基聚合性成分(A)的含量，下限值，以70質量%以上為佳，以75質量%以上為佳，進一步以80質量%以上更佳。此外，上限值，以99質量%以下為佳，以97質量%以下為佳，進一步以95質量%以下為佳。 The lower limit of the content of the radically polymerizable component (A) in the adhesive composition P is preferably 70% by mass or more, more preferably 75% by mass or more, and more preferably 80% by mass or more. In addition, the upper limit is preferably 99 mass % or less, more preferably 97 mass % or less, and more preferably 95 mass % or less.

(1-2)離子聚合性成分(B) (1-2) Ionically polymerizable component (B)

在本實施形態的離子聚合性成分(B)，以藉由紫外線活化離子聚合起始劑(D)所產生的離子進行離子聚合，發揮既定的接著性的成分為佳。離子聚合性成分(B)，可為陽離子聚合性成分，亦可為陰離子聚合性成分，由材料選擇的多樣性的觀點，以陽離子聚合性成分為佳。離子聚合性成分(B)，能夠1種單獨使用，亦可組合2種以上使用。 The ionically polymerizable component (B) of the present embodiment is preferably a component that exhibits a predetermined adhesiveness by ion-polymerizing by ions generated by the ultraviolet-activated ion-polymerization initiator (D). The ionically polymerizable component (B) may be a cationically polymerizable component or an anionically polymerizable component, and the cationically polymerizable component is preferable from the viewpoint of the variety of material selection. The ionically polymerizable component (B) may be used alone or in combination of two or more.

陽離子聚合性成分，可為單體，亦可為預聚物。單體的陽離子聚合性成分，可列舉例如茚、香豆酮等的烷基取代烯、乙基乙烯基醚、正丁基乙烯基醚、環己基乙烯基醚、丁二醇二乙烯基醚、二乙二醇二乙烯基醚等的乙烯基醚類、雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、乙二醇二縮水甘油醚，該等的氫添加物等的縮水甘油醚類、3-乙基-3-羥基 乙基氧環丁烷、1,4-雙[(3-乙基-3-氧環丁烷基甲氧基)甲基]苯等的氧環丁烷類、3,4-環氧基環己基甲基(3,4-環氧基)環己烷羧酸酯、雙(3,4-環氧基環己基)己二酸酯等的脂環式環氧基類、N-乙烯基咔唑等。上述之中，由更正確地進行自由基聚合及離子聚合的2階段聚合反應的觀點，以縮水甘油醚類或脂環式環氧類為佳。 The cationically polymerizable component may be a monomer or a prepolymer. The cationically polymerizable components of the monomers include, for example, alkyl-substituted alkenes such as indene and coumarone, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, butanediol divinyl ether, Vinyl ethers such as diethylene glycol divinyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethylene glycol diglycidyl ether, and glycidyl ethers such as hydrogen additives oxetane, 3-ethyl-3-hydroxyethyl oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, etc. cyclohexyl, 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate, bis(3,4-epoxycyclohexyl)adipate, etc. Epoxy, N-vinylcarbazole, etc. Among the above, glycidyl ethers or alicyclic epoxies are preferred from the viewpoint of more accurate two-stage polymerization reactions of radical polymerization and ion polymerization.

此外，預聚物的陽離子聚合性成分，可列舉例如，環氧系樹脂、氧環丁烷樹脂、乙烯醚樹脂等。作為環氧系樹脂，可列舉例如，雙酚樹脂或酚醛樹脂等的多元酚類，以表氯醇等進行環氧化的化合物；將直鏈狀烯烴化合物或環狀烯烴化合物，以過氧化物等進行氧化而得的化合物。 Moreover, as a cationically polymerizable component of a prepolymer, an epoxy resin, an oxetane resin, a vinyl ether resin, etc. are mentioned, for example. Examples of epoxy resins include polyhydric phenols such as bisphenol resins and phenolic resins, compounds epoxidized with epichlorohydrin, etc.; linear olefin compounds or cyclic olefin compounds, such as peroxides, etc. A compound obtained by oxidation.

上述之中，以具有環氧基或縮水甘油醚基為佳，以具有脂環式結構之物特別佳。具體而言，以上述縮水甘油醚類為佳，以雙酚A二縮水甘油醚及加氫雙酚A二縮水甘油醚特別佳，進一步以加氫雙酚A二縮水甘油醚為佳。具有環氧基或縮水甘油醚基的化合物，由於能夠陽離子聚合，發揮既定的接著性，可良好地使用。此外，由於脂環式結構體積大，而為疏水性，故藉由使用具有脂環式結構的陽離子聚合性成分，所得黏接著劑可成為耐起泡性更優良之物。再者，具有雙酚A骨架的二縮水甘油醚，由於與前述使用前述二環己基甲烷二異氰酸酯所得胺甲酸乙酯丙烯酸酯系寡聚物的化學結構類似，故相容性良好。 Among the above, those having an epoxy group or a glycidyl ether group are preferred, and those having an alicyclic structure are particularly preferred. Specifically, the above-mentioned glycidyl ethers are preferred, bisphenol A diglycidyl ether and hydrogenated bisphenol A diglycidyl ether are particularly preferred, and further preferred are hydrogenated bisphenol A diglycidyl ether. A compound having an epoxy group or a glycidyl ether group can be cationically polymerized and can be used favorably because it exhibits a predetermined adhesiveness. In addition, since the alicyclic structure is bulky and hydrophobic, by using a cationically polymerizable component having an alicyclic structure, the obtained adhesive can be more excellent in foaming resistance. Furthermore, the diglycidyl ether having a bisphenol A skeleton is similar in chemical structure to the urethane acrylate-based oligomer obtained by using the aforementioned dicyclohexylmethane diisocyanate, and thus has good compatibility.

由上述，自由基聚合性成分(A)及離子聚合性成分(B)，分別含有脂環式結構為佳。 From the above, it is preferable that the radically polymerizable component (A) and the ionically polymerizable component (B) each contain an alicyclic structure.

在黏接著劑組合物P中的離子聚合性成分(B)的含量，由段差追隨性更優良的觀點而言，作為下限值，以0.1質量%以上為佳，以0.5質量%以上為佳，進一步以1質量%以上為佳。另一方面，作為上限值，由進一步發揮藉由自由基聚合性成分(A)的性能的觀點而言，以40以質量%以下為佳，以30%質量以下更佳，進一步以20質量%以下為佳。 The lower limit of the content of the ionically polymerizable component (B) in the adhesive composition P is preferably 0.1 mass % or more, and more preferably 0.5 mass % or more, from the viewpoint of better step followability. , more preferably 1 mass % or more. On the other hand, from the viewpoint of further exerting the performance of the radical polymerizable component (A), the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass % or less is better.

此外，離子聚合性成分(B)的含量，對自由基聚合性成分(A)100質量份，由段差追隨性的觀點而言，作為下限值，以1質量份以上為佳，以2質量份以上為佳，進一步以4質量份以上為佳。另一方面，由進一步發揮以自由基聚合性成分(A)的性能的觀點而言，作為上限值，以100質量份以下為佳，以50質量份以下為佳，進一步以15質量份以下為佳。 In addition, the content of the ionically polymerizable component (B) is preferably 1 part by mass or more, and 2 parts by mass is the lower limit from the viewpoint of step followability with respect to 100 parts by mass of the radically polymerizable component (A). part or more is preferable, and more preferably 4 parts by mass or more. On the other hand, from the viewpoint of further exerting the performance of the radically polymerizable component (A), the upper limit is preferably 100 parts by mass or less, preferably 50 parts by mass or less, and further preferably 15 parts by mass or less better.

(1-3)可見光活化自由基聚合起始劑(C) (1-3) Visible Light Activated Radical Polymerization Initiator (C)

在本實施形態的可見光活化自由基聚合起始劑(C)，以可藉由可見光照射活化產生自由基，使前述自由基聚合性成分(A)聚合即可。可見光活化自由基聚合起始劑(C)，能夠1種單獨使用，亦可組合2種以上使用。 In the visible-light-activated radical polymerization initiator (C) of the present embodiment, the radical-polymerizable component (A) may be polymerized by being activated to generate radicals by irradiation with visible light. The visible light-activated radical polymerization initiator (C) may be used alone or in combination of two or more.

該可見光活化自由基聚合起始劑(C)，可列舉例如，醯基膦氧化物系化合物；4,4'-雙(二乙基胺)二苯甲酮、4,4'-雙(N,N'-二甲基胺基)二苯甲酮等的二烷基胺基二苯甲酮化合物；雙(η5-2-4-環戊二烯-1-基)雙[2,6-二氟-3-(1H-吡咯-1-基)苯基]鈦等的二茂金屬類；樟腦醌等，該等之中，對塗層液的溶解性及色調的觀點而言，以醯基膦氧化物系化合物為佳。 The visible light-activated radical polymerization initiator (C) includes, for example, acylphosphine oxide-based compounds; 4,4' - bis(diethylamine)benzophenone, 4,4' - bis(N , N ' -dimethylamino) benzophenone and other dialkylamino benzophenone compounds; bis(η5-2-4-cyclopentadien-1-yl)bis[2,6- Difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium and other metallocenes; camphorquinone and the like, among these, from the viewpoint of solubility and color tone of the coating liquid, the Preferred are phosphine oxide-based compounds.

作為醯基膦氧化物系化合物，可列舉例如2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基-二苯基一亞磷酸酯等，該等之中，由塗層液的溶解性及板片的色調(主要是黃色調)的觀點，以2,4,6-三甲基苯甲醯基-二苯基-氧化膦為佳。 Examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)- Phenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenyl monophosphite, etc. Among these, the solubility of the coating solution and the color tone of the sheet (mainly yellow ), 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide is preferred.

在黏接著劑組合物P中，可見光活化自由基聚合起始劑(C)的含量，相對於自由基聚合性成分(A)100質量份，作為下限值，以0.05質量份以上為佳，以0.1質量份以上更佳，進一步以0.2質量份以上為佳。另一方面，作為上限值，以5質量份以下為佳，以3質量份以下更佳，進一步以1.5質量份以下為佳。 In the adhesive composition P, the content of the visible light-activated radical polymerization initiator (C) is preferably 0.05 parts by mass or more as a lower limit with respect to 100 parts by mass of the radical polymerizable component (A). More preferably, it is 0.1 part by mass or more, and more preferably 0.2 part by mass or more. On the other hand, the upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 1.5 parts by mass or less.

(1-4)紫外線活化離子聚合起始劑(D) (1-4) Ultraviolet Activated Ionic Polymerization Initiator (D)

在本實施形態的紫外線活化離子聚合起始劑(D)，只要是可藉由紫外線的照射活化產生離子，使前述離子聚合性成分(B)聚合之物即可。紫外線活化離子聚合起始劑(D)，能夠1種單獨使用，亦可組合2種以上使用。 The ultraviolet-activated ionic polymerization initiator (D) of the present embodiment may be any one that can be activated to generate ions by irradiation with ultraviolet rays to polymerize the ionically polymerizable component (B). The ultraviolet-activated ionic polymerization initiator (D) may be used alone or in combination of two or more.

作為該紫外線活化離子聚合起始劑(D)，可列舉例如，芳香族鋶離子、芳香族氧鋶離子、芳香族錪鎓離子等的鎓離子，與四氟硼酸鹽、六氟磷酸鹽、六氟銻酸鹽、六氟砷酸鹽等的陰離子所形成的化合物。具體而言，可舉錪‧(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽(1-)、三芳基鋶六氟磷酸鹽、三芳基鋶四-(五氟苯基)硼酸鹽等，該等之中，由塗層液的溶解性及操作性的觀點而言，以錪‧(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽(1-)為佳。 Examples of the ultraviolet-activated ionic polymerization initiator (D) include onium ions such as aromatic perionium ions, aromatic oxonium ions, and aromatic iodonium ions; A compound formed by anions of fluoroantimonate, hexafluoroarsenate, etc. Specifically, iodo·(4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-), triaryl perylene hexafluorophosphate, triaryl Perylene tetrakis-(pentafluorophenyl) borate, etc. Among these, from the viewpoint of solubility of coating liquid and workability, iodo-(4-methylphenyl)[4-(2- Methylpropyl)phenyl]-hexafluorophosphate (1-) is preferred.

在黏接著劑組合物P中的紫外線活化離子聚合起始劑(D)的含量，相對於離子聚合性成分(B)100質量份，作為下限值，以0.5質量份以上為佳，以2質量份以上更佳，進一步以5質量份以上為佳。另一方面，作為上限值，以50質量份以下為佳，以40質量份以下為佳，進一步以30質量份以下為佳。 The content of the ultraviolet-activated ionic polymerization initiator (D) in the adhesive composition P is preferably 0.5 parts by mass or more, preferably 2 More preferably, it is at least 5 parts by mass, and more preferably at least 5 parts by mass. On the other hand, the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

(1-5)各種添加劑 (1-5) Various additives

在黏接著劑組合物P，可根據所期望，添加各種添加劑，例如，矽烷偶合劑、紫外線吸收劑、抗靜電劑、黏著賦予劑、抗氧化劑、光安定劑、軟化劑、填充劑、折射率調整劑等。再者，後述的聚合溶劑及稀釋溶劑，不包含在構成黏接著劑組合物P的添加劑。 In the adhesive composition P, various additives such as silane coupling agents, ultraviolet absorbers, antistatic agents, adhesion imparting agents, antioxidants, light stabilizers, softeners, fillers, and refractive index can be added as desired. adjuster, etc. In addition, the polymerization solvent and dilution solvent mentioned later are not included in the additive which comprises the adhesive composition P.

在此，黏接著劑組合物P含有矽烷偶合劑，則可提升所得黏接著劑，與玻璃構件及塑膠板的密著性。藉此，所得的黏接著劑，成為在高溫高濕條件下的段差追隨性及耐起泡性更優良之物。 Here, when the adhesive composition P contains a silane coupling agent, the adhesiveness of the obtained adhesive with the glass member and the plastic plate can be improved. Thereby, the obtained adhesive becomes more excellent in step followability and foaming resistance under high temperature and high humidity conditions.

作為矽烷偶合劑，係在分子內至少具有1個烷氧基矽基的有機矽化合物，以與上述各成分的相溶性佳，具有光穿透性之物為佳。 As the silane coupling agent, it is an organosilicon compound having at least one alkoxysilyl group in the molecule, and it is preferably one having good compatibility with the above-mentioned components and having light transmittance.

該矽烷偶合劑，可列舉例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧丙基三甲氧基矽烷等的含聚合性不飽和基矽化合物、3-縮水甘油氧丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等的具有環氧結構的矽化合物、3-氫硫基丙基三甲氧基矽烷、3-氫硫基丙基三乙 氧基矽烷、3-氫硫基丙基二甲氧基甲基矽烷等的含氫硫基矽化合物、3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等的含胺基矽化合物、3-氯丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷、或該等的至少1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的含烷基矽化合物的縮合物等。該等，能夠1種單獨使用，亦可組合2種以上使用。 Examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, and 3-glycidoxysilane. Silicon compounds having epoxy structures such as propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane, 3-hydrogen Hydrogen-containing thiosilicon compounds such as thiopropyltriethoxysilane, 3-hydrothiopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, N-(2-amine aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and other amino-containing silicon compounds, 3- Chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, or at least 1 of these, together with methyltriethoxysilane, ethyltriethoxysilane, methyltriethoxysilane Condensates of alkyl silicon compounds such as oxysilane, ethyltrimethoxysilane, etc. These can be used alone or in combination of two or more.

黏接著劑組合物P，含有矽烷偶合劑時，其含量相對於自由基聚合性成分(A)及離子聚合性成分(B)(聚合性成分)的合計100質量份，以0.01質量份以上為佳，以0.05質量份以上特別佳，進一步以0.1質量份以上為佳。此外，該含量，相對於聚合性成分的合計100質量份，以1質量份以下為佳，以0.5質量份以下特別佳，進一步以0.3質量份以下為佳。 When the adhesive composition P contains a silane coupling agent, its content is 0.01 part by mass or more relative to 100 parts by mass of the total of the radically polymerizable component (A) and the ionically polymerizable component (B) (polymerizable component). Preferably, it is especially preferable that it is 0.05 mass part or more, and it is more preferable that it is 0.1 mass part or more. In addition, the content is preferably 1 part by mass or less, particularly preferably 0.5 part by mass or less, and more preferably 0.3 part by mass or less, relative to 100 parts by mass of the total of the polymerizable components.

(2)黏接著劑組合物的製造 (2) Manufacture of adhesive composition

黏接著劑組合物P，可藉由混合自由基聚合性成分(A)、離子聚合性成分(B)、可見光活化自由基聚合起始劑(C)、紫外線活化離子聚合起始劑(D)的同時，根據所期望加入添加劑而製造。 The adhesive composition P can be prepared by mixing the radical polymerizable component (A), the ion polymerizable component (B), the visible light activated radical polymerization initiator (C), and the ultraviolet activated ionic polymerization initiator (D) At the same time, it is manufactured by adding additives as desired.

在此，作為自由基聚合性成分(A)，使用含(甲基)丙烯醯基單體或含乙烯基單體時，由於此等分子量相對較小、黏度低，故能夠不需要溶劑而混合各成分。該等的黏接著劑組合物P，可作為無溶劑型黏接著劑組合物，直接作為塗佈液使用。 Here, when a (meth)acryloyl group-containing monomer or a vinyl group-containing monomer is used as the radically polymerizable component (A), since the molecular weight is relatively small and the viscosity is low, it can be mixed without a solvent. ingredients. These adhesive compositions P can be used directly as a coating liquid as a solvent-free adhesive composition.

[黏接著劑] [adhesive]

關於本實施形態的黏接著劑，係對黏接著劑組合物P(通常係黏接著劑組合物P的塗膜)，照射可見光，使自由基聚合性成分(A)聚合而得，為半硬化狀態。由結構來看，關於本實施形態的黏接著劑，來自自由基聚合性成分(A)聚合物，含有丙烯酸系聚合物、離子聚合性成分(B)、及可藉由紫外線活化的紫外線活化離子聚合起始劑(D)為佳。再者，關於本實施形態的黏接著劑，在上述成分以外，亦可含有可見光活化自由基聚合起始劑(C)的殘渣。 The adhesive of the present embodiment is obtained by irradiating the adhesive composition P (usually a coating film of the adhesive composition P) with visible light to polymerize the radically polymerizable component (A), and is semi-cured condition. In terms of structure, the adhesive of the present embodiment is derived from the radically polymerizable component (A) polymer, and contains an acrylic polymer, an ionomerizable component (B), and an ultraviolet-activatable ultraviolet-activatable ion. The polymerization initiator (D) is preferred. In addition, the adhesive agent of this embodiment may contain the residue of a visible light-activated radical polymerization initiator (C) in addition to the said component.

可見光活化自由基聚合起始劑(C)的殘渣，係包含在黏接著劑組合物P中的可見光活化自由基聚合起始劑(C)，經由可見光照射仍未裂解而殘存之物。因此，其含量並不多，通常，在黏接著劑中為0.00001質量%以上，0.1質量%以下，以0.0001質量%以上，0.01質量%以下為佳。 The residue of the visible-light-activated radical polymerization initiator (C) is what remains of the visible-light-activated radical polymerization initiator (C) contained in the adhesive composition P without being cleaved by visible light irradiation. Therefore, the content thereof is not much, and is usually 0.00001 mass % or more and 0.1 mass % or less, preferably 0.0001 mass % or more and 0.01 mass % or less in the adhesive.

可見光的照射，可藉由例如，經由可選擇波長的光學濾光片，照射高壓水銀燈、Fusion H燈、氙氣燈等的光線進行為佳。此時，藉由可選擇波長的光學濾光片，將光線的波長限制在380nm以上，以390nm以上為佳。 Irradiation of visible light can be preferably performed by, for example, irradiating light from a high-pressure mercury lamp, a Fusion H lamp, a xenon lamp, or the like through an optical filter with a selectable wavelength. At this time, the wavelength of the light is limited to 380 nm or more, preferably 390 nm or more, by means of a wavelength-selectable optical filter.

上述的可選擇波長的光學濾光片，可列舉例如短波長截止濾光片、帶通濾光片、水銀曝光用濾光片、或在390nm以下具有吸收波長的光學基材、例如，三乙醯纖維素薄膜、聚奈二甲酸乙二酯薄膜、施加可吸收390nm以下的吸收波長的表面處理塗層的透明樹脂薄膜等。 The above-mentioned wavelength-selectable optical filters include, for example, short-wavelength cut-off filters, bandpass filters, filters for mercury exposure, or optical substrates having absorption wavelengths below 390 nm, for example, triethyl ether Acetyl cellulose film, polyethylene naphthalate film, transparent resin film with a surface treatment coating that can absorb absorption wavelengths below 390 nm, etc.

可見光的照射量，以照度5mW/cm2以上為佳，以 15mW/cm2以上特別佳，進一步以30mW/cm2以上為佳。此外，照度，以300mW/cm2以下為佳，以250mW/cm2以下特別佳，進一步以200mW/cm2以下為佳。光量，以200mJ/cm2以上為佳，以300mJ/cm2以上特別佳，進一步以500mJ/cm2以上為佳。此外，光量，以5000mJ/cm2以下為佳，以4000mJ/cm2以下特別佳，進一步以2000mJ/cm2以下為佳。 The irradiation amount of visible light is preferably 5 mW/cm 2 or more, particularly preferably 15 mW/cm 2 or more, and more preferably 30 mW/cm 2 or more. In addition, the illuminance is preferably 300 mW/cm 2 or less, particularly preferably 250 mW/cm 2 or less, and more preferably 200 mW/cm 2 or less. The amount of light is preferably 200 mJ/cm 2 or more, particularly preferably 300 mJ/cm 2 or more, and more preferably 500 mJ/cm 2 or more. Further, the amount of light is preferably 5000 mJ/cm 2 or less, particularly preferably 4000 mJ/cm 2 or less, and more preferably 2000 mJ/cm 2 or less.

關於本實施形態的黏接著劑，由於係對含有自由基聚合性成分(A)、離子聚合性成分(B)、可見光活化自由基聚合起始劑(C)、及紫外線活化離子聚合起始劑(D)的黏接著劑組合物P照射可見光，故不會使離子聚合性成分(B)聚合，而只讓自由基聚合性成分(A)進行自由基聚合，藉此，可成為半硬化狀態。如此的半硬化狀態的黏接著劑，貼附在具有段差的顯示體構成構件時，可容易追隨段差，可抑制在段差附近發生空隙、浮起等，初期的段差追隨性優良。 The adhesive of the present embodiment contains a radical polymerizable component (A), an ion polymerizable component (B), a visible light-activated radical polymerization initiator (C), and an ultraviolet-activated ion polymerization initiator. The adhesive composition P of (D) is irradiated with visible light, so that the ionically polymerizable component (B) is not polymerized, but only the radically polymerizable component (A) is radically polymerized, whereby a semi-hardened state can be obtained. . Such an adhesive in a semi-hardened state can easily follow the level difference when it is attached to a display component having a level difference, and can suppress generation of voids, floating, etc. near the level difference, and is excellent in initial level difference followability.

關於本實施形態的黏接著劑的凝膠分率，以30%以上為佳，以35%以上特別佳，進一步以40%以上為佳。此外，該凝膠分率，以70%以下為佳，以66%以下特別佳，進一步以63%以下為佳。藉由使黏接著劑的凝膠分率在上述範圍，可使初期的段差追隨性更優良。在此，黏接著劑的凝膠分率的測定方法，係如後述的試驗例所示。 The gel fraction of the adhesive of the present embodiment is preferably at least 30%, particularly preferably at least 35%, and more preferably at least 40%. In addition, the gel fraction is preferably 70% or less, particularly preferably 66% or less, and more preferably 63% or less. By making the gel fraction of the adhesive within the above range, the initial step followability can be made more excellent. Here, the method for measuring the gel fraction of the adhesive is as shown in the test example described later.

[黏接著板片] [Attach the board]

本實施形態的黏接著板片，係具有由前述黏接著劑所形成的黏接著劑層者，以具有用於將一顯示體構成構件與其他顯示體構成構件接著的黏接著劑層，該黏接著劑層，係由前述黏接著劑所形成為佳。 The adhesive sheet of the present embodiment has an adhesive layer formed of the above-mentioned adhesive, so as to have an adhesive layer for adhering one display component member to another display component member, and the adhesive layer is The adhesive layer is preferably formed by the aforementioned adhesive.

將關於本實施形態的黏接著板片的一例的具體構成顯示於圖1。如圖1所示，關於一實施形態的黏接著板片1，係由2片剝離板片12a、12b，以及以接於該等2片剝離板片12a、12b的剝離面的方式被該2片的剝離板片12a、12b夾持的黏接著劑層11所構成。再者，在本說明書的剝離板片的剝離面，係指在剝離板片具有剝離性的面，包含施以剝離處理的面及即使沒有施以剝離處理亦顯示剝離性的面的任一種。 A specific configuration of an example of the adhesive sheet of the present embodiment is shown in FIG. 1 . As shown in FIG. 1, the adhesive sheet 1 of one embodiment is composed of two peeling sheets 12a, 12b, and the two peeling sheets 12a, 12b are bonded to the peeling surfaces of the two peeling sheets 12a, 12b It is constituted by the adhesive layer 11 sandwiched between the release sheets 12a and 12b of the sheet. In addition, the peeling surface of the peeling sheet in this specification refers to the surface which has peelability in a peeling sheet, and includes any of a peeling-treated surface and a surface showing peeling property even without a peeling treatment.

(1)黏接著劑層 (1) Adhesive layer

黏接著劑層11，係由上述的黏接著劑構成，即，係由對黏接著劑組合物P照射可見光、半硬化而成的黏接著劑所構成。 The adhesive layer 11 is formed of the above-mentioned adhesive, that is, formed of an adhesive obtained by irradiating the adhesive composition P with visible light and semi-hardening.

關於本實施形態的黏接著板片1的黏接著劑層11的厚度(遵照JIS K7130：1999測定之值)，以10μm以上為佳，以25μm以上更佳，以50μm以上特別佳，進一步以75μm以上為佳。此外，該厚度以1000μm以下為佳，以400μm以下更佳，以300μm以下特別佳。再者，黏接著劑層11，能夠以單層形成，亦可層積複數層而形成。 The thickness of the adhesive layer 11 of the adhesive sheet 1 of the present embodiment (value measured in accordance with JIS K7130:1999) is preferably 10 μm or more, more preferably 25 μm or more, particularly preferably 50 μm or more, and further preferably 75 μm The above is better. Further, the thickness is preferably 1000 μm or less, more preferably 400 μm or less, and particularly preferably 300 μm or less. In addition, the adhesive layer 11 may be formed as a single layer, or may be formed by laminating a plurality of layers.

藉由使黏接著劑層11的厚度在10μm以上，可容易地發揮所期望的黏著力。此外，黏接著劑層11的厚度在1000μm以下，可使加工性良好。 By setting the thickness of the adhesive layer 11 to be 10 μm or more, a desired adhesive force can be easily exhibited. Moreover, the thickness of the adhesive bond layer 11 is 1000 micrometers or less, and can make processability favorable.

再者，前述黏接著劑組合物P為無溶劑型黏接著劑組合物時，由於無須塗層後的溶劑的揮發步驟，可容易形成厚膜(以厚度100μm以上為佳)的黏接著劑層11。 Furthermore, when the aforementioned adhesive composition P is a solvent-free adhesive composition, since the volatilization step of the solvent after coating is not required, an adhesive layer with a thick film (preferably a thickness of 100 μm or more) can be easily formed. 11.

(2)剝離板片 (2) Peel off the sheet

剝離板片12a、12b，係保護黏接著劑層11直到使用黏接著板片1時，在使用黏接著板片1(黏接著劑層11)時會被剝離。在關於本實施形態的黏接著板片1，剝離板片12a、12b的一方或是兩方並非必要之物。 The peeling sheets 12a and 12b protect the adhesive layer 11 until the adhesive sheet 1 is used, and are peeled off when the adhesive sheet 1 (the adhesive layer 11) is used. In the adhesive sheet 1 of the present embodiment, one or both of the peeling sheets 12a and 12b is not necessary.

作為剝離板片12a、12b，可使用例如聚乙烯薄膜、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、聚萘二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚氨酯薄膜、乙烯-醋酸乙烯酯薄膜、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。此外，可使用該等的架橋薄膜。進一步，亦可為該等的層積薄膜。 As the release sheets 12a, 12b, for example, polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polybutylene films, Ethylene phthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate film, ionomer resin film, ethylene·(meth)acrylic acid Copolymer film, ethylene·(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, these bridging films can be used. Furthermore, these laminated films may be used.

上述剝離板片12a，12b的剝離面(特別是接於黏接著劑層11的面)以施以剝離處理為佳。用於剝離處理的剝離劑，可列舉例如，醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。再者，剝離板片12a、12b之中，使一方的剝離板片作成剝離力大的重剝離型剝離板片，使另一方的剝離板片作成剝離力小的輕剝離型剝離板片為佳 It is preferable that the peeling process is given to the peeling surface (especially the surface which is attached to the adhesive bond layer 11) of the said peeling sheet 12a, 12b. The release agent used for the release treatment includes, for example, alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. In addition, among the peeling sheets 12a and 12b, it is preferable to make one peeling sheet a heavy peeling type peeling sheet with a large peeling force, and make the other peeling sheet a light peeling type peeling sheet with a small peeling force.

關於剝離板片12a、12b的厚度，並無特別限制，通常為20μm以上，150μm以下。 Although there is no restriction|limiting in particular about the thickness of the peeling sheet pieces 12a, 12b, Usually, it is 20 micrometers or more and 150 micrometers or less.

(3)物性(全光線穿透率) (3) Physical properties (total light transmittance)

關於本實施形態的黏接著板片1的黏接著劑層11的全光線穿透率，以90%以上為佳，以95%以上特別佳，進一步以98%以上為佳。全光線穿透率在90%以上，則透明性非常地高，適於作為光學用途。再者，在本說明書的全光線穿透率，係遵照JIS K7361-1：1997測定之值。 The total light transmittance of the adhesive layer 11 of the adhesive sheet 1 of the present embodiment is preferably 90% or more, particularly preferably 95% or more, and more preferably 98% or more. When the total light transmittance is more than 90%, the transparency is very high, and it is suitable for optical use. In addition, the total light transmittance in this specification is a value measured according to JIS K7361-1:1997.

(4)黏接著板片的製造 (4) Manufacture of bonded sheets

作為黏接著板片1的一製造例，係在一方的剝離板片12a(或12b)的剝離面，塗佈上述黏接著劑組合物P形成塗佈層，在該塗佈層，疊合另一方的剝離板片12b(或12a)的剝離面之後，對塗佈層進行可見光照射(及加熱處理)，使黏接著劑組合物P半硬化，形成黏接著劑層11。 As an example of production of the adhesive sheet 1, the above-mentioned adhesive composition P is applied to the peeling surface of one release sheet 12a (or 12b) to form a coating layer, and the other is laminated on the coating layer. After peeling off the peeling surface of one sheet piece 12b (or 12a ), the coating layer is irradiated with visible light (and heat treatment) to semi-harden the adhesive composition P to form the adhesive layer 11 .

作為黏接著板片1的其他的製造例，在一方的剝離板片12a(或12b)的剝離面，塗佈上述黏接著劑組合物P，進行可見光照射(及加熱處理)，使黏接著劑組合物P半硬化，形成黏接著劑層11之後，使黏接著劑層11，與另一方的剝離板片12b(或12a)的剝離面疊合。 As another production example of the adhesive sheet 1, the above-mentioned adhesive composition P is applied to the peeling surface of one peeling sheet 12a (or 12b), and the adhesive composition P is irradiated with visible light (and heat-treated) to make the adhesive After the composition P is semi-hardened and the adhesive layer 11 is formed, the adhesive layer 11 is superimposed on the peeling surface of the other peeling sheet 12b (or 12a).

塗佈上述黏接著劑組合物P的塗佈液的方法，可利用例如，棒塗佈法、刮刀塗佈法、輥塗法、刮板塗佈法、模具塗佈法、凹版塗佈法等。 As a method for applying the coating liquid of the above-mentioned adhesive composition P, for example, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, etc. can be used. .

在以如上所述地製造的關於本實施形態的黏接著板片1，由於接著劑層11為半硬化狀態，故即使黏貼於具有段差的顯示體構成構件時，容易追隨段差，而初期段差追隨性優良。 In the adhesive sheet 1 of the present embodiment manufactured as described above, since the adhesive layer 11 is in a semi-hardened state, it is easy to follow the level difference even when it is adhered to a display component having a level difference, and the initial level difference follows Excellent sex.

[顯示體] [display body]

如圖2所示，關於本實施形態的顯示體2，其具備由：至少在貼合側的面具有段差的第1顯示體構成構件21(一顯示體 構成構件)；第2顯示體構成構件22(其他顯示體構成構件)；及位於該等之間，將第1顯示體構成構件21及第2顯示體構成構件22互相接著的黏接著劑層11所構成。關於本實施形態的顯示體2，第1顯示體構成構件21，在黏接著劑層11側的面具有段差，具體而言，具有以印刷層3的段差。 As shown in FIG. 2 , the display body 2 of the present embodiment includes a first display body constituting member 21 (a display body) having a level difference at least on the surface on the bonding side. component); the second display component 22 (other display component); and the adhesive layer 11 between the first display component 21 and the second display component 22 that adheres to each other constituted. Regarding the display body 2 of the present embodiment, the first display body constituent member 21 has a level difference on the surface on the adhesive layer 11 side, specifically, a level difference with the print layer 3 .

在上述顯示體2的硬化後黏接著劑層11'，係對前述黏接著板片1的黏接著劑層11，照射紫外線，使離子聚合性成分(B)聚合而得，為硬化狀態。該硬化後黏接著劑層11'，由構造來看，含有來自自由基聚合性成分(A)的聚合物、與來自離子聚合性成分(B)的聚合物。在硬化後黏接著劑層11'，可推測來自離子聚合性成分(B)的聚合物，纏繞在來自自由基聚合性成分(A)的聚合物。再者，硬化後黏接著劑層11'，亦可含有紫外線活化離子聚合起始劑(D)的殘渣，進一步亦可含有可見光活化自由基聚合起始劑(C)的殘渣。 The cured adhesive layer 11 ′ of the display body 2 is in a cured state by irradiating the adhesive layer 11 of the adhesive sheet 1 with ultraviolet rays to polymerize the ionomerizable component (B). This post-curing adhesive layer 11 ′ contains a polymer derived from the radically polymerizable component (A) and a polymer derived from the ionically polymerizable component (B) in terms of structure. It is presumed that the polymer derived from the ionically polymerizable component (B) is entangled with the polymer derived from the radically polymerizable component (A) after the adhesive layer 11 ′ is cured. In addition, the adhesive layer 11 ' after hardening may contain the residue of an ultraviolet-ray activated ion polymerization initiator (D), and may further contain the residue of a visible light-activated radical polymerization initiator (C).

紫外線活化離子聚合起始劑(D)的殘渣，係包含在黏接著劑層11的紫外線活化離子聚合起始劑(D)，在經由紫外線照射仍未裂解而殘存之物。因此，其含量並不多，在硬化後黏接著劑中為0.00001質量%以上，0.1質量%以下，以0.0001質量%以上，0.01質量%以下為佳。再者，可見光活化自由基聚合起始劑(C)的殘渣，則與包含於黏接著劑層11的量相同或為其以下。 The residue of the ultraviolet-activated ionic polymerization initiator (D) is what remains of the ultraviolet-activated ionic polymerization initiator (D) contained in the adhesive layer 11 without being cracked by ultraviolet irradiation. Therefore, the content thereof is not much, and is preferably 0.00001 mass % or more and 0.1 mass % or less, preferably 0.0001 mass % or more and 0.01 mass % or less in the adhesive after curing. In addition, the residue of the visible light-activated radical polymerization initiator (C) is the same as or less than the amount contained in the adhesive layer 11 .

顯示體2，可列舉例如，液晶(LCD)顯示器、發光二極體(LED)顯示器、有機電致發光(有機EL)顯示器、電子紙等，亦可為觸控面板。此外，顯示體2，亦可為構成該等的一部分的構件。 The display body 2 includes, for example, a liquid crystal (LCD) display, a light emitting diode (LED) display, an organic electroluminescence (organic EL) display, electronic paper, and the like, and may be a touch panel. In addition, the display body 2 may be a member constituting a part of these.

第1顯示體構成構件21，除了玻璃板、塑膠板等之外，以包含該等的層積體等所形成的保護面板為佳。此時，印刷層3，係在第1顯示體構成構件21的黏接著劑層11側，一般形成為畫框狀。 In addition to a glass plate, a plastic plate, and the like, the first display body constituent member 21 is preferably a protective panel formed of a laminate or the like including these. At this time, the printed layer 3 is formed on the adhesive layer 11 side of the first display body constituent member 21, and is generally formed in a picture frame shape.

上述玻璃板，並無特別限定，可列舉例如，化學強化玻璃、無鹼玻璃、石英玻璃、鈉鈣玻璃、含有鋇鍶的玻璃、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，並無特別限定，通常為0.1mm以上，以0.2mm以上為佳。此外，該厚度通常為5mm以下，以2mm以下為佳。 The above-mentioned glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, glass containing barium and strontium, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass Acid glass, etc. The thickness of the glass plate is not particularly limited, but is usually 0.1 mm or more, preferably 0.2 mm or more. In addition, the thickness is usually 5 mm or less, preferably 2 mm or less.

上述塑膠板，並無特別限定，可舉例如丙烯酸板、聚碳酸酯板等。塑膠板的厚度，並無特別限定，通常為0.2mm以上，以0.4mm以上為佳。此外該厚度，通常為5mm以下，以3mm以下為佳。 The said plastic board is not specifically limited, For example, an acrylic board, a polycarbonate board, etc. are mentioned. The thickness of the plastic plate is not particularly limited, but is usually 0.2 mm or more, preferably 0.4 mm or more. In addition, the thickness is usually 5 mm or less, preferably 3 mm or less.

再者，在上述玻璃板或塑膠板的一面或雙面，亦可設置各種功能層(透明導電膜、金屬層、二氧化矽層、硬塗層、防眩層等)，亦可層積光學構件。此外，透明導電膜及金屬層，亦可圖案化。 Furthermore, various functional layers (transparent conductive films, metal layers, silicon dioxide layers, hard coat layers, anti-glare layers, etc.) can be provided on one side or both sides of the above-mentioned glass plate or plastic plate, and optical layers can also be laminated. member. In addition, the transparent conductive film and the metal layer can also be patterned.

第2顯示體構成構件22，以應貼附於第1顯示體構成構件的光學構件、顯示體模組(例如，液晶(LCD)模組、發光二極體(LED)模組、有機電致發光(有機EL)模組等)、作為顯示體模組的一部分的光學構件、或含有顯示體模組的層積體為佳。 The second display component 22 is an optical component that should be attached to the first display component, a display module (for example, a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electro A light-emitting (organic EL) module, etc.), an optical member as a part of a display module, or a laminate including a display module are preferred.

上述光學構件，可列舉例如，防飛散薄膜、偏光 板(偏光薄膜)、偏光片、相位差板(相位差薄膜)、視野角補償薄膜、亮度提升薄膜、對比提升薄膜、液晶高分子薄膜、擴散薄膜、半穿透反射薄膜、透明導電性薄膜等。防飛散薄膜，可例示在基材薄膜一面形成硬塗層而成的硬塗層薄膜等。 The above-mentioned optical members include, for example, anti-scattering films, polarizers (polarizing films), polarizers, retardation films (retardation films), viewing angle compensation films, brightness enhancement films, contrast enhancement films, liquid crystal polymer films, diffusers Film, transflective film, transparent conductive film, etc. As the anti-scattering film, a hard coat film formed by forming a hard coat layer on one side of a base film can be exemplified.

構成印刷層3的材料，並無特別限定，可使用印刷用的習知的材料。印刷層3的厚度，即段差的高度的下限值，以3μm以上為佳，以5μm以上更佳，以7μm以上特別佳，以10μm以上最佳。藉由使下限值在上述以上，可充分確保由視認者側看不到電性配線等的隱蔽性。此外，上限值，以60μm以下為佳，以50μm以下更佳，以40μm以下特別佳，進一步以20μm以下為佳。藉由使上限值在上述以下，可防止硬化後黏著劑層11'對該印刷層3的段差追隨性的惡化。 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 lower limit of the height of the step is preferably 3 μm or more, more preferably 5 μm or more, particularly preferably 7 μm or more, and most preferably 10 μm or more. By making the lower limit value more than the above, it is possible to sufficiently ensure the concealment of the electrical wiring and the like from the viewer's side. Further, the upper limit is preferably 60 μm or less, more preferably 50 μm or less, particularly preferably 40 μm or less, and more preferably 20 μm or less. By setting the upper limit to the above-mentioned or less, the adhesive layer 11 ′ after hardening can prevent the deterioration of the step followability of the printed layer 3 .

製造上述顯示體2，作為一例，將黏接著板片1的一方的剝離板片12a剝離，將黏接著板片1的露出的黏接著劑層11，貼合在第1顯示體構成構件21的存在印刷層3側的面。此時，黏接著劑層11，由於初期的段差追隨性優良，可抑制在印刷層3的段差附近發生空隙或浮起。 To manufacture the above-mentioned display body 2, as an example, one peeling sheet 12a of the adhesive sheet 1 is peeled off, and the exposed adhesive layer 11 of the adhesive sheet 1 is bonded to the first display body constituent member 21. There is a surface on the side of the printed layer 3 . At this time, since the adhesive layer 11 is excellent in the followability of the step in the initial stage, the generation of voids or floating in the vicinity of the step of the printing layer 3 can be suppressed.

接著，由黏接著板片1的黏接著劑層11剝離另一面的剝離板片12b，使黏接著板片1的露出的黏接著劑層11與第2顯示體構成構件22貼合得到層積體。此外，作為其他的例，亦可交換第1顯示體構成構件21及第2顯示體構成構件22的貼合順序。 Next, the peeling sheet 12b on the other side is peeled off from the adhesive layer 11 of the adhesive sheet 1, and the exposed adhesive layer 11 of the adhesive sheet 1 is bonded to the second display body constituent member 22 to obtain a laminate. body. Moreover, as another example, you may exchange the bonding order of the 1st display body structure member 21 and the 2nd display body structure member 22.

之後，對上述層積體中的黏接著劑層11照射紫外線。藉此，紫外線活化離子聚合起始劑(D)進行活化而產生離 子，藉由該離子使黏接著劑層11中的離子聚合性成分(B)聚合。如此地黏接著劑層11硬化，成為硬化後黏接著劑層11'。對黏接著劑層11的紫外線照射，通常，係隔著第1顯示體構成構件21或第2顯示體構成構件22的任意一方進行，較佳的是隔著保護面板的第1顯示體構成構件21進行。 Then, ultraviolet rays are irradiated to the adhesive bond layer 11 in the said laminated body. Thereby, the ultraviolet-activated ion polymerization initiator (D) is activated to generate ions, and the ion polymerizable component (B) in the adhesive layer 11 is polymerized by the ions. In this way, the adhesive layer 11 is cured, and the cured adhesive layer 11 ′ is obtained. The ultraviolet irradiation to the adhesive layer 11 is usually carried out through either the first display body constituting member 21 or the second display body constituting member 22, preferably through the first display body constituting member of the protective panel 21 to proceed.

紫外線的照射，能夠藉由高壓水銀燈、Fusion H燈、氙氣燈等進行，紫外線的照射量，以照度20mW/cm2以上為佳，以50mW/cm2以上特別佳，進一步以100mW/cm2以上為佳。此外，照度，以500mW/cm2以下為佳，以300mW/cm2以下特別佳，進一步以200mW/cm2以下為佳。光量，以500mJ/cm2以上為佳，以700mJ/cm2以上特別佳，進一步以1000mJ/cm2以上為佳。此外，光量，以10000mJ/cm2以下為佳，以8000mJ/cm2以下特別佳，進一步以5000mJ/cm2以下為佳。 The irradiation of ultraviolet rays can be carried out by high pressure mercury lamps, Fusion H lamps, xenon lamps, etc. The irradiation amount of ultraviolet rays is preferably 20mW/ cm2 or more, particularly preferably 50mW/ cm2 or more, and further 100mW/ cm2 or more. better. In addition, the illuminance is preferably 500 mW/cm 2 or less, particularly preferably 300 mW/cm 2 or less, and more preferably 200 mW/cm 2 or less. The amount of light is preferably 500 mJ/cm 2 or more, particularly preferably 700 mJ/cm 2 or more, and more preferably 1000 mJ/cm 2 or more. Further, the amount of light is preferably 10,000 mJ/cm 2 or less, particularly preferably 8,000 mJ/cm 2 or less, and more preferably 5,000 mJ/cm 2 or less.

構成硬化後黏接著劑層11'的硬化後黏接著劑的凝膠分率，以60%以上為佳，以65%以上特別佳，進一步以67%以上為佳。此外，該凝膠分率，以99%以下為佳，以85%以下特別佳，進一步以80%以下為佳。藉由使硬化後黏接著劑的上述凝膠分率，變得較前述黏接著劑(紫外線照射前)的凝膠分率高，藉此，可辨識離子聚合性成分(B)進行聚合。藉由使凝膠分率在上述範圍，可使高溫高濕條件下的段差追隨性及耐起泡性更優良。在此，硬化後黏接著劑的凝膠分率的測定方法，係如後述的試驗例所示。 The gel fraction of the cured adhesive constituting the cured adhesive layer 11 ′ is preferably 60% or more, particularly preferably 65% or more, and more preferably 67% or more. In addition, the gel fraction is preferably 99% or less, particularly preferably 85% or less, and more preferably 80% or less. By making the said gel fraction of the adhesive agent after hardening higher than the gel fraction of the said adhesive agent (before ultraviolet irradiation), it is possible to recognize that the ionomerizable component (B) is polymerized. By making the gel fraction in the above-mentioned range, the step followability and foaming resistance under high temperature and high humidity conditions can be made more excellent. Here, the method for measuring the gel fraction of the adhesive after curing is as shown in the test example described later.

硬化後黏接著劑層11'的霧度值，以2.0%以下為佳，以1.5%以下特別佳，進一步以1.0%以下為佳。硬化後黏 接著劑層11'的霧度值在1.0%以下，則透明性高，適合用於光學用途(顯示體用)。再者，在本說明書的霧度值，係遵照JIS K7136：2000測定之值。 The haze value of the adhesive layer 11 ′ after curing is preferably 2.0% or less, particularly preferably 1.5% or less, and more preferably 1.0% or less. When the haze value of the adhesive layer 11 ′ after curing is 1.0% or less, the transparency is high, and it is suitable for use in optical applications (for displays). In addition, the haze value in this specification is the value measured according to JISK7136:2000.

在以上的顯示體2，由於硬化後黏接著劑層11'顯示很高的凝聚力及強固的接著性，故在高溫高濕條件下的段差追隨性及耐起泡性優良。因此，即使將顯示體2，放置在高溫高濕條件下(例如，85℃，85%RH，72小時)，也可抑制在段差附近發生氣泡、浮起、剝落的等。此外，顯示體2放置在高溫高濕條件下(例如，85℃、85%RH、72小時)，即使由塑膠板等形成的顯示體構成構件發生脫氣時，可抑制在硬化後黏接著劑層11'與顯示體構成構件21、22的界面發生氣泡、浮起、剝落的等的起泡。 In the above-mentioned display body 2, since the adhesive layer 11 ' shows high cohesion force and strong adhesiveness after curing, it is excellent in step followability and foaming resistance under high temperature and high humidity conditions. Therefore, even if the display body 2 is placed under high temperature and high humidity conditions (eg, 85° C., 85% RH, 72 hours), generation of bubbles, floating, peeling, etc. near the level difference can be suppressed. In addition, when the display body 2 is placed under high temperature and high humidity conditions (for example, 85° C., 85% RH, 72 hours), even if the display body constituent members formed of plastic plates or the like are degassed, the adhesive agent can be suppressed from curing after hardening. At the interface between the layer 11 ′ and the display body constituent members 21 and 22 , blisters such as bubbles, floating, and peeling occur.

在此，在上述顯示體2的硬化後黏接著劑層11'，使用含有(甲基)丙烯酸羥基烷基酯作為自由基聚合性成分(A)的黏接著劑組合物P所形成時，對該顯示體2施以高溫高濕條件之後，可抑制恢復到常溫時的白化，耐濕熱白化性優良。 Here, when the adhesive layer 11 ′ after curing of the above-mentioned display body 2 is formed using the adhesive composition P containing hydroxyalkyl (meth)acrylate as the radically polymerizable component (A), the After this display 2 is subjected to high temperature and high humidity conditions, whitening at the time of returning to normal temperature can be suppressed, and it is excellent in wet-heat whitening resistance.

關於硬化後黏接著劑層11'的優良的耐濕熱白化性，可如下進行評估。例如，將黏接著劑層11的兩面，以2片透明導電膜薄膜(在一面設有由錫摻雜氧化銦(ITO)形成的透明導電膜的聚對苯二甲酸乙二醇酯薄膜；透明導電膜在黏接著劑層側)包夾，隔著該透明導電膜薄膜，由至少一側照射紫外線得到層積體。將該層積體，在85℃、85%RH的條件(濕熱條件)下保管120小時，之後取出到23℃，50%RH的常溫常濕下。計算由上述層積體的濕熱條件後的霧度值(%)(遵照JIS K7136：2000測定的值。以下相同)扣除濕熱條件前的霧度值(%)之值(濕熱條件之後的霧度值的上升)。 Regarding the excellent wet-heat whitening resistance of the adhesive layer 11 ′ after curing, it can be evaluated as follows. For example, two sides of the adhesive layer 11 are made of two transparent conductive films (polyethylene terephthalate films with a transparent conductive film formed of tin-doped indium oxide (ITO) on one side; transparent The conductive film is sandwiched on the adhesive layer side), and the transparent conductive film is irradiated with ultraviolet rays from at least one side to obtain a laminate. The laminate was stored for 120 hours under the conditions of 85°C and 85% RH (moist heat conditions), and then taken out at 23°C and 50% RH at normal temperature and normal humidity. The value obtained by deducting the haze value (%) before the moist heat condition (the value after the moist heat condition) from the haze value (%) of the laminate after the moist heat condition (the value measured in accordance with JIS K7136:2000. The same applies hereinafter) was calculated. rise in value).

濕熱條件後的霧度值的上升，以未滿0.50點為佳，以未滿0.20點特別佳。再者，在上述評估，係以上述無鹼性玻璃，使用霧度值為約0%的為佳。此外，上述濕熱條件後的黏接著劑層的霧度值，以2.0%以下為佳，以1.5%以下特別佳，進一步以1.0%以下為佳。 The increase in the haze value after the moist heat condition is preferably less than 0.50 point, and particularly preferably less than 0.20 point. Furthermore, in the above evaluation, it is preferable to use the above-mentioned alkali-free glass with a haze value of about 0%. In addition, the haze value of the adhesive layer after the above-mentioned moist heat conditions is preferably 2.0% or less, particularly preferably 1.5% or less, and more preferably 1.0% or less.

以上所說明的實施形態，係為容易理解本發明所記載，而並非用於限定本發明而記載。因此，揭示於上述實施形態的各要素，係包含屬於本發明的技術範圍的全部設計變更或均等物在內的主旨。 The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above-described embodiment is intended to include all design changes and equivalents that belong to the technical scope of the present invention.

例如，在黏接著板片1的剝離板片12a、12b的任何一方或雙方可省略，此外，可將剝離板片12a及/或12b以層積所期望的光學構件取代。此外，第1顯示體構成構件21，可為具有印刷層3以外的段差。再者，不只是第1顯示體構成構件21，第2顯示體構成構件22亦可在黏著劑層11側具有段差。 For example, either one or both of the peeling sheets 12a and 12b of the adhesive sheet 1 may be omitted, and the peeling sheets 12a and/or 12b may be replaced by laminating desired optical members. In addition, the first display body constituent member 21 may have steps other than the printed layer 3 . In addition, not only the first display body constituent member 21 but also the second display body constituent member 22 may have a level difference on the adhesive layer 11 side.

[實施例] [Example]

以下，將本發明以實施例等進行更具體地說明，惟本發明的範圍並非限定於該等實施例等。 Hereinafter, the present invention will be described in more detail by way of Examples and the like, but the scope of the present invention is not limited to these Examples and the like.

[實施例1] [Example 1]

1.胺甲酸乙酯丙烯酸酯系寡聚物的調製 1. Preparation of urethane acrylate oligomers

使1莫耳重量平均分子量為9,200的聚丙二醇(PPG)，與2莫耳異佛爾酮二異氰酸酯(IPDI)、2莫耳丙烯酸2-羥基乙酯 (HEA)聚合，得到作為胺甲酸乙酯丙烯酸酯系寡聚物的重量平均分子量9,900的聚醚胺甲酸乙酯丙烯酸酯。 Polypropylene glycol (PPG) having a weight-average molecular weight of 1 mole of 9,200 was polymerized with 2 moles of isophorone diisocyanate (IPDI) and 2 moles of 2-hydroxyethyl acrylate (HEA) to obtain urethane A polyether urethane acrylate having a weight average molecular weight of 9,900 for the acrylate-based oligomer.

再者，聚丙二醇及聚醚胺甲酸乙酯丙烯酸酯的重量平均分子量，係以凝膠滲透層析儀(GPC)，以如下條件測定的標準聚苯乙烯換算值。 In addition, the weight average molecular weights of polypropylene glycol and polyether urethane acrylate are standard polystyrene conversion values measured by gel permeation chromatography (GPC) under the following conditions.

‧GPC測定裝置：TOSOH公司製，HLC-8020 ‧GPC measurement device: TOSOH Corporation, HLC-8020

‧GPC管柱：TOSOH公司製(以下，依通過順序記載) ‧GPC column: manufactured by TOSOH (below, listed in order of adoption)

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 ‧Measurement solvent: tetrahydrofuran

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

2.黏接著劑組合物的調製 2. Preparation of adhesive composition

將40質量份作為含(甲基)丙烯醯基單體的丙烯酸2-乙基己酯、20質量份丙烯酸異莰酯及10質量份丙烯酸2-羥基乙酯、30質量份以上述步驟1調製的作為胺甲酸乙酯丙烯酸酯系寡聚物的聚醚胺甲酸乙酯丙烯酸酯混合、攪拌，得到自由基聚合性成分(A)。 40 parts by mass of 2-ethylhexyl acrylate as a (meth)acryloyl group-containing monomer, 20 parts by mass of isobornyl acrylate, 10 parts by mass of 2-hydroxyethyl acrylate, and 30 parts by mass were prepared in the above-mentioned step 1 The polyether urethane acrylate as the urethane acrylate oligomer was mixed and stirred to obtain a radically polymerizable component (A).

將100質量份所得的自由基聚合性成分(A)、30質量份作為離子聚合性成分(B)的加氫雙酚A二縮水甘油醚、1質量份作為可見光活化自由基聚合起始劑(C)的2,4,6-三甲基苯甲醯基-二苯基-氧化膦、1質量份作為紫外線活化離子聚合起始劑(D)的錪‧(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽(1-)與碳酸丙烯酯以3：1的質量比混合的混合物、0.2質量份作為矽烷偶合劑的3-縮水甘油氧基丙基三甲氧基矽烷混合‧攪拌之後，靜置脫泡，得到無溶劑型黏接著劑組合物。 100 parts by mass of the obtained radically polymerizable component (A), 30 parts by mass of hydrogenated bisphenol A diglycidyl ether as the ionically polymerizable component (B), and 1 part by mass as a visible light-activated radical polymerization initiator ( C) 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, 1 part by mass of iodo·(4-methylphenyl)[ A mixture of 4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and propylene carbonate in a mass ratio of 3:1, 0.2 parts by mass of 3-glycidyl oxide as a silane coupling agent After mixing and stirring with propylpropyltrimethoxysilane, it was left to stand for defoaming to obtain a solvent-free adhesive composition.

3.黏接著板片的製造 3. Manufacture of bonded sheets

將上述步驟2所得無溶劑型黏接著劑組合物，以刮刀塗佈機塗佈在，經矽酮系剝離劑對聚對苯二甲酸乙二酯薄膜的一面進行剝離處理的重剝離型剝離板片(LINTEC公司製，產品名「SP-PET752150」)的剝離處理面上。 The solvent-free adhesive composition obtained in the above step 2 is coated with a knife coater on a heavy-peeling peeling board that is peeled off one side of the polyethylene terephthalate film by a silicone-based peeling agent. The peel-treated side of the sheet (manufactured by LINTEC, product name "SP-PET752150").

接著，將上述所得的重剝離型剝離片上的塗佈層，與經矽酮系剝離劑對聚對苯二甲酸乙二酯薄膜的一面進行剝離處理的輕剝離型剝離板片(LINTEC公司製，產品名「SP-PET382120」)，使該輕剝離型剝離板片的剝離處理面與塗佈層接觸的方式貼合。 Next, the coating layer on the heavy peeling type release sheet obtained above was combined with a light peeling type peeling sheet (manufactured by LINTEC, Inc. Product name "SP-PET382120"), and the peeling-treated surface of the light peeling-type peeling sheet was attached so that the coating layer was in contact with each other.

之後，經由重剝離型剝離板片，對塗佈層，以下述條件照射可見光(波長390nm以上)，選擇性地只讓自由基聚合性成分(A)聚合。藉此，得到由重剝離型剝離板片/黏接著劑層(厚度：100μm)/輕剝離型剝離板片的構成所形成的黏接著板片。再者，可見光的照射，係隔著可將波長390nm以上的光線、選擇性穿透的三乙醯纖維素薄膜(厚度80μm)，照射高壓水銀燈的光線進行。 Then, the coating layer was irradiated with visible light (wavelength 390 nm or more) through the heavy peeling type release sheet under the following conditions to selectively polymerize only the radically polymerizable component (A). Thereby, the adhesive sheet formed with the structure of a heavy peeling type release sheet/adhesive layer (thickness: 100 micrometers)/light peeling type release sheet was obtained. In addition, the irradiation of visible light was performed by irradiating the light of a high pressure mercury lamp through a triacetyl cellulose film (thickness 80 μm) that can selectively transmit light having a wavelength of 390 nm or more.

<可見光照射條件> <Visible light irradiation conditions>

‧光源：高壓水銀燈 ‧Light source: high pressure mercury lamp

‧光學濾光片：厚度80μm的三乙醯纖維素薄膜 ‧Optical filter: 80μm thick triacetate cellulose film

‧照度：100mW/cm2 ‧Illuminance: 100mW/cm 2

‧積算光亮：2000mJ/cm2 ‧Accumulated brightness: 2000mJ/cm 2

‧UV照度‧光量計使用EYE GRAPHICS公司製「UVPF-A1」 ‧UV illuminance and light meter use "UVPF-A1" manufactured by EYE GRAPHICS

[實施例2] [Example 2]

除了將離子聚合性成分(B)的調配量變更為5質量份以外，以與實施例1同樣地製作黏接著板片。 An adhesive sheet was produced in the same manner as in Example 1, except that the blending amount of the ionomerizable component (B) was changed to 5 parts by mass.

[比較例1] [Comparative Example 1]

除了不調配離子聚合性成分(B)及紫外線活化離子聚合起始劑(D)以外，以與實施例1同樣地製作黏接著板片。 An adhesive sheet was produced in the same manner as in Example 1, except that the ion-polymerizable component (B) and the ultraviolet-activated ion-polymerization initiator (D) were not prepared.

[比較例2] [Comparative Example 2]

取代離子聚合性成分(B)及紫外線活化離子聚合起始劑(D)，調配15質量份兩末端羥基氫化聚丁二烯(日本曹達公司製，產品名「GI-1000」)以外，以與實施例1同樣地製作黏接著板片。 In place of the ion polymerizable component (B) and the ultraviolet-activated ion polymerization initiator (D), 15 parts by mass of hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd., product name "GI-1000") was prepared to mix with In Example 1, an adhesive sheet was produced in the same manner.

[試驗例1](凝膠分率的測定) [Test Example 1] (Measurement of gel fraction)

將實施例及比較例所得的黏接著板片，裁切成80mm×80mm的尺寸，將該黏接著劑層裝在聚酯製網格(mesh)(網格尺寸200)，將其質量以精密天平秤量，扣除上述網格單獨的質量，算出只有黏接著劑的質量。此時的質量為M1。 The adhesive sheets obtained in the examples and comparative examples were cut into a size of 80 mm × 80 mm, and the adhesive layer was mounted on a polyester mesh (mesh size 200), and the quality of the adhesive sheet was measured with precision. The balance is weighed, and the mass of the above-mentioned grid alone is deducted to calculate the mass of only the adhesive. The mass at this time is M1.

接著，將裝在上述聚酯製網格的黏接著劑，以室溫下(23℃)浸漬在醋酸乙酯72小時。之後，取出黏接著劑，在溫度23℃，相對濕度50%的環境下，風乾24小時，進一步在80℃的烘箱中乾燥12小時。乾燥之後，以精密天平秤量其質量，扣除上述網格單獨的質量，算出只有黏接著劑的質量。此時的質量為M2。凝膠分率(%)，係以(M2/M1)×100表示。藉此， 導出黏接著劑的凝膠分率(可見光照射後)。將結果示於表1。 Next, the adhesive placed on the polyester mesh was immersed in ethyl acetate at room temperature (23° C.) for 72 hours. After that, the adhesive was taken out, air-dried for 24 hours in an environment with a temperature of 23° C. and a relative humidity of 50%, and further dried in an oven at 80° C. for 12 hours. After drying, the mass is weighed with a precision balance, and the mass of the above-mentioned grid alone is deducted to calculate the mass of only the adhesive. The mass at this time is M2. The gel fraction (%) is represented by (M2/M1)×100. Thereby, the gel fraction of the adhesive agent (after visible light irradiation) was derived. The results are shown in Table 1.

另一方面，對實施例及比較例所得的黏接著板片的黏接著劑層，隔著輕剝離型剝離板片，以下述條件照射紫外線，使離子聚合性成分(B)聚合，使黏接著劑層硬化作成硬化後黏接著劑層。關於該硬化後黏接著劑層的黏接著劑，與上述同樣地導出凝膠分率(紫外線照射後)。將結果示於表1。 On the other hand, the adhesive layers of the adhesive sheets obtained in the Examples and Comparative Examples were irradiated with ultraviolet rays through the light peeling type release sheets under the following conditions to polymerize the ionomerizable component (B) and make the adhesive bond The adhesive layer is hardened to form a hardened adhesive layer. About the adhesive agent of the adhesive agent layer after hardening, the gel fraction (after ultraviolet irradiation) was derived|derived similarly to the above. The results are shown in Table 1.

<紫外線照射條件> <Ultraviolet irradiation conditions>

‧光源：高壓水銀燈 ‧Light source: high pressure mercury lamp

‧照度：200mW/cm2 ‧Illuminance: 200mW/cm 2

‧積算光量：4000mJ/cm2 ‧Accumulated light quantity: 4000mJ/cm 2

‧UV照度‧光量計使用EYE GRAPHICS公司製「UVPF-A1」 ‧UV illuminance and light meter use "UVPF-A1" manufactured by EYE GRAPHICS

[試驗例2](全光線穿透率的測定) [Test Example 2] (Measurement of total light transmittance)

由實施例及比較例所得的黏接著板片，剝離輕剝離型剝離板片，使露出的黏接著劑層與厚度1.1mm的鈉鈣玻璃(日本板硝子公司製)貼合。接著，以與試驗例1同樣的條件，隔著重剝離型剝離板片照射紫外線，使黏接著劑層硬化作成硬化後黏接著劑層之後，剝離重剝離型剝離板片，以此作為測定樣品。以鈉鈣玻璃進行背景測定之後，對上述測定樣品，遵照JIS K7361-1：1997，使用霧度計(日本電色工業公司製，產品名「NDH-2000」)測定全光線穿透率(%)。將結果示於表1。 From the adhesive sheets obtained in Examples and Comparative Examples, the light peeling type release sheet was peeled off, and the exposed adhesive layer was bonded to soda lime glass (manufactured by Nippon Plate Glass Co., Ltd.) with a thickness of 1.1 mm. Next, under the same conditions as in Test Example 1, ultraviolet rays were irradiated through the heavy-peeling release sheet to harden the adhesive layer to obtain a post-hardening adhesive layer, and then the heavy-peeling release sheet was peeled off as a measurement sample. After background measurement was performed on soda lime glass, the total light transmittance (%) was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH-2000") in accordance with JIS K7361-1:1997 for the measurement sample. ). The results are shown in Table 1.

[試驗例3](段差追隨性的評估) [Test example 3] (Evaluation of step followability)

在玻璃板(NSG PRECISION公司製，產品名「康寧玻璃EAGLE XG」，長90mm×寬50mm×厚0.5mm)的表面，以畫框狀(外形：長90mm×寬50mm，間隔5mm)網版印刷紫外線硬化 型墨水(帝國INK公司製，產品名「POS-911墨」)。接著，照射紫外線(80W/cm2，金屬鹵素水銀燈2盞，燈高度15cm，輸送帶速度10~15m/分)，使印刷的上述紫外線硬化型油墨硬化，製作具有以印刷的段差(段差的高度：40μm)的附有段差的玻璃板。 On the surface of a glass plate (manufactured by NSG PRECISION, product name "Corning Glass EAGLE XG", length 90mm x width 50mm x thickness 0.5mm), screen-printed in the shape of a picture frame (outline: length 90mm x width 50mm, interval 5mm) UV-curable ink (manufactured by Imperial INK, product name "POS-911 ink"). Next, ultraviolet rays (80 W/cm 2 , 2 metal halide mercury lamps, lamp height 15 cm, conveyor speed 10 to 15 m/min) were irradiated to harden the above-mentioned UV-curable ink printed, and a printing step (the height of the step difference) was produced. : 40 μm) glass plate with level difference.

由實施例及比較例所得的黏接著板片剝下輕剝離型剝離板片，將露出的黏接著劑層，貼合於具有易接著層的聚對苯二甲酸乙二酯薄膜(東洋紡公司製，產品名「PET A4300」，厚度：100μm)的易黏著層。接著，剝下重剝離型剝離板片，使黏接著劑層露出，使用層壓機(FUJIPLA公司製，產品名「LPD3214」)，使黏接著劑層披覆畫框狀的印刷的全面的方式，層壓於上述附有段差的玻璃板。之後，以50℃、0.5MPa的條件下，高壓釜處理30分鐘，在常壓，23℃、50%RH放置24小時。 The light peeling type release sheet was peeled off from the adhesive sheets obtained in Examples and Comparative Examples, and the exposed adhesive layer was attached to a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.) having an easily adhesive layer. , product name "PET A4300", thickness: 100μm) easy-adhesive layer. Next, the heavy peeling type release sheet is peeled off to expose the adhesive layer, and a laminator (manufactured by FUJIPLA, product name "LPD3214") is used to apply the adhesive layer to the entire surface of the frame-like printing , laminated on the above glass plate with step difference. After that, under the conditions of 50° C. and 0.5 MPa, autoclave treatment was performed for 30 minutes, and then it was left to stand at normal pressure, 23° C., and 50% RH for 24 hours.

對所得層積體的黏接著劑層，隔著上述聚對苯二甲酸乙二酯薄膜，以與試驗例1同樣的條件照射紫外線，使黏接著劑層硬化做成硬化後黏接著劑層。接著，以85℃、85%RH的高溫高濕條件下，保管72小時(耐久試驗)，之後，將黏接著劑層(特別是印刷層的段差的附近)，以目視確認，以如下基準評估段差追隨性。將結果示於表2。 The adhesive layer of the obtained laminate was irradiated with ultraviolet rays under the same conditions as in Test Example 1 via the polyethylene terephthalate film to cure the adhesive layer to form a cured adhesive layer. Next, under high temperature and high humidity conditions of 85° C. and 85% RH, it was stored for 72 hours (endurance test), after which the adhesive layer (especially the vicinity of the step of the printed layer) was visually confirmed and evaluated according to the following criteria Segment followability. The results are shown in Table 2.

○：在段差附近沒有氣泡(浮起‧剝落)，黏接著劑無間隙地追隨。 ○: No air bubbles (floating and peeling) were present in the vicinity of the level difference, and the adhesive followed without a gap.

△：在段差附近的一部分有氣泡混入。 △: Air bubbles were mixed in a part of the vicinity of the level difference.

×：在段差周圍的全體有氣泡混入。 ×: Air bubbles were mixed in the whole around the level difference.

[試驗例4](耐起泡性的評估) [Test Example 4] (Evaluation of foaming resistance)

將實施例及比較例所得的黏接著板片的黏接著劑層，以一面設有由錫摻雜氧化銦(ITO)所形成的透明導電膜的聚對苯二甲酸乙二酯薄膜(尾池工業公司製，ITO薄膜，厚度：125μm)的透明導電膜，及具有聚甲基丙烯酸甲酯層及聚碳酸酯層的樹脂板(三菱氣體化學公司製，產品名「Iupilon sheet MR-58U」，厚度：0.8mm)的聚碳酸酯層側的面包夾。之後，以50℃、0.5MPa的條件下，高壓釜處理30分鐘，以常壓，23℃、50%RH放置24小時。 The adhesive layer of the adhesive sheets obtained in the Examples and Comparative Examples was a polyethylene terephthalate film (tail pool) provided with a transparent conductive film formed of tin-doped indium oxide (ITO) on one side. A transparent conductive film made of ITO film, thickness: 125 μm, manufactured by Kogyo Co., Ltd., and a resin sheet having a polymethyl methacrylate layer and a polycarbonate layer (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "Iupilon sheet MR-58U", Thickness: 0.8mm) on the polycarbonate layer side of the bread clip. Then, under the conditions of 50°C and 0.5 MPa, autoclave treatment was carried out for 30 minutes, and it was left to stand at normal pressure, 23°C, and 50% RH for 24 hours.

對所得層積體的黏接著劑層，隔著上述樹脂板，以與試驗例1同樣的條件照射紫外線，使黏接著劑層硬化作成硬化後黏接著劑層。接著，以85℃、85%RH的高溫高濕條件下保管72小時。之後，以目視確認硬化後黏接著劑層與被著體的界面的狀態，以如下基準評估耐起泡性。將結果示於表2。 The adhesive layer of the obtained laminate was irradiated with ultraviolet rays under the same conditions as in Test Example 1 via the resin plate to cure the adhesive layer to obtain an adhesive layer after curing. Next, it was stored under high temperature and high humidity conditions of 85° C. and 85% RH for 72 hours. Then, the state of the interface between the adhesive layer and the to-be-attached body after curing was visually confirmed, and the foaming resistance was evaluated according to the following criteria. The results are shown in Table 2.

○：沒有確認到氣泡、浮起‧剝落。 ○: No bubbles, floating or peeling were observed.

△：在一部分可確認到氣泡，但沒有確認到浮起‧剝落。 △: Bubbles were partially observed, but no floating or peeling was observed.

×：在全面可確認到氣泡或浮起‧剝落。 ×: Bubbles or floating and peeling were observed on the entire surface.

[試驗例5](耐濕熱白化性的評估) [Test Example 5] (Evaluation of moist heat whitening resistance)

將實施例及比較例所得的黏著板片的黏著劑層，以一面設有由錫摻雜氧化銦(ITO)所形成的透明導電膜的聚對苯二甲酸乙二酯薄膜(尾池工業公司製，產品名「ITO薄膜」，厚度：125μm)2片包夾，得到層積體。此時，將該薄膜的設有透明導電膜的面與黏接著劑層貼附。將所得層積體，在50℃，0.5MPa的條件下，高壓釜處理30分鐘，以常壓，23℃、50%RH放置 24小時。之後，使用霧度計(日本電色工業公司製，產品名「NDH2000」)，JIS K7136：2000測定霧度值(%)。 The adhesive layer of the adhesive sheets obtained in the examples and comparative examples was a polyethylene terephthalate film (Oike Industry Co., Ltd.) provided with a transparent conductive film formed of tin-doped indium oxide (ITO) on one side. manufactured, product name "ITO film", thickness: 125 μm) 2 sheets were sandwiched to obtain a laminate. At this time, the surface provided with the transparent conductive film of the film is attached to the adhesive layer. The obtained laminate was subjected to autoclave treatment at 50°C and 0.5 MPa for 30 minutes, and left to stand at normal pressure, 23°C, and 50% RH for 24 hours. Then, the haze value (%) was measured using a haze meter (manufactured by Nippon Denshoku Industries, Ltd., product name "NDH2000") in accordance with JIS K7136:2000.

接著，對上述層積體的黏接著劑層，隔著上述薄膜以與試驗例1同樣的條件照射紫外線，使黏接著劑層硬化作成硬化後黏接著劑層。接著，將該層積體，以85℃、85%RH的濕熱條件下，保管120小時(耐久試驗)。之後，恢復到23℃、50%RH的常溫常濕，對該層積體，再次測定霧度值(%)測定。再者，該霧度值，係將層積體恢復到常溫常濕的30分鐘以內測定。 Next, the adhesive layer of the laminate was irradiated with ultraviolet rays through the film under the same conditions as in Test Example 1, and the adhesive layer was cured to obtain an adhesive layer after curing. Next, the laminated body was stored for 120 hours under moist heat conditions of 85° C. and 85% RH (durability test). Then, it returned to normal temperature and normal humidity of 23 degreeC and 50%RH, and the haze value (%) of this laminated body was measured again. In addition, this haze value is measured within 30 minutes after the laminated body is returned to normal temperature and normal humidity.

由上述耐久試驗前的霧度值(%)算出上述耐久試驗後的霧度值(%)的上升值。將結果示於表2。 The increase value of the haze value (%) after the above-mentioned durability test was calculated from the haze value (%) before the above-mentioned durability test. The results are shown in Table 2.

Figure 106113727-A0202-12-0039-1
Figure 106113727-A0202-12-0039-1

Figure 106113727-A0202-12-0039-2
Figure 106113727-A0202-12-0039-2

由表2可知，由實施例所得的黏接著板片，段差追隨性及耐起泡性優良的同時，光學特性及耐濕熱白化性亦優 良 As can be seen from Table 2, the adhesive sheets obtained by the examples have excellent step followability and foam resistance, and at the same time, optical properties and damp-heat whitening resistance are also excellent.

【產業上的可利性】 【Industrial Profitability】

本發明的黏接著劑組合物、黏接著劑及黏接著板片，例如能夠良好地使用於貼合具有段差的保護面板，與所期望的顯示體構成構件。 The adhesive composition, the adhesive, and the adhesive sheet of the present invention can be favorably used, for example, for bonding a protective panel having a level difference to a desired display body constituent member.

1‧‧‧黏接著板片 1‧‧‧Bond bonding

11‧‧‧黏接著劑層 11‧‧‧Adhesive layer

12a、12b‧‧‧剝離板片 12a, 12b‧‧‧Peel off the sheet

Claims (10)

一種黏接著劑組合物，其特徵在於，含有：自由基聚合性成分(A)；離子聚合性成分(B)；可藉由可見光活化的可見光活化自由基聚合起始劑(C)；及可藉由紫外線活化的紫外線活化離子聚合起始劑(D)，其中前述自由基聚合性成分(A)，包含具有自由基聚合性基的胺甲酸乙酯寡聚物及在分子中具有羥基之含(甲基)丙烯醯基單體，前述自由基聚合性成分(A)中、前述分子中具有羥基之含(甲基)丙烯醯基單體的含量為2質量%以上、30質量%以下。 An adhesive composition, characterized in that it contains: a radically polymerizable component (A); an ionically polymerizable component (B); a visible-light-activatable radical-polymerization initiator (C) that can be activated by visible light; An ultraviolet-activated ion polymerization initiator (D) activated by ultraviolet rays, wherein the radically polymerizable component (A) includes a urethane oligomer having a radically polymerizable group and a urethane oligomer having a hydroxyl group in the molecule. The content of the (meth)acryloyl group-containing monomer having a hydroxyl group in the aforementioned radical polymerizable component (A) in the molecule is 2 mass % or more and 30 mass % or less. 如申請專利範圍第1項所述的黏接著劑組合物，其中前述離子聚合性成分(B)，含有具有環氧基或縮水甘油醚基的化合物。 The adhesive composition according to claim 1, wherein the ionically polymerizable component (B) contains a compound having an epoxy group or a glycidyl ether group. 如申請專利範圍第1項所述的黏接著劑組合物，其中前述黏接著劑組合物係無溶劑型黏接著劑組合物。 The adhesive composition according to claim 1, wherein the adhesive composition is a solvent-free adhesive composition. 一種黏接著劑之製造方法，其特徵在於，藉由對如申請專利範圍第1至3項的任何一項所述的黏接著劑組合物，照射可見光，使前述自由基聚合性成分(A)聚合得到黏接著劑。 A method for producing an adhesive, characterized in that the above-mentioned radically polymerizable component (A) is irradiated with visible light to the adhesive composition according to any one of claims 1 to 3 of the patent application scope. Polymerization to obtain an adhesive. 一種黏接著劑，其特徵在於，含有：來自包含具有自由基聚合性基的胺甲酸乙酯寡聚物之自由基聚合性成分(A)的聚合物；離子聚合性成分(B)；及可藉由紫外線活化的紫外線活化離子聚合起始劑(D)。 An adhesive comprising: a polymer derived from a radically polymerizable component (A) comprising a urethane oligomer having a radically polymerizable group; an ionically polymerizable component (B); and a polymerizable component The ionic polymerization initiator (D) is activated by UV-activated UV light. 一種黏接著板片，其具有如申請專利範圍第5項所述的黏接著劑所形成的黏接著劑層。 An adhesive sheet is provided with an adhesive layer formed by the adhesive described in item 5 of the patent application scope. 如申請專利範圍第6項所述的黏接著板片，其中前述黏接著板片，具備2片剝離板片，前述黏接著劑層，以接於前述2片剝離板片的剝離面的方式被前述剝離板片夾持。 The adhesive sheet according to claim 6, wherein the adhesive sheet includes two release sheets, and the adhesive layer is bonded to the release surfaces of the two release sheets. The aforementioned peeling plate is clamped. 一種黏接著板片之製造方法，其係具有黏接著劑層的黏接著板片之製造方法，其特徵在於，將如申請專利範圍第1至3項的任何一項所述的黏接著劑組合物塗層，藉由對前述黏接著劑組合物的塗膜照射可見光，使前述自由基聚合性成分(A)聚合作成黏接著劑層。 A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet with an adhesive layer, characterized in that the adhesive as described in any one of claims 1 to 3 of the scope of application is combined By irradiating visible light to the coating film of the adhesive composition, the radically polymerizable component (A) is polymerized to form an adhesive layer. 一種顯示體之製造方法，其係具備：一顯示體構成構件；其他顯示體構成構件；及將前述一顯示體構成構件與前述其他顯示體構成構件互相接著的硬化後黏接著劑層的顯示體之製造方法，其特徵在於：前述一顯示體構成構件與前述其他顯示體構成構件的至少一者至少在貼合側的面具有段差，前述硬化後黏接著劑層的厚度為25μm以上、1000μm以下，對於含有包含具有自由基聚合性基的胺甲酸乙酯寡聚物之自由基聚合性成分(A)及離子聚合性成分(B)的黏接著劑組合物的層照射可見光，藉此使前述自由基聚合性成分(A)聚合，形成來自該自由基聚合性成分(A)之聚合物，作成黏接 著劑層，經由前述黏接著劑層將前述一顯示體構成構件與前述其他顯示體構成構件互相貼合，其次，對前述黏接著劑層照射紫外線，使前述離子聚合性成分(B)聚合，形成來自該離子聚合性成分(B)之聚合物，作成前述硬化後黏接著劑層。 A method for manufacturing a display body, comprising: a display body constituting member; other display body constituting members; The manufacturing method is characterized in that: at least one of the one display component member and the other display component component has a level difference at least on the surface on the bonding side, and the thickness of the adhesive layer after curing is 25 μm or more and 1000 μm or less. to irradiate the layer containing the adhesive composition containing the radically polymerizable component (A) and the ionically polymerizable component (B) of the urethane oligomer having a radically polymerizable group with visible light, whereby the aforementioned The radically polymerizable component (A) is polymerized to form a polymer derived from the radically polymerizable component (A) to form an adhesive bond an adhesive layer, wherein the one display component member and the other display component member are bonded to each other via the adhesive layer, and then the adhesive layer is irradiated with ultraviolet rays to polymerize the ionomerizable component (B), A polymer derived from the ionomerizable component (B) is formed to form the above-mentioned post-curing adhesive layer. 一種顯示體的製造方法，其特徵在於，製作將一顯示體構成構件與其他顯示體構成構件、經由如申請專利範圍第6或7項所述的黏接著板片的黏接著劑層黏合而成的層積體，對前述層積體的前述黏接著劑層照射紫外線，使前述離子聚合性成分(B)聚合作成硬化後黏接著劑層。 A manufacturing method of a display body, characterized in that, a display body constituting member and other display body constituting members are produced by adhering to an adhesive layer of an adhesive sheet as described in item 6 or 7 of the patent application scope. The laminated body of the said laminated body is irradiated with ultraviolet rays to the said adhesive agent layer of the said laminated body, and the said ionomerizable component (B) is polymerized to form the adhesive agent layer after hardening.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000072854A (en) * 1998-08-28 2000-03-07 Sekisui Chem Co Ltd Photosetting composition, its production, photosetting adhesive sheet, its production and jointing
CN104220547A (en) * 2012-04-10 2014-12-17 乐金华奥斯有限公司 Semi-hardened pressure-sensitive adhesive film
JP2015040278A (en) * 2013-08-23 2015-03-02 東洋インキＳｃホールディングス株式会社 Active energy ray-polymerizable resin composition and laminate

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3022775B2 (en) * 1995-10-27 2000-03-21 積水化学工業株式会社 Curable adhesive sheet, member joining method, and photopolymerizable composition
JPH10147754A (en) * 1996-11-20 1998-06-02 Sekisui Chem Co Ltd Hardenable tacky adhesive sheet and method for bonding member
JP3730787B2 (en) * 2000-02-14 2006-01-05 積水化学工業株式会社 Photocurable composition, photocurable composition manufacturing method, photocurable adhesive sheet, photocurable adhesive sheet manufacturing method, and bonding method
JP2009007501A (en) * 2007-06-29 2009-01-15 Toyo Ink Mfg Co Ltd Curable sticky adhesive material
JP2010097070A (en) 2008-10-17 2010-04-30 Nitto Denko Corp Transparent pressure-sensitive adhesive sheet for flat panel display, and flat panel display
JP4561936B1 (en) * 2009-09-04 2010-10-13 東洋インキ製造株式会社 Polarizing plate and light curable adhesive for forming polarizing plate
JP5533568B2 (en) * 2009-11-05 2014-06-25 日立化成株式会社 Thermal polymerization initiator system and adhesive composition
KR101400471B1 (en) * 2011-12-28 2014-05-29 (주)엘지하우시스 Composition of adhesive film for rework process of touch screen panel
JP5688520B1 (en) * 2013-07-04 2015-03-25 東洋インキＳｃホールディングス株式会社 Active energy ray-polymerizable adhesive and laminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000072854A (en) * 1998-08-28 2000-03-07 Sekisui Chem Co Ltd Photosetting composition, its production, photosetting adhesive sheet, its production and jointing
CN104220547A (en) * 2012-04-10 2014-12-17 乐金华奥斯有限公司 Semi-hardened pressure-sensitive adhesive film
JP2015040278A (en) * 2013-08-23 2015-03-02 東洋インキＳｃホールディングス株式会社 Active energy ray-polymerizable resin composition and laminate

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