TWI793226B - Adhesives, Adhesive Sheets and Displays - Google Patents
Adhesives, Adhesive Sheets and Displays Download PDFInfo
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- TWI793226B TWI793226B TW107145173A TW107145173A TWI793226B TW I793226 B TWI793226 B TW I793226B TW 107145173 A TW107145173 A TW 107145173A TW 107145173 A TW107145173 A TW 107145173A TW I793226 B TWI793226 B TW I793226B
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
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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
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
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- 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
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- 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
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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
- 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
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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
- 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
- C09J2301/312—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 parameters being the characterizing feature
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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
- 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)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Laminated Bodies (AREA)
Abstract
本發明提供一種黏著劑，其係將無溶劑型黏著性組合物固化而成的黏著劑，其中所述無溶劑型黏著性組合物具有：選自聚合性乙烯基單體、聚合性乙烯基預聚物、多官能（甲基）丙烯酸酯單體及多官能（甲基）丙烯酸酯低聚物中的一種以上的光聚合成分；濃度為0.1質量%的乙腈溶液中的波長380nm的吸光度為1.0以上的光聚合起始劑；及紫外線吸收劑，且相對於光聚合成分100質量份，紫外線吸收劑的含量為0.1質量份以上4.0質量份以下，其特徵在於，黏著劑的凝膠分率為50%以上90%以下，波長380nm處的透射率為30%以下。The present invention provides an adhesive, which is an adhesive obtained by curing a solvent-free adhesive composition, wherein the solvent-free adhesive composition has: selected from polymerizable vinyl monomers, polymerizable vinyl prepolymers Polymer, multifunctional (meth)acrylate monomer and multifunctional (meth)acrylate oligomer; the absorbance of the wavelength 380nm in the acetonitrile solution with a concentration of 0.1 mass % is 1.0 The above photopolymerization initiator; and the ultraviolet absorber, and relative to 100 mass parts of the photopolymerization component, the content of the ultraviolet absorber is not less than 0.1 mass parts and not more than 4.0 mass parts, it is characterized in that the gel fraction of the adhesive is More than 50% and less than 90%, and the transmittance at a wavelength of 380nm is less than 30%.
Description
本發明關於黏著劑、黏著片及顯示體。The present invention relates to an adhesive, an adhesive sheet and a display body.
紫外線不僅對人體有害，還會使構成機器的構件等劣化。因此，正在進行藉由將具有紫外線吸收能力的構件貼合於透射紫外線的材料（例如，玻璃）、或者將該構件組裝於機器內，從而保護人體或機器免受紫外線的傷害。Ultraviolet rays are not only harmful to the human body, but also degrade components that make up equipment. Therefore, protection of a human body or a machine from ultraviolet rays is being carried out by attaching a member having ultraviolet absorbing ability to a material (for example, glass) that transmits ultraviolet rays, or assembling the member in a machine.
例如，專利文獻1公開了在貼合於車輛、建築物等的窗戶玻璃的黏著片中，使黏著劑含有紫外線吸收劑。該包含紫外線吸收劑的黏著劑可藉由利用電子束照射的聚合反應而得到。For example,
並且，作為需保護免受紫外線傷害的機器，可例示出在室外使用的可攜式電話機、智慧手機、平板電腦終端等各種移動電子機器。In addition, various mobile electronic devices such as mobile phones, smartphones, and tablet terminals used outdoors can be exemplified as devices that need to be protected from ultraviolet rays.
這樣的各種移動電子設備具備使用了顯示體模組的顯示體（顯示器），該顯示體模組具有液晶元件、發光二極管（LED元件）、有機電致發光二極管（有機EL）元件等。並且，近年來，顯示器兼作觸摸面板的情況越來越多。Such various mobile electronic devices include a display (display) using a display module including a liquid crystal element, a light emitting diode (LED element), an organic electroluminescent diode (organic EL) element, and the like. In addition, in recent years, displays are increasingly used as touch panels.
這樣的顯示體藉由將多個顯示體構成構件組合並一體化而構成。作為顯示體構成構件，例如可例示出保護面板、顯示體模組、具有既定的光學功能的膜等。這些顯示體構成構件藉由黏著劑貼合並一體化。Such a display body is constituted by combining and integrating a plurality of display body constituting members. Examples of display constituent members include, for example, a protective panel, a display module, a film having a predetermined optical function, and the like. These display body components are pasted and integrated by an adhesive.
如上所述，由於移動電子機器在室外使用，因此其構成構件會因紫外線的影響而劣化。為了抑制這樣的劣化，具有紫外線吸收能力的構件被組裝於電子設備內。As described above, since mobile electronic devices are used outdoors, their components are degraded by the influence of ultraviolet rays. In order to suppress such deterioration, members having ultraviolet absorbing ability are incorporated in electronic equipment.
作為這樣的構件，已知使貼合配置於電子設備的表面側的保護面板與其他構成構件的黏著劑具有紫外線吸收能力。例如，專利文獻2公開了，用於將構成顯示體的顯示體構成構件彼此貼合的黏著片具有紫外線吸收層。As such a member, it is known to impart ultraviolet absorbing ability to an adhesive that is bonded to a protective panel disposed on the front side of an electronic device and other constituent members. For example,
並且，專利文獻3公開了用於將構成顯示體的顯示體構成構件彼此貼合的黏著劑為紫外線固化型，且包含紫外線吸收劑。Furthermore,
然而，用於將顯示體構成構件彼此貼合的黏著劑不僅具有紫外線吸收能力，而且具有因顯示體構成構件的形狀而要求的特性。However, the adhesive used to bond the display constituent members to each other has not only ultraviolet absorbing capability but also properties required by the shape of the display constituent members.
例如，有以下情況：有時在保護面板的顯示體模組側形成有框狀的印刷層，其在顯示體的厚度方向作為段差而存在。黏著劑層貼合保護面板與顯示體模組之情形，若黏著劑層未追隨它們段差而貼合，則黏著劑層在段差附近浮起並形成空隙。其結果，因該空隙而產生光的反射損失，顯示器的畫質會降低。因此，對於貼合於具有段差的保護面板的黏著劑層，要求段差追隨性。For example, there may be cases where a frame-shaped printed layer is formed on the display module side of the protective panel and exists as steps in the thickness direction of the display. When the adhesive layer is attached to the protective panel and the display module, if the adhesive layer does not follow the level difference between them, the adhesive layer will float near the level difference and form a gap. As a result, reflection loss of light occurs due to the gap, and the image quality of the display decreases. Therefore, step followability is required for the adhesive layer bonded to the protective panel having steps.
進一步，隨著電子機器的薄型化、輕量化，還研究了將保護面板由以往的玻璃板變更為壓克力板或聚碳酸酯板等塑料板。藉由黏著劑層將保護面板與顯示體模組貼合的構成中，產生以下新的問題：將保護面板變更為塑料板之情形，在高溫高濕條件下，會從塑料板發生排氣，從而發生氣泡、浮起、剝落等起泡。因此，對於用於將顯示體模組與保護面板貼合的黏著劑層，要求耐起泡性的情況也越來越多。 [現有技術文獻] [專利文獻]Further, along with the reduction in thickness and weight of electronic equipment, studies have been made to change the protective panel from the conventional glass plate to a plastic plate such as an acrylic plate or a polycarbonate plate. In the composition of bonding the protective panel and the display body module through the adhesive layer, the following new problems arise: when the protective panel is changed to a plastic plate, under high-temperature and high-humidity conditions, exhaust gas will occur from the plastic plate, Thus, foaming such as air bubbles, floating, and peeling occurs. Therefore, foaming resistance is increasingly required for an adhesive layer for laminating a display module and a protective panel. [Prior art literature] [Patent Document]
專利文獻1：日本特開2013-249345號公報 專利文獻2：日本特開2012-211305號公報 專利文獻3：日本特開2016-155981號公報Patent Document 1: Japanese Patent Laid-Open No. 2013-249345 Patent Document 2: Japanese Patent Laid-Open No. 2012-211305 Patent Document 3: Japanese Patent Laid-Open No. 2016-155981
[本發明所欲解決的問題][Problem to be solved by the present invention]
專利文獻1中公開的黏著劑為藉由利用電子束照射的聚合反應而得到的固化物。利用電子束照射的聚合反應中，通常在聚合反應後的固化物中存在較多的未聚合的單體。這樣的殘留的單體量（單體殘留量）多的情形，會產生黏著劑的耐起泡性降低，或者在金屬感測器等金屬與黏著劑接觸的情形，會產生金屬腐蝕、黏著力降低等不良情況。進一步，由於專利文獻1中公開的黏著劑不是用於將顯示體的構成構件彼此貼合的黏著劑，因此根本沒有考慮段差追隨性。The adhesive disclosed in
並且，專利文獻2中公開的黏著片具有層疊有黏著劑層與紫外線吸收層的構成、以及由具有紫外線吸收劑的黏著劑層而成的構成。然而，在黏著劑層包含紫外線吸收劑之情形中，藉由使黏著劑組合物熱固化而得到固化物。在此情形中，可能會因加熱而發生形成有黏著劑組合物的基材的熱劣化、熱收縮等。並且，黏著劑組合物中的揮發成分可能會消失。因此，聚合反應較佳為藉由活性能量射線的照射而進行。In addition, the adhesive sheet disclosed in
專利文獻3中公開的黏著劑不適合於貼合具有段差的顯示體構成構件，尤其，有在段差大之情形的追隨性差的問題。The adhesive disclosed in
並且，對於貼合保護面板與顯示體模組的黏著劑層，要求與段差追隨性不同的特性。貼合黏著劑層時，有時會捲入存在於作業環境中的垃圾等。其結果，例如在保護面板附近有時會存在點狀的異物。這樣的點狀的異物具有球形、不定形等各種形狀，但必須使黏著劑層充分追隨異物的形狀，從而不產生成為黏著劑層的剝離的起點的空隙。換而言之，對於黏著劑層，要求能將點狀的異物填埋於黏著劑層中的異物填埋性。In addition, the adhesive layer for laminating the protective panel and the display module requires characteristics different from step followability. When adhering the adhesive layer, garbage and the like that exist in the working environment may be caught. As a result, for example, dot-shaped foreign matter may exist near the protective panel. Such point-shaped foreign matter has various shapes such as spherical shape and indeterminate shape, but it is necessary for the adhesive layer to sufficiently follow the shape of the foreign matter so as not to generate a void that becomes a starting point of peeling of the adhesive layer. In other words, foreign matter embedding properties capable of embedding point-shaped foreign matter in the adhesive layer are required for the adhesive layer.
尤其，存在比段差的高度還要大的異物等之情形，必須沿著異物所具有的各種形狀而追隨，異物填埋性為與段差追隨性不同的所需特性。段差追隨性與異物填埋性為不同的特性，但就為用於追隨既定的形狀的特性這一點而言是共通的，因此在本說明書中，將包含段差追隨性與異物填埋性的特性定義為形狀追隨性。In particular, when there is a foreign object larger than the height of the step, it is necessary to follow various shapes of the foreign object, and the foreign object burying property is a required characteristic different from the step followability. The level difference followability and the foreign matter filling property are different characteristics, but they are common in that they follow a predetermined shape. Therefore, in this specification, the level difference following property and the foreign matter filling property are included. Defined as shape following.
本發明是鑒於上述實際情況而完成的，其目的在於提供一種具有紫外線吸收能力，並同時包含作為不同特性的段差追隨性及異物填埋性的形狀追隨性良好的黏著劑、以及具有一個構成構件、另一個構成構件、及貼合一個構成構件與另一個構成構件的黏著劑的顯示體。 [解決技術問題的技術手段]The present invention has been made in view of the above-mentioned circumstances, and its object is to provide an adhesive with excellent shape followability that has ultraviolet absorbing ability, step followability and foreign matter embedding performance as different characteristics, and has a constituent member , another constituent member, and a display body in which an adhesive bonded the one constituent member and the other constituent member. [Technical means to solve technical problems]
本發明的第一態樣為： [1] 一種黏著劑，其係將無溶劑型黏著性組合物固化而成的黏著劑，其中所述無溶劑型黏著性組合物具有：選自由聚合性乙烯基單體、聚合性乙烯基預聚物、多官能（甲基）丙烯酸酯單體及多官能（甲基）丙烯酸酯低聚物構成之群組中的一種以上的光聚合成分； 濃度為0.1質量%的乙腈溶液中的波長380nm的吸光度為1.0以上的光聚合起始劑；及 紫外線吸收劑， 且相對於光聚合成分100質量份，紫外線吸收劑的含量為0.1質量份以上且4.0質量份以下， 其特徵在於， 黏著劑的凝膠分率為50%以上且90%以下， 波長380nm處的透射率為30%以下。The first aspect of the present invention is: [1] An adhesive obtained by curing a solvent-free adhesive composition, wherein the solvent-free adhesive composition has: a polymerizable vinyl monomer, a polymerizable vinyl prepolymer, More than one photopolymerizable component in the group consisting of polymers, multifunctional (meth)acrylate monomers and multifunctional (meth)acrylate oligomers; A photopolymerization initiator having an absorbance of 1.0 or more at a wavelength of 380 nm in an acetonitrile solution having a concentration of 0.1% by mass; and UV absorbers, And with respect to 100 mass parts of photopolymerizable components, the content of the ultraviolet absorber is 0.1 mass part or more and 4.0 mass parts or less, It is characterized in that, The gel fraction of the adhesive is 50% or more and 90% or less, The transmittance at a wavelength of 380nm is 30% or less.
[2] 如[1]所記載的黏著劑，其特徵在於，黏著劑中的單體的殘留量的合計為1000ppm以下。[2] The adhesive according to [1], wherein the total amount of residual monomers in the adhesive is 1000 ppm or less.
本發明的第二態樣為： [3] 一種黏著片，其為具有黏著劑層的黏著片，其特徵在於，黏著劑層由[1]或[2]所記載的黏著劑構成。The second aspect of the present invention is: [3] An adhesive sheet having an adhesive layer, wherein the adhesive layer is composed of the adhesive described in [1] or [2].
[4] 如[3]所記載的黏著片，其特徵在於，黏著片具備兩片剝離片，黏著劑層以與兩片剝離片的剝離面相接觸的方式被剝離片夾持。[4] The adhesive sheet according to [3], wherein the adhesive sheet includes two release sheets, and the adhesive layer is sandwiched by the release sheets so as to be in contact with the release surfaces of the two release sheets.
本發明的第三態樣為： [5] 一種顯示體，其為具有第一顯示體構成構件、第二顯示體構成構件、及將第一顯示體構成構件與第二顯示體構成構件相互貼合的黏著劑層之顯示體，其特徵在於，黏著劑層由[1]或[2]所記載的黏著劑、或者[3]或[4]所記載的黏著片所具有的黏著劑層構成。The third aspect of the present invention is: [5] A display comprising a first display constituting member, a second display constituting member, and an adhesive layer for bonding the first display constituting member and the second display constituting member together, It is characterized in that the adhesive layer is composed of the adhesive described in [1] or [2], or the adhesive layer included in the adhesive sheet described in [3] or [4].
[6] 如[5]所記載的顯示體，其特徵在於，第一顯示體構成構件及/或第二顯示體構成構件具有段差，黏著劑層沿著段差而被貼合。 [發明效果][6] The display according to [5], wherein the first display constituent member and/or the second display constituent member have steps, and the adhesive layer is bonded along the steps. [Invention effect]
根據本發明，能夠提供一種具有紫外線吸收能力，並同時包含作為不同特性的段差追隨性及異物填埋性的形狀追隨性良好的黏著劑、以及具有一個構成構件、另一個構成構件、及貼合一個構成構件與另一個構成構件的黏著劑的顯示體。According to the present invention, it is possible to provide an adhesive having ultraviolet absorbing ability and good shape followability including step followability and foreign matter embedding property as different characteristics, and an adhesive having one constituent member, another constituent member, and bonding adhesive. A display of the adhesive between one constituent element and another constituent element.
[具體實施形態][specific implementation form]
以下，基於具體的實施形態，對本發明詳細地進行說明。Hereinafter, the present invention will be described in detail based on specific embodiments.
（1. 黏著劑） 本實施形態的黏著劑藉由將既定的無溶劑型黏著性組合物固化而成。以下，對本實施形態的無溶劑型黏著性組合物詳細地進行說明。(1. Adhesive) The adhesive of this embodiment is formed by curing a predetermined solvent-free adhesive composition. Hereinafter, the solventless adhesive composition of this embodiment is demonstrated in detail.
（2. 無溶劑型黏著性組合物） 本實施形態的無溶劑型黏著性組合物具有：選自由聚合性乙烯基單體、聚合性乙烯基預聚物、多官能（甲基）丙烯酸酯單體及多官能（甲基）丙烯酸酯低聚物構成之群組中的一種以上的光聚合成分；濃度為0.1質量%的乙腈溶液中的波長380nm的吸光度為1.0以上的光聚合起始劑；及紫外線吸收劑。另外，本說明書中，「（甲基）丙烯酸酯」意指丙烯酸酯及甲基丙烯酸酯。其他的類似用語也相同。(2. Solvent-free adhesive composition) The solvent-free adhesive composition of this embodiment has the following properties: selected from polymerizable vinyl monomers, polymerizable vinyl prepolymers, multifunctional (meth)acrylate monomers and multifunctional (meth)acrylate low One or more photopolymerization components in the group consisting of polymers; a photopolymerization initiator having an absorbance of 1.0 or more at a wavelength of 380 nm in an acetonitrile solution having a concentration of 0.1% by mass; and an ultraviolet absorber. In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. The same applies to other similar terms.
本實施形態的無溶劑型黏著性組合物主要藉由聚合成分而具有適度的黏度。因此，本實施形態的無溶劑型黏著性組合物可在不添加稀釋劑等的情況下直接用作塗布溶液。The solvent-free adhesive composition of this embodiment has moderate viscosity mainly by a polymerization component. Therefore, the non-solvent type adhesive composition of this embodiment can be used as a coating solution as it is without adding a diluent etc.
這樣的無溶劑型黏著性組合物可藉由將光聚合成分、光聚合起始劑及紫外線吸收劑混合而製備。另外，亦可根據需要而加入各種添加劑。Such a solvent-free adhesive composition can be prepared by mixing a photopolymerization component, a photopolymerization initiator, and an ultraviolet absorber. Moreover, various additives can also be added as needed.
（2.1. 光聚合成分） 光聚合成分只要為在後述的光聚合起始劑的存在下藉由活性能量射線的照射而固化的成分，則沒有特別限制。例如可以為單體、低聚物、或聚合物中的任一種，也可以為它們的混合物。(2.1. Photopolymerizable components) The photopolymerization component is not particularly limited as long as it is a component that is cured by irradiation of active energy rays in the presence of a photopolymerization initiator described later. For example, any one of monomers, oligomers, and polymers may be used, or a mixture thereof may be used.
本實施形態中，光聚合成分為選自由聚合性乙烯基單體、聚合性乙烯基預聚物、多官能（甲基）丙烯酸酯單體及多官能（甲基）丙烯酸酯低聚物構成之群組中的一種以上。以下，對各成分進行詳細說明。In this embodiment, the photopolymerizable component is selected from polymerizable vinyl monomers, polymerizable vinyl prepolymers, multifunctional (meth)acrylate monomers, and multifunctional (meth)acrylate oligomers. More than one of the group. Each component will be described in detail below.
（2.1.1. 聚合性乙烯基單體） 作為聚合性乙烯基單體，只要具有含乙烯基的基團則沒有特別限制，可適當使用以往公知的聚合性乙烯基單體。另外，本實施形態中的聚合性乙烯基單體，意指具有一個含乙烯基的基團的聚合性乙烯基單體，不與後述的多官能（甲基）丙烯酸酯單體重複。(2.1.1. Polymerizable vinyl monomers) The polymerizable vinyl monomer is not particularly limited as long as it has a vinyl group-containing group, and conventionally known polymerizable vinyl monomers can be appropriately used. In addition, the polymerizable vinyl monomer in this embodiment means the polymerizable vinyl monomer which has one vinyl group-containing group, and does not overlap with the polyfunctional (meth)acrylate monomer mentioned later.
作為聚合性乙烯基單體的具體例，可列舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸環己酯、（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）丙烯酸十二烷基酯、（甲基）丙烯酸肉豆蔻酯、（甲基）丙烯酸棕櫚酯、（甲基）丙烯酸硬脂基酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸異莰酯、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苄酯、聚氧亞烷基改性（甲基）丙烯酸酯等在分子內不具有除了含乙烯基的基團以外的官能團的（甲基）丙烯酸酯。其中，從對得到的黏著劑賦予適宜的黏著性及形狀追隨性的觀點而言，更佳為使用丙烯酸2-乙基己酯，並且，從使得到的黏著劑顯示黏著性並同時賦予其適宜的凝聚力的觀點而言，較佳為使用丙烯酸異莰酯。Specific examples of polymerizable vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) Amyl acrylate, Hexyl (meth)acrylate, Cyclohexyl (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, (Meth) Isocamphoryl acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, polyoxyalkylene modified (meth)acrylate, etc. do not have groups other than vinyl groups in the molecule (Meth)acrylates with other functional groups. Among them, from the viewpoint of imparting suitable adhesiveness and shape followability to the obtained adhesive, it is more preferable to use 2-ethylhexyl acrylate, and at the same time, it is possible to make the obtained adhesive exhibit adhesiveness while imparting suitable From the viewpoint of cohesion, it is preferable to use isocamphoryl acrylate.
並且，聚合性乙烯基單體亦可在分子內進一步具有除了含乙烯基的基團以外的官能團。作為該官能團的例子，可列舉出羥基、羧基、巰基、及一或二級胺基等。作為具有這樣的官能團的聚合性乙烯基單體的具體例，可列舉出（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸3-羥基丁酯、（甲基）丙烯酸4-羥基丁酯等（甲基）丙烯酸羥基烷基酯；N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺等含羥基的丙烯醯胺類；丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、伊康酸、檸康酸等乙烯性不飽和羧酸等。其中，從使得到的黏著劑的凝聚力適宜、且使耐濕熱白化性良好的觀點而言，較佳為（甲基）丙烯酸羥基烷基酯，尤其，更佳為使用丙烯酸2-羥基乙酯及丙烯酸4-羥基丁酯。In addition, the polymerizable vinyl monomer may further have a functional group other than the vinyl group-containing group in the molecule. As an example of this functional group, a hydroxyl group, a carboxyl group, a mercapto group, and a primary or secondary amino group etc. are mentioned. Specific examples of polymerizable vinyl monomers having such functional groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; N-methylol Acrylamide, N-methylolmethacrylamide and other hydroxyl-containing acrylamides; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and other ethylenically unsaturated Carboxylic acid etc. Among these, hydroxyalkyl (meth)acrylate is preferable from the viewpoint of making the cohesive force of the obtained adhesive suitable and making the heat-and-moisture whitening resistance good, especially, 2-hydroxyethyl acrylate and 4-Hydroxybutyl acrylate.
並且，作為其他聚合性乙烯基單體，可列舉出乙酸乙烯酯、丙酸乙烯酯等乙烯基酯類；乙烯、丙烯、異丁烯等烯烴類；氯乙烯、偏二氯乙烯等鹵代烯烴類；苯乙烯、α-甲基苯乙烯等苯乙烯類單體；丁二烯、異戊二烯、氯丁二烯等二烯類單體；丙烯腈、甲基丙烯腈等腈類單體；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、N-乙烯基吡咯烷酮等醯胺類單體；(甲基)丙烯酸N,N-二乙基胺基乙酯、N-(甲基)丙烯醯
(2.1.2.聚合性乙烯基預聚物) (2.1.2. Polymerizable vinyl prepolymer)
作為聚合性乙烯基預聚物，沒有特別限定，可適當使用以往公知的聚合性乙烯基預聚物，但較佳為使用將上述的聚合性乙烯基單體聚合而成的聚合性乙烯基預聚物。另外，本說明書中，預聚物為單體聚合而成的化合物，意指可藉由進行進一步的聚合而構成聚合物的化合物。 The polymerizable vinyl prepolymer is not particularly limited, and conventionally known polymerizable vinyl prepolymers can be appropriately used, but polymerizable vinyl prepolymers obtained by polymerizing the above-mentioned polymerizable vinyl monomers are preferably used. Polymer. In addition, in this specification, a prepolymer is a compound obtained by polymerizing a monomer, and means the compound which can form a polymer by performing further polymerization.
另外，藉由將上述的聚合性乙烯基單體聚合而得到聚合性乙烯基預聚物之情形，可以單獨將一種該單體聚合，也可以將多種共聚合。 In addition, when the polymerizable vinyl prepolymer is obtained by polymerizing the above-mentioned polymerizable vinyl monomer, one kind of the monomer may be polymerized alone, or a plurality of kinds may be copolymerized.
並且，聚合性乙烯基預聚物可以藉由自由基聚合而得到，也可以藉由活性聚合而得到，特別是也可以為殘留有RAFT(Reversible Addition-Fragmentation Chain Transfer Polymerization，可逆加成斷裂鏈轉移聚合)末端的聚合物。 In addition, the polymerizable vinyl prepolymer can be obtained by radical polymerization or living polymerization, and in particular, it can be obtained by residual RAFT (Reversible Addition-Fragmentation Chain Transfer Polymerization, reversible addition-fragmentation chain transfer) Polymerization) terminal polymers.
聚合性乙烯基預聚物的重量平均分子量較佳為6,000以上，特佳為7,500以上，再佳為10,000以上。並且，該重量平均分子量較佳為1,500,000以下，特佳為1,000,000以下，再佳為100,000以下。藉由使該重量平均分子量為上述範圍內，易於使無溶劑型黏著性組合物的黏度為期望的範圍。另外，本說明書中的重量平均分子量為利用凝膠滲透層析(GPC)法測定的標準聚苯乙烯換算的值。 The weight average molecular weight of the polymerizable vinyl prepolymer is preferably at least 6,000, particularly preferably at least 7,500, and still more preferably at least 10,000. In addition, the weight average molecular weight is preferably at most 1,500,000, particularly preferably at most 1,000,000, further preferably at most 100,000. By making this weight average molecular weight into the said range, it becomes easy to make the viscosity of a non-solvent type adhesive composition into a desired range. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
(2.1.3.多官能(甲基)丙烯酸酯單體) (2.1.3. Multifunctional (meth)acrylate monomer)
作為多官能(甲基)丙烯酸酯單體，沒有特別限定，可適當使用以往公知的多官能（甲基）丙烯酸酯單體。It does not specifically limit as a polyfunctional (meth)acrylate monomer, A conventionally well-known polyfunctional (meth)acrylate monomer can be used suitably.
尤其，作為多官能（甲基）丙烯酸酯單體，可較佳列舉出在一分子中具有兩個以上（甲基）丙烯醯基的單體。作為這樣的單體的例子，可列舉出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、羥基新戊酸新戊二醇二（甲基）丙烯酸酯、二環戊基二（甲基）丙烯酸酯、己內酯改性二環戊烯基二（甲基）丙烯酸酯、環氧乙烷改性磷酸二（甲基）丙烯酸酯、二（丙烯醯氧基乙基）異氰脲酸酯、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、丙酸改性二新戊四醇三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、環氧丙烷改性三羥甲基丙烷三（甲基）丙烯酸酯、參（丙烯醯氧基乙基）異氰脲酸酯、雙（丙烯醯氧基乙基）羥基乙基異氰脲酸酯、異氰脲酸環氧乙烷改性二丙烯酸酯、異氰脲酸環氧乙烷改性三丙烯酸酯、ε-己內酯改性參（丙烯醯氧基乙基）異氰脲酸酯、二甘油四（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、丙酸改性二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、己內酯改性二新戊四醇六（甲基）丙烯酸酯等。In particular, as a polyfunctional (meth)acrylate monomer, the monomer which has two or more (meth)acryl groups in one molecule is mentioned preferably. Examples of such monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylates, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl Di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, bis(acryloxyethyl) Isocyanurate, Allylated Cyclohexyl Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Dineopentaerythritol Tri(meth)acrylate, Propionic Acid Modification Dineopentylthritol tri(meth)acrylate, neopentylthritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, ginseng (acryloxyethyl base) isocyanurate, bis(acryloxyethyl) hydroxyethyl isocyanurate, isocyanurate ethylene oxide modified diacrylate, isocyanurate ethylene oxide modified Triacrylate, ε-caprolactone-modified ginseng (acryloxyethyl) isocyanurate, diglycerol tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, propionic acid Modified diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, caprolactone-modified dipenteoerythritol hexa(meth)acrylate, etc.
（2.1.4. 多官能（甲基）丙烯酸酯低聚物） 作為多官能（甲基）丙烯酸酯低聚物，沒有特別限定，可適當使用以往公知的多官能（甲基）丙烯酸酯低聚物，但較佳為使用在一分子中具有兩個以上的（甲基）丙烯醯基的多官能（甲基）丙烯酸酯低聚物。作為這樣的低聚物的例子，可列舉出胺基甲酸乙酯丙烯酸酯類、聚酯丙烯酸酯類、環氧丙烯酸酯類、聚醚丙烯酸酯類、聚丁二烯丙烯酸酯類、矽酮丙烯酸酯類等低聚物。(2.1.4. Multifunctional (meth)acrylate oligomers) The polyfunctional (meth)acrylate oligomer is not particularly limited, and conventionally known polyfunctional (meth)acrylate oligomers can be appropriately used, but it is preferable to use ( Multifunctional (meth)acrylate oligomer of meth)acryl groups. Examples of such oligomers include urethane acrylates, polyester acrylates, epoxy acrylates, polyether acrylates, polybutadiene acrylates, silicone acrylates, Oligomers such as esters.
胺基甲酸乙酯丙烯酸酯類低聚物例如能夠藉由以下方式得到：使用（甲基）丙烯酸或（甲基）丙烯酸衍生物，對藉由聚亞烷基多元醇、聚醚多元醇、聚酯多元醇、具有羥基末端的氫化異戊二烯、具有羥基末端的氫化丁二烯之類的化合物與聚異氰酸酯的反應而得到的聚胺酯低聚物進行酯化。Urethane acrylate oligomers can be obtained, for example, by using (meth)acrylic acid or (meth)acrylic acid derivatives, by polyalkylene polyols, polyether polyols, poly A polyurethane oligomer obtained by reacting polyisocyanate with a compound such as ester polyol, hydrogenated isoprene having a hydroxyl end, or hydrogenated butadiene having a hydroxyl end is esterified.
此處，作為胺基甲酸乙酯丙烯酸酯類低聚物的製備中使用的聚亞烷基多元醇的例子，可列舉出聚丙二醇、聚乙二醇、聚丁二醇、聚己二醇等，特佳為使用聚丙二醇。另外，得到的胺基甲酸乙酯丙烯酸酯類低聚物的官能基數為3以上之情形，適當組合甘油、三羥甲基丙烷、三乙醇胺、新戊四醇、乙二胺、二乙烯三胺、山梨醇、蔗糖等即可。Here, examples of the polyalkylene polyol used in the preparation of the urethane acrylate oligomer include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polyethylene glycol, etc. , particularly preferably polypropylene glycol. In addition, when the number of functional groups of the obtained urethane acrylate oligomer is 3 or more, an appropriate combination of glycerin, trimethylolpropane, triethanolamine, neopentylthritol, ethylenediamine, and diethylenetriamine , sorbitol, sucrose, etc.
此外，作為聚異氰酸酯的例子，可列舉出六亞甲基二異氰酸酯、三亞甲基二異氰酸酯等脂肪族二異氰酸酯；甲苯二異氰酸酯、苯二亞甲基二異氰酸酯、二苯基二異氰酸酯等芳香族二異氰酸酯；二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯等脂環式二異氰酸酯等，其中，較佳為使用脂肪族二異氰酸酯，特佳為使用六亞甲基二異氰酸酯。另外，聚異氰酸酯不限於雙官能，還可使用三官能以上的聚異氰酸酯。In addition, examples of polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylene diisocyanate; aromatic diisocyanates such as toluene diisocyanate, xylylene diisocyanate and diphenyl diisocyanate; Isocyanates; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate, etc. Among them, aliphatic diisocyanate is preferably used, and hexamethylene diisocyanate is particularly preferably used. In addition, the polyisocyanate is not limited to difunctional ones, and trifunctional or higher polyisocyanates can also be used.
並且，作為（甲基）丙烯酸衍生物，可列舉出丙烯酸2-羥基乙酯、丙烯酸4-羥基丁酯等（甲基）丙烯酸羥基烷基酯、丙烯酸2-異氰基乙酯、甲基丙烯酸2-異氰基乙酯、1,1-雙（丙烯醯氧基甲基）乙基異氰酸酯等，特佳為使用丙烯酸2-異氰基乙酯。In addition, examples of (meth)acrylic acid derivatives include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, 2-isocyanoethyl acrylate, methacrylic acid 2-Isocyanoethyl ester, 1,1-bis(acryloxymethyl)ethyl isocyanate, etc., especially preferably use 2-isocyanoethyl acrylate.
作為胺基甲酸乙酯丙烯酸酯類低聚物的其他製備方法，還可藉由聚亞烷基多元醇、聚醚多元醇、聚酯多元醇、具有羥基末端的氫化異戊二烯、具有羥基末端的氫化丁二烯之類的化合物所具有的羥基與（甲基）丙烯酸異氰基烷基酯所具有的-N＝C＝O部分之間的反應而得到胺基甲酸乙酯丙烯酸酯類低聚物。在此情形，作為該（甲基）丙烯酸異氰基烷基酯，可使用上述的丙烯酸2-異氰基乙酯、甲基丙烯酸2-異氰基乙酯、1,1-雙（丙烯醯氧基甲基）乙基異氰酸酯等。As other preparation methods of urethane acrylate oligomers, polyalkylene polyols, polyether polyols, polyester polyols, hydrogenated isoprene with hydroxyl ends, The reaction between the hydroxyl groups of compounds such as terminal hydrogenated butadiene and the -N=C=O moieties of isocyanoalkyl (meth)acrylates gives urethane acrylates Oligomer. In this case, as the isocyanoalkyl (meth)acrylate, the above-mentioned 2-isocyanoethyl acrylate, 2-isocyanoethyl methacrylate, 1,1-bis(acryl Oxymethyl) ethyl isocyanate, etc.
聚酯丙烯酸酯類低聚物例如能夠藉由以下方式得到：使用（甲基）丙烯酸，將藉由多元羧酸與多元醇的縮合而得到的在兩末端具有羥基的聚酯低聚物的羥基酯化；或者使用（甲基）丙烯酸，將對多元羧酸加成烯化氧而得到的低聚物的末端的羥基酯化。The polyester acrylate oligomer can be obtained, for example, by using (meth)acrylic acid to convert the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polycarboxylic acid and a polyhydric alcohol to Esterification; Alternatively, using (meth)acrylic acid, the terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid is esterified.
環氧丙烯酸酯類低聚物例如能夠藉由使（甲基）丙烯酸與較低分子量的雙酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧環進行反應並進行酯化而得到。並且，還能夠使用將環氧丙烯酸酯類低聚物用二元羧酸酐進行部分改性而得到的羧基改性型的環氧丙烯酸酯類低聚物。The epoxy acrylate oligomer can be obtained by, for example, reacting (meth)acrylic acid with an epoxy ring of a relatively low molecular weight bisphenol-type epoxy resin or a novolac-type epoxy resin to esterify them. In addition, a carboxyl-modified epoxy acrylate oligomer obtained by partially modifying an epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
聚醚丙烯酸酯類低聚物例如能夠藉由將聚醚多元醇的羥基用（甲基）丙烯酸進行酯化而得到。The polyether acrylate oligomer can be obtained by esterifying the hydroxyl group of polyether polyol with (meth)acrylic acid, for example.
多官能（甲基）丙烯酸酯低聚物的重量平均分子量較佳為10,000以上，特佳為20,000以上。並且，該重量平均分子量較佳為350,000以下，特佳為200,000以下。The weight average molecular weight of the polyfunctional (meth)acrylate oligomer is preferably at least 10,000, particularly preferably at least 20,000. In addition, the weight average molecular weight is preferably at most 350,000, particularly preferably at most 200,000.
（2.1.5. 摻合比例） 用聚合性乙烯基單體的質量除以聚合性乙烯基單體中具有除了含乙烯基的基團以外的官能團的聚合性乙烯基單體的質量而得到的比例較佳為1.7以上，更佳為2以上，再佳為3以上。並且，該比例較佳為10以下，更佳為5以下，再佳為4以下。只要該比例為上述的值的範圍，則得到的黏著劑可發揮良好的耐濕熱白化性。(2.1.5. Blending ratio) The ratio obtained by dividing the mass of the polymerizable vinyl monomer by the mass of the polymerizable vinyl monomer having functional groups other than vinyl-containing groups in the polymerizable vinyl monomer is preferably 1.7 or more, more preferably It is 2 or more, more preferably 3 or more. And, this ratio is preferably 10 or less, more preferably 5 or less, and still more preferably 4 or less. As long as the ratio is within the range of the above-mentioned value, the obtained adhesive can exhibit good heat-and-moisture whitening resistance.
並且，使用聚合性乙烯基單體及多官能（甲基）丙烯酸酯低聚物這兩種作為聚合成分之情形，用聚合性乙烯基單體的質量除以多官能（甲基）丙烯酸酯低聚物的質量而得到的比例較佳為0.18以上，更佳為1以上，再佳為1.5以上。若該比例為上述的值，則得到的黏著劑變得易發揮適宜的黏著力。並且，該比例較佳為999以下，更佳為19以下，特佳為9以下，進一步，從得到的黏著劑發揮適宜的凝聚力的觀點而言，特佳為3以下。若該比例為上述的值的範圍，則得到的黏著劑可發揮良好的耐起泡性及形狀追隨性。In addition, when two polymerizable vinyl monomers and polyfunctional (meth)acrylate oligomers are used as polymerization components, the mass of the polymerizable vinyl monomer divided by the polyfunctional (meth)acrylate low The ratio obtained based on the mass of the polymer is preferably at least 0.18, more preferably at least 1, and even more preferably at least 1.5. When this ratio is the value mentioned above, the obtained adhesive becomes easy to exhibit suitable adhesive force. In addition, the ratio is preferably 999 or less, more preferably 19 or less, particularly preferably 9 or less, and further preferably 3 or less from the viewpoint that the obtained adhesive exhibits a suitable cohesive force. If this ratio is in the range of the said value, the obtained adhesive can exhibit favorable anti-foaming property and shape followability.
（2.2. 光聚合起始劑） 本實施形態的光聚合起始劑為在濃度為0.1質量%的乙腈溶液中的波長380nm的吸光度為1.0以上的光聚合起始劑。即，藉由使光聚合起始劑的吸光亦產生在較長波長側，即使本實施形態的無溶劑型黏著性組合物中包含後述的紫外線吸收劑，也可利用具有比該紫外線吸收劑所吸收的光的波長更長的波長的光的能量，而使無溶劑型黏著性組合物充分聚合，製成具有紫外線吸收能力的黏著劑。(2.2. Photopolymerization initiator) The photopolymerization initiator of this embodiment is a photopolymerization initiator whose absorbance at a wavelength of 380 nm in an acetonitrile solution having a concentration of 0.1% by mass is 1.0 or more. That is, by making the light absorption of the photopolymerization initiator also occur on the longer wavelength side, even if the ultraviolet absorber described later is included in the non-solvent type adhesive composition of this embodiment, it is possible to utilize The energy of light with a longer wavelength than the absorbed light allows the solvent-free adhesive composition to be fully polymerized to form an adhesive with ultraviolet absorbing ability.
並且，本實施形態的光聚合起始劑較佳為僅由在波長400nm以上具有吸收帶的光聚合起始劑構成。「在波長400nm以上具有吸收帶」意指在波長400nm以上，吸光度為0.5以上。Moreover, it is preferable that the photoinitiator of this embodiment consists of only the photoinitiator which has an absorption band in wavelength 400nm or more. "Having an absorption band at a wavelength of 400 nm or more" means that the absorbance is 0.5 or more at a wavelength of 400 nm or more.
光聚合起始劑的波長380nm的吸光度較佳為1.1以上，更佳為1.2以上。該吸光度的上限值沒有特別限定，但通常較佳為2.5以下，更佳為2.0以下。若吸光度過大，則在形成或保管黏著片時，有會因螢光燈等環境光而進行由光聚合起始劑所致之光聚合成分的固化反應的情形。另外，光聚合起始劑的吸光度利用後述的實施例所示的方法進行測定即可。The absorbance at a wavelength of 380 nm of the photopolymerization initiator is preferably at least 1.1, more preferably at least 1.2. The upper limit of the absorbance is not particularly limited, but is usually preferably 2.5 or less, more preferably 2.0 or less. When the absorbance is too large, the curing reaction of the photopolymerization component by the photopolymerization initiator may proceed due to ambient light such as a fluorescent lamp when the adhesive sheet is formed or stored. In addition, the absorbance of a photoinitiator may be measured by the method shown in the Example mentioned later.
並且，光聚合起始劑中，濃度為0.1質量%的乙腈溶液中的波長200~500nm的吸光度的最大吸收波長較佳在360nm以上，更佳在370nm以上，再佳在380nm以上。另外，在波長200~500nm的吸光度的最大吸收波長存在多個之情形中，至少一個最大吸收波長在上述範圍內即可。In addition, in the photopolymerization initiator, the maximum absorption wavelength of the absorbance at a wavelength of 200 to 500 nm in an acetonitrile solution having a concentration of 0.1% by mass is preferably at least 360 nm, more preferably at least 370 nm, and even more preferably at least 380 nm. In addition, when there are a plurality of maximum absorption wavelengths of absorbance at a wavelength of 200 to 500 nm, at least one of the maximum absorption wavelengths may be within the above-mentioned range.
尤其，本實施形態的光聚合起始劑較佳為僅由最大吸收波長為360nm以上的光聚合起始劑構成。Especially, it is preferable that the photoinitiator of this embodiment consists of only the photoinitiator whose maximum absorption wavelength is 360 nm or more.
藉由使最大吸收波長在上述的範圍內，可將可使本實施形態的無溶劑型黏著性組合物充分聚合的程度的能量供給至無溶劑型黏著性組合物。其結果，可得到具有紫外線吸收能力、且形狀追隨性及耐起泡性更優異的黏著劑。By setting the maximum absorption wavelength within the above-mentioned range, it is possible to supply to the solvent-free adhesive composition the energy of the grade that can sufficiently polymerize the solvent-free adhesive composition of the present embodiment. As a result, it is possible to obtain an adhesive that has ultraviolet absorbing ability and is more excellent in shape followability and anti-foaming property.
另一方面，上述最大吸收波長的上限值沒有特別限制，但從與吸光度相同的、防止因環境光造成的聚合反應的觀點而言，較佳為450nm以下，更佳為410nm以下，再佳為405nm以下。On the other hand, the upper limit of the above-mentioned maximum absorption wavelength is not particularly limited, but from the viewpoint of preventing polymerization reaction caused by ambient light, which is the same as the absorbance, it is preferably 450 nm or less, more preferably 410 nm or less, and even more preferably Below 405nm.
並且，光聚合起始劑的熔點（MP）較佳為60℃以上，更佳為80℃以上。熔點的上限沒有特別限制，但本實施形態中為150℃左右。In addition, the melting point (MP) of the photopolymerization initiator is preferably 60° C. or higher, more preferably 80° C. or higher. The upper limit of the melting point is not particularly limited, but is about 150°C in the present embodiment.
若熔點過低，則有會因活性能量射線照射中的熱（因黏著劑的聚合反應導致的熱、來自光源的熱等）而產生從固體往液體的狀態變化的情形。若產生這樣的光聚合起始劑的狀態變化，則交聯結構的形成程度也有發生變化的傾向。其結果，有覆膜強度產生偏差，使形狀追隨性惡化的傾向。If the melting point is too low, a state change from solid to liquid may occur due to heat in active energy ray irradiation (heat due to polymerization reaction of the adhesive, heat from a light source, etc.). When such a state change of the photopolymerization initiator occurs, the degree of formation of the crosslinked structure also tends to change. As a result, the film strength tends to vary, which tends to degrade the shape followability.
作為這樣的光聚合起始劑，例如可列舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦、苯基雙（2,4,6-三甲基苯甲醯基）氧化膦等。此等可以單獨使用，也可以組合兩種以上使用。Examples of such photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl base) phosphine oxide, etc. These may be used alone or in combination of two or more.
相對於光聚合成分100質量份，光聚合起始劑的含量為0.1質量份以上，較佳為0.5質量份以上。並且，光聚合起始劑的含量為4.0質量份以下，較佳為3.0質量份以下。Content of a photoinitiator is 0.1 mass part or more with respect to 100 mass parts of photopolymerization components, Preferably it is 0.5 mass part or more. In addition, the content of the photopolymerization initiator is not more than 4.0 parts by mass, preferably not more than 3.0 parts by mass.
（2.3. 紫外線吸收劑） 本實施形態的無溶劑型黏著性組合物含有紫外線吸收劑。藉由含有紫外線吸收劑，例如即使顯示體的保護面板由透射紫外線的玻璃或塑料等構成，無溶劑型黏著性組合物固化而成的黏著劑也可吸收紫外線。因此，可抑制構成顯示體的構件的劣化。(2.3. UV absorber) The solvent-free adhesive composition of this embodiment contains an ultraviolet absorber. By containing the ultraviolet absorber, for example, even if the protective panel of the display body is made of glass or plastic that transmits ultraviolet rays, the adhesive obtained by curing the solvent-free adhesive composition can absorb ultraviolet rays. Therefore, deterioration of members constituting the display body can be suppressed.
作為紫外線吸收劑，例如可列舉出二苯甲酮類紫外線吸收劑、苯并***類紫外線吸收劑、三𠯤類紫外線吸收劑、水楊酸類紫外線吸收劑、草酸苯胺類紫外線吸收劑、氰基丙烯酸酯類紫外線吸收劑等。這些紫外線吸收劑可以單獨使用一種或者組合兩種以上使用。Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, trioxetine-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid aniline-based ultraviolet absorbers, cyano Acrylic UV absorbers, etc. These ultraviolet absorbers can be used alone or in combination of two or more.
作為二苯甲酮類紫外線吸收劑，例如可列舉出2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-苄氧基二苯甲酮、2-羥基-4-甲氧基-5-磺醯氧基二苯甲酮（2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone)、2-羥基-4-甲氧基-5-磺醯氧基三水合物二苯甲酮（2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone)、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基-5-硫氧基二苯甲酮鈉、雙（5-苯甲醯基-4-羥基-2-甲氧基苯基）甲烷、2-羥基-4-正十二烷基氧基二苯甲酮、2-羥基-4-甲氧基-2’-羧基二苯甲酮等。Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxydiphenyl Methanone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonyloxybenzophenone (2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone ), 2-hydroxy-4-methoxy-5-sulfonyloxytrihydrate benzophenone (2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone), 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 Sodium '-dihydroxy-4,4'-dimethoxy-5-sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2 -Hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.
作為苯并***類紫外線吸收劑，例如可列舉出2-（2-羥基-5-甲基苯基）苯并***、2-（2-羥基-5-三級辛基苯基）苯并***、2-（2-羥基-3,5-二異丙苯基苯基）苯基苯并***、2-（2-羥基-3-三級丁基-5-甲基苯基）-5-氯代苯并***、2,2’-亞甲基雙[4-（1,1,3,3-四甲基丁基）-6-（2H-苯并***-2-基）苯酚]、2-（2-羥基-3,5-二-三級丁基苯基）苯并***、2-（2-羥基-3,5-二-三級丁基苯基）-5-氯代苯并***、2-（2-羥基-3,5-二-三級戊基苯基）苯并***、2-（2-羥基-5-三級辛基苯基）苯并***、2-（2-羥基-5-三級丁基苯基）苯并***、2-（2-羥基-4-辛氧基苯基）苯并***、2,2’-亞甲基雙（4-異丙苯基-6-苯并***苯基）、2,2’-對亞苯基雙（1,3-苯并㗁𠯤-4-酮、2-[2-羥基-3-（3,4,5,6-四氫鄰苯二甲醯亞胺甲基）-5-甲基苯基]苯并***等。Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tertiary octylphenyl)benzene Triazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tertiary butyl-5-methylphenyl )-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2 -yl)phenol], 2-(2-hydroxy-3,5-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl )-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tertiary pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tertiary octylbenzene base) benzotriazole, 2-(2-hydroxy-5-tertiary butylphenyl) benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl) benzotriazole, 2, 2'-methylenebis(4-isopropylphenyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzo㗁𠯤-4-one, 2 -[2-Hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc.
作為三𠯤類紫外線吸收劑，例如可列舉出2-（2-羥基-4-甲氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-乙氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-丙氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-丁氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-己氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-辛氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-十二烷氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2-（2-羥基-4-苄氧基苯基）-4,6-二苯基-1,3,5-三𠯤、2,4-雙（2-羥基-4-丁氧基苯基）-6-（2,4-二丁氧基苯基）-1,3,5-三𠯤、2,4,6-參（2-羥基-4-己氧基-3-甲基苯基）-1,3,5-三𠯤、2-（2-羥基-4-[1-辛氧基羰基乙氧基]苯基）-4,6-雙（4-苯基苯基）-1,3,5-三𠯤、2-[4-[（2-羥基-3-十二烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-[4-[（2-羥基-3-十三烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-[4-[（2-羥基-3-（2’-乙基）己基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2,4-雙（2,4-二甲基苯基）-6-[2-羥基-4-（3-辛氧基-2-羥基丙氧基）-5-α-異丙苯基苯基]-s-三𠯤、2,4-雙（2,4-二甲基苯基）-6-[2-羥基-4-（3-壬氧基-2-羥基丙氧基）-5-α-異丙苯基苯基]-s-三𠯤、2,4-雙（2,4-二甲基苯基）-6-[2-羥基-4-（3-癸氧基-2-羥基丙氧基）-5-α-異丙苯基苯基]-s-三𠯤、2-（2-羥基-4-丙烯醯基氧基乙氧基苯基）-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤等。Examples of trioxetine-based ultraviolet absorbers include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triphosphonium, 2-(2- Hydroxy-4-ethoxyphenyl)-4,6-diphenyl-1,3,5-triphenyl, 2-(2-hydroxy-4-propoxyphenyl)-4,6-diphenyl Base-1,3,5-trimethanone, 2-(2-hydroxy-4-butoxyphenyl)-4,6-diphenyl-1,3,5-trimethanium, 2-(2-hydroxy -4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triphenylene, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-diphenyl -1,3,5-Triphenyl, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-diphenyl-1,3,5-Triphenyl, 2-(2- Hydroxy-4-benzyloxyphenyl)-4,6-diphenyl-1,3,5-trimethanone, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-( 2,4-dibutoxyphenyl)-1,3,5-trimethanone, 2,4,6-paraffin (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3 ,5-Trisalpine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5- Trisalpine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-tri-(3-tridecyl)-, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2 ,4-Dimethylphenyl)-1,3,5-trimethanone, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl ]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl, 2,4-bis(2,4-dimethylphenyl)-6-[2- Hydroxy-4-(3-octyloxy-2-hydroxypropoxy)-5-α-cumylphenyl]-s-trimethanone, 2,4-bis(2,4-dimethylbenzene base)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropoxy)-5-α-cumylphenyl]-s-tri-sulfone, 2,4-bis( 2,4-Dimethylphenyl)-6-[2-hydroxy-4-(3-decyloxy-2-hydroxypropoxy)-5-α-cumylphenyl]-s-tri 𠯤, 2-(2-hydroxy-4-acryloxyethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl, etc.
作為水楊酸類紫外線吸收劑，例如可列舉出水楊酸苯酯、水楊酸對三級丁基苯酯、水楊酸對辛基苯基酯等。Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tertiary butylphenyl salicylate, p-octylphenyl salicylate, and the like.
作為氰基丙烯酸酯類紫外線吸收劑，例如可列舉出2-乙基己基-2-氰基-3,3’-二苯基丙烯酸酯、乙基-2-氰基-3,3’-二苯基丙烯酸酯等。Examples of cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, Phenylacrylate, etc.
其中，較佳為選自二苯甲酮類紫外線吸收劑、苯并***類紫外線吸收劑及三𠯤類紫外線吸收劑中的一種以上，更佳為選自二苯甲酮類紫外線吸收劑及苯并***類紫外線吸收劑中的一種以上。Among them, preferably more than one selected from benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazole-based ultraviolet absorbers, more preferably selected from benzophenone-based ultraviolet absorbers and One or more types of benzotriazole-based ultraviolet absorbers.
相對於光聚合成分100質量份（固體成分），紫外線吸收劑的含量為0.1質量份以上且4.0質量份以下。若紫外線吸收劑的含量過少，則紫外線的吸收變得不充分，有無法抑制構成顯示體的構件的劣化的傾向。另一方面，若紫外線吸收劑的含量過多，則無溶劑型黏著性組合物的固化中利用的光也被一定程度地吸收，有無溶劑型黏著性組合物的固化不充分的傾向。Content of an ultraviolet absorber is 0.1 mass part or more and 4.0 mass parts or less with respect to 100 mass parts of photopolymerization components (solid content). When the content of the ultraviolet absorber is too small, absorption of ultraviolet rays becomes insufficient, and there is a tendency that deterioration of members constituting the display body cannot be suppressed. On the other hand, when the content of the ultraviolet absorber is too large, the light used for curing the solvent-free adhesive composition is also absorbed to some extent, and the curing of the solvent-free adhesive composition tends to be insufficient.
並且，紫外線吸收劑的含量較佳為0.3質量份以上，更佳為0.5質量份以上。並且，紫外線吸收劑的含量較佳為3.0質量份以下，更佳為2.0質量份以下。Furthermore, the content of the ultraviolet absorber is preferably at least 0.3 parts by mass, more preferably at least 0.5 parts by mass. In addition, the content of the ultraviolet absorber is preferably at most 3.0 parts by mass, more preferably at most 2.0 parts by mass.
（1.4. 矽烷偶聯劑） 本實施形態的無溶劑型黏著性組合物較佳為進一步含有矽烷偶聯劑。藉此，若被黏物為玻璃構件，則得到的黏著劑與該玻璃構件的密著性提高。此外，即使被黏物為塑料板，得到的黏著劑與塑料板的密著性也提高。因此，得到的黏著劑在高溫高濕條件下的形狀追隨性及耐起泡性更加優異。(1.4. Silane coupling agent) It is preferable that the solvent-free adhesive composition of this embodiment further contains a silane coupling agent. Thereby, if the to-be-adhered body is a glass member, the adhesiveness of the obtained adhesive agent and this glass member improves. Moreover, even if the adherend is a plastic board, the adhesiveness of the obtained adhesive agent and a plastic board improves. Therefore, the obtained adhesive is more excellent in shape followability and anti-foaming property under high-temperature and high-humidity conditions.
本實施形態中，作為矽烷偶聯劑，較佳為在分子內具有至少一個烷氧基甲矽烷基且具有透光性的有機矽化合物。In this embodiment, as the silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule and having light transparency is preferable.
作為這樣的矽烷偶聯劑，例如可列舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷等含有聚合性不飽和基團的矽化合物；3-縮水甘油醚氧基丙基三甲氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷等具有環氧結構的矽化合物；3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等含巰基的矽化合物；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含胺基的矽化合物；3-氯丙基三甲氧基矽烷；3-異氰酸酯基丙基三乙氧基矽烷；或這些矽烷偶聯劑中的至少一種與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等含烷基的矽化合物的縮合物等。它們可以單獨使用一種，也可以組合兩種以上使用。Examples of such silane coupling agents include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane. ; 3-glycidyl etheroxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane and other silicon compounds with epoxy structure; 3-mercaptopropyl trimethoxy Silane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane and other mercapto-containing silicon compounds; 3-aminopropyltrimethoxysilane, N-(2-amino Amino-containing silicon compounds such as ethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-chloro Propyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane; or at least one of these silane coupling agents in combination with methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxy Condensates of alkyl-containing silicon compounds such as silane and ethyltrimethoxysilane. These may be used alone or in combination of two or more.
相對於光聚合成分100質量份，矽烷偶聯劑的含量較佳為0.05質量份以上，更佳為0.1質量份以上，再佳為0.15質量份以上。並且，該含量較佳為1.0質量份以下，更佳為0.8質量份以下，再佳為0.5質量份以下。The content of the silane coupling agent is preferably at least 0.05 parts by mass, more preferably at least 0.1 parts by mass, and still more preferably at least 0.15 parts by mass with respect to 100 parts by mass of the photopolymerizable component. And, the content is preferably at most 1.0 parts by mass, more preferably at most 0.8 parts by mass, and even more preferably at most 0.5 parts by mass.
（2.5. 各種添加劑） 本實施形態的無溶劑型黏著性組合物也可以根據需要含有各種添加劑。作為這樣的添加劑，例如可例示出抗靜電劑、增黏劑、抗氧化劑、光穩定劑、軟化劑、填充劑、折射率調節劑等。(2.5. Various additives) The solvent-free adhesive composition of this embodiment may contain various additives as needed. Examples of such additives include antistatic agents, thickeners, antioxidants, light stabilizers, softeners, fillers, and refractive index modifiers.
（2.6. 無溶劑型黏著性組合物的固化） 上述的無溶劑型黏著性組合物的固化藉由活性能量射線的照射而進行。活性能量射線是指電磁波或帶電粒子束中具有能量量子的活性能量射線，具體而言，可列舉出紫外線、電子束等。本實施形態中，作為活性能量射線，較佳為包含具有200~450nm的波長的光的活性能量射線。(2.6. Curing of solvent-free adhesive composition) Curing of the above-mentioned solvent-free adhesive composition is performed by irradiation of active energy rays. The active energy ray refers to an active energy ray having an energy quantum in an electromagnetic wave or a charged particle beam, and specific examples thereof include ultraviolet rays, electron beams, and the like. In this embodiment, active energy rays containing light having a wavelength of 200 to 450 nm are preferable as the active energy rays.
滿足上述條件的活性能量射線例如可藉由使用高壓汞燈、融合H燈（fusion H lamp）、氙氣燈等能照射紫外線的光源而得到。高壓汞燈之情形，主波長雖為365nm，但由於也照射具有405nm、436nm的波長的光，因此可將比主波長更靠近長波長側的光用於無溶劑型黏著性組合物的固化。Active energy rays satisfying the above conditions can be obtained, for example, by using a light source capable of irradiating ultraviolet light, such as a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp. In the case of a high-pressure mercury lamp, although the dominant wavelength is 365nm, since light having wavelengths of 405nm and 436nm is also irradiated, light on the longer wavelength side than the dominant wavelength can be used for curing the solvent-free adhesive composition.
活性能量射線的照射條件的照度較佳為10mW/cm2 以上且1000mW/cm2 以下，更佳為20mW/cm2 以上且500mW/cm2 以下。光量較佳為50mJ/cm2 以上，更佳為80mJ/cm2 以上，特佳為200mJ/cm2 以上。並且，光量較佳為10000mJ/cm2 以下，更佳為5000mJ/cm2 以下，特佳為2000mJ/cm2 以下。The illuminance of the irradiation conditions of active energy rays is preferably from 10 mW/cm 2 to 1000 mW/cm 2 , more preferably from 20 mW/cm 2 to 500 mW/cm 2 . The amount of light is preferably at least 50 mJ/cm 2 , more preferably at least 80 mJ/cm 2 , and most preferably at least 200 mJ/cm 2 . In addition, the amount of light is preferably at most 10000 mJ/cm 2 , more preferably at most 5000 mJ/cm 2 , and most preferably at most 2000 mJ/cm 2 .
並且，用於使無溶劑型黏著性組合物固化的活性能量射線的照射可以進行一次，也可以進行兩次以上。In addition, the irradiation of the active energy ray for curing the non-solvent type adhesive composition may be performed once, or may be performed twice or more.
（2.7. 凝膠分率） 本實施形態的黏著劑的凝膠分率為50%以上且90%以下。藉由使黏著劑的凝膠分率在上述範圍內，段差追隨性變得極其良好，可顯示良好的形狀追隨性。即，除了段差追隨性以外，對於即使段差追隨性良好也難以進行追隨的點狀的異物、尤其是比印刷段差更大的異物的追隨性也變得良好。(2.7. Gel Fraction) The adhesive of this embodiment has a gel fraction of not less than 50% and not more than 90%. By setting the gel fraction of the adhesive within the above-mentioned range, step followability becomes extremely good, and good shape followability can be exhibited. That is, in addition to the level difference followability, the followability to dot-shaped foreign matter that is difficult to follow even if the level difference followability is good, especially foreign matter larger than the printing level difference becomes good.
藉由使形狀追隨性變得良好，例如即使在作為黏著劑的貼合面的保護面板附近存在比印刷段差更大的異物之情形，黏著劑也可沿著異物的表面充分地追隨。藉此，可抑制在異物與黏著劑之間形成空隙。即，即使在黏著劑的貼合面存在一些異物，也能夠使貼合的黏著劑充分地追隨段差，同時可在黏著劑內填埋異物（收進），可得到具有在實際使用中不會成為問題的程度的外觀品質的顯示體。本說明書中，將具有比印刷段差更大的球形的矽珠看作異物，將黏著劑對其表面的追隨性定義為異物填埋性。By improving the shape followability, for example, even if there is a foreign matter larger than the printing step near the protective panel as the bonding surface of the adhesive, the adhesive can sufficiently follow the surface of the foreign matter. Thereby, the formation of a void between the foreign matter and the adhesive can be suppressed. That is, even if there are some foreign matter on the bonding surface of the adhesive, the bonded adhesive can fully follow the level difference, and at the same time, the foreign matter can be buried (retracted) in the adhesive, and it is possible to obtain a The display body of the appearance quality of the degree which becomes a problem. In this specification, a silicon bead having a spherical shape larger than a printing step is regarded as a foreign matter, and the followability of the adhesive on its surface is defined as foreign matter embedding property.
凝膠分率較佳為60%以上，更佳為64%以上，再佳為68%以上，特佳為70%以上。並且，該凝膠分率較佳為90%以下，更佳為85%以下，從形狀追隨性的觀點而言，特佳為79%以下。黏著劑的凝膠分率藉由後述的試驗例所示的方法進行測定即可。The gel fraction is preferably above 60%, more preferably above 64%, even more preferably above 68%, and most preferably above 70%. In addition, the gel fraction is preferably at most 90%, more preferably at most 85%, and particularly preferably at most 79% from the viewpoint of shape followability. What is necessary is just to measure the gel fraction of an adhesive by the method shown in the test example mentioned later.
（2.8. 單體殘留量） 可利用活性能量射線而使無溶劑型黏著性組合物所包含的單體的大部分固化而得到本實施形態的黏著劑。因此，該黏著劑中殘留有既定量（單體殘留量）的未固化（聚合）的單體，若單體殘留量過多，則可能引起金屬感測器的腐蝕或耐起泡性的降低，有無法得到期望的黏著力的傾向。從上述的觀點而言，單體殘留量的合計較佳為1000ppm以下，更佳為450ppm以下。單體殘留量的下限值沒有特別限定，但通常為0ppm以上。(2.8. Monomer residues) The adhesive agent of this embodiment can be obtained by hardening most of the monomer contained in a solventless adhesive composition by an active energy ray. Therefore, a predetermined amount (residual amount of monomer) of uncured (polymerized) monomer remains in the adhesive. If the amount of residual monomer is too large, it may cause corrosion of the metal sensor or decrease the resistance to foaming. There is a tendency that the desired adhesion cannot be obtained. From the above viewpoint, the total amount of residual monomers is preferably at most 1000 ppm, more preferably at most 450 ppm. The lower limit of the residual monomer amount is not particularly limited, but is usually 0 ppm or more.
（3. 黏著片）
如圖1所示，本實施形態的黏著片1具有由上述的黏著劑構成的黏著劑層11、與剝離片12a、12b。兩片剝離片12a、12b以其剝離面與該黏著劑層的兩個主面接觸的方式而配置。換而言之，黏著劑層11被兩片剝離片12a、12b夾持。另外，本說明書中的剝離片的剝離面是指剝離片中具有剝離性的面，也包含經剝離處理的面以及雖未經剝離處理但顯示剝離性的面中的任一種。(3. Adhesive sheet)
As shown in FIG. 1, the
（3.1. 黏著劑層）
黏著劑層11由上述的黏著劑構成。黏著劑層11的厚度較佳為150μm以上，更佳為200μm以上。另一方面，該厚度較佳為1000μm以下，更佳為600μm以下。由於無溶劑型黏著性組合物能夠以一次塗布而形成的黏著劑層的厚度厚，因此即使黏著劑層11的厚度如上述般厚，也可抑制步驟數量的增加。(3.1. Adhesive layer)
The
（3.2. 剝離片）
剝離片12a、12b保護黏著劑層11直至使用黏著片1時，其在使用黏著片1（黏著劑層11）時被剝離。本實施形態的黏著片1中，剝離片12a、12b中的一者或兩者不一定是必需的。(3.2. Peeling sheet)
The
作為剝離片12a、12b，例如可列舉出聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺酯膜、乙烯乙酸乙烯酯膜、離子聚合物樹脂膜、乙烯-（甲基）丙烯酸共聚物膜、乙烯-（甲基）丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。並且，還可以使用它們的交聯膜。進一步，也可以為它們的層疊膜。As the
較佳為對上述剝離片12a、12b的剝離面（特別是與黏著劑層11接觸的面）實施剝離處理。作為用於剝離處理的剝離劑，例如可列舉出醇酸類、矽酮類、氟類、不飽和聚酯類、聚烯烴類、蠟類的剝離劑。It is preferable to perform a release process on the release surfaces of the
另外，在剝離片12a、12b中，較佳為將一個剝離片設為剝離力大的重剝離型剝離片，將另一個剝離片設為剝離力小的輕剝離型剝離片。In addition, among the
雖然對於剝離片12a、12b的厚度沒有特別限制，但通常為20μm以上且150μm以下。Although the thickness of the
（3.3. 物性） 本實施形態的黏著片具有以下所示的物性。(3.3. Physical properties) The adhesive sheet of this embodiment has the physical properties shown below.
（3.3.1. 黏著力）
本實施形態的黏著片1對鈉鈣玻璃的黏著力較佳為5N/25mm以上，更佳為10N/25mm以上，特佳為15N/25mm以上，再佳為21N/25mm以上。並且，該黏著力較佳為50N/25mm以下，特佳為40N/25mm以下，再佳為35N/25mm以下。(3.3.1. Adhesion)
The adhesive force of the
若黏著片1的黏著力過小，則有耐起泡性差的傾向。並且，若黏著片1的黏著力過大，則有難以獲得良好的再加工性的傾向。即，產生貼合失誤之情形，無法再利用昂貴的顯示體構成構件。本說明書中的黏著力是指基本上根據JIS Z0237:2009的180度剝離法而測定的黏著力，具體的測定方法如後述的試驗例所示。When the adhesive force of the
（3.3.2. 霧度值）
本實施形態的黏著片1的黏著劑層11的霧度值較佳為5%以下，特佳為3%以下，再佳為1%以下。若黏著劑層11的霧度值為5%以下，則透明性高，適宜作為光學用途（顯示體用）。霧度值的下限值沒有特別限定，但通常為0%以上。另外，本說明書中的霧度值為依據JIS K7136:2000所測定的值。(3.3.2. Haze value)
The haze value of the
（3.3.3. 儲能模數）
針對本實施形態的黏著片1的黏著劑層11，以頻率1kHz測定的儲能模數較佳為0.40MPa以下，更佳為0.20MPa以下，特佳為0.09MPa以下。另一方面，該儲能模數較佳為0.01MPa以上，更佳為0.03MPa以上，特佳為0.05MPa以上。(3.3.3. Energy storage modulus)
The storage modulus of the
在黏著劑層11的儲能模數為上述範圍內之情形，黏著劑層11具有適宜的柔軟性，變得易於顯示良好的形狀追隨性。而且，由於變得易於具有適宜的凝聚力及黏著性，因此可表現良好的耐起泡性。When the storage modulus of the
（3.3.4. 損耗正切）
針對本實施形態的黏著片1的黏著劑層11，損耗正切（tanδ）較佳為1.0以上，更佳為1.5以上。另一方面，該損耗正切較佳為2.1以下，更佳為1.8以下。(3.3.4. Loss tangent)
For the
損耗正切（tanδ）被定義為「損耗模數/儲能模數」，為利用動態黏彈性測定裝置並依據對應於施加至對象物的拉伸應力或扭轉應力等應力的應答而測定的值，具體而言意指藉由實施例中記載的方法而測定的值。Loss tangent (tanδ) is defined as "loss modulus/storage modulus", and is a value measured using a dynamic viscoelasticity measuring device based on the response to stress such as tensile stress or torsional stress applied to the object, Specifically, it means the value measured by the method described in an Example.
在黏著劑層11的損耗正切（tanδ）為上述範圍內之情形中，黏著劑層11具有適宜的黏彈性，表現良好的形狀追隨性。並且，也表現適宜的凝聚性，並可抑制在與顯示體構成構件貼合後，黏著劑層從顯示體構成構件的端部溢出之類的不良情況的發生。進一步，由於具有適宜的凝聚性及黏著性，因此可表現良好的耐起泡性。In the case where the loss tangent (tan δ) of the
（3.4. 黏著片的製造）
作為製造黏著片1的方法，沒有特別限制，利用公知的方法進行製造即可。例如，藉由在一個剝離片12a（或12b）的剝離面上塗布上述的無溶劑型黏著性組合物，形成具有既定的厚度的塗布層。在形成的塗布層上重疊另一個剝離片12b（或12a）的剝離面後，對塗布層進行活性能量射線照射並使其固化，形成黏著劑層11。(3.4. Manufacture of adhesive sheet)
The method for manufacturing the
作為黏著片1的其他製造例，在一個剝離片12a（或12b）的剝離面上塗布無溶劑型黏著性組合物的塗布液，進行活性能量射線照射使無溶劑型黏著性組合物固化，在形成黏著劑層11後，在該黏著劑層11上重疊另一個剝離片12b（或12a）的剝離面。As another production example of the
作為塗布無溶劑型黏著性組合物的塗布液的方法，例如可例示出棒塗法、刮刀塗布法、輥塗法、刮板塗布法、模具塗布法、凹板塗布法等。As a method of applying the coating liquid of the solvent-free adhesive composition, 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, and the like can be exemplified.
（4. 顯示體）
如圖2所示，本實施形態的顯示體2具有：具有段差的第一顯示體構成構件21、第二顯示體構成構件22、以及位於其等之間並將第一顯示體構成構件21及第二顯示體構成構件22互相貼合的黏著劑層11。黏著劑層11沿著第一顯示體構成構件21的段差而被貼合。此段差因形成於第一顯示體構成構件21的印刷層3的厚度而產生。(4. Display body)
As shown in FIG. 2, the
黏著劑層11由上述的黏著劑、或者上述的黏著片1所具有的黏著劑層11構成。因此，黏著劑層11具有紫外線吸收能力，並同時具有良好的形狀追隨性。The
作為顯示體2，例如可列舉出液晶（LCD）顯示器、發光二極管（LED）顯示器、有機電致發光（有機EL）顯示器、電子紙等，也可以為觸摸面板。並且，作為顯示體2，也可以為構成其等的一部分的構件。Examples of the
第一顯示體構成構件21，除了玻璃板、塑料板等以外，較佳為由包括其等的層疊體等構成的保護面板。此情形中，印刷層3通常以框狀形成在第一顯示體構成構件21中的黏著劑層11側。The first
本實施形態中，在顯示體2中，由於即使作為第一顯示體構成構件21的保護面板由玻璃板構成，黏著劑層也可吸收紫外線，因此可抑制另一個顯示體構成構件的劣化。並且，在顯示體2中，即使作為第一顯示體構成構件21的保護面板由塑料板構成，黏著劑層也具有優異的耐起泡性。In this embodiment, in the
作為上述玻璃板，沒有特別限制，例如可列舉出化學強化玻璃、無鹼玻璃、石英玻璃、鈉鈣玻璃、含鋇鍶玻璃、鋁矽酸鹽玻璃、鉛玻璃、硼矽酸玻璃、鋇硼矽酸鹽玻璃等。玻璃板的厚度雖沒有特別限制，但通常為0.1mm以上，較佳為0.2mm以上。並且，該厚度通常為5mm以下，較佳為2mm以下。The above-mentioned glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda-lime glass, barium-strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass, and barium borosilicate glass. acid glass etc. Although the thickness of the glass plate is not particularly limited, it is usually at least 0.1 mm, preferably at least 0.2 mm. And, the thickness is usually not more than 5 mm, preferably not more than 2 mm.
作為上述塑料板，沒有特別限制，例如可列舉出壓克力板、聚碳酸酯板等。塑料板的厚度雖沒有特別限制，但通常為0.2mm以上，較佳為0.4mm以上。並且，該厚度通常為5mm以下，較佳為3mm以下。It does not specifically limit as said plastic board, For example, an acryl board, a polycarbonate board, etc. are mentioned. Although the thickness of the plastic plate is not particularly limited, it is usually at least 0.2 mm, preferably at least 0.4 mm. And, the thickness is usually not more than 5 mm, preferably not more than 3 mm.
另外，在上述玻璃板或塑料板的單面或雙面可設有各種功能層（透明導電膜、金屬層、二氧化矽層、硬塗層、防眩層等），也可層疊光學構件。並且，透明導電膜及金屬層也可被圖案化。In addition, various functional layers (transparent conductive film, metal layer, silicon dioxide layer, hard coat layer, anti-glare layer, etc.) can be provided on one or both sides of the above-mentioned glass plate or plastic plate, and optical members can also be laminated. Furthermore, the transparent conductive film and the metal layer may also be patterned.
第二顯示體構成構件22較佳為應貼附於第一顯示體構成構件21的光學構件、顯示體模組（例如液晶（LCD）模組、發光二極管（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、或包含顯示體模組的層疊體。The
作為上述光學構件，例如可列舉出防飛散膜、偏光片（偏光膜）、偏光鏡、相位差板（相位差膜）、視角補償膜、亮度增強膜、對比度增強膜、液晶聚合物膜、擴散膜、半透射反射膜、透明導電性膜等。作為防散射膜，可例示出在基材膜的單面形成硬塗層而成的硬塗膜等。Examples of the aforementioned optical members include anti-scattering films, polarizers (polarizing films), polarizers, retardation plates (retardation films), viewing angle compensation films, brightness enhancement films, contrast enhancement films, liquid crystal polymer films, diffusion film, semi-transmissive reflective film, transparent conductive film, etc. As an anti-scattering film, the hard coat film etc. which formed the hard coat layer on the one side of a base film are illustrated.
構成印刷層3的材料，沒有特別限制，可使用印刷用的公知的材料。印刷層3的厚度，亦即段差的高度，較佳為3μm以上，更佳為5μm以上，特佳為10μm以上。並且，該高度較佳為50μm以下，更佳為40μm以下。The material constituting the
為了製造上述的顯示體2，作為一例，將黏著片1的一個剝離片12a剝離後，將黏著片1的露出的黏著劑層11貼合於第一顯示體構成構件21的存在印刷層3的一側的面。之後，從黏著片1的黏著劑層11上剝離另一個剝離片12b，將黏著片1的露出的黏著劑層11與第二顯示體構成構件22貼合。並且，作為另一例，也可以更換第一顯示體構成構件21及第二顯示體構成構件22的貼合順序。In order to manufacture the above-mentioned
（5. 本實施形態的效果） 本實施形態中，使無溶劑型黏著性組合物含有光聚合起始劑與紫外線吸收劑，為了使光聚合起始劑進行聚合反應，將具有充分的吸光度的光的波長範圍與紫外線吸收劑所吸收的光的波長範圍錯開。藉此，可藉由活性能量射線的照射使具有紫外線吸收劑的無溶劑型黏著性組合物充分聚合（固化）。(5. Effects of this embodiment) In this embodiment, the non-solvent type adhesive composition contains a photopolymerization initiator and an ultraviolet absorber, and in order to cause the photopolymerization initiator to undergo a polymerization reaction, the wavelength range of light having sufficient absorbance and the range of the ultraviolet absorber are adjusted. The wavelength range of the absorbed light is staggered. Thereby, the solvent-free adhesive composition which has an ultraviolet absorber can fully polymerize (cure) by irradiation of an active energy ray.
其結果，將該無溶劑型黏著性組合物固化而成的黏著劑具有紫外線吸收能力，且段差追隨性及耐起泡性優異。而且，藉由將黏著劑的凝膠分率設定為上述的範圍內，除了段差追隨性以外，作為與段差追隨性為不同特性的異物填埋性也優異。尤其，即使在存在比段差更大且具有各種形狀的點狀的異物之情形，也可充分地追隨其形狀。As a result, the adhesive obtained by curing the solvent-free adhesive composition has ultraviolet absorbing ability, and is excellent in step followability and anti-foaming property. Furthermore, by setting the gel fraction of the adhesive within the above-mentioned range, in addition to the level difference followability, the foreign matter embedding property, which is a characteristic different from the step difference followability, is also excellent. In particular, even when there are dot-shaped foreign objects that are larger than the level difference and have various shapes, the shape can be sufficiently followed.
因此，可保護使用此黏著劑貼合具有段差的構成構件與其他構成構件而成的顯示體免受紫外線的傷害，而且可維持良好的畫質。Therefore, it is possible to protect a display body formed by bonding a structural member having a step and other structural members using the adhesive from ultraviolet rays, and maintain a good image quality.
（6. 變形例）
上述的實施形態中，黏著片雖具有兩片剝離片12a、12b，但也可以省略黏著片1的剝離片12a、12b中的任一個或兩個。(6. Modifications)
In the above-mentioned embodiment, although the adhesive sheet has the two
並且，也可以層疊既定的光學構件來代替剝離片12a及/或12b。Furthermore, instead of the
並且，第一顯示體構成構件21也可具有除了印刷層3以外的段差。進一步，不僅第一顯示體構成構件21可以具有段差，第二顯示體構成構件22也可以在黏著劑層11側具有段差。Furthermore, the first
以上，雖針對本發明的實施形態進行了說明，但本發明並不受上述的實施形態的任何限定，可在本發明的範圍內以各種態樣進行改變。 [實施例]As mentioned above, although embodiment of this invention was demonstrated, this invention is not limited to the above-mentioned embodiment at all, It can change in various aspects within the range of this invention. [Example]
以下，使用實施例，更詳細地說明發明，但本發明並不限定於此等實施例。Hereinafter, the invention will be described in more detail using examples, but the invention is not limited to these examples.
（製造例1） 1. 胺基甲酸乙酯丙烯酸酯類低聚物的製備 將重量平均分子量為3000的聚丙二醇100質量份（固體成分換算值；以下相同）、六亞甲基二異氰酸酯4質量份、以及二月桂酸二辛基錫0.02質量份聚合，得到反應物。對於得到的反應物，利用紅外線光譜法測定IR光譜，結果確認到異氰酸酯基幾乎消失。(Manufacturing example 1) 1. Preparation of Urethane Acrylate Oligomers 100 parts by mass of polypropylene glycol having a weight average molecular weight of 3,000 (solid content conversion; the same applies hereinafter), 4 parts by mass of hexamethylene diisocyanate, and 0.02 parts by mass of dioctyltin dilaurate were polymerized to obtain a reactant. As a result of measuring the IR spectrum of the obtained reactant by infrared spectroscopy, it was confirmed that the isocyanate group almost disappeared.
然後，相對於得到的反應物的總量，混合丙烯酸2-異氰基乙酯1質量份並進行聚合，藉此得到胺基甲酸乙酯丙烯酸酯類低聚物。對於得到的胺基甲酸乙酯丙烯酸酯類低聚物，利用紅外線光譜法測定IR光譜，結果確認到異氰酸酯基幾乎消失。並且，利用以下所示的方法對得到的胺基甲酸乙酯丙烯酸酯類低聚物的分子量進行測定，結果重量平均分子量（Mw）為25,000。Then, a urethane acrylate oligomer was obtained by mixing and
重量平均分子量（Mw）是利用凝膠滲透層析法（GPC），在以下的條件下測定（GPC測定）的聚苯乙烯換算的重量平均分子量。 （測定條件） ·GPC測定裝置：TOSOH CORPORATION製造，HLC-8020 ·GPC管柱（依照以下順序通過）：TOSOH CORPORATION製造 TSK guard column HXL-H TSK gel GMHXL（×2） TSK gel G2000HXL ·測定溶劑：四氫呋喃 ·測定溫度：40℃The weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) under the following conditions (GPC measurement). (measurement conditions) ・GPC measurement device: manufactured by TOSOH CORPORATION, HLC-8020 ・GPC column (passed in the following order): Manufactured by TOSOH CORPORATION TSK guard column HXL-H TSK gel GMHXL (×2) TSK gel G2000HXL ·Measurement solvent: tetrahydrofuran ·Measurement temperature: 40℃
2. 液狀組合物的製備 將作為聚合性乙烯基單體的丙烯酸2-乙基己酯40質量份、作為聚合性乙烯基單體的丙烯酸異莰酯10質量份、作為聚合性乙烯基單體的丙烯酸2-羥基乙酯20質量份、以及作為多官能（甲基）丙烯酸酯低聚物之如上所述而製備的胺基甲酸乙酯丙烯酸酯類低聚物30質量份混合並進行攪拌，藉此得到製造例1的液狀組合物（A1）。2. Preparation of Liquid Composition 40 parts by mass of 2-ethylhexyl acrylate as a polymerizable vinyl monomer, 10 parts by mass of isocamphoryl acrylate as a polymerizable vinyl monomer, 2-hydroxyethyl acrylate as a polymerizable vinyl monomer 20 parts by mass and 30 parts by mass of the urethane acrylate oligomer prepared as described above as a polyfunctional (meth)acrylate oligomer were mixed and stirred to obtain the Liquid composition (A1).
（製造例2） 將製造例1的液狀組合物（A1）100質量份（固體成分換算值；以下相同）與多官能丙烯酸酯單體（ε-己內酯改性參-（2-丙烯醯氧基乙基）異氰脲酸酯）3.0質量份混合並進行攪拌，藉此得到製造例2的液狀組合物（A2）。(Manufacturing example 2) Mix 100 parts by mass of the liquid composition (A1) of Production Example 1 (in terms of solid content; the same applies below) with a polyfunctional acrylate monomer (ε-caprolactone-modified ginseng-(2-acryloyloxyethyl ) isocyanurate) 3.0 parts by mass were mixed and stirred to obtain the liquid composition (A2) of Production Example 2.
（實施例1） 1. 無溶劑型黏著性組合物的製備 藉由將製造例1的液狀組合物（A1）100質量份、作為光聚合起始劑的2,4,6-三甲基苯甲醯基-二苯基-氧化膦（B1）1.0質量份、作為紫外線吸收劑的2-二羥基-4-甲氧基二苯甲酮（C1）0.50質量份、以及作為矽烷偶聯劑的3-縮水甘油醚氧基丙基三甲氧基矽烷（D1）0.2質量份進行混合，得到無溶劑型黏著性組合物。(Example 1) 1. Preparation of Solvent-Free Adhesive Composition By adding 100 parts by mass of the liquid composition (A1) of Production Example 1 and 1.0 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (B1) as a photopolymerization initiator parts, 0.50 parts by mass of 2-dihydroxy-4-methoxybenzophenone (C1) as a UV absorber, and 3-glycidyloxypropyltrimethoxysilane (D1) as a silane coupling agent ) were mixed at 0.2 parts by mass to obtain a solvent-free adhesive composition.
2. 黏著片的製造 利用刮刀塗布機，在利用矽酮類剝離劑將聚對苯二甲酸乙二酯膜的單面進行剝離處理而成的重剝離型剝離片（LINTEC CORPORATION製造，產品名稱「SP-PET752150」）的剝離處理面上，塗布上述得到的無溶劑型黏著性組合物。2. Fabrication of Adhesive Sheets A heavy release type release sheet (manufactured by LINTEC CORPORATION, product name "SP-PET752150") prepared by peeling one side of a polyethylene terephthalate film with a silicone release agent using a knife coater The solvent-free adhesive composition obtained above was coated on the peeling treated surface.
接著，將上述得到的重剝離型剝離片上的塗布層、與利用矽酮類剝離劑將聚對苯二甲酸乙二酯膜的單面進行剝離處理而成的輕剝離型剝離片（LINTEC CORPORATION製造，產品名稱「SP-PET382120」），以該輕剝離型剝離片的剝離處理面與塗布層接觸的方式進行貼合。Next, the coating layer on the heavy release type release sheet obtained above and the light release type release sheet (manufactured by LINTEC CORPORATION , product name "SP-PET382120"), and bonded in such a way that the release-treated surface of the light-release type release sheet is in contact with the coating layer.
然後，隔著重剝離型剝離片，利用以下的條件對塗布層照射活性能量射線，使無溶劑型黏著性組合物固化並製成黏著劑層，藉此製作由重剝離型剝離片/黏著劑層（厚度：200μm）/輕剝離型剝離片的構成而成的黏著片。 （活性能量射線照射條件） ·光源：高壓汞燈 ·光量：1000mJ/cm2 ·照度：100mW/cm2 Then, the coating layer was irradiated with active energy rays under the following conditions through the heavy-peeling type release sheet to cure the solvent-free adhesive composition to form an adhesive layer, thereby producing a heavy-peeling type release sheet/adhesive layer ( Thickness: 200μm) / Adhesive sheet composed of a light-peeling type release sheet. (Active energy ray irradiation conditions) Light source: high pressure mercury lamp Light quantity: 1000mJ/cm 2 Illuminance: 100mW/cm 2
（實施例2~6、比較例1~6） 除了將液狀組合物的種類、以及光聚合起始劑、紫外線吸收劑及矽烷偶聯劑的種類及摻合量變更為如表1所示以外，與實施例1同樣地進行，製造黏著片。另外，關於即使利用上述的條件照射活性能量射線，無溶劑型黏著性組合物也不固化的試樣，將表2的「固化性」的項目標記為「×」。(Examples 2~6, Comparative Examples 1~6) The adhesive sheet was produced in the same manner as in Example 1, except that the type of the liquid composition, and the type and blending amount of the photopolymerization initiator, ultraviolet absorber, and silane coupling agent were changed as shown in Table 1. . Moreover, about the sample which did not harden|cure even if it irradiated the active energy ray under the said conditions, the item of "curability" of Table 2 was marked as "x".
[表1]
表1中所記載的簡略符號等的詳細情況如下所示。 （液狀組合物） A1：丙烯酸2-乙基己酯（2EHA）40質量份、丙烯酸異莰酯（IBXA）10質量份、丙烯酸2-羥基乙酯（HEA）20質量份、以及胺基甲酸乙酯丙烯酸酯類低聚物30質量份的混合物 A2：100質量份的A1與3.0質量份的ε-己內酯改性參-（2-丙烯醯氧基乙基）異氰脲酸酯的混合物 （光聚合起始劑） B1：2,4,6-三甲基苯甲醯基-二苯基-氧化膦（熔點：90℃，波長380nm的吸光度：1.5，波長200~500nm的吸光度中的最大吸收波長：295、368、380、393nm） B2：苯基雙（2,4,6-三甲基苯甲醯基）氧化膦（熔點：130℃，波長380nm的吸光度：1.8，波長200~500nm的吸光度中的最大吸收波長：295、370nm） B3：1-羥基-環己基-苯基-酮（熔點：47℃，波長380nm的吸光度：0，波長200~500nm的吸光度中的最大吸收波長：246、280、333nm） （紫外線吸收劑） C1：2-二羥基-4-甲氧基二苯甲酮 C2：2-甲氧基-1-甲基乙基乙酸酯、苯丙酸、3-（2H-苯並***-2-基）-5-（1,1-二甲基乙基）-4-羥基、C7-9側鏈及直鏈烷基酯 （矽烷偶聯劑） D1：3-縮水甘油醚氧基丙基三甲氧基矽烷 D2：1,6-雙（三甲氧基甲矽烷基）己烷The details of the abbreviations and the like described in Table 1 are as follows. (liquid composition) A1: 40 parts by mass of 2-ethylhexyl acrylate (2EHA), 10 parts by mass of isocamphoryl acrylate (IBXA), 20 parts by mass of 2-hydroxyethyl acrylate (HEA), and urethane acrylate low Mixture of 30 parts by mass of polymer A2: A mixture of 100 parts by mass of A1 and 3.0 parts by mass of ε-caprolactone modified ginseng-(2-acryloxyethyl)isocyanurate (photopolymerization initiator) B1: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (melting point: 90°C, absorbance at 380nm: 1.5, maximum absorption wavelength at absorbance at 200-500nm: 295, 368 , 380, 393nm) B2: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (melting point: 130°C, absorbance at 380nm: 1.8, maximum absorption wavelength at absorbance at 200-500nm: 295, 370nm ) B3: 1-hydroxy-cyclohexyl-phenyl-ketone (melting point: 47°C, absorbance at wavelength 380nm: 0, maximum absorption wavelength among absorbance at wavelength 200~500nm: 246, 280, 333nm) (ultraviolet absorber) C1: 2-Dihydroxy-4-methoxybenzophenone C2: 2-methoxy-1-methylethyl acetate, phenylpropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl) -4-Hydroxy, C7-9 Side Chain and Linear Alkyl Ester (silane coupling agent) D1: 3-Glycidyloxypropyltrimethoxysilane D2: 1,6-bis(trimethoxysilyl)hexane
（吸光度的測定） 製備實施例及比較例中使用的光聚合起始劑的濃度為0.1質量%的乙腈溶液，使用紫外線-可見光-近紅外線（UV-Vis-NIR）分光光度計（Shimadzu Corporation製造，產品名稱「UV-3600」）對該溶液中的波長200~500nm的範圍的吸光度進行測定。基於其結果，導出波長380nm的吸光度、以及波長200~500nm的吸光度中的最大吸收波長（nm）。(measurement of absorbance) The concentration of the photopolymerization initiator used in the preparation examples and comparative examples was an acetonitrile solution of 0.1% by mass, using an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer (manufactured by Shimadzu Corporation, product name "UV -3600") to measure the absorbance in the solution in the wavelength range of 200 to 500 nm. Based on the results, the maximum absorption wavelength (nm) among the absorbance at a wavelength of 380 nm and the absorbance at a wavelength of 200 to 500 nm was derived.
（紫外線吸收能力的評價） 對實施例及比較例中得到的黏著片照射200~500nm的波長範圍的光，利用分光光度計測定透射率。在波長380nm下，若透射率的測定值為30%以下則判定為「有」紫外線吸收能力；若為30%以上則判定為「無」紫外線吸收能力。將判定結果揭示於表2。(Evaluation of ultraviolet absorbing ability) Light in the wavelength range of 200 to 500 nm was irradiated to the adhesive sheets obtained in Examples and Comparative Examples, and the transmittance was measured with a spectrophotometer. At a wavelength of 380nm, if the measured value of the transmittance is 30% or less, it is judged as "with" ultraviolet absorption ability; if it is more than 30%, it is judged as "no" ultraviolet absorption ability. The judgment results are shown in Table 2.
另外，得到了以下結果：沒有紫外線吸收能力的比較例1、3及7在波長300nm前後的透射率皆大於0（紫外線未被吸收而開始透射），在波長370nm處，透射率為80%左右。In addition, the following results were obtained: Comparative Examples 1, 3, and 7, which have no ultraviolet absorbing ability, have a transmittance greater than 0 before and after the wavelength of 300nm (the ultraviolet rays are not absorbed and start to transmit), and at a wavelength of 370nm, the transmittance is about 80% .
另一方面，實施例1~6中，在波長370nm之前，透射率為0，若波長大於370nm，則透射率大於0，但是即使波長為380nm，透射率也如表2所示地小於30%。即，關於至少在波長300~370nm的紫外線區域的紫外線吸收能力，確認到在實施例與比較例中產生了非常大的差異。On the other hand, in Examples 1 to 6, the transmittance is 0 before the wavelength of 370nm, and the transmittance is greater than 0 when the wavelength exceeds 370nm, but even if the wavelength is 380nm, the transmittance is less than 30% as shown in Table 2 . That is, it was confirmed that there was a very large difference between the examples and the comparative examples regarding the ultraviolet absorbing ability in the ultraviolet region of at least a wavelength of 300 to 370 nm.
（凝膠分率的評價） 將在實施例與比較例中所得到的黏著片裁切為50mm×50mm的大小，用聚酯製的網（網眼尺寸200）包覆該黏著劑層，使用精密天平測定其質量，藉由減去上述網單獨的質量，算出黏著劑自身的質量。將此時的質量記作M1。(Evaluation of gel fraction) The adhesive sheets obtained in the examples and comparative examples were cut into a size of 50 mm × 50 mm, and the adhesive layer was covered with a polyester net (mesh size 200), and its mass was measured using a precision balance. The mass of the adhesive itself is calculated by subtracting the mass of the net alone. Let the mass at this time be M1.
然後，將上述被包裹在聚酯製網中的黏著劑，在室溫（23℃）下浸漬於乙酸乙酯中3天。然後取出黏著劑，在100℃的烘箱中乾燥3小時。乾燥後，在溫度23℃、相對濕度50%的環境下靜置3小時後，使用精密天平測定其質量，藉由減去上述網單獨的質量，可算出黏著劑自身的質量。將此時的質量記作M2。凝膠分率（%）用（M2/M1）×100表示。將結果揭示於表2。Then, the above-mentioned adhesive wrapped in the polyester net was immersed in ethyl acetate at room temperature (23° C.) for 3 days. Then take out the adhesive and dry it in an oven at 100°C for 3 hours. After drying, let it stand for 3 hours in an environment with a temperature of 23°C and a relative humidity of 50%, then measure its mass with a precision balance, and calculate the mass of the adhesive itself by subtracting the mass of the net alone. Let the mass at this time be M2. The gel fraction (%) is represented by (M2/M1)×100. The results are shown in Table 2.
（黏著力的評價） 從實施例及比較例中得到的黏著片剝離輕剝離型剝離片，將露出的黏著劑層貼合於具有易黏合層的聚對苯二甲酸乙二酯（PET）膜（TOYOBO CO.,LTD.製造，產品名稱「PET A4300」，厚度：100μm）的易黏合層，得到剝離片/黏著劑層/PET膜的層疊體。將得到的層疊體裁成25mm寬、150mm長，將其作為樣品。(evaluation of adhesion) The light-release type release sheet was peeled off from the adhesive sheet obtained in Examples and Comparative Examples, and the exposed adhesive layer was attached to a polyethylene terephthalate (PET) film (TOYOBO CO., LTD. .Manufacture, product name "PET A4300", thickness: 100 μm) easy-adhesive layer, and obtain a laminated body of release sheet/adhesive layer/PET film. The obtained laminated body was cut into 25 mm width and 150 mm length, and this was used as a sample.
在23℃、50%RH的環境下，從上述樣品剝離重剝離型剝離片，將露出的黏著劑層貼附於鈉鈣玻璃（NIPPON SHEET GLASS CO.,LTD.製造）後，藉由使2kg的滾輪往復一次，從而進行壓接。然後，在23℃、50%RH的條件下放置24小時後，使用拉伸試驗機（ORIENTEC Co., Ltd.，TENSILON），以剝離速度300mm/min、剝離角度180度的條件，測定黏著力（N/25mm）。未記載於此的條件依據JIS Z0237:2009進行測定。將結果揭示於表2。In an environment of 23°C and 50% RH, the heavy release type release sheet was peeled off from the above sample, and the exposed adhesive layer was attached to soda lime glass (manufactured by NIPPON SHEET GLASS CO., LTD. The roller reciprocates once for crimping. Then, after standing at 23°C and 50%RH for 24 hours, the adhesive force was measured using a tensile tester (ORIENTEC Co., Ltd., TENSILON) at a peeling speed of 300mm/min and a peeling angle of 180 degrees. (N/25mm). Conditions not described here were measured in accordance with JIS Z0237:2009. The results are shown in Table 2.
（霧度值的評價） 從實施例及比較例中得到的黏著片剝下輕剝離型剝離片，將露出的黏著劑層貼附於厚度為1.1mm的鈉鈣玻璃（NIPPON SHEET GLASS CO.,LTD.製造）後，剝下重剝離型剝離片，藉此得到評價用樣品。(Evaluation of haze value) Peel off the light-peelable release sheet from the adhesive sheets obtained in Examples and Comparative Examples, stick the exposed adhesive layer on soda lime glass (manufactured by NIPPON SHEET GLASS CO., LTD.) with a thickness of 1.1 mm, and peel off A heavy peel-off type release sheet was used to obtain a sample for evaluation.
從該評價樣品的黏著劑層側射入霧度計（NIPPON DENSHOKU INDUSTRIES, CO., LTD.製造，產品名稱「NDH-7000」）的測定光，測定霧度值（%）。測定分別進行三次，算出其等的平均值。將其結果揭示於表2。Measurement light of a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES, CO., LTD., product name "NDH-7000") was injected from the adhesive layer side of the evaluation sample, and the haze value (%) was measured. The measurement was performed three times, and the average value thereof was calculated. The results are shown in Table 2.
（耐起泡性的評價） 將實施例及比較例中得到的黏著片的輕剝離型剝離片進行剝離，並將露出的黏著劑層貼附於鈉鈣玻璃（NIPPON SHEET GLASS CO.,LTD.製造）。進一步，從黏著片剝離重剝離型剝離片，將露出的黏著劑層貼附在由聚甲基丙烯酸甲酯（PMMA）與聚碳酸酯（PC）層疊而成的樹脂板（厚度：0.7mm，非UV吸收性）的聚碳酸酯側的面上，藉此得到試驗片。(Evaluation of blister resistance) The light-peelable release sheets of the adhesive sheets obtained in Examples and Comparative Examples were peeled off, and the exposed adhesive layer was attached to soda lime glass (manufactured by NIPPON SHEET GLASS CO., LTD.). Furthermore, the heavy-release type release sheet was peeled off from the adhesive sheet, and the exposed adhesive layer was attached to a resin plate (thickness: 0.7mm, Non-UV absorbing) polycarbonate side surface, thereby obtaining a test piece.
將得到的試驗片在50℃、0.5MPa的條件下進行30分鐘壓熱處理後，在常壓、23℃、50%RH下放置24小時。接著，在85℃、85%RH的高溫高濕條件下保管72小時。然後，目視確認黏著劑層與被黏物的界面的浮起剝離，根據以下的基準評價耐起泡性。將結果揭示於表2。 ○：無法確認氣泡及浮起剝離。 △：雖稍微產生微小的氣泡，但無法確認大的氣泡或剝離。 ×：可確認大的氣泡或浮起剝離。The obtained test piece was autoclaved for 30 minutes under conditions of 50° C. and 0.5 MPa, and then left to stand under normal pressure, 23° C., and 50% RH for 24 hours. Next, it stored for 72 hours under the high-temperature, high-humidity conditions of 85 degreeC and 85%RH. Then, the floating and peeling of the interface between the adhesive layer and the adherend was visually confirmed, and the foaming resistance was evaluated according to the following criteria. The results are shown in Table 2. ◯: Air bubbles and floating peeling cannot be confirmed. △: Microscopic air bubbles were slightly generated, but large air bubbles and peeling could not be confirmed. ×: Large air bubbles or floating peeling can be confirmed.
（耐濕熱白化性的評價） 用兩片鈉鈣玻璃（NIPPON SHEET GLASS CO.,LTD.製造）夾持實施例或比較例中得到的黏著片的黏著劑層，得到層疊體。將得到的層疊體在50℃、0.5MPa的條件下進行30分鐘壓熱處理後，在常壓、23℃、50%RH下放置24小時。然後，使用霧度計（NIPPON DENSHOKU INDUSTRIES, CO., LTD.製造，產品名稱「NDH2000」），按照JIS K7136:2000測定霧度值（%）。(Evaluation of Moisture and Heat Whitening Resistance) The adhesive layer of the adhesive sheet obtained in Example or Comparative Example was sandwiched between two sheets of soda-lime glass (manufactured by NIPPON SHEET GLASS CO., LTD.) to obtain a laminate. The obtained laminate was autoclaved at 50° C. and 0.5 MPa for 30 minutes, and then left to stand at normal pressure, 23° C., and 50% RH for 24 hours. Then, the haze value (%) was measured in accordance with JIS K7136:2000 using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES, CO., LTD., product name "NDH2000").
根據評價耐濕熱白化性前的霧度值（%）到評價耐濕熱白化性後的霧度值（%）的上升值，基於以下的基準評價耐濕熱白化性。將結果揭示於表2。 ○：評價耐濕熱白化性後的霧度值（%）的上升值為1.50%以下。 ×：評價耐濕熱白化性後的霧度值（%）的上升值大於1.50%。Moist heat whitening resistance was evaluated based on the following criteria based on the rise value from the haze value (%) before the evaluation of the moist heat whitening resistance to the haze value (%) after the evaluation of the moist heat whitening resistance. The results are shown in Table 2. ◯: The increase value of the haze value (%) after evaluating the moist heat whitening resistance is 1.50% or less. ×: The rise value of the haze value (%) after evaluating the moist heat whitening resistance is more than 1.50%.
（段差追隨性的評價） 以使塗布厚度成為10、20、40μm的方式，將紫外線固化型油墨（TEIKOKU PRINTING INKS MFG. CO., LTD.製造，產品名稱「POS-911SUMI」）以框狀（外形：長90mm×寬50mm，寬度5mm）絲網印刷在玻璃板（NSG PRECISION製造，產品名稱「CORNING Glass EAGLE XG」，長90mm×寬50mm×厚0.5mm）的表面上。接著，照射紫外線（80W/cm2 ，金屬鹵化物燈2盞，燈高15cm，帶速10~15m/分鐘），使印刷的上述紫外線固化型油墨固化，製作具有由印刷所致之段差的附段差玻璃板。(Evaluation of Step Followability) UV-curable ink (manufactured by TEIKOKU PRINTING INKS MFG. CO., LTD., product name "POS-911SUMI") was placed in a frame shape ( Appearance: length 90mm x width 50mm, width 5mm) screen-printed 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). Next, irradiate ultraviolet light (80W/cm 2 , 2 metal halide lamps, lamp height 15cm, belt speed 10~15m/min) to cure the above-mentioned ultraviolet curable ink printed, and make an attachment with a step difference caused by printing. Segmented glass panels.
從實施例與比較例中得到的黏著片剝下輕剝離型剝離片，將露出的黏著劑層貼合於具有易黏合層的聚對苯二甲酸乙二酯膜（TOYOBO CO.,LTD.製造，產品名稱「PET A4300」，厚度：100μm）。接著，剝掉重剝離型剝離片，使黏著劑層露出。然後，使用層壓機（FUJIPLA INC.製造，產品名稱「LPD3214」），以黏著劑層覆蓋框狀的印刷整面的方式貼合黏著劑層的露出的面與上述附段差玻璃板的具有段差的面，並將其作為評價用樣品。Peel off the easy-release type release sheet from the adhesive sheets obtained in Examples and Comparative Examples, and attach the exposed adhesive layer to a polyethylene terephthalate film (manufactured by TOYOBO CO., LTD. , product name "PET A4300", thickness: 100μm). Next, the heavy release type release sheet was peeled off to expose the adhesive layer. Then, using a laminator (manufactured by FUJIPLA INC., product name "LPD3214"), the exposed surface of the adhesive layer and the stepped glass plate with the aforementioned step were bonded so that the adhesive layer covered the entire surface of the frame-shaped print. , and used it as a sample for evaluation.
將得到的評價用樣品在50℃、0.5MPa的條件下進行30分鐘壓熱處理後，在常壓、23℃、50%RH下放置24小時。接著，在85℃、85%RH的高溫高濕條件下保管72小時（耐久試驗），然後，藉由目視確認黏著劑層（尤其是由印刷層所致之段差的附近），並根據以下的基準評價段差追隨性。將結果揭示於表2。 A：追隨所有的段差，未觀察到氣泡、浮起剝離。 B：段差的高度為40μm時，在段差部觀察到氣泡、浮起剝離。 C：段差的高度為20、40μm時，在段差部觀察到氣泡、浮起剝離。 D：段差的高度為10、20、40μm時，在段差部觀察到氣泡、浮起剝離。The obtained sample for evaluation was autoclaved for 30 minutes under conditions of 50° C. and 0.5 MPa, and then left to stand at normal pressure, 23° C., and 50% RH for 24 hours. Next, store it under high temperature and high humidity conditions of 85°C and 85%RH for 72 hours (durability test), and then check the adhesive layer (especially the vicinity of the level difference caused by the printed layer) by visual inspection, and follow the following Benchmark evaluation step followability. The results are shown in Table 2. A: All steps were followed, and no air bubbles or floating peeling were observed. B: When the height of the step was 40 μm, air bubbles, floating and peeling were observed at the step portion. C: When the height of the step is 20 or 40 μm, air bubbles, floating and peeling are observed at the step portion. D: When the height of the step difference is 10, 20, and 40 μm, air bubbles, floating and peeling are observed at the step difference portion.
（異物填埋性的評價） 在厚度為1.1mm的鈉鈣玻璃（NIPPON SHEET GLASS CO.,LTD.製造）的表面散佈粒徑為50μm的矽珠，將露出的黏著劑層從其上方貼合於玻璃板，並將其作為評價用樣品。(Evaluation of Landfillability of Foreign Matter) Silicon beads with a particle diameter of 50 μm were scattered on the surface of soda lime glass (manufactured by NIPPON SHEET GLASS CO., LTD.) with a thickness of 1.1 mm, and the exposed adhesive layer was bonded to the glass plate from above, and used as Samples for evaluation.
將得到的評價用樣品在50℃、0.5MPa的條件下進行30分鐘壓熱處理後，在常壓、23℃、50%RH下放置24小時。接著，在85℃、85%RH的高溫高濕條件下保管72小時（耐久試驗），然後，藉由目視確認矽珠的狀態，並根據以下的基準評價異物填埋性。將結果揭示於表2。 ◎：以珠為基點，沒有產生氣泡，被黏著劑填埋。 ○：以珠為基點，以外觀上沒有問題的級別稍微產生氣泡，但不至於發展至黏著劑的剝離，被黏著劑填埋。 △：雖然沒有黏著劑的剝離，但是以珠為基點，確認到外觀上有問題的級別的氣泡的產生。 ×：以珠為基點，產生氣泡，確認到黏著劑的剝離。The obtained sample for evaluation was autoclaved for 30 minutes under conditions of 50° C. and 0.5 MPa, and then left to stand at normal pressure, 23° C., and 50% RH for 24 hours. Next, it was stored under high-temperature and high-humidity conditions of 85°C and 85%RH for 72 hours (durability test), and then the state of the silicon beads was checked visually, and the foreign matter embedding property was evaluated according to the following criteria. The results are shown in Table 2. ◎: With beads as the base point, no air bubbles are generated, and they are filled by the adhesive. ◯: Based on the beads, bubbles are slightly generated at a level with no problem in appearance, but they do not develop to peel off the adhesive and are filled with the adhesive. △: Although there was no peeling of the adhesive, generation of air bubbles of a problematic level was confirmed based on the beads. x: Bubbles were generated based on the beads, and peeling of the adhesive was confirmed.
（儲能模數及損耗正切的評價） 從實施例及比較例中得到的黏著片剝下輕剝離型剝離片，將露出的黏著劑層衝孔成直徑8mm的圓形，得到用於測定黏著劑層的黏彈性的試樣。使用黏彈性測定裝置（TA Instruments.製造，ARES），對上述的試樣施加頻率1Hz的應變，測定-50~150℃的儲能模數及損耗模數，根據其等的值算出在23℃的損耗正切tanδ。將結果揭示於表2。(Evaluation of energy storage modulus and loss tangent) The light-peeling release sheet was peeled off from the adhesive sheets obtained in Examples and Comparative Examples, and the exposed adhesive layer was punched into a circle with a diameter of 8 mm to obtain a sample for measuring the viscoelasticity of the adhesive layer. Using a viscoelasticity measurement device (manufactured by TA Instruments, ARES), apply a strain at a frequency of 1 Hz to the above-mentioned sample, measure the storage modulus and loss modulus at -50 to 150°C, and calculate the temperature at 23°C from the values The loss tangent tanδ. The results are shown in Table 2.
（單體殘留量的評價） 對於實施例及比較例中得到的黏著片，製作基於既定量的單體的標準曲線，藉由氣相層析法進行分析，測定黏著劑中含有的單體殘留量。將結果揭示於表2。(Evaluation of monomer residues) For the adhesive sheets obtained in Examples and Comparative Examples, a calibration curve based on a predetermined amount of monomer was prepared and analyzed by gas chromatography to measure the residual amount of monomer contained in the adhesive. The results are shown in Table 2.
[表2]
根據表1、2，實施例1~6具有紫外線吸收能力，而且段差追隨性及異物填埋性優異，且耐起泡性也優異。 [產業上的可利用性]From Tables 1 and 2, Examples 1 to 6 have ultraviolet absorbing ability, and are excellent in step followability and foreign matter embedding property, and are also excellent in foaming resistance. [industrial availability]
本發明的黏著劑及黏著片例如可適用於貼合顯示體構成構件。The adhesive agent and adhesive sheet of this invention can be used suitably for bonding a display body constituent member, for example.
1‧‧‧黏著片
11‧‧‧黏著劑層
12a、12b‧‧‧剝離片
2‧‧‧顯示體
21‧‧‧第一顯示體構成構件
22‧‧‧第二顯示體構成構件
3‧‧‧印刷層1‧‧‧
圖1是本發明的一個實施形態的黏著片的剖面圖。 圖2是本發明的一個實施形態的層疊體的剖面圖。Fig. 1 is a cross-sectional view of an adhesive sheet according to one embodiment of the present invention. Fig. 2 is a cross-sectional view of a laminate according to an embodiment of the present invention.
1‧‧‧黏著片 1‧‧‧adhesive sheet
11‧‧‧黏著劑層 11‧‧‧adhesive layer
12a、12b‧‧‧剝離片 12a, 12b‧‧‧Peeling sheet
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