TW201000582A - Adhesive compositions and optical films using the same - Google Patents
Adhesive compositions and optical films using the same Download PDFInfo
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- TW201000582A TW201000582A TW098111669A TW98111669A TW201000582A TW 201000582 A TW201000582 A TW 201000582A TW 098111669 A TW098111669 A TW 098111669A TW 98111669 A TW98111669 A TW 98111669A TW 201000582 A TW201000582 A TW 201000582A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/02—Polyamines
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
201000582 六、發明說明： 【發明所屬之技術領域】 本發明提供一種黏著劑組成物，以及一種使用此黏著 劑組成物之光學膜。本發明尤其提供一種具絕佳黏著性且 能用於需透射率之光學膜的黏著劑組成物，以及一種使用 此黏著劑組成物之光學膜。 此申請案主張於2008年4月8曰向KIPO申請之韓國第 10-2008-0032563號專利申請案的優先權，其中整體揭示合 併於此以供參酌。 【先前技術】 對於偏光板的結構，一般係使用由pvA系水溶液構成 之水性黏著劑層，將三醋酸纖維素（後文則稱丁八匸）膜層疊在 聚乙烯醇（PVA)構件之偏光片（偏光膜）的兩側（圖1)。上述結 構的偏光板，如果沒有使用獨立之補償膜的話，則會劣化 視角，因此兩TAC臈其令一者有時候須以零延遲丁 AC (後文 則稱Z-TAC)膜取代，此Z_TAC膜幾乎不會發生厚度方向及 平面内延遲作用，故可改善視角。201000582 VI. Description of the Invention: [Technical Field of the Invention] The present invention provides an adhesive composition, and an optical film using the same. In particular, the present invention provides an adhesive composition which is excellent in adhesion and can be used for an optical film having a transmittance, and an optical film using the adhesive composition. The priority of the Korean Patent Application No. 10-2008-0032563, filed on Apr. 8, 2008, to KIPO, the entire disclosure of which is incorporated herein by reference. [Prior Art] For the structure of a polarizing plate, an aqueous adhesive layer composed of a pvA aqueous solution is generally used, and a cellulose triacetate (hereinafter referred to as Ding Baic) film is laminated on a polarizer of a polyvinyl alcohol (PVA) member. Both sides of the (polarizing film) (Fig. 1). The polarizing plate of the above structure may deteriorate the viewing angle if a separate compensation film is not used, so that the two TACs sometimes have to be replaced by a zero-delay butyl AC (hereinafter referred to as Z-TAC) film, which is a Z_TAC film. The thickness direction and the in-plane retardation hardly occur, so that the viewing angle can be improved.
然而，對於具有TAC成分的膜濕度而言，因為z_TAC 基本上不# ’當長期使用時，因尺寸發生變化而有耐用性 問題。為了解決此缺點’致力於使用如環烯烴系樹脂或丙 稀酸系樹脂之膜組成物’其具有高抗濕性與低延遲性。具 體而言’當膜含有丙烯酸系組成物時，τ知其光學性、耐 用性及成本等方面有利。 ’ 3 201000582 至於使用TAC膜做為保護膜製造偏光板時，為了與 PVA成分之偏光片黏著，主要使用水性Pva黏著劑，此時 為了改善黏著強度，TAC膜的表面需經過鹼處理或電暈處 理。然而’當使用丙稀酸膜及水性PVA黏著劑製造偏光板 時’難以輕易確保經過鹼處理或電暈處理的黏著強度。至 於已知TAC膜，由於引入如羥基之親水性基團接於經過鹼 處理或電暈處理的膜表面，故可經由與pvA系黏著劑之氫 鍵而輕易確保黏著強度。不過，即使丙烯酸膜表面經過電 暈處理或電漿處理，但因為引入的親水性基團量少，所以 與PVA系黏著劑之氫鍵仍不足，故仍無法確保丙烯酸膜及 PVA成分之偏光片之間有足夠的黏著強度。 為了貼合丙烯酸膜及偏光片，可以使用丙烯酸系1]、可 固化性黏著劑，但卻會有以下問題：⑴因為使用水性黏著 劑，所以在一般偏光板製作過程中，使用UV可固化性黏著 劑時，則需要進行獨立uv固化步驟，且因為使用具揮發性 =燃單體，故需額外的防爆設備；（2)然;而藉由控制固體 3量及製程嘗理，製作出厚度⑽⑽以内之已知水性a 黏者劑時’會難以將丙烯酸*uv可固化黏著劑的厚度控制 nmUf^或以1" ’如此隨著黏著劑層脆度增加則會發生 ，光板破裂的問題；以及（3)可以輕易達到與丙烯酸膜的黏 :仁無法輕易確保與偏光片的黏著強度。為了確保與偏 =黏著強度’可含大量酸性反應基，但鑑於因酸及操 壤土兄所產生的製裎腐敍作用，此並非較佳選擇。 201000582 传ί l作使用丙烯酸膜作為偏 光板，較有利是使用能夠用於已知製程 膜的偏 穩定偏光板特性的水性黏著劑。據此，需要發展二:供 偏光板及光學膜的水性黏著劑。 又於 【發明内容】 本么明之目的係在提供一種黏著劑組成物，其具 2黏者f生’且使用於光學膜上時，不會降低光學膜的光 及耐用性。具體而言，當使用丙烯酸膜做為偏光片的 保5蒦膜時，黏著劑組成物對於偏光片可提供優異的黏著 性，且不會減少由其所製叙偏光板的光學性及耐用性。 此外，本發明的目的在於提供一種使用此黏著劑組成物製 得之光學膜與偏光板。 為了完成本發明上述目的，本發明提供一種黏著劑組 成物，其包括：一具有以下式丨所示之三亞甲亞胺根 (azetidinium)官能基的化合物： [式1] + Α·However, for the film moisture having the TAC component, since z_TAC is substantially not used, there is a problem of durability due to dimensional changes when used for a long period of time. In order to solve this drawback, it has been devoted to the use of a film composition such as a cycloolefin resin or an acrylic resin, which has high moisture resistance and low retardation. Specifically, when the film contains an acrylic composition, it is advantageous in terms of optical properties, durability, cost, and the like. ' 3 201000582 When using a TAC film as a protective film to make a polarizing plate, in order to adhere to the PVA component polarizer, an aqueous Pva adhesive is mainly used. In order to improve the adhesion strength, the surface of the TAC film is subjected to alkali treatment or corona. deal with. However, when a polarizing plate is produced using an acrylic film and an aqueous PVA adhesive, it is difficult to easily ensure the adhesion strength by alkali treatment or corona treatment. As for the known TAC film, since a hydrophilic group such as a hydroxyl group is introduced to the surface of the film subjected to alkali treatment or corona treatment, the adhesion strength can be easily ensured by hydrogen bonding with a pvA-based adhesive. However, even if the surface of the acrylic film is subjected to corona treatment or plasma treatment, since the amount of the hydrophilic group introduced is small, the hydrogen bond with the PVA-based adhesive is still insufficient, so that the acrylic film and the PVA component polarizer cannot be ensured. There is enough adhesive strength between them. In order to bond the acrylic film and the polarizer, an acrylic 1] curable adhesive can be used, but there are the following problems: (1) Since the aqueous adhesive is used, UV curability is used in the production of a general polarizing plate. In the case of an adhesive, an independent uv curing step is required, and because of the use of volatile = flammable monomer, additional explosion-proof equipment is required; (2); and by controlling the amount of solid 3 and the process, a thickness is produced. (10) When the known water-based a-adhesive agent is less than (10), it may be difficult to control the thickness of the acrylic *uv curable adhesive to nmUf^ or 1" 'so as the brittleness of the adhesive layer increases, the problem of the light-plate rupture occurs; And (3) the adhesion to the acrylic film can be easily achieved: the adhesion strength of the polarizer cannot be easily ensured. In order to ensure that the adhesive strength can contain a large amount of acidic reactive groups, this is not a preferred choice in view of the stagnation effect caused by the acid and the soil brother. 201000582 It is advantageous to use an acrylic film as a polarizing plate, and it is advantageous to use an aqueous adhesive which can be used for the characteristics of a partially stable polarizing plate of a known process film. Accordingly, there is a need to develop two: an aqueous adhesive for a polarizing plate and an optical film. Further, the object of the present invention is to provide an adhesive composition which does not reduce the light and durability of the optical film when it is used in an optical film. Specifically, when an acrylic film is used as the protective film of the polarizer, the adhesive composition can provide excellent adhesion to the polarizer without reducing the optical properties and durability of the polarizing plate produced therefrom. . Further, it is an object of the invention to provide an optical film and a polarizing plate which are produced using the adhesive composition. In order to accomplish the above object of the present invention, the present invention provides an adhesive composition comprising: a compound having an azetidinium functional group represented by the following formula: [Formula 1] + Α·
-fx- Λτγ* RUr/ \xR3 RrS R5R6 5 201000582 其中’ X與Y為脂肪族碳氯基’ X與γ中至少一者為人 有一種以上選自胺基、醯胺基及酮基的脂肪族碳氫基且χ 與Υ可相互連接形成環形； R1至R6分別選自由氫、羥基、CliC2dg肪族碳氫基、 炫基敌酸醋基、及氰基所組群組； A·為單價陰離子；以及 η的範圍為30至7,000。 較佳為，X與γ中至少一者含脂肪族碳氫基。式丨化合 物的重量平均分子量落於1〇,〇〇〇至2 〇〇〇 〇〇〇之範圍則較 佳。 此外，本發明提供一種光學膜’其具有一含兩層以上 之層狀、纟σ構，该光學膜包括··一黏著劑層，其位於該些膜 間之至y介面上，其係使用一含具有三亞甲亞胺根官能 基之化合物的黏著劑組成物所形成。 另^卜，本發明提供一種偏光板，其具有一層狀結構， 其中一第一膜、—偏光片、及一第二膜依序層疊，該偏光 板包括·一黏著劑層，其位於該第一膜及該第二膜之至少 -者與4偏光片之間，其係使用—含具有三亞甲亞胺根官 能基之化合物的黏著劑組成物所形成。 再者’本發明提供一種電子裝置，其包括上述光學膜 或偏光板。 因為本發明之黏著劑組成物具有優秀的黏著性，且可 她用於已知層狀結構之光學瞑製程，而無需額外步驟及設 備且不會減少光學膜的透明性，故可用於光學膜的製作。 201000582 此外，含黏著劑層(其使用本發明黏著劑組成物所製)之光學 膜具有優異的耐用性，尤其當使用丙稀酸膜做為偏光片的 保護膜時，黏著劑組成物對於偏光片可以提供絕佳的黏著 性，同使不會減少由其製得之偏光板的光學性及耐用性。 【實施方式】 本發明光學臈的特徵在於，此光學膜含使用黏著劑组 r, 削勿所形成之黏著劑層，而黏著劑組成物含有具有三亞甲 11 亞胺根官能基的化合物。 具有三亞甲亞胺根官能基的化合物，可藉由三亞甲亞 胺根官能基，與光學膜表面上官能基（如m基）反應，且此化 σ物▼有正（+)電荷。因此’此化合物對於表面經由電晕處 理、電毁處理及類似處理而具有親水基或富含負㈠電荷之 光學臈’具有優異的可濕性。另外，親水基可透過三亞甲 亞胺根官能基開環而形成，且親水基可與光學膜（如偏光片） 表面羥基之間形成氫鍵。關於此點，具有三亞甲亞胺根官 〇 ㊣基的化合物’除了三亞甲亞胺根官能基之外，更可含有 親水基，例如羥基、羧基、胺基、醯胺基、以及類似基團。 相較於已知黏著劑，例如PVA系黏著劑，具有三亞甲亞胺 根官能基的化合物基於相同理由，可提供絕佳的黏著性。 此外因為具有二亞甲亞胺根官能基的化合物，可在黏著 劑層中進行自體交聯作用，故可改善黏著劑的耐水性，並 改善使用此化合物之偏光板及光學膜的耐用性，進而防止 各層間在嚴峻環境下發生剝離現象。 7 201000582 至於具有三亞甲亞胺根官能基的化合物，可使用下式i 所示之化合物： [式1] -+Χ Ν一γ如-fx- Λτγ* RUr/ \xR3 RrS R5R6 5 201000582 where 'X and Y are aliphatic chlorocarbon groups'. At least one of X and γ is one or more fats selected from the group consisting of amine groups, guanylamino groups and ketone groups. a hydrocarbon group and χ and Υ may be interconnected to form a ring; R1 to R6 are respectively selected from the group consisting of hydrogen, a hydroxyl group, a CliC2dg aliphatic hydrocarbon group, a sulfhydryl oleic acid group, and a cyano group; Anions; and η range from 30 to 7,000. Preferably, at least one of X and γ contains an aliphatic hydrocarbon group. The weight average molecular weight of the ruthenium compound falls within 1 〇, and the range of 〇〇〇 to 2 〇〇〇 较 is preferred. In addition, the present invention provides an optical film having a layered, 纟σ structure comprising two or more layers, the optical film comprising an adhesive layer located between the films to the y interface, which is used An adhesive composition comprising a compound having a trimethylene iodide functional group is formed. In addition, the present invention provides a polarizing plate having a layered structure, wherein a first film, a polarizing film, and a second film are sequentially stacked, and the polarizing plate includes an adhesive layer located at the same Between at least one of the first film and the second film and the fourth polarizer, which is formed using an adhesive composition containing a compound having a trimethyleneimine functional group. Further, the present invention provides an electronic device comprising the above optical film or polarizing plate. Because the adhesive composition of the present invention has excellent adhesion, and can be used in an optical tanning process of a known layered structure without additional steps and equipment and without reducing the transparency of the optical film, it can be used for an optical film. Production. 201000582 In addition, an optical film containing an adhesive layer (which is prepared using the adhesive composition of the present invention) has excellent durability, especially when an acrylic film is used as a protective film for a polarizer, the adhesive composition is for polarized light. The sheet provides excellent adhesion without compromising the optical and durability of the polarizer made therefrom. [Embodiment] The optical enamel of the present invention is characterized in that the optical film contains an adhesive layer r, and the adhesive composition is formed, and the adhesive composition contains a compound having a trimethylene 11 imine functional group. The compound having a trimethyleneimine functional group can be reacted with a functional group (e.g., an m group) on the surface of the optical film by a trimethyleneamine functional group, and the sigma ▼ has a positive (+) charge. Therefore, this compound has excellent wettability to a surface having a hydrophilic group or a negative (a) charge-rich optical 臈' via a corona treatment, an electrocution treatment, and the like. Further, the hydrophilic group can be formed by ring opening of the trimethyleneimine functional group, and the hydrophilic group can form a hydrogen bond with the surface hydroxyl group of the optical film such as a polarizer. In this regard, the compound having a trimethylene group of the methyleneimine root may further contain a hydrophilic group other than the trimethyleneimine functional group, such as a hydroxyl group, a carboxyl group, an amine group, a guanamine group, and the like. . Compounds having a trimethyleneimine functional group provide excellent adhesion for the same reason as known adhesives, such as PVA adhesives. In addition, since the compound having a dimethyleneimine functional group can be auto-crosslinked in the adhesive layer, the water resistance of the adhesive can be improved, and the durability of the polarizing plate and the optical film using the compound can be improved. In addition, the peeling phenomenon between the layers in a severe environment is prevented. 7 201000582 As for the compound having a trimethyleneimine functional group, a compound represented by the following formula i can be used: [Formula 1] - + Ν Ν γ
其中，X與Y為脂肪族碳氫基，X與γ中至少一者為含 有一種以上選自胺基、醯胺基及酮基的脂肪族碳氫基，且X 與Y可相互連接形成環形； R1至R6分別選自由氫、羥基、（^至匕。脂肪族碳氫基、 烷基羧酸酯基、及氰基所組群組； A·為單價陰離子；以及 η的範圍為30至7,000。 較佳為，X與Υ中至少一者包含親水基，式1化合物的 重量平均分子量落於1 〇,〇〇〇至2 000 000之範圍則較佳。 式1化合物包括以下式2所示之化合物。 [式2] + Α· +C0X.C0NHX"-N-rNH4^Wherein X and Y are aliphatic hydrocarbon groups, and at least one of X and γ is an aliphatic hydrocarbon group containing one or more selected from the group consisting of an amine group, a mercapto group and a ketone group, and X and Y are bonded to each other to form a ring. ; R1 to R6 are each selected from the group consisting of hydrogen, hydroxyl, (^ to hydrazine, aliphatic hydrocarbon group, alkyl carboxylate group, and cyano group; A· is a monovalent anion; and η ranges from 30 to Preferably, at least one of X and oxime comprises a hydrophilic group, and the weight average molecular weight of the compound of formula 1 falls within 1 〇, preferably from 2 000 000. The compound of formula 1 includes the following formula 2 The compound shown is [Formula 2] + Α· +C0X.C0NHX"-N-rNH4^
其中’ X’、X”及γ’分別為(：1至(：：2〇脂肪族碳氫基 8 201000582 R1至R6分別選自由氫、羥基、（^至匸2。脂肪族碳氣基、 燒基叛酸S旨基、及乳基所組群組； A·為單價陰離子；以及 η的範圍為30至7,000。 式2化合物包括以下式3所示之聚醯胺多胺環氧氯丙院 (polyaminoamide-epichlorohydrin，PAE)。 [式3]Wherein 'X', X" and γ' are respectively (:1 to (::2〇 aliphatic hydrocarbon group 8 201000582 R1 to R6 are respectively selected from hydrogen, hydroxyl, (^ to 匸2. aliphatic carbon gas group, a group of a base group and a group of a base group; A· is a monovalent anion; and η ranges from 30 to 7,000. The compound of the formula 2 includes a polyamine amine polyamine epoxide C represented by the following formula 3. (polyaminoamide-epichlorohydrin, PAE). [Formula 3]
其中，η的範圍為30至7,000。 本發明黏著劑組成物更可包括溶劑（例如水），以形成 黏著劑層。此時，具有三亞甲亞胺根官能基之化合物，其 濃度範圍為0· 1至30 wt%，較佳為0.5至1 〇 Wt%。本發明點著 劑組成物的pH範圍為2至11，較佳為4至10。本發明黏著劑 組成物的pH可使用添加驗或類似方法控制’驗的種類沒有 特別限制，較佳舉例包括Na0H、K0H、nh4〇h及類似鹼類。 本發明黏著劑組成物更可包括聚乙烯醇（PVA)系樹 脂，經由更包含聚乙烯醇系樹脂，更能改善對於光學膜（如 聚乙烯醇系偏光片或TAC膜）的黏著性。尤其，使用含乙醯 乙醯基及類似基團之變性pvA，會有利於與具有三亞甲亞 胺根S能基之化合物的黏著性及交聯。詳細舉例如日本合 成化子有限公司（japan Synthetic Chemical，c〇，Ltd )所製 9 201000582 之G—M z_100、z_200、z_2〇〇H、ζ_2ι〇、z_22〇、 Z-320及類似物可被使用，但不限於此。此時，聚乙烯醇系 樹脂的重量比沒有特殊限定’且其範圍可根據所要貼合的 膜種類而小幅更動。舉例而t ’當聚乙稀醇系偏光片與丙 烯酸系膜相互貼合時，基於1〇〇重量份之具有三亞甲亞胺根 官能基之化合物，使用10至1,000重量份的範圍較佳。至於 聚乙烯醇系偏光片用量少於10重量份時，則對於聚乙烯醇 偏光元件或TAC膜的黏著強度會變差，而當其含量超過 1，〇〇〇重量份時，則對於丙烯酸膜的黏著強度差。 本發明提供一種光學膜，其具有含兩層以上之層狀結構， 且包括一黏著劑層，其位於該些膜間之至少—介面上，其 係使用含具有二亞甲亞胺根官能基之化合物的黏著劑組 成物所形成。在本發明中，已知光學膜為履行光學功能的 膜，包括狹義上透射率為80%以上的透明膜、以及任何透射 率50%以下的光學膜，只要能執行特定光學功能（像偏光板） 的膜即可。 層疊膜沒有特別限定’但尤其可使用丙烯酸系膜、pET 膜、尤其經丙烯酸系底漆處理之PET膜、TAC膜、C〇p膜、 聚碳酸酯（PC)膜、聚降莰烯系（PNB)膜、 及類似膜。具體而 5 ’相較於已知聚乙烯醇系黏著劑，丙烯酸系膜及經丙烯 西文系底漆處理之PET膜可大幅改善黏著強度。層疊膜可使用 相同材料或不同材料製得。 10 201000582 層疊膜可經過表面處理改善黏著強 、電暈處理、電漿處理、底漆處理Where η ranges from 30 to 7,000. The adhesive composition of the present invention may further comprise a solvent (e.g., water) to form an adhesive layer. In this case, the compound having a trimethyleneimine functional group has a concentration ranging from 0.1 to 30% by weight, preferably from 0.5 to 1% by weight. The pH of the composition of the present invention ranges from 2 to 11, preferably from 4 to 10. The pH of the adhesive composition of the present invention can be controlled by an additive test or the like without particular limitation, and preferred examples include NaOH, KOH, nh4〇h and the like. The adhesive composition of the present invention may further comprise a polyvinyl alcohol (PVA)-based resin, and furthermore, the adhesion to an optical film (e.g., a polyvinyl alcohol-based polarizer or a TAC film) can be further improved by further including a polyvinyl alcohol-based resin. In particular, the use of denatured pvA containing an ethylidene group and the like may contribute to adhesion and crosslinking with a compound having a trimethylene imino group. For example, G-M z_100, z_200, z_2〇〇H, ζ_2ι〇, z_22〇, Z-320, and the like, which are manufactured by japan Synthetic Chemical, c〇, Ltd., 9 201000582 can be Use, but not limited to. At this time, the weight ratio of the polyvinyl alcohol-based resin is not particularly limited' and the range thereof may be slightly changed depending on the type of the film to be bonded. For example, when the polyvinyl alcohol-based polarizer and the acrylic film are bonded to each other, it is preferably used in the range of 10 to 1,000 parts by weight based on 1 part by weight of the compound having a trimethyleneimine functional group. When the amount of the polyvinyl alcohol-based polarizer is less than 10 parts by weight, the adhesion strength to the polyvinyl alcohol polarizing element or the TAC film may be deteriorated, and when the content exceeds 1, the part by weight is acrylic acid. The adhesion strength of the film is poor. The present invention provides an optical film having a layered structure comprising two or more layers, and comprising an adhesive layer located on at least the interface between the films, which uses a functional group having a dimethylimine group The adhesive composition of the compound is formed. In the present invention, an optical film is known as a film that performs an optical function, and includes a transparent film having a transmittance of 80% or more in a narrow sense, and an optical film having a transmittance of 50% or less, as long as a specific optical function (such as a polarizing plate) can be performed. The film can be. The laminated film is not particularly limited, but in particular, an acrylic film, a pET film, a PET film treated with an acrylic primer, a TAC film, a C〇p film, a polycarbonate (PC) film, a polynormene system ( PNB) films, and similar films. Specifically, the acrylic film and the PET film treated with the acrylic-based primer can greatly improve the adhesion strength compared to the known polyvinyl alcohol-based adhesive. The laminated film can be produced using the same material or different materials. 10 201000582 Laminated film can be surface treated to improve adhesion, corona treatment, plasma treatment, primer treatment
此外，本發明提供一種偏光板，其結構為··第—膜、一 偏先片、及第二臈依序層疊，且其包括：-黏著劑層，1 位於該第-膜及該第二膜之至少—者與該偏光片之間^ 係使用—含具有三亞甲亞胺根官能基之化合物的黏著劑： 成物所形成。此時，第—膜或第二膜可經過上述表面處理。 丙稀酸系膜、PET膜、尤其經丙稀酸系底漆處理之pET 膜、TAC膜、COP膜、_、觸膜、及類似膜可使用做 為第-膜及第二膜。第一膜及第二膜可以相同材料製得， 或者以不同材料製得。舉例而言，第一膜及第二膜可都為 丙烯酸系膜或TAC膜（圖2)，或者其中任一者可為丙烯酸系 膜，另一者為TAC膜（圖3)。In addition, the present invention provides a polarizing plate having a structure in which a first film, a first film, and a second film are sequentially laminated, and includes: an adhesive layer, 1 being located in the first film, and the second At least one of the film is formed between the polarizer and an adhesive containing a compound having a trimethyleneimine functional group: a product. At this time, the first film or the second film may be subjected to the above surface treatment. An acrylic film, a PET film, a pET film treated with an acrylic primer, a TAC film, a COP film, a contact film, and the like can be used as the first film and the second film. The first film and the second film may be made of the same material or may be made of different materials. For example, both the first film and the second film may be an acrylic film or a TAC film (Fig. 2), or either of them may be an acrylic film and the other is a TAC film (Fig. 3).
如果有需要的話， 度，舉例可實行鹼處理 及類似處理。 黏著劑層係使用本發明黏著劑組成物所形成。詳而言 之，直接塗覆黏著劑組成物於膜上後，乾燥黏著劑層，或 者在兩層膜之間或多層膜之間塗覆黏著劑組成物後使用 壓輥壓合黏著劑組成物，乾燥黏著劑層，使黏著劑層形成。 黏著劑層的厚度較佳於1〇至500 nm的範圍，更佳於2〇至2〇〇 nm的範圍。 本發明偏光板的透射率於35至45%的範圍較佳，而偏 光私度於9 8以上較佳。 由於黏著劑組成物（含有二亞曱亞胺根官能基的化合 物）具有絕佳的透明性，光學產品（如本發明光學膜或偏光板） 201000582 及類似產品，可保姓m 光學產品其透光性不=光==f，'故所製得的 著強度，故:同時改善所製得的光學產品::::色的黏 的偏L其二::(:=反广因為黏著劑組成物所造成 之變化，幾乎與使用::：、偏光度、色彩及類似性質) 立製程條件中^ α聚乙烯醇糸黏者劑時相同，在獨 h條件中亦無變化’故可取代習知而應用於量產線。 本發明提供—種電子裝置，其包括前述光學膜或偏光 至於電子裝置’有液晶顯示裝置及類似裂置，不過電 子裝置的種類沒有特別限制’只要需要前述光學膜或偏光 板之電子裝置即可。除了電子裝置須包含黏著劑層（係使用 本發明黏著劑組成物所製得）之外’域電子裝置可與本領 域習知裝置具有相同的結構；舉例而言，電子裝置可為液 曰曰顯不裝置，其包括液晶單元、本發明偏光板（裝配於液晶 單元的兩側）以及背光單元。 參考實施例，後文將詳細描述本發明，然而本發明可 具體實施成各種形式，不應被解釋成限縮於所舉出之實施 例，而應是提供這些實施例讓本領域中通常知識者完全了 解本發明概念。 實施例 實施例1 以純水稀釋 Kymene-557H (Hercules Korea，12.5 wt% 水溶液，具有三亞曱亞胺根官能基及胺基的化合物）而製備 出6 wt%水溶液，並使用此水溶液，將經過電暈處理之丙缔 12 201000582 酸系膜貼於偏光片兩側，對於丙烯酸系膜則使用由OPTES, Co., Ltd所製造且厚度為80 μιη的T膜，膜表面係經過50 W/m2/min條件的電暈處理。在偏光片及其兩側的丙烯酸系 膜之間注入黏著劑，並使用壓輥加壓後，於80°C下使用熱 風乾燥5分鐘，而後製備出偏光板。 實施例2 在添加 NaOH 水溶液使 Kymene-557H (Hercules Korea，12.5wt%水溶液，pH = 5)的pH值變成7之後，以純 f ^ 水稀釋製得6 wt%黏著劑組成物，使用此黏著劑組成物將經 過電暈處理之丙烯酸系膜貼於偏光片兩側。 實施例3 使用實施例2之黏著劑組成物，將經過電暈處理之丙烯 酸系膜貼於偏光片一側，並將經過鹼處理之TAC膜貼於偏 光板之另一側。 實施例4 基於 100 重量份之 Kymene-557H (Hercules Korea, 12.5 f , wt%)，添加100重量份之變性聚乙烯醇樹脂Gohsefimer Z-200 (Japan Synthesis Chemical, Co.，Ltd)，並添加 NaOH 水溶液，使其pH值調整成7，再使用4.5 wt%黏著劑組成物 (其係藉由純水稀釋而製得），將經過電暈處理之丙烯酸系膜 貼於偏光片一側，並將經過鹼處理之TAC膜貼於偏光板之 另一侧。 比較例1 201000582 將聚乙稀g手樹脂（平均聚合度為2,4〇〇且皂化度為 99·9/〇)α解於純水中’製備们聚乙烯醇水溶液並使 用此將經過電暈處理之丙烯酸系膜貼於偏光片兩側。 比較例2 將變性聚乙烯醇樹脂Gohsefimer Z-200 (japan Synthesis Chemical，c〇 , Ltd)溶解於純水中，並於1〇〇重量 份之變性聚乙烯醇樹脂中，添加1G重量份之胺系金屬交聯 劑，進而製出黏著劑，以製得4.5 wt%變性聚乙稀醇水溶 液再使用此將紐過電晕處理之丙稀酸系膜貼於偏光片兩 側。 比較例3 使用比車乂例2之黏著劑，將經過電暈處理之丙烯酸系膜 貼於偏光#側’並將經過驗處理之膜貼於偏光板之 另一側。 評估方法 1.黏著強度 使用切斷器刀鋒於偏光板表面形成刮痕後，刮痕周圍 剝離程度以百分比顯示（圖4)，當此值低時，表示黏著強度 2. 对水性 使用壓感黏著劑將偏光板一側貼於破璃板，並將其浸 入60〇C之恆溫浴持續⑽小時後，以偏光片收縮及保護： 剝離程度評估耐水性。 、 3. 光學性質 201000582 使用分光光度計測量偏光板之單體透射率（single body transmittance, Ts)、平行透射率（parallel transmittance, Tp)、正交透射率（crossed transmittance, Tc)，偏光度則以下 列等式計算。 (等式 1)偏光度（P) = V(Tp - Tc) / (Tp + Tc) 評估結果 [表1]偏光板之黏著強度、耐水性、光學性質的評估結果 保護膜 黏著劑 黏著強度 (到痕剝離） 耐水性 光學性質 丙烯酸 膜側 TAC膜 側 4 hr後 48 hr 後 Ts (%) P 實施例1 A/A K1 10% 無 無剝離 無剝離 42.3 99.9 實施例2 A/A K2 <10% 無 無剝離 無剝離 42.3 99.9 實施例3 A/TAC K2 0% <10% 無剝離 無剝離 42.6 99.9 實施例4 A/TAC K3 0% 0% 無剝離 無剝離 42.7 99.9 比較例1 A/A P1 100% 益 i »»> 剝離 剝離 42.4 99.9 比較例2 A/A P2 80% 益 < »*> 無剝離 剝離 42.3 99.9 比較例3 A/TAC P2 50% 0% 無剝離 剝離 42.7 99.9 * A :丙烯酸膜 * K1 ： 6 wt% Kymene-557H (pH = 5) * K2 : 6 wt% Kymene-557H (pH = 7) * K3 ： 4.5 wt% Kymene-557H : Z200 = 1 ： 1 (pH = 7)If necessary, an alkali treatment and the like can be applied as an example. The adhesive layer is formed using the adhesive composition of the present invention. Specifically, after directly applying the adhesive composition to the film, drying the adhesive layer, or applying an adhesive composition between the two films or between the multilayer films, the adhesive composition is pressed using a press roll. The adhesive layer is dried to form an adhesive layer. The thickness of the adhesive layer is preferably in the range of 1 Å to 500 nm, more preferably in the range of 2 Å to 2 〇〇 nm. The transmittance of the polarizing plate of the present invention is preferably in the range of 35 to 45%, and the degree of polarization is preferably 98 or more. Since the adhesive composition (a compound containing a dimercaptoidine functional group) has excellent transparency, an optical product (such as the optical film or polarizing plate of the present invention) 201000582 and the like can protect the surname of the optical product. Light does not = light == f, 'The strength of the resulting, therefore: at the same time improve the optical products produced:::: the viscosity of the color of the L. Second:: (: = anti-wide because of the adhesive The changes caused by the composition are almost the same as the use of :::, degree of polarization, color and similar properties. The process conditions are the same as in the case of α-polyvinyl alcohol oxime adhesive, and there is no change in the condition of the single h. It is conventionally applied to mass production lines. The present invention provides an electronic device including the foregoing optical film or polarized light to the electronic device having a liquid crystal display device and the like, but the type of the electronic device is not particularly limited as long as the electronic device of the optical film or the polarizing plate is required. . In addition to the electronic device having to include an adhesive layer (made using the adhesive composition of the present invention), the 'domain electronic device can have the same structure as the device of the prior art; for example, the electronic device can be liquid helium A display device includes a liquid crystal cell, a polarizing plate of the present invention (mounted on both sides of the liquid crystal cell), and a backlight unit. The invention will be described in detail below with reference to the preferred embodiments of the present invention, which should be construed as The full concept of the invention is fully understood. EXAMPLES Example 1 A 6 wt% aqueous solution was prepared by diluting Kymene-557H (Hercules Korea, a 12.5 wt% aqueous solution, a compound having a trihydrazinium group functional group and an amine group) with pure water, and using this aqueous solution, Corona treatment of Cyanide 12 201000582 The acid film is attached to both sides of the polarizer. For the acrylic film, a T film made by OPTES, Co., Ltd. and having a thickness of 80 μm is used, and the film surface is 50 W/m2. Corona treatment with /min condition. An adhesive was injected between the polarizer and the acrylic film on both sides thereof, and after pressurization with a press roll, it was dried by hot air at 80 ° C for 5 minutes, and then a polarizing plate was prepared. Example 2 After adding a NaOH aqueous solution to adjust the pH of Kymene-557H (Hercules Korea, 12.5 wt% aqueous solution, pH = 5) to 7, a 6 wt% adhesive composition was prepared by dilution with pure f ^ water, and the adhesive was used. The composition was attached to both sides of the polarizer by a corona-treated acrylic film. Example 3 Using the adhesive composition of Example 2, a corona-treated acrylic film was attached to one side of a polarizer, and an alkali-treated TAC film was attached to the other side of the polarizing plate. Example 4 100 parts by weight of a denatured polyvinyl alcohol resin Gohsefimer Z-200 (Japan Synthesis Chemical, Co., Ltd.) was added and 100% by weight was added based on 100 parts by weight of Kymene-557H (Hercules Korea, 12.5 f, wt%). The aqueous solution was adjusted to pH 7, and then 4.5 wt% of the adhesive composition (which was prepared by dilution with pure water) was applied, and the corona-treated acrylic film was attached to one side of the polarizer, and The alkali treated TAC film is attached to the other side of the polarizing plate. Comparative Example 1 201000582 A solution of polyethylene b-hand resin (average degree of polymerization of 2,4 Torr and a degree of saponification of 99·9/〇) in pure water was prepared as an aqueous solution of polyvinyl alcohol and used to pass electricity. The acrylic film of the halo treatment is attached to both sides of the polarizer. Comparative Example 2 A denatured polyvinyl alcohol resin Gohsefimer Z-200 (japan Synthesis Chemical, c., Ltd.) was dissolved in pure water, and 1 part by weight of an amine was added to 1 part by weight of the denatured polyvinyl alcohol resin. A metal cross-linking agent is prepared to prepare an adhesive to prepare a 4.5 wt% denatured polyethylene aqueous solution, and then the corona-treated acrylic film is attached to both sides of the polarizer. Comparative Example 3 A corona-treated acrylic film was attached to the polarizing # side using an adhesive of the ruthless example 2, and the treated film was attached to the other side of the polarizing plate. Evaluation method 1. Adhesive strength After the scratch is formed on the surface of the polarizing plate by the cutter blade, the degree of peeling around the scratch is shown as a percentage (Fig. 4). When the value is low, the adhesion strength is 2. The pressure is applied to the water. The agent was attached to the glass plate with one side of the polarizing plate, and immersed in a constant temperature bath of 60 ° C for 10 hours, and then the polarizer was shrunk and protected: the degree of peeling was evaluated for water resistance. 3. Optical properties 201000582 Using a spectrophotometer to measure the single body transmittance (Ts), parallel transmittance (Tp), crossed transmittance (Tc), and degree of polarization of the polarizing plate. Calculated by the following equation. (Equation 1) Polarization degree (P) = V(Tp - Tc) / (Tp + Tc) Evaluation result [Table 1] Evaluation results of adhesion strength, water resistance, and optical properties of a polarizing plate Protective film adhesive adhesion strength ( To the trace peeling) Water resistance Optical properties Acrylic film side TAC film side 4 hr after 48 hr Ts (%) P Example 1 A/A K1 10% No peeling no peeling 42.3 99.9 Example 2 A/A K2 < 10% No peeling and no peeling 42.3 99.9 Example 3 A/TAC K2 0% < 10% No peeling and no peeling 42.6 99.9 Example 4 A/TAC K3 0% 0% No peeling and no peeling 42.7 99.9 Comparative example 1 A/ A P1 100% benefit i »»> Peel stripping 42.4 99.9 Comparative example 2 A/A P2 80% benefit <»*> No peeling peeling 42.3 99.9 Comparative example 3 A/TAC P2 50% 0% No peeling peeling 42.7 99.9 * A : Acrylic film * K1 : 6 wt% Kymene-557H (pH = 5) * K2 : 6 wt% Kymene-557H (pH = 7) * K3 : 4.5 wt% Kymene-557H : Z200 = 1 : 1 ( pH = 7)
* PI ： 3% PVA * P2 : 4.5% Z200 :交聯劑=10 : 1 上述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於上述實施例。 【圖式簡單說明】 圖1係習知偏光板的結構不意圖。 201000582 圖2係本發明具體實施例之偏光板的結構示意圖。 圖3係本發明具體實施例之偏光板的結構示意圖。 圖4係評估黏著強度之刮痕剝離評估法的說明圖。 【主要元件符號說明】 無。 16* PI : 3% PVA * P2 : 4.5% Z200 : Crosslinking agent = 10 : 1 The above examples are for illustrative purposes only, and the scope of the claims should be based on the scope of the patent application. It is not limited to the above embodiment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a conventional polarizing plate. 201000582 FIG. 2 is a schematic structural view of a polarizing plate according to a specific embodiment of the present invention. 3 is a schematic structural view of a polarizing plate according to a specific embodiment of the present invention. Fig. 4 is an explanatory diagram of a scratch peeling evaluation method for evaluating the adhesion strength. [Main component symbol description] None. 16
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| KR (1) | KR101057628B1 (en) |
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| KR20120032195A (en) * | 2010-09-28 | 2012-04-05 | 동우 화인켐 주식회사 | A polarizing plate and liquid crystal display comprising the same |
| MY168781A (en) * | 2012-06-14 | 2018-12-04 | Alcon Inc | Azetidinium-containing copolymers and uses thereof |
| KR102246299B1 (en) * | 2019-03-12 | 2021-04-29 | 주식회사 온빛 | The manufacturing method of high-refraction polarizing lens |
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| US4528316A (en) * | 1983-10-18 | 1985-07-09 | Kimberly-Clark Corporation | Creping adhesives containing polyvinyl alcohol and cationic polyamide resins |
| JPH0345678A (en) * | 1989-07-14 | 1991-02-27 | Kuraray Co Ltd | Adhesives and glass substrates |
| EP0743172B1 (en) * | 1995-05-18 | 1999-08-04 | Fort James Corporation | Novel creping adhesive formulations, method of creping and creped fibrous web |
| JP3704786B2 (en) * | 1996-03-18 | 2005-10-12 | 住友化学株式会社 | Polarizer |
| US5865950A (en) * | 1996-05-22 | 1999-02-02 | The Procter & Gamble Company | Process for creping tissue paper |
| US5944954A (en) | 1996-05-22 | 1999-08-31 | The Procter & Gamble Company | Process for creping tissue paper |
| ZA983874B (en) * | 1997-05-09 | 1998-11-09 | Procter & Gamble | Adhesive composition providing a signal means and adhesively laminated paper product |
| US6677427B1 (en) * | 2000-06-13 | 2004-01-13 | Hercules Incorporated | Enzyme-catalyzed polyamides and compositions and processes of preparing and using the same |
| EP1180559A1 (en) * | 2000-08-04 | 2002-02-20 | Armstrong World Industries, Inc. | Binder composition for fibrous sheet |
| JP2004334168A (en) * | 2003-04-16 | 2004-11-25 | Sumitomo Chem Co Ltd | Polarizing plate and manufacturing method thereof |
| JP2005128294A (en) * | 2003-10-24 | 2005-05-19 | Sumitomo Chemical Co Ltd | Polarizer |
| JP2007533817A (en) * | 2004-04-20 | 2007-11-22 | ステイト オブ オレゴン アクティング バイ アンド スルー ザ ステイト ボード オブ ハイヤー エデュケーション オン ビハーフ オブ オレゴン ステイト ユニバーシティー | Formaldehyde-free lignocellulose adhesive and composite made from the adhesive |
| CN100520453C (en) * | 2004-08-03 | 2009-07-29 | 捷时雅株式会社 | Polarizing plate and process for producing the same |
| JP2006235613A (en) * | 2005-01-25 | 2006-09-07 | Sumitomo Chemical Co Ltd | Composite polarizing plate |
| RU2448126C2 (en) * | 2006-08-24 | 2012-04-20 | Геркулес Инкорпорейтед | Adhesive composition of low-molecular weight polyamidoamine-epihalohydrin (pae) resin and protein |
| US7932349B2 (en) * | 2006-09-18 | 2011-04-26 | Hercules Incorporated | Membrane separation process for removing residuals polyamine-epihalohydrin resins |
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| KR20090107444A (en) | 2009-10-13 |
| CN102015954A (en) | 2011-04-13 |
| JP2011519982A (en) | 2011-07-14 |
| KR101057628B1 (en) | 2011-08-19 |
| CN103396756A (en) | 2013-11-20 |
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| WO2009125980A3 (en) | 2010-01-14 |
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