TW202012573A - Adhesive composition adhesive polarizing plate and liquid crystal display device - Google Patents
Adhesive composition adhesive polarizing plate and liquid crystal display device Download PDFInfo
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- TW202012573A TW202012573A TW108119147A TW108119147A TW202012573A TW 202012573 A TW202012573 A TW 202012573A TW 108119147 A TW108119147 A TW 108119147A TW 108119147 A TW108119147 A TW 108119147A TW 202012573 A TW202012573 A TW 202012573A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本發明係關於黏著劑組成物、黏著偏光板及液晶顯示裝置。The invention relates to an adhesive composition, an adhesive polarizing plate and a liquid crystal display device.
矽烷偶合劑為,於分子中具有2個以上相異的官能基,作為連結通常不容易結合的有機質材料與無機質材料之仲介角色而作用。 矽烷偶合劑所具有的官能基之一方為水解性矽基,藉由水之存在而生成矽烷醇基,因該矽烷醇基與無機材質表面之羥基進行反應而與無機材質表面形成化學鍵。又,其他官能基為,與如各種合成樹脂之有機質材料形成化學鍵之乙烯基、環氧基、胺基、(甲基)丙烯酸基、巰基等有機反應基。 利用這些反應基之特性,可作為有機・無機樹脂之改質劑、接著助劑、各種添加劑等而廣泛被利用。The silane coupling agent has two or more different functional groups in the molecule, and acts as an intermediary role for linking the organic material and the inorganic material that are usually not easily combined. One of the functional groups possessed by the silane coupling agent is a hydrolyzable silane group, and a silanol group is generated by the presence of water. The silanol group reacts with the hydroxyl group on the surface of the inorganic material to form a chemical bond with the surface of the inorganic material. The other functional groups are organic reactive groups such as vinyl groups, epoxy groups, amine groups, (meth)acrylic groups, and mercapto groups that form chemical bonds with organic materials such as various synthetic resins. Using the characteristics of these reactive groups, they can be widely used as modifiers for organic and inorganic resins, adhesives, and various additives.
亦於矽烷偶合劑之用途中,黏著劑之作為接著性改質劑的用途為該代表者,例如貼合液晶單元與光學薄膜時的黏著劑會隨著液晶顯示裝置(LCD)之尺寸的大型化、加寬化而使所要求的接著性能變高。 例如,以LCD之情況而言,與當初預相反,原以為難達成20英吋以上之大型化,反而變成大型化的急速發展。主要製造商雖主力於這些20英吋以下的小型面板之生產,但隨著近年來的趨勢,積極地導入最新技術,而使製品範圍往20英吋以上之大型尺寸進展。Also in the application of silane coupling agent, the use of the adhesive as the adhesive modifier is the representative. For example, the adhesive when bonding the liquid crystal cell and the optical film will increase with the size of the liquid crystal display device (LCD). The widening and widening will increase the required adhesion performance. For example, in the case of LCD, contrary to the original prediction, it was originally difficult to achieve a large size of more than 20 inches, but it has become a rapid development of large size. Although the main manufacturers are mainly engaged in the production of these small panels under 20 inches, but with the trend in recent years, they have actively introduced the latest technology to make the product range move toward large sizes above 20 inches.
如此對於此等般的光學薄膜,使用於液晶顯示板之製造時的玻璃有大型化之趨勢。如此狀況下,於初期貼合時會產生不良製品,自液晶單元將光學用薄膜除去並洗淨液晶單元後,若必須再使用此之情況產生時,對於具有過去高黏著力之黏著劑,因該強力的接著力,不僅使光學薄膜之再剝離或除去變得困難,破壞高價液晶單元之可能性亦變大,作為結果,變得大幅度提高生產成本。For such optical films, the glass used in the manufacture of liquid crystal display panels tends to be large. Under such circumstances, defective products will be generated during the initial bonding. After removing the optical film from the liquid crystal cell and cleaning the liquid crystal cell, if it is necessary to use this again, for adhesives that have high adhesion in the past, because This strong adhesive force not only makes it difficult to re-peel or remove the optical film, but also increases the possibility of damaging the high-priced liquid crystal cell. As a result, the production cost is greatly increased.
因此,隨著LCD之大型化,繼續嘗試開發出兼具接著性、再加工性等各種黏著性能之高功能性黏著劑。 例如,於專利文獻1中提出之在提供於高溫多濕的環境下之耐久性優良的偏光板之目的下,含有環氧矽烷之丙烯酸系黏著劑組成物。 又,不僅於基板表面上可使偏光板在良好的接著強度下進行接著,對應必要欲對於基板不會產生損傷或殘留黏著劑,且欲使自基板的表面可剝離偏光板,於專利文獻2及專利文獻3中有提出含有丙烯酸系聚合物,與具有β-酮酯基及水解矽基之化合物,或其水解縮合物的黏著劑組成物,於專利文獻4~7中提出含有丙烯酸系聚合物,與具有雜環結構基、胺基甲酸酯或尿素連結基及水解矽基的化合物之黏著劑組成物。 進一步於專利文獻8~10中作為黏著劑,提出含有於聚醚末端具有烷氧基矽基之有機矽化合物的丙烯酸系黏著劑,該黏著劑為除初期接著力為低,再加工性優良以外,且貼合後在高溫多濕下接著力增強,長期性耐久性優良者。Therefore, with the enlargement of LCDs, we continue to try to develop highly functional adhesives with various adhesive properties such as adhesiveness and reworkability. For example, in the purpose of providing a polarizing plate with excellent durability in a high-temperature and humid environment proposed in Patent Document 1, an acrylic adhesive composition containing epoxy silane. In addition, not only can the polarizing plate be adhered on the surface of the substrate with good adhesion strength, it is necessary to prevent damage to the substrate or residual adhesive, and the polarizing plate can be peeled from the surface of the substrate, in Patent Document 2 And Patent Document 3 proposes an adhesive composition containing an acrylic polymer, a compound having a β-ketoester group and a hydrolyzed silicon group, or a hydrolyzed condensate thereof, and Patent Documents 4 to 7 propose containing an acrylic polymer It is an adhesive composition of compounds with heterocyclic structural groups, carbamate or urea linking groups, and hydrolyzed silicon groups. Further, as an adhesive in Patent Documents 8 to 10, an acrylic adhesive containing an organosilicon compound having an alkoxysilyl group at the end of polyether has been proposed. The adhesive has the advantages of low initial adhesion and excellent reworkability. , And the bonding strength is enhanced under high temperature and humidity after bonding, and the long-term durability is excellent.
藉由使用含有如以上矽烷化合物之黏著劑,於基板與偏光板之間,不僅可保持在實際使用的環境中所要求程度之適當接著強度,該接著強度不會因藉由加熱等而過度變高,且對於液晶元件不會賦予損傷,變得可容易剝離偏光板。By using an adhesive containing the above silane compound, between the substrate and the polarizing plate, not only can maintain the appropriate adhesion strength required in the actual use environment, the adhesion strength will not be excessively changed by heating, etc. It is high and does not damage the liquid crystal element, making it easy to peel off the polarizing plate.
然而,使用於支持LCD的大型傾向之黏著劑所要求的性能,不僅為貼合於玻璃時的初期接著力要低,且再加工性亦優良以外,在高溫多濕下必須表現高接著力,若非此等情況時,恐怕有產生氣泡或剝離顯像等耐久性脆弱之情況產生。 此點,在專利文獻11中因提供即使在高溫多濕下,凝集力及接著力的經時性變化為小,且曲面接著力亦優的黏著劑組成物,故提出在矽烷系化合物之存在下使丙烯酸系單體進行聚合而得之丙烯酸系樹脂中添加硬化劑的技術。 其中亦記載藉由添加該矽烷化合物,基板與偏光板可保持在實際使用的環境所要求程度之適當接著強度,接著強度不會因加熱等而過度高,對於液晶元件不會賦予損傷,且可容易地剝離偏光板。However, the performance required for adhesives used to support large LCD trends is not only low in initial adhesion when attached to glass, but also excellent in reworkability. It must exhibit high adhesion under high temperature and humidity. If this is not the case, there may be cases where the durability is weak, such as bubbles or peeling development. In this regard, Patent Document 11 proposes the presence of a silane-based compound in order to provide an adhesive composition that has small changes in cohesion force and adhesion force over time under high temperature and humidity, and is excellent in curved surface adhesion force. The following is a technique of adding a hardener to an acrylic resin obtained by polymerizing an acrylic monomer. It is also stated that by adding the silane compound, the substrate and the polarizing plate can maintain the appropriate adhesion strength required by the actual use environment, and the adhesion strength will not be excessively high due to heating, etc., and will not damage the liquid crystal element, and may The polarizing plate is easily peeled off.
然而,與其在高溫多濕下可使凝集力及接著力的經時變化變小,接著力高,無氣泡或剝離顯像且耐久性優良者為佳。即,在貼合於玻璃的初期,顯示可進行再剝離之適當初期接著力,但因隨著時間過去,剝離的必要性消失,而保持強化且安定化的接著力成為必要。However, instead of reducing the cohesion force and the adhesion force over time under high temperature and humidity, the adhesion force is high, there is no bubble or peeling development, and the durability is preferably excellent. That is, in the initial stage of bonding to glass, an appropriate initial adhesion force capable of re-peeling is shown, but since the necessity of peeling disappears over time, it is necessary to maintain a strengthened and stable adhesion force.
由如此觀點來看,於上述專利文獻2~10所記載的含有有機矽化合物的接著性改質劑所可改良的再加工性、貼合後的耐濕特性、接著力等並未充分,尚有改良的空間。 由上述得知,期待初期之再加工性為良好,且在高溫多濕下可取得保持高接著強度之平衡的黏著劑之開發。 [先前技術文獻] [專利文獻]From such a point of view, the reworkability, the moisture resistance characteristics after bonding, the adhesion, etc., which can be improved by the adhesive modifier containing the organosilicon compound described in the above Patent Documents 2 to 10, are not sufficient. There is room for improvement. From the above, it is expected that the initial reworkability will be good, and the development of an adhesive that maintains a balance of high adhesive strength under high temperature and humidity can be expected. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利第3022993號公報 [專利文獻2]日本專利第3533446號公報 [專利文獻3]日本專利第5262672號公報 [專利文獻4]日本專利第4771102號公報 [專利文獻5]日本專利第5365609號公報 [專利文獻6]日本專利第5365610號公報 [專利文獻7]日本特表2008-506028號公報 [專利文獻8]日本特開2011-219765號公報 [專利文獻9]日本專利第4840888號公報 [專利文獻10]國際公開第2010/26995號 [專利文獻11]日本特開平8-199144號公報[Patent Document 1] Japanese Patent No. 3022993 [Patent Document 2] Japanese Patent No. 3533446 [Patent Document 3] Japanese Patent No. 5262672 [Patent Document 4] Japanese Patent No. 4771102 [Patent Document 5] Japanese Patent No. 5365609 [Patent Document 6] Japanese Patent No. 5365610 [Patent Document 7] Japanese Patent Publication No. 2008-506028 [Patent Document 8] Japanese Patent Laid-Open No. 2011-219765 [Patent Document 9] Japanese Patent No. 4840888 [Patent Literature 10] International Publication No. 2010/26995 [Patent Document 11] Japanese Patent Laid-Open No. 8-199144
[發明所解決的問題][Problems solved by the invention]
本發明為有鑑於上述情事所得者,以提供於貼合於玻璃等被接著體時,初期接著力為低且再加工性優良,於貼合後,在高溫或高溫多濕的條件下,與玻璃等被接著體的接著力增加,賦予長期耐久性優良的黏著劑層之黏著劑組成物、具有由該組成物所形成的黏著層之黏著偏光板,及具有該黏著偏光板之液晶顯示裝置為目的。 [解決課題的手段]The present invention is obtained in view of the above-mentioned circumstances, and is provided when bonding to an adherend such as glass, the initial adhesion is low and the reworkability is excellent, and after bonding, under the condition of high temperature or high temperature and high humidity, and The adhesive force of an adherend such as glass increases, an adhesive composition that provides an adhesive layer with excellent long-term durability, an adhesive polarizing plate having an adhesive layer formed of the composition, and a liquid crystal display device having the adhesive polarizing plate for purpose. [Means to solve the problem]
本發明者欲解決上述課題進行詳細檢討結果,發現將具有所定的可交聯之官能基的(甲基)丙烯酸系聚合物,與嵌段化異氰酸酯矽烷化合物以所定比例下含有的組成物具有優良的再加工性,且經貼合後,在高溫或高溫多濕之條件下,與玻璃等被接著體之接著力增加,可賦予具有優良長期耐久性之黏著劑層,而完成本發明。The present inventors conducted a detailed review to solve the above-mentioned problems and found that the composition containing a (meth)acrylic polymer having a predetermined crosslinkable functional group and a blocked isocyanate silane compound in a predetermined ratio has excellent The reworkability, and after lamination, under the condition of high temperature or high temperature and humidity, the adhesion with the adherend such as glass increases, which can give an adhesive layer with excellent long-term durability, and completed the present invention.
即,本發明為提供以下者: 1.一種黏著劑組成物,其特徵為含有(A)具有可交聯的官能基之(甲基)丙烯酸系聚合物,與(B)嵌段化異氰酸酯矽烷化合物;前述可交聯的官能基為選自羥基、羧基、酸酐基及烷氧基矽基的1種或2種以上的基,對於前述(A)成分100質量份而言,(B)成分以0.001~10質量份含有者。 2.前述(B)嵌段化異氰酸酯矽烷化合物為下述式(1)所示黏著劑組成物; (式中,R1 各獨立表示碳原子數1~8的烷基,L表示2價連結基,X表示-O-或-NR2 -,Y表示氫原子或1價有機基,R2 表示氫原子、碳原子數1~8的烷基或與Y鍵結可形成環結構的基,m表示1~3的整數)。 3.前述(B)嵌段化異氰酸酯矽烷化合物為下述式(2)或(3)所示黏著劑組成物; (式中,R1 、R2 、Y及m表示與前述相同意思,R3 及R4 各獨立表示氫原子或1價有機基,但R3 與R4 或R2 與Y彼此連結可形成環結構)。 4.前述(A)具有可交聯的官能基之(甲基)丙烯酸系聚合物為(a)單體與(b)單體的共聚物;前述(a)單體為(甲基)丙烯酸之非取代碳原子數1~12烷基酯單體,前述(b)單體為具有選自羥基、羧基、酸酐基及烷氧基矽基的1種或2種以上的基之乙烯基系單體以及(甲基)丙烯酸系單體的至少一方單體,於前述(a)單體與(b)單體之合計100質量份中(b)單體的含有量為0.1~10質量份之1~3中任一項之黏著劑組成物。 5.前述(a)單體為選自含有丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯及異壬基(甲基)丙烯酸酯所成群的1種或2種以上的單體之4的黏著劑組成物。 6.前述(b)單體為選自含有2-羥基乙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯、(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯醯氧基丙基三乙氧基矽烷、(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、(甲基)丙烯醯氧基甲基甲基二甲氧基矽烷、(甲基)丙烯醯氧基甲基甲基二乙氧基矽烷、(甲基)丙烯酸、(甲基)丙烯酸二聚體、衣康酸、馬來酸及馬來酸酐所成群的1種或2種以上的單體之4或5的黏著劑組成物。 7.使選自含有(C)異氰酸酯系化合物、環氧系化合物、氮雜環丙烷系化合物及金屬螯合物系化合物所成群的1種或2種以上之多官能***聯劑,以對於前述(A)成分100質量份而言為0.01~10質量份之含有量含有之1~6中任一項的黏著劑組成物。 8.一種黏著偏光板,其為具有偏光薄膜與層合於該偏光薄膜的單面或雙面上的黏著劑層,前述黏著劑層為猶如1~6中任一項的黏著劑組成物所形成者。 9.具有選自保護層、反射層、相位差板、光視野角補償薄膜及亮度提高薄膜的1種以上之功能層的8之黏著偏光板。 10.一種液晶顯示裝置,其特徵為含有以下液晶面板,該液晶面板為具有具備一對玻璃基板與於此等間封入的液晶之液晶單元,及貼著於該液晶單元之單面或雙面的如8或9之黏著偏光板。 [發明之效果]That is, the present invention provides the following: 1. An adhesive composition characterized by containing (A) a (meth)acrylic polymer having a crosslinkable functional group, and (B) a block isocyanate silane Compound; the cross-linkable functional group is one or more groups selected from hydroxyl group, carboxyl group, acid anhydride group, and alkoxysilyl group, for 100 parts by mass of component (A), component (B) Contains 0.001 to 10 parts by mass. 2. The aforementioned (B) block isocyanate silane compound is an adhesive composition represented by the following formula (1); (In the formula, R 1 independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X represents -O- or -NR 2 -, Y represents a hydrogen atom or a monovalent organic group, and R 2 represents (A hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group bonded to Y to form a ring structure, m represents an integer of 1 to 3). 3. The aforementioned (B) block isocyanate silane compound is an adhesive composition represented by the following formula (2) or (3); (In the formula, R 1 , R 2 , Y and m represent the same meaning as described above, R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group, but R 3 and R 4 or R 2 and Y may form Ring structure). 4. The aforementioned (A) (meth)acrylic polymer having a crosslinkable functional group is a copolymer of (a) monomer and (b) monomer; the aforementioned (a) monomer is (meth)acrylic acid The unsubstituted alkyl ester monomer having 1 to 12 carbon atoms, the (b) monomer is a vinyl system having one or more groups selected from a hydroxyl group, a carboxyl group, an acid anhydride group and an alkoxysilyl group At least one monomer of the monomer and the (meth)acrylic monomer, the content of (b) monomer in the total of 100 parts by mass of the (a) monomer and (b) monomer is 0.1 to 10 parts by mass The adhesive composition of any one of 1 to 3. 5. The aforementioned (a) monomer is selected from the group consisting of butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, and methyl (meth)acrylate , N-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth) Adhesive composition of 4 of one or more monomers composed of acrylate, isooctyl (meth)acrylate and isononyl (meth)acrylate. 6. The aforementioned (b) monomer is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethyl Glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, (meth)acryl propyl propyl trimethoxy silane, (meth) acrylic propyl propyl triethoxy silane , (Meth)acryloxypropylmethyldimethoxysilane, (meth)acryloxypropylmethyldiethoxysilane, (meth)acryloxymethyltrimethoxysilane Silane, (meth)acryloyloxymethyltriethoxysilane, (meth)acryloyloxymethylmethyldimethoxysilane, (meth)acryloyloxymethylmethyldiethyl Adhesive for 4 or 5 of 1 or more monomers in groups of oxysilane, (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride Composition. 7. Use one or more polyfunctional crosslinking agents selected from the group consisting of (C) isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds and metal chelate-based compounds in order to The (A) component is 100% by mass of the adhesive composition of any one of 1 to 6 contained in a content of 0.01 to 10 parts by mass. 8. An adhesive polarizing plate comprising a polarizing film and an adhesive layer laminated on one or both sides of the polarizing film, the adhesive layer is composed of an adhesive composition like any one of 1 to 6. Former. 9. An adhesive polarizing plate of 8 having one or more functional layers selected from a protective layer, a reflective layer, a phase difference plate, a light viewing angle compensation film, and a brightness enhancement film. 10. A liquid crystal display device characterized by comprising a liquid crystal panel comprising a liquid crystal cell having a pair of glass substrates and liquid crystal sealed in between, and one or both sides attached to the liquid crystal cell Such as 8 or 9 polarized polarizer. [Effect of invention]
本發明之黏著劑組成物具有以下之特徵:因其為含有作為接著性改質劑成分的嵌段化異氰酸酯矽烷化合物之(甲基)丙烯酸系黏著劑組成物,故貼合於玻璃等時,初期接著力為低而再加工性優良,藉由在貼合後的高溫或高溫多濕下之濕熱處理可表現高接著力,該接著力具有優良長期耐久性之特徵。 即,藉由使用具有嵌段化異氰酸酯基的矽烷偶合劑,與使用於既存技術的矽烷偶合劑做比較,有機部分所佔比例變多,其結果與樹脂之相溶性提高,且與具有羥基之基體樹脂的結合力、相互作用提高,含有基體樹脂的黏著劑與基材之接著性提高。又,具有嵌段化異氰酸酯基的矽烷偶合劑,因矽基水解性低故可使初期再加工性呈飛躍性地提高。The adhesive composition of the present invention has the following characteristics: Since it is a (meth)acrylic adhesive composition containing a blocked isocyanate silane compound as an adhesive modifier component, when it is bonded to glass, etc., The initial adhesive force is low and the reworkability is excellent. The wet heat treatment at high temperature or high temperature and high humidity after lamination can express high adhesive force, which is characterized by excellent long-term durability. That is, by using a silane coupling agent having a blocked isocyanate group, compared with the silane coupling agent used in the existing technology, the proportion of the organic portion becomes larger, and as a result, the compatibility with the resin is improved, and the The binding force and interaction of the matrix resin are improved, and the adhesion between the adhesive containing the matrix resin and the substrate is improved. In addition, the silane coupling agent having a blocked isocyanate group can dramatically improve the initial reworkability due to the low hydrolyzability of the silicon group.
[實施發明的型態][Type of implementation of invention]
以下對於本發明做具體說明。且,對於本發明,「矽烷偶合劑」含於「有機矽化合物」中。 有關本發明的黏著劑組成物為含有(A)具有可交聯的官能基之(甲基)丙烯酸系聚合物與(B)嵌段化異氰酸酯矽烷化合物。The present invention will be described in detail below. Moreover, for the present invention, the "silane coupling agent" is contained in the "organosilicon compound". The adhesive composition of the present invention contains (A) a (meth)acrylic polymer having a crosslinkable functional group and (B) a blocked isocyanate silane compound.
(A)具有可交聯的官能基之丙烯酸系聚合物 作為(A)成分之具有可交聯的官能基之丙烯酸系聚合物,若為具有選自羥基、羧基、酸酐基、及烷氧基矽基的1種或2種以上之可交聯的官能基,較佳為具有羥基之丙烯酸系聚合物即可,並無特別限定,但本發明中,以使用下述(a)單體與(b)單體之共聚物者為佳。 (a)單體 (甲基)丙烯酸的非取代烷基酯單體(該非取代烷基之碳原子數為1~12) (b)單體 具有選自羥基、羧基、酸酐基及烷氧基矽基的1種或2種以上之基的乙烯基系單體以及(甲基)丙烯酸系單體的至少1種 且於本說明書中之「(甲基)丙烯酸」表示「丙烯酸」及/或「甲基丙烯酸」的意思。(A) Acrylic polymer with crosslinkable functional groups The acrylic polymer having a cross-linkable functional group as the component (A), if it has one or more cross-linkable functions selected from a hydroxyl group, a carboxyl group, an acid anhydride group, and an alkoxysilyl group The group is preferably an acrylic polymer having a hydroxyl group, and is not particularly limited, but in the present invention, a copolymer of the following (a) monomer and (b) monomer is preferably used. (a) Monomer (Meth)acrylic acid unsubstituted alkyl ester monomer (the unsubstituted alkyl group has 1 to 12 carbon atoms) (b) monomer At least one vinyl monomer and (meth)acrylic monomer having one or more groups selected from hydroxyl, carboxyl, acid anhydride group, and alkoxysilyl group In addition, "(meth)acrylic acid" in this specification means "acrylic acid" and/or "methacrylic acid".
(a)單體的(甲基)丙烯酸之非取代烷基酯單體,因烷基為長鏈形態時,會有黏著劑之凝集力降低的情況產生,故欲在高溫下可保持凝集力,非取代烷基之碳原子數雖為1~12,但以2~8為佳。 作為(a)單體之具體例子,可舉出丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、n-辛基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、異壬基(甲基)丙烯酸酯等,這些可單獨使用1種,亦可併用2種以上。(a) The unsubstituted alkyl ester monomer of (meth)acrylic acid of the monomer, when the alkyl group is in a long-chain form, the cohesive force of the adhesive may decrease, so it is necessary to maintain the cohesive force at high temperature Although the number of carbon atoms of the unsubstituted alkyl group is 1-12, it is preferably 2-8. Specific examples of the monomer (a) include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, and methyl (meth)acrylic acid. Ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth) ) Acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, etc. These may be used alone or in combination of two or more.
(b)單體為,在高溫或高溫多濕的條件下,欲使其不會產生黏著劑之凝集力的破壞,而藉由化學鍵賦予凝集力或接著強度的成分。 (b)作為單體的具體例子,可舉出含有2-羥基乙基(甲基)丙烯酸酯、3-羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯等羥基的單體;含有(甲基)丙烯酸、(甲基)丙烯酸二聚體、衣康酸、馬來酸、馬來酸酐等羧基之單體;(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯醯氧基丙基三乙氧基矽烷、(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、含有(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、(甲基)丙烯醯氧基甲基甲基二甲氧基矽烷、(甲基)丙烯醯氧基甲基甲基二乙氧基矽烷等烷氧基矽基的單體等,這些單體可單獨使用1種,亦可併用2種以上,使用至少含有羥基之單體者為佳。(b) The monomer is a component that imparts a cohesive force or adhesion strength by a chemical bond under the condition of high temperature or high temperature and humidity, so as not to cause the cohesive force of the adhesive to be destroyed. (b) Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Monomers such as diethylene glycol mono(meth)acrylate and dipropylene glycol mono(meth)acrylate; containing (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid , Maleic anhydride and other carboxyl monomers; (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxypropyl Methylmethyldimethoxysilane, containing (meth)acryloyloxypropylmethyldiethoxysilane, (meth)acryloyloxymethyltrimethoxysilane, (meth)acryloyloxy Alkoxysilyl groups such as methylmethyltriethoxysilane, (meth)acryloyloxymethylmethyldimethoxysilane, (meth)acryloyloxymethylmethyldiethoxysilane These monomers may be used alone or in combination of two or more. It is preferred to use monomers containing at least hydroxyl groups.
(b)單體之使用量,在(a)單體與(b)單體之合計100質量份中,以0.1~10質量份為佳,以1~9質量份為較佳。(b)單體的使用量在0.1質量份以上時,可使在高溫多濕下的凝集破壞難以產生,另一方面,在10質量份以下時,藉由適合性減少的表面移動、流動性減少或凝集力提高的應力緩和能力之降低可受到抑制。(b) The usage amount of the monomer is preferably 0.1 to 10 parts by mass, and preferably 1 to 9 parts by mass in 100 parts by mass of the total of (a) monomer and (b) monomer. (b) When the amount of the monomer is 0.1 parts by mass or more, it is difficult to cause aggregation failure under high temperature and high humidity. On the other hand, when it is 10 parts by mass or less, the surface migration and fluidity are reduced by the suitability. The reduction in the stress relaxation capacity that reduces or increases the cohesive force can be suppressed.
且,對於本發明,於具有可交聯的官能基之丙烯酸系聚合物的製造時,欲調節黏著劑組成物之玻璃轉移溫度,且賦予其他功能性時,可進一步使用其他共聚合性單體。 作為其他共聚合性單體之具體例子,可舉出丙烯腈、苯乙烯、縮水甘油基(甲基)丙烯酸酯、乙烯基乙酸酯等。其他共聚合性單體之配合比例為,在使其共聚合的全單體100質量份中,以0.1~9.9質量份為佳,以0.5~8質量份為較佳。Furthermore, in the present invention, when the acrylic polymer having a crosslinkable functional group is produced, if the glass transition temperature of the adhesive composition is to be adjusted and other functionality is imparted, other copolymerizable monomers may be further used . Specific examples of other copolymerizable monomers include acrylonitrile, styrene, glycidyl (meth)acrylate, and vinyl acetate. The mixing ratio of other copolymerizable monomers is preferably 0.1 to 9.9 parts by mass, and preferably 0.5 to 8 parts by mass, out of 100 parts by mass of all monomers copolymerized.
黏著劑組成物之黏彈性特性主要依據高分子鏈之分子量、分子量分布或分子結構之存在量,特別藉由分子量而決定,故使用於本發明之(甲基)丙烯酸系聚合物之分子量(重量平均分子量:Mw)以80萬~200萬為佳,以90萬~190萬為較佳。若為如此範圍,可得到所期待的黏彈性特性,且成為容易處理之黏度。 且,重量平均分子量為藉由凝膠滲透層析法(GPC)所測定的標準聚苯乙烯換算值。The viscoelastic properties of the adhesive composition mainly depend on the molecular weight of the polymer chain, the molecular weight distribution or the amount of molecular structure present, especially determined by the molecular weight, so the molecular weight (weight) of the (meth)acrylic polymer used in the present invention The average molecular weight: Mw) is preferably 800,000 to 2 million, preferably 900,000 to 1.9 million. Within such a range, the expected viscoelastic properties can be obtained, and the viscosity becomes easy to handle. In addition, the weight average molecular weight is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
如此(甲基)丙烯酸系聚合物,可經由一般自由基共聚合過程而製造。 對於本發明之聚合物的聚合方法並無特別限定,可藉由溶液聚合法、光聚合法、本體聚合法、懸浮聚合法、乳化聚合法等一般方法而製造。此等之中,亦以溶液聚合法由生產性之觀點來看為佳,特別在將單體進行均勻混合的狀態下添加起始劑者為佳。此時,聚合溫度為50~140℃,反應時間為1~24小時為佳。In this way, the (meth)acrylic polymer can be produced through a general radical copolymerization process. The polymerization method of the polymer of the present invention is not particularly limited, and can be produced by a general method such as a solution polymerization method, a photopolymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, the solution polymerization method is also preferable from the viewpoint of productivity, and it is particularly preferable to add an initiator in a state where the monomers are uniformly mixed. At this time, the polymerization temperature is 50 to 140°C, and the reaction time is preferably 1 to 24 hours.
作為起始劑之具體例子,可舉出二-tert-丁基過氧化物、苯甲醯基過氧化物、月桂基過氧化物、tert-丁基過氧苯甲酸酯、異丙苯過氧化氫、二異丙基過氧二碳酸酯、二丙基過氧二碳酸酯、tert-丁基過氧新癸酸酯、tert-丁基過氧新戊酸酯、(3,5,5-三甲基己醯基)過氧化物等過氧化物;偶氮二異丁腈、偶氮二戊腈、1,1’-偶氮雙(環己烷-1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯)、2,2’-偶氮雙(2-羥基甲基丙腈)等偶氮二化合物或高分子偶氮聚合起始劑等,這些可單獨使用,亦可組合2種以上後使用。 且,起始劑通常對於單體之合計量100質量份而言,使用0.01~10質量份之量。Specific examples of the initiator include di-tert-butyl peroxide, benzoyl peroxide, lauryl peroxide, tert-butyl peroxybenzoate, and cumene peroxide Hydrogen oxide, diisopropyl peroxy dicarbonate, dipropyl peroxy di carbonate, tert-butyl peroxy neodecanoate, tert-butyl peroxy pivalate, (3,5,5 -Trimethylhexyl) peroxides and other peroxides; azobisisobutyronitrile, azobisvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2, 2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) and other azobis compounds or high molecular azo polymerization initiators, etc. It can be used alone or in combination of two or more. In addition, the initiator is generally used in an amount of 0.01 to 10 parts by mass for 100 parts by mass of the total amount of monomers.
(B)嵌段化異氰酸酯矽烷化合物 (B)成分的嵌段化異氰酸酯矽烷化合物為作為黏著劑組成物的接著性改質劑而作用之成分,本發明中,以具有下述式(1)所示嵌段化異氰酸酯基的有機矽化合物為佳。 且,除嵌段化異氰酸酯矽烷單體以外,因水解性矽基部分經一部水解的結構,或進一步進行分子間縮合成為寡聚物的部分水解縮合物亦可表現同樣性能,故可作為本發明之接著性改質成分使用。(B) Blocked isocyanate silane compound (B) The component-blocked isocyanate silane compound is a component that acts as an adhesive modifier of the adhesive composition. In the present invention, a silicone having a block-isocyanate group represented by the following formula (1) is used The compound is preferred. In addition to the blocked isocyanate silane monomer, the partially hydrolyzed condensate of the hydrolyzable silicon-based part undergoing a partial hydrolysis or further intermolecular condensation to an oligomer can also exhibit the same performance, so it can be used as this Inventive use of modified ingredients.
式(1)中,R1 各獨立表示碳原子數1~8的烷基,L表示2價連結基,X表示-O-或-NR2 -,Y表示氫原子或1價的有機基,R2 表示氫原子、碳原子數1~8的烷基或與Y鍵結而可形成環結構的基,m表示1~3的整數,較佳為表示3。In formula (1), R 1 independently represents an alkyl group having 1 to 8 carbon atoms, L represents a divalent linking group, X represents -O- or -NR 2 -, and Y represents a hydrogen atom or a monovalent organic group, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a group bonded to Y to form a ring structure, and m represents an integer of 1 to 3, preferably 3.
R1 的碳原子數1~8的烷基可為直鏈狀、支鏈狀、環狀中任一種,作為該具體例子,可舉出甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、tert-丁基、n-戊基、新戊基、n-己基、環己基、n-庚基、n-辛基等,其中以甲基、乙基為佳。The alkyl group having 1 to 8 carbon atoms of R 1 may be linear, branched, or cyclic. Examples of the specific examples include methyl, ethyl, n-propyl, and isopropyl. , N-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, etc., with methyl and ethyl as good.
作為L的2價連結基之具體例子,可舉出伸烷基、-O-、-S-、-NR-、CO-、-COO-、-NRCO-、-SO2 -及這些組合所成者。其中,R表示氫原子或碳原子數1~4的烷基,以氫原子為佳。且,作為烷基,於上述所例示的烷基之中,可舉出碳原子數1~4者,此等中,由製造有機矽化合物時的原料之獲得容易性來看,作為二價的連結基,以-(CH2 )n -(n為1~10,以1~6為佳,較佳為1~4的整數)所示伸烷基,或此-(CH2 )n -之中1個以上伸甲基單位由-O-、-S-、 -NH-、-CO-及-COO-所取代的基為佳,以-(CH2 )3 -(三伸甲基)為較佳。Specific examples of the divalent linking group of L include alkylene, -O-, -S-, -NR-, CO-, -COO-, -NRCO-, -SO 2 -and combinations of these By. Among them, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Moreover, as the alkyl group, among the alkyl groups exemplified above, those having 1 to 4 carbon atoms can be mentioned. Among these, from the viewpoint of the ease of obtaining raw materials when manufacturing an organosilicon compound, as a divalent The linking group is represented by -(CH 2 ) n -(n is 1~10, preferably 1~6, preferably an integer of 1~4), or this -(CH 2 ) n- It is preferred that more than one methylene unit in the group is substituted by -O-, -S-, -NH-, -CO-, and -COO-, with -(CH 2 ) 3 -(trimethylidene) as Better.
式(1)中之X雖為-O-或-NR2 -,其為形成嵌段化異氰酸酯矽烷化合物之保護基的一部分之基,因藉由加熱會脫離,故非特別限制者。 對於X之-NR2 -,R2 表示氫原子、碳原子數1~8的烷基或與Y鍵結而可形成環結構之基。 作為R2 的碳原子數1~8的烷基,可舉出與在上述R1 所例示的基之相同者,但其中亦以直鏈或分支的碳原子數1~5的烷基為佳,以甲基或乙基為較佳。 對於-NR2 -,R2 表示與Y鍵結而可形成環結構之基時,-NR2 -以與式(1)中之Y形成雜環結構者為佳。作為如此雜環結構中之雜原子,以含有2個以上氮原子者為佳,以含有2個氮原子者為較佳。作為雜環結構,以5員環或6員環結構為佳,以5員環結構為較佳。Although X in the formula (1) is -O- or -NR 2 -, it is a group that forms part of the protective group of the blocked isocyanate silane compound, and it is detached by heating, so it is not particularly limited. For -NR 2 -of X, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group bonded to Y to form a ring structure. The alkyl group having 1 to 8 carbon atoms in R 2 may be the same as the group exemplified in R 1 above, but a linear or branched alkyl group having 1 to 5 carbon atoms is also preferred. , Preferably methyl or ethyl. Regarding -NR 2 -, when R 2 represents a group bonded to Y to form a ring structure, -NR 2 -preferably forms a heterocyclic structure with Y in formula (1). As a hetero atom in such a heterocyclic structure, those containing two or more nitrogen atoms are preferred, and those containing two nitrogen atoms are preferred. As the heterocyclic structure, a 5-membered ring or 6-membered ring structure is preferred, and a 5-membered ring structure is preferred.
於式(1)中之Y雖為氫原子或1價有機基,但其為形成嵌段化異氰酸酯矽烷化合物的保護基之一部分的基,因藉由加熱可進行脫離,故並非特別限制者。 作為Y的1價有機基之具體例子,可舉出可具有碳原子數1~20的取代基之1價烴基、-OH基(但,除X為-O-之情況以外)、N=R5 (R5 表示可由碳原子數6~20的芳基所取代的碳原子數1~10的亞烷基)等。 作為上述碳原子數1~20的1價烴基,直鏈狀、支鏈狀、環狀中任一種皆可,可舉出碳原子數1~20的烷基、碳原子數6~20的芳基、碳原子數7~20的芳烷基等。 作為上述烷基的具體例子,除在R1 所例示的基以外,亦可舉出n-壬基、n-癸基、十一烷基、十二烷基、十三烷基、二十烷基等。 作為上述芳基的具體例子,可舉出苯基、萘基等。 作為上述芳烷基的具體例子,可舉出苯甲基、苯基乙基等。 又,這些基為,該氫原子的至少一部分可由其他取代基所取代,作為其他取代基,可舉出羧基、酯基、羥基等。 R5 中作為可由碳原子數6~20的芳基或雜芳基所取代的碳原子數1~10的亞烷基,可為直鏈狀、支鏈狀、環狀中任一種,作為該具體例子,可舉出亞甲基、苯基亞甲基、二苯基亞甲基、亞乙基、亞丙基、丙烷-2-亞基、丁亞基、丁烷-2-亞基、亞戊基、4-甲基戊烷-2-亞基、亞己基、環亞己基、亞庚基、亞辛基、亞壬基、亞癸基等。 作為碳原子數6~20的雜芳基之具體例子,可舉出吡咯-1-基、1H-吡咯-2-基、咪唑-1-基、咪唑-2-基、吡唑-1-基、吡唑-3-基、吡啶-2-基、吡啶-3-基等。Although Y in formula (1) is a hydrogen atom or a monovalent organic group, it is a group that forms part of the protective group of the blocked isocyanate silane compound, and can be detached by heating, so it is not particularly limited. Specific examples of the monovalent organic group of Y include a monovalent hydrocarbon group that may have a substituent of 1 to 20 carbon atoms, a -OH group (however, except when X is -O-), N=R 5 (R 5 represents an alkylene group having 1 to 10 carbon atoms which may be substituted by an aryl group having 6 to 20 carbon atoms), etc. The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms and an aromatic group having 6 to 20 carbon atoms. Group, aralkyl group having 7 to 20 carbon atoms, etc. As specific examples of the above-mentioned alkyl groups, in addition to the groups exemplified in R 1 , n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, eicosane Base etc. Specific examples of the aryl group include phenyl, naphthyl and the like. Specific examples of the aralkyl group include benzyl group, phenylethyl group and the like. In addition, these groups are such that at least a part of the hydrogen atom may be substituted with other substituents. Examples of the other substituents include carboxyl groups, ester groups, and hydroxyl groups. R 5 may be any one of linear, branched, or cyclic as an alkylene group having 1 to 10 carbon atoms which may be substituted by an aryl group or a heteroaryl group having 6 to 20 carbon atoms. Specific examples include methylene, phenylmethylene, diphenylmethylene, ethylene, propylene, propane-2-ylidene, butylene, butane-2-ylidene, and pentylene. Group, 4-methylpentane-2-ylene, hexylene, cyclohexylene, heptylene, octylene, nonylene, decylene, etc. Specific examples of the heteroaryl group having 6 to 20 carbon atoms include pyrrol-1-yl, 1H-pyrrol-2-yl, imidazol-1-yl, imidazol-2-yl, and pyrazol-1-yl , Pyrazol-3-yl, pyrid-2-yl, pyrid-3-yl, etc.
上述式(1)所示嵌段化異氰酸酯矽烷化合物中特別以下述式(2)或(3)所示者為佳。Among the blocked isocyanate silane compounds represented by the above formula (1), those represented by the following formula (2) or (3) are particularly preferred.
(式中,R1 、R2 、Y及m表示與上述相同意思,R3 及R4 各獨立表示氫原子或1價有機基,但R3 與R4 或R2 與Y彼此連結可形成環結構)。 (In the formula, R 1 , R 2 , Y and m represent the same meaning as above, R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group, but R 3 and R 4 or R 2 and Y may form Ring structure).
作為上述R3 及R4 的1價有機基,可舉出碳原子數1~20的1價烴基、碳數6~20的雜芳基。 作為碳原子數1~20的1價烴基之具體例子,可舉出與在上述Y所例示的基相同者,但以碳原子數1~20的烷基、碳數6~20的芳基為佳,作為這些具體例子亦可舉出與上述同樣者。 作為碳原子數6~20的雜芳基,可舉出與上述R5 所例示基的相同者。 作為R3 與R4 彼此連結而形成的環結構,可舉出環戊烷環、環己烷環等。 且,這些烴基或雜芳基可具有取代基。作為取代基之具體例子,可舉出羧基、羥基、酯基等。 作為R3 -亞甲基-R4 所示基,可舉出在上述R5 所例示的亞烷基,其中亦以二苯基亞甲基、丙烷-2-亞基、丁烷-2-亞基、4-甲基戊烷-2-亞基、環亞己基為佳。Examples of the monovalent organic group for R 3 and R 4 include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a heteroaryl group having 6 to 20 carbon atoms. Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same as those exemplified in Y above, but the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are Preferably, as these specific examples, the same ones as described above can also be mentioned. Examples of the heteroaryl group having 6 to 20 carbon atoms are the same as those exemplified in the above R 5 . Examples of the ring structure formed by connecting R 3 and R 4 to each other include a cyclopentane ring and a cyclohexane ring. Furthermore, these hydrocarbon groups or heteroaryl groups may have a substituent. Specific examples of the substituent include carboxyl groups, hydroxyl groups, and ester groups. Examples of the group represented by R 3 -methylene-R 4 include the alkylene groups exemplified in R 5 above, among which diphenylmethylene, propane-2-ylidene, butane-2- Subunits, 4-methylpentane-2-ylidene, and cyclohexylene are preferred.
作為R2 及Y的具體例子,雖與上述相同,但其中亦以與這些彼此鍵結的氮原子同時形成環結構者為佳。作為環結構,以5員環或6員環為佳,以5員環為較佳。 又,該環結構以具有2個氮原子者為佳,以咪唑環、吡唑環、1,2,3-***環、1,2,4-***環為較佳,以吡唑環為更一層佳。 且,上述環結構亦可具有碳原子數1~20的烷基、碳原子數6~20的芳基、羧基、羥基、酯基、氧代基(=O)等取代基。 作為較佳環結構,可舉出下述者,但並未限定於此等。Although specific examples of R 2 and Y are the same as described above, it is also preferable that they form a ring structure simultaneously with these nitrogen atoms bonded to each other. As the ring structure, a 5-member ring or a 6-member ring is preferred, and a 5-member ring is preferred. In addition, the ring structure is preferably one having 2 nitrogen atoms, preferably imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, preferably pyrazole ring Better for the better. Furthermore, the ring structure may have substituents such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxyl group, a hydroxyl group, an ester group, and an oxo group (=O). As a preferable ring structure, the following are mentioned, but it is not limited to these.
(B)作為成分之嵌段化異氰酸酯矽烷化合物的較佳具體例子,可舉出下述化合物,但並未限定於此等。(B) Preferred specific examples of the blocked isocyanate silane compound as a component include the following compounds, but are not limited thereto.
在本發明之黏著劑組成物中,對於(A)成分100質量份,(B)成分的含有量為0.001~10質量份。 (B)成分的含有量若未達下限值時,不會表現所望接著性改質效果,若超過上限值時,效果呈現飽和,除降低成本效益以外,有著原先矽烷偶合劑所具有的密著性提高效果之影響變大,且初期密著性過高的疑慮。In the adhesive composition of the present invention, the content of (B) component is 0.001 to 10 parts by mass with respect to 100 parts by mass of component (A). (B) If the content of the component does not reach the lower limit, the desired adhesive modification effect will not be exhibited. If it exceeds the upper limit, the effect will be saturated. In addition to reducing cost efficiency, it has the original silane coupling agent. There is a concern that the effect of improving the adhesiveness becomes larger and the initial adhesiveness is too high.
[黏著劑組成物] 本發明之黏著劑組成物雖為作為必須成分而含有上述(A)、(B)成分者,但進一步含有(C)多官能***聯劑者為佳。該(C)成分之多官能***聯劑因與(A)成分所具有羧基或羥基等進行反應而成為提高黏著劑之凝集力的角色。 (C)成分之含有量雖無特別限定,但若考慮到適度地提高黏著劑之凝集力,對於(A)成分100質量份而言,以0.01~10質量份為佳,以0.05~5質量份為佳。[Adhesive composition] Although the adhesive composition of the present invention contains the aforementioned components (A) and (B) as an essential component, it is preferable to further contain (C) a multifunctional crosslinking agent. The multifunctional crosslinking agent of the component (C) reacts with the carboxyl group or the hydroxyl group of the component (A), thereby becoming a role of improving the cohesive force of the adhesive. (C) The content of the component is not particularly limited, but if the cohesive force of the adhesive is appropriately increased, it is preferably 0.01 to 10 parts by mass, and 0.05 to 5 parts for 100 parts by mass of the component (A). Servings are better.
多官能***聯劑可舉出異氰酸酯系、環氧系、氮雜環丙烷系、金屬螯合物系交聯劑等,其若考慮到使用容易性,以異氰酸酯系交聯劑為佳。 作為異氰酸酯系交聯劑,可舉出於1分子中具有2個異氰酸酯基之聚異氰酸酯化合物,作為該具體例子,可舉出甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、六伸甲基二異氰酸酯、異構體二異氰酸酯、四甲基二甲苯二異氰酸酯、萘二異氰酸酯、這些與三羥甲基丙烷等多元醇之反應物(三羥甲基丙烷甲苯二異氰酸酯加成物等)等,這些可單獨使用,亦可組合2種以上使用。Examples of the multifunctional crosslinking agent include isocyanate-based, epoxy-based, aziridine-based, and metal chelate-based crosslinking agents. In consideration of ease of use, isocyanate-based crosslinking agents are preferred. Examples of the isocyanate-based crosslinking agent include polyisocyanate compounds having two isocyanate groups in one molecule. Examples of the specific examples include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, and hexamethylene. Methyl diisocyanate, isomer diisocyanate, tetramethyl xylene diisocyanate, naphthalene diisocyanate, these reactants with trimethylolpropane and other polyols (trimethylolpropane toluene diisocyanate adduct, etc.) These can be used alone or in combination of two or more.
作為環氧系交聯劑,可舉出於1分子中具有2個以上縮水甘油基之聚縮水甘油基化合物,作為該具體例子,可舉出乙二醇二縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、N,N,N’,N’-四縮水甘油基乙二胺、甘油二縮水甘油基醚、甘油三縮水甘油基醚、聚甘油聚縮水甘油基醚、山梨醇系聚縮水甘油基醚等,這些可單獨使用,亦可組合2種以上使用。Examples of the epoxy-based crosslinking agent include polyglycidyl compounds having two or more glycidyl groups in one molecule. As specific examples thereof, ethylene glycol diglycidyl ether and trimethylol groups can be cited. Propane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, sorbitol series Polyglycidyl ether and the like can be used alone or in combination of two or more.
作為氮雜環丙烷系交聯劑,可舉出於1分子中具有2個以上氮丙啶基之聚氮雜環丙烷化合物,作為該具體例子,可舉出N,N’-甲苯-2,4-雙(1-氮雜環丙烷碳氧化物)、N,N’-二苯基甲烷-4,4’-雙(1-氮雜環丙烷碳氧化物)、三伸乙基三聚氰胺、雙異脯胺醯基-1-(2-甲基氮雜環丙烷)、三-1-氮丙啶膦氧化物等,這些可單獨使用,亦可組合2種以上使用。 作為金屬螯合物系交聯劑的具體例子,可舉出鋁、鐵、鋅、錫、鈦、銻、鎂、釩等多價金屬配位於乙醯丙酮或乙醯乙酸乙酯的化合物等,這些可單獨使用,亦可組合2種以上使用。Examples of the aziridine-based crosslinking agent include polyaziridine compounds having two or more aziridine groups in one molecule. As specific examples thereof, N,N'-toluene-2, 4-bis(1-aziridine carbon oxide), N,N'-diphenylmethane-4,4'-bis(1-aziridine carbon oxide), triethylidene melamine, bis Isoprolinamide-1-(2-methylaziridine), tri-1-aziridinephosphine oxide, etc., these can be used alone or in combination of two or more kinds. Specific examples of the metal chelate-based crosslinking agent include compounds in which polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and vanadium are coordinated with acetone or ethyl acetate. These can be used alone or in combination of two or more.
於本發明之黏著劑組成物中可添加欲調節黏著性能的(D)黏著性賦予樹脂。 (D)成分之含有量若非特別限定者,由可充分地發揮添加效果之同時,亦可防止凝集性之降低的觀點來看,對於(A)成分100質量份而言以1~100質量份為佳,以5~90質量份為較佳。 作為黏著性賦予樹脂之具體例子,可舉出(氫化)烴系樹脂、(氫化)松香樹脂、(氫化)松香酯樹脂、(氫化)萜烯樹脂、(氫化)萜烯酚樹脂、聚合松香樹脂、聚合松香酯樹脂等,這些可單獨使用,亦可組合2種以上使用。To the adhesive composition of the present invention, (D) adhesiveness-imparting resin whose adhesive properties are to be adjusted can be added. (D) If the content of the component is not particularly limited, from the viewpoint that the addition effect can be sufficiently exerted and the reduction of the cohesiveness can be prevented, the amount of (A) component is 1 to 100 parts by mass Preferably, 5 to 90 parts by mass is better. Specific examples of the adhesiveness-imparting resin include (hydrogenated) hydrocarbon resins, (hydrogenated) rosin resins, (hydrogenated) rosin ester resins, (hydrogenated) terpene resins, (hydrogenated) terpene phenol resins, and polymerized rosin resins. , Polymerized rosin ester resin, etc. These can be used alone or in combination of two or more.
且,在本發明之黏著劑組成物中,除上述各成分以外,在不損害本發明之目的的範圍下,視必要可將可塑劑、塗平劑等低分子聚體或環氧樹脂及硬化劑等作為追加成分而添加,又可將紫外線安定劑、抗氧化劑、除色劑、補強劑、填充劑、消泡劑、界面活性劑等配合一般目的而添加。In addition, in the adhesive composition of the present invention, in addition to the above-mentioned components, a low-molecular polymer such as a plasticizer, a coating agent, or an epoxy resin can be hardened and cured as necessary without impairing the purpose of the present invention. Agents and the like are added as additional components, and ultraviolet stabilizers, antioxidants, color removers, reinforcing agents, fillers, defoamers, surfactants, and the like can be added for general purposes.
本發明之黏著劑組成物,例如可將上述必須成分及任意成分以通常方法而混合。 混合條件並無特別限定,以在10~150℃的10分~10小時為佳。此時,上述(B)成分的嵌段化異氰酸酯矽烷化合物,在使(A)成分的丙烯酸系聚合物進行聚合後,即使在配合步驟中添加,亦與在(A)成分的丙烯酸系聚合物之製造步驟中添加顯示相同效果。 又,(C)成分之多官能***聯劑對於黏著劑組成物之配合過程,於幾乎不產生交聯劑之官能基交聯反應的情況時可均勻地塗布。於塗布後,經由乾燥及熟成過程後可形成交聯結構,可得到具有彈性且凝集力強之黏著劑層。For the adhesive composition of the present invention, for example, the above-mentioned essential components and optional components can be mixed by a usual method. The mixing condition is not particularly limited, but it is preferably 10 minutes to 10 hours at 10 to 150°C. In this case, the blocked isocyanate silane compound of the component (B), after polymerizing the acrylic polymer of the component (A), is added to the acrylic polymer of the component (A) even if it is added in the compounding step Add the same effect in the manufacturing step. In addition, the compounding process of the multifunctional crosslinking agent of the component (C) with the adhesive composition can be applied evenly when the functional group crosslinking reaction of the crosslinking agent hardly occurs. After coating, a cross-linked structure can be formed through drying and aging processes, and an adhesive layer with elasticity and strong cohesive force can be obtained.
將如此所得之本發明的黏著劑組成物,塗布於玻璃板、塑質薄膜、紙等被接著體,以在25~150℃於20~90%RH進行5分鐘~5小時為佳,較佳為在40~80℃於25~60%RH進行10分鐘~3小時進行硬化而可形成黏著劑層。The adhesive composition of the present invention thus obtained is applied to adherends such as glass plates, plastic films, paper, etc., preferably at 25 to 150°C and 20 to 90% RH for 5 minutes to 5 hours, preferably The adhesive layer can be formed for curing at 40~80℃ and 25~60%RH for 10 minutes~3 hours.
本發明之黏著劑組成物為,充分地除去於內部會誘發出揮發成分、反應殘留物等氣泡的成分後再使用為佳。 在交聯密度或分子量過度低,黏著劑層的彈性率過低時,在高溫狀態下存在於玻璃板等被接著體與黏著劑層之間的小氣泡會變大,於黏著劑層的內部形成有散射體。又,將彈性率過度大的黏著劑層長期間使用時,藉由過度交聯反應,於黏著劑層(薄片)之末端部位上產生有剝離顯像。The adhesive composition of the present invention is preferably used after sufficiently removing components that induce bubbles such as volatile components and reaction residues inside. When the crosslinking density or molecular weight is excessively low, and the elasticity of the adhesive layer is too low, small bubbles existing between the adherend such as a glass plate and the adhesive layer at a high temperature will become larger and become inside the adhesive layer A scatterer is formed. In addition, when an adhesive layer having an excessively high elastic modulus is used for a long period of time, a peeling image is generated on the end portion of the adhesive layer (sheet) by excessive cross-linking reaction.
又,考慮到黏著劑層之凝集力與接著耐久性等的平衡時,黏著劑層的交聯密度以5~95質量%為佳,以7~93質量%為較佳。交聯密度為藉由一般已知的黏著劑之凝膠含量測定法,將形成未溶解於溶劑的交聯結構之部分的量以質量%方式獲得之值。In addition, when considering the balance between the cohesive force of the adhesive layer and the adhesion durability, the crosslink density of the adhesive layer is preferably 5 to 95% by mass, preferably 7 to 93% by mass. The cross-link density is a value obtained by mass% of the amount of a portion that forms a cross-linked structure that is not dissolved in a solvent by the gel content measurement method of a generally known adhesive.
[黏著偏光板] 本發明之黏著偏光板為具有偏光薄膜或偏光元件,與貼合於該偏光薄膜或偏光元件的單面或雙面上的由上述黏著劑組成物所形成的黏著劑層者。 對於構成偏光板的偏光薄膜或偏光元件並非特別限定者,可適宜地選自過去公知者而使用。 作為偏光薄膜的具體例子,可舉出於含有聚乙烯醇系樹脂所成的薄膜中使碘或異色性染料等偏光成分含有並延伸而得之薄膜等。偏光薄膜之厚度亦未被限定,可採用一般厚度。 作為上述聚乙烯醇系樹脂,可使用聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯縮醛、乙烯・乙酸乙烯基共聚物之鹼化物等。[Adhesive polarizer] The adhesive polarizing plate of the present invention includes a polarizing film or a polarizing element, and an adhesive layer formed of the above adhesive composition attached to one or both sides of the polarizing film or the polarizing element. The polarizing film or polarizing element constituting the polarizing plate is not particularly limited, and can be appropriately selected from those known in the past and used. As a specific example of the polarizing film, a film made of a polyvinyl alcohol-based resin in which polarizing components such as iodine or a heterochromic dye are contained and stretched can be cited. The thickness of the polarizing film is also not limited, and a general thickness can be used. As the polyvinyl alcohol-based resin, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, an alkalizate of ethylene/vinyl acetate copolymer, and the like can be used.
對於本發明,對於偏光薄膜形成黏著劑層的方法並無特別限制。 例如於偏光薄膜表面上使用直接棒等塗布等對黏著劑組成物進行塗布並使其乾燥的方法,一旦將黏著劑組成物塗布於剝離性基材表面上並經乾燥後,將形成於該剝離性基材表面的黏著劑層轉印於偏光薄膜表面上,再進行熟成的方法等可舉出。此時,乾燥已在25~150℃並於20~90%RH下進行5分鐘~5小時為佳,熟成以在25~150℃並於20~90%RH下進行5分鐘~5小時為佳。For the present invention, the method for forming the adhesive layer of the polarizing film is not particularly limited. For example, a method of coating and drying the adhesive composition on the surface of the polarizing film using a direct bar or the like, once the adhesive composition is applied on the surface of the peelable substrate and dried, it will be formed on the peeling The adhesive layer on the surface of the flexible substrate is transferred onto the surface of the polarizing film, and then the method of aging is mentioned. At this time, drying is preferably performed at 25 to 150°C and 20 to 90% RH for 5 minutes to 5 hours, and ripening is preferably performed at 25 to 150°C and 20 to 90% RH for 5 minutes to 5 hours .
黏著劑層的厚度亦並未特別限制,但若考慮到欲適切地表現對黏著劑層所要求的效果,以0.01~100μm為佳,以0.1~50μm為較佳。The thickness of the adhesive layer is also not particularly limited, but if considering the desired effect on the adhesive layer, 0.01 to 100 μm is preferred, and 0.1 to 50 μm is preferred.
且,對於具有如此所得之本發明的黏著劑層之偏光薄膜(黏著偏光板),可層合一種以上的提供保護層、反射層、相位差板、光視野角補償薄膜、亮度提高薄膜等追加功能之層。Furthermore, for the polarizing film (adhesive polarizing plate) having the adhesive layer of the present invention thus obtained, more than one type of protective layer, reflective layer, retardation plate, light viewing angle compensation film, brightness enhancement film, etc. can be laminated and added Function layer.
特別於具有黏著劑層的偏光薄膜之雙面上形成:三乙醯纖維素等纖維素系薄膜;聚碳酸酯薄膜;聚乙烯對苯二甲酸酯薄膜等聚酯系薄膜;聚醚碸系薄膜;聚乙烯、聚丙烯、如這些共聚物的聚烯烴系薄膜等保護薄膜經層合的多層薄膜等為佳。此時,這些保護薄膜之厚度亦無特別限定,採用一般的厚度即可。Specially formed on both sides of polarizing film with adhesive layer: cellulose-based films such as triacetyl cellulose; polycarbonate films; polyester-based films such as polyethylene terephthalate films; polyether satin Films; multi-layered films such as polyethylene, polypropylene, and polyolefin-based films such as these copolymers are preferably laminated. At this time, the thickness of these protective films is also not particularly limited, and a general thickness may be used.
[液晶顯示裝置] 本發明之黏著偏光板可應用於一般的所有液晶顯示裝置,該液晶面板的種類並無特別限定。特別以具備將本發明之黏著偏光板貼合在於一對玻璃基板間封入液晶的液晶單元之單面或雙面的液晶面板之液晶顯示裝置為佳。[Liquid crystal display device] The adhesive polarizing plate of the present invention can be applied to all general liquid crystal display devices, and the type of the liquid crystal panel is not particularly limited. In particular, a liquid crystal display device including a single-sided or double-sided liquid crystal panel in which a liquid crystal cell in which liquid crystal cells are sealed with a polarizing plate of the present invention bonded between a pair of glass substrates is preferably used.
本發明之黏著劑組成物為,除上述偏光薄膜以外,可使用於產業用薄片,特別可使用於反射薄片、結構用黏著薄片、照片用黏著薄片、車道顯示用黏著薄片、光學用黏著製品、電子零件用等種種用途上。 又,可適用於多層結構之層合製品,換言之,亦可使用於一般商業用黏著薄片製品、醫療貼片、加熱活性用等作用概念相同的應用領域中。 [實施例]The adhesive composition of the present invention can be used for industrial sheets in addition to the above-mentioned polarizing film, in particular, for reflective sheets, adhesive sheets for structures, adhesive sheets for photographs, adhesive sheets for lane display, adhesive products for optics, For various purposes such as electronic parts. In addition, it can be applied to a laminated product with a multi-layer structure. In other words, it can also be used in an application field having the same action concept as general commercial adhesive sheet products, medical patches, and heating activity. [Example]
以下舉出合成例、實施例及比較例進一步具體說明本發明,但本發明並未限定於此等實施例者。Hereinafter, the present invention will be described in more detail by using synthesis examples, examples, and comparative examples, but the present invention is not limited to those examples.
[1](甲基)丙烯酸系聚合物之合成 [合成例1] 於具備攪拌機、迴流冷卻器、滴液漏斗及溫度計之1L可分離燒瓶中,放入n-丁基丙烯酸酯(BA)98.1g、丙烯酸(AA)0.6g、2-羥基乙基甲基丙烯酸酯(2-HEMA)1.3g,作為溶劑裝入乙酸乙酯100g並使其溶解。其後,欲除去氧而進行1小時的氮氣起泡,將反應系統中由氮氣取代而保持於62℃。於其中,一邊攪拌一邊投入作為聚合起始劑的偶氮二異丁腈0.03g,在62℃進行8小時反應後得到(甲基)丙烯酸系聚合物(A-1)。[1] Synthesis of (meth)acrylic polymers [Synthesis Example 1] In a 1L separable flask equipped with a stirrer, reflux cooler, dropping funnel and thermometer, put 98.1g of n-butyl acrylate (BA), 0.6g of acrylic acid (AA), 2-hydroxyethyl methacrylate (2-HEMA) 1.3g. 100g of ethyl acetate was charged as a solvent and dissolved. Thereafter, nitrogen gas was bubbled for 1 hour to remove oxygen, and the reaction system was replaced with nitrogen gas and maintained at 62°C. To this, 0.03 g of azobisisobutyronitrile was added as a polymerization initiator while stirring, and the reaction was carried out at 62° C. for 8 hours to obtain a (meth)acrylic polymer (A-1).
[2]黏著劑組成物的調製及黏著劑層的形成 [實施例1] 將在合成例1所得之(甲基)丙烯酸系聚合物(A-1)、以下述B-1所示化合物、(C)三羥甲基丙烷甲苯二異氰酸酯加成物(TDI)以表1所示的配合組成進行混合而調製出黏著劑組成物。[2] Preparation of adhesive composition and formation of adhesive layer [Example 1] The (meth)acrylic polymer (A-1) obtained in Synthesis Example 1, the compound shown in B-1 below, and (C) trimethylolpropane toluene diisocyanate adduct (TDI) are shown in Table 1. The composition shown is mixed to prepare an adhesive composition.
[實施例2~7、比較例1~6] 將(B)成分的配合量或種類變更為如表1所示以外,與實施例1同樣地調製出黏著劑組成物。[Examples 2-7, Comparative Examples 1-6] An adhesive composition was prepared in the same manner as in Example 1 except that the blending amount or type of component (B) was changed as shown in Table 1.
且,表1中的簡稱如以下所示。 B-1:上式(4-a)所示矽烷化合物 B-2:上式(4-b)所示矽烷化合物 B-3:上式(8-a)所示矽烷化合物 B-4:上式(8-b)所示矽烷化合物 B-5:上式(8-a)所示矽烷化合物 B-6:上式(8-b)所示矽烷化合物 B’-1:環氧丙氧基丙基三甲氧基矽烷(信越化學工業(股)製、KBM-403) B’-2:下式所示矽烷化合物In addition, the abbreviations in Table 1 are as follows. B-1: Silane compound represented by the above formula (4-a) B-2: Silane compound represented by the above formula (4-b) B-3: Silane compound represented by the above formula (8-a) B-4: Silane compound represented by the above formula (8-b) B-5: Silane compound represented by the above formula (8-a) B-6: Silane compound represented by the above formula (8-b) B’-1: Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) B’-2: Silane compound represented by the following formula
B’-3:兩末端烷氧基矽基變性PO型聚醚化合物(Kaneka (股)製、Sail SAT10) TDI:三羥甲基丙烷之甲苯二異氰酸酯加成物B’-3: Modified PO type polyether compound with alkoxysilyl groups at both ends (Kaneka Co., Ltd., Sail SAT10) TDI: toluene diisocyanate adduct of trimethylolpropane
將在上述各實施例及比較例所得之黏著劑組成物,塗布於脫模紙並乾燥後,得到25μm之均勻的黏著劑層。將如此製造的黏著劑層,於厚度185μm之碘系偏光板上進行黏著加工後,切斷所得之偏光板,使用於各評估。 對於所製造的偏光板之試片,經由以下所示的評估試驗方法,對於耐久性、玻璃接著性、再加工性、高溫下及高溫多濕下的接著力之變化進行評估。結果如表2、3所示。The adhesive composition obtained in each of the above examples and comparative examples was applied to release paper and dried to obtain a uniform adhesive layer of 25 μm. The adhesive layer thus produced was subjected to adhesion processing on an iodine-based polarizing plate with a thickness of 185 μm, and the resulting polarizing plate was cut and used for each evaluation. The test piece of the manufactured polarizing plate was evaluated for changes in durability, glass adhesion, reworkability, adhesion at high temperature and high temperature and humidity under the evaluation test method shown below. The results are shown in Tables 2 and 3.
評估試驗 (1)耐久性 將塗布有黏著劑的偏光板(90mm×170mm)於玻璃基板(110mm×190mm×0.7mm)上在兩面以光學吸收軸成為交叉狀態進行貼合後得到試驗片。此時,所加入的壓力約5kgf/cm2 ,為了不要產生氣泡或異物而在潔淨室中進行作業。 欲評估該試驗片之耐濕耐熱特性,在60℃/90%相對濕度之條件下放置1,000小時後,確認氣泡或剝離之生成有無。耐熱特性為在80℃/30%相對濕度下放置1,000小時後,觀察氣泡或剝離的情況。且,在評估試驗片狀態前,在室溫(25℃)下靜置24小時。結果如表2所示。 對於耐久性評估之評估基準,如以下所示。 ○:無氣泡或剝離顯像 △:稍有氣泡或剝離顯像 ×:有多數氣泡或剝離顯像Evaluation test (1) Durability A polarizing plate (90 mm×170 mm) coated with an adhesive was attached to a glass substrate (110 mm×190 mm×0.7 mm) on both sides with the optical absorption axis in a crossed state to obtain a test piece. At this time, the added pressure is about 5 kgf/cm 2 , and work is performed in a clean room so as not to generate bubbles or foreign substances. To evaluate the moisture resistance and heat resistance characteristics of the test piece, after standing for 1,000 hours under the condition of 60°C/90% relative humidity, confirm the presence or absence of bubbles or peeling. The heat resistance characteristic is that after standing at 80°C/30% relative humidity for 1,000 hours, bubbles or peeling is observed. And, before evaluating the state of the test piece, it was allowed to stand at room temperature (25°C) for 24 hours. The results are shown in Table 2. The evaluation criteria for durability evaluation are shown below. ○: No bubbles or peeling development △: Slight bubbles or peeling development ×: Most bubbles or peeling development
(2)在玻璃接著力、高溫及高溫多濕條件下的接著力變化 將塗布有黏著劑之偏光板,於常溫(23℃/60%RH)中經7天熟成後,將該偏光板各切斷成1英吋×6英吋尺寸,使用2kg的橡膠滾筒貼合於0.7mm厚度之無鹼玻璃上。在常溫下保管後,於1小時後測定初期接著力,其次,在50℃下進行4小時老化,其後在常溫經1小時保管後,測定接著力。結果如表2所示。 又,為了要見到在高溫及高溫多濕條件下的接著力上昇之程度,各在100℃/30%RH之條件下配合時間進行老化後,在常溫下冷卻1小時,測定接著力。結果如表3所示。 此時,接著力之測定則使用拉引試驗機,以300mm/分鐘的速度、180°的角度測定剝離強度(gf/in)。(2) Adhesion changes under glass adhesion, high temperature and high temperature and humidity conditions After the polarizing plate coated with the adhesive was matured at room temperature (23°C/60%RH) for 7 days, the polarizing plate was cut into 1 inch x 6 inch sizes, and the 2kg rubber roller was used for lamination On 0.7mm thick non-alkali glass. After storage at room temperature, the initial adhesion was measured after 1 hour, followed by aging at 50°C for 4 hours, and then after storage at room temperature for 1 hour, the adhesion was measured. The results are shown in Table 2. In addition, in order to see the degree of increase in adhesion under high temperature and high temperature and humidity conditions, after aging under conditions of 100°C/30% RH each for a period of time, it was cooled at room temperature for 1 hour, and the adhesion was measured. The results are shown in Table 3. At this time, the peel strength (gf/in) was measured at a speed of 300 mm/min and an angle of 180° using a tensile tester for the measurement of the adhesive force.
(3)再加工性 將塗布有黏著劑之偏光板(90mm×170mm)貼合於玻璃基板(110mm×190mm×0.7mm)後,在常溫下經過1小時(初期接著力)及經50℃×4小時老化後,在常溫下冷卻1小時後,將偏光板自玻璃剝離。結果如表2所示。 對於再加工性之評估基準如以下所示。 ○:可容易再剝離 △:再剝離稍有困難 ×:不能剝離且玻璃破損(3) Reworkability After attaching the polarizing plate (90mm×170mm) coated with adhesive to the glass substrate (110mm×190mm×0.7mm), after aging at room temperature for 1 hour (initial adhesion) and after aging at 50°C for 4 hours, After cooling at room temperature for 1 hour, the polarizing plate was peeled from the glass. The results are shown in Table 2. The evaluation criteria for reworkability are shown below. ○: Can be easily peeled off △: It is slightly difficult to peel off ×: No peeling and glass breakage
如表2、3所示得知,比較例1因無添加嵌段化異氰酸酯矽烷化合物,故經熱硬化後未能表現充分接著性。 比較例2為使用已知技術的環氧矽烷偶合劑之情況,初期接著力過高而無法表現再加工性。 比較例3、4為賦予再加工性與硬化後的密著的已知矽烷材料,但硬化後的最終密著強度並不充分,亦缺乏信賴性。 比較例5為所使用的嵌段化異氰酸酯矽烷化合物成分過於少,故效果並不充分,另一方面,比較例6因該成分之配合量過多,故自初期即表現不需要的密著性,成為再加工性不充分者。 另一方面,得之實施例1~7為因使用所定量的嵌段化異氰酸酯矽烷化合物,可解決在各比較例所產生的問題。 由上述得知,本發明之組成物為具有優良的初期再加工性,藉由高溫及高溫多濕處理可表現充分的與玻璃之接著力,且長期耐久性亦優良的黏著劑組成物。As shown in Tables 2 and 3, since Comparative Example 1 does not add a block isocyanate silane compound, it does not exhibit sufficient adhesion after heat curing. Comparative Example 2 is a case of using a known technology epoxy silane coupling agent, and the initial adhesive force is too high to express reworkability. Comparative Examples 3 and 4 are known silane materials that impart reworkability and adhesion after curing, but the final adhesion strength after curing is insufficient and lacks reliability. Comparative Example 5 is that the block isocyanate silane compound used is too small, so the effect is not sufficient. On the other hand, Comparative Example 6 has too much compounding of this component, so it exhibits unnecessary adhesion from the beginning, Become inadequate reworkability. On the other hand, the obtained Examples 1 to 7 are based on the use of the quantified blocked isocyanate silane compound, which can solve the problems in each comparative example. From the above, the composition of the present invention is an adhesive composition that has excellent initial reworkability, can exhibit sufficient adhesion to glass by high-temperature, high-temperature and high-humidity treatment, and has excellent long-term durability.
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