TW201700693A - Adhesive composition, adhesive obtained using same, and adhesive for polarizing plates - Google Patents
Adhesive composition, adhesive obtained using same, and adhesive for polarizing plates Download PDFInfo
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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
- C09J133/24—Homopolymers or copolymers of amides or imides
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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
- 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
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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Abstract
Description
本發明關於黏接劑組成物及利用該黏接劑組成物所構成之黏接劑與偏光板用黏接劑,更詳細而言關於可形成在室溫及低溫條件下之抗靜電性、耐久性及熟成特性平衡佳且優良的黏接劑之黏接劑組成物及利用該黏接劑組成物所構成之黏接劑與偏光板用黏接劑。The present invention relates to an adhesive composition and an adhesive for using the adhesive composition and an adhesive for a polarizing plate, and more particularly to an antistatic property and durability which can be formed at room temperature and low temperature. An adhesive composition having excellent balance of properties and aging properties and an excellent adhesive, and an adhesive for using the adhesive composition and a polarizing plate.
液晶顯示板通常係藉由介隔黏接劑而將偏光板貼附於在夾持有配向於2片玻璃板之間的液晶成分之液晶單元的表面而獲得。此偏光板以往係使用由聚乙烯醇系樹脂構成的偏光片受到由三乙醯纖維素系樹脂構成的保護膜夾持而成的3層結構。The liquid crystal display panel is usually obtained by attaching a polarizing plate to a surface of a liquid crystal cell sandwiching a liquid crystal component interposed between two glass plates by interposing an adhesive. In the polarizing plate, a three-layer structure in which a polarizer made of a polyvinyl alcohol-based resin is sandwiched by a protective film made of a triacetyl cellulose resin is used.
近年,作為液晶顯示板用之偏光板,已開發出於保護上述偏光片(聚乙烯醇系膜)之雙面的保護膜使用丙烯酸系樹脂、或環烯烴系樹脂等疏水性高的樹脂。但是,保護膜使用該等疏水性樹脂之偏光板比起以往於保護膜使用三乙醯基纖維素系膜之偏光板容易帶電,故由於和液晶顯示板的背光源等摩擦所致之摩擦帶電等原因,會發生液晶配向受到擾亂所導致顯示不良(即所謂顯示不均勻,白化現象)的情況,並成為問題。In recent years, as a polarizing plate for a liquid crystal display panel, a resin having a high hydrophobicity such as an acrylic resin or a cycloolefin resin has been developed for protecting the double-sided protective film of the polarizing plate (polyvinyl alcohol film). However, the polarizing plate using the hydrophobic resin as the protective film is more easily charged than the polarizing plate using the triacetyl cellulose film in the protective film, and thus is frictionally charged due to friction with the backlight of the liquid crystal display panel. For other reasons, the liquid crystal alignment is disturbed and the display is poor (so-called uneven display, whitening phenomenon), and it becomes a problem.
於此,作為上述摩擦帶電的問題之解決對策,有人提出嘗試在用來和液晶單元黏著(壓接)而設置於上述偏光板之表面的黏接劑層中,添加比以往更多量的抗靜電劑使抗靜電性能提昇(參照專利文獻1)。 [先前技術文獻] [專利文獻]Here, as a solution to the problem of the above-described triboelectric charging, it has been proposed to add a larger amount of anti-adhesion than the conventional one in the adhesive layer provided on the surface of the polarizing plate for bonding (crimping) to the liquid crystal cell. The electrostatic agent improves the antistatic property (refer to Patent Document 1). [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2009-79205號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-79205
[發明所欲解決之課題] 但是,若增加如專利文獻1之偏光板黏著用的黏接劑組成物中所添加之抗靜電劑量的話,在高溫高濕條件、或低溫條件、熱循環試驗等嚴苛的條件下,上述組成物中的抗靜電劑會隨時間從黏接劑層滲出,會有招致抗靜電性能降低、或偏光板剝離等耐久性(耐候性)降低的可能。又,如專利文獻1之偏光板用黏接劑主要使用鋰鹽系之抗靜電劑,故熟成會耗費時間。[Problems to be Solved by the Invention] However, when the antistatic amount added to the adhesive composition for polarizing plate adhesion of Patent Document 1 is increased, high temperature and high humidity conditions, low temperature conditions, thermal cycle tests, etc. Under severe conditions, the antistatic agent in the above composition may bleed out from the adhesive layer with time, and there is a possibility that the antistatic property is lowered or the durability (weather resistance) such as peeling of the polarizing plate is lowered. Further, as the adhesive for polarizing plate of Patent Document 1 mainly uses a lithium salt-based antistatic agent, it takes time to mature.
因此欲尋求即使添加多量的抗靜電劑仍不會滲出且可保持抗靜電性能,熟成特性亦優良的黏接劑組成物。Therefore, an adhesive composition which does not bleed out even if a large amount of an antistatic agent is added and which maintains antistatic properties and has excellent ripening characteristics is sought.
本發明鑒於如此的情事,目的在於提供即使增加抗靜電劑的含量仍不會發生滲出,不至於對耐久性造成不良影響,即使在在各種環境下可歷經長時間安定而發揮抗靜電性能,且熟成特性亦優良的黏接劑組成物及利用該黏接劑組成物所構成之黏接劑與偏光板用黏接劑。 [解決課題之手段]The present invention has been made in view of such circumstances, and an object thereof is to provide that even if the content of the antistatic agent is increased, bleeding does not occur, and the durability is not adversely affected, and the antistatic property can be exerted over a long period of time even under various environments, and An adhesive composition having excellent ripening characteristics and an adhesive for using the adhesive composition and an adhesive for a polarizing plate. [Means for solving the problem]
本案發明人等為了解決上述課題反覆深入研究的結果發現:在含有丙烯酸系樹脂(A)與抗靜電劑(B)之黏接劑組成物中,使用特定量的銨系之抗靜電劑作為上述抗靜電劑(B),同時使樹脂成分整體含有醯胺基與醯胺基以外的官能基之2種官能基作為丙烯酸系樹脂(A),藉由將此「醯胺基以外的官能基」的含量[亦即,源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量]設定為較以往的技術常識所認為適切的量更多,即使增加抗靜電劑的含量仍不會發生滲出(bleed),使用作為偏光板用黏接劑時,可高水準且平衡佳地維持抗靜電性能與耐久性能,此外由於使用特定量之銨鹽系抗靜電劑可得到熟成特性亦優良的黏接劑組成物,乃至完成本發明。In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a specific amount of an ammonium-based antistatic agent is used as the above-mentioned binder composition containing the acrylic resin (A) and the antistatic agent (B). In the antistatic agent (B), two functional groups including a functional group other than a mercapto group and a mercapto group as a whole of the resin component are used as the acrylic resin (A), and a functional group other than the "nonylamine group" is used. The content of the structural unit (that is, the content of the structural unit derived from the monomer (a1) having a functional group other than the amidino group) is set to be more appropriate than the conventional technical knowledge, even if the content of the antistatic agent is increased. Bleed is still not generated, and when used as an adhesive for polarizing plates, antistatic properties and durability can be maintained at a high level and balance, and maturation characteristics can be obtained by using a specific amount of an ammonium salt antistatic agent. It is also an excellent binder composition, or even the completion of the present invention.
亦即,本發明的要旨關於一種黏接劑組成物,含有丙烯酸系樹脂(A)及抗靜電劑(B);其特徵在於:丙烯酸系樹脂(A)含有醯胺基與醯胺基以外的官能基,且源自含有醯胺基以外的官能基之單體(a1)的結構單元佔丙烯酸系樹脂(A)的1~10重量%;抗靜電劑(B)由銨系抗靜電劑所構成,此抗靜電劑(B)的含量相對於100重量份之丙烯酸系樹脂(A),為1.2~15重量份。That is, the gist of the present invention relates to an adhesive composition comprising an acrylic resin (A) and an antistatic agent (B); characterized in that the acrylic resin (A) contains a non-amine group other than a mercapto group. The functional group, and the structural unit derived from the monomer (a1) having a functional group other than the amide group accounts for 1 to 10% by weight of the acrylic resin (A); and the antistatic agent (B) is composed of the ammonium-based antistatic agent The content of the antistatic agent (B) is 1.2 to 15 parts by weight based on 100 parts by weight of the acrylic resin (A).
此外,本發明關於一種黏接劑,係利用交聯劑(C)將上述黏接劑組成物交聯所構成;以及一種偏光板用黏接劑,係利用該黏接劑所構成。 [發明之效果]Further, the present invention relates to an adhesive comprising a crosslinking agent (C) for crosslinking the above-mentioned adhesive composition, and an adhesive for a polarizing plate which is constituted by the adhesive. [Effects of the Invention]
本發明之黏接劑組成物及將該黏接劑組成物交聯而得的黏接劑,其抗靜電性能之隨時間之安定性優良,且即使比習知品摻合更多的抗靜電劑仍不會發生滲出,兼具優良的抗靜電性能與耐久性,此外凝膠分率在短時間即會上昇故熟成特性亦優良。The adhesive composition of the present invention and the adhesive obtained by crosslinking the adhesive composition have excellent antistatic properties over time, and even more antistatic agents are blended than conventional products. It does not bleed out, and has excellent antistatic properties and durability. In addition, the gel fraction increases in a short period of time, so that the ripening property is also excellent.
此外,上述黏接劑組成物及利用該黏接劑組成物而得的黏接劑不僅耐久性優良,耐漏光性、或重工性(rework)亦優良。Further, the above-described adhesive composition and the adhesive obtained by using the adhesive composition are excellent in durability, light leakage resistance, and rework.
以下針對本發明進行詳細地說明。 另外,本發明中分別以(甲基)丙烯酸基意指丙烯酸基或甲基丙烯酸基、(甲基)丙烯酸酯意指丙烯酸酯或甲基丙烯酸酯、(甲基)丙烯醯胺意指丙烯醯胺或甲基丙烯醯胺。又,丙烯酸系樹脂係指將含有至少1種(甲基)丙烯酸酯系單體之聚合成分予以聚合而得的樹脂。而且,本發明中的單體係指具有聚合性不飽和基之化合物,單體所具有的官能基不包含上述聚合性不飽和基。The invention will be described in detail below. Further, in the present invention, a (meth)acrylic group means an acrylic group or a methacrylic group, a (meth) acrylate means an acrylate or a methacrylate, and a (meth) acrylamide means an acryl oxime. Amine or methacrylamide. Further, the acrylic resin refers to a resin obtained by polymerizing a polymerization component containing at least one (meth)acrylate monomer. Further, the single system in the present invention means a compound having a polymerizable unsaturated group, and the functional group of the monomer does not contain the above polymerizable unsaturated group.
本發明之黏接劑組成物含有丙烯酸系樹脂(A)及抗靜電劑(B);丙烯酸系樹脂(A)含有醯胺基與醯胺基以外的官能基;抗靜電劑(B)由銨系抗靜電劑構成。The adhesive composition of the present invention contains an acrylic resin (A) and an antistatic agent (B); the acrylic resin (A) contains a functional group other than a guanamine group and a guanamine group; and the antistatic agent (B) is made of ammonium. It is composed of an antistatic agent.
<丙烯酸系樹脂(A)> 構成本發明之黏接劑組成物之丙烯酸系樹脂(A)含有醯胺基與醯胺基以外的官能基,且源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量為丙烯酸系樹脂(A)整體之1~10重量%。作為源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量宜為1.5~8重量%,為2~5重量%更佳,為2.5~4重量%特佳。源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量過多的話,由於官能基大量殘存,故會有容易造成物性隨時間變化的傾向,且由於黏接劑之極性成分的比例會變高,黏接劑層變得容易吸收水分,故會有加熱所導致起泡等耐久性降低的傾向。源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量過少的話,由於交聯反應中丙烯酸系樹脂無法與交聯劑充分地反應,無法展現出作為黏接劑之足夠的凝聚力,故會有耐久性降低的傾向。<Acrylic Resin (A)> The acrylic resin (A) constituting the adhesive composition of the present invention contains a functional group other than a mercaptoamine group and a mercapto group, and is derived from a functional group other than a mercapto group. The content of the structural unit of the body (a1) is 1 to 10% by weight based on the entire acrylic resin (A). The content of the structural unit derived from the monomer (a1) having a functional group other than a guanamine group is preferably 1.5 to 8% by weight, more preferably 2 to 5% by weight, particularly preferably 2.5 to 4% by weight. When the content of the structural unit derived from the monomer (a1) having a functional group other than a guanamine group is too large, since the functional group remains in a large amount, the physical property tends to change with time, and the polar component of the adhesive is present. The ratio of the adhesive layer becomes high, and the adhesive layer tends to absorb moisture, so that the durability such as foaming tends to be lowered by heating. When the content of the structural unit derived from the monomer (a1) having a functional group other than the amide group is too small, the acrylic resin cannot sufficiently react with the crosslinking agent in the crosslinking reaction, and it is not sufficient to exhibit an adhesive. Because of the cohesive force, there is a tendency for durability to decrease.
作為前述含有醯胺基以外的官能基之單體(a1),可舉具有和後述交聯劑(C)反應的官能基之單體,例如可列舉:含有羥基之單體、含有羧基之單體、含有乙醯乙醯基(acetoacetyl)之單體、含有異氰酸酯基之單體、含有環氧丙基之單體等。該等之中就可有效率地交聯反應之觀點,宜為含有羥基之單體、含有羧基之單體,此外併用含有羥基之單體與含有羧基之單體為佳。The monomer (a1) having a functional group other than the amidoxime group may be a monomer having a functional group reactive with a crosslinking agent (C) to be described later, and examples thereof include a monomer having a hydroxyl group and a monomer having a carboxyl group. A monomer, a monomer containing an acetoacetyl group, a monomer containing an isocyanate group, a monomer containing a glycidyl group, and the like. Among these, the viewpoint of efficiently crosslinking the reaction is preferable, and it is preferably a monomer having a hydroxyl group or a monomer having a carboxyl group, and a monomer having a hydroxyl group and a monomer having a carboxyl group are preferably used in combination.
作為上述含有羥基之單體,例如可列舉:(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸-5-羥基戊酯、(甲基)丙烯酸-6-羥己酯、(甲基)丙烯酸-8-羥辛酯等之丙烯酸羥基烷酯;己內酯改性(甲基)丙烯酸-2-羥乙酯等之己內酯改性單體;(甲基)丙烯酸二乙二醇酯、(甲基)丙烯酸聚乙二醇酯等之氧伸烷基改性單體等。Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 5-hydroxypentyl (meth)acrylate. a hydroxyalkyl acrylate such as hexamethylene acrylate or octahydroxyoctyl (meth)acrylate; a caprolactone modified by a caprolactone-modified (2-hydroxyethyl methacrylate) A monomer; an alkylene-modified monomer such as diethylene glycol (meth)acrylate or polyethylene glycol (meth)acrylate.
作為上述含有羧基之單體,例如可列舉:(甲基)丙烯酸、丙烯酸二聚物、巴豆酸、馬來酸、馬來酸酐、富馬酸、檸康酸、戊烯二酸、伊康酸、N-乙醇酸、桂皮酸等。其中,考慮共聚合性、或耐久性的觀點,適合使用(甲基)丙烯酸。Examples of the carboxyl group-containing monomer include (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, and itaconic acid. , N-glycolic acid, cinnamic acid, and the like. Among them, (meth)acrylic acid is preferably used from the viewpoint of copolymerizability or durability.
作為上述含有乙醯乙醯基之單體,例如可使用:(甲基)丙烯酸-2-(乙醯乙醯氧基)乙酯、乙醯乙酸烯丙酯等。As the monomer containing the ethyl oxime group, for example, 2-(ethionethoxy)ethyl (meth)acrylate or allyl acetate can be used.
作為上述含有異氰酸酯基之單體,例如可使用:異氰酸-2-丙烯醯氧乙酯、異氰酸-2-甲基丙烯醯氧乙酯、或該等之環氧烷加成物等。As the monomer containing an isocyanate group, for example, isocyanate-2-propenyloxyethyl ester, isocyanic acid-2-methylpropenyloxyethyl ester, or such an alkylene oxide adduct can be used. .
作為上述含有環氧丙基之單體,例如可使用:(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸烯丙基環氧丙酯等。As the above-mentioned monomer containing a glycidyl group, for example, glycidyl (meth)acrylate or allyl g-propyl (meth)acrylate can be used.
另外,上述含有醯胺基以外的官能基之單體(a1)可單獨使用亦可將2種以上併用。In addition, the monomer (a1) having a functional group other than the amidoxime group may be used singly or in combination of two or more kinds.
又,本發明中,就短時間凝膠分率即會上昇且熟成性變佳的觀點,丙烯酸系樹脂(A)宜具有羧基作為醯胺基以外的官能基,作為上述含有醯胺基以外的官能基之單體(a1),源自含有羧基之單體的結構單元宜含有1~5重量%。作為源自含有羧基之單體的結構單元之含量,為1.5~4重量%更佳,為,2~3.5重量%特佳。丙烯酸系樹脂(A)中源自含有羧基之單體的結構單元之含量過少的話,不易獲得交聯反應中的羧基之催化性效果,故會有與交聯劑反應之官能基,尤其羥基與異氰酸酯系交聯劑之反應無法充分進行而有熟成耗費時間的傾向,含量過多的話,由於具有反應性之官能基殘存,故有觀察到物性容易隨時間變化的傾向,而且由於黏接劑組成物中極性成分的比例變高,故有觀察到黏接劑層變得容易吸收水分、加熱導致起泡等耐久性降低的傾向。In the present invention, the acrylic resin (A) preferably has a carboxyl group as a functional group other than the guanamine group, and the other than the above-described guanamine group, in view of the fact that the gel fraction is increased in a short period of time and the aging property is improved. The functional group monomer (a1) preferably contains from 1 to 5% by weight of the structural unit derived from the carboxyl group-containing monomer. The content of the structural unit derived from the monomer having a carboxyl group is preferably from 1.5 to 4% by weight, more preferably from 2 to 3.5% by weight. When the content of the structural unit derived from the monomer having a carboxyl group in the acrylic resin (A) is too small, the catalytic effect of the carboxyl group in the crosslinking reaction is not easily obtained, so that a functional group reactive with a crosslinking agent, particularly a hydroxyl group, may be The reaction of the isocyanate-based crosslinking agent does not proceed sufficiently, and the ripening tends to take time. When the content is too large, since the reactive functional group remains, it is observed that the physical properties tend to change with time, and the adhesive composition is observed. Since the ratio of the medium-polar component becomes high, it has been observed that the adhesive layer tends to absorb moisture, and the durability such as foaming due to heating tends to decrease.
又,本發明之丙烯酸系樹脂(A)含有醯胺基,源自含有醯胺基之單體(a2)的結構單元宜含有1~25重量%,為2~10重量%更佳,為3~7重量%特佳。源自含有醯胺基之單體(a2)的結構單元的含量過多的話,丙烯酸系樹脂之極性成分的比例變高,與其交聯所構成之黏接劑層變得容易吸收水分,故有耐久性降低的傾向,過少的話,會有無法展現出作為黏接劑之足夠的凝聚力而有加熱及加濕後之耐久性降低的傾向。Further, the acrylic resin (A) of the present invention contains a guanamine group, and the structural unit derived from the amide group-containing monomer (a2) preferably contains 1 to 25% by weight, more preferably 2 to 10% by weight, and more preferably 3 ~7% by weight is particularly good. When the content of the structural unit derived from the amidino group-containing monomer (a2) is too large, the ratio of the polar component of the acrylic resin becomes high, and the adhesive layer formed by crosslinking is easily absorbed with water, so that it is durable. When the degree of the decrease is small, there is a tendency that the cohesive force as the adhesive agent is not exhibited and the durability after heating and humidification is lowered.
作為上述含有醯胺基之單體(a2),例如可舉含有醯胺基之(甲基)丙烯酸酯。作為上述含有醯胺基之(甲基)丙烯酸酯,例如可列舉:甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、異丙氧基甲基(甲基)丙烯醯胺、正丁氧基甲基(甲基)丙烯醯胺、異丁氧基甲基(甲基)丙烯醯胺等之烷氧基烷基(甲基)丙烯醯胺系單體;二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺等之二烷基(甲基)丙烯醯胺系單體;(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯醯啉等。其中,考慮和後述抗靜電劑(B)之相容性及耐久性的觀點,宜為二烷基(甲基)丙烯醯胺系單體,為二甲基(甲基)丙烯醯胺特佳。The monomer (a2) containing the guanamine group may, for example, be a (meth) acrylate containing a guanamine group. Examples of the above-mentioned (meth) acrylate containing a guanamine group include methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, and propoxymethyl ( Methyl) acrylamide, isopropoxymethyl (meth) acrylamide, n-butoxymethyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, etc. Alkoxyalkyl (meth) acrylamide monomer; dialkyl (meth) acrylamide such as dimethyl (meth) acrylamide or diethyl (meth) acrylamide Monomer; (meth) acrylamide, N-methylol (meth) acrylamide, (meth) propylene oxime Porphyrin and the like. Among them, from the viewpoint of compatibility and durability with the antistatic agent (B) described later, it is preferably a dialkyl (meth) acrylamide monomer, which is preferably dimethyl (meth) acrylamide. .
另外,上述含有醯胺基之單體(a2)可單獨使用亦可將2種以上併用。Further, the amidoxime group-containing monomer (a2) may be used alone or in combination of two or more.
本發明之丙烯酸系樹脂(A)宜更含有源自(甲基)丙烯酸烷酯系單體(a3)的結構單元,且亦可因應需要含有源自其他可共聚合之乙烯性不飽和單體(a4)(以下有時會記載為「其他共聚合性單體(a4)」)的結構單元。The acrylic resin (A) of the present invention preferably further contains a structural unit derived from the alkyl (meth)acrylate monomer (a3), and may also contain other ethylenically unsaturated monomers copolymerizable from other copolymers as needed. (a4) (The following may be described as a structural unit of "other copolymerizable monomer (a4)").
源自(甲基)丙烯酸烷酯系單體(a3)的結構單元係為佔丙烯酸系樹脂(A)之主要結構單元,含量宜為50~99重量%,為60~98重量%更佳,為70~95重量%再更佳,為70~93重量%特佳。源自(甲基)丙烯酸烷酯系單體(a3)的結構單元的含量過多的話,會有源自含有醯胺基之單體(a2)的結構單元及源自含有醯胺基以外的官能基之單體(a1)的結構單元的含量減少且難以獲得本發明之效果的傾向,過少的話,會有丙烯酸系樹脂的高分子量化困難、或生產性降低的傾向。The structural unit derived from the alkyl (meth) acrylate monomer (a3) is a main structural unit of the acrylic resin (A), and the content is preferably 50 to 99% by weight, more preferably 60 to 98% by weight. It is more preferably 70 to 95% by weight, and particularly preferably 70 to 93% by weight. When the content of the structural unit derived from the alkyl (meth) acrylate monomer (a3) is too large, a structural unit derived from the monomer (a2) containing a guanamine group and a functional group derived from a amide containing group may be derived. The content of the structural unit of the monomer (a1) is reduced, and it is difficult to obtain the effect of the present invention. When the amount is too small, the acrylic resin tends to be difficult to polymerize or the productivity tends to be lowered.
作為上述(甲基)丙烯酸烷酯系單體(a3),例如通常為烷基之碳數為1~20者,宜為1~18者,為1~12者更佳,為1~8者特佳,具體而言可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯等。其中,考慮通用性、黏接物性的觀點,宜為(甲基)丙烯酸正丁酯、(甲基)丙烯酸-2-乙基己酯。該等可單獨使用或將2種以上併用。As the alkyl (meth)acrylate monomer (a3), for example, the number of carbon atoms of the alkyl group is usually from 1 to 20, preferably from 1 to 18, more preferably from 1 to 12, and from 1 to 8 Particularly preferred are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tertiary (meth)acrylate. Butyl ester, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate And lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, and the like. Among them, from the viewpoint of versatility and adhesive properties, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable. These may be used alone or in combination of two or more.
作為源自其他共聚合性單體(a4)的結構單元之含量,宜為0~50重量%,為3~20重量%更佳,為5~20重量%再更佳,為6~15重量%特佳。其他共聚合性單體(a4)的含量過多的話,會有玻璃轉移溫度變高,重工性降低的傾向,過少的話,會有調整折射率之效果難以顯現的傾向。The content of the structural unit derived from the other copolymerizable monomer (a4) is preferably from 0 to 50% by weight, more preferably from 3 to 20% by weight, even more preferably from 5 to 20% by weight, even more preferably from 6 to 15% by weight. % is particularly good. When the content of the other copolymerizable monomer (a4) is too large, the glass transition temperature tends to be high, and the workability tends to be lowered. When the content is too small, the effect of adjusting the refractive index tends to be difficult to be exhibited.
作為上述其他共聚合性單體(a4),例如可列舉:(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基二乙二醇酯、(甲基)丙烯酸鄰苯基苯氧基乙酯等含有芳香環之單體;(甲基)丙烯酸環己基氧烷酯、(甲基)丙烯酸三級丁基環己基氧乙酯、(甲基)丙烯酸二環戊酯等含有脂環之單體;丙烯腈、甲基丙烯腈、乙酸乙烯酯、硬脂酸乙烯酯、氯乙烯、偏二氯乙烯、乙烯基甲苯、乙烯基吡咯烷酮、甲乙酮、二甲基烯丙基乙烯基酮等。該等可單獨使用或將2種以上併用。Examples of the other copolymerizable monomer (a4) include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate. Monocyclic aromatic monomer such as o-phenylphenoxyethyl methacrylate; cyclohexyl oxyalkyl (meth) acrylate, tert-butylcyclohexyloxyethyl (meth) acrylate, (methyl) An alicyclic monomer such as dicyclopentanyl acrylate; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl toluene, vinyl pyrrolidone, methyl ethyl ketone, two Methyl allyl vinyl ketone and the like. These may be used alone or in combination of two or more.
該等之中,考慮折射率的調整及雙折射的調整之容易度的觀點,宜為含有芳香環之單體,使用(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基二乙二醇酯更佳。又,就折射率的調整及雙折射的調整容易且與低極性被黏著體(環烯烴)之密合性優良的觀點,適合使用含有脂環之單體。Among these, in view of the adjustment of the refractive index and the ease of adjustment of birefringence, it is preferred to use a monomer containing an aromatic ring, and use benzyl (meth)acrylate or phenoxyethyl (meth)acrylate. Phenoxydiethylene glycol (meth)acrylate is more preferred. Moreover, it is preferable to use an alicyclic-containing monomer from the viewpoint of easy adjustment of the refractive index and adjustment of birefringence and excellent adhesion to the low-polarity adherend (cycloolefin).
其中,其他共聚合性單體(a4)為含有芳香環之單體及含有脂環之單體以外的情況,源自其他共聚合性單體(a4)的結構單元之含量宜為0~10重量%,為0~5重量%更佳。含量過多的話,會見到黏接劑組成物之長期保存安定性降低、或相容性降低的傾向。In the case where the other copolymerizable monomer (a4) is a monomer containing an aromatic ring and a monomer containing an alicyclic ring, the content of the structural unit derived from the other copolymerizable monomer (a4) is preferably 0 to 10 The weight % is preferably 0 to 5% by weight. When the content is too large, there is a tendency that the long-term storage stability of the adhesive composition is lowered or the compatibility is lowered.
另外,丙烯酸系樹脂(A)中源自各單體(a1)~(a4)的結構單元之含有比例,例如可用下述方式測量。亦即,從利用後述方法得到之附有黏接劑層的偏光板只挑取(picking)黏接劑層,並使用後述NMR設備,利用以下的〈測量條件〉,藉由實施1 H-NMR測量(CDCl3 , 300K)及13 C-NMR測量(CDCl3 , MAS, 300K),可計算出黏接劑層中之丙烯酸系樹脂之源自各單體(a1)~(a4)的結構單元之含有比例。In addition, the content ratio of the structural unit derived from each of the monomers (a1) to (a4) in the acrylic resin (A) can be measured, for example, in the following manner. In other words, the adhesive layer is picked up from the polarizing plate with the adhesive layer obtained by the method described later, and the 1 H-NMR is performed by the following <measurement conditions> using the NMR apparatus described later. Measurement (CDCl 3 , 300K) and 13 C-NMR measurement (CDCl 3 , MAS, 300K), the structural unit derived from the monomers (a1) to (a4) of the acrylic resin in the adhesive layer can be calculated. The proportion of the content.
〈測量設備〉 NMR(Bruker Biospin AVANCE-600(1 H),Varian, UNITY-INOVA-400(13 C))<Measurement Equipment> NMR (Bruker Biospin AVANCE-600 ( 1 H), Varian, UNITY-INOVA-400 ( 13 C))
〈測量條件〉 觀測頻率:600MHz(1 H);100MHz(13 C) 測量溶劑:CDCl3 (測量13 C時添加少量吡啶-d5) 測量溫度:300K(1 H);300K(13 C) 化學位移標準:測量溶劑(1 H:7.25ppm;13 C:77.05ppm) 樣本轉速:20Hz(1 H);2,000Hz(13 C)<Measurement conditions> Observation frequency: 600MHz ( 1 H); 100MHz ( 13 C) Measurement solvent: CDCl 3 (add a small amount of pyridine-d5 when measuring 13 C) Measurement temperature: 300K ( 1 H); 300K ( 13 C) Chemical shift Standard: Measurement solvent ( 1 H: 7.25 ppm; 13 C: 77.05 ppm) Sample speed: 20 Hz ( 1 H); 2,000 Hz ( 13 C)
本發明所使用的丙烯酸系樹脂(A)可藉由將適當選擇而成之含有醯胺基以外的官能基之單體(a1)、含有醯胺基之單體(a2),含有(甲基)丙烯酸烷酯系單體(a3)及其他共聚合性單體(a4)之共聚合成分予以聚合而製造。上述聚合時可利用溶液自由基聚合、懸浮聚合、塊狀聚合、乳化聚合等以往習知的方法實施。The acrylic resin (A) used in the present invention may contain a monomer (a1) having a functional group other than a guanamine group and a monomer (a2) containing a guanamine group, which are appropriately selected. The copolymerization component of the alkyl acrylate monomer (a3) and the other copolymerizable monomer (a4) is produced by polymerization. The above polymerization can be carried out by a conventional method such as solution radical polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization.
亦即,丙烯酸系樹脂(A)例如可在有機溶劑中混合或滴加含有上述適當選擇而成之單體的共聚合成分、聚合起始劑,並以預定的聚合條件進行聚合。該等聚合方法之中,宜使用溶液自由基聚合、塊狀聚合,使用溶液自由基聚合更佳。In other words, the acrylic resin (A) may be obtained by, for example, mixing or dropping a copolymerization component containing a monomer selected as described above and a polymerization initiator in an organic solvent, and polymerizing under predetermined polymerization conditions. Among these polymerization methods, solution radical polymerization and bulk polymerization are preferably used, and radical polymerization using a solution is more preferable.
作為上述聚合反應所使用的有機溶劑,例如可列舉:甲苯、二甲苯等芳香烴類;己烷等脂肪族烴類;乙酸乙酯、乙酸丁酯等酯類;正丙醇、異丙醇等脂肪族醇類;丙酮、甲乙酮、甲基異丁酮、環己酮等酮類等。該等溶劑之中,考慮聚合反應之容易性、鏈轉移之效果、或黏接劑塗佈時的乾燥之容易性、安全上的觀點,宜為乙酸乙酯、丙酮、甲乙酮、乙酸丁酯、甲苯、甲基異丁酮,其中,適合使用乙酸乙酯、丙酮、甲乙酮。Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; n-propanol and isopropanol. Aliphatic alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these solvents, ethyl acetate, acetone, methyl ethyl ketone, butyl acetate, and ethyl acetate, acetone, methyl ethyl ketone, and butyl acetate are preferable in view of easiness of polymerization reaction, effect of chain transfer, and ease of drying and adhesion at the time of application of the adhesive. Toluene and methyl isobutyl ketone, among which ethyl acetate, acetone, and methyl ethyl ketone are suitably used.
又,作為上述溶液自由基聚合所使用的聚合起始劑,例如可列舉一般的自由基聚合起始劑即:2,2’-偶氮雙異丁腈、2,2’-偶氮雙-2-甲基丁腈、4,4’-偶氮雙(4-氰基戊酸)、2,2’-偶氮雙(甲基丙酸)等偶氮系起始劑;過氧化苯甲醯、過氧化月桂醯、二(三級丁基)過氧化物、異丙苯過氧化氫等有機過氧化物等,可配合所使用的單體而適當選擇使用。該等溶劑可單獨使用或將2種以上併用。Moreover, as a polymerization initiator used for the radical polymerization of the solution, for example, a general radical polymerization initiator: 2,2'-azobisisobutyronitrile, 2,2'-azobis- Azo-based initiators such as 2-methylbutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(methylpropionic acid); benzoic acid peroxide An organic peroxide such as hydrazine, oxidized laurel, bis(tributyl) peroxide or cumene hydroperoxide may be appropriately selected and used in combination with the monomer to be used. These solvents may be used singly or in combination of two or more.
本發明中,丙烯酸系樹脂(A)的重量平均分子量宜為60萬~250萬,為100萬~180萬更佳,為120萬~155萬再更佳,為140萬~155萬特佳。重量平均分子量過小的話,會見到耐久性降低的傾向,重量平均分子量過大的話,由於製造時大量地需要稀釋溶劑,故會見到乾燥性降低的傾向。In the present invention, the weight average molecular weight of the acrylic resin (A) is preferably from 600,000 to 2.5 million, more preferably from 1,000,000 to 1.8 million, and even more preferably from 1.2 million to 1.55 million, and is preferably from 1.4 to 1.5 million. When the weight average molecular weight is too small, the durability tends to be lowered. When the weight average molecular weight is too large, the solvent is required to be diluted in a large amount at the time of production, so that the drying property tends to be lowered.
另外,上述重量平均分子量為利用標準聚苯乙烯分子量換算而得之重量平均分子量,藉由使用在高效液相層析儀(日本Waters公司製,「Waters 2695(本體)」與「Waters 2414(檢測器)」)串聯3支管柱:Shodex GPC KF-806L(排除極限分子量:2×107 ,分離範圍:100~2×107 ,理論板數:10,000板/支,填充劑材質:苯乙烯-二乙烯苯共聚物,填充劑粒徑:10μm)測量而得。Further, the weight average molecular weight is a weight average molecular weight obtained by converting the molecular weight of the standard polystyrene, and is used in a high performance liquid chromatography apparatus ("Waters 2695 (main body)" and "Waters 2414" manufactured by Waters Corporation, Japan. ")") 3 columns in series: Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 7 , separation range: 100 ~ 2 × 10 7 , theoretical number of plates: 10,000 plates / support, filler material: styrene - Divinylbenzene copolymer, filler particle size: 10 μm).
本發明中,丙烯酸系樹脂(A)可為由單一丙烯酸系樹脂構成者,亦可混摻2種以上之丙烯酸系樹脂。其中,考慮可寬廣地調整物性的觀點、或能微調利用混摻而得之凝膠分率的觀點,更考慮耐久性的觀點,宜為將2種以上丙烯酸系樹脂混摻者,尤其考慮生產性等,宜混摻2種丙烯酸系樹脂而成。In the present invention, the acrylic resin (A) may be composed of a single acrylic resin, or two or more acrylic resins may be blended. In view of the viewpoint of broadly adjusting the physical properties, or the fineness of the gel fraction obtained by blending, and considering the durability, it is preferable to mix two or more kinds of acrylic resins, especially considering production. Sex, etc., should be mixed with two kinds of acrylic resin.
丙烯酸系樹脂(A)係將2種丙烯酸系樹脂混摻而成之丙烯酸系樹脂組成物時,源自含有醯胺基之單體(a2)的結構單元可含於所混摻的2種丙烯酸系樹脂中,亦可僅含於任一之丙烯酸系樹脂中,宜含於不含源自含有醯胺基以外的官能基之單體(a1)的結構單元之丙烯酸系樹脂中。When the acrylic resin (A) is an acrylic resin composition obtained by blending two kinds of acrylic resins, the structural unit derived from the amidino group-containing monomer (a2) may be contained in the two kinds of acrylic acid to be blended. The resin may be contained only in any of the acrylic resins, and is preferably contained in an acrylic resin containing no structural unit derived from the monomer (a1) having a functional group other than a mercapto group.
又,源自含有醯胺基以外的官能基之單體(a1)的結構單元亦可含於所混摻的2種丙烯酸系樹脂中,也可僅含於任一之丙烯酸系樹脂中,宜僅含於任一之丙烯酸系樹脂中,含於不含源自含有醯胺基之單體(a2)的結構單元之丙烯酸系樹脂中更佳。Further, the structural unit derived from the monomer (a1) having a functional group other than a guanamine group may be contained in the two kinds of acrylic resins to be blended, or may be contained only in any of the acrylic resins. It is more preferably contained in the acrylic resin containing only one of the structural units derived from the monomer (a2) containing the guanamine group.
亦即,作為丙烯酸系樹脂(A),尤其設定為含有2種丙烯酸系樹脂而成的丙烯酸系樹脂組成物時,作為上述所混摻的2種丙烯酸系樹脂之組合可為:含有源自含有醯胺基之單體(a2)的結構單元與源自含有醯胺基以外的官能基之單體(a1)的結構單元兩者之丙烯酸系樹脂(Aab)彼此的組合;含有源自含有醯胺基之單體(a2)的結構單元且不含源自含有醯胺基以外的官能基之單體(a1)的結構單元之丙烯酸系樹脂(Aa),與含有源自含有醯胺基以外的官能基之單體(a1)的結構單元且不含源自含有醯胺基之單體(a2)的結構單元之丙烯酸系樹脂(Ab)的組合,且亦可在含有源自含有醯胺基之單體(a2)的結構單元與源自含有醯胺基以外的官能基之單體(a1)的結構單元兩者之丙烯酸系樹脂(Aab)中組合上述丙烯酸系樹脂(Aa)或丙烯酸系樹脂(Ab)中任一者。In other words, when the acrylic resin (A) is in particular an acrylic resin composition containing two kinds of acrylic resins, the combination of the two kinds of acrylic resins to be blended may be: a combination of a structural unit of a guanamine group monomer (a2) and an acrylic resin (Aab) derived from a structural unit derived from a monomer (a1) having a functional group other than a guanamine group; The structural unit of the amino group monomer (a2) does not contain an acrylic resin (Aa) derived from a structural unit of the monomer (a1) having a functional group other than a guanamine group, and contains a source derived from a guanamine-containing group. a functional unit of the monomer (a1) and a combination of an acrylic resin (Ab) derived from a structural unit of the amidino group-containing monomer (a2), and may also contain a source derived from a decylamine The above-mentioned acrylic resin (Aa) or acrylic acid is combined with an acrylic resin (Aab) of a structural unit of the monomer (a2) and a structural unit derived from a monomer (a1) having a functional group other than a guanamine group. Any of the resins (Ab).
其中,在本發明中混摻含有源自含有醯胺基之單體(a2)的結構單元且不含源自含有醯胺基以外的官能基之單體(a1)的結構單元之丙烯酸系樹脂(Aa),與含有源自含有醯胺基以外的官能基之單體(a1)的結構單元且不含源自含有醯胺基之單體(a2)的結構單元之丙烯酸系樹脂(Ab)的話,就黏接特性、或耐久性的觀點較理想。In the present invention, an acrylic resin containing a structural unit derived from a monomer (a2) containing a mercapto group and containing no monomer (a1) derived from a functional group other than a mercapto group is blended in the present invention. (Aa), an acrylic resin (Ab) containing a structural unit derived from a monomer (a1) having a functional group other than a guanamine group, and containing no structural unit derived from a monomer (a2) containing a guanamine group In terms of adhesion characteristics or durability, the viewpoint is preferable.
據推測此係由於藉由丙烯酸系樹脂(Aa)與(Ab)之交互作用,2種丙烯酸系樹脂之間形成擬交聯結構,藉此,所得到的黏接劑會發揮適當的凝聚力與優良的應力鬆弛性。據認為尤其使用含有羧基之丙烯酸系樹脂作為含有醯胺基以外的官能基之丙烯酸系樹脂(Ab)時,藉由給電子基即醯胺基與吸電子基即羧基之間的電子***互作用,丙烯酸系樹脂(Aa)與(Ab)之間產生物理性之擬鍵結力,內部凝聚力會變更高,故會形成應力鬆弛性優良、耐久性良好的黏接劑層。It is presumed that due to the interaction between the acrylic resin (Aa) and (Ab), a pseudo-crosslinked structure is formed between the two acrylic resins, whereby the obtained adhesive exhibits an appropriate cohesive force and excellent Stress relaxation. It is considered that when an acrylic resin containing a carboxyl group is used as an acrylic resin (Ab) having a functional group other than a guanamine group, an electron interaction between an electron donor group, that is, a sulfhydryl group and an electron withdrawing group, that is, a carboxyl group, is considered. When the acrylic resin (Aa) and (Ab) have a physical pseudo bond force and the internal cohesive force is changed to be high, an adhesive layer having excellent stress relaxation properties and excellent durability is formed.
丙烯酸系樹脂(Aa)中的含有醯胺基之單體(a2)的含量相對於丙烯酸系樹脂(Aa)之聚合成分整體,宜為1~25重量%,為2~15重量%更佳,為3~10重量%再更佳,為4~7重量%特佳。相對於聚合成分整體之比例過少的話,就黏接劑而言無法展現足夠的凝聚力,會觀察到加熱及加濕後之耐久性降低的傾向。相反地,相對於聚合成分整體之比例過多的話,由於黏接劑之極性成分的比例變高,黏接劑層變得容易吸收水分,故在加熱試驗會觀察到起泡等,同樣地耐久性降低的傾向。The content of the amidino group-containing monomer (a2) in the acrylic resin (Aa) is preferably from 1 to 25% by weight, more preferably from 2 to 15% by weight, based on the total of the polymerization component of the acrylic resin (Aa). It is more preferably 3 to 10% by weight, and particularly preferably 4 to 7% by weight. When the ratio of the entire polymerization component is too small, the adhesive does not exhibit sufficient cohesive force, and the tendency to deteriorate after heating and humidification is observed. On the other hand, when the ratio of the polar component of the adhesive is high, the adhesive layer is likely to absorb moisture, so that foaming or the like is observed in the heating test, and durability is similar. The tendency to decrease.
丙烯酸系樹脂(Ab)中的含有醯胺基以外的官能基之單體(a1)的摻合量相對於丙烯酸系樹脂(Ab)之聚合成分整體,宜為1~20重量%,為1.5~15重量%更佳,為2~12重量%再更佳,為2.5~8重量%特佳。相對於聚合成分整體之比例過少的話,由於官能基大量殘存,故有容易造成物性隨時間變化的傾向,且由於黏接劑之極性成分的比例變高,黏接劑層變得容易吸收水分,故會有加熱所導致起泡等耐久性降低的傾向。相對於聚合成分整體之比例過多的話,丙烯酸系樹脂和交聯反應中之交聯劑無法充分反應而無法展現就黏接劑而言足夠的凝聚力,故有耐久性降低的傾向。 作為丙烯酸系樹脂(Ab)中的含有醯胺基以外的官能基之單體(a1),宜為含有羥基之單體、含有羧基之單體,將含有羥基之單體與含有羧基之單體併用特佳。The blending amount of the monomer (a1) having a functional group other than the amide group in the acrylic resin (Ab) is preferably from 1 to 20% by weight, based on the total amount of the polymerization component of the acrylic resin (Ab), and is 1.5 to 1.5%. More preferably, 15% by weight, more preferably 2 to 12% by weight, and particularly preferably 2.5 to 8% by weight. When the ratio of the polymer component is too small, the functional group tends to remain in a large amount, so that the physical properties tend to change with time, and since the ratio of the polar component of the binder becomes high, the adhesive layer easily absorbs moisture. Therefore, there is a tendency that the durability such as foaming due to heating tends to decrease. When the ratio of the total amount of the polymerization component is too large, the acrylic resin and the crosslinking agent in the crosslinking reaction are not sufficiently reacted to exhibit sufficient cohesive force with respect to the binder, and thus the durability tends to be lowered. The monomer (a1) which is a functional group other than a mercapto group in the acrylic resin (Ab) is preferably a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having a hydroxyl group and a monomer having a carboxyl group. And use the best.
作為將2種丙烯酸系樹脂予以混摻時的混摻之比率,例如為具有源自含有醯胺基之單體(a2)的結構單元之丙烯酸系樹脂(Aa)與具有源自含有醯胺基以外的官能基之單體(a1)的結構單元之丙烯酸系樹脂(Ab)的組合時,宜為(Ab):(Aa)=100:40~100:500(重量比),為(Ab):(Aa)=100:60~100:400(重量比)更佳,為(Ab):(Aa)=100:80~100:350(重量比)再更佳。丙烯酸系樹脂(Aa)相對於丙烯酸系樹脂(Ab)的比例過多的話,會有黏接劑之交聯度下降、凝聚力降低的傾向,過少的話,會有黏接劑之交聯度上昇、應力鬆弛性降低的傾向。The ratio of the blending when the two kinds of acrylic resins are blended is, for example, an acrylic resin (Aa) having a structural unit derived from a monomer (a2) containing a mercapto group, and having a mercapto group derived therefrom. When the combination of the acrylic resin (Ab) of the structural unit of the monomer (a1) other than the functional group is (Ab): (Aa) = 100: 40 to 100: 500 (weight ratio), (Ab) : (Aa) = 100: 60 ~ 100: 400 (weight ratio) is better, (Ab): (Aa) = 100: 80 ~ 100: 350 (weight ratio) is even better. When the ratio of the acrylic resin (Aa) to the acrylic resin (Ab) is too large, the degree of crosslinking of the adhesive decreases, and the cohesive force tends to decrease. When the amount is too small, the degree of crosslinking of the adhesive increases, and the stress increases. The tendency to reduce slack.
在混摻2種以上丙烯酸系樹脂時,各別的丙烯酸系樹脂之重量平均分子量宜為100萬~200萬,為130萬~160萬特佳。重量平均分子量過小的話,會有耐久性降低的傾向,重量平均分子量過大的話,會有相容性降低且黏接特性不均勻的傾向。When two or more kinds of acrylic resins are blended, the weight average molecular weight of each of the acrylic resins is preferably from 1,000,000 to 2,000,000, and is preferably from 1.3 to 1.6 million. When the weight average molecular weight is too small, the durability tends to be lowered, and if the weight average molecular weight is too large, the compatibility tends to be lowered and the adhesive properties tend to be uneven.
在混摻上述2種以上丙烯酸系樹脂時,2種以上所混摻的丙烯酸系樹脂(A)之分散度(重量平均分子量/數目平均分子量)宜為30以下,為15以下更佳,為7以下再更佳,為5以下特佳。分散度過高的話,會有凝聚力容易降低的傾向。另外,上述分散度之下限通常為2。When two or more kinds of the above acrylic resins are blended, the degree of dispersion (weight average molecular weight/number average molecular weight) of the two or more kinds of the acrylic resin (A) to be blended is preferably 30 or less, more preferably 15 or less, and is 7 or more. The following is even better, especially below 5. If the degree of dispersion is too high, the cohesive force tends to decrease. Further, the lower limit of the above dispersion is usually 2.
<抗靜電劑(B)> 然後,針對本發明之黏接劑組成物所使用的抗靜電劑(B)進行說明。本發明之黏接劑組成物所使用的抗靜電劑(B)為銨系抗靜電劑,具體而言可舉烷基銨磺酸鹽等四級銨鹽之陽離子型抗靜電劑。作為上述烷基銨鹽例如可列舉:甲基三正丁基銨雙(三氟甲磺醯基)醯亞胺[熔點27.5℃(製造商公佈值)(3M公司製,產品名:FC-4400)]、四丁基銨雙(三氟甲磺醯基)醯亞胺[熔點92℃(製造商公佈值)(MERCK公司製)]、溴化四丁基銨[熔點119℃(製造商公佈值)(和光純藥工業公司製)]、溴化四戊基銨[熔點98℃(製造商公佈值)(和光純藥工業公司製)]、溴化四辛基銨[熔點99℃(製造商公佈值)(和光純藥工業公司製)]、乙基二甲基丙基銨雙(三氟甲磺醯基)醯亞胺[熔點-11℃(製造商公佈值)(MERCK公司製)]、正丁基三甲基銨雙(三氟甲磺醯基)醯亞胺[熔點19℃(依據離子液體II CMC出版 ISBN978-4-7813-0878-4)]、甲基三辛基銨雙(三氟甲磺醯基)醯亞胺[熔點-75℃(依據離子液體II CMC出版 ISBN978-4-7813-0878-4)]、甲基三丁基硫酸銨甲酯[固體(Ardrich公司製)]、、四乙基三氟甲磺酸銨、四丁基苯甲酸銨、四丁基硫酸銨甲酯、四丁基九氟丁磺酸銨、四正丁基六氟磷酸銨、四丁基三氟乙酸銨、四己基四氟硼酸銨、溴化四己基銨等。該等可單獨使用亦可將2種以上併用。<Antistatic agent (B)> Next, the antistatic agent (B) used for the adhesive composition of the present invention will be described. The antistatic agent (B) used in the adhesive composition of the present invention is an ammonium-based antistatic agent, and specifically, a cationic antistatic agent of a quaternary ammonium salt such as an alkylammonium sulfonate. Examples of the alkylammonium salt include methyltri-n-butylammonium bis(trifluoromethanesulfonyl) quinone imine [melting point 27.5 ° C (manufacturer published value) (manufactured by 3M Company, product name: FC-4400) )], tetrabutylammonium bis(trifluoromethanesulfonyl) quinone imine [melting point 92 ° C (manufacturer published value) (manufactured by MERCK)], tetrabutylammonium bromide [melting point 119 ° C (manufacturer announced) Value) (made by Wako Pure Chemical Industries, Ltd.), tetraamylammonium bromide [melting point 98 ° C (manufacturer published value) (manufactured by Wako Pure Chemical Industries, Ltd.)], tetraoctyl ammonium bromide [melting point 99 ° C (manufacture) (published value) (made by Wako Pure Chemical Industries, Ltd.), ethyl dimethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine [melting point -11 ° C (manufacturer published value) (manufactured by MERCK) ], n-butyltrimethylammonium bis(trifluoromethanesulfonyl) quinone imine [melting point 19 ° C (published according to ionic liquid II CMC ISBN 978-4-7813-0878-4)], methyl trioctyl ammonium Bis(trifluoromethanesulfonyl) quinone imine [melting point -75 ° C (published according to ionic liquid II CMC ISBN 978-4-7813-0878-4)], methyl tributyl ammonium sulfate methyl ester [solid (Ardrich ,], tetraethylammonium trifluoromethanesulfonate, tetrabutylammonium benzoate, tetrabutylsulfate Methyl ester, tetrabutylammonium nonafluorobutanesulfonate, tetra-n-butylammonium hexafluorophosphate, tetrabutyl ammonium trifluoroacetate, tetra hexyl ammonium tetrafluoroborate, tetra hexyl ammonium. These may be used alone or in combination of two or more.
上述抗靜電劑(B)在常溫(25℃)宜為固體,又考慮溶解性的觀點,熔點宜為25~120℃,為25~100℃尤佳,為25~50℃更佳。熔點過低的話,會有滲出時耐久性極度降低的傾向,過高的話,會有溶解時抗靜電劑變成團塊而至溶解為止會耗費長時間的傾向。另外,作為抗靜電劑(B)將2種以上混合時的熔點,係將由混合的抗靜電劑各別的熔點與摻合比例(分配比)計算而得的平均之熔點的值視為熔點。The above antistatic agent (B) is preferably a solid at normal temperature (25 ° C), and from the viewpoint of solubility, the melting point is preferably 25 to 120 ° C, preferably 25 to 100 ° C, more preferably 25 to 50 ° C. When the melting point is too low, the durability tends to be extremely lowered at the time of bleeding. When the melting point is too high, the antistatic agent becomes agglomerated during dissolution, and it tends to take a long time until it dissolves. In addition, the melting point at the time of mixing two or more types of the antistatic agent (B) is a melting point calculated from the average melting point calculated from the respective melting points and blending ratios (distribution ratios) of the mixed antistatic agents.
因此,抗靜電劑(B)在前述例子之中,考慮熔點的觀點宜使用:甲基三正丁基銨雙(三氟甲磺醯基)醯亞胺(3M公司製)、四丁基銨雙(三氟甲磺醯基)醯亞胺(MERCK公司製)、溴化四丁基銨(和光純藥工業公司製)、溴化四戊基銨(和光純藥工業公司製),溴化四辛基銨(和光純藥工業公司製)、甲基三丁基硫酸銨甲酯(Ardrich公司製),使用甲基三正丁基銨雙(三氟甲磺醯基)醯亞胺(3M公司製)特佳。Therefore, in the above examples, the antistatic agent (B) is preferably used in view of the melting point: methyl tri-n-butylammonium bis(trifluoromethanesulfonyl) quinone imine (manufactured by 3M Company), tetrabutylammonium Bis(trifluoromethanesulfonyl) quinone imine (manufactured by MERCK Co., Ltd.), tetrabutylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.), tetraamyl ammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.), bromination Tetraoctyl ammonium (manufactured by Wako Pure Chemical Industries, Ltd.), methyl tributylammonium sulfate (manufactured by Ardrich Co., Ltd.), methyl tri-n-butylammonium bis(trifluoromethanesulfonyl) quinone imine (3M) Company system) is particularly good.
又,考慮抗靜電性能的觀點,宜為上述抗靜電劑(B)的陰離子成分為(三氟甲磺醯基)醯亞胺陰離子之抗靜電劑,其中,使用甲基三正丁基銨雙(三氟甲磺醯基)醯亞胺(3M公司製)特佳。Further, from the viewpoint of antistatic property, it is preferred that the anion component of the above antistatic agent (B) is an antistatic agent of (trifluoromethanesulfonyl) quinone imine anion, wherein methyl tri-n-butylammonium double is used. (Trifluoromethanesulfonyl) quinone imine (made by 3M Company) is particularly preferred.
又,作為本發明之銨系抗靜電劑(B)的陽離子成分,宜為烷基銨陽離子,就和丙烯酸系樹脂(A)之相容性優良的觀點,具有烷基鏈的碳數為1~6之烷基的烷基銨陽離子特佳。烷基鏈的碳數過大的話,會有熔點及導電率降低的傾向。In addition, the cationic component of the ammonium-based antistatic agent (B) of the present invention is preferably an alkylammonium cation, and has a carbon number of 1 in the viewpoint of excellent compatibility with the acrylic resin (A). The alkylammonium cation of the alkyl group of ~6 is particularly preferred. When the carbon number of the alkyl chain is too large, the melting point and the electrical conductivity tend to decrease.
上述抗靜電劑(B)的含量相對於100重量份之丙烯酸系樹脂(A),宜為1.2~15重量份,為2.5~14重量份更佳,為5~13重量份再更佳,為9~12重量份特佳。抗靜電劑(B)的含量過少的話,會見到無法得到足夠的抗靜電性能、或抗靜電性能隨時間之安定性降低的傾向,過多的話,會有抗靜電劑(B)一部分以結晶的方式滲出並成為液晶顯示板之亮點,使外觀不良發生等、或耐久性顯著降低的傾向。The content of the antistatic agent (B) is preferably 1.2 to 15 parts by weight, more preferably 2.5 to 14 parts by weight, even more preferably 5 to 13 parts by weight, based on 100 parts by weight of the acrylic resin (A). 9~12 parts by weight is especially good. When the content of the antistatic agent (B) is too small, there is a tendency that sufficient antistatic performance or antistatic property stability with time is not obtained, and if too much, the antistatic agent (B) is partially crystallized. The bleed out is a bright spot of the liquid crystal display panel, and the appearance is poor, and the durability tends to be remarkably lowered.
另外,在本發明中,上述抗靜電劑(B)係由銨系抗靜電劑構成者,但亦可併用此銨系抗靜電劑以外的抗靜電劑。作為其他的抗靜電劑可舉一般常用者,例如可列舉:咪唑鹽、脂肪族磺酸鹽、高級醇硫酸酯鹽、高級醇環氧烷加成物硫酸酯鹽、高級醇磷酸酯鹽、高級醇環氧烷加成物磷酸酯鹽等陰離子型抗靜電劑;雙(氟磺醯基)醯亞胺化鉀、雙(三氟磺醯基)醯亞胺化鋰、或氯化鋰等鹼金屬鹽;鹼土金屬鹽、高級醇環氧烷加成物、聚伸烷基二醇脂肪酸酯等。另外,併用上述其他的抗靜電劑時,在不妨礙上述銨系抗靜電劑之效果的範圍內使用即可,具體而言,其他的抗靜電劑之摻合量通常在抗靜電劑整體之5重量%以下的範圍內使用。Further, in the present invention, the antistatic agent (B) is composed of an ammonium antistatic agent, but an antistatic agent other than the ammonium antistatic agent may be used in combination. Other antistatic agents are generally used, and examples thereof include an imidazole salt, an aliphatic sulfonate, a higher alcohol sulfate salt, a higher alcohol alkylene oxide adduct sulfate salt, a higher alcohol phosphate salt, and an advanced one. An anionic antistatic agent such as an alcohol alkylene oxide adduct phosphate salt; a potassium bis(fluorosulfonyl) sulfonium iodide, a lithium bis(trifluorosulfonyl) ruthenium iodide or a base such as lithium chloride Metal salts; alkaline earth metal salts, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters, and the like. In addition, when the other antistatic agent is used in combination, it may be used in a range that does not interfere with the effect of the above-mentioned ammonium antistatic agent. Specifically, the amount of other antistatic agent is usually 5 in the entire antistatic agent. It is used in the range of % by weight or less.
本發明之黏接劑組成物含有上述特定的丙烯酸系樹脂(A)及抗靜電劑(B)作為必要成分,藉由將此黏接劑組成物利用交聯劑(C)進行交聯可得到本發明之黏接劑。The adhesive composition of the present invention contains the specific acrylic resin (A) and the antistatic agent (B) as essential components, and the binder composition is crosslinked by the crosslinking agent (C). The adhesive of the present invention.
作為上述交聯劑(C),例如可使用:異氰酸酯系交聯劑、環氧系交聯劑、氮丙啶系交聯劑、三聚氰胺系交聯劑、醛系交聯劑、胺系交聯劑、金屬螯合物系交聯劑等。As the crosslinking agent (C), for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a melamine crosslinking agent, an aldehyde crosslinking agent, and an amine crosslinking can be used. Agent, metal chelate crosslinking agent, and the like.
作為上述異氰酸酯系交聯劑,例如可列舉:2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯、二異氰酸氫化甲苯酯、二異氰酸-1,3-苯二甲酯、二異氰酸-1,4-苯二甲酯、二異氰酸六亞甲酯、4,4-二異氰酸二苯基甲烷酯、二異氰酸異佛爾酮酯、1,3-雙(異氰酸甲酯基)環己烷、二異氰酸四甲基苯二甲酯、1,5-二異氰酸萘酯、三異氰酸三苯基甲烷酯、及該等聚異氰酸酯化合物與三羥甲基丙烷等多元醇化合物之加成物、該等聚異氰酸酯化合物之縮二脲體、或異氰尿酸酯體等。其中就適用期長的觀點、或和樹脂之相容性優良的觀點,為2,4-二異氰酸甲苯酯與三羥甲基丙烷之加成物特佳。Examples of the isocyanate crosslinking agent include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, toluene diisocyanate, and diisocyanate-1,3. - phenyl dimethyl ester, diisocyanate - 1,4- phenyl dimethyl ester, hexamethylene diisocyanate, 4,4-diisocyanate diphenylmethane, diisocyanate isophor Ketoester, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylphenyl diisocyanate, naphthyl 1,5-diisocyanate, triphenyl triisocyanate a methane ester, an adduct of the polyisocyanate compound and a polyhydric alcohol compound such as trimethylolpropane, a biuret or a isocyanurate of the polyisocyanate compound. Among them, the viewpoint of a long pot life or an excellent compatibility with a resin is particularly preferable as an addition product of toluene 2,4-diisocyanate and trimethylolpropane.
作為上述環氧系交聯劑,例如可列舉:雙酚A・環氧氯丙烷型環氧樹脂、乙二醇二環氧丙醚、聚乙二醇二環氧丙醚、甘油二環氧丙醚、甘油三環氧丙醚、1,6-己二醇二環氧丙醚、三羥甲基丙烷三環氧丙醚、山梨糖醇聚環氧丙醚、聚甘油聚環氧丙醚、新戊四醇聚環氧丙基赤藻醇、二甘油基聚環氧丙醚、1,3-雙(N,N’-二環氧丙基胺甲基)環己烷、N,N,N’N’-四環氧丙基-間苯二甲基二胺等。其中就反應性高的觀點,為1,3-雙(N,N’-二環氧丙基胺甲基)環己烷、N,N,N’N’-四環氧丙基-間苯二甲基二胺特佳。Examples of the epoxy-based crosslinking agent include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerol diepoxypropyl acrylate. Ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, Pentaerythritol polyepoxypropyl erythritol, diglyceryl polyglycidyl ether, 1,3-bis(N,N'-diepoxypropylaminemethyl)cyclohexane, N,N, N'N'-tetraepoxypropyl-m-xylylenediamine. Among them, in view of high reactivity, it is 1,3-bis(N,N'-diepoxypropylaminemethyl)cyclohexane, N,N,N'N'-tetraepoxypropyl-m-phenylene Dimethyldiamine is particularly good.
作為上述氮丙啶系交聯劑,例如可列舉:丙酸四羥甲基甲烷-三-β-氮丙啶酯、丙酸三羥甲基丙烷-三-β-氮丙啶酯、N,N’-二苯基甲烷-4,4’-雙(1-氮丙啶甲醯胺)、N,N’-六亞甲基-1,6-雙(1-氮丙啶甲醯胺)等。Examples of the aziridine-based crosslinking agent include tetramethylolethane propionate-tri-β-aziridine propionate, trimethylolpropane propionate-tri-β-aziridine ester, and N. N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide) Wait.
作為上述三聚氰胺系交聯劑,例如可列舉:六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、六戊氧基甲基三聚氰胺、六己氧基甲基三聚氰胺、三聚氰胺樹脂等。Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, and hexaethoxyoxymethyl melamine. , hexahexyloxymethyl melamine, melamine resin, and the like.
作為上述醛系交聯劑,例如可列舉:乙二醛、丙二醛、丁二醛、順丁烯二醛、戊二醛、甲醛、乙醛、苯甲醛等。Examples of the aldehyde crosslinking agent include glyoxal, malondialdehyde, succinaldehyde, maleic aldehyde, glutaraldehyde, formaldehyde, acetaldehyde, and benzaldehyde.
作為上述胺系交聯劑,例如可列舉:六亞甲二胺、三乙二胺、聚伸乙亞胺、六亞甲四胺、二伸乙三胺、三伸乙四胺、異佛爾酮二胺、胺基樹脂、聚醯胺等。Examples of the amine-based crosslinking agent include hexamethylenediamine, triethylenediamine, polyethylenimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, and isophor. Ketodiamine, amine based resin, polydecylamine, and the like.
作為上述金屬螯合物系交聯劑,例如可列舉:鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻、鋯等多價金屬之乙醯基丙酮、或乙醯乙醯酯(acetoacetyl ester)配位化合物等。Examples of the metal chelate-based crosslinking agent include ethyl mercaptoacetone or a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, or zirconium. An acetoacetyl ester coordination compound, and the like.
該等之中,就耐久性、或耐漏光性優良的觀點,宜為異氰酸酯系交聯劑、環氧系交聯劑,併用異氰酸酯系交聯劑與環氧系交聯劑特佳。又,在本發明中,考慮銨系抗靜電劑之觸媒效果所致之熟成性提昇的觀點,亦宜為異氰酸酯系交聯劑。Among these, from the viewpoint of excellent durability and light leakage resistance, an isocyanate crosslinking agent and an epoxy crosslinking agent are preferable, and an isocyanate crosslinking agent and an epoxy crosslinking agent are particularly preferable. Further, in the present invention, from the viewpoint of improving the ripeness due to the catalytic effect of the ammonium-based antistatic agent, an isocyanate-based crosslinking agent is also preferable.
另外,該等交聯劑(C)可單獨使用亦可將2種以上併用。In addition, these crosslinking agents (C) may be used alone or in combination of two or more.
上述交聯劑(C)的含量相對於100重量份之丙烯酸系樹脂(A),宜為0.001~10重量份,為0.1~8重量份更佳,為0.3~7重量份再更佳,為0.5~6重量份特佳。交聯劑(C)過少的話,會見到耐久性降低的傾向,過多的話,會見到應力鬆弛性降低、或熟成性降低的傾向。The content of the crosslinking agent (C) is preferably 0.001 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, even more preferably 0.3 to 7 parts by weight, per 100 parts by weight of the acrylic resin (A). 0.5 to 6 parts by weight is particularly good. When the amount of the crosslinking agent (C) is too small, the durability tends to be lowered. When the amount is too large, the stress relaxation property is lowered or the ripening property tends to be lowered.
又,本發明之黏接劑組成物宜更含有矽烷偶聯劑(D)。藉由摻合此矽烷偶聯劑(D),在製成黏接劑時可使對光學構件之密合性提昇。Further, the adhesive composition of the present invention preferably further contains a decane coupling agent (D). By blending the decane coupling agent (D), the adhesion to the optical member can be improved when the adhesive is formed.
作為上述矽烷偶聯劑(D),例如可列舉:含有環氧基之矽烷偶聯劑、含有(甲基)丙烯醯基之矽烷偶聯劑、含有巰基之矽烷偶聯劑、含有羥基之矽烷偶聯劑、含有羧基之矽烷偶聯劑、含有胺基之矽烷偶聯劑、含有醯胺基之矽烷偶聯劑、含有異氰酸酯基之矽烷偶聯劑等。該等可單獨使用亦可將2種以上併用。Examples of the decane coupling agent (D) include a cyclodecane coupling agent containing an epoxy group, a decane coupling agent containing a (meth) acrylonitrile group, a decane coupling agent containing a mercapto group, and a decane containing a hydroxyl group. A coupling agent, a decane coupling agent containing a carboxyl group, a decane coupling agent containing an amine group, a decane coupling agent containing a guanamine group, a decane coupling agent containing an isocyanate group, and the like. These may be used alone or in combination of two or more.
該等之中,宜使用含有環氧基之矽烷偶聯劑、含有巰基之矽烷偶聯劑,併用含有環氧基之矽烷偶聯劑與含有巰基之矽烷偶聯劑就濕熱耐久性之提昇與黏接力不過度上昇的觀點亦為理想。又,部分水解並聚縮合之寡聚物型矽烷化合物就耐久性與重工性優良的觀點亦為理想。Among these, it is preferred to use an epoxy group-containing decane coupling agent, a mercapto group-containing decane coupling agent, and an epoxy group-containing decane coupling agent and a mercapto group-containing decane coupling agent to improve wet heat durability. The idea that the adhesion does not rise excessively is also ideal. Further, the oligomer-type decane compound which is partially hydrolyzed and polycondensed is also preferable from the viewpoint of excellent durability and reworkability.
作為上述含有環氧基之矽烷偶聯劑之具體例,例如可列舉:γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、甲基三(環氧丙基)矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷等,作為其中較理想者可列舉:γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷等。Specific examples of the epoxy group-containing decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and γ-. Glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, methyltris(epoxypropyl)decane, β-(3,4 ring Oxycyclohexyl)ethyltrimethoxydecane, β-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, etc., as preferred, γ-glycidoxypropyltrimethoxy Decane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4 epoxycyclohexyl)ethyltrimethoxy Decane and so on.
作為上述含有巰基之矽烷偶聯劑之具體例,例如可列舉:γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-巰基丙基二甲氧基甲基矽烷、含有SH基之矽酮烷氧寡聚物(巰基改性矽酸乙酯/矽酸甲酯低縮合物)等。Specific examples of the mercapto group-containing decane coupling agent include γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, and γ-mercaptopropyldimethoxymethylnonane. An oxime ketone alkoxy oligomer (fluorenyl-modified ethyl decanoate/methyl decanoate low condensate) containing SH group.
作為上述矽烷偶聯劑(D)的含量相對於100重量份之丙烯酸系樹脂(A),通常為0.001~10重量份,宜為0.01~1重量份,為0.03~0.8重量份更佳,為0.05~0.5重量份特佳。上述矽烷偶聯劑(D)的含量過少的話,會見到對光學構件之密合性無法提昇的傾向,過多的話,會見到滲出而耐久性降低的傾向。且會有黏接劑之密合性過度上昇而重工性性降低的傾向。The content of the decane coupling agent (D) is usually 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the acrylic resin (A), more preferably 0.03 to 0.8 part by weight. 0.05 to 0.5 parts by weight is particularly preferred. When the content of the decane coupling agent (D) is too small, the adhesion to the optical member tends to be unfavorable, and if it is too large, the bleeding tends to be observed and the durability tends to be lowered. Further, there is a tendency that the adhesion of the adhesive is excessively increased and the workability is lowered.
此外,本發明之黏接劑組成物中,在不損及本發明之效果的範圍內可摻合:其他黏接劑、胺甲酸乙酯樹脂、松香、松香酯、氫化松香酯、酚樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、苯乙烯系樹脂等賦黏劑;著色劑、填充劑、抗氧化劑、紫外線吸收劑、功能性色素等各種添加劑;或藉由照射紫外線或放射線而呈色或引起變色之類的化合物。又,上述添加劑之外,亦可少量含有黏接劑組成物之構成成分的製造原料等所含的雜質等。該等摻合量可適當地設定以獲得期望的物性。Further, the adhesive composition of the present invention may be blended in a range which does not impair the effects of the present invention: other adhesives, urethane resin, rosin, rosin ester, hydrogenated rosin ester, phenol resin, An adhesive such as an aliphatic petroleum resin, an alicyclic petroleum resin or a styrene resin; various additives such as a coloring agent, a filler, an antioxidant, an ultraviolet absorber, and a functional dye; or by irradiation with ultraviolet rays or radiation A compound that develops color or causes discoloration. Further, in addition to the above additives, impurities and the like contained in the raw material for production of the constituent components of the binder composition may be contained in a small amount. These blending amounts can be appropriately set to obtain desired physical properties.
在本發明中,藉由將上述本發明之黏接劑組成物予以交聯所構成之黏接劑層疊層形成於光學構件(光學疊層體)上,可獲得設有黏接劑層之光學構件。In the present invention, an adhesive layer layer formed by crosslinking the above-described adhesive composition of the present invention is formed on an optical member (optical laminate), whereby an optical layer provided with an adhesive layer can be obtained. member.
上述設有黏接劑層之光學構件,在和黏接劑層之光學構件面相反的面上,宜再設置脫模片材。The optical member provided with the adhesive layer is preferably provided with a release sheet on a surface opposite to the surface of the optical member of the adhesive layer.
作為上述設有黏接劑層之光學構件之製造方法有:[1]將黏接劑組成物塗佈於光學構件上,乾燥後貼合脫模片材並實施在室溫(23℃)或加溫狀態下之熟成處理的方法、[2]將黏接劑組成物塗佈於偏光板上並進行乾燥,再實施於室溫或加溫狀態下之熟成處理後貼合脫模片材的方法、[3]將黏接劑組成物塗佈於脫模片材上,乾燥後貼合偏光板並實施在室溫或加溫狀態下之熟成處理的方法、[4]將黏接劑組成物塗佈於脫模片材上並進行乾燥,實施在室溫或加溫狀態下之熟成處理後貼合偏光板的方法等。其中,上述[2]的方法就不損傷基材的觀點及和基材之黏著性優良的觀點較理想。The method for producing the optical member provided with the adhesive layer is as follows: [1] applying the adhesive composition to the optical member, drying the bonded release sheet, and performing the method at room temperature (23 ° C) or a method of aging treatment under heating, [2] applying the adhesive composition to a polarizing plate and drying, and then performing the aging treatment at room temperature or under heating to bond the release sheet The method [3] applies the adhesive composition to the release sheet, and after drying, the polarizing plate is attached and subjected to a ripening treatment at room temperature or under heating, [4] comprising an adhesive. The object is applied onto a release sheet and dried, and a method of laminating a polarizing plate after aging treatment at room temperature or in a heated state is carried out. Among them, the method of the above [2] is preferable from the viewpoint of not damaging the substrate and the adhesion to the substrate.
上述熟成處理就黏接劑之化學交聯的反應時間而言,係為了取得黏接物性之平衡而實施,作為熟成之條件,溫度通常為室溫~70℃、時間通常為1天~30天,具體而言,例如在23℃、1天~20天;23℃、3天~10天;40℃、1天~7天等條件下實施即可。The above-mentioned ripening treatment is carried out in order to obtain a balance of the adhesive properties in terms of the reaction time of the chemical crosslinking of the adhesive. As a condition of ripening, the temperature is usually from room temperature to 70 ° C, and the time is usually from 1 day to 30 days. Specifically, for example, it can be carried out under conditions of 23 ° C, 1 day to 20 days, 23 ° C, 3 days to 10 days, 40 ° C, 1 day to 7 days, and the like.
上述熟成處理係為了取得黏接物性之平衡而實施的處理,例如使用異氰酸酯系交聯劑將黏接劑組成物予以交聯時,熟成在23℃約7天特佳。In the above-mentioned ripening treatment, in order to obtain a balance of the adhesive properties, for example, when the adhesive composition is crosslinked by using an isocyanate crosslinking agent, the ripening is particularly preferable at 23 ° C for about 7 days.
另外,本發明之黏接劑組成物由於熟成特性優良,交聯會在短時間內進行,凝膠分率上昇且安定化,故即使熟成處理時間短仍可獲得黏接物性優良的黏接劑。因此,比起以往可更縮短熟成處理時間,在生產性方面非常有利。又,由於黏接物性在短時間內安定,故亦可抑制例如將設有黏接劑層之膜以卷軸狀保存時,保護膜之抗黏連層的粒子轉印至黏接劑,即所謂「橘皮(orange peel)」之問題。Further, since the adhesive composition of the present invention is excellent in aging characteristics, crosslinking is carried out in a short period of time, and the gel fraction is increased and stabilized, so that an adhesive having excellent adhesive properties can be obtained even if the aging treatment time is short. . Therefore, the ripening treatment time can be shortened more than in the past, and it is very advantageous in terms of productivity. Further, since the adhesive property is stabilized in a short period of time, it is also possible to prevent, for example, when the film having the adhesive layer is stored in a roll shape, the particles of the anti-adhesion layer of the protective film are transferred to the adhesive, that is, the so-called adhesive The problem of "orange peel".
塗佈上述黏接劑組成物時,宜將此黏接劑組成物稀釋於溶劑後塗佈,作為稀釋濃度,以加熱殘留成分濃度計宜為5~60重量%,為10~30重量%更佳。又,作為上述溶劑,若為使黏接劑組成物溶解者即無特別限制,例如可使用:乙酸甲酯、乙酸乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯等酯系溶劑;丙酮、甲乙酮、甲基異丁酮等酮系溶劑;甲苯、二甲苯等芳香族系溶劑;甲醇、乙醇、丙醇等醇系溶劑。該等之中,考慮溶解性、乾燥性、價格等觀點適合使用:酯系溶劑,尤其乙酸乙酯;酮系溶劑,尤其甲乙酮。When applying the above-mentioned adhesive composition, it is preferable to dilute the adhesive composition in a solvent and apply it as a dilution concentration, preferably 5 to 60% by weight based on the concentration of the residual component of the heating, and 10 to 30% by weight. good. Further, the solvent is not particularly limited as long as it dissolves the binder composition, and for example, an ester solvent such as methyl acetate, ethyl acetate, methyl acetate or ethyl acetate; acetone; A ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an aromatic solvent such as toluene or xylene; or an alcohol solvent such as methanol, ethanol or propanol. Among these, it is suitable to use in view of solubility, drying property, price, etc.: an ester solvent, especially ethyl acetate; a ketone solvent, especially methyl ethyl ketone.
又,關於上述黏接劑組成物之塗佈,係利用輥塗佈、模具塗佈、凹版塗佈、逗塗塗佈、網版印刷等慣用的方法實施。Further, the application of the above-mentioned adhesive composition is carried out by a conventional method such as roll coating, die coating, gravure coating, smear coating, or screen printing.
關於利用上述方法製造的黏接劑層之凝膠分率,在將黏接劑組成物溶液之塗佈・乾燥後經過1天之黏接劑層的凝膠分率定義為「初始凝膠分率Gi」,於室溫(23℃)環境下再熟成6天之樣本的凝膠分率定義為「熟成後凝膠分率Ga」,此外在上述6天之熟成後於80℃烘箱中加熱24小時之黏接劑層的凝膠分率定義為「加熱後凝膠分率Gh」時,黏接劑層之凝膠分率Ga考慮耐久性能與抗漏光性能的觀點,宜為40~85%,為45~75%更佳,為50~70%再更佳。凝膠分率Ga過低的話,會有黏接劑層之凝聚力變弱,於高溫環境下容易產生氣泡的傾向,過高的話,會有黏接劑層變硬,於高溫高濕環境下的黏著性降低且容易產生剝離的傾向。凝膠分率例如可藉由調整交聯劑的量、或種類;調整黏接劑組成物成分之丙烯酸系樹脂(A)的混摻比、或丙烯酸系樹脂(A)之單體組成、分子量等而調整。Regarding the gel fraction of the adhesive layer produced by the above method, the gel fraction of the adhesive layer after one day of application and drying of the adhesive composition solution is defined as "initial gel fraction". Rate Gi", the gel fraction of the sample which was re-cooked for 6 days at room temperature (23 ° C) was defined as "the gel fraction Ga after ripening", and was heated in an oven at 80 ° C after the above 6 days of ripening. When the gel fraction of the adhesive layer for 24 hours is defined as "the gel fraction Gh after heating", the gel fraction Ga of the adhesive layer is considered to be 40 to 85 in view of durability and light leakage resistance. %, 45~75% is better, 50~70% is better. When the gel fraction Ga is too low, the cohesive force of the adhesive layer becomes weak, and the bubble tends to be generated in a high-temperature environment. If the gel content is too high, the adhesive layer becomes hard, and the adhesive layer is hardened in a high-temperature and high-humidity environment. The adhesiveness is lowered and the tendency to peel off is likely to occur. The gel fraction can be adjusted, for example, by adjusting the amount or type of the crosslinking agent; adjusting the blending ratio of the acrylic resin (A) of the binder composition component, or the monomer composition and molecular weight of the acrylic resin (A). Wait and adjust.
又,利用上述方法製造的黏接劑層之熟成後凝膠分率Ga之相對於上述初始凝膠分率Gi之變化率(Ga/Gi),通常未達300%,宜為未達150%。上述熟成後凝膠分率Ga之變化率(Ga/Gi)過高時,會有黏接劑層之物性到達安定之熟成時間變長,生產性降低的傾向。Moreover, the rate of change of the gel fraction Ga of the adhesive layer produced by the above method relative to the initial gel fraction Gi (Ga/Gi) is usually less than 300%, preferably less than 150%. . When the rate of change (Ga/Gi) of the gel fraction Ga after the above-mentioned aging is too high, the maturing time of the physical properties of the adhesive layer reaching stability is prolonged, and the productivity tends to be lowered.
此外,上述黏接劑層之加熱後凝膠分率Gh之相對於上述熟成後凝膠分率Ga之變化率(Gh/Ga),通常為90~110%,宜為95~105%。上述加熱後凝膠分率Gh之變化率(Gh/Ga)過低或過高時,會有依保存場所之環境而作為黏接劑之物性產生偏差且耐久性等降低的傾向。Further, the rate of change (Gh/Ga) of the gel fraction Gh after heating of the adhesive layer relative to the gel fraction Ga after the ripening is usually 90 to 110%, preferably 95 to 105%. When the rate of change (Gh/Ga) of the gel fraction Gh after heating is too low or too high, there is a tendency that the physical properties of the adhesive agent vary depending on the environment of the storage place, and durability and the like tend to be lowered.
另外,上述凝膠分率係組成物之交聯度(硬化程度)的示值,例如利用以下的方法計算而得。亦即,從由黏接劑層形成於作為基材之光學構件(例如偏光板)所構成之黏接片材刮取黏接劑層,並將黏接層以200網目之SUS製金屬網包覆,再以23℃×24小時之條件浸漬於乙酸乙酯中,將金屬網中殘存之不溶解的黏接劑成分(交聯成分)之重量百分率定為凝膠分率。關於上述初始凝膠分率Gi、熟成後凝膠分率Ga、加熱後凝膠分率Gh亦包含其熟成條件、或測量方法等,皆以後述實施例進行詳細地說明。Further, the gel fraction ratio is an indication of the degree of crosslinking (degree of hardening) of the composition, which is calculated, for example, by the following method. That is, the adhesive layer is scraped from the adhesive sheet formed of the adhesive member layer formed on the optical member (for example, a polarizing plate) as a substrate, and the adhesive layer is made of SUS metal mesh of 200 mesh. The coating was further immersed in ethyl acetate under the conditions of 23 ° C × 24 hours, and the weight percentage of the insoluble binder component (crosslinking component) remaining in the metal mesh was determined as the gel fraction. The initial gel fraction Gi, the gel fraction Ga after ripening, and the gel fraction Gh after heating also include the ripening conditions, measurement methods, and the like, which will be described in detail later.
上述初始黏接力係以下述方式計算而得。針對設有黏接劑層之偏光板裁切成寬幅25mm之寬度,將脫模片材剝離,並將黏接劑層側推壓至無鹼玻璃板(CORNING公司製,「EAGLE XG」)而將偏光板與玻璃板貼合。其後,實施高溫高壓(autoclave)處理(50℃、0.5MPa、20分鐘)後,放置於23℃・50%RH24小時後,實施180°剝離試驗。The above initial adhesion is calculated in the following manner. The polarizing plate provided with the adhesive layer was cut into a width of 25 mm in width, the release sheet was peeled off, and the adhesive layer side was pressed to an alkali-free glass plate ("EAGLE XG" manufactured by CORNING Co., Ltd.) The polarizing plate is attached to the glass plate. Thereafter, autoclave treatment (50° C., 0.5 MPa, 20 minutes) was carried out, and after standing at 23° C. and 50% RH for 24 hours, a 180° peel test was performed.
又,設有黏接劑層之光學構件中的黏接劑層之厚度宜為5~300μm,為10~50μm更佳,為10~30μm再更佳。此黏接劑層之厚度過薄的話,會見到黏接物性不易安定的傾向,過厚的話,會見到生產時含有氣泡等外觀不良會增加的傾向。Further, the thickness of the adhesive layer in the optical member provided with the adhesive layer is preferably 5 to 300 μm, more preferably 10 to 50 μm, still more preferably 10 to 30 μm. When the thickness of the adhesive layer is too small, the adhesive property tends to be difficult to be stabilized. When the thickness is too thick, there is a tendency that appearance defects such as bubbles are increased during production.
作為本發明中的光學構件並無特別限制,可列舉適用於液晶顯示裝置、有機EL顯示裝置、PDP等影像顯示裝置之光學膜,例如:偏光板、或相位差板、橢圓偏光板、光學補償膜、亮度提昇膜、或該等疊層而得者等。其中,為偏光板的話在本發明中係為有效,尤其為需求耐受偏光片之收縮等高耐久性之偏光板的話本發明係為有效。The optical member in the present invention is not particularly limited, and examples thereof include an optical film which is applied to an image display device such as a liquid crystal display device, an organic EL display device, or a PDP, for example, a polarizing plate, a phase difference plate, an elliptically polarizing plate, and optical compensation. A film, a brightness enhancement film, or the like, or the like. Among them, the present invention is effective in the case of a polarizing plate, and is particularly effective in the case of a polarizing plate which is required to withstand high shrinkage such as shrinkage of a polarizing plate.
因此,使用本發明之黏接劑將偏光板貼附於液晶單元(玻璃板)之液晶顯示板,即使在高溫高濕等嚴苛的條件下持續使用,其表面之抗靜電性能歷經長時間仍不降低,可製成不發生偏光板剝離等瑕疵之耐久性優良的液晶顯示板。Therefore, by using the adhesive of the present invention, the polarizing plate is attached to the liquid crystal display panel of the liquid crystal cell (glass plate), and the antistatic property of the surface remains for a long time even if it is continuously used under severe conditions such as high temperature and high humidity. Without failing, it is possible to produce a liquid crystal display panel which is excellent in durability without causing peeling of the polarizing plate or the like.
又,本發明所使用的偏光板通常係於偏光膜之雙面疊層保護膜而成者,又,為了薄膜化,亦有去掉偏光板貼合側之保護膜的單保護膜偏光板等。作為上述保護膜,例如可列舉:丙烯酸系膜、聚乙烯系膜、聚丙烯系膜、環烯烴系膜等疏水性高的樹脂膜。另外,本發明中亦能使用通常之使用三乙醯基纖維素膜者作為保護膜。In addition, the polarizing plate used in the present invention is usually formed by laminating a protective film on both sides of a polarizing film, and a single protective film polarizing plate or the like having a protective film on the side where the polarizing plate is bonded is removed for thinning. Examples of the protective film include a highly hydrophobic resin film such as an acrylic film, a polyethylene film, a polypropylene film, or a cycloolefin film. Further, in the present invention, a conventional use of a triethylenesulfonated cellulose film can also be used as a protective film.
作為上述偏光膜,使用將由平均聚合度為1,500~10,000、皂化度為85~100莫耳%之聚乙烯醇系樹脂構成的膜作為原捲膜,再利用碘-碘化鉀之水溶液或二色性染料予以染色而得之單軸延伸膜(通常約2~10倍,宜為約3~7倍之延伸倍率)。As the polarizing film, a film made of a polyvinyl alcohol-based resin having an average degree of polymerization of 1,500 to 10,000 and a degree of saponification of 85 to 100 mol% is used as a raw film, and an aqueous solution of iodine-potassium iodide or a dichroic dye is used. The uniaxially stretched film obtained by dyeing (usually about 2 to 10 times, preferably about 3 to 7 times the stretching ratio).
作為上述聚乙烯醇系樹脂,通常係將乙酸乙烯酯聚合而得的聚乙酸乙烯酯予以皂化而製造,但亦可含有少量的不飽和羧酸(包含鹽、酯、醯胺、腈等)、烯烴類、乙烯醚類、不飽和磺酸鹽等能和乙酸乙烯酯共聚合之成分。又,亦可利用使聚乙烯醇在酸的存在下與醛類反應者,例如:聚乙烯醇縮丁醛樹脂,聚乙烯醇縮甲醛樹脂等之即所謂聚乙烯系縮醛樹脂及聚乙烯醇衍生物。The polyvinyl alcohol-based resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but may contain a small amount of an unsaturated carboxylic acid (including a salt, an ester, a guanamine, a nitrile, etc.), A component which can be copolymerized with vinyl acetate, such as an olefin, a vinyl ether or an unsaturated sulfonate. Further, it is also possible to use a polyvinyl alcohol in the presence of an acid to react with an aldehyde, for example, a polyvinyl butyral resin, a polyvinyl formal resin, or the like, a so-called polyethylene acetal resin and polyvinyl alcohol. derivative.
就利用上述方法製造之設有黏接劑層之偏光板的抗靜電性能而言,在製造上述設有黏接劑層之偏光板後,於23℃×50%RH環境氣體下靜置24小時後,去除黏接劑層之分隔件(separator),並使用後述表面電阻率測量裝置測量該黏接劑層之表面電阻值所得到的「初始表面電阻值Ri」宜未達1.0×1012 Ω/□,未達1.0×1011 Ω/□更佳,未達5.0×109 Ω/□再更佳。初始表面電阻值Ri過高的話,和液晶顯示板之背光源的摩擦等導致偏光板帶電,會有引起顯示不良的傾向。For the antistatic property of the polarizing plate provided with the adhesive layer manufactured by the above method, after the polarizing plate provided with the adhesive layer is manufactured, it is allowed to stand under 23 ° C × 50% RH ambient gas for 24 hours. After that, the separator of the adhesive layer is removed, and the surface resistance value of the adhesive layer measured by the surface resistivity measuring device described later is preferably less than 1.0×10 12 Ω. /□, less than 1.0 × 10 11 Ω / □ is better, less than 5.0 × 10 9 Ω / □ and even better. When the initial surface resistance value Ri is too high, the polarizing plate is charged by friction with the backlight of the liquid crystal display panel or the like, and display defects tend to occur.
又,就上述設有黏接劑層之偏光板之抗靜電性之隨時間安定性而言,在製造上述設有黏接劑層之偏光板後,於溫度40℃、濕度90%RH之烘箱中保存100小時,再於23℃×50%RH環境氣體下靜置24小時後,去除黏接劑層之分隔件,並使用後述表面電阻率測量裝置測量該黏接劑層之表面電阻值,將所得到的值定義為「加濕後表面電阻值Rt」時,在「加濕後表面電阻值Rt」/「初始表面電阻值Ri」=隨時間之變化率中,隨時間之變化率(Rt/Ri)宜維持在0.6~1.4之範圍內,在0.8~1.2之範圍內更佳,在0.9~1.1之範圍內再更佳。抗靜電性能隨時間之變化(隨時間之變化率的變動)過大的話,取決於產品,會產生偏差,且在長時間、或高溫高濕環境下的使用,和液晶顯示板之背光源的摩擦等導致偏光板帶電,有觀察到顯示不良的傾向。又,作為觸控面板用等而使用時,感測器的感度出現變化,會有觀察到無法正常驅動的傾向。 [實施例]Moreover, in terms of the stability over time of the antistatic property of the polarizing plate provided with the adhesive layer, after manufacturing the polarizing plate provided with the adhesive layer, the oven is heated at a temperature of 40 ° C and a humidity of 90% RH. After storing for 100 hours, and then standing at 23 ° C × 50% RH ambient gas for 24 hours, the separator of the adhesive layer was removed, and the surface resistivity of the adhesive layer was measured using a surface resistivity measuring device described later. When the obtained value is defined as "surface resistance value Rt after humidification", the rate of change with time in the "surface resistance value Rt after humidification" / "initial surface resistance value Ri" = rate of change with time ( Rt/Ri) should be maintained in the range of 0.6 to 1.4, more preferably in the range of 0.8 to 1.2, and even better in the range of 0.9 to 1.1. If the antistatic property changes with time (variation of the rate of change with time) is too large, depending on the product, deviations may occur, and the use in a long time, high temperature and high humidity environment, and the backlight of the liquid crystal display panel When the polarizing plate is charged, the tendency to display defects is observed. Moreover, when used as a touch panel or the like, the sensitivity of the sensor changes, and there is a tendency that it is not normally driven. [Examples]
以下,舉實施例更具體地說明本發明,但本發明只要不超過其要旨,則不受以下實施例限制。另外,例中的「份」、「%」係意指重量基準。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples as long as it does not exceed the gist of the invention. In addition, "part" and "%" in the example mean the weight basis.
首先,如下所述製得各種丙烯酸系樹脂。另外,關於丙烯酸系樹脂之重量平均分子量、黏接劑之凝膠分率的測量係遵照前述方法而測量。First, various acrylic resins were produced as follows. Further, the measurement of the weight average molecular weight of the acrylic resin and the gel fraction of the adhesive was carried out in accordance with the above method.
[丙烯酸系樹脂(A)之製備] 在以下樹脂的製造中,於物質名後附記之(a1)~(a4)係表示單體的種類,各別表示:(a1)為含有醯胺基以外的官能基之單體、(a2)為含有醯胺基之單體、(a3)為(甲基)丙烯酸烷酯系單體、(a4)為其他共聚合性單體。[Preparation of Acrylic Resin (A)] In the production of the following resin, (a1) to (a4) appended to the substance name indicate the type of the monomer, and each of them indicates that (a1) is other than the amidino group. The monomer of the functional group, (a2) is a monomer containing a guanamine group, (a3) is an alkyl (meth) acrylate monomer, and (a4) is another copolymerizable monomer.
<丙烯酸系樹脂(A-1)之製造> 將丙烯酸丁酯[BA](a3)82.5份、丙烯酸苄酯[BzA](a4)10份、丙烯酸-2-羥乙酯[HEA](a1)0.5份、丙烯酸[AAc](a1)7份、作為溶劑之乙酸乙酯47.2份、丙酮42份、作為聚合起始劑之偶氮雙異丁腈[AIBN]0.013份進料於具備有回流冷卻器、攪拌器、氮氣吹入口及溫度計之4口圓底燒瓶中,邊適當地追加AIBN與乙酸乙酯邊在回流溫度反應3.25小時後,利用乙酸乙酯稀釋獲得丙烯酸系樹脂(A-1)(重量平均分子量150萬、分散度3.3)之溶液。<Production of Acrylic Resin (A-1)> 82.5 parts of butyl acrylate [BA] (a3), 10 parts of benzyl acrylate [BzA] (a4), and 2-hydroxyethyl acrylate [HEA] (a1) 0.5 parts, 7 parts of [AAc](a1) acrylic acid, 47.2 parts of ethyl acetate as a solvent, 42 parts of acetone, and 0.013 parts of azobisisobutyronitrile [AIBN] as a polymerization initiator were provided with reflux cooling. In a 4-neck round bottom flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer, an AIBN and an ethyl acetate were added to react at a reflux temperature for 3.25 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A-1). A solution having a weight average molecular weight of 1.5 million and a dispersion of 3.3.
<丙烯酸系樹脂(A-2)之製造> 將丙烯酸丁酯(a3)88.5份、丙烯酸苄酯(a4)10份、丙烯酸-2-羥乙酯(a1)0.5份、丙烯酸(a1)1份、作為溶劑之乙酸乙酯47.2份、丙酮42份、作為聚合起始劑之偶氮雙異丁腈[AIBN]0.013份進料於具備有回流冷卻器、攪拌器、氮氣吹入口及溫度計之4口圓底燒瓶中,邊適當地追加AIBN與乙酸乙酯邊在回流溫度反應3.25小時後,利用乙酸乙酯稀釋獲得丙烯酸系樹脂(A-2)(重量平均分子量150萬、分散度3.4)之溶液。<Production of Acrylic Resin (A-2)> 88.5 parts of butyl acrylate (a3), 10 parts of benzyl acrylate (a4), 0.5 part of 2-hydroxyethyl acrylate (a1), and 1 part of acrylic acid (a1) 47.2 parts of ethyl acetate as a solvent, 42 parts of acetone, and 0.013 parts of azobisisobutyronitrile [AIBN] as a polymerization initiator were supplied with a reflux cooler, a stirrer, a nitrogen gas inlet, and a thermometer. In the round bottom flask, AIBN and ethyl acetate were added to react at reflux temperature for 3.25 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A-2) (weight average molecular weight: 1.5 million, degree of dispersion: 3.4). Solution.
<丙烯酸系樹脂(A-3)之製造> 將丙烯酸丁酯(a3)93份、甲基丙烯酸甲酯[MMA](a3)2份、二甲基丙烯醯胺[DMAA](a2)5份、作為溶劑之乙酸乙酯43份、丙酮42份、作為聚合起始劑之偶氮雙異丁腈[AIBN]0.011份進料於具備有回流冷卻器、攪拌器、氮氣吹入口及溫度計之4口圓底燒瓶中,邊適當地追加AIBN與乙酸乙酯邊在回流溫度反應3.25小時後,利用乙酸乙酯稀釋獲得丙烯酸系樹脂(A-3)(重量平均分子量140萬、分散度4.6)之溶液。<Production of Acrylic Resin (A-3)> 93 parts of butyl acrylate (a3), 2 parts of methyl methacrylate [MMA] (a3), and 5 parts of dimethyl acrylamide [DMAA] (a2) 43 parts of ethyl acetate as a solvent, 42 parts of acetone, and 0.011 parts of azobisisobutyronitrile [AIBN] as a polymerization initiator were supplied with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer. In the round-bottomed round flask, the AFBN and ethyl acetate were added and reacted at reflux temperature for 3.25 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A-3) (weight average molecular weight: 1.4 million, degree of dispersion: 4.6). Solution.
<丙烯酸系樹脂(A-4)之製造> 將丙烯酸丁酯(a3)78份、甲基丙烯酸甲酯(a3)2份、二甲基丙烯醯胺(a2)20份、作為溶劑之乙酸乙酯43份、丙酮42份、作為聚合起始劑之偶氮雙異丁腈[AIBN]0.011份進料於具備有回流冷卻器、攪拌器、氮氣吹入口及溫度計之4口圓底燒瓶中,邊適當地追加AIBN與乙酸乙酯邊在回流溫度反應3.25小時後,利用乙酸乙酯稀釋獲得丙烯酸系樹脂(A-4)(重量平均分子量140萬、分散度3.6)之溶液。<Production of Acrylic Resin (A-4)> 78 parts of butyl acrylate (a3), 2 parts of methyl methacrylate (a3), 20 parts of dimethyl acrylamide (a2), and acetic acid B as a solvent 43 parts of ester, 42 parts of acetone, and 0.011 part of azobisisobutyronitrile [AIBN] as a polymerization initiator were fed into a 4-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer. A solution of the acrylic resin (A-4) (weight average molecular weight: 1.4 million, dispersion degree: 3.6) was obtained by diluting with ethyl acetate by appropriately adding AIBN and ethyl acetate at a reflux temperature for 3.25 hours.
<丙烯酸系樹脂(A-5)之製造> 將丙烯酸丁酯(a3)89.8份、二甲基丙烯醯胺(a2)5份、丙烯酸-2-羥乙酯(a1)0.2份、丙烯酸(a1)5份、作為溶劑之乙酸乙酯43份、丙酮42份、作為聚合起始劑之偶氮雙異丁腈[AIBN]0.011份進料於具備有回流冷卻器、攪拌器、氮氣吹入口及溫度計之4口圓底燒瓶中,邊適當地追加AIBN與乙酸乙酯邊在回流溫度反應3.25小時後,利用乙酸乙酯稀釋獲得丙烯酸系樹脂(A-5)(重量平均分子量150萬、分散度3.5)之溶液。<Production of Acrylic Resin (A-5)> 89.8 parts of butyl acrylate (a3), 5 parts of dimethyl acrylamide (a2), 0.2 parts of 2-hydroxyethyl acrylate (a1), acrylic acid (a1) 5 parts, 43 parts of ethyl acetate as a solvent, 42 parts of acetone, and 0.011 part of azobisisobutyronitrile [AIBN] as a polymerization initiator were provided with a reflux condenser, a stirrer, a nitrogen gas inlet, and In a four-necked round bottom flask, a mixture of AIBN and ethyl acetate was added at a reflux temperature for 3.25 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A-5) (weight average molecular weight: 1.5 million, dispersion degree) 3.5) solution.
針對如上所述製得的丙烯酸系樹脂(A-1)~(A-5),將原料單體成分的含量、重量平均分子量(Mw)及分散度表示於下述表1。The content of the raw material monomer component, the weight average molecular weight (Mw), and the degree of dispersion of the acrylic resins (A-1) to (A-5) obtained as described above are shown in Table 1 below.
【表1】 丙烯酸系樹脂(A)之摻合
<抗靜電劑(B)> 又,作為抗靜電劑(B),準備以下之化合物。 (B-1):甲基三正丁基銨雙(三氟甲磺醯基)醯亞胺 熔點27.5℃(製造商公佈值)(3M公司製,「FC-4400」) (B-2):四丁基銨雙(三氟甲磺醯基)醯亞胺 熔點92℃(製造商公佈值)(MERCK公司製) (B-3):甲基三丁基硫酸銨甲酯 固體(Ardrich公司製) (B-4):1-丁基-2,3-二甲基三氟甲磺酸咪唑 熔點100℃(製造商公佈值)(MERCK公司製) (B-5):溴化四丁基鏻 熔點100℃(製造商公佈值)(和光純藥工業公司製) (B-6):雙三氟甲磺醯亞胺鋰(四乙二醇二甲醚分散液)(三光化學公司製,「SANKONORU TGR」)<Antistatic agent (B)> Further, as an antistatic agent (B), the following compounds were prepared. (B-1): Methyl tri-n-butylammonium bis(trifluoromethanesulfonyl) quinone imine melting point 27.5 ° C (manufacturer published value) (manufactured by 3M Company, "FC-4400") (B-2) : tetrabutylammonium bis(trifluoromethanesulfonyl) quinone imine melting point 92 ° C (manufacturer published value) (manufactured by MERCK) (B-3): methyl tributyl ammonium sulfate methyl ester solid (Ardrich (B-4): 1-butyl-2,3-dimethyltrifluoromethanesulfonate imidazole melting point 100 ° C (manufacturer published value) (manufactured by MERCK) (B-5): tetrabutyl bromide Base melting point 100 ° C (manufacturer's published value) (manufactured by Wako Pure Chemical Industries, Ltd.) (B-6): lithium bistrifluoromethanesulfonimide (tetraethylene glycol dimethyl ether dispersion) (manufactured by Sanko Chemical Co., Ltd.) , "SANKONORU TGR")
<交聯劑(C)> 然後,作為交聯劑(C),準備以下之化合物。 (C-1):三羥甲基丙烷之二異氰酸甲苯酯加成物的55%乙酸乙酯溶液(日本聚胺酯公司製,「CORONATE L-55E」) (C-2):1,3-雙(N,N’-二環氧丙基胺甲基)環己烷(三菱瓦斯化學公司製,「TETRAD-C」)<Crosslinking agent (C)> Then, as the crosslinking agent (C), the following compounds were prepared. (C-1): a 55% ethyl acetate solution of a toluene diisocyanate adduct of trimethylolpropane (manufactured by Nippon Polyurethane Co., Ltd., "CORONATE L-55E") (C-2): 1,3 -Bis(N,N'-diepoxypropylaminomethyl)cyclohexane ("TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.)
<矽烷偶聯劑(D)> 又,作為矽烷偶聯劑(D),準備以下之化合物。 (D-1):環氧系矽烷偶聯劑[3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業公司製,「KBM-403」)]<Hydrane coupling agent (D)> Further, as a decane coupling agent (D), the following compounds were prepared. (D-1): epoxy-based decane coupling agent [3-glycidoxypropyltrimethoxydecane ("KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.)]
[實施例1~10、比較例1~7] [黏接劑組成物(溶液)之製備] 藉由將如上所述製備、準備的各摻合成分,以下述表2所示之比例進行摻合,製得黏接劑組成物,並將其利用乙酸乙酯稀釋,製得黏接劑組成物溶液(固體成分濃度13%)。另外,下述表2中,抗靜電劑(B)、交聯劑(C)、矽烷偶聯劑(D)之各摻合量係將丙烯酸系樹脂(A)整體定為100重量份換算而得的值。[Examples 1 to 10, Comparative Examples 1 to 7] [Preparation of Adhesive Composition (Solution)] Each of the blended components prepared and prepared as described above was blended at a ratio shown in Table 2 below. The adhesive composition was prepared and diluted with ethyl acetate to prepare a binder composition solution (solid content concentration: 13%). In the following Table 2, the respective amounts of the antistatic agent (B), the crosslinking agent (C), and the decane coupling agent (D) are converted into 100 parts by weight based on the total amount of the acrylic resin (A). The value obtained.
【表2】 【Table 2】
然後,將實施例及比較例之黏接劑組成物溶液塗佈於聚酯系脫模片材,使乾燥後之厚度成為25μm,並於100℃乾燥3分鐘後,將形成的黏接劑組成物層轉印於偏光板(保護膜:富士膜公司製TAC膜),並於23℃×65%RH之條件下熟成7天,獲得供試驗用之設有黏接劑層之偏光板。Then, the adhesive composition solutions of the examples and the comparative examples were applied to a polyester release sheet so that the thickness after drying became 25 μm, and after drying at 100 ° C for 3 minutes, the formed adhesive was composed. The layer was transferred to a polarizing plate (protective film: TAC film manufactured by Fujifilm Co., Ltd.), and aged for 7 days under conditions of 23 ° C × 65% RH to obtain a polarizing plate provided with an adhesive layer for testing.
使用上述所得到之設有黏接劑層之偏光板,遵循以下所示的各方法測量・評價抗靜電性能[初始及加濕後表面電阻值及其變化率]、熟成特性[初始及熟成後、加熱後凝膠分率及其變化率]、以及耐久性[耐熱性及耐濕熱性]。將該等結果合併表示於後述表3。另外,設有黏接劑層之偏光板之供試驗品係以相對於偏光板之延伸軸為0度(平行)的方式裁切使用。Using the polarizing plate provided with the above-mentioned adhesive layer, the antistatic property [initial and surface resistance after humidification and its rate of change] and the ripening characteristics [initial and after ripening] were measured and evaluated according to the methods described below. , gel fraction after heating and its rate of change], and durability [heat resistance and heat and humidity resistance]. These results are combined and shown in Table 3 below. Further, the test piece of the polarizing plate provided with the adhesive layer was cut and used so as to be 0 degree (parallel) with respect to the extending axis of the polarizing plate.
[初始抗靜電性能之評價] 將上述設有黏接劑層之偏光板之供試驗品於23℃×50%RH環境氣體下靜置24小時後,將黏接劑層的分隔件剝離並使用表面電阻率測量裝置(三菱化學ANALYTECH公司製,裝置名「Hiresta-UP MCP-HT450」)測量黏接劑層之表面電阻值。將此測量值定為初始表面電阻值。評價基準如下所述。 (評價基準) ◎:未達5.0×109 Ω/□ ○:5.0×109 Ω/□以上未達1.0×1011 Ω/□ △:1.0×1011 Ω/□以上未達1.0×1012 Ω/□ ×:1.0×1012 Ω/□以上[Evaluation of initial antistatic property] After the test piece of the above polarizing plate provided with the adhesive layer was allowed to stand under an ambient gas of 23 ° C × 50% RH for 24 hours, the separator of the adhesive layer was peeled off and used. The surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation ANALYTECH, the device name "Hiresta-UP MCP-HT450") measures the surface resistance value of the adhesive layer. This measurement is taken as the initial surface resistance value. The evaluation criteria are as follows. (Evaluation Criteria) ◎: Less than 5.0 × 10 9 Ω / □ ○: 5.0 × 10 9 Ω / □ or more and less than 1.0 × 10 11 Ω / □ △: 1.0 × 10 11 Ω / □ or more and less than 1.0 × 10 12 Ω/□ ×: 1.0×10 12 Ω/□ or more
[加濕後之抗靜電性能之評價] 為了觀察抗靜電性隨時間之變化,將上述設有黏接劑層之偏光板之供試驗品保存於溫度40℃、相對濕度90%之烘箱100小時後,再於23℃×50%RH環境氣體下靜置24小時後,將黏接劑層之分隔件剝離並測量黏接劑層之表面電阻值。將其定為歷時(加熱)後之表面電阻值。變化率係使用初始表面電阻值與加熱後表面電阻值,並利用下式計算出變化率。評價基準如下所述。 變化率(隨時間之變化)=[加熱後表面電阻值]/[初始表面電阻值] (評價基準) ◎:變化率為0.9以上未達1.1 ○:變化率為0.8以上未達0.9、或1.1以上未達1.2 △:變化率為0.6以上未達0.8、或1.2以上未達1.4 ×:變化率未達0.6、或1.4以上[Evaluation of antistatic property after humidification] In order to observe changes in antistatic property with time, the test piece of the above polarizing plate provided with the adhesive layer was stored in an oven at a temperature of 40 ° C and a relative humidity of 90% for 100 hours. Thereafter, after standing for 24 hours under an ambient gas of 23 ° C × 50% RH, the separator of the adhesive layer was peeled off and the surface resistance value of the adhesive layer was measured. It is set as the surface resistance value after duration (heating). The rate of change is the initial surface resistance value and the surface resistance value after heating, and the rate of change is calculated using the following formula. The evaluation criteria are as follows. Rate of change (change with time) = [surface resistance value after heating] / [initial surface resistance value] (evaluation basis) ◎: The rate of change is 0.9 or more and less than 1.1 ○: The rate of change is 0.8 or more and less than 0.9, or 1.1 The above does not reach 1.2 △: the rate of change is less than 0.6 or less than 0.8, or 1.2 or less is less than 1.4 ×: the rate of change is less than 0.6, or 1.4 or more
[熟成特性之評價] 將樹脂溶液塗佈於聚酯系之脫模片材,使乾燥後之厚度成為25μm,並於100℃乾燥3分鐘後,將形成的黏接劑組成物層轉印於偏光板(保護膜:富士膜公司製TAC膜),於23℃×65%RH之條件下經過1天者作為「初始凝膠分率」測量用樣本、熟成7天(於上述1天再加上6天)者作為「熟成後凝膠分率」測量用樣本、將上述熟成7天者再放入80℃之烘箱中24小時者作為「加熱後凝膠分率」測量用樣本。[Evaluation of ripening characteristics] The resin solution was applied to a polyester-based release sheet to have a thickness of 25 μm after drying, and dried at 100 ° C for 3 minutes, and then the formed adhesive composition layer was transferred. A polarizing plate (protective film: TAC film manufactured by Fujifilm Co., Ltd.) was used as a sample for measuring "initial gel fraction" for one day under conditions of 23 ° C × 65% RH, and matured for 7 days (added in the above 1 day) For the first 6 days, the sample for the measurement of the gel fraction after the ripening was placed in the oven at 80 ° C for 24 hours, and the sample was measured as the "gel fraction after heating".
凝膠分率的測量亦如先前所述,利用以下的方法計算而得。亦即,從形成有黏接劑層於作為基材之偏光板而成的黏接片材(未裝設分隔件者)刮取黏接劑層,並將黏接劑層以200網目之SUS製金屬網包覆,浸漬於乙酸乙酯中23℃×24小時,將殘留於金屬網中之不溶解的黏接劑成分之重量百分率定為「凝膠分率」。The measurement of the gel fraction was also calculated by the following method as described previously. That is, the adhesive sheet is scraped from the adhesive sheet (the separator is not provided) in which the adhesive layer is formed on the polarizing plate as the substrate, and the adhesive layer is made of 200 mesh SUS. The metal mesh was coated and immersed in ethyl acetate at 23 ° C for 24 hours, and the weight percentage of the insoluble binder component remaining in the metal mesh was defined as "gel fraction".
從利用上述方法所得到的「初始凝膠分率」、「熟成後凝膠分率」,藉由下式計算出熟成後凝膠分率之變化率。評價基準如下所述。 熟成後凝膠分率之變化率(%)=[熟成後凝膠分率]/[初始凝膠分率]×100 (熟成後凝膠分率之變化率的評價基準) ○:變化率未達150% △:變化率為150%以上,未達300% ×:變化率為300%以上From the "initial gel fraction" obtained by the above method and the "gel fraction after ripening", the rate of change of the gel fraction after ripening was calculated by the following formula. The evaluation criteria are as follows. Rate of change of gel fraction after ripening (%) = [gel fraction after ripening] / [initial gel fraction] × 100 (basis of evaluation of rate of change of gel fraction after ripening) ○: rate of change not Up to 150% △: The rate of change is 150% or more, less than 300% ×: The rate of change is more than 300%
又,從利用上述方法所得到的「熟成後凝膠分率」、「加熱後凝膠分率」,藉由下式計算出加熱後凝膠分率之變化率。評價基準如下所述。 加熱後凝膠分率之變化率(%)=[加熱後凝膠分率]/[熟成後凝膠分率]×100 (加熱後凝膠分率之變化率的評價基準) ○:變化率為95%以上未達105% △:為90%以上未達95%、或為105%以上未達110% ×:變化率未達90%、或為110%以上Moreover, the rate of change of the gel fraction after heating was calculated from the "gel fraction after ripening" and "gel fraction after heating" by the above method. The evaluation criteria are as follows. Rate of change of gel fraction after heating (%) = [gel fraction after heating] / [gel fraction after ripening] × 100 (Evaluation criteria for rate of change of gel fraction after heating) ○: Rate of change 95% or more is less than 105% △: 90% or more is less than 95%, or 105% or more is less than 110% ×: the rate of change is less than 90%, or 110% or more
[耐久性之評價] 將得到的設有黏接劑層之偏光板樣本的脫模片材剝離,並將黏接劑層側推壓於無鹼玻璃板(CORNING公司製,EAGLE XG),而將偏光板與玻璃板貼合後,實施高溫高壓處理(50℃、0.5MPa、20分),其後以目視實施下述耐久試驗(耐熱試驗,耐濕熱試驗)中起泡、剝離之評價。另外,試驗所使用的試驗片之尺寸為20cm×15cm(沖壓)。[Evaluation of Durability] The release sheet of the obtained polarizing plate sample provided with the adhesive layer was peeled off, and the adhesive layer side was pressed against an alkali-free glass plate (EAGLE XG, manufactured by CORNING Co., Ltd.). After the polarizing plate and the glass plate were bonded together, high temperature and high pressure treatment (50 ° C, 0.5 MPa, 20 minutes) was carried out, and thereafter, evaluation of foaming and peeling in the following endurance test (heat resistance test, moisture heat resistance test) was carried out visually. Further, the size of the test piece used in the test was 20 cm × 15 cm (stamping).
[耐久性] (1)耐熱試驗 利用80℃、240小時之耐久試驗如下所述進行評價。 (2)耐濕熱試驗 利用60℃×90%RH×240小時之耐久試驗及85℃×85%RH×240小時之耐久試驗如下所述進行評價。 (評價基準) 各別針對(1)、(2)之試驗是否有缺點(起泡、條紋、浮翹、剝離)藉由光學顯微鏡觀察及目視進行評價。評價基準如下所述。 (評價基準) ◎:在光學顯微鏡觀察中未見到缺點。 ○:在光學顯微鏡觀察中,在距偏光板之端部0.5mm以內之緣部觀察到缺點。 △:在距偏光片之端部0.5mm以內之緣部觀察到可用目視確認的約1mm之缺點。 ×:在距偏光板之端部0.5mm更內側(靠近中央)處觀察到可用目視確認之缺點、或見到1mm以上之剝離。[Durability] (1) Heat resistance test The durability test at 80 ° C for 240 hours was carried out as follows. (2) Moisture resistance test The durability test at 60 ° C × 90% RH × 240 hours and the endurance test at 85 ° C × 85% RH × 240 hours were evaluated as follows. (Evaluation Criteria) Whether or not the tests (1) and (2) have disadvantages (foaming, streaking, floating, peeling) were evaluated by optical microscopy and visual observation. The evaluation criteria are as follows. (Evaluation Criteria) ◎: No defects were observed in optical microscope observation. ○: In the optical microscope observation, a defect was observed at an edge portion within 0.5 mm from the end portion of the polarizing plate. △: A defect of about 1 mm which was visually confirmed was observed at a portion within 0.5 mm from the end portion of the polarizer. ×: A defect visually confirmed or a peel of 1 mm or more was observed at a side (close to the center) 0.5 mm from the end portion of the polarizing plate.
該等試驗結果與評價匯整表示於下述表3。The results of these tests and the evaluations are shown in Table 3 below.
【表3】 試驗結果(評價)
根據上述表3的評價結果得知:由本發明之黏接劑組成物構成的實施例1~10之黏接劑之抗靜電性能、耐久性、熟成特性平衡佳且優良,相對於此,源自含有醯胺基以外的官能基之單體(a1)的結構單元未達丙烯酸系樹脂(A)之1重量%的比較例2及3之黏接劑,其熟成特性顯著不良,耐久性亦不佳。又得知:丙烯酸系樹脂(A)不含源自含有醯胺基之單體(a2)的結構單元之比較例4之黏接劑,無法滿足抗靜電性能隨時間之安定性,且耐久性亦不佳。According to the evaluation results of the above Table 3, the adhesives of Examples 1 to 10 which are composed of the adhesive composition of the present invention have a good balance of antistatic property, durability, and ripening characteristics, and are excellent in comparison thereto. The structural unit of the monomer (a1) having a functional group other than a guanamine group is less than 1% by weight of the acrylic resin (A). The adhesives of Comparative Examples 2 and 3 have significantly poor aging characteristics and durability. good. It is also known that the acrylic resin (A) does not contain the binder of Comparative Example 4 derived from the structural unit of the amidino group-containing monomer (a2), and cannot satisfy the stability of antistatic property with time, and durability. Also not good.
此外得知:使用銨系抗靜電劑以外之抗靜電劑作為抗靜電劑(B)之比較例5~7之黏接劑亦無法滿足抗靜電性能隨時間之安定性、或熟成特性、耐久性中至少一種。而且得知:抗靜電劑(B)之摻合量比限定範圍少的比較例1之黏接劑無法滿足初始抗靜電性能。Further, it was found that the adhesives of Comparative Examples 5 to 7 using an antistatic agent other than the ammonium antistatic agent as the antistatic agent (B) could not satisfy the stability of the antistatic property with time, or the ripening property and durability. At least one of them. Further, it was found that the adhesive of Comparative Example 1 in which the amount of the antistatic agent (B) was less than the limited range could not satisfy the initial antistatic property.
另外,根據上述表3所記載之評價結果得知:即使在摻合比較多的抗靜電劑(B)之實施例2、3及9、10並未見到耐久試驗後從黏接劑層有抗靜電劑之滲出所導致之缺點的發生,且本發明之黏接劑由於使抗靜電性能隨時間之安定性提昇,即使在摻合故比較多的抗靜電劑時,耐久性、熟成特性均平衡且優良。Further, according to the evaluation results described in the above Table 3, it was found that even in Examples 2, 3, and 9, 10 in which the antistatic agent (B) having a relatively large amount of blending was not observed, there was no adhesion test from the adhesive layer. The defects caused by the exudation of the antistatic agent occur, and the adhesive of the present invention improves the stability of the antistatic property with time, and the durability and the ripening property are even when the antistatic agent is blended in a relatively large amount. Balanced and excellent.
此外,使用利用上述實施例1~3、8~10及比較例1之黏接劑組成物而得到的設有黏接劑層之偏光板,在低溫條件下之抗靜電性能[表面電阻值、靜電放電(ESD GUN)不均勻消失時間]遵循下述所示之各方法進行測量・評價。試驗如後述表4所示。Further, the polarizing plate provided with the adhesive layer obtained by using the adhesive compositions of the above Examples 1 to 3, 8 to 10 and Comparative Example 1 was used for antistatic properties under low temperature conditions [surface resistance value, Electrostatic discharge (ESD GUN) unevenness disappearing time] Measurement and evaluation were carried out in accordance with each method shown below. The test is shown in Table 4 below.
[低溫條件下之抗靜電性能評價] 將上述各實施例及比較例所製得之設有黏接劑層之偏光板於4℃×55%RH環境氣體下靜置24小時後,將黏接劑層之分隔件剝離並使用表面電阻率測量裝置(三菱化學ANALYTECH公司製,裝置名「Hiresta-UP MCP-HT450」),於4℃×55%RH環境氣體下測量黏接劑層之表面電阻值之評價基準如下所述。 (評價基準) ◎:未達5.0×109 Ω/□ ○:5.0×109 Ω/□以上未達1.0×1011 Ω/□ △:1.0×1011 Ω/□以上未達1.0×1012 Ω/□ ×:1.0×1012 Ω/□以上[Evaluation of Antistatic Property under Low Temperature Conditions] The polarizing plate provided with the adhesive layer prepared in each of the above Examples and Comparative Examples was allowed to stand under a 4 ° C × 55% RH ambient gas for 24 hours, and then bonded. The separator of the agent layer was peeled off and the surface resistivity of the adhesive layer was measured under a 4 ° C × 55% RH ambient gas using a surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation, apparatus name "Hiresta-UP MCP-HT450"). The evaluation criteria for the values are as follows. (Evaluation Criteria) ◎: Less than 5.0 × 10 9 Ω / □ ○: 5.0 × 10 9 Ω / □ or more and less than 1.0 × 10 11 Ω / □ △: 1.0 × 10 11 Ω / □ or more and less than 1.0 × 10 12 Ω/□ ×: 1.0×10 12 Ω/□ or more
[液晶之顯示不均勻試驗(靜電放電(ESD GUN)不均勻消失時間)] 將上述各實施例及比較例所製得之設有黏接劑層之偏光板裁切成100mm×100mm後,將脫模片材剝離並貼附於液晶面板(INNOLAX公司製)。另外,在反對面將另外準備之設有黏接劑層之偏光板貼附成正交偏光(crossed nicol)狀態,成為透射光受阻隔之狀態。 然後將已貼附設有黏接劑層之偏光板的液晶面板靜置於背光源上,朝實施例所製得之偏光板的表面以靜電試驗器(NOISE研究所公司製的ESSB3011(靜電試驗器)及GT-30R(放電槍))使其接觸放電+15kV之靜電。此時測量從產生所引發之靜電不均勻(白化現象)到回到原本狀態的時間(秒)並進行評價。時間愈短為電特性愈優良的狀態。偏光板表面產生靜電的話,由於靜電不均勻而發生白化現象,液晶會顯示不良。測量係於23℃、55%RH環境氣體下及4℃、55%RH環境氣體下實施。 (評價基準) ◎:靜電不均勻未達1秒時消失。 ○:靜電不均勻在1秒以上未達5秒時消失。 △:靜電不均勻在5秒以上未達20秒時消失。 ×:靜電不均勻在20秒以上消失。[Liquid crystal display unevenness test (electrostatic discharge (ESD GUN) uneven disappearance time)] After the polarizing plate provided with the adhesive layer prepared in each of the above examples and comparative examples was cut into 100 mm × 100 mm, The release sheet was peeled off and attached to a liquid crystal panel (manufactured by INNOLAX Co., Ltd.). Further, a polarizing plate provided with an adhesive layer prepared separately is attached to a crossed nicol state on the opposite side, and the transmitted light is blocked. Then, the liquid crystal panel to which the polarizing plate of the adhesive layer was attached was placed on the backlight, and the surface of the polarizing plate prepared in the example was subjected to an electrostatic tester (ESSB3011 (electrostatic tester) manufactured by NOISE Research Co., Ltd. ) and GT-30R (discharge gun) make it contact with discharge +15kV static electricity. At this time, the time (seconds) from the occurrence of the static unevenness (whitening phenomenon) caused by the generation to the original state was measured and evaluated. The shorter the time, the better the electrical characteristics. When static electricity is generated on the surface of the polarizing plate, whitening occurs due to uneven static electricity, and the liquid crystal may exhibit poor display. The measurement was carried out at 23 ° C, 55% RH ambient gas and 4 ° C, 55% RH ambient gas. (Evaluation criteria) ◎: The static electricity unevenness disappeared after less than 1 second. ○: Static electricity unevenness disappeared after 1 second or more and less than 5 seconds. △: Static electricity unevenness disappeared after 5 seconds or more and less than 20 seconds. ×: Static electricity unevenness disappeared for 20 seconds or more.
【表4】
根據上述表4所記載之評價結果得知:由本發明之黏接劑組成物所構成的實施例1~3及8~10之黏接劑即使在低溫條件下,表面電阻值仍低,具有優良的抗靜電性能。又得知:針對實施例1~3及8~10,雖然在低溫條件下,偏光板之表面電阻值均為同等之評價結果,未見到抗靜電劑(B)之摻合量所致之差異,但在更接近實用狀態之液晶面板的顯示不均勻試驗中,大量摻合抗靜電劑(B)之實施例2、3及9、10,顯示不均勻的消失時間短,具有更優良的抗靜電性能,此外在實施例3、10得知具有與室溫條件下(上述初始抗靜電性能評價之條件)相同程度之針對顯示不均勻的性能。 藉此得知:本發明之黏接劑即使在為了提昇抗靜電性能隨時間之安定性而摻合比較多的抗靜電劑時,耐久性、熟成特性仍皆平衡且優良,此外即使在低溫條件下亦具有優良的抗靜電性能。According to the evaluation results described in the above Table 4, the adhesives of Examples 1 to 3 and 8 to 10 which are composed of the adhesive composition of the present invention have excellent surface resistance values even under low temperature conditions, and are excellent. Antistatic properties. It is also known that, for Examples 1 to 3 and 8 to 10, although the surface resistance values of the polarizing plates are equal to the evaluation results under low temperature conditions, no mixing amount of the antistatic agent (B) is observed. Difference, but in the display unevenness test of the liquid crystal panel closer to the practical state, the examples 2, 3, and 9, 10 in which a large amount of the antistatic agent (B) is blended exhibit a short disappearance time of unevenness, and are more excellent. The antistatic property was further known in Examples 3 and 10 to have the same degree of display unevenness as the room temperature conditions (the conditions for the evaluation of the initial antistatic property described above). Therefore, it is known that the adhesive of the present invention is balanced and excellent even when a relatively large amount of the antistatic agent is blended in order to improve the stability of the antistatic property with time, and further, even in a low temperature condition. It also has excellent antistatic properties.
上述實施例中係針對本發明中的具體形態而表示,但上述實施例僅為單純的例示,並非作限定性解釋。對於該技術領域中具有通常知識者而言明顯的種種變化皆意欲包括於本發明之範圍內。 [產業上利用性]The above embodiments are shown in the specific embodiments of the present invention, but the above embodiments are merely illustrative and not limiting. Various changes apparent to those skilled in the art are intended to be included within the scope of the present invention. [Industrial use]
本發明之黏接劑組成物以及將該黏接劑組成物交聯所構成的黏接劑,即使增加抗靜電劑的含量亦不會發生滲出,不會對耐久性造成不良影響,可歷經長時間安定而發揮抗靜電性能,且熟成特性亦優良,故作為光學構件用黏接劑使用而獲得之設有黏接劑層之光學構件,尤其,作為塗佈在使用疏水性高的樹脂於保護膜之偏光板的表面之黏著用黏接劑非常有效。The adhesive composition of the present invention and the adhesive agent formed by crosslinking the adhesive composition do not bleed out even if the content of the antistatic agent is increased, and the adhesive durability is not adversely affected. The optical member having the adhesive layer obtained by using the adhesive for the optical member is excellent in antistatic property and excellent in aging characteristics, and is particularly protected by coating with a highly hydrophobic resin. Adhesives for adhesion of the surface of the polarizing plate of the film are very effective.
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US11008485B2 (en) | 2016-07-08 | 2021-05-18 | Nitto Denko Corporation | Adhesive composition, adhesive layer, optical film provided with adhesive layer, image display panel, and liquid crystal display |
TWI735614B (en) * | 2016-07-08 | 2021-08-11 | 日商日東電工股份有限公司 | Adhesive composition, adhesive layer, optical film with adhesive layer, image display panel and liquid crystal display device |
TWI734000B (en) * | 2017-03-28 | 2021-07-21 | 日商日東電工股份有限公司 | Polarizing film with adhesive layer, polarizing film with adhesive layer for built-in liquid crystal panel, built-in liquid crystal panel and liquid crystal display device |
TWI794483B (en) * | 2017-03-28 | 2023-03-01 | 日商日東電工股份有限公司 | Polarizing film with adhesive layer, polarizing film with adhesive layer for built-in liquid crystal panel, built-in liquid crystal panel and liquid crystal display device |
TWI794482B (en) * | 2017-03-28 | 2023-03-01 | 日商日東電工股份有限公司 | Polarizing film with adhesive layer, polarizing film with adhesive layer for built-in liquid crystal panel, built-in liquid crystal panel and liquid crystal display device |
TWI828535B (en) * | 2017-03-28 | 2024-01-01 | 日商日東電工股份有限公司 | Built-in LCD panel and LCD display device |
Also Published As
Publication number | Publication date |
---|---|
KR101721397B1 (en) | 2017-03-29 |
JPWO2016163287A1 (en) | 2017-04-27 |
JP6042036B1 (en) | 2016-12-14 |
CN106795408A (en) | 2017-05-31 |
WO2016163287A1 (en) | 2016-10-13 |
CN106795408B (en) | 2018-05-04 |
TWI620804B (en) | 2018-04-11 |
KR20170021892A (en) | 2017-02-28 |
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