TWI397569B - Method for manufacturing component having optical function comprising an adhesive - Google Patents
Method for manufacturing component having optical function comprising an adhesive Download PDFInfo
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- TWI397569B TWI397569B TW095115003A TW95115003A TWI397569B TW I397569 B TWI397569 B TW I397569B TW 095115003 A TW095115003 A TW 095115003A TW 95115003 A TW95115003 A TW 95115003A TW I397569 B TWI397569 B TW I397569B
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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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
Description
本發明涉及黏著劑組成物和使用該組成物的帶有黏著劑的光學功能性構件。更詳細的是，本發明涉及在液晶胞等玻璃基板上貼附偏振片和相位差片等光學功能性構件，能獲得在濕熱條件下好的初期黏接性和耐久黏接性的黏著劑組成物，以及具有由該黏著劑組成物製得的黏著劑層的偏振片和相位差片等帶黏著劑的光學功能性構件。The present invention relates to an adhesive composition and an optical functional member with an adhesive using the composition. More specifically, the present invention relates to an optical functional member such as a polarizing plate and a retardation film attached to a glass substrate such as a liquid crystal cell, and an adhesive composition capable of obtaining good initial adhesion and durability adhesiveness under moist heat conditions. And an optically functional member with an adhesive such as a polarizing plate and a retardation film having an adhesive layer made of the adhesive composition.
作為在玻璃基板上貼附的光學功能性構件公知的有例如偏振片和相位差片等。作為偏振片的必要構成要素的顯示裝置能列舉有液晶顯示裝置。As the optical functional member to be attached to the glass substrate, for example, a polarizing plate, a retardation film, or the like is known. A liquid crystal display device can be exemplified as a display device which is an essential component of the polarizing plate.
液晶顯示裝置是用液晶層具有的電光學特性調製入射的直線偏振光，用出射側的偏振片使透過率有強弱和顯色的信號視覺化的裝置，因為其顯示原理上使用偏振光，故偏振片是必須的構件。該偏振片是使自然光轉變成直線偏振光的元件，目前液晶顯示裝置用偏振片多是由在聚乙烯醇系偏振光鏡的兩面上貼合了光學各向同性的薄膜例如三乙醯纖維素(TAC)薄膜等這樣具有3層結構的偏振薄膜來構成的。接著，為了貼合到玻璃基板(液晶胞)上，在其單面上設有黏著劑層。The liquid crystal display device is a device that modulates incident linearly polarized light by electro-optical characteristics of a liquid crystal layer, and visualizes a signal having a strong transmittance and coloration by using a polarizing plate on the exit side, since the display principle uses polarized light, A polarizing plate is an essential component. The polarizing plate is an element for converting natural light into linearly polarized light. At present, a polarizing plate for a liquid crystal display device is mainly composed of an optically isotropic film such as triacetyl cellulose on both sides of a polyvinyl alcohol-based polarizing mirror. (TAC) film or the like having a three-layer structure of a polarizing film. Next, in order to adhere to a glass substrate (liquid crystal cell), an adhesive layer is provided on one surface.
對於在這種用途中使用的黏著劑組成物，要求其即使在濕熱條件下具有初期黏接性是當然的，並且耐久黏接性優良。It is a matter of course that the adhesive composition used in such an application has an initial adhesive property even under moist heat conditions, and is excellent in durability adhesiveness.
專利文獻1中公開了一種通過在透光性被黏著物上引入黏著劑層並且固定偏振片而製得的固定偏振片的構造物，其中該黏著劑層是在丙烯酸聚合物上以一定比例混合在一個末端具有環氧基的矽烷偶聯劑而製得的丙烯酸系黏著劑組成物構成，即使在高溫和高濕度條件下也難以產生發泡和剝離。Patent Document 1 discloses a structure of a fixed polarizing plate which is obtained by introducing an adhesive layer on a light-transmitting adherend and fixing a polarizing plate, wherein the adhesive layer is mixed in a certain ratio on an acrylic polymer. The acrylic pressure-sensitive adhesive composition obtained by using a decane coupling agent having an epoxy group at one end is difficult to cause foaming and peeling even under high temperature and high humidity conditions.
但是矽烷偶聯劑中有反應性非常高的物質，使用這樣的矽烷偶聯劑的話，設置在光學功能性構件上的黏著劑層中的矽烷偶聯劑會歷時而失活，產生耐久黏接性降低的問題，所以必須選擇矽烷偶聯劑。However, a highly reactive substance is present in the decane coupling agent. When such a decane coupling agent is used, the decane coupling agent disposed in the adhesive layer on the optical functional member is inactivated over time, resulting in durable bonding. The problem of reduced sex, so the decane coupling agent must be selected.
在上述公報的實施例中，作為矽烷偶聯劑目前正在使用的有γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷。它們中的三甲氧基矽烷系和二甲氧基矽烷系的偶聯劑反應性非常高，含有這些矽烷偶聯劑的黏著劑層經過本發明人的研究，發現在濕熱條件下的耐久黏接性明顯差。In the examples of the above publication, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, and 3 are currently used as a decane coupling agent. Methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane. Among them, the trimethoxydecane-based and dimethoxydecane-based coupling agents are highly reactive, and the adhesive layer containing these decane coupling agents has been studied by the inventors and found to be durable bonded under moist heat conditions. Sexually poor.
專利文獻1：特開平7-20314號公報Patent Document 1: Japanese Patent Publication No. 7-20314
本發明的目的在於基於目前這樣的情況，提供一種在液晶胞等玻璃基板上貼附偏振片和相位差片等光學功能性構件，以獲得在濕熱條件下初期黏接性和耐久黏接性良好的黏著劑組成物，以及具有由該黏著劑組成物製得的黏著劑層的偏振片和相位差片等帶黏著劑的光學功能性構件。An object of the present invention is to provide an optical functional member such as a polarizing plate and a retardation film on a glass substrate such as a liquid crystal cell to obtain an initial adhesive property and a durable adhesive property under wet heat conditions. An adhesive composition, and an optically functional member with an adhesive such as a polarizing plate and a retardation film having an adhesive layer prepared from the adhesive composition.
本發明人為了實現上述目標而進行了反復的經心研究，結果發現通過使用含有具有交聯性官能團的(甲基)丙烯酸酯系共聚物和交聯劑、矽烷偶聯劑，且具有特定性質的製品作為黏著劑組成物，可以實現該目的。而且發現，具有上述特定性質的黏著劑組成物是通過使用特定結構的化合物作為矽烷偶聯劑來獲得的。The present inventors conducted repeated centrifugation studies in order to achieve the above object, and as a result, found that by using a (meth) acrylate-based copolymer having a crosslinkable functional group and a crosslinking agent, a decane coupling agent, and having specific properties The article can be used as an adhesive composition for this purpose. Further, it has been found that an adhesive composition having the above specific properties is obtained by using a compound of a specific structure as a decane coupling agent.
本發明基於該發現來完成。The present invention has been completed based on this finding.
即，本發明提供：(1)一種黏著劑組成物，其特徵在於該黏著劑組成物含有(a)具有交聯性官能團的(甲基)丙烯酸酯系共聚物，(b)交聯劑和(c)矽烷偶聯劑，其滿足(i)在厚度為50μm的聚對苯二甲酸乙二醇酯薄膜上設置將上述黏著劑組成物交聯化而形成的厚度為25μm的黏著劑層，再將其貼附在非鹼性玻璃上，在溫度50℃、壓力0.5MPa下保持20分鐘後，在溫度23℃、相對濕度為50%的環境下放置24小時後的黏性和在溫度60℃、相對濕度90%的環境下放置24小時後的黏性分別作為A和B，此時B/A為1.5~3，以及(ii)在厚度為50μm的聚對苯二甲酸乙二醇酯薄膜上設置將上述黏著劑組成物交聯化而形成的厚度為25μm的黏著劑層，在該黏著劑層上以貼附厚度為38μm的聚對苯二甲酸乙二醇酯剝離薄膜的狀態下，在溫度60℃、相對濕度90%的環境下放置7天後，貼附在非鹼性玻璃上在溫度50℃、壓力0.5MPa下保持20分鐘後，再在溫度60℃、相對濕度90%的環境下放置24小時後的黏性作為C，此時(C/B)×100為70%或以上。That is, the present invention provides: (1) an adhesive composition characterized in that the adhesive composition contains (a) a (meth) acrylate copolymer having a crosslinkable functional group, (b) a crosslinking agent and (c) a decane coupling agent which satisfies (i) an adhesive layer having a thickness of 25 μm formed by crosslinking the above-mentioned adhesive composition on a polyethylene terephthalate film having a thickness of 50 μm. After attaching it to non-alkaline glass and holding it at a temperature of 50 ° C and a pressure of 0.5 MPa for 20 minutes, the viscosity after leaving it at an environment of 23 ° C and a relative humidity of 50% for 24 hours and at a temperature of 60 The viscosity after leaving for 24 hours at °C and 90% relative humidity is taken as A and B, respectively, B/A is 1.5 to 3, and (ii) polyethylene terephthalate having a thickness of 50 μm. An adhesive layer having a thickness of 25 μm formed by crosslinking the above-mentioned adhesive composition was provided on the film, and a polyethylene terephthalate release film having a thickness of 38 μm was attached to the adhesive layer. After being placed in an environment of 60 ° C and 90% relative humidity for 7 days, it is attached to non-alkaline glass at a temperature of 50 ° C and pressure. After holding at 0.5 MPa for 20 minutes, the viscosity after standing for 24 hours in an environment of a temperature of 60 ° C and a relative humidity of 90% was taken as C, and (C/B) × 100 was 70% or more.
(2)上述(1)中記載的黏著劑組成物，其特徵在於作為(c)成分的矽烷偶聯劑是通式(I)表示的化合物，
(式中，Z是能和(a)成分的交聯性官能團反應的官能團或具有該官能團的有機基團，R1 是碳原子數為2~4的伸烷基，R2 是碳原子數為1~10的烴基，n為0或1，R3 是碳原子數為1~4的烷基，2或3個R3 O可以彼此相同或不同，其至少一個為乙氧基。)。(wherein Z is a functional group capable of reacting with a crosslinkable functional group of the component (a) or an organic group having the functional group, R 1 is an alkylene group having 2 to 4 carbon atoms, and R 2 is a carbon atom The hydrocarbon group of 1 to 10, n is 0 or 1, R 3 is an alkyl group having 1 to 4 carbon atoms, and 2 or 3 R 3 O may be the same or different from each other, and at least one of them is an ethoxy group.
(3)上述(1)或(2)中記載的黏著劑組成物，其特徵在於(c)成分的矽烷偶聯劑的含量對每100重量份的(a)成分為0.001~5重量份。(3) The adhesive composition according to the above (1) or (2), wherein the content of the decane coupling agent of the component (c) is 0.001 to 5 parts by weight per 100 parts by weight of the component (a).
(4)一種帶有黏著劑的光學功能性構件，其特徵在於具有由上述(1)~(3)中的任何一項記載的黏著劑組成物形成的黏著劑層。(4) An optical functional member having an adhesive, comprising the adhesive layer formed of the adhesive composition according to any one of the above (1) to (3).
(5)上述(4)中記載的帶有黏著劑的光學功能性構件，其特徵在於光學功能性構件為偏振片。(5) The optical functional member with an adhesive according to (4) above, wherein the optical functional member is a polarizing plate.
(6)上述(4)中記載的帶有黏著劑的光學功能性構件，其特徵在於光學功能性構件為相位差片。(6) The optical functional member with an adhesive according to (4) above, wherein the optical functional member is a retardation film.
根據本發明，能夠提供一種在液晶胞等玻璃基板上貼附偏振片和相位差片等光學功能性構件，以獲得在濕熱條件下初期黏接性和耐久黏接性良好的黏著劑組成物，以及具有由該黏著劑組成物製得的黏著劑層的偏振片和相位差片等帶黏著劑的光學功能性構件。According to the present invention, it is possible to provide an optically functional member such as a polarizing plate or a retardation film on a glass substrate such as a liquid crystal cell to obtain an adhesive composition having excellent initial adhesion and durable adhesion under wet heat conditions. And an optical functional member having an adhesive such as a polarizing plate and a retardation film having an adhesive layer obtained from the adhesive composition.
本發明的黏著劑組成物中，作為必要成分含有(a)具有交聯性官能團的(甲基)丙烯酸酯系共聚物，(b)交聯劑和(c)矽烷偶聯劑。The adhesive composition of the present invention contains (a) a (meth) acrylate copolymer having a crosslinkable functional group, (b) a crosslinking agent, and (c) a decane coupling agent as essential components.
作為(a)成分的具有交聯性官能團的(甲基)丙烯酸酯系共聚物沒有特別限制，可以在目前作為黏著劑的樹脂成分所常用的(甲基)丙烯酸酯系共聚物中任意選擇來使用。The (meth) acrylate-based copolymer having a crosslinkable functional group as the component (a) is not particularly limited, and can be arbitrarily selected from the (meth) acrylate copolymer which is conventionally used as a resin component of an adhesive. use.
作為這樣的具有交聯性官能團的(甲基)丙烯酸酯系共聚物優選列舉酯部分的烷基碳原子數為1~20的(甲基)丙烯酸酯、具有帶活性氫的官能團的單體和根據需要使用的其他單體的共聚物。The (meth)acrylate copolymer having such a crosslinkable functional group is preferably a (meth) acrylate having an alkyl group having 1 to 20 carbon atoms in the ester moiety, a monomer having a functional group having an active hydrogen, and Copolymers of other monomers used as needed.
這裏，作為酯部分的烷基碳原子數為1~20的(甲基)丙烯酸酯的例子列舉有(甲基)丙烯酸甲酯、(甲基)丙烯乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2－乙基己基酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸十八烷酯等。它們可以單獨使用，也可以2種或以上結合使用。Here, examples of the (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an ester moiety include methyl (meth)acrylate, (meth) propylene ethyl ester, and propyl (meth) acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclomethacrylate Ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, ( Cetylmethyl methacrylate, octadecyl (meth) acrylate, and the like. They may be used singly or in combination of two or more.
作為另一方的具有帶活性氫的官能團的單體的例子能列舉有(甲基)丙烯酸2－羥乙酯、(甲基)丙烯酸2－羥丙酯、(甲基)丙烯酸3－羥丙酯、(甲基)丙烯酸2－羥丁酯、(甲基)丙烯酸3－羥丁酯、(甲基)丙烯酸4－羥丁酯等(甲基)丙烯酸羥烷基酯；丙烯醯胺、甲基丙烯醯胺、N－甲基丙烯醯胺、N－甲基甲基丙烯醯胺、N－羥甲基丙烯醯胺、N－羥甲基甲基丙烯醯胺等丙烯醯胺類；(甲基)丙烯酸單甲基氨基乙酯、(甲基)丙烯酸單乙基氨基乙酯、(甲基)丙烯酸單甲基氨基丙酯、(甲基)丙烯酸單乙基氨基丙酯等(甲基)丙烯酸單烷基氨基烷基酯；丙烯酸、甲基丙烯酸、丁烯酸、馬來酸、衣康酸、檸康酸等乙烯系不飽和羧酸等。這些單體可以單獨使用，也可以2種或以上結合使用。Examples of the other monomer having a functional group having an active hydrogen include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. , hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; acrylamide, methyl Acrylamide such as acrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide; ) (meth)acrylic acid such as monomethylaminoethyl acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate A monoalkylaminoalkyl ester; an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or citraconic acid. These monomers may be used singly or in combination of two or more.
而且，根據需要使用的其他單體的例子能列舉有醋酸乙烯酯、丙酸乙烯酯等乙烯酯類；乙烯、丙烯、異丁烯等烯烴類；氯乙烯、偏二氯乙烯等鹵化烯烴類；苯乙烯、α－甲基苯乙烯等苯乙烯系單體；丁二烯、異戊二烯、氯丁二烯等二烯系單體；丙烯腈、甲基丙烯腈等腈系單體；N,N－二甲基丙烯醯胺、N,N－二甲基甲基丙烯醯胺等的N,N－二烷基取代丙烯醯胺類等。它們可以單獨使用，也可以2種或以上結合使用。Further, examples of other monomers to be used include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; and styrene; a styrene monomer such as α-methylstyrene; a diene monomer such as butadiene, isoprene or chloroprene; a nitrile monomer such as acrylonitrile or methacrylonitrile; N, N An N,N-dialkyl-substituted acrylamide such as dimethyl methacrylate or N,N-dimethyl methacrylamide. They may be used singly or in combination of two or more.
本發明的黏著劑組成物中，作為(a)成分使用的(甲基)丙烯酸酯系共聚物例如可以通過常規的自由基聚合來獲得。作為聚合引發劑能列舉有偶氮二異丁腈和過氧化苯甲醯等。它們的共聚形態沒有特別限制，可以是無規、嵌段、接枝共聚物的任何一種。而且，分子量在重量平均分子量為50萬~250萬範圍內選定。其重量平均分子量若不到50萬會有和被黏著物的黏接性和耐久黏接性不充分的疑慮，超過250萬的話相對於基材的伸縮的追蹤性降低。考慮黏接性、耐久黏接性和追蹤性等，該重量平均分子量較佳為80萬~180萬，特佳為120萬~160萬的製品。In the adhesive composition of the present invention, the (meth) acrylate-based copolymer used as the component (a) can be obtained, for example, by a conventional radical polymerization. Examples of the polymerization initiator include azobisisobutyronitrile and benzammonium peroxide. The copolymerization form thereof is not particularly limited and may be any of random, block, and graft copolymers. Further, the molecular weight is selected in the range of a weight average molecular weight of 500,000 to 2.5 million. If the weight average molecular weight is less than 500,000, there is a concern that the adhesion to the adherend and the durability of the adhesive are insufficient. When the weight average molecular weight exceeds 2.5 million, the tracking property against the expansion and contraction of the substrate is lowered. The weight average molecular weight is preferably from 800,000 to 1.8 million, and particularly preferably from 1.2 million to 1.6 million, in view of adhesiveness, durability, and traceability.
另外，上述重量平均分子量是以聚苯乙烯為標樣，根據凝膠滲透色譜法(GPC)測定的值。Further, the above weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard.
而且，該(甲基)丙烯酸酯系共聚物中具有帶活性氫的官能團的單體單元的含量從交聯點和黏著劑組成物性能等方面考慮，較佳在0.05~20重量%的範圍，特佳為0.1~10重量%。Further, the content of the monomer unit having a functional group having an active hydrogen in the (meth) acrylate-based copolymer is preferably from 0.05 to 20% by weight in terms of the crosslinking point and the performance of the adhesive composition. Particularly preferably 0.1 to 10% by weight.
本發明中，該(a)成分的(甲基)丙烯酸酯系共聚物可以單獨使用1種，也可以使用2種或以上的結合。In the present invention, the (meth) acrylate-based copolymer of the component (a) may be used singly or in combination of two or more.
本發明的黏著劑組成物中，為了賦予緩和應力的性能，根據期望可以用低分子量的(甲基)丙烯酸酯系聚合物替換部分上述(a)成分的(甲基)丙烯酸酯系共聚物。In the adhesive composition of the present invention, in order to impart stress relaxation properties, a part of the (meth) acrylate copolymer of the above component (a) may be replaced with a low molecular weight (meth) acrylate polymer as desired.
作為上述低分子量的(甲基)丙烯酸酯系聚合物可以是選自酯部分的烷基碳原子數為1~20的(甲基)丙烯酸酯中的一種單獨聚合的製品，也可以是選自其中的二種或以上共聚合的製品，或者是將選自上述(甲基)丙烯酸酯中的1種或多種的單體和其他單體共聚合的製品。The low molecular weight (meth) acrylate polymer may be a single polymerized product selected from the group consisting of (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, and may be selected from the group consisting of Two or more of the copolymerized products, or an article obtained by copolymerizing one or more monomers selected from the above (meth) acrylates with other monomers.
作為上述酯部分的烷基碳原子數為1~20的(甲基)丙烯酸酯以及其他單體可以列舉有和上述(a)成分的(甲基)丙烯酸酯系共聚物的說明中分別列出的化合物相同的化合物。The (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as the ester moiety and other monomers may be listed separately from the description of the (meth) acrylate copolymer of the above component (a). The same compound as the compound.
該低分子量的(甲基)丙烯酸酯系聚合物的重量平均分子量通常在5000~300000的範圍內選擇。該重量平均分子量不到5000的話，對於黏著劑組成物，該低分子量聚合物會滲出，從通過該黏著劑組成物剝離貼附在被黏著物上的基材時會有污染被黏著物的擔心。而且，重量平均分子量超過300000的話，會有不能充分發揮黏著劑組成物對基材伸縮的追蹤性(應力緩和性)的改善效果的擔心。考慮到被黏著物的污染和對基材伸縮的追蹤性等，該低分子量(甲基)丙烯酸酯系聚合物的較佳重量平均分子量在8000~200000的範圍內。The weight average molecular weight of the low molecular weight (meth) acrylate-based polymer is usually selected from the range of 5,000 to 300,000. When the weight average molecular weight is less than 5,000, the low molecular weight polymer bleed out with respect to the adhesive composition, and there is a fear of contamination of the adherend when the substrate adhered to the adherend is peeled off by the adhesive composition. . In addition, when the weight average molecular weight exceeds 300,000, there is a concern that the effect of improving the tracking property (stress relaxation property) of the adhesive composition on the expansion and contraction of the substrate may not be sufficiently exhibited. The low molecular weight (meth) acrylate-based polymer preferably has a weight average molecular weight in the range of 8,000 to 200,000 in view of contamination by the adherend and traceability to the substrate.
另外，上述重量平均分子量和數平均分子量是以聚苯乙烯為標樣，根據GPC法測定換算的值。In addition, the weight average molecular weight and the number average molecular weight are the values measured by the GPC method using polystyrene as a standard.
本發明中，該低分子量(甲基)丙烯酸酯系聚合物可以使用1種，也可以將2種或以上結合使用。In the present invention, the low molecular weight (meth)acrylate polymer may be used singly or in combination of two or more.
對於本發明的黏著劑組成物，該低分子量(甲基)丙烯酸酯系聚合物在與上述(a)成分的(甲基)丙烯酸酯系共聚物合計量為100重量份下，其通常能以5~50重量份的比例來包含。該低分子量聚合物的量不到5重量份的話，會有黏著劑組成物對基材伸縮的追蹤性(應力緩和性)不充分的擔心，超過50重量份的話，會有對被黏著物的黏接性降低的情況。考慮到對基材伸縮的追蹤性和對被黏著物的黏接性等，該低分子量聚合物較佳的含量為10~40重量份範圍，特佳在10~30重量份的範圍內。In the adhesive composition of the present invention, the low molecular weight (meth) acrylate polymer is usually 100 parts by weight based on the total amount of the (meth) acrylate copolymer of the component (a). The ratio of 5 to 50 parts by weight is included. When the amount of the low molecular weight polymer is less than 5 parts by weight, there is a concern that the adhesive composition has insufficient tracking property (stress relaxation property) to the substrate, and if it exceeds 50 parts by weight, there is a possibility of adhering to the adherend. The case of reduced adhesion. The low molecular weight polymer is preferably contained in an amount of from 10 to 40 parts by weight, particularly preferably from 10 to 30 parts by weight, in view of traceability to substrate stretching and adhesion to an adherend.
作為本發明的黏著劑組成物中的(b)成分的交聯劑沒有特別限制，可以從現有的丙烯酸系黏著劑中作為交聯劑常用的化合物中任意選擇來使用。作為這樣的交聯劑能列舉有例如聚異氰酸酯化合物、環氧樹脂、三聚氰胺樹脂、尿醛樹酯、二醛類、羥甲基聚合物、金屬螯合化合物、金屬氯化物等，但是本發明中較佳使用聚異氰酸酯化合物。The crosslinking agent of the component (b) in the adhesive composition of the present invention is not particularly limited, and can be arbitrarily selected from the conventionally used compounds of the acrylic adhesive as a crosslinking agent. Examples of such a crosslinking agent include a polyisocyanate compound, an epoxy resin, a melamine resin, a urethane resin, a dialdehyde, a methylol polymer, a metal chelate compound, a metal chloride, etc., but in the present invention A polyisocyanate compound is preferably used.
這裡，作為聚異氰酸酯化合物的例子能列舉有甲苯二異氰酸酯、二異氰酸二苯基甲烷、苯二甲基二異氰酸酯等芳香族聚異氰酸酯、六亞甲基二異氰酸酯等脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、二異氰酸氫化二苯基甲烷等脂環式聚異氰酸酯等以及其縮二脲體、三聚異氰酸酯體，除此以外還有和乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等低分子含活性氫的化合物的反應物的加合物體等。Here, examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and benzodimethyl diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate; An alicyclic polyisocyanate such as ketone diisocyanate or diphenylmethane diisocyanate, and a biuret or a trimeric isocyanate, in addition to ethylene glycol, propylene glycol, neopentyl glycol, An adduct of a reactant of a low molecular weight active hydrogen-containing compound such as trimethylolpropane or castor oil.
本發明中，該(b)成分交聯劑可以單獨使用1種，也可以結合2種或以上來使用。而且，其使用量根據交聯劑的種類，通常可以在相對於100重量份的上述(a)成分的(甲基)丙烯酸酯系共聚物為0.001~50重量份的範圍內，較佳在0.01~10重量份的範圍內選定。In the present invention, the crosslinking agent (b) may be used singly or in combination of two or more. Further, the amount thereof to be used may be usually 0.001 to 50 parts by weight, preferably 0.01, based on 100 parts by weight of the (meth) acrylate-based copolymer of the component (a). Selected within a range of ~10 parts by weight.
本發明黏著劑組成物中的(c)成分矽烷偶聯劑是為了在濕熱條件下以更好的初期黏性和耐久黏性將光學功能性構件等基材貼附在帶有黏著劑組成物層的液晶胞等玻璃基板上而使用的。The component (c) decane coupling agent in the adhesive composition of the present invention is for attaching a substrate such as an optical functional member to an adhesive composition under a moist heat condition with better initial viscosity and durability. It is used on a glass substrate such as a liquid crystal cell of a layer.
作為具有這樣的功能的矽烷偶聯劑能較佳列舉有例如通式(I)表示的化合物。As the decane coupling agent having such a function, for example, a compound represented by the formula (I) can be preferably exemplified.
通式(I)中，Z表示和上述(a)成分的交聯性官能團反應的官能團或具有該官能團的有機基團。作為這樣的基團能列舉有例如環氧基、異氰酸酯基等，且作為具有該官能團的有機基團能列舉有例如縮水甘油氧基、3,4－環氧基環己基等。In the formula (I), Z represents a functional group reactive with the crosslinkable functional group of the above component (a) or an organic group having the functional group. Examples of such a group include an epoxy group and an isocyanate group. Examples of the organic group having the functional group include a glycidyloxy group and a 3,4-epoxycyclohexyl group.
R1 表示碳原子數為2~4的伸烷基。該伸烷基可以是直鏈狀、支鏈狀的任何一種，可以列舉有例如伸乙基、伸丙基、三亞甲基、四亞甲基、1－甲基三亞甲基等，它們中較佳碳原子數為2或3的伸烷基，具體為亞乙基和三亞甲基。R2 表示碳原子數為1~10的烴基。作為該烴基表示碳原子數為1~10的直鏈狀、支鏈狀、環狀的烷基、碳原子數為6~10的芳基或碳原子數為7~10的芳烷基。作為碳原子數為1~10的烷基能列舉有例如甲基、乙基、正丙基、異丙基、各種丁基、各種戊基、各種己基、各種辛基、各種癸基、環戊基、環己基等。作為碳原子數為6~10的芳基能列舉有例如苯基、甲苯基、二甲苯基、萘基、甲基萘基等，作為碳原子數為7~10的芳烷基能列舉有例如苄基、甲基苄基、苯乙基、甲基苯乙基、萘甲基等。R 1 represents an alkylene group having 2 to 4 carbon atoms. The alkylene group may be any of a linear chain and a branched chain, and examples thereof include an ethyl group, a propyl group, a trimethylene group, a tetramethylene group, a 1-methyltrimethylene group, and the like. Preferred are alkylene groups having 2 or 3 carbon atoms, specifically ethylene and trimethylene. R 2 represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various fluorenyl groups, and cyclopentane groups. Base, cyclohexyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include, for example, Benzyl, methylbenzyl, phenethyl, methylphenethyl, naphthylmethyl and the like.
n表示0或1，R3 表示碳原子數為1~4的烷基，例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基。2或3個R3 O彼此可以相同或不同，但是其至少一個為乙氧基。另外，從容易製備該矽烷偶聯劑上考慮，該R3 O是相同的，即2或3個R3 O全是乙氧基是較佳的。n represents 0 or 1, and R 3 represents an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. . 2 or 3 R 3 O may be the same or different from each other, but at least one of them is an ethoxy group. Further, from the viewpoint of easy preparation of the decane coupling agent, the R 3 O is the same, that is, 2 or 3 R 3 O are all ethoxy groups.
作為上述通式(I)表示的矽烷偶聯劑能列舉有例如3－異氰酸酯丙基三乙氧基矽烷、3－異氰酸酯丙基(甲基)二乙氧基矽烷、2－異氰酸酯乙基三乙氧基矽烷、2－異氰酸酯乙基(甲基)二乙氧基矽烷、3－環氧丙氧基丙基三乙氧基矽烷、3－環氧丙氧基丙基(甲基)二乙氧基矽烷、2－環氧丙氧基乙基三乙氧基矽烷、2－環氧丙氧基乙基(甲基)二乙氧基矽烷、3－(3,4－環氧基環己基)丙基三乙氧基矽烷、3－(3,4－環氧基環己基)丙基(甲基)二乙氧基矽烷、2－(3,4－環氧基環己基)乙基三乙氧基矽烷、2－(3,4－環氧基環己基)乙基(甲基)二乙氧基矽烷等三乙氧基系和二乙氧基系矽烷偶聯劑，特佳為乙氧基系矽烷偶聯劑。它們可以單獨使用1種，也可以結合2種或以上來使用。Examples of the decane coupling agent represented by the above formula (I) include 3-isocyanate propyl triethoxy decane, 3-isocyanate propyl (methyl) diethoxy decane, and 2-isocyanate ethyl triethyl hydride. Oxydecane, 2-isocyanate ethyl(methyl)diethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyl(methyl)diethoxylate Baseline, 2-glycidoxyethyltriethoxydecane, 2-glycidoxyethyl(methyl)diethoxydecane, 3-(3,4-epoxycyclohexyl) Propyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyl(methyl)diethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethyl a triethoxy-based and diethoxy-based decane coupling agent such as oxydecane or 2-(3,4-epoxycyclohexyl)ethyl(methyl)diethoxydecane, particularly preferably ethoxylated A base decane coupling agent. These may be used alone or in combination of two or more.
本發明的黏著劑組成物中，作為(c)成分的矽烷偶聯劑，為了提高初期黏接性等，可以將上述通式(I)表示的化合物和三甲氧基系矽烷偶聯劑和二甲氧基系矽烷偶聯劑結合起來使用。In the adhesive composition of the present invention, the decane coupling agent as the component (c) may be a compound represented by the above formula (I) and a trimethoxy decane coupling agent and two in order to improve initial adhesion and the like. The methoxy decane coupling agents are used in combination.
作為這樣的三甲氧基系矽烷偶聯劑和二甲氧基系矽烷偶聯劑，可以列舉有例如將上述列出的化合物中的乙氧基替換成甲氧基的化合物。這些三甲氧基系矽烷偶聯劑和二甲氧基系矽烷偶聯劑可以單獨使用1種，也可以結合2種或以上來使用。Examples of such a trimethoxy decane coupling agent and a dimethoxy decane coupling agent include compounds in which an ethoxy group in the above-exemplified compounds is replaced with a methoxy group. These trimethoxy decane coupling agents and dimethoxy decane coupling agents may be used alone or in combination of two or more.
本發明的黏著劑組成物中，(c)成分矽烷偶聯劑的含量出於初期黏性和耐久黏性以及經濟上平衡等方面的考慮，相對於100重量份的(a)成分(甲基)丙烯酸酯系共聚物通常為0.001~5重量份，較佳在0.005~1重量份的範圍內選定。In the adhesive composition of the present invention, the content of the component (c) decane coupling agent is based on 100 parts by weight of the component (a) in terms of initial viscosity, durability viscosity, and economic balance. The acrylate-based copolymer is usually selected from the range of 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight.
而且，將三乙氧基系和二乙氧基系矽烷偶聯劑(稱之為乙氧基系矽烷偶聯劑)和三甲氧基系和二甲氧基系矽烷偶聯劑(稱之為甲氧基系矽烷偶聯劑)結合使用的情況下，乙氧基系矽烷偶聯劑和甲氧基系矽烷偶聯劑的使用比例以重量比計通常在0.5：1~20：1的範圍內選定，較佳為1：1~10：1。Further, a triethoxy group and a diethoxy decane coupling agent (referred to as an ethoxy decane coupling agent) and a trimethoxy group and a dimethoxy decane coupling agent are referred to as When a methoxy decane coupling agent is used in combination, the ratio of use of the ethoxy decane coupling agent and the methoxy decane coupling agent is usually in the range of 0.5:1 to 20:1 by weight. Selected internally, preferably 1:1~10:1.
本發明的黏著劑組成物中，在不損害本發明目的的範圍內，可以根據期望添加在丙烯酸系黏著劑中常用的各種添加劑，例如增黏劑、防氧化劑、紫外線吸收劑、光穩定劑、軟化劑、填充劑等。In the adhesive composition of the present invention, various additives commonly used in acrylic adhesives, such as tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, etc., may be added as desired within the range not impairing the object of the present invention. Softeners, fillers, etc.
對於這樣獲得的本發明的黏著劑組成物，在厚度為50μm的聚對苯二甲酸乙二醇酯薄膜上設置將該黏著劑組成物交聯化而形成的厚度為25μm的黏著劑層，再將其貼附在非鹼性玻璃上，在溫度50℃、壓力0.5MPa下保持20分鐘後，在溫度23℃、相對濕度為50%(50%RH)的環境下放置24小時後的黏性和在溫度60℃、相對濕度90%(90%RH)的環境下放置24小時後的黏性分別作為A和B，B/A為1.5~3。而且，在厚度為50μm的聚對苯二甲酸乙二醇酯薄膜上設置將該黏著劑組成物交聯化而形成的厚度為25μm的黏著劑層，在該黏著劑層上以貼附厚度為38μm的聚對苯二甲酸乙二醇酯剝離薄膜的狀態下，在溫度60℃、相對濕度90%(90%RH)的環境下放置7天後，貼附在非鹼性玻璃上，在溫度50℃、壓力0.5MPa下保持20分鐘後，再在溫度60℃、相對濕度90%(90%RH)的環境下放置24小時後的黏性作為C，此時，(C/B)×100為70%或以上。With the adhesive composition of the present invention thus obtained, an adhesive layer having a thickness of 25 μm formed by crosslinking the adhesive composition on a polyethylene terephthalate film having a thickness of 50 μm was placed thereon. It was adhered to non-alkaline glass and kept at a temperature of 50 ° C and a pressure of 0.5 MPa for 20 minutes, and then allowed to stand for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50% (50% RH). The viscosity after standing for 24 hours in an environment of a temperature of 60 ° C and a relative humidity of 90% (90% RH) was taken as A and B, respectively, and B/A was 1.5 to 3. Further, an adhesive layer having a thickness of 25 μm formed by crosslinking the adhesive composition was formed on a polyethylene terephthalate film having a thickness of 50 μm, and the thickness was attached to the adhesive layer. The 38 μm polyethylene terephthalate release film was placed in a non-alkaline glass at a temperature of 60 ° C and a relative humidity of 90% (90% RH) for 7 days, at a temperature. After holding at 50 ° C and a pressure of 0.5 MPa for 20 minutes, the viscosity after leaving it at a temperature of 60 ° C and a relative humidity of 90% (90% RH) for 24 hours was taken as C. At this time, (C/B) × 100 It is 70% or more.
像這樣，本發明的黏著劑組成物通過使用具有上述特定結構的化合物作為矽烷偶聯劑，在玻璃基板上貼附長期保管的帶黏著劑的光學功能性構件的惰況下，即使在濕熱條件下也是初期黏性和耐久黏性優良的製品。As described above, the adhesive composition of the present invention is used as a decane coupling agent by using a compound having the above specific structure as a decane coupling agent, and is attached to a glass substrate in an inert state of an optically functional member with an adhesive for long-term storage, even in a damp heat condition. The product is also excellent in initial viscosity and durable viscosity.
本發明還提供具有由上述黏著劑組成物制得的黏著劑層的、帶黏著劑的光學功能性構件。The present invention also provides an optically functional member with an adhesive having an adhesive layer prepared from the above adhesive composition.
作為光學功能性構件較佳列舉具有TAC薄膜的偏振片和相位差片等。作為上述偏振片有例如液晶顯示裝置用、調整光量用、偏光干涉應用裝置用、光學缺陷檢測器用等的偏振片。As the optical functional member, a polarizing plate having a TAC film, a retardation film, or the like is preferably used. The polarizing plate is, for example, a polarizing plate for a liquid crystal display device, a light amount adjusting device, a polarizing interference application device, or an optical defect detector.
作為帶黏著劑的光學功能性構件特別適合的是在液晶顯示裝置的液晶胞用偏振片和相位差片上設置由上述黏著劑組成物製得的層的製品。由該黏著劑組成物製得的層的厚度通常為5~100μm左右，較佳為10~50μm。Particularly preferred as the optical functional member with an adhesive is a product in which a layer made of the above-described adhesive composition is provided on a polarizing plate for a liquid crystal cell of a liquid crystal display device and a retardation film. The thickness of the layer obtained from the adhesive composition is usually from about 5 to 100 μm, preferably from 10 to 50 μm.
作為上述的帶黏著劑的光學功能性構件的製備方法能使用例如在剝離薄膜的剝離層上塗布該黏著劑組成物，乾燥形成黏著劑層，再將其印刷在光學功能性構件上的方法等。As a method of preparing the above-mentioned optical functional member with an adhesive, for example, a method of applying the adhesive composition on a release layer of a release film, drying to form an adhesive layer, and printing the same on an optical functional member can be used. .
作為剝離薄膜能列舉有例如玻璃紙、塗層紙、鑄塗紙等紙基材、在這些紙基材上層壓聚乙烯等熱塑性樹脂的層壓紙、或者在聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯等聚酯薄膜、聚丙烯和聚乙烯等聚烯烴薄膜等塑膠薄膜上塗布矽樹脂等剝離劑的製品等。該剝離薄膜的厚度沒有特別限制，通常為20~150μm左右。Examples of the release film include paper substrates such as cellophane, coated paper, and cast coated paper, laminated papers obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates, or polyethylene terephthalate. A polyester film such as polybutylene terephthalate or polyethylene naphthalate or a polyolefin film such as polypropylene or polyethylene is coated with a release agent such as a bismuth resin. The thickness of the release film is not particularly limited, but is usually about 20 to 150 μm.
接著，根據實施例來更詳細地說明本發明，但是本發明並不限於這些實施例。Next, the present invention will be described in more detail based on examples, but the invention is not limited to the examples.
另外，各項特性是根據下面示出的方法來獲得的。In addition, various characteristics are obtained according to the method shown below.
(1)黏性A在非鹼性玻璃[NSG Precision(股)製造的"Corning # 1737]上貼附實施例或比較例中得到的帶黏著劑層的PET薄膜(25mm寬)後，使用高壓釜[栗原製作所(股)製造]在50℃、0.5MPa下處理20分鐘後，在23℃、50%RH條件下放置24小時後，根據JIS Z 0237的標準測定黏性。(1) Viscous A After attaching a PET film (25 mm wide) with an adhesive layer obtained in the examples or the comparative examples to a non-alkaline glass [Corning # 1737 manufactured by NSG Precision Co., Ltd.), a high pressure was used. The kettle [manufactured by Kurihara Seisakusho Co., Ltd.] was treated at 50 ° C and 0.5 MPa for 20 minutes, and then allowed to stand at 23 ° C and 50% RH for 24 hours, and then the viscosity was measured in accordance with JIS Z 0237.
(2)黏性B(初期黏性)在上述非鹼性玻璃上(如前述)貼附實施例或比較例中得到的帶黏著劑層的PET薄膜(25mm寬)後，使用上述高壓釜(如前述)在50℃、0.5MPa下處理20分鐘後，在60℃、90%RH條件下放置24小時，取出後，再在23℃、50%RH條件下放置2小時，調節空氣濕度，根據JIS Z 0237的標準測定黏性。(2) Viscous B (initial viscosity) After attaching the PET film (25 mm wide) with the adhesive layer obtained in the example or the comparative example on the above non-alkaline glass (as described above), the above autoclave was used ( After treatment at 50 ° C, 0.5 MPa for 20 minutes, at 60 ° C, 90% RH for 24 hours, after taking out, and then placed at 23 ° C, 50% RH for 2 hours, adjust the air humidity, according to The standard of JIS Z 0237 measures the viscosity.
(3)黏性C(耐久黏性)將實施例或比較例中得到的帶黏著劑層的PET薄膜(25mm寬)以薄膜的狀態(附在剝離薄膜上的狀態)在60℃、90%RH的條件下放置7天後，貼附在上述非鹼性玻璃(如前述)上後，使用上述高壓釜(如前述)在50℃、0.5MPa下處理20分鐘後，在60℃、90%RH條件下放置24小時，再在23℃、50%RH條件下放置2小時，調節空氣濕度，根據JIS Z 0237的標準測定黏性。(3) Viscous C (durable viscosity) The PET film (25 mm wide) with an adhesive layer obtained in the examples or the comparative examples was in a state of a film (a state attached to the release film) at 60 ° C, 90%. After standing for 7 days under the conditions of RH, after attaching to the above non-alkaline glass (as described above), the above autoclave (as described above) was treated at 50 ° C, 0.5 MPa for 20 minutes, at 60 ° C, 90%. The mixture was allowed to stand under RH for 24 hours, and then allowed to stand at 23 ° C and 50% RH for 2 hours to adjust the air humidity, and the viscosity was measured in accordance with JIS Z 0237.
(4)耐久性將實施例或比較例中得到的帶黏著劑層的偏振片(尺寸為233mm×309mm)在40℃的恒溫槽內放置2個月後，取出後，再在23℃、50%RH條件下放置24小時，調節空氣濕度。然後，貼附在上述非鹼性玻璃(如前述)上，使用上述高壓釜(如前述)在50℃、0.5MPa下處理20分鐘後，在80℃和60℃、90%RH的各熱衝擊(從－20℃到60℃，30分鐘一個週期)條件下進行500小時，使用放大鏡目視觀察偏振片的外觀變化，根據下面標準來評價耐久性。(4) Durability The polarizing plate (having a size of 233 mm × 309 mm) with an adhesive layer obtained in the examples or the comparative examples was allowed to stand in a thermostatic chamber at 40 ° C for 2 months, and then taken out at 23 ° C, 50. Allow to stand for 24 hours under %RH to adjust the air humidity. Then, it is attached to the above non-alkaline glass (as described above), and subjected to thermal shock at 80 ° C and 60 ° C, 90% RH after treatment at 50 ° C, 0.5 MPa for 20 minutes using the above autoclave (as described above). The film was subjected to 500 hours under conditions of -20 ° C to 60 ° C for 30 minutes, and the appearance change of the polarizing plate was visually observed using a magnifying glass, and the durability was evaluated according to the following criteria.
o：沒有氣泡、條紋等缺點△：有微小的氣泡、條紋×：有氣泡、條紋××：有剝離o: No shortcomings such as bubbles and streaks △: There are tiny bubbles, stripes ×: There are bubbles, stripes × ×: peeling
製造例1在200重量份的醋酸乙酯中添加99重量份的丙烯酸正丁酯、1重量份的丙烯酸4－羥丁酯以及作為聚合引發劑的0.2重量份的偶氮二異丁腈，在60℃下攪拌17小時，得到重均分子量為150萬的丙烯酸酯共聚物溶液。Production Example 1 Into 200 parts by weight of ethyl acetate, 99 parts by weight of n-butyl acrylate, 1 part by weight of 4-hydroxybutyl acrylate, and 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator were added. The mixture was stirred at 60 ° C for 17 hours to obtain an acrylate copolymer solution having a weight average molecular weight of 1.5 million.
製造例2在100重量份的醋酸乙酯和100重量份的甲苯的混合溶劑中添加36重量份的丙烯酸正丁酯、20重量份的丙烯酸甲酯、44重量份的甲基丙烯酸正丁酯以及作為聚合引發劑的0.5重量份的偶氮二異丁腈，在70℃下攪拌17小時，得到重均分子量為20萬的丙烯酸酯共聚物溶液。Production Example 2 In a mixed solvent of 100 parts by weight of ethyl acetate and 100 parts by weight of toluene, 36 parts by weight of n-butyl acrylate, 20 parts by weight of methyl acrylate, 44 parts by weight of n-butyl methacrylate, and 0.5 part by weight of azobisisobutyronitrile as a polymerization initiator was stirred at 70 ° C for 17 hours to obtain an acrylate copolymer solution having a weight average molecular weight of 200,000.
實施例1在製造例1中得到的丙烯酸酯共聚物溶液中，相對於其中的100重量份丙烯酸酯共聚物，添加作為交聯劑的1.60重量份的聚異氰酸酯化合物"Coronate"[三井武田化學(股)製造]和0.67重量份的"Takenate D－110N"[三井武田化學(股)製造]、作為矽烷偶聯劑的0.35重量份"KBE－402"[信越化學工業(股)製造，化學名：3－環氧丙氧基丙基(甲基)二乙氧基矽烷]，在甲基乙基酮中稀釋成固體分濃度約為20重量%的溶液，製備黏著劑組成物。Example 1 In the acrylate copolymer solution obtained in Production Example 1, 1.60 parts by weight of a polyisocyanate compound "Coronate" (Mitsui Takeda Chemical Co., Ltd.) was added as a crosslinking agent to 100 parts by weight of the acrylate copolymer. [manufacturing] and 0.67 parts by weight of "Takenate D-110N" [manufactured by Mitsui Takeda Chemical Co., Ltd.], 0.35 parts by weight of "KBE-402" as a decane coupling agent [manufactured by Shin-Etsu Chemical Co., Ltd., chemical name : 3-glycidoxypropyl (methyl) diethoxy decane], which was diluted with methyl ethyl ketone to a solution having a solid concentration of about 20% by weight to prepare an adhesive composition.
接着，用刮刀塗布器在厚度為38μm的聚對苯二甲酸乙二醇酯(PET)剝離薄膜[Lintech(股)製造的"SP－PET3811"]的剝離處理面上塗布該黏著劑組成物，在90℃下乾燥1分鐘，然後層壓偏振片(三乙醯纖維素薄膜/聚乙烯醇薄膜/三乙醯纖維素薄膜的3層叠層體，總厚度180μm)或厚度為50μm的PET薄膜[東洋紡織(股)製造的"Cosmoshine A4300"]，得到厚度為25μm的帶黏著劑層的偏振片或帶黏著劑層的PET薄膜。Next, the adhesive composition was applied on a release-treated surface of a polyethylene terephthalate (PET) release film ("PE-PET 3811" manufactured by Lintech Co., Ltd.) having a thickness of 38 μm by a knife coater. Drying at 90 ° C for 1 minute, and then laminating a polarizing plate (three-layer cellulose film / polyvinyl alcohol film / three-layer film of triethylene cellulose film, total thickness of 180 μm) or a PET film having a thickness of 50 μm [ "Cosmoshine A4300" manufactured by Toyobo Co., Ltd., obtained a polarizing plate with an adhesive layer or a PET film with an adhesive layer having a thickness of 25 μm.
測定它的各項特性。結果示於表1中。Determine its properties. The results are shown in Table 1.
實施例2在實施例1中，除了上述矽烷偶聯劑"KBE－402"(如前述)的添加量變為0.70重量份以外，進行和實施例1一樣的操作。結果示於表1中。Example 2 In Example 1, the same operation as in Example 1 was carried out except that the addition amount of the above decane coupling agent "KBE-402" (as described above) was changed to 0.70 parts by weight. The results are shown in Table 1.
實施例3在實施例1中，除了使用0.18重量份的上述"KBE－402"(如前述)、0.07重量份的"KBM－303"[信越化學工業(股)製造，化學品：2－(3,4－環氧基環己基)乙基三甲氧基矽烷]作為矽烷偶聯劑以外，進行和實施例1一樣的操作。結果示於表1中。Example 3 In Example 1, except that 0.18 parts by weight of the above "KBE-402" (as described above), 0.07 parts by weight of "KBM-303" [Shin-Etsu Chemical Co., Ltd., Chemicals: 2-( The same operation as in Example 1 was carried out, except that 3,4-epoxycyclohexyl)ethyltrimethoxydecane was used as the decane coupling agent. The results are shown in Table 1.
實施例4在實施例1中，除了使用0.35重量份的上述"KBE－402"、0.07重量份的上述"KBM－303"(如前述)作為矽烷偶聯劑以外，進行和實施例1一樣的操作。結果示於表1中。Example 4 In Example 1, the same procedure as in Example 1 was carried out except that 0.35 parts by weight of the above "KBE-402" and 0.07 parts by weight of the above "KBM-303" (as described above) were used as the decane coupling agent. operating. The results are shown in Table 1.
實施例5將製造例1中得到的丙烯酸酯共聚物溶液和製造例2中得到的丙烯酸酯共聚物溶液以其各自溶液中的丙烯酸酯共聚物分別為80重量份和20重量份的比例混合，在該溶液中加入作為交聯劑的1.60重量份上述聚異氰酸酯化合物"Cornate"(如前述)和0.67重量份上述"Takenate D－110N"(如前述)，作為矽烷偶聯劑的0.35重量份的上述"KBE－402"(如前述)，在甲基乙基酮中稀釋成固體分濃度為約20重量%的溶液，製備黏著劑組成物。Example 5 The acrylate copolymer solution obtained in Production Example 1 and the acrylate copolymer solution obtained in Production Example 2 were mixed at a ratio of 80 parts by weight and 20 parts by weight, respectively, of the acrylate copolymer in the respective solutions. To the solution, 1.60 parts by weight of the above polyisocyanate compound "Cornate" (as described above) and 0.67 parts by weight of the above "Takenate D-110N" (as described above) were added as a crosslinking agent as 0.35 parts by weight of the decane coupling agent. The above "KBE-402" (as described above) was diluted with methyl ethyl ketone to a solution having a solid concentration of about 20% by weight to prepare an adhesive composition.
下面進行和實施例一樣的操作。結果示於表1中。The same operations as in the embodiment are performed below. The results are shown in Table 1.
實施例6在實施例5中，除了將矽烷偶聯劑"KBE－402"的添加量變為0.70重量份以外，進行和實施例5一樣的操作。結果示於表1中。Example 6 In Example 5, the same operation as in Example 5 was carried out except that the addition amount of the decane coupling agent "KBE-402" was changed to 0.70 parts by weight. The results are shown in Table 1.
實施例7在實施例5中，除了使用0.18重量份的上述"KBE－402"(如前述)和0.07重量份上述"KBM－303"(如前述)作為矽烷偶聯劑以外，進行和實施例5一樣的操作。結果示於表1中。Example 7 In Example 5, except that 0.18 parts by weight of the above "KBE-402" (as described above) and 0.07 parts by weight of the above "KBM-303" (as described above) were used as the decane coupling agent, 5 the same operation. The results are shown in Table 1.
實施例8在實施例5中，除了使用0.35重量份的上述"KBE－402"(如前述)和0.07重量份"KBM－303"(如前述)作為矽烷偶聯劑以外，進行和實施例5一樣的操作。結果示於表1中。Example 8 In Example 5, except that 0.35 parts by weight of the above "KBE-402" (as described above) and 0.07 parts by weight of "KBM-303" (as described above) were used as the decane coupling agent, and Example 5 was carried out. The same operation. The results are shown in Table 1.
比較例1在實施例1中，除了使用0.35重量份的上述"KBM－303"(如前述)作為矽烷偶聯劑以外，進行和實施例1相同的操作。結果示於表1中。Comparative Example 1 In Example 1, the same operation as in Example 1 was carried out except that 0.35 parts by weight of the above "KBM-303" (as described above) was used as the decane coupling agent. The results are shown in Table 1.
比較例2在實施例5中，除了使用0.35重量份的上述"KBM－303"(如前述)作為矽烷偶聯劑以外，進行和實施例5相同的操作。結果示於表1中。Comparative Example 2 In Example 5, the same operation as in Example 5 was carried out except that 0.35 parts by weight of the above "KBM-303" (as described above) was used as the decane coupling agent. The results are shown in Table 1.
本發明的黏著劑組成物可以在濕熱條件下以良好的初期黏性和耐久黏性，在液晶單元等玻璃基板上貼附偏振片和相位差片等光學功能性構件。The adhesive composition of the present invention can adhere an optical functional member such as a polarizing plate or a retardation film to a glass substrate such as a liquid crystal cell under a moist heat condition with good initial viscosity and durability.
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| JP2005131326A JP5523650B2 (en) | 2005-04-28 | 2005-04-28 | Method for producing optical functional member with adhesive |
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| TW200704734A TW200704734A (en) | 2007-02-01 |
| TWI397569B true TWI397569B (en) | 2013-06-01 |
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| JP (1) | JP5523650B2 (en) |
| KR (1) | KR101327631B1 (en) |
| CN (1) | CN1854214B (en) |
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| KR100948778B1 (en) * | 2007-01-23 | 2010-03-24 | 주식회사 엘지화학 | Optically Compensated Acrylic Pressure-Sensitive Adhesive Composition, Polarizing Plate and Liquid Crystal Display Device containing the same |
| JP5889088B2 (en) * | 2012-03-30 | 2016-03-22 | リンテック株式会社 | Adhesive composition and adhesive sheet |
| JP6632349B2 (en) * | 2015-11-27 | 2020-01-22 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Pressure sensitive adhesive for optical film, pressure sensitive adhesive layer for optical film, optical member and image display device |
| JP6632350B2 (en) * | 2015-11-27 | 2020-01-22 | 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． | Pressure-sensitive adhesive for optical film, pressure-sensitive adhesive layer, optical member, and image display device |
| KR20210077412A (en) | 2019-12-17 | 2021-06-25 | 주식회사 엘지화학 | Water-based acrylic pressure sensitive adhesive composition, method for preparing the same and label comprising the same |
| JP2022128081A (en) * | 2021-02-22 | 2022-09-01 | 日東電工株式会社 | Adhesive composition and adhesive tape |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866657A (en) * | 1996-11-18 | 1999-02-02 | Takeda Chemical Industries, Ltd. | Primer composition |
| US6287701B1 (en) * | 1998-05-25 | 2001-09-11 | Chuo Rika Kogyo Corporation | Resin compositions, processes for their production and their uses |
| US20040180193A1 (en) * | 2003-03-11 | 2004-09-16 | Nissan Motor Co., Ltd. | Resin composition, filler, and method of producing resin composition |
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| JPH08120236A (en) * | 1994-10-26 | 1996-05-14 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
| JPH08259922A (en) * | 1995-03-17 | 1996-10-08 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
| JP3426410B2 (en) * | 1995-05-12 | 2003-07-14 | 日本合成化学工業株式会社 | Adhesive composition |
| JPH1180688A (en) * | 1997-09-03 | 1999-03-26 | Nippon Kayaku Co Ltd | Light scattering adhesive |
| KR20040040368A (en) * | 2002-11-06 | 2004-05-12 | 스미또모 가가꾸 고교 가부시끼가이샤 | Acrylic resin, adhesive comprising the resin, and optical laminate comprising the adhesive |
| JPWO2006009250A1 (en) * | 2004-07-22 | 2008-05-01 | 綜研化学株式会社 | Adhesive composition for polarizing plate and polarizing plate |
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2005
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- 2006-04-20 KR KR1020060035698A patent/KR101327631B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866657A (en) * | 1996-11-18 | 1999-02-02 | Takeda Chemical Industries, Ltd. | Primer composition |
| US6287701B1 (en) * | 1998-05-25 | 2001-09-11 | Chuo Rika Kogyo Corporation | Resin compositions, processes for their production and their uses |
| US20040180193A1 (en) * | 2003-03-11 | 2004-09-16 | Nissan Motor Co., Ltd. | Resin composition, filler, and method of producing resin composition |
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| CN1854214A (en) | 2006-11-01 |
| KR20060113413A (en) | 2006-11-02 |
| KR101327631B1 (en) | 2013-11-12 |
| CN1854214B (en) | 2010-12-08 |
| TW200704734A (en) | 2007-02-01 |
| JP2006307003A (en) | 2006-11-09 |
| JP5523650B2 (en) | 2014-06-18 |
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