TW202122541A - Adhesive composition, adhesive film, laminate and preparation method thereof - Google Patents

Adhesive composition, adhesive film, laminate and preparation method thereof Download PDF

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Publication number
TW202122541A
TW202122541A TW109125726A TW109125726A TW202122541A TW 202122541 A TW202122541 A TW 202122541A TW 109125726 A TW109125726 A TW 109125726A TW 109125726 A TW109125726 A TW 109125726A TW 202122541 A TW202122541 A TW 202122541A
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TW
Taiwan
Prior art keywords
adhesive
oligomer
film
coated
base layer
Prior art date
Application number
TW109125726A
Other languages
Chinese (zh)
Inventor
黃俊植
裴淵雄
鄭丞勛
俞善我
Original Assignee
美商3M新設資產公司
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Publication of TW202122541A publication Critical patent/TW202122541A/en

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F220/10—Esters
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C—CHEMISTRY; METALLURGY
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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
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    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2463/00—Presence of epoxy resin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an adhesive film having a variable adhesive strength, a double coated adhesive tape using the same, and an adhesive composition for preparing the same. The adhesive composition comprises a base polymer; a crosslinking agent reacting with the base polymer; a first oligomer to be cured after the reaction of the base polymer and the crosslinking agent; and an initiator curing the first oligomer, wherein the adhesive composition has a first adhesive strength before curing of the first oligomer and a second adhesive strength after curing of the first oligomer after the reaction of the base polymer and the crosslinking agent, wherein the second adhesive strength is lower than the first adhesive strength.

Description

黏著劑組成物、黏著劑膜、層壓體及其製備方法 Adhesive composition, adhesive film, laminate and preparation method thereof

本發明係關於黏著劑組成物、黏著劑膜、層壓體、及其製備方法。更具體而言，本發明係關於一種具有可變黏著強度之黏著劑膜、其製備方法、用於製備該黏著劑膜之組成物、及包括該黏著劑膜之雙塗佈黏著劑膠帶及層壓體。 The present invention relates to an adhesive composition, an adhesive film, a laminate, and a preparation method thereof. More specifically, the present invention relates to an adhesive film with variable adhesive strength, a preparation method thereof, a composition for preparing the adhesive film, and a double-coated adhesive tape and layer including the adhesive film Pressure body.

在顯示面板及類似者中使用的基材通常需要用於保護表面免於受到外部衝擊而損壞或與其他組件接合的膠帶。例如，在有機發光二極體(organic light emitting diode,OLED)面板中，使用黏著劑膠帶來接合組件與聚醯亞胺基材。 Substrates used in display panels and the like generally require tapes for protecting the surface from damage caused by external impacts or bonding with other components. For example, in an organic light emitting diode (OLED) panel, an adhesive tape is used to join the component and the polyimide substrate.

同時，在顯示面板上，為了功能原因，較佳地有一區域沒有黏著劑膠帶，且例如，較佳的是，在與其他端子連接的區域中沒有黏著劑膠帶。具體而言，在最近受到矚目的可折疊顯示面板之製造程序中，由於黏著劑膠帶不應存在於面板經折疊之區域中，所以需要精確膠帶封紮程序(參見美國專利公開案第2011-0210937號)。 At the same time, on the display panel, for functional reasons, it is preferable that there is no adhesive tape in an area, and for example, it is preferable that there is no adhesive tape in the area connected to other terminals. Specifically, in the manufacturing process of a foldable display panel that has recently attracted attention, since the adhesive tape should not be present in the folded area of the panel, a precise tape sealing process is required (see U.S. Patent Publication No. 2011-0210937 number).

在此一程序中，具有能夠僅附接所欲部分至基材之可變黏著強度之膠帶係有利的，此係藉由將黏著劑膠帶初始地附接至基材，然後藉由降低僅不必要部分之黏著強度而輕易地移除不必要的部分。 In this procedure, an adhesive tape with variable adhesion strength capable of attaching only the desired part to the substrate is advantageous by initially attaching the adhesive tape to the substrate, and then by lowering the Adhesive strength of necessary parts makes it easy to remove unnecessary parts.

此外，最近已在用於家庭電器之顯示面板中使用的大面積玻璃基材係易碎的，且佔據大量空間，此令其難以儲存。已在行動顯示器面板中使用的小面積玻璃基材具有由於表面刮痕及剪切應力而難以堆疊及儲存的問題。據此，需要能夠在有效率地堆疊及儲存基材(諸如玻璃，其係難以儲存者)之後，依需要輕易地分離的黏著劑膠帶。 In addition, large-area glass substrates that have recently been used in display panels for household appliances are fragile and occupy a large amount of space, which makes it difficult to store. The small-area glass substrates that have been used in mobile display panels have the problem of being difficult to stack and store due to surface scratches and shear stress. Accordingly, there is a need for an adhesive tape that can be easily separated as needed after efficiently stacking and storing substrates (such as glass, which is difficult to store).

[先前技術文件] [Prior Technical Document]

[專利文件] [Patent Document]

專利文獻1：美國專利公開案第2011-0210937號 Patent Document 1: U.S. Patent Publication No. 2011-0210937

目前，已開發藉由將各種添加劑混合至黏著劑中來實施可變黏著強度的黏著劑膜，但具有可變黏著強度之這些習知膜具有黏著劑與添加劑之間的相容性不良好、或黏著強度變化不大的問題。 At present, adhesive films with variable adhesive strength have been developed by mixing various additives into adhesives. However, these conventional films with variable adhesive strength have poor compatibility between the adhesive and the additives, Or the problem of little change in adhesive strength.

因此，本發明之一目的係提供一種具有可變黏著強度之黏著劑膜(其藉由解決相關技術領域中的問題而能夠展現高效能)、其製備方法、用於製備其之組成物、及包括其之層壓體及設備。 Therefore, one object of the present invention is to provide an adhesive film with variable adhesive strength (which can exhibit high performance by solving problems in the related technical field), its preparation method, a composition for preparing it, and Including its laminates and equipment.

根據本發明之一態樣，提供一種黏著劑組成物，其包含：基底聚合物；交聯劑，其與該基底聚合物反應；第一寡聚物，其在該基底聚合物與該交聯劑之該反應之後待固化；及起始劑，其固化該第一寡聚物。該黏著劑組成物在該基底聚合物與該交聯劑之該反應之後具有在固化該第一寡聚物之前的第一黏著強度，及在固化該第一寡聚物之後的第二黏著強度，其中該第二黏著強度低於該第一黏著強度。 According to one aspect of the present invention, there is provided an adhesive composition comprising: a base polymer; a cross-linking agent that reacts with the base polymer; a first oligomer that is cross-linked with the base polymer The reaction of the agent is to be cured; and the initiator, which cures the first oligomer. The adhesive composition has a first adhesive strength before curing the first oligomer after the reaction of the base polymer and the crosslinking agent, and a second adhesive strength after curing the first oligomer , Wherein the second adhesive strength is lower than the first adhesive strength.

根據本發明之另一態樣，提供一種黏著劑膜，其包含基底聚合物與交聯劑之反應產物，其中該黏著劑膜含有第一寡聚物及起始劑，該第一寡聚物可藉由該起始劑固化，且該黏著劑膜具有在固化該第一寡聚物之前的第一黏著強度及在固化該第一寡聚物之後的第二黏著強度，其中該第二黏著強度低於該第一黏著強度。 According to another aspect of the present invention, there is provided an adhesive film comprising a reaction product of a base polymer and a crosslinking agent, wherein the adhesive film contains a first oligomer and an initiator, the first oligomer It can be cured by the initiator, and the adhesive film has a first adhesive strength before curing the first oligomer and a second adhesive strength after curing the first oligomer, wherein the second adhesive The strength is lower than the first adhesive strength.

根據本發明之又另一態樣，提供一種黏著劑膜之製備方法，其包含：混合基底聚合物、第一寡聚物、起始劑、及交聯劑；使該交聯劑與該基底聚合物反應以形成膜狀聚合物；及保持該第一寡聚物及該起始劑於該膜狀聚合物中以獲得黏著劑膜。 According to yet another aspect of the present invention, there is provided a method for preparing an adhesive film, which comprises: mixing a base polymer, a first oligomer, an initiator, and a cross-linking agent; making the cross-linking agent and the base The polymer reacts to form a film-like polymer; and the first oligomer and the initiator are kept in the film-like polymer to obtain an adhesive film.

根據本發明之又另一態樣，提供一種層壓體，其包含基材及附接至該基材之該黏著劑膜。 According to yet another aspect of the present invention, there is provided a laminate including a substrate and the adhesive film attached to the substrate.

根據本發明，該黏著劑膜可初始地以優異的黏著強度將該膜附接至該基材，然後可藉由輕易地移除不必要的部分而僅將所欲部分附接至該基材。 According to the present invention, the adhesive film can initially attach the film to the substrate with excellent adhesive strength, and then can attach only the desired part to the substrate by easily removing unnecessary parts .

具體而言，本發明的黏著劑膜在組分之間具優異的相容性，且具非常優異的可變黏著強度，此係因為初始黏著強度足夠高，而最終黏著強度足夠低。 Specifically, the adhesive film of the present invention has excellent compatibility between the components, and has very excellent variable adhesive strength, because the initial adhesive strength is sufficiently high, and the final adhesive strength is sufficiently low.

因此，本發明之黏著劑膜、使用其之雙塗佈黏著劑膠帶、及用於製備其之黏著劑組成物可實用地施用於需要可變黏著強度之程序，諸如製造OLED顯示面板。 Therefore, the adhesive film of the present invention, the double-coated adhesive tape using the same, and the adhesive composition for preparing the adhesive film of the present invention can be practically applied to processes that require variable adhesive strength, such as manufacturing OLED display panels.

11:雙塗佈黏著劑膠帶 11: Double-coated adhesive tape

12:雙塗佈黏著劑膠帶 12: Double-coated adhesive tape

100:黏著劑膜 100: Adhesive film

101:雙塗佈黏著劑膜 101: Double-coated adhesive film

111:具有經移除部分區域之黏著劑膜 111: Adhesive film with removed partial area

120:在黏著劑膜中具有經降低黏著強度之區域 120: There are areas with reduced adhesive strength in the adhesive film

150:緩衝片材 150: Buffer sheet

200:基材 200: base material

210:單塗佈膠帶A/單塗佈黏著劑膠帶 210: Single-coated tape A/Single-coated adhesive tape

211:基底層A 211: basal layer A

212:黏著劑層A 212: Adhesive layer A

213:離型層 213: Release layer

220:單塗佈膠帶B/單塗佈黏著劑膠帶 220: Single-coated tape B/Single-coated adhesive tape

221:基底層B 221: basal layer B

222:黏著劑層B/基底層B/黏著劑層A 222: Adhesive layer B/base layer B/adhesive layer A

223:離型層 223: Release layer

300:輻照 300: Irradiation

400:遮罩 400: Mask

〔圖1〕繪示根據一實施例之儲存模數及黏著強度根據黏著劑組成物的UV輻照(寡聚物固化)之變化。 [Figure 1] shows the storage modulus and adhesion strength according to one embodiment of the adhesive composition according to UV radiation (oligomer curing) changes.

〔圖2〕繪示儲存模數根據實例中所獲得之黏著劑組成物的UV輻照之變化。 [Figure 2] shows the variation of the storage modulus according to the UV irradiation of the adhesive composition obtained in the example.

〔圖3〕繪示根據一實施例之使用黏著劑膜之層壓體的製備方法。 [Figure 3] shows a method for preparing a laminate using an adhesive film according to an embodiment.

〔圖4A〕至〔圖4B〕繪示根據一實施例及其應用實例之雙塗佈黏著劑膠帶的截面圖。 [FIG. 4A] to [FIG. 4B] show cross-sectional views of a double-coated adhesive tape according to an embodiment and its application examples.

〔圖5A〕至〔圖5B〕繪示根據另一實施例及其應用實例之雙塗佈黏著劑膠帶的截面圖。 [FIG. 5A] to [FIG. 5B] show cross-sectional views of a double-coated adhesive tape according to another embodiment and its application examples.

自下文參考附圖所詳細描述之實施例將更清楚地理解本發明之優點與特徵以及用於達成其的方法。然而，本發明不限於下文描述之實施例，並可以許多不同形式體現。然而，提供這些實施例以使本發明之揭露完整，且向本發明所屬技術領域中具有通常知識者完整地宣告本發明所屬之範圍，且本發明僅由申請專利範圍之範圍所定義。 The advantages and features of the present invention and the methods for achieving them will be more clearly understood from the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below, and may be embodied in many different forms. However, these embodiments are provided to complete the disclosure of the present invention, and to fully declare the scope of the present invention to those with ordinary knowledge in the technical field to which the present invention belongs, and the present invention is only defined by the scope of the patent application.

用於描述本發明之圖式中繪示的形狀、大小、比例、角度、數量、及類似者僅是闡釋性，且本發明不限於此。在整份說明書中，相同的元件符號表示相同的組件。此外，在描述本發明時，當判定已知的相關技術的詳細解釋會不必要地混淆本發明之標的時，將省略其詳細說明。 The shapes, sizes, ratios, angles, numbers, and the like shown in the drawings used to describe the present invention are only illustrative, and the present invention is not limited thereto. Throughout the specification, the same reference numerals indicate the same components. In addition, when describing the present invention, when it is determined that a detailed explanation of a known related technology would unnecessarily confuse the subject of the present invention, the detailed explanation will be omitted.

在本說明書中使用的諸如「包括(including)」、「具有(having)」、及「包含(comprising)」等用語通常係意欲允許新增除所詳細描述外的組件，除非搭配用語「僅(only)」使用。當組件以單數形式表示時，單數形式的任何參考可包括複數形式，除非另有明確說明。 Terms such as "including", "having", and "comprising" used in this manual are generally intended to allow the addition of components other than those described in detail, unless the collocation term "only ( only)” is used. When a component is expressed in the singular form, any reference in the singular form may include the plural form, unless expressly stated otherwise.

即使沒有明確說明，組件也解釋為包括尋常的誤差範圍。 Even if not explicitly stated, the components are interpreted as including the usual margin of error.

在描述位置關係中，當使用用語諸如「上(on)」、「上方(above)」、「下方(below)」、與「旁邊(next)」描述兩個部件之間的位置關係時，一或多個其他部件可位於兩個部件之間，除非用語使用了用語「緊接著(immediately)」或「直接(directly)」。 In describing the positional relationship, when using terms such as "on", "above", "below", and "next" to describe the positional relationship between two components, one Or multiple other components may be located between the two components, unless the term "immediately" or "directly" is used.

本發明之實施例的各別特徵可部分地或完全地彼此接合或組合，且可技術上互鎖或以各種方式驅動。 The individual features of the embodiments of the present invention can be partially or completely engaged or combined with each other, and can be technically interlocked or driven in various ways.

在下文中，將參考圖式詳細描述本發明之實施例。以下的實施例經提供作為實例，使得本發明之精神將完全傳達給所屬技術領域中具有通常知識者。因此，本發明不限於下文要描述的實施例，並可以用各種不同形成予以體現。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The following embodiments are provided as examples, so that the spirit of the present invention will be fully conveyed to those having ordinary knowledge in the technical field. Therefore, the present invention is not limited to the embodiments to be described below, and can be embodied in various forms.

[黏著劑組成物] [Adhesive composition]

根據本發明之一態樣，提供一種黏著劑組成物，其包括基底聚合物、交聯劑、第一寡聚物、及起始劑。 According to one aspect of the present invention, an adhesive composition is provided, which includes a base polymer, a cross-linking agent, a first oligomer, and an initiator.

該基底聚合物可在該第一寡聚物藉由該起始劑固化之前與該交聯劑反應。例如，該基底聚合物可與該交聯劑反應，而該第一寡聚物及該起始劑被保留。在反應之後該黏著劑組成物的黏著強度可在固化該第一寡聚物之後進一步降低。 The base polymer can react with the crosslinking agent before the first oligomer is cured by the initiator. For example, the base polymer can react with the crosslinking agent, while the first oligomer and the initiator are retained. After the reaction, the adhesive strength of the adhesive composition can be further reduced after curing the first oligomer.

根據一實施例的黏著劑組成物可包括基底聚合物；交聯劑，其與該基底聚合物反應；第一寡聚物，其在該基底聚合物與該交聯劑之該反應之後待固化；及起始劑，其固化該第一寡聚物。該黏著劑組成物在該基底聚合物與該交聯劑之該反應之後具有在固化該第一寡聚物之前的第一黏著強度，及在固化該第一寡聚物之後的第二黏著強度，且該第二黏著強度低於該第一黏著強度。 The adhesive composition according to an embodiment may include a base polymer; a cross-linking agent which reacts with the base polymer; a first oligomer which is to be cured after the reaction of the base polymer and the cross-linking agent ; And an initiator, which cures the first oligomer. The adhesive composition has a first adhesive strength before curing the first oligomer after the reaction of the base polymer and the crosslinking agent, and a second adhesive strength after curing the first oligomer , And the second adhesive strength is lower than the first adhesive strength.

該第一寡聚物可藉由一光起始劑或一熱起始劑來固化。具體而言，當該光起始劑包括在黏著劑組成物中時，在UV輻照之 後，該第一寡聚物可藉由該光起始劑固化，且當熱起始劑包括在黏著劑組成物中時，在加熱之後，該第一寡聚物可藉由該熱起始劑固化。 The first oligomer can be cured by a photoinitiator or a thermal initiator. Specifically, when the photoinitiator is included in the adhesive composition, the Later, the first oligomer can be cured by the photoinitiator, and when the thermal initiator is included in the adhesive composition, after heating, the first oligomer can be initiated by the heat Agent curing.

黏著劑組成物之特性 Characteristics of adhesive composition

根據實施例之黏著劑組成物包括第一寡聚物，且具有不同於在藉由UV輻照來固化該第一寡聚物時的固化之前結構之結構。 The adhesive composition according to the embodiment includes the first oligomer and has a structure different from the structure before curing when the first oligomer is cured by UV irradiation.

圖1係繪示根據一實施例之儲存模數及黏著強度根據黏著劑組成物的UV輻照之變化的圖表。如圖1所示，該黏著劑組成物在UV輻照之前具有低儲存模數，而在UV輻照之後具有迅速增加的儲存模數。據此，該黏著劑組成物在UV輻照之前具有優異的黏著強度，而在UV輻照之後具有迅速降低的黏著強度。 FIG. 1 is a graph showing changes in storage modulus and adhesive strength according to UV radiation of the adhesive composition according to an embodiment. As shown in FIG. 1, the adhesive composition has a low storage modulus before UV irradiation, and has a rapidly increasing storage modulus after UV irradiation. Accordingly, the adhesive composition has excellent adhesive strength before UV irradiation, and has a rapidly decreasing adhesive strength after UV irradiation.

在基底聚合物交聯時的黏著強度 Adhesive strength when the base polymer is cross-linked

在黏著劑組成物中，基底聚合物與交聯劑反應(即，經交聯)以形成膜及類似者，且所形成之膜因此就物理特性(諸如黏著強度)而言具有不同於相關技術之特性。 In the adhesive composition, the base polymer reacts with the cross-linking agent (ie, is cross-linked) to form a film and the like, and the formed film is therefore different from related technologies in terms of physical properties (such as adhesive strength) The characteristics.

據此，在下文中，將主要描述在交聯劑與基底聚合物反應之後，當第一寡聚物及起始劑被保留時黏著劑組成物之特性。 Accordingly, in the following, the characteristics of the adhesive composition when the first oligomer and the initiator are retained after the crosslinking agent reacts with the base polymer will be mainly described.

黏著劑組成物在固化第一寡聚物(即，當第一寡聚物及起始劑被保留時)之前具有第一黏著強度。該第一黏著強度可係350gf/in或更多、400gf/in或更多、500gf/in或更多、或1,000gf/in或更 多。具體而言，該第一黏著強度可在350gf/in至10,000gf/in、或500gf/in至5,000gf/in的一範圍中。 The adhesive composition has a first adhesive strength before curing the first oligomer (ie, when the first oligomer and the initiator are retained). The first adhesive strength can be 350gf/in or more, 400gf/in or more, 500gf/in or more, or 1,000gf/in or more many. Specifically, the first adhesive strength may be in a range of 350 gf/in to 10,000 gf/in, or 500 gf/in to 5,000 gf/in.

在本說明書中，黏著強度(第一黏著強度、第二黏著強度等)可藉由ASTM D3330測量，其係所屬技術領域中之一般測量方法，且例如可係測量聚醯亞胺之黏著強度。測量方法的更詳細實例已在下列實施例中具體描述。 In this specification, the adhesion strength (first adhesion strength, second adhesion strength, etc.) can be measured by ASTM D3330, which is a general measurement method in the technical field, and can be, for example, the measurement of the adhesion strength of polyimide. More detailed examples of the measurement method have been specifically described in the following examples.

此外，在固化該第一寡聚物之後，該黏著劑組成物具有第二黏著強度。該第二黏著強度可係200gf/in或更少、150gf/in或更少、100gf/in或更少、50gf/in或更少、或30gf/in或更少。具體而言，該第二黏著強度可在0gf/in至200gf/in、0gf/in至100gf/in、或0gf/in至30gf/in的一範圍中。 In addition, after curing the first oligomer, the adhesive composition has a second adhesive strength. The second adhesive strength may be 200 gf/in or less, 150 gf/in or less, 100 gf/in or less, 50 gf/in or less, or 30 gf/in or less. Specifically, the second adhesive strength may be in a range of 0 gf/in to 200 gf/in, 0 gf/in to 100 gf/in, or 0 gf/in to 30 gf/in.

作為一實例，第一黏著強度可係350gf/in或更多，且第二黏著強度可係200gf/in或更少。作為另一實例，第一黏著強度可係400gf/in或更多，且第二黏著強度可係150gf/in或更少。作為又另一實例，該第一黏著強度可在500gf/in至5,000gf/in之範圍中，且該第二黏著強度可在0gf/in至30gf/in之範圍中。 As an example, the first adhesive strength may be 350 gf/in or more, and the second adhesive strength may be 200 gf/in or less. As another example, the first adhesive strength may be 400 gf/in or more, and the second adhesive strength may be 150 gf/in or less. As yet another example, the first adhesive strength may be in the range of 500 gf/in to 5,000 gf/in, and the second adhesive strength may be in the range of 0 gf/in to 30 gf/in.

在該黏著劑組成物中，該第二黏著強度低於該第一黏著強度。例如，該第二黏著強度可比該第一黏著強度低150gf/in或更多、200gf/in或更多、500gf/in或更多、或1,000gf/in或更多。 In the adhesive composition, the second adhesive strength is lower than the first adhesive strength. For example, the second adhesive strength may be 150 gf/in or more, 200 gf/in or more, 500 gf/in or more, or 1,000 gf/in or more lower than the first adhesive strength.

此外，該第一黏著強度對該第二黏著強度之一比率(第一黏著強度/第二黏著強度)可係20或更多、30或更多、50或更多、70或更多、或100或更多。此外，該第二黏著強度對該第一黏著強度 的一比率(第二黏著強度/第一黏著強度)可係0.06或更少、0.03或更少、0.02或更少、或0.01或更少。 In addition, a ratio of the first adhesive strength to the second adhesive strength (first adhesive strength/second adhesive strength) can be 20 or more, 30 or more, 50 or more, 70 or more, or 100 or more. In addition, the second adhesion strength to the first adhesion strength A ratio of (second adhesive strength/first adhesive strength) can be 0.06 or less, 0.03 or less, 0.02 or less, or 0.01 or less.

當該黏著劑組成物進一步包括第二寡聚物時，可進一步降低該第二黏著強度。即，與僅添加該第一寡聚物的情況相比較，在一起添加該第二寡聚物的情況中，進一步降低該第二黏著強度。 When the adhesive composition further includes a second oligomer, the second adhesive strength can be further reduced. That is, compared with the case where only the first oligomer is added, when the second oligomer is added together, the second adhesive strength is further reduced.

另一方面，在固化寡聚物之前，與僅添加該第一寡聚物的情況相比較，在一起添加該第二寡聚物的情況中，可進一步增加該第一黏著強度。因此，可藉由該第二寡聚物進一步增加該第一黏著強度與該第二黏著強度之間的一差異。 On the other hand, before curing the oligomer, compared with the case where only the first oligomer is added, in the case where the second oligomer is added together, the first adhesive strength can be further increased. Therefore, a difference between the first adhesive strength and the second adhesive strength can be further increased by the second oligomer.

即，可藉由該第一寡聚物及該第二寡聚物的添加量來調整該第一黏著強度及該第二黏著強度。 That is, the first adhesive strength and the second adhesive strength can be adjusted by the addition amount of the first oligomer and the second oligomer.

在基底聚合物交聯時的特性 Characteristics when the base polymer is cross-linked

在固化第一寡聚物之後，黏著劑組成物可滿足作為光學透明黏著劑之要求。例如，在固化該第一寡聚物之後，該黏著劑組成物可具有5%或更少、2%或更少、或1%或更少的霧度。此外，在固化該第一寡聚物之後，該黏著劑組成物可具有80%或更多、90%或更多、或95%或更多的光透射率。 After curing the first oligomer, the adhesive composition can meet the requirements of being an optically transparent adhesive. For example, after curing the first oligomer, the adhesive composition may have a haze of 5% or less, 2% or less, or 1% or less. In addition, after curing the first oligomer, the adhesive composition may have a light transmittance of 80% or more, 90% or more, or 95% or more.

此外，即使在第二寡聚物被額外包括並固化之後，黏著劑組成物可滿足作為光學透明黏著劑的要求。例如，當黏著劑組成物包括第一寡聚物及第二寡聚物時，在固化之後的霧度可係5%或更少、 或2%或更少。當黏著劑組成物包括第一寡聚物及第二寡聚物時，固化之後的光透射率可係80%或更多、或90%或更多。 In addition, even after the second oligomer is additionally included and cured, the adhesive composition can meet the requirements as an optically transparent adhesive. For example, when the adhesive composition includes a first oligomer and a second oligomer, the haze after curing can be 5% or less, Or 2% or less. When the adhesive composition includes the first oligomer and the second oligomer, the light transmittance after curing may be 80% or more, or 90% or more.

黏著劑組成物之組分 Components of the adhesive composition

根據實施例之黏著劑組成物包括基底聚合物、交聯劑、第一寡聚物、及起始劑。此外，根據實施例之黏著劑組成物可進一步包括第二寡聚物，該第二寡聚物不同於第一寡聚物。此外，根據實施例之黏著劑組成物可進一步包括有機酸。此外，根據實施例之黏著劑組成物可進一步包括溶劑及其他添加劑。 The adhesive composition according to the embodiment includes a base polymer, a crosslinking agent, a first oligomer, and an initiator. In addition, the adhesive composition according to the embodiment may further include a second oligomer, which is different from the first oligomer. In addition, the adhesive composition according to the embodiment may further include an organic acid. In addition, the adhesive composition according to the embodiment may further include a solvent and other additives.

在下文中，將詳細敘述黏著劑組成物之各組分。 Hereinafter, each component of the adhesive composition will be described in detail.

基底聚合物 Base polymer

根據實施例之黏著劑組成物包括基底聚合物。 The adhesive composition according to the embodiment includes a base polymer.

該基底聚合物作為該黏著劑組成物之一主要組分展現黏著性質。此外，基底聚合物可與交聯劑反應(即，經交聯)以形成膜及類似者。 The base polymer as a main component of the adhesive composition exhibits adhesive properties. In addition, the base polymer can react with a crosslinking agent (ie, be crosslinked) to form a film and the like.

以黏著劑組成物之重量計，基底聚合物可包括在35wt%至95wt%之範圍中。具體而言，以黏著劑組成物之重量計，基底聚合物可包括在40wt%至90wt%、45wt%至85wt%、或50wt%至80wt%之範圍中。此時，基底聚合物之含量及黏著劑組成物之重量可基於固體含量。 Based on the weight of the adhesive composition, the base polymer may be included in the range of 35 wt% to 95 wt%. Specifically, based on the weight of the adhesive composition, the base polymer may be included in the range of 40 wt% to 90 wt%, 45 wt% to 85 wt%, or 50 wt% to 80 wt%. At this time, the content of the base polymer and the weight of the adhesive composition may be based on the solid content.

基底聚合物可含有與交聯劑反應之官能基。例如，基底聚合物可具有選自由下列所組成之群組的至少一種官能基：羧基、羥基、丙烯醯基、甲基丙烯醯基、乙酸酯基、及乙烯基。 The base polymer may contain functional groups that react with the crosslinking agent. For example, the base polymer may have at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acrylic group, a methacrylic group, an acetate group, and a vinyl group.

作為一實例，基底聚合物可係丙烯酸樹脂。 As an example, the base polymer may be an acrylic resin.

具體而言，基底聚合物可係丙烯酸共聚物樹脂。 Specifically, the base polymer may be an acrylic copolymer resin.

例如，丙烯酸共聚物樹脂可係與選自由下列所組成之群組之至少兩種單體共聚合的樹脂：丙烯酸2-乙基己酯(2-EHA)、丙烯酸丁酯(BA)、丙烯酸甲酯(MA)、乙酸乙烯酯(VAc)、丙烯酸(AA)、及丙烯酸2-羥基乙酯(2-HEA)。作為具體實例，構成丙烯酸共聚物樹脂之至少兩種單體的組合可包括2-EHA/MA、BA/MA、AA/2-HEA、MA/2-HEA、BA/2-HEA、MA/AA/2-HEA、及類似者。 For example, the acrylic copolymer resin may be a resin copolymerized with at least two monomers selected from the group consisting of: 2-ethylhexyl acrylate (2-EHA), butyl acrylate (BA), methyl acrylate Ester (MA), vinyl acetate (VAc), acrylic acid (AA), and 2-hydroxyethyl acrylate (2-HEA). As a specific example, the combination of at least two monomers constituting the acrylic copolymer resin may include 2-EHA/MA, BA/MA, AA/2-HEA, MA/2-HEA, BA/2-HEA, MA/AA /2-HEA, and the like.

基底聚合物可係一熱可固化樹脂或一光可固化樹脂。例如，基底聚合物可係熱可固化樹脂。 The base polymer may be a thermally curable resin or a photo-curable resin. For example, the base polymer may be a thermally curable resin.

此外，基底聚合物可係壓敏性黏著劑(pressure sensitive adhesive,PSA)樹脂。 In addition, the base polymer can be a pressure sensitive adhesive (PSA) resin.

基底聚合物之重量平均分子量(Mw)可係10,000至2,000,000或100,000至2,000,000。 The weight average molecular weight (Mw) of the base polymer can be 10,000 to 2,000,000 or 100,000 to 2,000,000.

第一寡聚物 First oligomer

根據實施例之黏著劑組成物包括第一寡聚物。 The adhesive composition according to the embodiment includes a first oligomer.

第一寡聚物係在基底聚合物與交聯劑之反應之後待固化。即，甚至在基底聚合物與交聯劑反應之後，第一寡聚物可以未固化狀態存在。 The first oligomer is to be cured after the reaction between the base polymer and the crosslinking agent. That is, even after the base polymer reacts with the crosslinking agent, the first oligomer may exist in an uncured state.

因此，未固化狀態中的第一寡聚物可能不涉及基底聚合物與交聯劑之反應產物的黏著強度。然而，在基底聚合物與交聯劑反應之後，第一寡聚物視需要經固化以迅速降低反應產物之黏著強度。 Therefore, the first oligomer in the uncured state may not be involved in the adhesive strength of the reaction product of the base polymer and the crosslinking agent. However, after the base polymer reacts with the crosslinking agent, the first oligomer is optionally cured to rapidly reduce the adhesive strength of the reaction product.

該第一寡聚物可藉由一光起始劑或一熱起始劑來固化。此外，第一寡聚物可具有與基底聚合物的相容性。 The first oligomer can be cured by a photoinitiator or a thermal initiator. In addition, the first oligomer may have compatibility with the base polymer.

第一寡聚物可包括衍生自環氧丙烯酸酯之重複單元。作為一實例，第一寡聚物可係由以下化學式1所表示之至少一種化合物。 The first oligomer may include repeating units derived from epoxy acrylate. As an example, the first oligomer may be at least one compound represented by the following Chemical Formula 1.

Figure 109125726-A0202-12-0012-1
Figure 109125726-A0202-12-0012-1

其中，X1各自獨立地係直鏈或支鏈C1-10伸烷基；L1各自獨立地係C1-10伸烷基、C3-20伸環烷基、或C1-10伸烷氧基；R1各自獨立地係H、C1-10烷基、C1-10烷氧基、C2-10烯基、或C6-14芳基；且m係0至10之整數。 Wherein, X 1 is each independently a linear or branched C 1-10 alkylene; L 1 is each independently a C 1-10 alkylene, a C 3-20 cycloalkylene, or a C 1-10 alkylene Alkoxy; R 1 is each independently H, C 1-10 alkyl, C 1-10 alkoxy, C 2-10 alkenyl, or C 6-14 aryl; and m is an integer from 0 to 10 .

C1-10伸烷基之具體實例可包括亞甲基、伸乙基、丙烯基、異丙烯基、伸丁基、異丁烯基、二級伸丁基、三級伸丁基、伸戊基、異伸戊基、三級伸戊基、伸己基、伸庚基、伸辛基、異伸辛基、 三級伸辛基、2-乙基伸己基、伸壬基、異伸壬基、伸癸基、異伸癸基、及類似物。C3-20伸環烷基的具體實例可包括伸環丙基、伸環丁基、伸環戊基、伸環己基、環庚基、伸十氫萘基(decalinylene group)、伸金剛烷基(adamantylene group)、及類似物。C1-10伸烷氧基之具體實例可包括亞甲基氧基、乙烯氧基、丙烯氧基、丁烯氧基、二級丁烯氧基、三級丁烯氧基、戊烯氧基、己烯氧基、庚烯氧基、辛烯氧基、2-乙基-己烯氧基、及類似物。C1-10烷基之具體實例可包括甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、異戊基、三級戊基、己基、庚基、辛基、異辛基、三級辛基、2-乙基己基、壬基、異壬基、癸基、異癸基、及類似物。C1-10烷氧基之具體實例可包括甲氧基、乙氧基、丙氧基、丁氧基、二級丁氧基、三級丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基、及類似物。C2-10烯基之具體實例可包括乙烯基、烯丙基、丁烯基、丙烯基、及類似物。C6-14芳基之具體實例可包括苯基、甲苯基、二甲苯基、萘基、及類似者。 Specific examples of C 1-10 alkylene may include methylene, ethylene, propenyl, isopropenyl, butylene, isobutenyl, two-butylene, tertiary butylene, pentylene, Isopentyl, tertiary pentyl, hexylene, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonylnyl, nonylnyl, decyl Base, isodecyl, and the like. Specific examples of C 3-20 cycloalkylene groups may include cycloalkylene, cyclobutylene, cyclopentyl, cyclohexyl, cycloheptyl, decalinylene group, adamantyl (adamantylene group), and the like. Specific examples of C 1-10 alkoxyl groups may include methyleneoxy, ethyleneoxy, propyleneoxy, butenoxy, secondary butenoxy, tertiary butenoxy, pentenoxy , Hexenyloxy, heptenyloxy, octenyloxy, 2-ethyl-hexenyloxy, and the like. Specific examples of C 1-10 alkyl groups may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, tertiary Pentyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, and the like. Specific examples of C 1-10 alkoxy may include methoxy, ethoxy, propoxy, butoxy, secondary butoxy, tertiary butoxy, pentoxy, hexyloxy, heptoxy Base, octyloxy, 2-ethylhexyloxy, and the like. Specific examples of the C 2-10 alkenyl group may include vinyl, allyl, butenyl, propenyl, and the like. Specific examples of the C 6-14 aryl group may include phenyl, tolyl, xylyl, naphthyl, and the like.

此外，環氧丙烯酸酯可具有雙酚A骨架。具體而言，第一寡聚物可包括雙酚A環氧丙烯酸酯作為結構單元。 In addition, the epoxy acrylate may have a bisphenol A skeleton. Specifically, the first oligomer may include bisphenol A epoxy acrylate as a structural unit.

第一寡聚物之重量平均分子量可在300至30,000、或500至10,000之範圍中。 The weight average molecular weight of the first oligomer may be in the range of 300 to 30,000, or 500 to 10,000.

以基底聚合物之100重量份計，在黏著劑組成物中的第一寡聚物之含量可係10重量份至100重量份。具體而言，以基底聚合物之100重量份計，在黏著劑組成物中的第一寡聚物之含量可係10重 量份至90重量份、10重量份至80重量份、或15重量份至70重量份。此時，基底聚合物及第一寡聚物之含量可基於固體含量。 Based on 100 parts by weight of the base polymer, the content of the first oligomer in the adhesive composition may range from 10 parts by weight to 100 parts by weight. Specifically, based on 100 parts by weight of the base polymer, the content of the first oligomer in the adhesive composition can be 10 parts by weight. Parts by weight to 90 parts by weight, 10 parts by weight to 80 parts by weight, or 15 parts by weight to 70 parts by weight. At this time, the content of the base polymer and the first oligomer may be based on the solid content.

第二寡聚物 Second oligomer

根據實施例之黏著劑組成物可進一步包括第二寡聚物，該第二寡聚物不同於第一寡聚物。 The adhesive composition according to the embodiment may further include a second oligomer, which is different from the first oligomer.

第二寡聚物可與剩餘在黏著劑組成物中的低分子酸化合物及類似者反應，以改善黏著劑組成物之初始黏著強度。此外，在基底聚合物與交聯劑反應之後，第二寡聚物視需要與第一寡聚物經固化以進一步降低反應產物之黏著強度。 The second oligomer can react with low-molecular-weight acid compounds and the like remaining in the adhesive composition to improve the initial adhesive strength of the adhesive composition. In addition, after the base polymer reacts with the cross-linking agent, the second oligomer is cured with the first oligomer as needed to further reduce the adhesive strength of the reaction product.

作為一實例，第二寡聚物可係由以下化學式2所表示之至少一種化合物。 As an example, the second oligomer may be at least one compound represented by the following Chemical Formula 2.

Figure 109125726-A0202-12-0014-2
Figure 109125726-A0202-12-0014-2

其中，X2各自獨立地係直鏈或支鏈C1-10伸烷基；L2各自獨立地係C1-10伸烷基、C3-20伸環烷基、或C1-10伸烷氧基；R2各自獨立地係H、C1-10烷基、C1-10烷氧基、C2-10烯基、或C6-14芳基；且n係0至10之整數。 Wherein, X 2 is each independently a linear or branched C 1-10 alkylene; L 2 is each independently a C 1-10 alkylene, a C 3-20 cycloalkylene, or a C 1-10 alkylene Alkoxy; R 2 is each independently H, C 1-10 alkyl, C 1-10 alkoxy, C 2-10 alkenyl, or C 6-14 aryl; and n is an integer from 0 to 10 .

C1-10伸烷基之具體實例可包括亞甲基、伸乙基、丙烯基、異丙烯基、伸丁基、異丁烯基、二級伸丁基、三級伸丁基、伸戊 基、異伸戊基、三級伸戊基、伸己基、伸庚基、伸辛基、異伸辛基、三級伸辛基、2-乙基伸己基、伸壬基、異伸壬基、伸癸基、異伸癸基、及類似物。C3-20伸環烷基的具體實例可包括伸環丙基、伸環丁基、伸環戊基、伸環己基、環庚基、伸十氫萘基(decalinylene group)、伸金剛烷基(adamantylene group)、及類似物。C1-10伸烷氧基之具體實例可包括亞甲基氧基、乙烯氧基、丙烯氧基、丁烯氧基、二級丁烯氧基、三級丁烯氧基、戊烯氧基、己烯氧基、庚烯氧基、辛烯氧基、2-乙基-己烯氧基、及類似物。C1-10烷基之具體實例可包括甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、異戊基、三級戊基、己基、庚基、辛基、異辛基、三級辛基、2-乙基己基、壬基、異壬基、癸基、異癸基、及類似物。C1-10烷氧基之具體實例可包括甲氧基、乙氧基、丙氧基、丁氧基、二級丁氧基、三級丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基、及類似物。C2-10烯基之具體實例可包括乙烯基、烯丙基、丁烯基、丙烯基、及類似物。C6-14芳基之具體實例可包括苯基、甲苯基、二甲苯基、萘基、及類似者。 Specific examples of C 1-10 alkylene may include methylene, ethylene, propenyl, isopropenyl, butylene, isobutenyl, two-butylene, tertiary butylene, pentylene, Iso-pentyl, tertiary pentyl, hexylene, heptyl, octyl, iso-octyl, tertiary octyl, 2-ethylhexyl, nonylnyl, isoxenyl, decyl Base, isodecyl, and the like. Specific examples of the C 3-20 cycloalkylene group may include cycloalkylene, cyclobutylene, cyclopentyl, cyclohexyl, cycloheptyl, decalinylene group, adamantyl (adamantylene group), and the like. Specific examples of C 1-10 alkoxyl groups may include methyleneoxy, ethyleneoxy, propyleneoxy, butenoxy, secondary butenoxy, tertiary butenoxy, pentenoxy , Hexenyloxy, heptenyloxy, octenyloxy, 2-ethyl-hexenyloxy, and the like. Specific examples of C 1-10 alkyl groups may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, tertiary Pentyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, and the like. Specific examples of C 1-10 alkoxy may include methoxy, ethoxy, propoxy, butoxy, secondary butoxy, tertiary butoxy, pentoxy, hexyloxy, heptoxy Group, octyloxy, 2-ethylhexyloxy, and the like. Specific examples of the C 2-10 alkenyl group may include vinyl, allyl, butenyl, propenyl, and the like. Specific examples of C 6-14 aryl groups may include phenyl, tolyl, xylyl, naphthyl, and the like.

具體而言，第二寡聚物可係具有雙酚A骨架的環氧樹脂。 Specifically, the second oligomer may be an epoxy resin having a bisphenol A skeleton.

第二寡聚物之重量平均分子量可在300至30,000、或500至10,000之範圍中。 The weight average molecular weight of the second oligomer may be in the range of 300 to 30,000, or 500 to 10,000.

以基底聚合物之100重量份計，黏著劑組成物中的第二寡聚物之含量可係0.1重量份至20重量份。具體而言，以基底聚合物 之100重量份計，黏著劑組成物中的第二寡聚物之含量可係0.1重量份至10重量份、或0.1重量份至5重量份。此時，第二寡聚物及基底聚合物之含量可基於固體含量。 Based on 100 parts by weight of the base polymer, the content of the second oligomer in the adhesive composition may range from 0.1 parts by weight to 20 parts by weight. Specifically, the base polymer Based on 100 parts by weight, the content of the second oligomer in the adhesive composition may range from 0.1 parts by weight to 10 parts by weight, or from 0.1 parts by weight to 5 parts by weight. At this time, the content of the second oligomer and the base polymer may be based on the solid content.

有機酸 Organic acid

根據實施例之黏著劑組成物可進一步包括有機酸。 The adhesive composition according to the embodiment may further include an organic acid.

有機酸與黏著劑組成物中存在的寡聚物之末端官能基(例如，環氧基等)反應，以改善黏著劑組成物之初始黏著強度。 The organic acid reacts with the terminal functional group (for example, epoxy group, etc.) of the oligomer present in the adhesive composition to improve the initial adhesive strength of the adhesive composition.

有機酸可具有1至5個、或1至3個官能基。有機酸除了具有羧基外，亦可具有選自由下列所組成之群組的至少一種官能基：羥基、丙烯醯基、甲基丙烯醯基、乙酸酯基、及乙烯基。具體而言，有機酸可具有乙烯基。 The organic acid may have 1 to 5, or 1 to 3 functional groups. In addition to the carboxyl group, the organic acid may also have at least one functional group selected from the group consisting of a hydroxyl group, an acrylic group, a methacrylic group, an acetate group, and a vinyl group. Specifically, the organic acid may have a vinyl group.

作為一實例，有機酸可係由下列化學式3表示之至少一種化合物。 As an example, the organic acid may be at least one compound represented by the following chemical formula 3.

Figure 109125726-A0202-12-0016-3
Figure 109125726-A0202-12-0016-3

其中，L3係單鍵、C1-10伸烷基、C3-20伸環烷基、或C1-10伸烷氧基。 Among them, L 3 is a single bond, a C 1-10 alkylene group, a C 3-20 cycloalkylene group, or a C 1-10 alkoxy group.

C1-10伸烷基之具體實例可包括亞甲基、伸乙基、丙烯基、異丙烯基、伸丁基、異丁烯基、二級伸丁基、三級伸丁基、伸戊基、異伸戊基、三級伸戊基、伸己基、伸庚基、伸辛基、異伸辛基、 三級伸辛基、2-乙基伸己基、伸壬基、異伸壬基、伸癸基、異伸癸基、及類似物。C3-20伸環烷基的具體實例可包括伸環丙基、伸環丁基、伸環戊基、伸環己基、環庚基、伸十氫萘基(decalinylene group)、伸金剛烷基(adamantylene group)、及類似物。C1-10伸烷氧基之具體實例可包括亞甲基氧基、乙烯氧基、丙烯氧基、丁烯氧基、二級丁烯氧基、三級丁烯氧基、戊烯氧基、己烯氧基、庚烯氧基、辛烯氧基、2-乙基-己烯氧基、及類似物。 Specific examples of C 1-10 alkylene may include methylene, ethylene, propenyl, isopropenyl, butylene, isobutenyl, two-butylene, tertiary butylene, pentylene, Isopentyl, tertiary pentyl, hexylene, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonylnyl, nonylnyl, decyl Base, isodecyl, and the like. Specific examples of C 3-20 cycloalkylene groups may include cycloalkylene, cyclobutylene, cyclopentyl, cyclohexyl, cycloheptyl, decalinylene group, adamantyl (adamantylene group), and the like. Specific examples of C 1-10 alkoxyl groups may include methyleneoxy, ethyleneoxy, propyleneoxy, butenoxy, secondary butenoxy, tertiary butenoxy, pentenoxy , Hexenyloxy, heptenyloxy, octenyloxy, 2-ethyl-hexenyloxy, and the like.

更具體而言，有機酸可包括甲基丙烯酸。 More specifically, the organic acid may include methacrylic acid.

有機酸之分子量可在50至1000、或50至500之範圍中。 The molecular weight of the organic acid can be in the range of 50 to 1,000, or 50 to 500.

以基底聚合物之100重量份計，組成物中之有機酸之含量可係0.1重量份至10重量份、0.1重量份至5重量份、或0.1重量份至3重量份。此時，有機酸及基底聚合物之含量可基於固體含量。 Based on 100 parts by weight of the base polymer, the content of the organic acid in the composition may be 0.1 parts by weight to 10 parts by weight, 0.1 parts by weight to 5 parts by weight, or 0.1 parts by weight to 3 parts by weight. At this time, the content of the organic acid and the base polymer may be based on the solid content.

起始劑 Initiator

根據實施例之黏著劑組成物包括起始劑。 The adhesive composition according to the embodiment includes an initiator.

起始劑係用以固化第一寡聚物。 The initiator is used to cure the first oligomer.

起始劑可係光起始劑或熱起始劑。 The initiator can be a photoinitiator or a thermal initiator.

以基底聚合物之100重量份計，組成物中的起始劑之含量可係0.1重量份至10重量份。具體而言，以基底聚合物之100重量份計，組成物中的起始劑之含量可係0.1重量份至5重量份。此時，起始劑及基底聚合物之含量可基於固體含量。 Based on 100 parts by weight of the base polymer, the content of the initiator in the composition can range from 0.1 parts by weight to 10 parts by weight. Specifically, based on 100 parts by weight of the base polymer, the content of the initiator in the composition may range from 0.1 parts by weight to 5 parts by weight. At this time, the content of the initiator and the base polymer may be based on the solid content.

可使用一般光起始劑作為起始劑，且例如，可使用選自由下列所組成之群組的至少一者作為光起始劑：酮類(二苯基酮、苯乙酮等)、安息香、安息香醚、苄基、及苄基縮酮。 A general photoinitiator can be used as the initiator, and for example, at least one selected from the group consisting of the following can be used as the photoinitiator: ketones (benzophenone, acetophenone, etc.), benzoin , Benzoin ether, benzyl, and benzyl ketal.

在一實例中，光起始劑可係安息香醚(例如，安息香甲醚或安息香異丙醚)或經取代的安息香醚。 In one example, the photoinitiator may be benzoin ether (for example, benzoin methyl ether or benzoin isopropyl ether) or substituted benzoin ether.

在另一實例中，光起始劑可係經取代的苯乙酮，例如，2,2-二乙氧基苯乙酮或2,2-二甲氧基-2-苯基苯乙酮。 In another example, the photoinitiator may be a substituted acetophenone, for example, 2,2-diethoxyacetophenone or 2,2-dimethoxy-2-phenylacetophenone.

在又另一實例中，光起始劑可係經取代的α-酮(例如2-甲基-2-羥基苯丙酮)、芳香磺醯氯(例如2-萘-磺醯基氯)、或光活性肟(例如1-苯基-1,2-丙二酮-2(O-乙氧基羰基)肟)。 In yet another example, the photoinitiator may be substituted α-ketones (e.g. 2-methyl-2-hydroxypropiophenone), aromatic sulfonyl chlorides (e.g. 2-naphthalene-sulfonyl chloride), or Photoactive oximes (e.g. 1-phenyl-1,2-propanedione-2(O-ethoxycarbonyl)oxime).

在又另一實例中，光起始劑可係1-羥基環己基苯基酮、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎福啉基苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎福啉基丙-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、及類似物。 In yet another example, the photoinitiator may be 1-hydroxycyclohexyl phenyl ketone, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 1-[4-( 2-Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine) Phenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-hydroxy-2-methyl-1-benzene Propan-1-one, and the like.

市售光起始劑之實例可包括來自Ciba Specialty Chemicals Co.,Ltd.之Ciba IRGACURE、來自IGM Resins Co.,Ltd.之Esacure KIP系列、及類似者。 Examples of commercially available photoinitiators may include Ciba IRGACURE from Ciba Specialty Chemicals Co., Ltd., Esacure KIP series from IGM Resins Co., Ltd., and the like.

根據欲使用的固化方法，可選擇性地使用水溶性或不溶於水(即，油溶性)熱起始劑作為熱起始劑。 According to the curing method to be used, a water-soluble or water-insoluble (ie, oil-soluble) thermal initiator can be selectively used as the thermal initiator.

可使用以下作為水溶性起始劑：過硫酸鹽，諸如過硫酸鉀、過硫酸銨、過硫酸鈉、及其混合物；氧化還原起始劑，諸如還原 劑(諸如偏二亞硫酸鹽，例如，偏二亞硫酸鈉)或硫酸氫鹽(例如，硫酸氫鈉)與過硫酸鹽之反應產物；或4,4’-偶氮雙(4-氰基戊酸)及其可溶性鹽(例如，鈉鹽、鉀鹽)、或類似者。 The following can be used as water-soluble initiators: persulfates, such as potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof; redox initiators, such as reduction The reaction product of an agent (such as metabisulphite, for example, sodium metabisulphite) or a bisulfate (for example, sodium bisulfate) and persulfate; ) And its soluble salts (for example, sodium salt, potassium salt), or the like.

可使用以下作為油溶性起始劑：偶氮，諸如2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(異丁腈)、及2,2'-偶氮雙(2,4-二甲基戊腈)；或過氧化物，諸如過氧化苯甲醯、過氧化環己烷、及過氧化月桂醯。 The following can be used as oil-soluble initiators: azo, such as 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), and 2,2' -Azobis(2,4-dimethylvaleronitrile); or peroxides such as benzyl peroxide, cyclohexane peroxide, and laurel peroxide.

交聯劑 Crosslinking agent

根據實施例之黏著劑組成物包括交聯劑。 The adhesive composition according to the embodiment includes a crosslinking agent.

交聯劑與基底聚合物反應以形成膜及類似者。 The crosslinking agent reacts with the base polymer to form a film and the like.

以基底聚合物之100重量份計，組成物中的交聯劑之含量可係0.1重量份至20重量份。具體而言，以基底聚合物之100重量份計，組成物中的交聯劑之含量可係0.1重量份至10重量份、或0.1重量份至5重量份。此時，交聯劑及基底聚合物之含量可基於固體含量。 Based on 100 parts by weight of the base polymer, the content of the crosslinking agent in the composition may range from 0.1 parts by weight to 20 parts by weight. Specifically, based on 100 parts by weight of the base polymer, the content of the crosslinking agent in the composition may range from 0.1 parts by weight to 10 parts by weight, or from 0.1 parts by weight to 5 parts by weight. At this time, the content of the crosslinking agent and the base polymer may be based on the solid content.

交聯劑可含有與基底聚合物之官能基反應的官能基。例如，交聯劑可具有選自由下列所組成之群組的一或至少兩個官能基：環氧基、異氰酸酯基、羧基、羥基、丙烯醯基、甲基丙烯醯基、乙酸酯基、及乙烯基。作為具體實例，交聯劑可具有環氧基或異氰酸酯基。 The crosslinking agent may contain a functional group that reacts with the functional group of the base polymer. For example, the crosslinking agent may have one or at least two functional groups selected from the group consisting of epoxy groups, isocyanate groups, carboxyl groups, hydroxyl groups, acrylic groups, methacrylic groups, acetate groups, And vinyl. As a specific example, the crosslinking agent may have an epoxy group or an isocyanate group.

交聯劑可係光交聯劑、熱交聯劑、或其組合。 The crosslinking agent can be a photocrosslinking agent, a thermal crosslinking agent, or a combination thereof.

可使用一般的多官能丙烯酸系化合物作為光交聯劑。例如，光交聯劑可係選自由二丙烯酸酯類及三丙烯酸酯類所組成之群組之至少一者。光交聯劑的具體實例可包括1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯(HDDA)、1,9-壬二醇二丙烯酸酯、三伸丙二醇二丙烯酸酯、四甘醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、及新戊四醇三丙烯酸酯。 A general multifunctional acrylic compound can be used as the photocrosslinking agent. For example, the photocrosslinking agent may be at least one selected from the group consisting of diacrylates and triacrylates. Specific examples of the photocrosslinking agent may include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate (HDDA), 1,9-nonanediol diacrylate, trimethylene glycol diacrylate Esters, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, and neopentylerythritol triacrylate.

熱交聯劑可係基於異氰酸酯、基於環氧樹脂、或基於金屬螯合物之化合物。基於異氰酸酯之化合物可係多官能性芳族或脂族異氰酸酯化合物。例如，基於異氰酸酯之化合物可係三聚異氰酸酯，諸如甲苯二異氰酸酯-三羥甲基丙烷(TDI-TMP)加成物。基於環氧樹脂之化合物可具有一或至少兩個環氧基，且可具有與基底聚合物反應的其他官能基。金屬螯合物化合物可係具有金屬(諸如Zn、Ni、Mn、Fe、Co、Cr、Al、Ti、或Zr)之基於螯合物之化合物。可商購的熱交聯劑之實例可包括來自Saiden Chemical Industry Co.,Ltd.的Saivinol硬化劑系列。 The thermal crosslinking agent may be a compound based on isocyanate, epoxy resin, or metal chelate. The isocyanate-based compound can be a polyfunctional aromatic or aliphatic isocyanate compound. For example, the isocyanate-based compound may be a trimeric isocyanate, such as toluene diisocyanate-trimethylolpropane (TDI-TMP) adduct. The epoxy resin-based compound may have one or at least two epoxy groups, and may have other functional groups that react with the base polymer. The metal chelate compound may be a chelate-based compound having a metal (such as Zn, Ni, Mn, Fe, Co, Cr, Al, Ti, or Zr). Examples of commercially available thermal crosslinking agents may include the Saivinol hardener series from Saiden Chemical Industry Co., Ltd.

溶劑 Solvent

根據實施例之黏著劑組成物可進一步包括溶劑。 The adhesive composition according to the embodiment may further include a solvent.

溶劑可作用以調整黏著劑組成物的黏度。 The solvent can act to adjust the viscosity of the adhesive composition.

溶劑的類型並無具體限制，且可係例如選自由甲苯、己烷/甲基乙基酮之混合物、二甲苯、及乙酸異丙酯所組成之群組之至少一者。 The type of the solvent is not specifically limited, and may be, for example, at least one selected from the group consisting of toluene, a mixture of hexane/methyl ethyl ketone, xylene, and isopropyl acetate.

溶劑的混合量無具體限制，但例如，黏著劑組成物之固體含量可經混合以在30wt%至90wt%、或50wt%至80wt%之範圍中。 The mixing amount of the solvent is not specifically limited, but for example, the solid content of the adhesive composition may be mixed to be in the range of 30 wt% to 90 wt%, or 50 wt% to 80 wt%.

添加劑 additive

根據實施例之黏著劑組成物可視需要進一步包括其他添加劑。 The adhesive composition according to the embodiment may further include other additives as needed.

添加劑的具體實例包括增黏劑(例如松酯、萜烯類、酚、及脂肪族合成烴樹脂、芳族合成烴樹脂、或脂肪族合成烴樹脂以及芳族合成烴樹脂之混合物)、界面活性劑、塑化劑(除物理發泡劑之外者)、成核劑(例如滑石、二氧化矽、或TiO2)、填料(例如無機填料以及有機填料)、纖維、老化抑制劑、抗氧化劑、UV吸收劑、抗靜電劑、潤滑劑、顏料、染料、增強劑、疏水性或親水性二氧化矽、碳酸鈣、增韌劑、阻燃劑、細磨聚合粒子(例如聚酯、尼龍、或聚丙烯)、穩定劑(例如UV穩定劑)、及彼等之組合。 Specific examples of additives include tackifiers (such as pine esters, terpenes, phenols, and aliphatic synthetic hydrocarbon resins, aromatic synthetic hydrocarbon resins, or mixtures of aliphatic synthetic hydrocarbon resins and aromatic synthetic hydrocarbon resins), interfacial activity Agents, plasticizers (other than physical foaming agents), nucleating agents (such as talc, silica, or TiO 2 ), fillers (such as inorganic fillers and organic fillers), fibers, aging inhibitors, antioxidants , UV absorbers, antistatic agents, lubricants, pigments, dyes, enhancers, hydrophobic or hydrophilic silica, calcium carbonate, tougheners, flame retardants, finely ground polymeric particles (e.g. polyester, nylon, Or polypropylene), stabilizers (such as UV stabilizers), and combinations of them.

添加劑之含量未具體限制如一適當量以獲得組成物之所欲性質，但可係例如以黏著劑組成物之重量計，0.1wt%至10wt%或0.1wt%至5w%。 The content of the additives is not specifically limited as an appropriate amount to obtain the desired properties of the composition, but can be, for example, 0.1 wt% to 10 wt% or 0.1 wt% to 5w% based on the weight of the adhesive composition.

特定組成物實例 Examples of specific components

根據實施例之黏著劑組成物可經組態使得以上例示之各種組分具有具體含量。 The adhesive composition according to the embodiment can be configured so that the various components exemplified above have specific contents.

根據一實施例，該黏著劑組成物可包括100重量份之該基底聚合物、0.1至20重量份之該交聯劑、10至90重量份之該第一寡聚物、及0.1至10重量份之該起始劑。 According to an embodiment, the adhesive composition may include 100 parts by weight of the base polymer, 0.1 to 20 parts by weight of the crosslinking agent, 10 to 90 parts by weight of the first oligomer, and 0.1 to 10 parts by weight Parts of the initiator.

根據另一實施例，該黏著劑組成物可包括100重量份之該基底聚合物、0.1至20重量份之該交聯劑、10至90重量份之該第一寡聚物、0.1至20重量份之該第二寡聚物、及0.1至10重量份之該起始劑。 According to another embodiment, the adhesive composition may include 100 parts by weight of the base polymer, 0.1 to 20 parts by weight of the crosslinking agent, 10 to 90 parts by weight of the first oligomer, and 0.1 to 20 parts by weight Parts of the second oligomer, and 0.1 to 10 parts by weight of the initiator.

根據另一實施例，該黏著劑組成物可包括100重量份之該基底聚合物、0.1至20重量份之該交聯劑、10至90重量份之該第一寡聚物、0.1至20重量份之該第二寡聚物、0.1至10重量份之該有機酸、及0.1至10重量份之該起始劑。 According to another embodiment, the adhesive composition may include 100 parts by weight of the base polymer, 0.1 to 20 parts by weight of the crosslinking agent, 10 to 90 parts by weight of the first oligomer, and 0.1 to 20 parts by weight Parts of the second oligomer, 0.1 to 10 parts by weight of the organic acid, and 0.1 to 10 parts by weight of the initiator.

此外，該黏著劑組成物可包括100重量份之該第一寡聚物、5至35重量份之該第二寡聚物、及1至6重量份之該有機酸。 In addition, the adhesive composition may include 100 parts by weight of the first oligomer, 5 to 35 parts by weight of the second oligomer, and 1 to 6 parts by weight of the organic acid.

該黏著劑組成物中的該等組分之含量可基於固體含量。 The content of the components in the adhesive composition may be based on the solid content.

黏著劑組成物之製備方法 Preparation method of adhesive composition

根據實施例之黏著劑組成物可藉由混合基底聚合物、第一寡聚物、交聯劑、及起始劑，並視需要進一步混合溶劑及其他添加劑來製備。此外，當製備黏著劑組成物時，可額外添加第一寡聚物及有機酸。 The adhesive composition according to the embodiment can be prepared by mixing the base polymer, the first oligomer, the crosslinking agent, and the initiator, and further mixing the solvent and other additives as necessary. In addition, when preparing the adhesive composition, the first oligomer and organic acid may be additionally added.

基底聚合物可藉由一般方法(諸如溶液聚合)來製備。 The base polymer can be prepared by a general method such as solution polymerization.

第一寡聚物、第二寡聚物、及有機酸可商購購買或分開製備。 The first oligomer, the second oligomer, and the organic acid can be purchased commercially or separately prepared.

此外，第一寡聚物、第二寡聚物、及有機酸可藉由這些化合物中之任何兩種的反應來製備。作為具體實例，當雙酚A環氧樹脂與甲基丙烯酸反應時，產生雙酚A環氧丙烯酸酯時，未反應的雙酚A環氧樹脂與甲基丙烯酸仍然存在，使得可分別提供雙酚A環氧丙烯酸酯、雙酚A環氧樹脂、及甲基丙烯酸作為第一寡聚物、第二寡聚物、及有機酸。 In addition, the first oligomer, the second oligomer, and the organic acid can be prepared by the reaction of any two of these compounds. As a specific example, when bisphenol A epoxy resin reacts with methacrylic acid to produce bisphenol A epoxy acrylate, unreacted bisphenol A epoxy resin and methacrylic acid still exist, so that bisphenol A can be provided separately A epoxy acrylate, bisphenol A epoxy resin, and methacrylic acid are used as the first oligomer, the second oligomer, and the organic acid.

在黏著劑組成物之製備中，混合基底聚合物、第一寡聚物、交聯劑、及起始劑的順序及條件並無特殊限制，且可視需要合適地修改程序。 In the preparation of the adhesive composition, the order and conditions of mixing the base polymer, the first oligomer, the crosslinking agent, and the initiator are not particularly limited, and the procedure may be appropriately modified as needed.

此外，在各混合步驟中可藉由使用溶劑來調整黏度。 In addition, the viscosity can be adjusted by using a solvent in each mixing step.

然而，黏著劑組成物的製備方法並無具體限制，且可視需要適當地修改程序條件。 However, the preparation method of the adhesive composition is not specifically limited, and the program conditions may be appropriately modified as needed.

根據該實施例之黏著劑組成物係用以形成具有可變黏著強度的黏著劑膜，且可有用地施用於需要可變黏著強度之程序(諸如有機發光二極體(OLED)顯示面板及液晶顯示器(LCD)面板之製造)。 The adhesive composition according to this embodiment is used to form an adhesive film with variable adhesive strength, and can be usefully applied to processes that require variable adhesive strength (such as organic light-emitting diode (OLED) display panels and liquid crystals). Display (LCD) panel manufacturing).

[黏著劑膜] [Adhesive Film]

根據本發明之另一態樣，提供一種由該黏著劑組成物形成之黏著劑膜。 According to another aspect of the present invention, an adhesive film formed from the adhesive composition is provided.

黏著劑膜在固化之後具有低於第一寡聚物固化之前黏著強度的黏著強度。 The adhesive film after curing has an adhesive strength lower than the adhesive strength before curing of the first oligomer.

根據一實施例之黏著劑膜係包括基底聚合物與交聯劑之反應產物的黏著劑膜。黏著劑膜含有第一寡聚物及起始劑，該第一寡聚物可藉由該起始劑固化，該黏著劑膜具有在固化第一寡聚物之前的第一黏著強度，及在固化第一寡聚物之後的第二黏著強度，且該第二黏著強度低於該第一黏著強度。 The adhesive film according to an embodiment includes an adhesive film of a reaction product of a base polymer and a crosslinking agent. The adhesive film contains a first oligomer and an initiator, the first oligomer can be cured by the initiator, the adhesive film has a first adhesive strength before curing the first oligomer, and The second adhesive strength after curing the first oligomer, and the second adhesive strength is lower than the first adhesive strength.

黏著劑膜之組分 Adhesive film components

根據實施例之黏著劑膜包括基底聚合物與交聯劑之反應產物。即，該黏著劑膜包括經交聯之基底聚合物。 The adhesive film according to the embodiment includes a reaction product of a base polymer and a crosslinking agent. That is, the adhesive film includes a cross-linked base polymer.

此外，包括該基底聚合物與該交聯劑之該反應產物的該黏著劑膜含有第一寡聚物及起始劑。例如，該第一寡聚物及該起始劑經分散於該基底聚合物與該交聯劑之該反應產物中。該第一寡聚物可具有與該基底聚合物與該交聯劑之該反應產物的相容性。第一寡聚物之固化可藉由起始劑之作用來起始(若需要)，以降低黏著劑膜之黏著強度。 In addition, the adhesive film including the reaction product of the base polymer and the crosslinking agent contains a first oligomer and an initiator. For example, the first oligomer and the initiator are dispersed in the reaction product of the base polymer and the crosslinking agent. The first oligomer may have compatibility with the reaction product of the base polymer and the crosslinking agent. The curing of the first oligomer can be initiated by the action of an initiator (if necessary) to reduce the adhesive strength of the adhesive film.

包括在該黏著劑膜中之該基底聚合物、該交聯劑、該第一寡聚物、及該起始劑之具體類型及含量係如以上黏著劑組成物中所述。 The specific types and contents of the base polymer, the crosslinking agent, the first oligomer, and the initiator included in the adhesive film are as described in the above adhesive composition.

此外，該黏著劑膜可進一步包括不同於該第一寡聚物之第二寡聚物，且該第二寡聚物可在該基底聚合物與該交聯劑之該反應產物中形成額外鍵。 In addition, the adhesive film may further include a second oligomer different from the first oligomer, and the second oligomer may form an additional bond in the reaction product of the base polymer and the crosslinking agent .

第二寡聚物的具體類型及含量係如包括在黏著劑組成物中的該第二寡聚物中所述。 The specific type and content of the second oligomer are as described in the second oligomer included in the adhesive composition.

此外，根據實施例之黏著劑膜可進一步包括其他添加劑，且其具體類型及含量係如包括在黏著劑組成物中的添加劑中所述。 In addition, the adhesive film according to the embodiment may further include other additives, and the specific type and content thereof are as described in the additives included in the adhesive composition.

黏著強度-在固化第一寡聚物之前及之後 Adhesion strength-before and after curing the first oligomer

根據實施例之黏著劑膜在固化該第一寡聚物之前具有第一黏著強度。該第一黏著強度較佳地係高如一預定位準或更多，以初始地將該黏著劑膜附接至該基材。例如，該第一黏著強度可係350gf/in或更多、400gf/in或更多、500gf/in或更多、或1,000gf/in或更多。具體而言，該第一黏著強度可在350gf/in至10,000gf/in、或500gf/in至5,000gf/in的一範圍中。 The adhesive film according to the embodiment has a first adhesive strength before curing the first oligomer. The first adhesive strength is preferably as high as a predetermined level or more to initially attach the adhesive film to the substrate. For example, the first adhesive strength may be 350 gf/in or more, 400 gf/in or more, 500 gf/in or more, or 1,000 gf/in or more. Specifically, the first adhesive strength may be in a range of 350 gf/in to 10,000 gf/in, or 500 gf/in to 5,000 gf/in.

在本說明書中，黏著強度(第一黏著強度、第二黏著強度等)可藉由ASTM D3330測量，其係所屬技術領域中之一般測量方法，且例如可係測量聚醯亞胺之黏著強度。測量方法的更詳細實例已在下列實施例中具體描述。 In this specification, the adhesion strength (first adhesion strength, second adhesion strength, etc.) can be measured by ASTM D3330, which is a general measurement method in the technical field, and can be, for example, the measurement of the adhesion strength of polyimide. More detailed examples of the measurement method have been specifically described in the following examples.

根據實施例之黏著劑膜在固化該第一寡聚物之後具有第二黏著強度。第二黏著強度較佳地係低如一預定位準或更少，以藉由 輕易地移除黏著劑膜之不必要部分，而在基材上僅留下所欲部分。例如，該第二黏著強度可係200gf/in或更少、150gf/in或更少、100gf/in或更少、50gf/in或更少、或30gf/in或更少。具體而言，該第二黏著強度可在0gf/in至200gf/in、0gf/in至100gf/in、或0gf/in至30gf/in的一範圍中。 The adhesive film according to the embodiment has a second adhesive strength after curing the first oligomer. The second adhesive strength is preferably as low as a predetermined level or less, so that by Easily remove unnecessary parts of the adhesive film, leaving only the desired part on the substrate. For example, the second adhesive strength may be 200 gf/in or less, 150 gf/in or less, 100 gf/in or less, 50 gf/in or less, or 30 gf/in or less. Specifically, the second adhesive strength may be in a range of 0 gf/in to 200 gf/in, 0 gf/in to 100 gf/in, or 0 gf/in to 30 gf/in.

該第二黏著強度低於該第一黏著強度。例如，該第二黏著強度可比該第一黏著強度小150gf/in或更多、200gf/in或更多、500gf/in或更多、或1,000gf/in或更多。 The second adhesive strength is lower than the first adhesive strength. For example, the second adhesive strength may be 150 gf/in or more, 200 gf/in or more, 500 gf/in or more, or 1,000 gf/in or more less than the first adhesive strength.

此外，該第一黏著強度對該第二黏著強度之一比率(第一黏著強度/第二黏著強度)可係3或更多、5或更多、10或更多、12或更多、或15或更多。此外，該第一黏著強度對該第一黏著強度之一比率(第二黏著強度/第一黏著強度)可係0.06或更少、0.03或更少、0.02或更少、或0.01或更少。 In addition, a ratio of the first adhesive strength to the second adhesive strength (first adhesive strength/second adhesive strength) can be 3 or more, 5 or more, 10 or more, 12 or more, or 15 or more. In addition, a ratio of the first adhesive strength to the first adhesive strength (second adhesive strength/first adhesive strength) may be 0.06 or less, 0.03 or less, 0.02 or less, or 0.01 or less.

作為一實例，第一黏著強度可係350gf/in或更多，且第二黏著強度可係200gf/in或更少。作為另一實例，第一黏著強度可係400gf/in或更多，且第二黏著強度可係150gf/in或更少。作為又另一實例，該第一黏著強度可在500gf/in至5,000gf/in之範圍中，且該第二黏著強度可在0gf/in至30gf/in之範圍中。 As an example, the first adhesive strength may be 350 gf/in or more, and the second adhesive strength may be 200 gf/in or less. As another example, the first adhesive strength may be 400 gf/in or more, and the second adhesive strength may be 150 gf/in or less. As yet another example, the first adhesive strength may be in the range of 500 gf/in to 5,000 gf/in, and the second adhesive strength may be in the range of 0 gf/in to 30 gf/in.

在固化第一寡聚物之後的霧度及透射率 Haze and transmittance after curing the first oligomer

該黏著劑膜可滿足作為光學透明黏著劑膜的要求。例如，在固化該第一寡聚物之後，該黏著劑膜具有5%或更少、2%或更 少、或1%或更少的霧度。此外，在固化該第一寡聚物之後，該黏著劑膜可具有80%或更多、90%或更多、或95%或更多的光透射率。 The adhesive film can meet the requirements of being an optically transparent adhesive film. For example, after curing the first oligomer, the adhesive film has 5% or less, 2% or more Less, or 1% or less haze. In addition, after curing the first oligomer, the adhesive film may have a light transmittance of 80% or more, 90% or more, or 95% or more.

甚至當額外包括該第二寡聚物時，該黏著劑膜可滿足作為光學透明黏著劑膜的要求。例如，當黏著劑膜包括第一寡聚物及第二寡聚物時，在固化之後的霧度可係5%或更少、或2%或更少。此外，當黏著劑膜包括第一寡聚物及第二寡聚物時，固化之後的光透射率可係80%或更多、或90%或更多。 Even when the second oligomer is additionally included, the adhesive film can meet the requirements as an optically transparent adhesive film. For example, when the adhesive film includes the first oligomer and the second oligomer, the haze after curing may be 5% or less, or 2% or less. In addition, when the adhesive film includes the first oligomer and the second oligomer, the light transmittance after curing may be 80% or more, or 90% or more.

膜之厚度 Film thickness

當製備為薄膜時，黏著劑膜之厚度可在0.2μm至1000μm、5μm至1000μm、10μm至100μm、或0.2μm至1μm之範圍中。替代地，當製備為厚膜時，該黏著劑膜的厚度可在0.1mm至5mm、或1mm至3mm之範圍中。 When prepared as a thin film, the thickness of the adhesive film may be in the range of 0.2 μm to 1000 μm, 5 μm to 1000 μm, 10 μm to 100 μm, or 0.2 μm to 1 μm. Alternatively, when prepared as a thick film, the thickness of the adhesive film may be in the range of 0.1 mm to 5 mm, or 1 mm to 3 mm.

黏著劑膜之製備方法 Preparation method of adhesive film

可藉由製備待形成為膜之黏著劑組成物來製備黏著劑膜。 The adhesive film can be prepared by preparing an adhesive composition to be formed into a film.

根據一實施例的黏著劑膜之製備方法包括混合基底聚合物、第一寡聚物、起始劑、及交聯劑；使該交聯劑與該基底聚合物反應以形成膜狀聚合物；及保持該第一寡聚物及該起始劑於該膜狀聚合物中以獲得黏著劑膜。 A method for preparing an adhesive film according to an embodiment includes mixing a base polymer, a first oligomer, an initiator, and a cross-linking agent; reacting the cross-linking agent with the base polymer to form a film-like polymer; And keeping the first oligomer and the initiator in the film-like polymer to obtain an adhesive film.

該黏著劑組成物之製備可根據上述條件與程序來執行。交聯劑與基底聚合物之反應可藉由一般熱固化程序來執行。例如，熱固化溫度可在40℃至150℃、60℃至150℃、60℃至120℃、或100℃至120℃之範圍中，且熱固化時間可係1分鐘至10分鐘、或2分鐘至5分鐘，但可根據固化烘箱之長度及數目來調整這些熱固化條件。此外，在熱固化之後，可進一步執行老化(例如，在約50℃老化3天)。 The preparation of the adhesive composition can be performed according to the above-mentioned conditions and procedures. The reaction between the crosslinking agent and the base polymer can be performed by a general thermal curing procedure. For example, the heat curing temperature can be in the range of 40°C to 150°C, 60°C to 150°C, 60°C to 120°C, or 100°C to 120°C, and the heat curing time can be 1 minute to 10 minutes, or 2 minutes Up to 5 minutes, but these thermal curing conditions can be adjusted according to the length and number of curing ovens. In addition, after thermal curing, aging may be further performed (for example, aging at about 50°C for 3 days).

當黏著劑組成物塗佈在基底膜上時，可執行熱固化程序。具體而言，可將黏著劑組成物以適當厚度塗佈在基底膜上，且可在此程序中執行熱固化。可藉由諸如切口棒塗佈、缺角輪塗佈、凹版塗布、或模具塗佈的方法來執行。此外，塗佈速率可在約1m/min至40m/min、或5m/min至30m/min之範圍中，但可根據固化烘箱的長度來調整條件。 When the adhesive composition is coated on the base film, a thermal curing process can be performed. Specifically, the adhesive composition can be coated on the base film with an appropriate thickness, and thermal curing can be performed in this process. It can be performed by methods such as notch bar coating, chipped wheel coating, gravure coating, or die coating. In addition, the coating rate can be in the range of about 1m/min to 40m/min, or 5m/min to 30m/min, but the conditions can be adjusted according to the length of the curing oven.

此外，在膜狀聚合物中保留第一寡聚物及起始劑可藉由抑制其中起始劑可在經塗佈(及熱固化)膜狀聚合物中作用的環境來執行(例如，防止UV光暴露)。 In addition, retaining the first oligomer and the initiator in the film-like polymer can be performed by suppressing the environment in which the initiator can act in the coated (and heat-cured) film-like polymer (for example, preventing UV light exposure).

施加至黏著劑膠帶 Apply to adhesive tape

根據實施例之黏著劑膜可施加為黏著劑膠帶。 The adhesive film according to the embodiment may be applied as an adhesive tape.

例如，根據實施例之黏著劑膜可形成於該基底膜之一個表面上以提供一基底類型黏著劑膠帶。 For example, the adhesive film according to the embodiment may be formed on a surface of the base film to provide a base type adhesive tape.

此外，在黏著劑膠帶中，離型膜可接合在黏著劑膜的一個表面上。 In addition, in the adhesive tape, the release film can be bonded to one surface of the adhesive film.

[雙塗佈黏著劑膠帶] [Double Coating Adhesive Tape]

根據本發明之又另一態樣，提供一種雙塗佈黏著劑膠帶，其包括該黏著劑膜。 According to yet another aspect of the present invention, there is provided a double-coated adhesive tape, which includes the adhesive film.

包括在根據實施例之雙塗佈黏著劑膠帶中的黏著劑膜具有與上述實施例之黏著劑膜相同的組成及特性。 The adhesive film included in the double-coated adhesive tape according to the embodiment has the same composition and characteristics as the adhesive film of the above-mentioned embodiment.

據此，具有黏著劑膜作為中心層的雙塗佈黏著劑膠帶可基於該中心層而分離成兩個單塗佈黏著劑膠帶，此係因為該中心層之黏著強度藉由UV輻照而降低。 Accordingly, the double-coated adhesive tape with the adhesive film as the central layer can be separated into two single-coated adhesive tapes based on the central layer, because the adhesive strength of the central layer is reduced by UV irradiation .

雙塗佈黏著劑膠帶可製備成薄膜或厚膜。 Double-coated adhesive tape can be prepared as a thin film or a thick film.

圖4A至圖4B繪示根據一實施例及其應用實例之雙塗佈黏著劑膠帶的截面圖。 4A to 4B show cross-sectional views of a double-coated adhesive tape according to an embodiment and application examples thereof.

參照圖4A，根據實施例之雙塗佈黏著劑膠帶11包括單塗佈膠帶A 210，其包括一基底層A 211及設置於該基底層A 211之一個表面上的一黏著劑層A 212；單塗佈膠帶B 220，其包括一基底層B 221及設置於該基底層B 222之一個表面上的一黏著劑層B 222；及一黏著劑膜100，其設置於基底層A 211與基底層B 221之間，以接合基底層A 211與基底層B 221。 4A, the double-coated adhesive tape 11 according to the embodiment includes a single-coated tape A 210, which includes a base layer A 211 and an adhesive layer A 212 disposed on a surface of the base layer A 211; Single-coated tape B 220, which includes a base layer B 221 and an adhesive layer B 222 disposed on a surface of the base layer B 222; and an adhesive film 100 disposed on the base layer A 211 and the base Between the layers B 221, to join the base layer A 211 and the base layer B 221.

離型層213及223可分別施加至黏著劑層A 212及黏著劑層B 222之表面上。 The release layers 213 and 223 can be applied to the surfaces of the adhesive layer A 212 and the adhesive layer B 222, respectively.

此外，黏著劑膜係薄膜對於分離步驟係有利的，且例如，厚度可係10μm或更少、或1μm或更少，具體而言，0.2μm至1μm。據此，雙塗佈黏著劑膠帶可經製備成薄的，且例如，雙塗佈黏著劑膠帶的總體厚度可係300μm或更少，具體而言，100μm至300μm。 In addition, the adhesive film-based film is advantageous for the separation step, and for example, the thickness may be 10 μm or less, or 1 μm or less, specifically, 0.2 μm to 1 μm. Accordingly, the double-coated adhesive tape can be prepared to be thin, and for example, the overall thickness of the double-coated adhesive tape can be 300 μm or less, specifically, 100 μm to 300 μm.

黏著劑層A及黏著劑層B可包括一般黏著劑，且可包括具有低或高黏著強度的丙烯酸壓敏黏著劑(pressure-sensitive adhesive,PSA)，其取決於暫時或永久黏著劑應用。 The adhesive layer A and the adhesive layer B may include general adhesives, and may include acrylic pressure-sensitive adhesives (PSA) with low or high adhesive strength, depending on the application of the temporary or permanent adhesive.

基底層A及基底層B可係透明聚合物膜，且例如，可係包括選自由下列所組成之群組的至少一種樹脂的透明膜：聚酯樹脂、聚胺甲酸酯樹脂、及聚烯烴(聚乙烯等)樹脂。替代地，基底層A及基底層B亦可由紙、塑膠膜、布、或金屬箔所構成。在一些實施例中，適合用於基底層A及基底層B的材料可包括例如：紙，包括平坦或光滑紙及紋理化紙，諸如皺紋紙；天然或合成聚合物膜；天然及/或合成纖維或由其組合所製成的非織造織物；纖維強化聚合物膜；纖維或紗線強化聚合物膜或非織造織物、及一多層層壓結構。 The base layer A and the base layer B may be transparent polymer films, and for example, may be a transparent film including at least one resin selected from the group consisting of polyester resin, polyurethane resin, and polyolefin (Polyethylene, etc.) Resin. Alternatively, the base layer A and the base layer B can also be composed of paper, plastic film, cloth, or metal foil. In some embodiments, suitable materials for the base layer A and the base layer B may include, for example: paper, including flat or smooth paper and textured paper, such as crepe paper; natural or synthetic polymer film; natural and/or synthetic Fiber or non-woven fabric made from a combination thereof; fiber-reinforced polymer film; fiber or yarn-reinforced polymer film or non-woven fabric, and a multilayer laminate structure.

參照圖4B，單塗佈膠帶A 210及單塗佈膠帶B 220可在固化黏著劑膜100之後彼此分離。據此，兩個單塗佈黏著劑膠帶210及220可由雙塗佈黏著劑膠帶11提供。 Referring to FIG. 4B, the single-coating tape A 210 and the single-coating tape B 220 may be separated from each other after curing the adhesive film 100. Accordingly, the two single-coated adhesive tapes 210 and 220 can be provided by the double-coated adhesive tape 11.

圖5A至圖5B繪示根據另一實施例及其應用實例之雙塗佈黏著劑膠帶的截面圖。 5A to 5B show cross-sectional views of a double-coated adhesive tape according to another embodiment and its application example.

參照圖5A，根據實施例之雙塗佈黏著劑膠帶12包括單塗佈膠帶A 210，其包括基底層A 211及設置於基底層A 211之一個表面上的黏著劑層A 222；單塗佈膠帶B 220，其包括基底層B 221及設置於基底層B 221之一個表面上的黏著劑層B 222；及雙塗佈黏著劑膜101，其包括緩衝片材150及分別設置於緩衝片材150之兩個表面上的黏著劑膜100，其中雙塗佈黏著劑膜101設置在基底層A 211與基底層B 221之間，以接合基底層A 211及基底層B 221。 5A, the double-coated adhesive tape 12 according to the embodiment includes a single-coated tape A 210, which includes a base layer A 211 and an adhesive layer A 222 disposed on one surface of the base layer A 211; single-coated Adhesive tape B 220, which includes a base layer B 221 and an adhesive layer B 222 arranged on one surface of the base layer B 221; and a double-coated adhesive film 101, which includes a buffer sheet 150 and is respectively arranged on the buffer sheet The adhesive film 100 on both surfaces of 150, wherein the double-coated adhesive film 101 is disposed between the base layer A 211 and the base layer B 221 to join the base layer A 211 and the base layer B 221.

離型層213及223可分別施加至黏著劑層A 212及黏著劑層B 222之表面上。 The release layers 213 and 223 can be applied to the surfaces of the adhesive layer A 212 and the adhesive layer B 222, respectively.

此外，黏著劑膜係薄膜對於分離步驟係有利的，且例如，厚度可係1μm或更少，具體而言，0.2μm至1μm。 In addition, the adhesive film-based thin film is advantageous for the separation step, and for example, the thickness may be 1 μm or less, specifically, 0.2 μm to 1 μm.

該緩衝片材可包含聚合物材料或發泡體材料，且具體而言，丙烯酸或熱塑性胺甲酸酯發泡體。此外，可依需要調整緩衝片材之厚度，且緩衝片材可製備為厚片材。 The buffer sheet may include a polymer material or a foam material, and specifically, an acrylic or thermoplastic urethane foam. In addition, the thickness of the buffer sheet can be adjusted as required, and the buffer sheet can be prepared as a thick sheet.

據此，雙塗佈黏著劑膠帶可經製備成厚的，且例如，雙塗佈黏著劑膠帶的總體厚度可係300μm或更多，具體而言，300μm至1000μm。 Accordingly, the double-coated adhesive tape can be prepared to be thick, and for example, the overall thickness of the double-coated adhesive tape can be 300 μm or more, specifically, 300 μm to 1000 μm.

參照圖5B，單塗佈膠帶A 210及單塗佈膠帶B 220可在固化黏著劑膜100之後彼此分離。據此，兩個單塗佈黏著劑膠帶210及220可由雙塗佈黏著劑膠帶12提供。 Referring to FIG. 5B, the single-coated tape A 210 and the single-coated tape B 220 may be separated from each other after curing the adhesive film 100. Accordingly, the two single-coated adhesive tapes 210 and 220 can be provided by the double-coated adhesive tape 12.

[層壓體] [Laminate]

根據本發明之又另一態樣，提供一種層壓體，其包括基材及根據實施例之黏著劑膜。 According to yet another aspect of the present invention, there is provided a laminate including a substrate and an adhesive film according to the embodiment.

層壓體之組分 Components of the laminate

層壓體中的基材可由諸如金屬、玻璃、聚合物、或類似者之材料製成。 The substrate in the laminate may be made of materials such as metal, glass, polymer, or the like.

具體而言，基材之材料可係不鏽鋼、玻璃、聚烯烴、聚醯亞胺、或類似者。更具體而言，該基材可包括聚醯亞胺。 Specifically, the material of the substrate can be stainless steel, glass, polyolefin, polyimide, or the like. More specifically, the substrate may include polyimide.

黏著劑膜可附接至基材的整個表面。不同於此，黏著劑膜可部分附接至基材之表面，且層壓體可具有黏著劑膜施加區域及黏著劑膜非施加區域。 The adhesive film can be attached to the entire surface of the substrate. Unlike this, the adhesive film may be partially attached to the surface of the substrate, and the laminate may have an adhesive film application area and an adhesive film non-application area.

在層壓體中，可分別包括至少一黏著劑膜施加區域及至少一黏著劑膜非施加區域，且該黏著劑膜施加區域及該黏著劑膜施加區域可形成特定圖案。 In the laminate, each may include at least one adhesive film application area and at least one adhesive film non-application area, and the adhesive film application area and the adhesive film application area may form a specific pattern.

層壓體中的黏著劑膜可係根據上述實施例之黏著劑膜。據此，層壓結構可包括具有上述組成物及特性的黏著劑膜。 The adhesive film in the laminate may be the adhesive film according to the above-mentioned embodiment. Accordingly, the laminated structure may include an adhesive film having the above-mentioned composition and characteristics.

層壓體之製備方法 Preparation method of laminate

層壓體之製備方法可包括製備根據實施例之黏著劑組成物；形成黏著劑膜，其中該第一寡聚物及該起始劑藉由使該基底聚合物與該交聯劑反應而保留；施加該黏著劑膜至基材；藉由該起始劑固 化含在該黏著劑膜之部分區域中的該第一寡聚物，以降低該區域之黏著強度；及自該黏著劑膜移除具有經降低之該黏著強度之該區域。 The preparation method of the laminate may include preparing the adhesive composition according to the embodiment; forming an adhesive film, wherein the first oligomer and the initiator are retained by reacting the base polymer with the crosslinking agent ; Apply the adhesive film to the substrate; solidify by the initiator The first oligomer contained in a partial area of the adhesive film is reduced to reduce the adhesive strength of the area; and the area having the reduced adhesive strength is removed from the adhesive film.

同時，未自該黏著劑膜移除的區域可維持對該基材的高黏著強度。 At the same time, the areas not removed from the adhesive film can maintain high adhesive strength to the substrate.

在層壓體的製備方法中，可在上述條件下執行黏著劑組成物的製備。此外，第一寡聚物之固化可藉由一般光固化或熱固化程序來執行。 In the preparation method of the laminate, the preparation of the adhesive composition may be performed under the above-mentioned conditions. In addition, the curing of the first oligomer can be performed by a general light curing or thermal curing process.

圖3繪示使用黏著劑膜之層壓體的製備方法之實例。參照圖3，層壓體之製備方法可包括施加根據實施例之黏著劑膜100至基材200；輻照(300)UV至黏著劑膜100之部分區域以降低黏著強度；及自該黏著劑膜移除具有經降低之黏著強度之區域120。 Fig. 3 shows an example of a method for preparing a laminate using an adhesive film. 3, the preparation method of the laminate may include applying the adhesive film 100 according to the embodiment to the substrate 200; irradiating (300) UV to a part of the adhesive film 100 to reduce the adhesive strength; and from the adhesive The film removes areas 120 with reduced adhesive strength.

在層壓體的製備方法中，黏著劑膜可藉由以與上述相同之方式使用黏著劑組成物來製備。 In the production method of the laminate, the adhesive film can be produced by using the adhesive composition in the same manner as described above.

UV光之輻照可在250nm至420nm之波長範圍中在500mJ/cm2至3,000mJ/cm2之能量條件下執行。在UV輻照中，遮罩400可施加至黏著劑膜100之表面。 The UV light irradiation can be performed under the energy condition of 500mJ/cm 2 to 3,000mJ/cm 2 in the wavelength range of 250nm to 420nm. In UV irradiation, the mask 400 may be applied to the surface of the adhesive film 100.

此外，可執行移除黏著劑膜之部分區域，使得所得作為結果之該黏著劑膜之剩餘區域具有諸如線、圖形、及圖案之形狀。 In addition, it is possible to remove a partial area of the adhesive film, so that the resulting remaining area of the adhesive film has shapes such as lines, graphics, and patterns.

作為一實例，可將遮罩施加至黏著劑膜(其係施加至基材)的表面，使得所欲區域被暴露，可輻照UV，可沿著黏著劑膜藉由UV幅照而具有經降低之黏著強度的區域之外側形成切割線，然後可將 黏著劑膠帶或類似者附接至待移除區域，且緩慢地掀起以沿著切割線移除黏著劑膜的一部分。 As an example, a mask can be applied to the surface of the adhesive film (which is applied to the substrate) so that the desired area is exposed, UV can be irradiated, and the adhesive film can be irradiated with UV radiation along A cutting line is formed outside the area where the adhesive strength is reduced, and then the Adhesive tape or the like is attached to the area to be removed and slowly lifted to remove part of the adhesive film along the cutting line.

[玻璃層壓體] [Glass Laminate]

此外，實施例之黏著劑膜或雙塗佈黏著劑膠帶可用於製備玻璃層壓體。據此，根據本發明的又另一態樣，提供一種使用實施例之黏著劑膜或雙塗佈黏著劑膠帶的玻璃層壓體。 In addition, the adhesive films or double-coated adhesive tapes of the examples can be used to prepare glass laminates. Accordingly, according to yet another aspect of the present invention, a glass laminate using the adhesive film or double-coated adhesive tape of the embodiment is provided.

即，該玻璃層壓體包括至少兩個玻璃基材；及根據實施例之雙塗佈黏著劑膠帶，其經***玻璃基材之間以接合玻璃基材。 That is, the glass laminate includes at least two glass substrates; and the double-coated adhesive tape according to the embodiment, which is inserted between the glass substrates to bond the glass substrates.

包括在玻璃層壓體中的雙塗佈黏著劑膠帶具有與上述實施例之雙塗佈黏著劑膠帶相同的組態及特性。 The double-coated adhesive tape included in the glass laminate has the same configuration and characteristics as the double-coated adhesive tape of the above-mentioned embodiment.

具體而言，包括在玻璃層壓體中的雙塗佈黏著劑膠帶包括單塗佈膠帶A，其包括基底層A及設置於該基底層A之一個表面上之黏著劑層A；單塗佈膠帶B，其包括基底層B及設置於該基底層B之一個表面上的黏著劑層B；及雙塗佈黏著劑膜，其包括緩衝片材及分別設置於該緩衝片材之兩個表面上的黏著劑膜，其中該雙塗佈黏著劑膜設置在該基底層A與該基底層B之間，以接合該基底層A及該基底層B。 Specifically, the double-coated adhesive tape included in the glass laminate includes a single-coated tape A, which includes a base layer A and an adhesive layer A disposed on one surface of the base layer A; single-coated Adhesive tape B, which includes a base layer B and an adhesive layer B arranged on one surface of the base layer B; and a double-coated adhesive film, which includes a buffer sheet and is respectively arranged on two surfaces of the buffer sheet The double-coated adhesive film is arranged between the base layer A and the base layer B to join the base layer A and the base layer B.

在雙塗佈黏著劑膠帶中所包括的黏著劑膜中，因為黏著強度藉由UV輻照來降低，以用於儲存玻璃基材，複數個玻璃基材藉由使用雙塗佈黏著劑膠帶彼此接合，然後在使用玻璃基材時，可藉由輻照UV至層壓體使這些玻璃基材彼此分開。 In the adhesive film included in the double-coated adhesive tape, since the adhesive strength is reduced by UV irradiation for storage of glass substrates, multiple glass substrates are each other by using double-coated adhesive tapes. Bonding, and then when using glass substrates, these glass substrates can be separated from each other by irradiating UV to the laminate.

據此，複數個玻璃基材易於儲存且可水平或垂直層壓，以增加儲存空間的效率，且個別玻璃基材可輕易地分開，使得可能不會留下殘留黏著劑、指紋、或灰塵。 Accordingly, a plurality of glass substrates are easy to store and can be laminated horizontally or vertically to increase the efficiency of the storage space, and individual glass substrates can be easily separated, so that no residual adhesive, fingerprints, or dust may be left.

[實例] [Example]

在下文中，將通過實例詳細描述本發明。然而，這些實例僅係本發明之說明，且本發明不限於此。 Hereinafter, the present invention will be described in detail through examples. However, these examples are only illustrative of the present invention, and the present invention is not limited thereto.

製備實例1：黏著劑(基底聚合物)之製備 Preparation example 1: Preparation of adhesive (base polymer)

各黏著劑(基底聚合物)係藉由使用下表中之組分的溶液聚合來製備。 Each adhesive (base polymer) was prepared by solution polymerization using the components in the table below.

Figure 109125726-A0202-12-0035-4
Figure 109125726-A0202-12-0035-4

實例1：黏著劑組成物之製備 Example 1: Preparation of adhesive composition

將製備實例1中所獲得之基底聚合物與UV寡聚物混合，加入光起始劑，最後混合交聯劑以獲得黏著劑組成物。此時，最終組成物中之各別材料的組分及含量顯示於下表中。 The base polymer obtained in Preparation Example 1 was mixed with the UV oligomer, a photoinitiator was added, and finally a crosslinking agent was mixed to obtain an adhesive composition. At this time, the components and contents of the respective materials in the final composition are shown in the table below.

Figure 109125726-A0202-12-0036-5
Figure 109125726-A0202-12-0036-5

- 基於異氰酸酯之交聯劑：固體含量45%，Saivinol硬化劑AL，Saiden Chemical Industry Co.,Ltd。 -Crosslinking agent based on isocyanate: solid content 45%, Saivinol hardener AL, Saiden Chemical Industry Co.,Ltd.

- 基於金屬(Al)螯合物之交聯劑：固體含量5%，Saivinol硬化劑M-2，Saiden Chemical Industry Co.,Ltd。 -Crosslinking agent based on metal (Al) chelate: solid content 5%, Saivinol hardener M-2, Saiden Chemical Industry Co., Ltd.

- 環氧丙烯酸酯 -Epoxy acrylate

Figure 109125726-A0202-12-0036-19
Figure 109125726-A0202-12-0036-19

- ESACURE KIP 150 -ESACURE KIP 150

Figure 109125726-A0202-12-0036-20
Figure 109125726-A0202-12-0036-20

測試實例1-1：對聚醯亞胺之黏著強度的測量 Test Example 1-1: Measurement of the adhesion strength of polyimide

(1)樣本之製備 (1) Preparation of samples

以1.0m/min之速率將待測試的黏著劑組成物塗佈在具有厚度75μm之聚對苯二甲酸乙二酯(PET)膜上。將經塗佈之PET膜在具有6m之總長度的烘箱中乾燥，該烘箱具有2m長度之三個乾燥區(分別在50℃、90℃、及120℃之溫度)。結果，在PET膜上形成具有25μm或75μm之厚度的黏著劑膜，然後切割以獲得單塗佈膠帶樣本。 The adhesive composition to be tested was coated on a polyethylene terephthalate (PET) film having a thickness of 75 μm at a rate of 1.0 m/min. The coated PET film was dried in an oven with a total length of 6 m, which had three drying zones with a length of 2 m (at a temperature of 50°C, 90°C, and 120°C, respectively). As a result, an adhesive film having a thickness of 25 μm or 75 μm was formed on the PET film, and then cut to obtain a single-coated tape sample.

(2)在UV固化之前/之後的黏著強度之測量 (2) Measurement of adhesion strength before/after UV curing

藉由使用PET雙塗佈膠帶將聚醯亞胺膜(製造商：SKC Kolon PI)附接至剛性丙烯酸板或玻璃板。將以上製備之單塗佈膠帶樣本層壓在聚醯亞胺膜之表面上以獲得一層壓體。 The polyimide film (manufacturer: SKC Kolon PI) was attached to a rigid acrylic plate or glass plate by using a PET double-coated tape. The single-coated tape sample prepared above was laminated on the surface of the polyimide film to obtain a laminate.

之後，在UV固化機(金屬鹵素燈，波長範圍250至420nm，主要波長為365nm，能量為1,000mJ/cm2)中固化該層壓體。此時，對於UV固化之前及之後的各者，測量層壓體中單塗佈膠帶的黏著強度。剝離強度(黏著強度)係根據ASTM D3330以305mm/min的剝離速率及2kgf的負載，藉由使用通用測試器(UTM,TA Instrument Co.,Ltd.)測量。結果係顯示於下表中。 After that, the laminate was cured in a UV curing machine (metal halide lamp, wavelength range of 250 to 420 nm, main wavelength of 365 nm, and energy of 1,000 mJ/cm 2 ). At this time, for each of before and after UV curing, the adhesive strength of the single-coated tape in the laminate was measured. The peel strength (adhesive strength) is measured by using a universal tester (UTM, TA Instrument Co., Ltd.) at a peel rate of 305 mm/min and a load of 2 kgf in accordance with ASTM D3330. The results are shown in the table below.

Figure 109125726-A0202-12-0037-6
Figure 109125726-A0202-12-0037-6

Figure 109125726-A0202-12-0038-7
Figure 109125726-A0202-12-0038-7

如表3所示，根據實例的黏著劑組成物在UV固化之後相較於UV固化之前具有顯著經降低的黏著強度，且在UV固化之前的黏著強度與僅黏著劑(基底聚合物)之黏著強度類似。 As shown in Table 3, the adhesive composition according to the examples has significantly reduced adhesive strength after UV curing compared to before UV curing, and the adhesive strength before UV curing is comparable to that of only the adhesive (base polymer) The intensity is similar.

測試實例1-2：對各種基材之黏著強度的測量 Test Example 1-2: Measurement of the adhesion strength of various substrates

重複與測試實例1-1相同的程序，但僅以黏著劑(基底聚合物)製備單塗佈膠帶樣本，且測量單塗佈膠帶樣本對不銹鋼及玻璃(而非聚醯亞胺膜)之黏著強度，且結果顯示於下表中。 Repeat the same procedure as Test Example 1-1, but only use the adhesive (base polymer) to prepare a single-coated tape sample, and measure the adhesion of the single-coated tape sample to stainless steel and glass (not polyimide film) Intensity, and the results are shown in the table below.

Figure 109125726-A0202-12-0038-8
Figure 109125726-A0202-12-0038-8

測試實例1-3：儲存模數之測量Test example 1-3: Measurement of storage modulus

以與測試實例1-1相同的方式製備單塗佈膠帶樣本，並測量其儲存模數。結果係顯示於下表中。 A single-coated tape sample was prepared in the same manner as Test Example 1-1, and its storage modulus was measured. The results are shown in the table below.

Figure 109125726-A0202-12-0038-9
Figure 109125726-A0202-12-0038-9

如表5所示，根據實例的黏著劑組成物在UV固化之後相較於UV固化之前具有快速增加之儲存模數。 As shown in Table 5, the adhesive composition according to the example has a storage modulus that increases rapidly after UV curing compared to before UV curing.

實例2：黏著劑組成物之製備 Example 2: Preparation of adhesive composition

在與實例1相同的條件下，將黏著劑、交聯劑、UV寡聚物、及光起始劑以下表中所示之組分及含量混合以製備黏著劑組成物。 Under the same conditions as in Example 1, the adhesive, crosslinking agent, UV oligomer, and photoinitiator were mixed with the components and contents shown in the following table to prepare an adhesive composition.

Figure 109125726-A0202-12-0039-10
Figure 109125726-A0202-12-0039-10

- 基於異氰酸酯之交聯劑：固體含量45%，Saivinol硬化劑AL，Saiden Chemical Industry Co.,Ltd。 -Crosslinking agent based on isocyanate: solid content 45%, Saivinol hardener AL, Saiden Chemical Industry Co.,Ltd.

- 雙酚A環氧丙烯酸酯、雙酚A環氧樹脂、及甲基丙烯酸：雙酚A環氧樹脂及甲基丙烯酸經反應以獲得雙酚A環氧丙烯酸酯；及使用含有重量比為82：15：3的雙酚A環氧丙烯酸酯：雙酚A環氧樹脂：甲基丙烯酸之反應混合物。 -Bisphenol A epoxy acrylate, bisphenol A epoxy resin, and methacrylic acid: Bisphenol A epoxy resin and methacrylic acid are reacted to obtain bisphenol A epoxy acrylate; and the weight ratio is 82 : 15:3 bisphenol A epoxy acrylate: bisphenol A epoxy resin: methacrylic acid reaction mixture.

測試實例2：對聚醯亞胺之黏著強度的測量 Test Example 2: Measurement of the adhesion strength of polyimide

單塗佈膠帶樣本係以與測試實例1-1中相同的方式，藉由使用在實例2中所製備之各別黏著劑組成物C至E來製備，測量UV固化之前及之後對聚醯亞胺膜的黏著強度，且結果顯示於下表中。 The single-coated tape samples were prepared in the same manner as in Test Example 1-1, by using the respective adhesive compositions C to E prepared in Example 2, and measuring the resistance to polyamide before and after UV curing. The adhesive strength of the amine film, and the results are shown in the table below.

Figure 109125726-A0202-12-0040-11
Figure 109125726-A0202-12-0040-11

如表7所示，根據實例的黏著劑組成物具有對聚醯亞胺基材之黏著強度，其在UV固化之後相較於UV固化之前顯著降低，且具體而言，在包括兩種寡聚物及有機酸的黏著劑組成物C的情況下，在UV固化之前與之後的黏著強度的差最大。 As shown in Table 7, the adhesive composition according to the example has the adhesive strength to the polyimide substrate, which is significantly lower after UV curing than before UV curing, and specifically, it includes two kinds of oligomers. In the case of the adhesive composition C of an organic acid and an organic acid, the difference in adhesive strength before and after UV curing is the largest.

[參考數字與符號的說明] [Explanation of reference numbers and symbols]

11,12：雙塗佈黏著劑膠帶 11,12: Double-coated adhesive tape

100：黏著劑膜 101：雙塗佈黏著劑膜 100: Adhesive film 101: Double-coated adhesive film

111：具有經移除部分區域之黏著劑膜 111: Adhesive film with removed partial area

120：在黏著劑膜中具有經降低黏著強度之區域 120: There are areas with reduced adhesive strength in the adhesive film

150：緩衝片材 200：基材 150: buffer sheet 200: base material

210：單塗佈膠帶A 211：基底層A 210: Single coated tape A 211: Base layer A

212：黏著劑層A 220：單塗佈膠帶B 212: Adhesive layer A 220: Single coating tape B

221：基底層B 222：黏著劑層B 221: Base layer B 222: Adhesive layer B

213,223：離型層 300：UV輻照 213,223: Release layer 300: UV irradiation

11:雙塗佈黏著劑膠帶 11: Double-coated adhesive tape

100:黏著劑膜 100: Adhesive film

210:單塗佈膠帶A/單塗佈黏著劑膠帶 210: Single-coated tape A/Single-coated adhesive tape

211:基底層A 211: basal layer A

212:黏著劑層A 212: Adhesive layer A

213:離型層 213: Release layer

220:單塗佈膠帶B/單塗佈黏著劑膠帶 220: Single-coated tape B/Single-coated adhesive tape

221:基底層B 221: basal layer B

222:黏著劑層B/基底層B 222: Adhesive layer B/base layer B

223:離型層 223: Release layer

Claims (15)

一種黏著劑組成物，其包含： An adhesive composition comprising: 基底聚合物； Base polymer 交聯劑，其與該基底聚合物反應； A crosslinking agent that reacts with the base polymer; 第一寡聚物，其在該基底聚合物與該交聯劑之該反應之後待固化；及 A first oligomer, which is to be cured after the reaction of the base polymer and the crosslinking agent; and 起始劑，其固化該第一寡聚物， An initiator, which cures the first oligomer, 其中該黏著劑組成物在該基底聚合物與該交聯劑之該反應之後具有在固化該第一寡聚物之前的第一黏著強度，及在固化該第一寡聚物之後的第二黏著強度，其中該第二黏著強度低於該第一黏著強度。 Wherein the adhesive composition has a first adhesive strength before curing the first oligomer after the reaction of the base polymer and the crosslinking agent, and a second adhesive strength after curing the first oligomer Strength, wherein the second adhesive strength is lower than the first adhesive strength. 如請求項1之黏著劑組成物，其進一步包含： Such as the adhesive composition of claim 1, which further comprises: 第二寡聚物，其不同於該第一寡聚物。 The second oligomer, which is different from the first oligomer. 如請求項2之黏著劑組成物，其進一步包含： Such as the adhesive composition of claim 2, which further comprises: 有機酸。 Organic acid. 如請求項3之黏著劑組成物，其中該黏著劑組成物包括100重量份之該第一寡聚物、5至35重量份之該第二寡聚物、及1至6重量份之該有機酸。 The adhesive composition of claim 3, wherein the adhesive composition includes 100 parts by weight of the first oligomer, 5 to 35 parts by weight of the second oligomer, and 1 to 6 parts by weight of the organic acid. 如請求項1之黏著劑組成物，其中該第一寡聚物包括衍生自環氧丙烯 酸酯之重複單元。 The adhesive composition of claim 1, wherein the first oligomer comprises propylene oxide Repeating units of acid esters. 如請求項5之黏著劑組成物，其中該環氧丙烯酸酯具有雙酚A骨架。 The adhesive composition of claim 5, wherein the epoxy acrylate has a bisphenol A skeleton. 如請求項2之黏著劑組成物，其中該第二寡聚物係具有雙酚A骨架的環氧樹脂。 The adhesive composition of claim 2, wherein the second oligomer is an epoxy resin having a bisphenol A skeleton. 如請求項3之黏著劑組成物，其中該有機酸具有乙烯基。 The adhesive composition of claim 3, wherein the organic acid has a vinyl group. 一種黏著劑膜，其包含： An adhesive film comprising: 基底聚合物與交聯劑之反應產物， The reaction product of the base polymer and the crosslinking agent, 其中該黏著劑膜含有第一寡聚物及起始劑，該第一寡聚物可藉由該起始劑固化，且 The adhesive film contains a first oligomer and an initiator, and the first oligomer can be cured by the initiator, and 其中該黏著劑膜具有在固化該第一寡聚物之前的第一黏著強度，及在固化該第一寡聚物之後的第二黏著強度，其中該第二黏著強度低於該第一黏著強度。 The adhesive film has a first adhesive strength before curing the first oligomer and a second adhesive strength after curing the first oligomer, wherein the second adhesive strength is lower than the first adhesive strength . 一種如請求項9之黏著劑膜的製備方法，其包含： A method for preparing an adhesive film according to claim 9, which comprises: 混合基底聚合物、第一寡聚物、起始劑、及交聯劑； Mixing the base polymer, the first oligomer, the initiator, and the crosslinking agent; 使該交聯劑與該基底聚合物反應以形成膜狀聚合物；及 Reacting the crosslinking agent with the base polymer to form a film-like polymer; and 保持該第一寡聚物及該起始劑於該膜狀聚合物中以獲得黏著劑膜。 Keep the first oligomer and the initiator in the film-like polymer to obtain an adhesive film. 一種雙塗佈黏著劑膠帶，其包含： A double-coated adhesive tape, which comprises: 單塗佈膠帶A，其包括基底層A及設置於該基底層A之一個表面上的黏著劑層A； Single-coated adhesive tape A, which includes a base layer A and an adhesive layer A disposed on one surface of the base layer A; 單塗佈膠帶B，其包括基底層B及設置於該基底層B之一個表面上的黏著劑層B；及 Single-coated adhesive tape B, which includes a base layer B and an adhesive layer B disposed on one surface of the base layer B; and 如請求項9之黏著劑膜，其設置於該基底層A與該基底層B之間，以接合該基底層A與該基底層B。 Such as the adhesive film of claim 9, which is arranged between the base layer A and the base layer B to join the base layer A and the base layer B. 一種雙塗佈黏著劑膠帶，其包含： A double-coated adhesive tape, which comprises: 單塗佈膠帶A，其包括基底層A及設置於該基底層A之一個表面上的黏著劑層A； Single-coated adhesive tape A, which includes a base layer A and an adhesive layer A disposed on one surface of the base layer A; 單塗佈膠帶B，其包括基底層B及設置於該基底層B之一個表面上的黏著劑層B；及 Single-coated adhesive tape B, which includes a base layer B and an adhesive layer B disposed on one surface of the base layer B; and 雙塗佈黏著劑膜，其包括緩衝片材及分別設置於該緩衝片材之兩個表面上的如請求項9之黏著劑膜，其中該雙塗佈黏著劑膜係設置在該基底層A與該基底層B之間，以接合該基底層A及該基底層B。 A double-coated adhesive film, which includes a buffer sheet and the adhesive film of claim 9 respectively disposed on two surfaces of the buffer sheet, wherein the double-coated adhesive film is disposed on the base layer A And the base layer B to join the base layer A and the base layer B. 如請求項11或12之雙塗佈黏著劑膠帶，其中在該黏著劑膜固化之後，該單塗佈膠帶A及該單塗佈膠帶B彼此分離。 The double-coated adhesive tape of claim 11 or 12, wherein after the adhesive film is cured, the single-coated tape A and the single-coated tape B are separated from each other. 一種層壓體，其包含： A laminate comprising: 基材及如請求項9之黏著劑膜，該黏著劑膜附接至該基材。 A substrate and the adhesive film of claim 9, which is attached to the substrate. 如請求項14之層壓體，其中該基材包括聚醯亞胺。 The laminate of claim 14, wherein the substrate comprises polyimide.
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