TWI564357B - Adhesive, adhesive sheet and laminated body for touch panel - Google Patents
Adhesive, adhesive sheet and laminated body for touch panel Download PDFInfo
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- TWI564357B TWI564357B TW101122598A TW101122598A TWI564357B TW I564357 B TWI564357 B TW I564357B TW 101122598 A TW101122598 A TW 101122598A TW 101122598 A TW101122598 A TW 101122598A TW I564357 B TWI564357 B TW I564357B
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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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/29—Laminated material
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0416—Control or interface arrangements specially adapted for digitisers
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Human Computer Interaction (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Position Input By Displaying (AREA)
Description
本發明係關於使用於觸控板用積層體之黏著劑、使此黏著劑形成為片狀之黏著片、及使用此黏著片而貼附構件之觸控板用積層體。 The present invention relates to an adhesive for a laminated body for a touch panel, an adhesive sheet for forming the adhesive into a sheet shape, and a laminated body for a touch panel for attaching a member using the adhesive sheet.
於目前主流所使用之觸控板大致區分為電阻膜式觸控板與靜電電容式之觸控板,此等均為各種材料之積層體,其貼合主要使用丙烯酸系黏著劑。觸控板單元係因配置於畫面之最表面,故要求高透明性,進一步,必須有高耐熱性、耐濕熱性等特性。具體上,觸控板單元為各種材料之積層體,配置於觸控板裝置之最表面,故有時會受到來自外部水分之滲入而產生白化現象,又,貼附時,捲入空氣所造成之起泡及積層的材料產生的釋氣(outgas)所造成之起泡等成為問題。 The touch panels used in the current mainstream are roughly classified into a resistive touch panel and a capacitive touch panel, and these are laminated bodies of various materials, and the adhesive mainly uses an acrylic adhesive. Since the touch panel unit is disposed on the outermost surface of the screen, high transparency is required, and further, it is required to have characteristics such as high heat resistance and moist heat resistance. Specifically, the touch panel unit is a laminated body of various materials and is disposed on the outermost surface of the touch panel device, so that it may be whitened by infiltration from external moisture, and may be caused by air entrapment when attached. The foaming caused by the outgas generated by the foaming and laminating materials becomes a problem.
又,在至今之觸控板的主流之電阻膜方式的觸控板中,為了聚碳酸酯(PC)或模內成膜(in mold film;IMF)的貼附可使用各種之黏著劑。 Further, in the resistive film type touch panel which is the mainstream of the touch panel, various adhesives can be used for attaching polycarbonate (PC) or in mold film (IMF).
然而,就PC之材料上的特性而言,有在高溫條件產生釋氣之特性,亦有在耐熱條件產生起泡,很難抑制在濕熱條件水分流入所產生之黏著劑層的白化現象之問題。進一步,IMF係因具有次微米級(submicron order)之段差,故亦有黏著劑無法追隨該段差而捲入氣泡之問題。 However, in terms of the properties of the material of the PC, there are characteristics of outgassing at high temperature conditions, foaming under heat-resistant conditions, and difficulty in suppressing whitening of the adhesive layer generated by moisture inflow in hot and humid conditions. . Further, since the IMF has a submicron order, there is also a problem that the adhesive cannot follow the step and is caught in the bubble.
以往,藉由於黏著劑摻合酸成分以解決如上述之問 題。亦即,酸成分係具有使所混入之水分分散而使其不會析出之功能,滲入黏著劑層之水分係受酸成分之分散力而分散於黏著劑層內而未析出,故防止黏著劑層白化,又,因形成氫鍵,故受其氫鍵所產生之高凝集力而抑制耐熱起泡之氣泡的發生。 In the past, by adding an acid component to the adhesive to solve the above problem question. In other words, the acid component has a function of dispersing the mixed water so as not to precipitate, and the water permeating into the adhesive layer is dispersed in the adhesive layer without being deposited by the dispersing force of the acid component, so that the adhesive is prevented. The layer is whitened, and since hydrogen bonds are formed, the occurrence of bubbles of heat-resistant bubbling is suppressed by the high cohesive force generated by the hydrogen bonds.
不過最近,隨著以多點觸控化為首之功能的充實化,靜電電容方式的觸控板逐漸取代電阻膜方式的觸控板而成為主流。在此靜電電容方式的觸控板中,當然必須有電阻膜方式的觸控板所要求的特性,但除此之外,因黏著劑與形成配線之導電層直接接觸,故黏著劑必須有不使導電層之特性變動的特性。導電層係以如氧化銦錫(ITO)或銀之金屬或金屬氧化物形成,因與酸之接觸引起腐蝕,其電阻值上昇,故以往所使用之利用酸成分而確保耐熱性、耐濕熱性等特性的手段係無法使用。 Recently, with the enhancement of the function of multi-touch, the capacitive touch panel has gradually replaced the resistive touch panel and became the mainstream. In the capacitive touch panel, it is of course necessary to have the characteristics required for the resistive touch panel. However, in addition, since the adhesive is in direct contact with the conductive layer forming the wiring, the adhesive must have A property of changing the characteristics of the conductive layer. The conductive layer is formed of a metal such as indium tin oxide (ITO) or silver or a metal oxide, and is corroded by contact with an acid, and the resistance value thereof is increased. Therefore, the acid component used in the prior art is used to ensure heat resistance and moist heat resistance. Means of other characteristics cannot be used.
關於由如此之ITO等金屬或金屬氧化物所構成的透明電極之腐蝕,在專利文獻1(日本特開2010-77287號公報)中係已揭示以丙烯酸烷氧基烷酯作為主成分之聚合物,在此專利文獻1中係已揭示使用聚合物,而該聚合物係使用重量平均分子量為40萬至160萬之丙烯酸烷氧基烷酯系的聚合物而且不使用含羧基之單體。 In the case of the corrosion of a transparent electrode made of a metal or a metal oxide such as ITO, a polymer having an alkoxyalkyl acrylate as a main component has been disclosed in Patent Document 1 (JP-A-2010-77287). In Patent Document 1, it has been disclosed to use a polymer which uses a polymer having an average weight molecular weight of 400,000 to 1,600,000 of an alkoxyalkyl acrylate-based polymer and does not use a carboxyl group-containing monomer.
如此地不使用含羧基之單體而使用40萬至160萬之丙烯酸烷氧基烷酯系的聚合物,藉此有關由ITO等金屬或金屬氧化物所構成的透明電極之腐蝕雖已有某種程度的改善,但有關濕熱白化性、耐熱起泡性等性能係無法得到充 分的效果。進一步,作業性亦難謂充分。 Thus, 400,000 to 1,600,000 of alkoxyalkyl acrylate-based polymer is used without using a carboxyl group-containing monomer, whereby corrosion of a transparent electrode composed of a metal or a metal oxide such as ITO is already present. The degree of improvement, but the properties such as wet heat whitening, heat and foaming are not available. The effect of the points. Further, workability is also difficult to say.
進一步,於專利文獻1所揭示之聚合物的重量平均分子量大至40萬至160萬,故將此溶解於溶劑而調製塗佈液時,若固形分之量變多,則聚合物溶液之黏度變成太高。在觸控板中,有時在具有額緣印刷所造成之段差的支撐體上積層黏著劑,為追蹤其段差,必須形成厚膜之黏著劑層,又,特別在靜電電容方式之觸控板中,為使表面支撐體與ITO等導電性膜接著,有時尋求厚膜之黏著劑層,但因使用重量平均分子量為40萬至160萬之丙烯酸烷氧基烷酯系聚合物,故無法調製固形分含量高之塗佈液,調製固形分含量低之塗佈液,必須重複塗佈,存在著很難以一次之塗佈形成所需之厚度的黏著劑層之問題。 Further, the weight average molecular weight of the polymer disclosed in Patent Document 1 is as large as 400,000 to 1,600,000. Therefore, when the solution is dissolved in a solvent to prepare a coating liquid, if the amount of the solid content is increased, the viscosity of the polymer solution becomes Too high. In the touch panel, an adhesive is sometimes laminated on a support having a step caused by the printing of the fore edge. In order to track the step difference, a thick film adhesive layer must be formed, and in particular, in a capacitive touch panel. In order to bring the surface support to a conductive film such as ITO, a thick film adhesive layer may be sought. However, since an alkoxyalkyl acrylate polymer having a weight average molecular weight of 400,000 to 1.6 million is used, it is impossible to prepare. A coating liquid having a high solid content and a coating liquid having a low solid content are required to be repeatedly coated, and there is a problem that it is difficult to form an adhesive layer having a desired thickness in one application.
另外,上述黏著劑係有時以在剝離性薄膜間形成有黏著劑層之轉移膠帶的形態來使用。如此之轉移膠帶係剝離剝離性薄膜並轉印至觸控板構件而使用,但轉移膠帶的黏著劑層係已形成黏著劑層中之交聯構造,成為對具有凹凸之構件的追隨性差者。因此,即使交聯,為了貼合於薄膜或基材,尋求具有適度的柔軟性,降低使源自貼合時捲入的起泡之黏著片。於專利文獻2中係記載使用脂肪族異氰酸酯系交聯劑而提昇耐黃變性之黏著劑組成物。使用脂肪族異氰酸酯系交聯劑而熟化之黏著片係較使用具有芳香族環之交聯劑而熟化的黏著片,柔軟性亦更優異。但,記載於專利文獻2之交聯對象的丙烯酸系聚合物的重量平均分子量係40萬以上160萬以下,具有上述問題點。 Further, the above-mentioned adhesive may be used in the form of a transfer tape in which an adhesive layer is formed between the release films. Such a transfer tape is used by peeling off the peelable film and transferring it to a touch panel member. However, the adhesive layer of the transfer tape has formed a crosslinked structure in the adhesive layer, and has poor followability to a member having irregularities. Therefore, even if it cross-links, in order to adhere to a film or a base material, it is seeking to have moderate softness, and it is set as the adhesive sheet which the foaming which originated in the fuse|bonding at the time of bonding. Patent Document 2 describes an adhesive composition which uses an aliphatic isocyanate crosslinking agent to enhance yellowing resistance. An adhesive sheet which is cured by using an aliphatic isocyanate crosslinking agent is more excellent in flexibility than an adhesive sheet which is cured by using a crosslinking agent having an aromatic ring. However, the acrylic polymer described in Patent Document 2 has a weight average molecular weight of 400,000 or more and 1.6 million or less, which has the above problems.
又,構成觸控板之表面支撐體的聚對苯二甲酸乙二酯或聚碳酸酯之表面係常經硬塗處理。因而,黏著片係亦尋求對於硬塗層之黏著力為良好。 Further, the surface of the polyethylene terephthalate or polycarbonate constituting the surface support of the touch panel is often subjected to a hard coat treatment. Therefore, the adhesive sheet also seeks to have good adhesion to the hard coat layer.
[專利文獻1]日本特開2010-77287號公報 [專利文獻2]日本特開2010-215923號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-77287 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-215923
本發明之目的在於提供一種在具有由金屬或金屬氧化物所構成之導電膜的觸控板用之黏著劑中,耐熱性、耐濕熱安定性、段差追隨性優異,無對於金屬或金屬氧化物之腐蝕性的黏著劑、黏著片及使用此之觸控板用積層體。 An object of the present invention is to provide an adhesive for a touch panel having a conductive film made of a metal or a metal oxide, which is excellent in heat resistance, heat and humidity stability, and step followability, and has no metal or metal oxide. A corrosive adhesive, an adhesive sheet, and a laminate for use with the touch panel.
又,本發明的目的在於提供一種作業性佳之黏著劑或黏著片。 Further, an object of the present invention is to provide an adhesive or an adhesive sheet which is excellent in workability.
本發明係例如以下之[1]至[29]。 The present invention is, for example, the following [1] to [29].
[1]一種黏著劑,其含有:丙烯酸系聚合物(A)、與相對於該丙烯酸系聚合物(A)100重量份之脂肪族異氰酸酯系交聯劑(B)0.1至5重量份;該丙烯酸系聚合物(A)係使含有如下所示之成分(a-1)及(a-2)(a-1)(甲基)丙烯酸烷氧酯20至99.9重量%、(a-2)具有交聯性官能基之單體0.1至10重量% 之單體(以全單體為100重量%)共聚合所得到之實質上不具有酸性基之重量平均分子量為5萬以上且未達40萬。 [1] An adhesive comprising: an acrylic polymer (A) and an aliphatic isocyanate crosslinking agent (B) in an amount of 100 parts by weight based on the acrylic polymer (A): 0.1 to 5 parts by weight; The acrylic polymer (A) contains the components (a-1) and (a-2) (a-1) alkoxylate (meth)acrylate shown below in an amount of 20 to 99.9% by weight, (a-2). 0.1 to 10% by weight of a monomer having a crosslinkable functional group The weight average molecular weight of the monomer (100% by weight of the total monomer) obtained by copolymerization without substantially having an acidic group is 50,000 or more and less than 400,000.
[2]如[1]項記載之黏著劑,其中上述脂肪族異氰酸酯系交聯劑(B)為於1分子內具有三個以上之異氰酸酯基。 [2] The adhesive according to [1], wherein the aliphatic isocyanate crosslinking agent (B) has three or more isocyanate groups in one molecule.
[3]如[1]或[2]項記載之黏著劑,其中形成上述丙烯酸系聚合物(A)之(a-2)具有交聯性官能基的單體為含羥基的單體。 [3] The adhesive according to [1] or [2] wherein the monomer having the crosslinkable functional group (a-2) forming the acrylic polymer (A) is a hydroxyl group-containing monomer.
[4]如[1]至[3]項中任一項之黏著劑,其中上述丙烯酸系聚合物(A)為使復含有5重量%以下(a-3)含氮單體之單體共聚合所得到。 [4] The adhesive according to any one of [1] to [3] wherein the acrylic polymer (A) is a monomer having a nitrogen content of 5 wt% or less (a-3) Aggregated.
[5]如[4]項之黏著劑,其中上述(a-3)含氮單體為由含胺基單體、含醯胺基單體、含氮系雜環之單體及含氰基的單體所構成之群中選出的至少1種。 [5] The adhesive according to [4], wherein the (a-3) nitrogen-containing monomer is an amino group-containing monomer, a guanamine-containing monomer, a nitrogen-containing heterocyclic monomer, and a cyano group. At least one selected from the group consisting of monomers.
[6]如[1]至[5]項中任一項之黏著劑,其中上述黏著劑為與金屬或金屬氧化物直接接觸之靜電電容方式的觸控板用之黏著劑。 [6] The adhesive according to any one of [1] to [5] wherein the adhesive is an electrostatic capacitance type touch panel adhesive which is in direct contact with a metal or a metal oxide.
[7]如[1]至[5]項中任一項之黏著劑,其中上述黏著劑為與觸控板之表面支撐體上的硬塗層直接接觸之靜電電容方式的觸控板用之黏著劑。 [7] The adhesive according to any one of [1] to [5] wherein the adhesive is an electrostatic capacitance type touch panel that is in direct contact with a hard coat layer on a surface support of the touch panel. Adhesive.
[8]如[7]項之黏著劑,其中上述硬塗層為矽氧系。 [8] The adhesive according to [7], wherein the hard coat layer is an anthracene oxygen system.
[9]一種黏著片,其具有由黏著劑所形成,且凝膠分率為40至80重量%,厚度為於10至1000μm的範圍內之黏著劑層;該黏著劑係含有:丙烯酸系聚合物(A)、與相對於該 丙烯酸系聚合物(A)100重量份之脂肪族異氰酸酯系交聯劑(B)0.1至5重量份;又該丙烯酸系聚合物(A)係使含有如下所示之成分(a-1)及(a-2)(a-1)(甲基)丙烯酸烷氧酯20至99.9重量%、(a-2)具有交聯性官能基之單體0.1至10重量%之單體(以全單體為100重量%)共聚合所得到之實質上不具有酸性基之重量平均分子量為5萬以上且未達40萬。 [9] An adhesive sheet comprising an adhesive layer formed of an adhesive and having a gel fraction of 40 to 80% by weight and a thickness of 10 to 1000 μm; the adhesive comprising: acrylic polymerization Object (A), and relative to the The acrylic polymer (A) is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the aliphatic isocyanate crosslinking agent (B); and the acrylic polymer (A) contains the component (a-1) shown below and (a-2) (a-1) alkoxylate of (meth)acrylic acid 20 to 99.9% by weight, (a-2) monomer having a crosslinking functional group of 0.1 to 10% by weight of a monomer (in a single order) The weight average molecular weight obtained by copolymerization of 100% by weight of the compound having substantially no acidic group is 50,000 or more and less than 400,000.
[10]如[9]項之黏著片,其中上述脂肪族異氰酸酯系交聯劑(B)為於一分子內具有三個以上之異氰酸酯基。 [10] The adhesive sheet according to [9], wherein the aliphatic isocyanate crosslinking agent (B) has three or more isocyanate groups in one molecule.
[11]如[9]或[10]項之黏著片,其中形成上述丙烯酸系聚合物(A)之(a-2)具有交聯性官能基的單體為含羥基的單體。 [11] The adhesive sheet according to [9] or [10] wherein the monomer having the crosslinkable functional group (a-2) forming the acrylic polymer (A) is a hydroxyl group-containing monomer.
[12]如[9]至[11]項中任一項之黏著片,其中上述丙烯酸系聚合物(A)為使復含有5重量%以下(a-3)含氮單體之單體共聚合所得到。 [12] The adhesive sheet according to any one of [9] to [11] wherein the acrylic polymer (A) is a monomer having a nitrogen content of 5% by weight or less (a-3). Aggregated.
[13]如[12]項之黏著片,其中上述(a-3)含氮單體為由含胺基單體、含醯胺基單體、含氮系雜環之單體及含氰基的單體所構成之群中選出的至少1種。 [13] The adhesive sheet according to [12], wherein the (a-3) nitrogen-containing monomer is an amino group-containing monomer, a guanamine-containing monomer, a nitrogen-containing heterocyclic monomer, and a cyano group. At least one selected from the group consisting of monomers.
[14]如[9]至[13]項中任一項之黏著片,其中形成上述黏著片之黏著劑為與金屬或金屬氧化物直接接觸之靜電電容方式的觸控板用之黏著劑。 [14] The adhesive sheet according to any one of [9] to [13] wherein the adhesive for forming the adhesive sheet is an adhesive for a capacitive touch panel in direct contact with a metal or a metal oxide.
[15]如[9]至[14]項中任一項之黏著片,其中形成上述黏著片之黏著劑為與觸控板之表面支撐體上的硬塗層直接接觸之靜電電容方式的觸控板用之黏著劑。 [15] The adhesive sheet according to any one of [9] to [14] wherein the adhesive forming the adhesive sheet is an electrostatic capacitive contact with a hard coating layer on a surface support of the touch panel. Adhesive for control board.
[16]如[15]項之黏著片,其中上述硬塗層為矽氧系。 [16] The adhesive sheet of [15], wherein the hard coat layer is a ruthenium oxygen system.
[17]如[9]至[16]項中任一項之黏著片,其中於上述黏著片之至少一面配置已實施剝離處理之覆蓋膜(cover film)。 [17] The adhesive sheet according to any one of [9] to [16] wherein a cover film which has been subjected to a release treatment is disposed on at least one side of the adhesive sheet.
[18]一種觸控板用積層體,其係於黏著片之一面,貼附有與該黏著片面對面之面的緣部經額緣印刷之表面支撐體,並在該黏著片之另一面貼附有由金屬或金屬氧化物所構成的透明導電膜、或者附電極支撐體之由金屬或金屬氧化物所構成的透明導電膜;該黏著片,具有由黏著劑所形成,且凝膠分率為40至80重量%,厚度為於10至1000μm的範圍內之黏著劑層;該黏著劑係含有:丙烯酸系聚合物(A)、與相對於該丙烯酸系聚合物(A)100重量份之脂肪族異氰酸酯系交聯劑(B)0.1至5重量份;又該丙烯酸系聚合物(A)係使含有如下所示之成分(a-1)及(a-2)(a-1)(甲基)丙烯酸烷氧酯20至99.9重量%、(a-2)具有交聯性官能基之單體0.1至10重量%之單體(以全單體為100重量%)共聚合所得到之實質上不具有酸性基之重量平均分子量為5萬以上且未達40萬。 [18] A laminated body for a touch panel, which is attached to one surface of an adhesive sheet, and has a surface supporting body printed on the edge of the surface facing the surface of the adhesive sheet, and is attached to the other side of the adhesive sheet. a transparent conductive film made of a metal or a metal oxide or a transparent conductive film made of a metal or a metal oxide; the adhesive sheet is formed of an adhesive and has a gel fraction An adhesive layer having a thickness of 40 to 80% by weight and a thickness of 10 to 1000 μm; the adhesive comprising: an acrylic polymer (A) and 100 parts by weight relative to the acrylic polymer (A) 0.1 to 5 parts by weight of the aliphatic isocyanate crosslinking agent (B); and the acrylic polymer (A) contains the components (a-1) and (a-2) (a-1) shown below ( 20 to 99.9% by weight of alkoxyalkyl methacrylate, (a-2) 0.1 to 10% by weight of a monomer having a crosslinkable functional group (100% by weight of all monomers) copolymerized The weight average molecular weight which does not substantially have an acidic group is 50,000 or more and less than 400,000.
[19]如[18]項之觸控板用積層體,其中上述觸控板用積層體為形成靜電電容方式觸控板之構件。 [19] The laminated body for a touch panel according to [18], wherein the laminated body for the touch panel is a member for forming a capacitive touch panel.
[20]如[18]或[19]項之觸控板用積層體,其中上述額緣印刷之厚度為於10至50μm的範圍內。 [20] The laminate for a touch panel according to [18] or [19], wherein the thickness of the margin printing is in a range of 10 to 50 μm.
[21]如[18]至[20]項中任一項之觸控板用積層體,其中上 述透明導電膜為使用ITO、ATO、或氧化錫之配線圖型,且上述黏著片直接接觸該配線圖型。 [21] The laminated body for a touch panel according to any one of [18] to [20], wherein The transparent conductive film is a wiring pattern using ITO, ATO, or tin oxide, and the above-mentioned adhesive sheet directly contacts the wiring pattern.
[22]如[18]至[21]項中任一項之觸控板用積層體,其中上述表面支撐體之厚度於25至2000μm的範圍內。 [22] The laminate for a touch panel according to any one of [18] to [21] wherein the surface support has a thickness in the range of 25 to 2000 μm.
[23]如[18]至[22]項中任一項之觸控板用積層體,其中上述透明導電膜的厚度於10至100nm之範圍內。 [23] The laminate for a touch panel according to any one of [18] to [22] wherein the transparent conductive film has a thickness in the range of 10 to 100 nm.
[24]如[18]至[23]項中任一項之觸控板用積層體,其中上述脂肪族異氰酸酯系交聯劑(B)為於一分子內具有三個以上之異氰酸酯基。 [24] The laminate for a touch panel according to any one of [18], wherein the aliphatic isocyanate crosslinking agent (B) has three or more isocyanate groups in one molecule.
[25]如[18]至[24]項中任一項之觸控板用積層體,其中形成上述丙烯酸系聚合物(A)之(a-2)具有交聯性官能基的單體為含羥基的單體。 [25] The laminate for a touch panel according to any one of [18] to [24] wherein the monomer having the crosslinkable functional group (a-2) forming the acrylic polymer (A) is A hydroxyl group-containing monomer.
[26]如[18]至[25]項中任一項之觸控板用積層體,其中上述丙烯酸系聚合物(A)為使復含有5重量%以下(a-3)含氮單體之單體共聚合所得到。 [26] The laminated body for a touch panel according to any one of [18], wherein the acrylic polymer (A) is a compound containing 5% by weight or less (a-3) of a nitrogen-containing monomer. The monomer is obtained by copolymerization.
[27]如[26]項之觸控板用積層體,其中上述(a-3)含氮單體為由含胺基單體、含醯胺基單體、含氮系雜環之單體及含氰基的單體所構成之群中選出的至少1種。 [27] The laminate for a touch panel according to [26], wherein the (a-3) nitrogen-containing monomer is a monomer comprising an amine group-containing monomer, a guanamine-containing monomer, and a nitrogen-containing heterocyclic ring. At least one selected from the group consisting of cyano group-containing monomers.
[28]如[18]至[27]項中任一項之觸控板用積層體,其中上述黏著片為與觸控板之表面支撐體上的硬塗層直接接觸。 [28] The laminated body for a touch panel according to any one of [18] to [27] wherein the adhesive sheet is in direct contact with a hard coat layer on a surface support of the touch panel.
[29]如[28]項之觸控板用積層體,其中上述硬塗層為矽氧系。 [29] The laminate for a touch panel according to [28], wherein the hard coat layer is a tantalum oxygen system.
本發明之黏著劑係因實質上不含有酸成分,故可有效 地抑制由ITO或銀等金屬或金屬氧化物所構成的配線之腐蝕所造成的劣化。 The adhesive of the present invention is effective because it does not substantially contain an acid component Deterioration caused by corrosion of wiring composed of a metal such as ITO or silver or a metal oxide is suppressed.
進一步,本發明之黏著劑係重量平均分子量(Mw)為5萬以上未達40萬,故可於溶劑中使固形分保持高濃度,可以一次的塗佈步驟進行充分的厚塗。 Further, since the weight average molecular weight (Mw) of the adhesive of the present invention is 50,000 or more and less than 400,000, the solid content can be maintained at a high concentration in a solvent, and a sufficient thick coating can be carried out in a single coating step.
繼而,藉由脂肪族異氰酸酯系交聯劑而形成交聯構造,故本發明之黏著劑係耐熱性、耐濕熱安定性優異,又,有柔軟性,故段差追隨性非常良好。進一步,對於經硬塗處理之薄膜的黏著性亦良好。 Then, since the crosslinked structure is formed by the aliphatic isocyanate crosslinking agent, the adhesive of the present invention is excellent in heat resistance and moist heat stability, and has flexibility, so that the step followability is very good. Further, the adhesion to the hard-coated film was also good.
因此,本發明之黏著劑、具有此黏著劑作為黏著層之黏著片、及使用此黏著片之觸控板用積層體係不易產生對於由ITO或銀等金屬或金屬氧化物所構成的透明導電膜之腐蝕,進一步,亦難以發生白化、起泡。 Therefore, the adhesive of the present invention, the adhesive sheet having the adhesive as an adhesive layer, and the laminated system for a touch panel using the adhesive sheet are less likely to produce a transparent conductive film composed of a metal or a metal oxide such as ITO or silver. Corrosion, further, it is also difficult to whiten and foam.
其次,具體地說明有關本發明之黏著劑、黏著片及觸控板用積層體。 Next, a laminate for the adhesive, the adhesive sheet and the touch panel of the present invention will be specifically described.
本發明之黏著劑係由丙烯酸系聚合物(A)與脂肪族異氰酸酯系交聯劑(B)所構成。 The adhesive of the present invention is composed of an acrylic polymer (A) and an aliphatic isocyanate crosslinking agent (B).
在本發明中,丙烯酸系聚合物(A)係使如下所示之成分(a-1)及(a-2)共聚合所得到之聚合物:(a-1)(甲基)丙烯酸烷氧酯、(a-2)具有交聯性官能基之單體。 In the present invention, the acrylic polymer (A) is a polymer obtained by copolymerizing the components (a-1) and (a-2) shown below: (a-1) alkoxylate (meth)acrylate Ester, (a-2) a monomer having a crosslinkable functional group.
此處所使用之構成丙烯酸系聚合物(A)的(a-1)(甲基)丙烯酸烷氧酯之例係可舉例如(甲基)丙烯酸甲氧基甲酯、 (甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸甲氧基丁酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸乙氧基丙酯、(甲基)丙烯酸乙氧基丁酯、甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、乙氧基三乙二醇(甲基)丙烯酸酯。此等之(a-1)(甲基)丙烯酸烷氧酯之中宜使用(甲基)丙烯酸甲氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯,此等係可單獨或組合而使用。 Examples of the (a-1) (meth)acrylic acid alkoxylate constituting the acrylic polymer (A) used herein include, for example, methoxymethyl (meth)acrylate, Methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, (meth)acrylic acid Oxyethyl ester, ethoxypropyl (meth)acrylate, ethoxybutyl (meth)acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (A) Acrylate, methoxytriethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate. Among these (a-1) alkoxylates of (meth)acrylic acid, methoxyethyl (meth)acrylate and methoxydiethylene glycol (meth)acrylate are preferably used. Or use in combination.
在本發明之丙烯酸系聚合物中,前述之(a-1)(甲基)丙烯酸烷氧酯係以20至99.9重量%,較佳係以30至99.1重量%,更佳係以50至98.3重量%的量共聚合。若(a-1)(甲基)丙烯酸烷氧酯多於99.9重量%,則必定具有官能基的單體之使用量變少,無法達成充分的交聯密度。又,若少於20重量%,則濕熱時無法抑制水分析出而黏著劑層白化,外觀出現異常。 In the acrylic polymer of the present invention, the aforementioned (a-1) alkoxylate of (meth)acrylate is 20 to 99.9% by weight, preferably 30 to 99.1% by weight, more preferably 50 to 98.3. The amount by weight is copolymerized. When the (a-1) alkoxylate of (meth)acrylic acid is more than 99.9% by weight, the amount of the monomer having a functional group must be reduced, and a sufficient crosslinking density cannot be obtained. On the other hand, when it is less than 20% by weight, it is impossible to suppress water analysis during wet heat, and the adhesive layer is whitened, and the appearance is abnormal.
又,與上述(a-1)(甲基)丙烯酸烷氧酯共聚合之(a-2)具有交聯性官能基的單體,宜為含羥基之單體。含羥基的單體宜為具有羥基作為官能基之(甲基)丙烯酸酯化合物,如此之具有羥基的(甲基)丙烯酸酯化合物的例,可舉例如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-氯-2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯。上述之具有羥基的(甲基)丙烯酸酯化合物宜為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯,此等之具有羥基的(甲基)丙 烯酸酯化合物係可單獨或組合而使用。 Further, the monomer having a crosslinkable functional group (a-2) copolymerized with the above (a-1) (meth)acrylic acid alkoxylate is preferably a hydroxyl group-containing monomer. The hydroxyl group-containing monomer is preferably a (meth) acrylate compound having a hydroxyl group as a functional group, and examples of the (meth) acrylate compound having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate. 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (A) Base) 8-hydroxyoctyl acrylate. The above (meth) acrylate compound having a hydroxyl group is preferably 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like (meth) propyl having a hydroxyl group. The enoate compounds can be used singly or in combination.
在本發明所使用之丙烯酸系聚合物(A)中,(a-2)具有交聯性官能基之單體係0.1至10重量%,宜為0.8至9重量%,更宜為於1.2至6重量%的範圍內之量進行共聚合。 In the acrylic polymer (A) used in the present invention, (a-2) a single system having a crosslinkable functional group is from 0.1 to 10% by weight, preferably from 0.8 to 9% by weight, more preferably from 1.2 to Copolymerization was carried out in an amount ranging from 6 wt%.
若具有交聯性官能基之單體的量少於上述,有時以脂肪族異氰酸酯系交聯劑所產生的交聯構造無法充分形成,若具有交聯性官能基之單體的量多於10重量%,有時作為丙烯酸系聚合物之特性未充分顯現。 When the amount of the monomer having a crosslinkable functional group is less than the above, the crosslinked structure produced by the aliphatic isocyanate crosslinking agent may not be sufficiently formed, and the amount of the monomer having a crosslinkable functional group may be more than 10% by weight may not be sufficiently exhibited as a characteristic of the acrylic polymer.
進一步,本發明之丙烯酸系聚合物除了上述(a-1)(甲基)丙烯酸烷氧酯及(a-2)具有交聯性官能基之單體以外,在無損此丙烯酸系聚合物之特性的範圍內亦可共聚合其他之丙烯酸系聚合物。 Further, the acrylic polymer of the present invention does not impair the characteristics of the acrylic polymer except for the above (a-1) alkoxylate of (meth)acrylate and (a-2) a monomer having a crosslinkable functional group. Other acrylic polymers may also be copolymerized within the range.
此處,形成丙烯酸系聚合物之其他單體的例係可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸二癸酯。此等之(甲基)丙烯酸酯係可單獨或組合而使用。此等之中,宜為使用(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸異丁酯,此等之(甲基)丙烯酸烷酯係丙烯酸系聚合物(A)中,可在0至79.9重量%之範圍使用,宜為0至69.1重量%,更 宜為於0至48.3重量%的範圍內使用。 Here, examples of the other monomer forming the acrylic polymer include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (methyl) Heptyl acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, eleven (meth) acrylate, ( Dimethyl methacrylate. These (meth) acrylates can be used singly or in combination. Among these, it is preferred to use butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, isobutyl (meth)acrylate, etc. The alkyl acrylate-based acrylic polymer (A) may be used in the range of 0 to 79.9% by weight, preferably 0 to 69.1% by weight, more preferably It is preferably used in the range of 0 to 48.3% by weight.
進一步,本發明使用之丙烯酸系聚合物(A),就提昇黏著劑之凝集力,進一步促進藉由異氰酸酯系交聯劑之交聯而言,宜為與(a-3)含氮單體共聚合。含氮單體宜為使用由含胺基的單體、含醯胺基的單體、含氮系雜環的單體及含氰基的單體所構成之群中選出的至少1種。 Further, the acrylic polymer (A) used in the present invention enhances the cohesive force of the adhesive and further promotes crosslinking by the isocyanate crosslinking agent, preferably in combination with the (a-3) nitrogen-containing monomer. polymerization. The nitrogen-containing monomer is preferably at least one selected from the group consisting of an amine group-containing monomer, a guanamine group-containing monomer, a nitrogen-containing heterocyclic monomer, and a cyano group-containing monomer.
此處含有胺基的單體之例係可舉例如(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯。 Examples of the monomer having an amino group herein include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
又,含醯胺基的單體之例係可舉例如(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺。 Further, examples of the guanamine group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl. Base (meth) acrylamide, N-hexyl (meth) acrylamide.
進一步,含有氮系雜環的單體之例係可舉例如乙烯基吡咯啶酮、丙烯醯基嗎啉、乙烯基己內醯胺。 Further, examples of the monomer containing a nitrogen-based heterocyclic ring include, for example, vinylpyrrolidone, acryloylmorpholine, and vinyl caprolactam.
又,含氰基的單體之例係可舉例如氰基(甲基)丙烯酸酯。 Further, examples of the cyano group-containing monomer include cyano (meth) acrylate.
如此之(a-3)含氮單體在丙烯酸系聚合物中,較佳係以5重量%以下,更佳係以0.1至4重量%,最宜為以0.5至3重量%之量進行共聚合。 The (a-3) nitrogen-containing monomer is preferably 5% by weight or less, more preferably 0.1 to 4% by weight, most preferably 0.5 to 3% by weight, based on the acrylic polymer. polymerization.
又,進一步,本發明使用之丙烯酸系聚合物(A)中係在不阻礙本案發明之效果的範圍中,可共聚合其他之單體。其他之單體係可舉例如醋酸乙烯酯;(甲基)丙烯腈;(甲基)丙烯酸環己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯酯;苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯及辛 基苯乙烯等烷基苯乙烯,氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘化苯乙烯、硝基苯乙烯、乙醯基苯乙烯及甲氧基苯乙烯等苯乙烯系單體;丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯,進一步係具有不飽和基之甲基丙烯酸甲酯聚合物、具有不飽和基之甲基丙烯酸第三丁酯聚合物及具有不飽和基之苯乙烯聚合物等巨單體。 Further, in the acrylic polymer (A) used in the present invention, other monomers may be copolymerized in a range that does not inhibit the effects of the present invention. Other single systems include, for example, vinyl acetate; (meth)acrylonitrile; cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate; styrene, methyl Styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octane Alkyl styrene such as styrene, styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, styrene iodide, nitrostyrene, ethyl styrene styrene and methoxy styrene a monomer; glycidyl acrylate, glycidyl methacrylate, further a methyl methacrylate polymer having an unsaturated group, a butyl methacrylate polymer having an unsaturated group, and an unsaturated group. Giant monomers such as styrene polymers.
本發明使用之丙烯酸系聚合物(A)係實質上不具有酸性基。在本說明書中係酸性基中不包括羥基。此處不具有酸性基係意指不刻意摻合酸性基,若以酸價表示,一般為0.5以下。此處具有酸性基之單體係(甲基)丙烯酸酯、馬來酸、伊康酸(itaconic acid)等具有羧基的單體,具有磷酸基之單體、具有硫酸基之單體等。在本發明之丙烯酸系聚合物(A)中,如上述之含有酸性基之單體係未共聚合。如此地使含有酸性基之單體不共聚合,故本發明之丙烯酸系聚合物(A)係即使與由金屬或金屬氧化物所構成之配線直接接觸,亦不腐蝕此等,可對本發明之黏著劑賦予經長期間不使配線之電阻值變動之特性。 The acrylic polymer (A) used in the present invention does not substantially have an acidic group. In the present specification, a hydroxyl group is not included in the acidic group. The absence of an acidic group herein means that the acidic group is not intentionally blended, and if it is represented by an acid value, it is generally 0.5 or less. Here, a monomer having a carboxyl group such as a single system (meth) acrylate having an acidic group, maleic acid or itaconic acid, a monomer having a phosphate group, a monomer having a sulfate group, or the like. In the acrylic polymer (A) of the present invention, the above-mentioned single system containing an acidic group is not copolymerized. Since the acid group-containing monomer is not copolymerized in this manner, the acrylic polymer (A) of the present invention does not corrode even if it is in direct contact with a wiring composed of a metal or a metal oxide, and can be used in the present invention. The adhesive imparts a characteristic that the resistance value of the wiring is not changed over a long period of time.
進一步,本發明使用之丙烯酸系聚合物(A)係於重量平均分子量為5萬以上且未達40萬,較佳係於10萬至38萬的範圍內。 Further, the acrylic polymer (A) used in the present invention has a weight average molecular weight of 50,000 or more and less than 400,000, preferably in the range of 100,000 to 380,000.
上述丙烯酸系聚合物(A)係可藉由公知的方法來製造,但宜藉由溶液聚合來製造。在溶液聚合中,就聚合溶劑而言,可使用例如酯酸乙酯、甲基乙基酮、甲苯、丙酮等。具體上係於反應容器內饋入聚合溶劑、單體,在氮氣 等惰性氣體環境下添加聚合起始劑,加熱至反應溫度為50至90℃左右,使之反應4至20小時。 The acrylic polymer (A) can be produced by a known method, but it is preferably produced by solution polymerization. In the solution polymerization, as the polymerization solvent, for example, ethyl ethate, methyl ethyl ketone, toluene, acetone or the like can be used. Specifically, a polymerization solvent, a monomer, and a nitrogen gas are fed into the reaction vessel. The polymerization initiator is added under an inert gas atmosphere, and heated to a reaction temperature of about 50 to 90 ° C for 4 to 20 hours.
使用於溶液聚合之反應起始劑係可舉例如偶氮系起始劑、過氧化物系起始劑。此等之反應起始劑相對於單體100重量份,一般在0.01至5重量份的範圍內之量使用。又,在上述聚合反應中,亦可適當添加聚合起始劑、鏈轉移劑、單體、溶劑。 The reaction initiator used in the solution polymerization may, for example, be an azo initiator or a peroxide initiator. These reaction initiators are generally used in an amount of from 0.01 to 5 parts by weight based on 100 parts by weight of the monomers. Further, in the above polymerization reaction, a polymerization initiator, a chain transfer agent, a monomer, and a solvent may be appropriately added.
在上述之條件中,重量平均分子量係依習知之技術,藉由調整所使用之溶劑的種類、聚合起始劑的種類及量、反應時間、反應溫度等反應條件來調節。 In the above conditions, the weight average molecular weight is adjusted by adjusting the reaction conditions such as the kind of the solvent to be used, the kind and amount of the polymerization initiator, the reaction time, and the reaction temperature, according to a known technique.
本發明之黏著劑係進一步含有脂肪族異氰酸酯系交聯劑(B)。脂肪族異氰酸酯系交聯劑(B)係交聯後,仍保持黏著片之柔軟性,同時並使黏著片之與聚對苯二甲酸乙二酯等硬塗處理面的黏著性良好。 The adhesive of the present invention further contains an aliphatic isocyanate crosslinking agent (B). After the aliphatic isocyanate crosslinking agent (B) is crosslinked, the flexibility of the adhesive sheet is maintained, and the adhesion of the adhesive sheet to a hard coated surface such as polyethylene terephthalate is good.
本發明使用之脂肪族異氰酸酯系交聯劑(B)的例係可舉例如六亞甲基二異氰酸酯、四亞甲基二異氰酸酯等於1分子內具有二個以上的異氰酸酯基的化合物,進一步係使其與公知之聚醚多元醇或聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯等進行加成反應的胺基甲酸酯(urethane)預聚物型的於1分子內具有二個以上之異氰酸酯基的化合物。其等之中,就可提昇貼附面的段差追隨性、使耐熱起泡性良好之點,宜為於1分子內具有三個以上之異氰酸酯基的化合物。於1分子內具有三個以上之異氰酸酯基的化合物係可舉例如上述於1分子內具有二個以上之 異氰酸酯基的化合物之加成物型化合物、使上述於1分子內具有二個以上之異氰酸酯基的化合物與新戊四醇等多元醇進行加成反應的化合物、上述於1分子內具有二個以上之異氰酸酯基的化合物之三聚異氰酸酯化合物、上述於1分子內具有二個以上之異氰酸酯基的化合物之縮二脲型化合物。上述加成物型化合物係可舉例如使於1分子內具有二個以上之異氰酸酯基的化合物與三羥甲基丙烷進行加成反應之化合物。 Examples of the aliphatic isocyanate crosslinking agent (B) used in the present invention include, for example, hexamethylene diisocyanate and tetramethylene diisocyanate having a compound having two or more isocyanate groups in one molecule, and further It is a urethane prepolymer type which is subjected to an addition reaction with a known polyether polyol or polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene or the like. A compound having two or more isocyanate groups in one molecule. Among these, it is preferable to improve the step-following property of the adhesion surface and to improve the heat-resistant foaming property, and it is preferably a compound having three or more isocyanate groups in one molecule. The compound having three or more isocyanate groups in one molecule may have, for example, two or more molecules in one molecule. An addition type compound of an isocyanate group-containing compound, a compound obtained by subjecting a compound having two or more isocyanate groups in one molecule to a polyhydric alcohol such as pentaerythritol, or more than two molecules in one molecule A trimeric isocyanate compound of the isocyanate group-containing compound, and a biuret type compound having a compound having two or more isocyanate groups in one molecule. The compound of the above-mentioned addition type is, for example, a compound obtained by subjecting a compound having two or more isocyanate groups in one molecule to addition reaction with trimethylolpropane.
如此之脂肪族異氰酸酯系交聯劑(B)係可單獨或組合而使用。本發明之黏著劑中的脂肪族異氰酸酯系交聯劑(B)之含量相對於丙烯酸系聚合物(A)100重量份為0.1至5重量份,宜為0.1至2重量份。 Such an aliphatic isocyanate crosslinking agent (B) can be used singly or in combination. The content of the aliphatic isocyanate crosslinking agent (B) in the adhesive of the present invention is 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the acrylic polymer (A).
如此地藉由摻合脂肪族異氰酸酯系交聯劑(B),黏著劑之凝集力提高,可抑制貼附時少量捲入之氣泡的膨脹。 By blending the aliphatic isocyanate crosslinking agent (B), the cohesive force of the adhesive is improved, and the expansion of the bubbles which are caught in a small amount during the attachment can be suppressed.
本發明之黏著劑亦宜為含有具源自含氮單體之構成單元的低分子量體。含氮單體係可舉例如上述所例示者。就構成低分子量體之含氮單體以外的單體而言,只要為具有不飽和基之單體,無特別限定,但宜可舉例如(甲基)丙烯酸酯等丙烯酸系聚合物、苯乙烯系單體等。低分子量體之重量平均分子量係宜為5000以上、未達5萬。本發明之黏著劑含有上述低分子量體時,具有提昇黏著劑之凝集力、進一步促進藉由異氰酸酯系交聯劑之交聯之效果。 The adhesive of the present invention is also preferably a low molecular weight body having a constituent unit derived from a nitrogen-containing monomer. The nitrogen-containing single system may, for example, be exemplified above. The monomer other than the nitrogen-containing monomer constituting the low molecular weight body is not particularly limited as long as it is a monomer having an unsaturated group, and is preferably an acrylic polymer such as (meth)acrylate or styrene. It is a monomer or the like. The weight average molecular weight of the low molecular weight body is preferably 5,000 or more and less than 50,000. When the adhesive of the present invention contains the above-mentioned low molecular weight body, it has an effect of enhancing the cohesive force of the adhesive and further promoting crosslinking by an isocyanate crosslinking agent.
本發明之黏著劑在無損本發明之黏著劑的效果之範圍,亦可進一步摻合抗氧化劑、抗金屬腐蝕劑、光安定劑、 增黏劑、可塑劑、抗靜電劑、交聯促進劑、重工劑等。 The adhesive of the present invention may further blend an antioxidant, a metal corrosion inhibitor, a light stabilizer, and the like insofar as the effect of the adhesive of the present invention is not impaired. Adhesives, plasticizers, antistatic agents, crosslinking accelerators, heavy chemicals, etc.
如此做法所得到之黏著劑係與公知之黏著劑同樣地,稀釋成適當的濃度後,塗佈、乾燥,藉此可使用於各種構件之黏著。於溶劑中含有本發明使用之丙烯酸系聚合物(A)、脂肪族異氰酸酯系交聯劑(B)之塗佈溶液係因丙烯酸系聚合物(A)之重量平均分子量(Mw)低,故可於醋酸乙酯、甲基乙基酮、丙酮、甲苯等溶劑中容易地調整不揮發成分之濃度。因此,藉由使用本發明之黏著劑,可使塗佈後之黏著劑的厚度容易地形成所希望的厚度。尤其,本發明之黏著劑係可容易地調製不揮發成分含量高的溶液,例如可使不揮發成分在10至70%、較佳係30至60%的範圍內調整。故可以較少的塗佈次數達成所希望之厚度。又,如此地藉由使用不揮發成分含量高之溶液,俾塗佈、乾燥後之塗膜的調平(leveling)性提昇,進一步,乾燥時間亦縮短,作業性提昇。進一步,揮發溶劑量少,故對環境的負荷亦變少。 The adhesive obtained in this manner is applied to a suitable concentration in the same manner as a known adhesive, and then applied and dried, whereby it can be used for adhesion of various members. The coating solution containing the acrylic polymer (A) and the aliphatic isocyanate crosslinking agent (B) used in the present invention in a solvent is low in weight average molecular weight (Mw) of the acrylic polymer (A). The concentration of the nonvolatile component is easily adjusted in a solvent such as ethyl acetate, methyl ethyl ketone, acetone or toluene. Therefore, by using the adhesive of the present invention, the thickness of the adhesive after application can be easily formed to a desired thickness. In particular, the adhesive of the present invention can easily prepare a solution having a high content of nonvolatile matter, for example, the nonvolatile content can be adjusted in the range of 10 to 70%, preferably 30 to 60%. Therefore, the desired thickness can be achieved with a small number of coatings. Further, by using a solution having a high content of nonvolatile components, the leveling property of the coating film after coating and drying is improved, and the drying time is also shortened, and the workability is improved. Further, since the amount of the volatile solvent is small, the load on the environment is also reduced.
利用如此之特性,本發明之黏著片係藉由使上述黏著劑塗佈成於10至1000μm的範圍內之厚度,較佳係於25至500μm之範圍內之厚度來得到。 With such characteristics, the adhesive sheet of the present invention is obtained by coating the above-mentioned adhesive into a thickness in the range of 10 to 1000 μm, preferably in the range of 25 to 500 μm.
此黏著劑片一般係將不揮發成分調整成10至70%(較佳係30至60%)之黏著劑的塗佈液,在表面經剝離處理之支撐體(例如剝離處理PET等)表面,以乾燥厚度成為於25至1000μm之範圍內的厚度,較佳係成為於25至500μm之範圍內的厚度之方式塗佈,除去溶劑後,於所形成之黏 著層表面貼附表面經剝離處理之覆蓋膜而一般以0至50℃之溫度熟化1日至10日來得到。 The adhesive sheet is generally prepared by adjusting a non-volatile component to a coating liquid of 10 to 70% (preferably 30 to 60%) of an adhesive on a surface of a support which is subjected to a release treatment (for example, a peeling treatment PET). The thickness is set to a thickness in the range of 25 to 1000 μm, preferably in a range of 25 to 500 μm, and after the solvent is removed, the formed viscosity is formed. The surface of the layer is attached to the surface of the cover film which is subjected to the release treatment, and is usually aged at 0 to 50 ° C for 1 to 10 days.
如此做法所得到之黏著劑層的凝膠分率在40至80%,宜於60至70%的範圍內。 The adhesive layer obtained in this manner has a gel fraction of 40 to 80%, preferably 60 to 70%.
如此做法所得到之黏著片係可對於各種構件進行貼附,但特別適宜於貼合異種構件之觸控板用構件的貼附。 The adhesive sheet obtained in this manner can be attached to various members, but is particularly suitable for attaching a member for a touch panel to which a different member is attached.
如第1圖及第2圖所示般,觸控板單元係有電阻膜方式觸控板之單元(參照第1圖)、與靜電電容方式觸控板的單元(參照第2圖)。 As shown in FIGS. 1 and 2, the touch panel unit is a unit of a resistive touch panel (see FIG. 1) and a unit of a capacitive touch panel (see FIG. 2).
於第1圖表示電阻膜方式觸控板單元10-1之例。如第1圖所示般,電阻膜方式觸控板單元10-1係藉由貼合劑30而形成間隙34般由上部積層體11-1與下部積層體13-1所構成,於間隙34內係為了有效地確保空間而配置間隔物32。 An example of the resistive film type touch panel unit 10-1 is shown in Fig. 1. As shown in FIG. 1, the resistive film type touch panel unit 10-1 is formed of the upper laminated body 11-1 and the lower laminated body 13-1 by forming the gap 34 by the bonding agent 30, and is formed in the gap 34. The spacers 32 are arranged in order to effectively secure the space.
於上部積層體11-1係面向間隙34而配置由金屬或金屬氧化物所構成之透明導電膜27-1。此透明導電膜27-1係以ITO、ATO、氧化錫等具有透明性的導電材料所形成,一般,如第1圖所示般,形成於聚對苯二甲酸乙二酯(PET)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)或玻璃所構成之上部電極支撐體25-1的表面。 A transparent conductive film 27-1 made of a metal or a metal oxide is disposed on the upper laminated body 11-1 so as to face the gap 34. The transparent conductive film 27-1 is formed of a transparent conductive material such as ITO, ATO or tin oxide. Generally, as shown in Fig. 1, it is formed on polyethylene terephthalate (PET) and poly The surface of the upper electrode support 25-1 is composed of carbonate (PC), polymethyl methacrylate (PMMA) or glass.
於上部積層體之最表面係配置表面支撐體21-1,此表面支撐體21-1一般係透明性高之玻璃或聚碳酸酯(PC)、聚對苯二甲酸乙二酯(PET)、聚甲基丙烯酸甲酯(PMMA)、環烯烴聚合物(COP)等透明薄膜、或透明板。為使上述表面支撐 體21-1與上部電極支撐體25-1接著,形成由本發明之黏著劑所構成的黏著劑層23-1。在與上述上部電極支撐體25-1及表面支撐體21-1之黏著劑層23-1相接的表面係宜設有硬塗層。硬塗層係可無限制地使用一般所使用者,但即使為一般以丙烯酸系黏著劑很難接著的矽氧系之硬塗層,黏著力亦提昇,而較佳。 The surface support 21-1 is disposed on the outermost surface of the upper laminate, and the surface support 21-1 is generally made of glass or polycarbonate (PC) or polyethylene terephthalate (PET) having high transparency. A transparent film such as polymethyl methacrylate (PMMA) or cycloolefin polymer (COP), or a transparent plate. For the above surface support Next, the body 21-1 and the upper electrode support 25-1 form an adhesive layer 23-1 composed of the adhesive of the present invention. A surface of the upper electrode support 25-1 and the adhesive layer 23-1 of the surface support 21-1 is preferably provided with a hard coat layer. The hard coat layer can be used without any limitation as a general user. However, even if it is an antimony-based hard coat layer which is generally difficult to be followed by an acrylic adhesive, the adhesion is improved, and it is preferable.
又,下部積層體13-1係同樣地面向間隙34而形成由金屬或金屬氧化物所構成之透明導電膜27-2,此透明導電膜27-2係以ITO、ATO、氧化錫等具有透明性的導電材料所形成,一般,如第1圖所示般,形成於由聚對苯二甲酸乙二酯(PET)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)等透明膜或玻璃所構成之下部電極支撐體25-2的表面。 Further, the lower laminated body 13-1 is formed to face the gap 34 to form a transparent conductive film 27-2 made of a metal or a metal oxide. The transparent conductive film 27-2 is transparent with ITO, ATO, tin oxide, or the like. It is formed of a conductive material and is generally formed of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), etc. as shown in Fig. 1. The film or glass constitutes the surface of the lower electrode support 25-2.
於下部積層體13-1的最深部係如與顯示器之表面對面般形成深部之表面支撐體21-2,此深部之表面支撐體21-2係玻璃或聚碳酸酯、聚對苯二甲酸乙二酯(PET)、聚甲基丙烯酸甲酯(PMMA)、環烯烴聚合物(COP)等透明性高的構件所形成。 The deepest portion of the lower laminated body 13-1 is formed as a deep surface supporting body 21-2 as opposed to the surface of the display, and the deep surface supporting body 21-2 is made of glass or polycarbonate or polyethylene terephthalate. A highly transparent member such as a diester (PET), a polymethyl methacrylate (PMMA) or a cycloolefin polymer (COP) is formed.
在下部積層體13-1中,為使深部之表面支撐體21-2與下部電極支撐體25-2接著,形成由本發明之黏著劑所構成的黏著劑層23-2。在與上述下部電極支撐體25-2及表面支撐體21-2之黏著劑層23-2相接的表面係宜設有硬塗層。硬塗層係可無限制地使用一般所使用者。如矽氧系之硬塗層,即使為一般之丙烯酸系黏著劑中無法得到充分黏著力的被黏體,本發明之丙烯酸系黏著劑係顯示充分的黏 著力,較宜使用。 In the lower laminated body 13-1, in order to connect the deep surface support 21-2 and the lower electrode support 25-2, the adhesive layer 23-2 composed of the adhesive of the present invention is formed. A surface of the lower electrode support 25-2 and the adhesive layer 23-2 of the surface support 21-2 is preferably provided with a hard coat layer. The hard coat layer can be used without limitation for a general user. For example, a hard coat layer of an oxygen-based type, the acrylic adhesive of the present invention exhibits sufficient viscosity even if it is a adherend which does not have sufficient adhesion in a general acrylic adhesive. Focus on, it is better to use.
又,就貼合劑30而言,有時亦使用本發明之黏著劑。 Further, in the case of the bonding agent 30, the adhesive of the present invention may be used.
又,上述透明導電膜27-1、27-2係藉由從表面支撐體21-1之上以手指等施加壓力,壓力施加之部分的間隙34消失而透明導電膜27-1、27-2接觸而通電,檢測加壓部分般來形成。 Further, the transparent conductive films 27-1 and 27-2 are pressed by a finger or the like from the surface support 21-1, and the gap 34 of the portion where the pressure is applied disappears, and the transparent conductive films 27-1 and 27-2 are removed. It is energized by contact, and is formed by detecting a pressurized portion.
電阻膜方式之觸控板單元10-1中,表面支撐體21-1之厚度一般為25至2000μm,上部透明導電膜27-1的厚度一般為10至100nm,上部電極支撐體25-1之厚度一般為25至2000μm。積層此等之黏著劑層23-1的厚度係如上述般,於10至1000μm,較佳係於25至500μm的範圍內。 In the resistive film type touch panel unit 10-1, the thickness of the surface supporting body 21-1 is generally 25 to 2000 μm, and the thickness of the upper transparent conductive film 27-1 is generally 10 to 100 nm, and the upper electrode supporting body 25-1 is The thickness is generally from 25 to 2000 μm. The thickness of the adhesive layer 23-1 laminated is such that it is in the range of 10 to 1000 μm, preferably 25 to 500 μm as described above.
同樣地,電阻膜方式之觸控板單元中,深部之表面支撐體21-2之厚度一般為25至2000μm,下部透明導電膜27-2的厚度一般為10至100nm,下部電極支撐體25-2之厚度一般為25至2000μm。積層此等之黏著劑層23-2的厚度係如上述般,於10至1000μm,較佳係於25至500μm的範圍內。 Similarly, in the resistive film type touch panel unit, the thickness of the surface support 21-2 in the deep portion is generally 25 to 2000 μm, and the thickness of the lower transparent conductive film 27-2 is generally 10 to 100 nm, and the lower electrode support 25- The thickness of 2 is generally 25 to 2000 μm. The thickness of the adhesive layer 23-2 laminated is such that it is in the range of 10 to 1000 μm, preferably 25 to 500 μm as described above.
又,在電阻膜方式之觸控板單元10-1中,形成於中央之間隙30的寬度一般於1至2000μm的範圍內。 Further, in the resistive film type touch panel unit 10-1, the width of the gap 30 formed in the center is generally in the range of 1 to 2000 μm.
另外,靜電電容方式的觸控板單元10-2一般係常具有挾住由玻璃、聚碳酸酯等透明性高的構件所構成之中央支撐體60而配置有上部積層體15-1與下部積層體15-2之構造。 Further, the capacitive touch panel unit 10-2 generally has a central support body 60 which is formed of a member having high transparency such as glass or polycarbonate, and is provided with an upper laminated body 15-1 and a lower laminated layer. The structure of the body 15-2.
在靜電電容方式的觸控板10-2之上部積層體15-1中係接觸於中央支撐體60而配置透明導電膜57-1,最表面係配置由覆蓋玻璃(cover glass)或聚對苯二甲酸乙二酯(PET)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、環烯烴聚合物(COP)等光透過性構件所構成之表面支撐體51-1。此透明導電膜57-1係以ITO、ATO、氧化錫等具有透明性的導電材料所形成。 In the upper laminated body 15-1 of the capacitive touch panel 10-2, the transparent conductive film 57-1 is disposed in contact with the central support 60, and the outermost surface is configured by cover glass or polyparaphenyl. A surface support 51-1 composed of a light transmissive member such as ethylene dicarboxylate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) or cycloolefin polymer (COP). The transparent conductive film 57-1 is formed of a conductive material having transparency such as ITO, ATO or tin oxide.
配置由本發明之黏著劑所構成的黏著劑層53-1,以使此透明導電膜57-1與表面支撐體51-1接著,此黏著劑層53-1係直接與透明導電膜57-1接觸。在與上述表面支撐體51-1之黏著劑層53-1相接的表面係宜設有硬塗層。硬塗層係可無限制地使用一般所使用者。如矽氧系之硬塗層,即使為一般之丙烯酸系黏著劑中無法得到充分黏著力的被黏體,本發明之丙烯酸系黏著劑係顯示充分的黏著力,較宜使用。 The adhesive layer 53-1 composed of the adhesive of the present invention is disposed such that the transparent conductive film 57-1 is adhered to the surface support 51-1, and the adhesive layer 53-1 is directly bonded to the transparent conductive film 57-1. contact. A surface coated with the adhesive layer 53-1 of the surface support 51-1 is preferably provided with a hard coat layer. The hard coat layer can be used without limitation for a general user. For example, in the case of a hard coat layer of an oxygen-based coating, the acrylic adhesive of the present invention exhibits sufficient adhesion and is preferably used even in the case of an adherend which does not have sufficient adhesion in a general acrylic adhesive.
另外,在靜電電容方式的觸控板單元10-2之下部積層體15-2中係接觸於中央支撐體60而配置透明導電膜57-2,最深部係配置由覆蓋玻璃或聚對苯二甲酸乙二酯(PET)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、環烯烴聚合物(COP)等光透過性構件所構成之表面支撐體51-2。此透明導電膜57-2係以ITO、ATO、氧化錫等具有透明性的導電材料所形成。配置由本發明之黏著劑所構成的黏著劑層53-2,以使此透明導電膜57-2與最深部之表面支撐體51-2接著,此黏著劑層53-2係直接與透明導電膜57-2 接觸。在與上述表面支撐體51-2之黏著劑層53-2相接的表面係宜設有硬塗層。硬塗層係可無限制地使用一般所使用者。如矽氧系之硬塗層,即使為一般之丙烯酸系黏著劑中無法得到充分黏著力的被黏體,本發明之丙烯酸系黏著劑係亦顯示充分的黏著力,較宜使用。 Further, in the laminated body 15-2 under the capacitive touch panel unit 10-2, the transparent conductive film 57-2 is disposed in contact with the central support 60, and the deepest portion is disposed by covering glass or polyphenylene. A surface support 51-2 composed of a light transmissive member such as ethylene formate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) or cycloolefin polymer (COP). The transparent conductive film 57-2 is formed of a conductive material having transparency such as ITO, ATO or tin oxide. The adhesive layer 53-2 composed of the adhesive of the present invention is disposed such that the transparent conductive film 57-2 is adhered to the deepest surface support 51-2, and the adhesive layer 53-2 is directly bonded to the transparent conductive film. 57-2 contact. A surface coated with the adhesive layer 53-2 of the surface support 51-2 is preferably provided with a hard coat layer. The hard coat layer can be used without limitation for a general user. For example, the hard coat layer of the oxime type is an adhesive body which does not have sufficient adhesion in a general acrylic pressure-sensitive adhesive, and the acrylic pressure-sensitive adhesive of the present invention exhibits sufficient adhesion and is preferably used.
在靜電電容方式的觸控板單元10-2中,最深部之表面支撐體51-2係配置成與顯示器對面。 In the capacitive touch panel unit 10-2, the deepest surface support 51-2 is disposed opposite to the display.
在上述靜電電容方式的觸控板單元10-2中,上部表面支撐體51-1之厚度一般為25至2000μm,上部透明導電膜57-1的厚度一般為10至100nm,接著兩者之黏著劑層53-1的厚度係如上述般,為10至1000μm。又,在下部積層體15-2中,下部透明導電膜57-2的厚度一般為10至100nm,最深部之表面支撐體51-2的厚度一般為25至2000μm,接著兩者之黏著劑層的厚度係如上述般為10至1000μm。位於上述上部積層體15-1與下部積層體15-2之間的中央支撐體60的厚度一般在於25至1000μm的範圍內。 In the above capacitive touch panel unit 10-2, the thickness of the upper surface supporting body 51-1 is generally 25 to 2000 μm, and the thickness of the upper transparent conductive film 57-1 is generally 10 to 100 nm, and then the adhesion of the two is adhered. The thickness of the agent layer 53-1 is 10 to 1000 μm as described above. Further, in the lower laminated body 15-2, the thickness of the lower transparent conductive film 57-2 is generally 10 to 100 nm, and the thickness of the surface support 51-2 at the deepest portion is generally 25 to 2000 μm, followed by the adhesive layers of the two. The thickness is 10 to 1000 μm as described above. The thickness of the central support 60 located between the upper laminated body 15-1 and the lower laminated body 15-2 is generally in the range of 25 to 1000 μm.
又,上部透明導電膜57-1及下部透明導電膜57-2係形成電路。又,在第2圖所示之靜電容量方式的觸控板單元10-2中係藉由使上部積層體15-1與下部積層體15-2分別獨立地設成X軸方向及Y軸方向之二系列的電路,而亦可省略上部積層體15-1或下部積層體15-2。 Further, the upper transparent conductive film 57-1 and the lower transparent conductive film 57-2 form an electric circuit. Further, in the capacitive touch panel unit 10-2 shown in FIG. 2, the upper laminated body 15-1 and the lower laminated body 15-2 are independently set to the X-axis direction and the Y-axis direction. In the second series of circuits, the upper laminated body 15-1 or the lower laminated body 15-2 may be omitted.
在靜電電容方式的觸控板中,係藉由讀取指頭接觸於觸控板單元10-2的表面所產生之接觸部分的靜電電容變 化而檢測接觸位置。 In the capacitive touch panel, the electrostatic capacitance of the contact portion generated by the read finger contacting the surface of the touch panel unit 10-2 is changed. The contact position is detected.
在如上述之觸控板單元係對例如第2圖以A所示之緣部的表面支撐體51-1的黏著劑層53-1接觸之面實施額緣印刷。此額緣印刷部分擴大成第3圖所示。在第3圖中額緣印刷部分係以編號62表示。此額緣印刷部分62之厚度(to)係一般為10至50μm,其截面約形成矩形。黏著劑層53-1係藉由使上述之本發明的黏著片貼附於表面支撐體51-1來形成,故形成於黏著片之黏著劑層為硬質且缺乏段差追隨性,如第4圖(a)所示般,為額緣印刷部分62之端部而與表面支撐體51-1之間形成黏著劑層53-1和表面支撐體51-1及額緣印刷部分62之緣部之任一者皆不接觸的空隙64,此部分係原來如第4圖(b)所示般不形成空隙64而表面支撐體51-1及額緣印刷部分62之緣部必須與黏著劑層53-1密接。 The touch panel unit as described above performs margin printing on the surface of the surface layer support 51-1 of the surface support 51-1 which is shown by the edge of FIG. This margin printed portion is expanded to the one shown in Figure 3. The portion printed on the fore edge in Fig. 3 is denoted by reference numeral 62. The thickness of the fore edge printed portion 62 is generally 10 to 50 μm, and the cross section thereof is formed into a rectangular shape. The adhesive layer 53-1 is formed by attaching the above-described adhesive sheet of the present invention to the surface support 51-1, so that the adhesive layer formed on the adhesive sheet is hard and lacks step followability, as shown in FIG. As shown in (a), the edge of the fore edge printed portion 62 and the surface support 51-1 form an edge between the adhesive layer 53-1 and the surface support 51-1 and the front edge printed portion 62. The void 64, which is not in contact with any of the portions, is originally formed as shown in Fig. 4(b), and the edge portion of the surface support 51-1 and the front edge printed portion 62 must be bonded to the adhesive layer 53. -1 is connected.
但,如習知般,在以重量平均分子量為40萬至160萬之丙烯酸系聚合物作為基材(base)之黏著劑中,對於如此之非常微細形態的變化,黏著劑層之形狀變化不足夠,而形成空隙64。 However, as is conventionally known, in the case of an adhesive having an acrylic polymer having a weight average molecular weight of 400,000 to 1,600,000 as a base, the shape of the adhesive layer does not change for such a very fine form change. Sufficient to form a void 64.
積層有表面支撐體、黏著劑層及(亦有時具有支撐體)透明導電膜之構成本發明的觸控板用構件的黏著劑層53-1係如上述般具有特定之組成,使用重量平均分子量(Mw)為5萬以上且未達40萬之丙烯酸系聚合物(A),使此等以脂肪族異氰酸酯系交聯劑(B)進行交聯,俾具有非常優異之段差追隨性,無於額緣印刷部分62之周邊形成空隙 64。 The adhesive layer 53-1 constituting the member for a touch panel of the present invention having a surface support, an adhesive layer, and (and sometimes a support) transparent conductive film has a specific composition as described above, and a weight average is used. The acrylic polymer (A) having a molecular weight (Mw) of 50,000 or more and less than 400,000 is crosslinked by the aliphatic isocyanate crosslinking agent (B), and the ruthenium has a very excellent step followability. Forming a gap around the periphery of the fore edge printing portion 62 64.
又,本發明之觸控板用構件如第5圖所示般,就支撐體51-2而言,使用如聚碳酸酯(PC)般易產生釋氣之構件時,例如若以耐熱試驗條件80℃之條件進行試驗,產生源自支撐體之釋氣而於支撐體與黏著劑層之間有時產生氣泡66。又,即使使用不產生釋氣之支撐體,亦有時於支撐體與黏著劑層之接著時捲入泡68,若此氣泡依溫度變化而成長,則成為起泡原因。本發明之黏著劑係具有特定之組成,使用重量平均分子量(Mw)為5萬以上且未達40萬之丙烯酸系聚合物(A),使此等以脂肪族異氰酸酯系交聯劑(B)進行交聯,故具有非常高的凝集力,以如上述之釋氣產生的起泡及捲入氣泡的成長所產生的起泡可藉高的凝集力而壓抑。因此,在本發明之觸控板用構件中如上述之起泡係可幾乎未被觀察到。 Further, as for the member for a touch panel of the present invention, as shown in Fig. 5, when the support member 51-2 is used as a member which is easy to generate a gas release like polycarbonate (PC), for example, if it is subjected to heat resistance test conditions The test was carried out under the conditions of 80 ° C to generate outgas from the support, and bubbles 66 were sometimes generated between the support and the adhesive layer. Further, even if a support that does not generate outgas is used, the bubble 68 may be wound around the support and the adhesive layer, and if the bubble grows due to temperature change, it may cause foaming. The adhesive of the present invention has a specific composition, and an acrylic polymer (A) having a weight average molecular weight (Mw) of 50,000 or more and less than 400,000 is used, and such an aliphatic isocyanate crosslinking agent (B) is used. Since cross-linking is carried out, it has a very high cohesive force, and foaming by the bubbling caused by the above-described outgassing and the growth of the entrapped bubbles can be suppressed by a high cohesive force. Therefore, in the member for a touch panel of the present invention, the above-described foaming system can be hardly observed.
又,在觸控板用構件中係於耐久試驗條件(85℃、85%)放置構件,如第6圖所示般,有時水分從支撐體及端部滲入。在溫度高的條件中此滲入之水分並未析出,但若溫度降低,則所滲入之水分析出而觸控板用構件白化,霧度明顯上昇。形成本發明之觸控板用構件之黏著劑層係藉由具有特定之組成,即使源自支撐體層的水分滲入,亦可抑制水分之析出,白化現象所造成之霧度上昇極不易發生。 Further, in the member for touch panel, the member was placed under endurance test conditions (85 ° C, 85%), and as shown in Fig. 6, moisture may infiltrate from the support and the end. In the high temperature condition, the infiltrated moisture is not precipitated, but if the temperature is lowered, the infiltrated water is analyzed and the components of the touch panel are whitened, and the haze is remarkably increased. The adhesive layer forming the member for a touch panel of the present invention has a specific composition, and even if moisture from the support layer penetrates, precipitation of moisture can be suppressed, and an increase in haze caused by whitening is extremely unlikely to occur.
進一步,於本發明之黏著劑中係實質上未含有酸性基,故由金屬或金屬氧化物所構成之透明導電膜即使與此黏著劑直接接觸,透明導電膜之電阻值變化係即使最大亦 為10%左右,此變化量係在驅動觸控板上為完全不成為問題的量。 Further, in the adhesive of the present invention, the acidic conductive group is substantially not contained, so that the transparent conductive film composed of a metal or a metal oxide is in direct contact with the adhesive, and the resistance value of the transparent conductive film is even the largest. At about 10%, this amount of change is on the drive touch panel to the extent that it is not a problem at all.
如上述般,本發明之觸控板用構件係就黏著劑而言,使用具有特定組成之重量平均分子量5萬以上且未達40萬之主丙烯酸系聚合物(A)、與脂肪族異氰酸酯系交聯劑(B)之黏著劑而使支撐體與透明導電膜黏著,具有優異之段差追隨性,於緣部形成之額緣印刷部分未形成空隙,又,可抑制捲入所造成之起泡及釋氣所產生之起泡的兩者,進一步,不易析出水分,故不會有黏著劑層白化而霧度亦上昇之情形。 As described above, the member for a touch panel of the present invention uses a main acrylic polymer (A) having a specific composition and having a weight average molecular weight of 50,000 or more and less than 400,000, and an aliphatic isocyanate system. The adhesive of the crosslinking agent (B) adheres the support to the transparent conductive film, and has excellent step followability. The printed portion of the edge formed at the edge portion does not form a void, and the blistering caused by the entrapment can be suppressed. Further, both of the foaming generated by the outgassing are not easy to precipitate moisture, so that the adhesive layer is not whitened and the haze is also increased.
其次,顯示本發明之實施例而更詳細說明本發明,但本發明係不受此等限定。 Next, the present invention will be described in more detail by showing examples of the invention, but the invention is not limited thereto.
依以下所示之方法,測定黏著劑之重量平均分子量、凝膠分率、濕熱白化性、耐熱起泡性、ITO腐蝕性、段差追隨性、黏著強度。 The weight average molecular weight, gel fraction, wet heat whitening property, heat foaming property, ITO corrosion property, step followability, and adhesion strength of the adhesive were measured by the methods shown below.
使用凝膠滲透色層分析(GPC),求出標準聚苯乙烯換算之重量平均分子量(Mw)。 The weight average molecular weight (Mw) in terms of standard polystyrene was determined by gel permeation chromatography (GPC).
裝置:HLC-8120 GPC(Tosoh(股)製) Device: HLC-8120 GPC (Tosoh system)
管柱:使用以下之五串聯管柱。 Column: Use the following five series of columns.
TSK-GEL HXL-H(Guard Column、Tosoh(股)製) TSK-GEL HXL-H (Guard Column, Tosoh)
TSK-GEL G7000 HXL(Tosoh(股)製) TSK-GEL G7000 HXL (Tosoh)
TSK-GEL GMHXL(Tosoh(股)製) TSK-GEL GMHXL (Tosoh)
TSK-GEL GMHXL(Tosoh(股)製) TSK-GEL GMHXL (Tosoh)
TSK-GEL G2500 HXL(Tosoh(股)製) TSK-GEL G2500 HXL (made by Tosoh)
試樣濃度:以四氫呋喃稀釋成為1.0mg/cm3 Sample concentration: diluted with tetrahydrofuran to 1.0 mg/cm 3
移動相溶劑:四氫呋喃 Mobile phase solvent: tetrahydrofuran
流速:1.0cm3/分鐘、 Flow rate: 1.0cm 3 / minute,
管柱溫度:40℃ Column temperature: 40 ° C
將於23℃熟成7日後之黏著劑組成物約0.1g(採取重量)採取至試樣瓶中,加入醋酸乙酯30cc而振盪4小時後,將此試樣瓶之內容物以200網目的不銹鋼製金屬網過濾,使金屬網上的殘留物以100℃乾燥2小時而測定乾燥重量,依如下式求出。 After about 7 days of curing at 23 ° C, about 0.1 g (by weight) of the adhesive composition was taken into the sample bottle, and after adding ethyl acetate 30 cc and shaking for 4 hours, the contents of the sample bottle were made of 200 mesh stainless steel. The metal mesh was filtered, and the residue on the metal mesh was dried at 100 ° C for 2 hours to measure the dry weight, and was determined by the following formula.
凝膠分率(%)=(黏著劑組成物之乾燥重量/黏著劑組成物之採取重量)×100 Gel fraction (%) = (dry weight of the adhesive composition / weight taken of the adhesive composition) × 100
將所得到之黏著片的單面經剝離處理之聚對苯二甲酸乙二酯薄膜(以下,亦有時稱為PET薄膜)剝離,貼合厚25μm的聚對苯二甲酸乙二酯薄膜,裁切成50mm×50mm之大小。然後,剝離另一剝離薄膜,貼合於厚2mm的聚碳酸酯(PC)板上,以50℃、5atm的高壓鍋(autoclave)處理2分鐘後,靜置1小時而製作試驗片。 The polyethylene terephthalate film (hereinafter, also referred to as a PET film) obtained by peeling off one side of the obtained adhesive sheet was peeled off, and a polyethylene terephthalate film having a thickness of 25 μm was bonded thereto. Cut to a size of 50mm × 50mm. Then, another peeling film was peeled off, bonded to a polycarbonate (PC) plate having a thickness of 2 mm, and treated with an autoclave at 50 ° C and 5 atm for 2 minutes, and then allowed to stand for 1 hour to prepare a test piece.
測定所製成之試驗片的耐久試驗前的霧度後,分別於 60℃且90%環境下、85℃且85%環境下靜置500小時,進行耐久試驗。其後,將各試驗片以常溫靜置1小時後,測定霧度,求出與耐久試驗前之霧度的差。 After measuring the haze of the test piece prepared before the endurance test, respectively The durability test was carried out by allowing to stand at 60 ° C and 90% environment at 85 ° C and 85% atmosphere for 500 hours. Thereafter, each test piece was allowed to stand at room temperature for 1 hour, and then the haze was measured to determine the difference from the haze before the endurance test.
於霧度之測定係使用MH-150(村上色彩技術研究所(股)製)。 For the measurement of the haze, MH-150 (manufactured by Murakami Color Technology Research Institute Co., Ltd.) was used.
將所得到之黏著片的單面經剝離處理之PET薄膜剝離,貼合蒸鍍有ITO之厚25μm的聚對苯二甲酸乙二酯薄膜,裁切成50mm×50mm之大小。然後,剝離另一剝離薄膜,貼合於厚2mm的聚碳酸酯(PC)板上,以50℃、5atm的高壓鍋處理2分鐘後,靜置1小時而製作試驗片。 The peeled PET film of one surface of the obtained adhesive sheet was peeled off, and a polyethylene terephthalate film having a thickness of 25 μm on which ITO was deposited was bonded and cut into a size of 50 mm × 50 mm. Then, another peeling film was peeled off, bonded to a polycarbonate (PC) plate having a thickness of 2 mm, and treated with a pressure cooker at 50 ° C and 5 atm for 2 minutes, and then allowed to stand for 1 hour to prepare a test piece.
將所製成之試驗片分別於60℃且90%環境下、85℃且乾環境下、85℃且85%環境下靜置500小時。其後,將各試驗片以常溫靜置1小時後,以目視確認起泡的情形,以如下之基準評估。 The prepared test pieces were allowed to stand at 60 ° C and 90% environment, 85 ° C and a dry environment, 85 ° C and 85% environment for 500 hours. Thereafter, each test piece was allowed to stand at room temperature for 1 hour, and the state of foaming was visually confirmed, and it evaluated on the following basis.
評估之基準係如下述者。 The benchmark for evaluation is as follows.
(評估)(內容) (assessment) (content)
◎:以目視於黏著劑層無法確認到起泡。 ◎: Foaming could not be confirmed by visually observing the adhesive layer.
○:以目視稍可確認到氣泡。 ○: The bubbles were slightly confirmed by visual observation.
△:為可實用之程度,但以目視可明顯確認到氣泡。 △: It is practical, but bubbles can be clearly observed by visual observation.
×:可確認到大的氣泡。又,黏著劑層從基材或被黏著體浮起。 ×: A large bubble can be confirmed. Further, the adhesive layer floats from the substrate or the adherend.
與起泡試驗同樣做法而製作試驗片,預先測定試驗片 之電阻值。然後,測定在85℃且85%環境下靜置500小時之試驗片的電阻值,求出對於預先所測定之值的電阻值變化率。 A test piece is prepared in the same manner as the foaming test, and the test piece is measured in advance. The resistance value. Then, the resistance value of the test piece which was allowed to stand at 85 ° C and 85% environment for 500 hours was measured, and the rate of change of the resistance value for the value measured in advance was obtained.
又,電阻值之測定係使用測定器(三和電氣計器(股)製、Digital Multimeter PC 510)而測定。 Further, the measurement of the electric resistance value was carried out by using a measuring instrument (manufactured by Sanhe Electric Co., Ltd., Digital Multimeter PC 510).
將所得到之黏著片的單面經剝離處理之PET薄膜剝離,貼合25μm的PET薄膜,裁切成50mm×50mm而製作試驗片。 The peeled PET film of one surface of the obtained adhesive sheet was peeled off, and a PET film of 25 μm was bonded and cut into 50 mm × 50 mm to prepare a test piece.
繼而,將裁切成25mm×25mm之PET薄膜置於玻璃板上,將所製成之試驗片的另一面經剝離處理之PET薄膜剝離,以覆蓋整面玻璃板上之PET薄膜之方式貼合,於80℃環境下靜置500小時後,於常溫下靜置1小時以目視觀察段差部分之外觀。 Then, the PET film cut into 25 mm × 25 mm was placed on a glass plate, and the peeled PET film was peeled off on the other side of the prepared test piece to fit the PET film on the entire surface glass plate. After standing at 80 ° C for 500 hours, it was allowed to stand at room temperature for 1 hour to visually observe the appearance of the step portion.
(評估)(內容) (assessment) (content)
◎:以目視於貼附段差部分無法確認到氣泡。 ◎: Bubbles could not be confirmed by visually observing the section of the attached portion.
○:以目視於貼附段差部分可稍確認到氣泡。 ○: The bubble can be slightly confirmed by visually attaching the step portion.
×:於貼附段差部分可確認到大的氣泡。又,黏著劑層從基材或被黏體浮起。 ×: Large bubbles were confirmed in the attached step portion. Further, the adhesive layer floats from the substrate or the adherend.
將所得到之黏著片的單面經剝離處理之PET薄膜剝離,貼合到25μm的PET薄膜,裁切成寬度25mm而製作試驗片。 The peeled PET film of one surface of the obtained adhesive sheet was peeled off, bonded to a 25 μm PET film, and cut into a width of 25 mm to prepare a test piece.
繼而,將試驗片的另一面剝離性PET薄膜剝離,貼合 於蒸鍍有ITO之PET薄膜。 Then, the peeling PET film on the other side of the test piece was peeled off and bonded. A PET film deposited with ITO was deposited.
使試驗片於180°方向以300mm/分鐘之速度剝離,測定其剝離強度。 The test piece was peeled off at a speed of 300 mm/min in the 180° direction, and the peel strength was measured.
將所得到之黏著片的單面經剝離處理之PET薄膜剝離,貼合25μm的PET薄膜,裁切成寬度25mm而製作試驗片。 The peeled PET film of one surface of the obtained adhesive sheet was peeled off, and the PET film of 25 micrometers was bonded, and it cut by the width of 25 mm, and the test piece was produced.
繼而,將試驗片的另一面剝離性PET薄膜剝離,貼合於矽氧硬塗PET薄膜。 Then, the other surface peeling PET film of the test piece was peeled off and bonded to the epoxy hard coat PET film.
使試驗片於180°方向以300mm/分鐘之速度剝離,測定其剝離強度。 The test piece was peeled off at a speed of 300 mm/min in the 180° direction, and the peel strength was measured.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物1。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 1 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管 之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯酸二甲基胺基乙酯(DMAEA)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 With a mixer, reflux cooler, thermometer and nitrogen inlet tube In the reaction apparatus, 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), 4 parts by weight of 2-hydroxyethyl acrylate (2-HEA), and dimethylamine acrylate were fed. 2 parts by weight of ethyl methacrylate (DMAEA), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物2。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 2 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、正-乙烯基吡咯啶酮(n-VP)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. (2-HEA) 4 parts by weight, n-vinylpyrrolidone (n-VP) 2 parts by weight, and ethyl acetate (EtAc) 100 parts by weight, methyl ethyl ketone (MEK) 20 parts by weight, while introducing nitrogen The temperature was raised to 70 ° C.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物3。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 3 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重 量份、丙烯醯基嗎啉(ACMO)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. (2-HEA) 4 heavy In an amount of 2 parts by weight of acryloylmorpholine (ACMO), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), the temperature was raised to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物4。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 4 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入甲氧基二乙二醇丙烯酸酯(ECA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxydiethylene glycol acrylate (ECA), 34 parts by weight of butyl acrylate (BA), and 2-acrylic acid were added to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 4 parts by weight of hydroxyethyl ester (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), and the temperature was raised while introducing nitrogen gas. 70 ° C.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物5。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 5 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)36重量份、丙烯酸2-羥乙酯(2-HEA)4重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 36 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed into a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 4 parts by weight of (2-HEA), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物6。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 6 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及甲基乙基酮(MEK)150重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), and 150 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量10萬的丙烯酸系聚合物7。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 7 having a weight average molecular weight of 100,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)20重量份、丙烯酸丁酯(BA)74重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 20 parts by weight of methoxyethyl acrylate (MEA), 74 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分 濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物8。 After the reaction, it was diluted with ethyl acetate (EtAc) and adjusted to a solid content. At a concentration of 30%, an acrylic polymer 8 having a weight average molecular weight of 300,000 was obtained.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)20重量份、丙烯酸2-乙基己酯(2EHA)74重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)110重量份、甲基乙基酮(MEK)10重量份,一邊導入氮氣一邊昇溫至70℃。 20 parts by weight of methoxyethyl acrylate (MEA), 74 parts by weight of 2-ethylhexyl acrylate (2EHA), and acrylic acid 2 were fed into a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 4 parts by weight of hydroxyethyl ester (2-HEA), 2 parts by weight of acrylamide (AM), 110 parts by weight of ethyl acetate (EtAc), and 10 parts by weight of methyl ethyl ketone (MEK), and heated while introducing nitrogen gas Up to 70 ° C.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量38萬的丙烯酸系聚合物9。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 9 having a weight average molecular weight of 380,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)37重量份、丙烯酸2-羥乙酯(2-HEA)1重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 In a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 60 parts by weight of methoxyethyl acrylate (MEA), 37 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed. (2-HEA) 1 part by weight, 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物10。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 10 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)35重量份、丙烯酸2-羥乙酯(2-HEA)3重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 35 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 3 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物11。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 11 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)29重量份、丙烯酸2-羥乙酯(2-HEA)9重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 29 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 9 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物12。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 12 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)33重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份、丙烯酸(AA)1重量份及醋酸乙酯(EtAc)100重量份、甲基乙基酮(MEK)20重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 33 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), 1 part by weight of acrylic acid (AA), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK). The temperature was raised to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量30萬的丙烯酸系聚合物13。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 13 having a weight average molecular weight of 300,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)120重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), and 120 parts by weight of ethyl acetate (EtAc) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量50萬的丙烯酸系聚合物14。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 14 having a weight average molecular weight of 500,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸丁酯(BA)63重量份、丙烯酸甲 酯(MA)31重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及醋酸乙酯(EtAc)105重量份、甲基乙基酮(MEK)15重量份,一邊導入氮氣一邊昇溫至70℃。 Into a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 63 parts by weight of butyl acrylate (BA) was fed, and acrylic acid was fed. 31 parts by weight of ester (MA), 4 parts by weight of 2-hydroxyethyl acrylate (2-HEA), 2 parts by weight of acrylamide (AM), and 105 parts by weight of ethyl acetate (EtAc), methyl ethyl ketone (MEK) 15 parts by weight, the temperature was raised to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量36萬的丙烯酸系聚合物15。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 15 having a weight average molecular weight of 360,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入丙烯酸甲氧基乙酯(MEA)60重量份、丙烯酸丁酯(BA)34重量份、丙烯酸2-羥乙酯(2-HEA)4重量份、丙烯醯胺(AM)2重量份及甲基乙基酮(MEK)180重量份,一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of methoxyethyl acrylate (MEA), 34 parts by weight of butyl acrylate (BA), and 2-hydroxyethyl acrylate were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube. 4 parts by weight of (2-HEA), 2 parts by weight of acrylamide (AM), and 180 parts by weight of methyl ethyl ketone (MEK) were heated to 70 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量3萬的丙烯酸系聚合物16。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust the solid concentration to 30% to obtain an acrylic polymer 16 having a weight average molecular weight of 30,000.
於具備有攪拌機、回流冷卻器、溫度計及氮氣導入管之反應裝置中,饋入甲基丙烯酸甲酯(MMA)95重量份、丙烯酸二甲基胺基乙酯(DMAEA)5重量份及甲苯150重量份,一邊導入氮氣一邊昇溫至85℃。 95 parts by weight of methyl methacrylate (MMA), 5 parts by weight of dimethylaminoethyl acrylate (DMAEA) and toluene 150 were fed to a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube. The temperature was raised to 85 ° C while introducing nitrogen gas.
然後,加入偶氮雙異丁腈(AIBN)0.2重量份,氮氣環境下,以70℃進行聚合反應5小時。 Then, 0.2 part by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 5 hours under a nitrogen atmosphere.
反應結束後,以醋酸乙酯(EtAc)稀釋,調整至固形分濃度30%,得到重量平均分子量1萬的低分子量體。 After completion of the reaction, the mixture was diluted with ethyl acetate (EtAc) to adjust to a solid concentration of 30% to obtain a low molecular weight body having a weight average molecular weight of 10,000.
相對於100重量份製造例1得到之丙烯酸系聚合物1,混合三羥甲基丙烷加成型之六亞甲基二異氰酸酯0.3重量份作為交聯劑,得到黏著劑組成物。 The adhesive composition was obtained by mixing 0.3 parts by weight of trimethylolpropane-molded hexamethylene diisocyanate as a crosslinking agent with respect to 100 parts by weight of the acrylic polymer 1 obtained in Production Example 1.
將所得到之黏著劑組成物以使乾燥後之厚度成為50μm之方式塗佈於已剝離處理之聚對苯二甲酸乙二酯(PET)薄膜上,以80℃乾燥2分鐘,除去溶劑而形成黏著劑層。在相對於與黏著劑層之PET薄膜相接的面之表面,貼合已剝離處理之PET薄膜,在23℃、65%環境下進行熟化(aging)7日,得到黏著片。 The obtained adhesive composition was applied onto a peeled polyethylene terephthalate (PET) film so as to have a thickness of 50 μm after drying, and dried at 80 ° C for 2 minutes to remove a solvent. Adhesive layer. The peeled PET film was bonded to the surface of the surface in contact with the PET film of the adhesive layer, and aging was performed for 7 days at 23 ° C in a 65% environment to obtain an adhesive sheet.
除使用100重量份丙烯酸系聚合物2取代100重量份丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight of the acrylic polymer 2 was used instead of 100 parts by weight of the acrylic polymer 1.
除使用100重量份丙烯酸系聚合物3取代100重量份丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight of the acrylic polymer 3 was used instead of 100 parts by weight of the acrylic polymer 1.
除使用100重量份丙烯酸系聚合物4取代100重量份丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that 100 parts by weight of the acrylic polymer 4 was used instead of 100 parts by weight of the acrylic polymer 1.
除使用六亞甲基二異氰酸酯的三聚異氰酸酯0.3重量份取代三羥甲基丙烷加成型之六亞甲基二異氰酸酯0.3重量份作為交聯劑以外,其餘係與實施例1同樣做法而得到黏著片。 The adhesion was obtained in the same manner as in Example 1 except that 0.3 parts by weight of a trimeric isocyanate of hexamethylene diisocyanate was used, and 0.3 parts by weight of a substituted trimethylolpropane-formed hexamethylene diisocyanate was used as a crosslinking agent. sheet.
除使用縮二脲型之六亞甲基二異氰酸酯0.3重量份取代三羥甲基丙烷加成型之六亞甲基二異氰酸酯0.3重量份作為交聯劑以外,其餘係與實施例1同樣做法而得到黏著片。 The same procedure as in Example 1 was carried out except that 0.3 parts by weight of a diuret-type hexamethylene diisocyanate was used, and 0.3 parts by weight of a substituted trimethylolpropane-formed hexamethylene diisocyanate was used as a crosslinking agent. Adhesive tablets.
除使用丙烯酸系聚合物5取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 5 was used instead of the acrylic polymer 1.
除了使用相對於100重量份製造例6得到之丙烯酸系聚合物6,混合製造例18得到之低分子量體5重量份、作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例1同樣做法而得到黏著片。 5 parts by weight of the low molecular weight body obtained in Production Example 18, and trimethylolpropane-formed hexamethylene diisocyanate as a crosslinking agent were used, except that 100 parts by weight of the acrylic polymer 6 obtained in Production Example 6 was used. An adhesive sheet was obtained in the same manner as in Example 1 except that 0.3 parts by weight of the obtained adhesive composition was obtained.
除使用丙烯酸系聚合物7取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 7 was used instead of the acrylic polymer 1.
除使用丙烯酸系聚合物8取代丙烯酸系聚合物1以 外,其餘係與實施例1同樣做法而得到黏著片。 In place of the acrylic polymer 1 in place of the acrylic polymer 1 The rest of the film was obtained in the same manner as in Example 1 to obtain an adhesive sheet.
除使用丙烯酸系聚合物9取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 9 was used instead of the acrylic polymer 1.
除使用丙烯酸系聚合物10取代丙烯酸系聚合物1,相對於100重量份丙烯酸系聚合物10,使作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯之量變更成1重量份以外,其餘係與實施例1同樣做法而得到黏著片。 The amount of hexamethylene diisocyanate to which trimethylolpropane as a crosslinking agent is added is changed to 1 in place of 100 parts by weight of the acrylic polymer 10, except that the acrylic polymer 10 is used in place of the acrylic polymer 1. An adhesive sheet was obtained in the same manner as in Example 1 except for the parts by weight.
除使用丙烯酸系聚合物11取代丙烯酸系聚合物1,相對於100重量份丙烯酸系聚合物11,使作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯之量變更成0.5重量份以外,其餘係與實施例1同樣做法而得到黏著片。 The amount of hexamethylene diisocyanate to which trimethylolpropane as a crosslinking agent is added is changed to 0.5, in place of the acrylic polymer 11 in place of the acrylic polymer 1 with respect to 100 parts by weight of the acrylic polymer 11. An adhesive sheet was obtained in the same manner as in Example 1 except for the parts by weight.
除使用丙烯酸系聚合物12取代丙烯酸系聚合物1,相對於100重量份丙烯酸系聚合物12,使作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯之量變更成0.1重量份以外,其餘係與實施例1同樣做法而得到黏著片。 The amount of hexamethylene diisocyanate to which trimethylolpropane is added as a crosslinking agent is changed to 0.1, in place of the acrylic polymer 12, in place of the acrylic polymer 12, with respect to 100 parts by weight of the acrylic polymer 12. An adhesive sheet was obtained in the same manner as in Example 1 except for the parts by weight.
除了使用相對於100重量份丙烯酸系聚合物1,作為交聯劑混合三羥甲基丙烷加成型之伸茬基二異氰酸酯0.4重量份取代三羥甲基丙烷加成型的六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例 1同樣做法而得到黏著片。 In addition to the use of 100 parts by weight of the acrylic polymer 1 as a crosslinking agent, trimethylolpropane-added decyl diisocyanate 0.4 parts by weight of substituted trimethylolpropane plus hexamethylene diisocyanate 0.3 Other than the adhesive composition obtained in parts by weight, the rest of the examples and examples 1 Get the adhesive sheet in the same way.
除了使用相對於100重量份丙烯酸系聚合物1,作為交聯劑混合縮二脲型之伸茬基二異氰酸酯0.3重量份取代三羥甲基丙烷加成型的六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例1同樣做法而得到黏著片。 In addition to using 0.3 parts by weight of a diuret-type decyl diisocyanate as a crosslinking agent, 0.3 part by weight of a substituted trimethylolpropane-formed hexamethylene diisocyanate is used as a crosslinking agent. The adhesive sheet was obtained in the same manner as in Example 1 except for the obtained adhesive composition.
除了使用相對於100重量份丙烯酸系聚合物1,作為交聯劑混合三羥甲基丙烷加成型之甲苯二異氰酸酯0.3重量份取代三羥甲基丙烷加成型的六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例1同樣做法而得到黏著片。 In addition to the use of 100 parts by weight of the acrylic polymer 1 as a crosslinking agent, trimethylolpropane-added toluene diisocyanate 0.3 parts by weight of substituted trimethylolpropane-formed hexamethylene diisocyanate 0.3 parts by weight The adhesive sheet was obtained in the same manner as in Example 1 except for the obtained adhesive composition.
除了使用相對於100重量份丙烯酸系聚合物1,作為交聯劑混合三羥甲基丙烷加成型之異佛酮二異氰酸酯0.3重量份取代三羥甲基丙烷加成型的六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例1同樣做法而得到黏著片。 In addition to the use of 100 parts by weight of the acrylic polymer 1, as a crosslinking agent, trimethylolpropane-added isophorone diisocyanate 0.3 parts by weight of substituted trimethylolpropane-formed hexamethylene diisocyanate 0.3 An adhesive sheet was obtained in the same manner as in Example 1 except for the adhesive composition obtained in parts by weight.
除使用丙烯酸系聚合物13取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 13 was used instead of the acrylic polymer 1.
除了使用利用丙烯酸系聚合物5取代丙烯酸系聚合物 1,相對於100重量份丙烯酸系聚合物14,作為交聯劑混合三羥甲基丙烷加成型之伸茬基二異氰酸酯0.3重量份取代三羥甲基丙烷加成型的六亞甲基二異氰酸酯0.3重量份而得到的黏著劑組成物以外,其餘係與實施例1同樣做法而得到黏著片。 In addition to using acrylic polymer 5 instead of acrylic polymer 1, 0.3 parts by weight of substituted trimethylolpropane-added hexamethylene diisocyanate 0.3 as a cross-linking agent mixed with trimethylolpropane-formed decyl diisocyanate as a crosslinking agent. An adhesive sheet was obtained in the same manner as in Example 1 except for the adhesive composition obtained in parts by weight.
除使用丙烯酸系聚合物14取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 14 was used instead of the acrylic polymer 1.
除相對於100重量份丙烯酸系聚合物1,使作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯之量變更成0.05重量份以外,其餘係與實施例1同樣做法而得到黏著片。 The same procedure as in Example 1 was carried out except that the amount of hexamethylene diisocyanate to which trimethylolpropane was added as a crosslinking agent was changed to 0.05 part by weight based on 100 parts by weight of the acrylic polymer 1. Get an adhesive patch.
除相對於100重量份丙烯酸系聚合物1,使作為交聯劑之三羥甲基丙烷加成型之六亞甲基二異氰酸酯之量變更成10重量份以外,其餘係與實施例1同樣做法而得到黏著片。 The same procedure as in Example 1 was carried out except that the amount of hexamethylene diisocyanate to which trimethylolpropane was added as a crosslinking agent was changed to 10 parts by weight based on 100 parts by weight of the acrylic polymer 1. Get an adhesive patch.
除使用丙烯酸系聚合物15取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 15 was used instead of the acrylic polymer 1.
除使用丙烯酸系聚合物16取代丙烯酸系聚合物1以外,其餘係與實施例1同樣做法而得到黏著片。 An adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic polymer 16 was used instead of the acrylic polymer 1.
表中之簡稱係如以下般。 The abbreviations in the table are as follows.
MEA:丙烯酸甲氧基乙酯 MEA: methoxyethyl acrylate
ECA:甲氧基二乙二醇丙烯酸酯 ECA: methoxydiethylene glycol acrylate
BA:丙烯酸丁酯 BA: butyl acrylate
2 EHA:丙烯酸2-乙基己酯 2 EHA: 2-ethylhexyl acrylate
MA:丙烯酸甲酯 MA: Methyl acrylate
2-HEA:丙烯酸2-羥乙酯 2-HEA: 2-hydroxyethyl acrylate
AM:丙烯醯胺 AM: acrylamide
DMAEA:丙烯酸二甲基胺基乙酯 DMAEA: dimethylaminoethyl acrylate
n-VP:正-乙烯基吡咯啶酮 n-VP: n-vinylpyrrolidone
ACMO:丙烯醯基嗎啉 ACMO: acryloyl morpholine
AA:丙烯酸 AA: Acrylic
HDI:六亞甲基二異氰酸酯基 HDI: hexamethylene diisocyanate
XDI:伸茬基二異氰酸酯基 XDI: thiol diisocyanate
TDI:甲苯二異氰酸酯基 TDI: toluene diisocyanate
IPDI:異佛酮二異氰酸酯基 IPDI: Isophorone diisocyanate
10-1‧‧‧電阻膜方式之觸控板單元 10-1‧‧‧Resistance film type touch panel unit
10-2‧‧‧靜電電容方式之觸控板單元 10-2‧‧‧Solid Capacitor Touch Panel Unit
11-1、15-1‧‧‧上部積層體 11-1, 15-1‧‧‧ upper laminate
13-1、15-2‧‧‧下部積層體 13-1, 15-2‧‧‧ lower layer
21-1、51-1、51-2‧‧‧表面支撐體 21-1, 51-1, 51-2‧‧‧ surface support
21-2‧‧‧深部之表面支撐體 21-2‧‧‧Deep surface support
23-1、23-2、53-1、53-2‧‧‧黏著劑層 23-1, 23-2, 53-1, 53-2‧‧‧ adhesive layer
25-1‧‧‧上部電極支撐體 25-1‧‧‧Upper electrode support
25-2‧‧‧下部電極支撐體 25-2‧‧‧Lower electrode support
27-1、27-2、57-1、57-2‧‧‧透明導電膜 27-1, 27-2, 57-1, 57-2‧‧‧ Transparent conductive film
30‧‧‧貼合劑 30‧‧‧Adhesive
32‧‧‧間隔物 32‧‧‧ spacers
34‧‧‧間隙 34‧‧‧ gap
60‧‧‧中央支撐體 60‧‧‧ central support
62‧‧‧額緣印刷部分 62‧‧‧ Front edge printing section
64‧‧‧空隙 64‧‧‧ gap
66‧‧‧氣泡 66‧‧‧ bubbles
68‧‧‧泡 68‧‧‧ bubble
第1圖係表示組裝有本發明的觸控板用積層體之電阻膜方式的觸控板之觸控板單元之例的示意截面圖。 1 is a schematic cross-sectional view showing an example of a touch panel unit of a touch panel of a resistive film type in which a laminate for a touch panel of the present invention is incorporated.
第2圖係表示組裝有本發明的觸控板用積層體之靜電電容方式的觸控板之觸控板單元之例的示意截面圖。 2 is a schematic cross-sectional view showing an example of a touch panel unit of a capacitive touch panel in which a laminated body for a touch panel of the present invention is incorporated.
第3圖係表示靜電電容方式之觸控板中的端部構成之例的示意截面圖。 Fig. 3 is a schematic cross-sectional view showing an example of an end portion of a capacitive touch panel.
第4圖係表示形成於觸控板端部的額緣印刷部分之黏著片的黏著狀態之示意截面圖。 Fig. 4 is a schematic cross-sectional view showing an adhesive state of an adhesive sheet formed on the edge printed portion of the end portion of the touch panel.
第5圖係用以說明於觸控板用積層體產生之起泡狀態 的截面圖。 Figure 5 is a diagram for explaining the foaming state of the laminated body for the touch panel. Sectional view.
第6圖係用以說明於觸控板用積層體產生之白化現象的發生的截面圖。 Fig. 6 is a cross-sectional view for explaining the occurrence of a whitening phenomenon generated in a laminate for a touch panel.
10-1‧‧‧電阻膜方式之觸控板單元 10-1‧‧‧Resistance film type touch panel unit
11-1‧‧‧上部積層體 11-1‧‧‧Upper laminate
13-1‧‧‧下部積層體 13-1‧‧‧Lower laminated body
21-1‧‧‧表面支撐體 21-1‧‧‧Surface support
21-2‧‧‧深部之表面支撐體 21-2‧‧‧Deep surface support
23-1、23-2‧‧‧黏著劑層 23-1, 23-2‧‧‧Adhesive layer
25-1‧‧‧上部電極支撐體 25-1‧‧‧Upper electrode support
25-2‧‧‧下部電極支撐體 25-2‧‧‧Lower electrode support
27-1、27-2‧‧‧透明導電膜 27-1, 27-2‧‧‧ Transparent conductive film
30‧‧‧貼合劑 30‧‧‧Adhesive
32‧‧‧間隔物 32‧‧‧ spacers
34‧‧‧間隙 34‧‧‧ gap
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CN102876263A (en) * | 2011-07-12 | 2013-01-16 | 综研化学株式会社 | Adhesive, adhesive sheet and laminate for touch panel |
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KR20130008467A (en) | 2013-01-22 |
CN102876263A (en) | 2013-01-16 |
JP2013018892A (en) | 2013-01-31 |
CN102876263B (en) | 2016-03-16 |
JP5688338B2 (en) | 2015-03-25 |
KR101962713B1 (en) | 2019-03-27 |
TW201305299A (en) | 2013-02-01 |
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