TWI521031B - Adhesive composition, adhesive sheet and laminate for touch panel - Google Patents

Adhesive composition, adhesive sheet and laminate for touch panel Download PDF

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TWI521031B
TWI521031B TW101127704A TW101127704A TWI521031B TW I521031 B TWI521031 B TW I521031B TW 101127704 A TW101127704 A TW 101127704A TW 101127704 A TW101127704 A TW 101127704A TW I521031 B TWI521031 B TW I521031B
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weight
parts
meth
touch panel
acrylate
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TW101127704A
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TW201319193A (en
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工藤良太
金塚洋平
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綜研化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Description

黏著劑組成物、黏著片及觸控面板用層合體 Adhesive composition, adhesive sheet and laminate for touch panel

本發明係關於用於貼合導電膜之黏著劑組成物、具有包含該黏著劑組成物之黏著劑層的黏著片、及採用該黏著片貼附構件之觸控面板用層合體。 The present invention relates to an adhesive composition for bonding a conductive film, an adhesive sheet having an adhesive layer containing the adhesive composition, and a laminate for a touch panel using the adhesive sheet attaching member.

目前，就主要使用之觸控面板單元(touch panel unit)而言，大略分為電阻膜式觸控面板與靜電容量式觸控面板，該等皆為各種材料之層合體，而在其貼合方面主要係使用丙烯酸系黏著劑。由於觸控面板單元係配置於畫面的最表面，故要求所使用之丙烯酸系黏著劑為高透明性，此外，由於耐久性試驗和加速試驗係處於高溫高濕之環境，故需有高耐熱性、耐濕熱安定性等特性。 At present, in terms of a touch panel unit that is mainly used, it is roughly classified into a resistive touch panel and an electrostatic capacitive touch panel, and these are laminated materials of various materials, and are laminated thereon. The main aspect is the use of an acrylic adhesive. Since the touch panel unit is disposed on the outermost surface of the screen, the acrylic adhesive to be used is required to have high transparency, and since the durability test and the accelerated test are in a high-temperature and high-humidity environment, high heat resistance is required. , resistance to humidity and heat stability.

具體而言，各種材料的層合體之觸控面板單元，由於係配置於觸控面板裝置的最表面，故會因來自外部的水分滲入而發生白化現象，此外，藉由黏著劑貼合層合體之構成層時，會因捲入空氣所致之發泡及因層合材料發生排氣(outgas)所致之發泡等而導致外觀不良之問題發生。 Specifically, since the touch panel unit of the laminate of various materials is disposed on the outermost surface of the touch panel device, whitening occurs due to moisture infiltration from the outside, and the laminate is adhered by an adhesive. When the layer is formed, there is a problem that the appearance is poor due to foaming due to entrapment of air and foaming due to outgas formation of the laminate.

此外，就目前觸控面板的主流之電阻膜式觸控面板而言，係聚碳酸酯(Polycarbonate；PC)或用以貼附模內貼膜(IMD)之各種黏著劑。 In addition, in the current mainstream of the touch panel, the resistive film type touch panel is made of polycarbonate (Polycarbonate; PC) or various adhesives for attaching an in-mold film (IMD).

然而，就PC材料方面之特性來說，亦有於高溫條件發生排氣，以及，由於水分容易通過PC，而於耐熱條件會發生發泡，於濕熱條件因水分流入而難以抑制黏著劑層之白 化現象的問題。此外，由於IMD具有次微米級(submicron order)之段差，故尚有黏著劑無法順應其段差而捲入氣泡之問題。 However, in terms of the characteristics of the PC material, it is also vented at a high temperature condition, and since water easily passes through the PC, foaming occurs under heat-resistant conditions, and it is difficult to suppress the adhesive layer due to moisture inflow in wet heat conditions. White The problem of the phenomenon. In addition, since the IMD has a submicron order step, there is a problem that the adhesive does not conform to the step difference and is caught in the bubble.

以往，係藉由於黏著劑中調配酸成分而解決如上所述之問題。亦即，酸成分係具有使混入的水分分散而不讓其析出之功能，因為滲入至黏著劑層的水分因酸成分之分散力被分散於黏著劑層內而未能析出，故會防止黏著劑層白化，並且形成氫鍵而藉由該氫鍵所致之高凝聚力、抑制耐熱發泡之氣泡產生。 In the past, the problem as described above has been solved by adjusting the acid component in the adhesive. In other words, the acid component has a function of dispersing the mixed water without allowing it to precipitate, and since the water which has penetrated into the adhesive layer is dispersed in the adhesive layer due to the dispersing force of the acid component and is not precipitated, adhesion is prevented. The agent layer is whitened, and hydrogen bonds are formed to cause high cohesive force due to the hydrogen bond, and generation of bubbles which inhibit heat-resistant foaming.

然而，近來，隨著以多點觸控(multi-touch)化為首之功能的充實化，靜電容量式觸控面板逐漸取代電阻膜式觸控面板而成為主流。該靜電容量式觸控面板自需具備電阻膜式之觸控面板所要求的特性，除此之外，由於黏著劑會與形成線路之導電層直接接觸，故黏著劑需具備不使導電層的特性改變之特性。導電層係以如氧化銦錫(ITO)、氧化銻錫(ATO)的金屬或是金屬氧化物所形成，由於會因與酸接觸而發生腐蝕、導致其電阻值值上昇，故無法採用以往所使用之用酸成分確保耐熱性、耐濕熱性等特性之手段。 However, recently, with the enrichment of functions led by multi-touch, electrostatic capacitive touch panels have gradually replaced the resistive touch panels and become mainstream. The electrostatic capacitance type touch panel needs to have the characteristics required for the resistive film type touch panel. In addition, since the adhesive is in direct contact with the conductive layer forming the line, the adhesive needs to have a conductive layer. Characteristics of characteristic changes. The conductive layer is formed of a metal such as indium tin oxide (ITO) or antimony tin oxide (ATO) or a metal oxide. Since corrosion occurs due to contact with an acid, and the resistance value thereof increases, it is impossible to adopt the conventional one. The use of an acid component to ensure properties such as heat resistance and moist heat resistance.

關於此種含ITO、ATO等金屬或金屬氧化物之透明電極的腐蝕，專利文獻1(日本特開2010-77287號公報)中，係揭示以丙烯酸烷氧基烷酯為主成分之聚合物；該專利文獻1係揭示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，而該聚合物係未使用含有羧基之單體的聚合物。 In the case of such a corrosion of a transparent electrode containing a metal such as ITO or ATO or a metal oxide, Patent Document 1 (JP-A-2010-77287) discloses a polymer containing an alkoxyalkyl acrylate as a main component; Patent Document 1 discloses the use of a polymer having an alkoxyalkyl acrylate of a weight average molecular weight of 400,000 to 1,600,000, and the polymer is a polymer which does not use a monomer having a carboxyl group.

藉由如此不使用含有羧基之單體而使用40萬至160萬之丙烯酸烷氧基烷酯系聚合物，雖然可某種程度地改善含ITO、ATO等金屬或金屬氧化物之透明電極的腐蝕，惟就濕熱白化性、耐熱發泡性等性能而言係無法得到充分的效果。此外，於透明電極塗裝黏著劑等時之作業性亦不充分。 By using 400,000 to 1.6 million acrylic acid alkoxyalkyl ester-based polymers without using a carboxyl group-containing monomer, the corrosion of a transparent electrode containing a metal or a metal oxide such as ITO or ATO can be improved to some extent. However, sufficient effects cannot be obtained in terms of properties such as wet heat whitening property and heat-resistant foaming property. Further, workability in coating an adhesive on a transparent electrode is also insufficient.

此外，由於專利文獻1所揭示之聚合物的重量平均分子量乃大至40萬到160萬，故將其溶解於溶劑以調製塗佈液時，固形分的量若變多，則聚合物溶液的黏度會變得過高。就觸控面板用途，尤其是靜電容量式觸控面板用途而言，需形成用以將表面支撐物與ITO、ATO等導電性膜進行接著，或用以提升感測靜電容量變化的感度之厚膜黏著劑層。但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會無法調製固形分含量高之塗佈液，故需調製固形分含有量低之塗佈液，重複塗佈，而有難以藉由一次塗裝形成所需厚度的黏著劑層之問題。 Further, since the weight average molecular weight of the polymer disclosed in Patent Document 1 is as large as 400,000 to 1,600,000, when it is dissolved in a solvent to prepare a coating liquid, if the amount of the solid content is increased, the polymer solution is The viscosity will become too high. For touch panel applications, especially for electrostatic capacitance type touch panel applications, it is necessary to form a thick surface for supporting the surface support with a conductive film such as ITO or ATO, or for improving the sensitivity of sensing electrostatic capacitance. Film adhesive layer. However, the use of an alkoxyalkyl acrylate-based polymer having a weight average molecular weight of 400,000 to 1,600,000 cannot modulate a coating liquid having a high solid content. Therefore, it is necessary to prepare a coating liquid having a low solid content and repeat the coating. There is a problem that it is difficult to form an adhesive layer of a desired thickness by one application.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2010-77287號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-77287

本發明之目的為提供耐熱發泡性、耐濕熱安定(耐白化)性優異，而對於金屬或金屬氧化物無腐蝕性之黏著劑組成物、黏著片、及採用該者之觸控面板用層合體；其中，黏著劑組成物係用於具有含金屬或金屬氧化物之導電膜的觸 控面板。 An object of the present invention is to provide an adhesive composition which is excellent in heat-resistant foaming property and moisture-heat-resistant stability (whitening resistance), and which is non-corrosive to metals or metal oxides, an adhesive sheet, and a layer for a touch panel using the same. a combination; wherein the adhesive composition is used for a touch having a conductive film containing a metal or a metal oxide Control panel.

又，本發明之目的為提供塗裝作業性佳黏著劑組成物。 Further, an object of the present invention is to provide a coating composition which is excellent in coating workability.

本發明之黏著劑組成物係一種用於貼合導電膜之黏著劑組成物，其含有丙烯酸系聚合物(A)與交聯劑(B)，而該丙烯酸系聚合物(A)係將包含下述成分(a-1)、(a-2)及(a-3)之單體共聚合而得之實質上不具有酸性基，且重量平均分子量為5萬以上未達40萬者；以全部單體為100重量%計，(a-1)(甲基)丙烯酸烷基酯，將其重量平均分子量50萬的均聚物以圓筒法(cup method)測定，於40℃ 90%RH的水蒸氣穿透率為500g/m2‧日以下者：50重量%以上，(a-2)具有羥基之單體：0.5至10重量%、(a-3)含氮單體：0.1至5重量%。 The adhesive composition of the present invention is an adhesive composition for bonding a conductive film, which comprises an acrylic polymer (A) and a crosslinking agent (B), and the acrylic polymer (A) will contain The monomers of the following components (a-1), (a-2) and (a-3) are copolymerized to have substantially no acidic groups, and the weight average molecular weight is 50,000 or more and less than 400,000; 100% by weight of all monomers, (a-1) alkyl (meth) acrylate, and a homopolymer having a weight average molecular weight of 500,000 was measured by a cup method at 40 ° C 90% RH The water vapor permeability is 500 g/m 2 ‧ days or less: 50% by weight or more, (a-2) the monomer having a hydroxyl group: 0.5 to 10% by weight, (a-3) the nitrogen-containing monomer: 0.1 to 5 wt%.

形成前述(甲基)丙烯酸系聚合物(A)之(a-2)具有羥基的單體，較佳為含羥基之(甲基)丙烯酸酯；前述(甲基)丙烯酸烷基酯(a-1)，較佳為具有脂肪族環或芳香族環，而更佳為上述脂肪族環及芳香族環係單環結構。 The (a-2) monomer having a hydroxyl group formed of the (meth)acryl-based polymer (A), preferably a hydroxyl group-containing (meth) acrylate; the aforementioned alkyl (meth) acrylate (a- 1) Preferably, it has an aliphatic ring or an aromatic ring, and more preferably the above aliphatic ring and aromatic ring system single ring structure.

另一方面，就本發明之黏著劑組成物而言，形成前述(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸烷基酯(a-1)的烷基之碳數較佳為8至22，前述烷基之碳數更佳為10至22。 On the other hand, in the adhesive composition of the present invention, the alkyl group of the alkyl (meth)acrylate (a-1) forming the (meth)acryl-based polymer (A) is preferably a carbon number. The number of carbon atoms of the above alkyl group is preferably from 10 to 22, and is from 8 to 22.

此外，本發明之黏著劑組成物係用於與一般金屬或金屬氧化物直接接觸之靜電容量式觸控面板用的黏著劑組成 物。 In addition, the adhesive composition of the present invention is used for an adhesive for an electrostatic capacitance type touch panel which is in direct contact with a general metal or metal oxide. Things.

本發明之黏著片係具有基材、與層合於該基材上之包含本發明黏著劑組成物之黏著劑層。 The adhesive sheet of the present invention has a substrate, and an adhesive layer comprising the adhesive composition of the present invention laminated on the substrate.

前述基材之例，可列舉如經施行剝離處理保護膜(cover film)。 Examples of the substrate include a cover film which is subjected to a release treatment.

本發明之觸控面板用層合體，係將表面支撐物，包含本發明黏著劑組成物之黏著劑層，包含金屬、金屬氧化物或是附電極支撐物的金屬或金屬氧化物之透明導電膜，依上述順序層合而成。 The laminate for a touch panel of the present invention comprises a surface support comprising an adhesive layer of the adhesive composition of the present invention, a metal or metal oxide or a transparent conductive film of a metal or metal oxide with an electrode support. , laminated in the above order.

前述黏著劑層之厚度通常為10至1000μm，前述表面支撐物之厚度通常於25至2000μm之範圍內，前述透明導電膜之厚度通常為10至100nm之範圍內。 The thickness of the above-mentioned adhesive layer is usually from 10 to 1000 μm, the thickness of the aforementioned surface support is usually in the range of from 25 to 2000 μm, and the thickness of the above transparent conductive film is usually in the range of from 10 to 100 nm.

此外，本發明之觸控面板用層合體較佳為形成靜電容量式觸控面板之構件者。 Further, the laminate for a touch panel of the present invention is preferably a member for forming a capacitive touch panel.

就此種用途而言，通常係在前述表面支撐物的與前述黏著劑層相對之面的邊緣部進行框緣印刷，該框緣印刷的厚度通常於10至50μm之範圍內。 For such use, the edge printing is usually performed on the edge portion of the surface support opposite to the surface of the adhesive layer, and the thickness of the frame printing is usually in the range of 10 to 50 μm.

前述透明導電膜通常係使用ITO或是ATO作為金屬氧化物之配線圖案，而該配線圖案係直接接觸前述黏著劑層。 The transparent conductive film generally uses ITO or ATO as a wiring pattern of a metal oxide, and the wiring pattern directly contacts the aforementioned adhesive layer.

由於本發明之黏著劑組成物實質上未含有酸成分，故可有效地抑制含ITO、ATO等金屬或金屬氧化物之線路的腐蝕所致之劣化。 Since the adhesive composition of the present invention does not substantially contain an acid component, deterioration due to corrosion of a line containing a metal such as ITO or ATO or a metal oxide can be effectively suppressed.

此外，本發明之黏著劑組成物，由於黏著劑成分之聚 合物的重量平均分子量(Mw)係5萬以上未達40萬，故溶劑中之固形分可保持高濃度，而以一次塗裝步驟即可塗成足夠厚度，且具有非常良好的段差順應性(段差貼合適應性)。 Further, the adhesive composition of the present invention is agglomerated by the adhesive component The weight average molecular weight (Mw) of the compound is less than 50,000 and less than 400,000, so that the solid content in the solvent can be maintained at a high concentration, and the coating can be applied to a sufficient thickness in a single coating step, and has a very good step difference compliance. (Segment difference is appropriate).

此外，藉由使用係均聚物時之水蒸氣穿透率為一定數值以下的(甲基)丙烯酸烷基酯作為(甲基)丙烯酸系聚合物之主成分，係可抑制水分滲入至黏著劑組成物所形成的黏著劑層，而可有效地抑制黏著劑層的白化。此外，因為(甲基)丙烯酸系聚合物在側鏈具有長烷基鏈，故對低極性被黏著物之塗裝性亦優異。 In addition, by using a (meth)acrylic acid alkyl ester having a water vapor permeability of a certain value or less as a main component of the (meth)acrylic polymer, the penetration of moisture into the adhesive can be suppressed. The adhesive layer formed by the composition can effectively suppress whitening of the adhesive layer. Further, since the (meth)acrylic polymer has a long alkyl chain in the side chain, it is excellent in coating property to a low-polar adherend.

而且，因為藉由交聯劑形成的交聯結構會提高凝聚力，故本發明之黏著劑組成物之耐熱發泡性及耐濕熱安定性優異。 Further, since the crosslinked structure formed by the crosslinking agent enhances the cohesive force, the adhesive composition of the present invention is excellent in heat-resistant foaming property and moisture-heat stability.

因此，本發明之黏著劑組成物、具有該黏著劑組成物作為黏著劑層之黏著片、及採用該黏著片之觸控面板用層合體係不易對含ITO、ATO等金屬或金屬氧化物之透明導電膜造成腐蝕，且透明導電膜之電氣特性變動少，同時亦不易發生白化、發泡。 Therefore, the adhesive composition of the present invention, the adhesive sheet having the adhesive composition as an adhesive layer, and the laminated system for a touch panel using the adhesive sheet are not easily used for a metal or metal oxide containing ITO, ATO or the like. The transparent conductive film causes corrosion, and the electrical characteristics of the transparent conductive film are less changed, and whitening and foaming are less likely to occur.

其次，具體說明本發明之黏著劑組成物、黏著片及觸控面板用層合體。 Next, the adhesive composition, the adhesive sheet, and the laminate for a touch panel of the present invention will be specifically described.

[黏著劑組成物] [Adhesive composition]

本發明之黏著劑組成物係含有丙烯酸系聚合物(A)與交聯劑(B)，而該丙烯酸系聚合物(A)係將包含下述成分(a-1)、(a-2)及(a-3)之單體共聚合而得之實質上不具有酸 性基，且重量平均分子量為5萬以上未達40萬者；以全部單體為100重量%計，(a-1)(甲基)丙烯酸烷基酯，將其重量平均分子量50萬的均聚物以圓筒法測定，於40℃ 90%RH的水蒸氣穿透率為500g/m2‧日以下者：50重量%以上，(a-2)具有羥基之單體：0.5至10重量%，(a-3)含氮單體：0.1至5重量%。 The adhesive composition of the present invention contains an acrylic polymer (A) and a crosslinking agent (B), and the acrylic polymer (A) will contain the following components (a-1) and (a-2). And the monomer of (a-3) is obtained by copolymerization, and has substantially no acidic group, and the weight average molecular weight is 50,000 or more and less than 400,000; (100% by weight of all monomers, (a-1) An alkyl (meth)acrylate having a weight average molecular weight of 500,000 homopolymer measured by a cylinder method, and a water vapor permeability of 90% RH at 40 ° C of 500 g / m 2 ‧ days or less: 50 weight More than %, (a-2) a monomer having a hydroxyl group: 0.5 to 10% by weight, and (a-3) a nitrogen-containing monomer: 0.1 to 5% by weight.

[(A)(甲基)丙烯酸系聚合物] [(A) (meth)acrylic polymer] <(a-1)(甲基)丙烯酸烷基酯> <(a-1)alkyl (meth)acrylate>

本發明之黏著劑組成物所使用之(甲基)丙烯酸系聚合物(A)中，係共聚合有(甲基)丙烯酸烷基酯(a-1)。 In the (meth)acrylic polymer (A) used in the adhesive composition of the present invention, an alkyl (meth)acrylate (a-1) is copolymerized.

就前述(甲基)丙烯酸烷基酯(a-1)而言，調製其重量平均分子量50萬的均聚物，並以上述均聚物形成50μm厚的薄膜，而以圓筒法測定之，於40℃ 90%RH的水蒸氣穿透率(WVTR)為500g/m2‧日以下，較佳為0至300g/m2‧日。 For the alkyl (meth)acrylate (a-1), a homopolymer having a weight average molecular weight of 500,000 is prepared, and a film having a thickness of 50 μm is formed from the above homopolymer, and is determined by a cylinder method. The water vapor transmission rate (WVTR) at 90 ° C for 90% RH is 500 g/m 2 ‧ days or less, preferably 0 to 300 g/m 2 ‧ days

前述圓筒法係JIS Z 0208之「防濕包裝材料的穿透濕度試驗方法」所規定的評估薄膜等之透濕度之試驗方法，在放有吸濕劑之專用圓筒的筒口放置試驗片，於試驗環境下靜置一定時間後，測定吸濕劑之質量，並由質量變化定量穿透試驗片的水蒸氣量之方法。水蒸氣穿透率係以下述式算出。 In the test method for evaluating the moisture permeability of a film or the like as defined in the "Test method for the penetration moisture of a moisture-proof packaging material" in the above-mentioned cylindrical method JIS Z 0208, a test piece is placed on the mouth of a dedicated cylinder in which the moisture absorbent is placed, After standing for a certain period of time in a test environment, the mass of the moisture absorbent is measured, and the amount of water vapor passing through the test piece is quantitatively determined by the mass change. The water vapor transmission rate was calculated by the following formula.

WVTR(g/m2‧日)=質量變化(g)/(透濕面積(m2)×時間(日)) WVTR (g/m 2 ‧ day) = mass change (g) / (moisture permeability area (m 2 ) × time (day))

一般之(甲基)丙烯酸烷基酯之水蒸氣穿透率(40℃、90%RH)係示於表1。 The water vapor transmission rate (40 ° C, 90% RH) of a general alkyl (meth)acrylate is shown in Table 1.

藉由導入此種防止水分滲入、且即使滲入也能將滲入者快速排出之單體作為聚合物主鏈的主要構成成分，可得到耐濕熱安定性優異的黏著劑組成物。 By introducing such a monomer which prevents moisture infiltration and allows the infiltrator to be quickly discharged even if it penetrates, it is a main constituent component of the polymer main chain, and an adhesive composition excellent in moist heat stability can be obtained.

又，本說明書中之重量平均分子量係以GPC(gel permeation chromatography)測定之標準聚苯乙烯換算之重量平均分子量。 Further, the weight average molecular weight in the present specification is a weight average molecular weight in terms of standard polystyrene measured by GPC (gel permeation chromatography).

前述(甲基)丙烯酸烷基酯(a-1)，較佳為具有脂肪族環及/或芳香族環之(甲基)丙烯酸烷基酯，而以具有脂肪族環或芳香族環之(甲基)丙烯酸烷基酯為宜。上述脂肪族環及芳香族環更佳為單環結構者。此種源自酯之醇的烴部分， 係藉由導入硬質(rigid)的環結構，或具有疏水性高的結構之(甲基)丙烯酸烷基酯，而可得到抑制水分滲入之(甲基)丙烯酸系聚合物。 The alkyl (meth)acrylate (a-1) is preferably an alkyl (meth)acrylate having an aliphatic ring and/or an aromatic ring, and has an aliphatic ring or an aromatic ring ( Alkyl methacrylate is preferred. The above aliphatic ring and aromatic ring are more preferably a single ring structure. The hydrocarbon portion of such an ester-derived alcohol, A (meth)acrylic polymer which inhibits penetration of moisture can be obtained by introducing a rigid ring structure or an alkyl (meth)acrylate having a highly hydrophobic structure.

滿足上述水蒸氣穿透率要素之前述具有脂肪族環或芳香族環之(甲基)丙烯酸烷基酯之例，可列舉如(甲基)丙烯酸環己酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苯甲酯。該等之中，從本發明之黏著劑組成物的耐濕熱安定性之觀點來看，較佳為丙烯酸環己酯、丙烯酸苯氧基乙酯。 Examples of the above-mentioned (meth)acrylic acid alkyl ester having an aliphatic ring or an aromatic ring satisfying the above-described water vapor permeability factor include cyclohexyl (meth)acrylate and phenoxy (meth)acrylate. Ethyl ester, phenyl (meth) acrylate, benzyl (meth) acrylate. Among these, from the viewpoint of moisture heat stability of the adhesive composition of the present invention, cyclohexyl acrylate or phenoxyethyl acrylate is preferred.

此外，前述(甲基)丙烯酸烷基酯(a-1)較佳為烷基之碳數為8至22之(甲基)丙烯酸烷基酯，更佳為烷基之碳數為10至22之(甲基)丙烯酸烷基酯。又，上述烷基係意指(甲基)丙烯酸烷基酯(a-1)之酯部之烷基。若烷基之碳數為上述範圍，則可將共聚合所得之(甲基)丙烯酸系聚合物(A)適度地疏水化，而使水蒸氣穿透率低。 Further, the alkyl (meth)acrylate (a-1) is preferably an alkyl (meth)acrylate having an alkyl group of 8 to 22 carbon atoms, more preferably an alkyl group having 10 to 22 carbon atoms. The alkyl (meth)acrylate. Further, the above alkyl group means an alkyl group of an ester moiety of the alkyl (meth)acrylate (a-1). When the carbon number of the alkyl group is in the above range, the (meth)acrylic polymer (A) obtained by the copolymerization can be appropriately hydrophobized to have a low water vapor transmission rate.

滿足上述水蒸氣穿透率要素之前述烷基的碳數為8至22之(甲基)丙烯酸烷基酯之例，可列舉如(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)丙烯酸月桂酯、(甲基)丙烯酸油酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸二癸酯、(甲基)丙烯酸異硬脂酯。 Examples of the (meth)acrylic acid alkyl ester having 8 to 22 carbon atoms of the alkyl group satisfying the above-mentioned water vapor permeability factor include, for example, 2-ethylhexyl (meth)acrylate and (methyl). Octyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, eleven (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate, (meth) acrylate N-stearyl ester, dinonyl (meth)acrylate, isostearyl (meth)acrylate.

該等之中，從本發明之黏著劑組成物的耐濕熱安定性之觀點來看，較佳為烷基之碳數為10至22之(甲基)丙烯酸月桂酯、(甲基)丙烯酸異硬脂酯。 Among these, from the viewpoint of the heat and humidity stability of the adhesive composition of the present invention, it is preferred that the alkyl group has a carbon number of 10 to 22 (la), (meth)acrylic acid, and (meth)acrylic acid. Stearyl ester.

以上所說明之(甲基)丙烯酸烷基酯(a-1)係可1種單獨使用，或將2種以上組合使用。 The alkyl (meth)acrylate (a-1) described above may be used alone or in combination of two or more.

相對於用於(甲基)丙烯酸系聚合物(A)聚合的全部單體，(甲基)丙烯酸烷基酯(a-1)係50重量%以上，較佳為60至97.9重量%。若未達50重量%，則無法得到優異的耐濕熱安定性。又，(甲基)丙烯酸系聚合物(A)中單體的裝入比例係等於共聚合比例。 The alkyl (meth)acrylate (a-1) is 50% by weight or more, preferably 60 to 97.9% by weight, based on the total of the monomers used for the polymerization of the (meth)acrylic polymer (A). If it is less than 50% by weight, excellent heat and humidity stability cannot be obtained. Further, the proportion of the monomer in the (meth)acryl-based polymer (A) is equal to the copolymerization ratio.

<(a-2)具有羥基的單體> <(a-2) monomer having a hydroxyl group>

本發明之黏著劑組成物所使用之(甲基)丙烯酸系聚合物(A)係(a-2)具有羥基的單體共聚合而成。 The (meth)acrylic polymer (A) (a-2) used in the adhesive composition of the present invention is obtained by copolymerizing a monomer having a hydroxyl group.

該單體(a-2)之至少一部分係藉由以後述交聯劑(B)進行交聯，而達成本發明黏著劑組成物之高凝聚力，並有效率地抑制發泡。 At least a part of the monomer (a-2) is crosslinked by the crosslinking agent (B) described later, thereby achieving high cohesive force of the adhesive composition of the present invention and efficiently suppressing foaming.

此外，(a-2)具有羥基的單體較佳為具有羥基之(甲基)丙烯酸酯。該種化合物之例，可列舉如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯及(甲基)丙烯酸8-羥基辛酯。 Further, (a-2) the monomer having a hydroxyl group is preferably a (meth) acrylate having a hydroxyl group. Examples of such a compound include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyl (meth)acrylate. Hexyl ester and 8-hydroxyoctyl (meth)acrylate.

從與交聯劑(B)的反應性之觀點來看，如上所述之具有羥基之(甲基)丙烯酸酯較佳為(甲基)丙烯酸2-羥基乙酯及(甲基)丙烯酸4-羥基丁酯。 From the viewpoint of reactivity with the crosslinking agent (B), the (meth) acrylate having a hydroxyl group as described above is preferably 2-hydroxyethyl (meth)acrylate and 4-(meth)acrylic acid. Hydroxybutyl ester.

以上所說明之(a-2)具有羥基的單體，係可1種單獨使用，或將2種以上組合使用。 The monomer having a hydroxyl group (a-2) described above may be used alone or in combination of two or more.

相對於(甲基)丙烯酸系聚合物(A)用於聚合的全部單 體，上述(a-2)具有羥基的單體係0.5至10重量%，較佳為2至8重量%。(a-2)具有羥基的單體的量若少於上述範圍，則其他之未具有交聯性官能基的單體之共聚合量必然會變多，而會有無法充分地形成以後述交聯劑(B)所成之交聯結構之情形。另一方面，共聚合量若多於上述範圍，則會過度形成交聯結構，段差順應性等其他特性會變得不充分。 All singles used for polymerization relative to the (meth)acrylic polymer (A) The above-mentioned (a-2) single system having a hydroxyl group is from 0.5 to 10% by weight, preferably from 2 to 8% by weight. (a-2) When the amount of the monomer having a hydroxyl group is less than the above range, the amount of copolymerization of the other monomer having no crosslinkable functional group is inevitably increased, and the amount of the monomer which is not sufficiently crosslinked may be insufficiently formed. The case of the crosslinked structure formed by the crosslinking agent (B). On the other hand, when the amount of copolymerization is more than the above range, a crosslinked structure is excessively formed, and other characteristics such as step compliance are insufficient.

<(a-3)含氮單體> <(a-3) nitrogen-containing monomer>

本發明之黏著劑組成物所使用之(甲基)丙烯酸系聚合物(A)係(a-3)含氮單體共聚合而成。 The (meth)acrylic polymer (A) used in the adhesive composition of the present invention is obtained by copolymerizing a nitrogen-containing monomer (a-3).

含氮單體較佳為使用選自由含胺基單體、含醯胺基單體、含氮系雜環單體、含氰基單體組成群組中之至少1種。 The nitrogen-containing monomer is preferably at least one selected from the group consisting of an amine group-containing monomer, a mercapto group-containing monomer, a nitrogen-containing heterocyclic monomer, and a cyano group-containing monomer.

其中，含胺基單體之例可列舉如(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯等；此外，含醯胺基單體之例，可列舉如(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)丙烯醯胺等；此外，含氮系雜環單體之例，可列舉如乙烯吡咯啶酮、丙烯醯嗎啉、乙烯己內醯胺等；此外，含氰基單體之例，可列舉如(甲基)丙烯酸氰酯等。 Examples of the amine group-containing monomer include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and the like; and examples of the amine-containing monomer, For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-hexyl (meth) acrylamide, etc., and examples of the nitrogen-containing heterocyclic monomer include, for example, vinylpyrrolidone, propylene morpholine, ethylene caprolactam, and the like; Examples thereof include cyanoacrylate (meth)acrylate and the like.

其中，從(a-1)單體及(a-2)單體之共聚合性之觀點來看，較佳為丙烯醯胺、丙烯酸二甲基胺基乙酯、乙烯吡咯啶酮、丙烯醯嗎啉。 Among them, from the viewpoint of the copolymerizability of the (a-1) monomer and the (a-2) monomer, acrylamide, dimethylaminoethyl acrylate, vinylpyrrolidone, and propylene oxime are preferred. Morpholine.

相對於用於(甲基)丙烯酸系聚合物(A)聚合的全部單 體，上述含氮單體(a-3)係0.1至5重量%，較佳為0.1至4重量%。(a-3)含氮單體的量若於上述範圍，則可使黏著劑組成物之凝聚力提升，此外，可促進以交聯劑(B)進行交聯，若未於上述範圍，則無法抑制源自被黏著物之排氣、捲入氣泡所致之發泡。 Relative to all singles used for the polymerization of (meth)acrylic polymer (A) The above nitrogen-containing monomer (a-3) is 0.1 to 5% by weight, preferably 0.1 to 4% by weight. (a-3) When the amount of the nitrogen-containing monomer is within the above range, the cohesive force of the adhesive composition can be improved, and crosslinking with the crosslinking agent (B) can be promoted, and if it is not within the above range, The foaming caused by the exhaust of the adherend and the entrapment of air bubbles is suppressed.

<其他單體> <other monomer>

就(甲基)丙烯酸系聚合物(A)而言，除了以上所說明之(甲基)丙烯酸烷基酯(a-1)、具有羥基的單體(a-2)及含氮單體(a-3)之外，亦可於不損及該聚合物(A)的特性之範圍內，共聚合其他的單體。 The (meth)acrylic polymer (A), in addition to the above-described (meth)acrylic acid alkyl ester (a-1), a hydroxyl group-containing monomer (a-2), and a nitrogen-containing monomer ( In addition to a-3), other monomers may be copolymerized within a range that does not impair the properties of the polymer (A).

其他單體之例，可列舉如(甲基)丙烯酸2-甲氧基乙酯等(甲基)丙烯酸烷氧基烷酯、甲氧基二乙二醇(甲基)丙烯酸酯等烷氧基聚烷二醇單(甲基)丙烯酸酯、(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)丙烯酸己酯及(甲基)丙烯酸庚酯等未滿足成分(a-1)之水蒸氣穿透率要素之(甲基)丙烯酸烷酯(又，(甲基)丙烯酸烷酯之烷基之碳數較佳為7以下)。該等係可單獨使用或組合使用。 Examples of the other monomer include alkoxy groups such as (meth)acrylic acid alkoxyalkyl esters such as 2-methoxyethyl (meth)acrylate and methoxydiethylene glycol (meth)acrylate. Polyalkylene glycol mono(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, and heptyl (meth)acrylate are not satisfied The (meth)acrylic acid alkyl ester of the water vapor permeability element of the component (a-1) (further, the carbon number of the alkyl group of the alkyl (meth)acrylate is preferably 7 or less). These lines can be used alone or in combination.

該等(甲基)丙烯酸烷氧基烷酯、烷氧基聚烷二醇單(甲基)丙烯酸酯及烷基成分(a-1)未滿足水蒸氣穿透率要素之(甲基)丙烯酸烷酯會被用來調整被黏著物的極性與丙烯酸系聚合物的極性，而在不阻礙本發明效果之範圍，可以相 對於用於(甲基)丙烯酸系聚合物(A)聚合的全部單體，該等之總計較佳係0至49.4重量%之範圍、更佳係0至37.9重量%之範圍進行使用。尤其是相對於(甲基)丙烯酸系聚合物(A)用於聚合的全部單體，上述(甲基)丙烯酸烷氧基烷酯及烷氧基聚烷二醇單(甲基)丙烯酸酯之總計，較佳為0重量%以上未達20重量%，更佳為0重量%至10重量%。 The (meth)acrylic acid alkoxyalkyl ester, the alkoxy polyalkylene glycol mono (meth) acrylate, and the alkyl component (a-1) (meth)acrylic acid which does not satisfy the water vapor permeability element The alkyl ester will be used to adjust the polarity of the adherend and the polarity of the acrylic polymer, and can be phased without hindering the effects of the present invention. For all the monomers used for the polymerization of the (meth)acrylic polymer (A), the total amount is preferably in the range of from 0 to 49.4% by weight, more preferably from 0 to 37.9% by weight. In particular, the above (meth)acrylic acid alkoxyalkyl ester and alkoxypolyalkylene glycol mono(meth)acrylate are all monomers used for the polymerization of the (meth)acrylic polymer (A). In total, it is preferably 0% by weight or more and less than 20% by weight, more preferably 0% by weight to 10% by weight.

此外，係可於不損及本發明作用效果之範圍使用乙酸乙烯酯；(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、戊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、硝苯乙烯、乙醯苯乙烯及甲氧基苯乙烯等苯乙烯系單量體；(甲基)丙烯酸縮水甘油酯等作為其他的單體。 Further, vinyl acetate may be used in a range that does not impair the effects of the present invention; (meth)acrylonitrile; cyclohexyl (meth)acrylate, benzyl (meth)acrylate, benzene (meth)acrylate Ester; alkylstyrene such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, amyl styrene and octyl styrene; ; styrene monoliths such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, styrene iodide, nitrostyrene, acetyl styrene, and methoxystyrene; (meth)acrylic acid; Glycidyl ester or the like is used as another monomer.

以上所說明之其他的單體，係可單獨使用1種或將2種以上組合使用。 The other monomers described above may be used alone or in combination of two or more.

<(A)(甲基)丙烯酸系聚合物> <(A) (meth)acrylic polymer>

本發明所使用之(甲基)丙烯酸系聚合物(A)雖係藉由將以上所說明之單體用上述比例共聚合而得到，但實質上未具有酸性基。其中之實質上未具有酸性基，意指在共聚合時，刻意不調配具有酸性基之單體，而以酸價表示所得之聚合物，通常係0.5mg KOH/g以下。本案說明書中，酸性基中不包含羥基。 The (meth)acrylic polymer (A) used in the present invention is obtained by copolymerizing the above-described monomers in the above ratio, but does not substantially have an acidic group. The fact that it does not substantially have an acidic group means that the monomer having an acidic group is deliberately not blended at the time of copolymerization, and the obtained polymer is usually represented by an acid value of 0.5 mg KOH/g or less. In the present specification, the acidic group does not contain a hydroxyl group.

其中，具有酸性基之單體，可列舉如(甲基)丙烯酸、 順丁烯二酸、伊康酸等具有羧基之單體；具有磷酸基之單體、具有磺酸基之單體等。 Among them, a monomer having an acidic group may, for example, be (meth)acrylic acid. a monomer having a carboxyl group such as maleic acid or itaconic acid; a monomer having a phosphate group; a monomer having a sulfonic acid group;

本發明之(甲基)丙烯酸系聚合物(A)中，未共聚合如前述之含酸性基之單體。因為如此之未使含酸性基之單體進行共聚合，因此本發明所使用之(甲基)丙烯酸系聚合物(A)即使與包含金屬或金屬氧化物之線路直接接觸，也不會對該等造成腐蝕，而可賦予本發明之黏著劑組成物不使線路之電阻值因經長時間而變化之特性。 In the (meth)acrylic polymer (A) of the present invention, the acid group-containing monomer as described above is not copolymerized. Since the acid group-containing monomer is not copolymerized as such, the (meth)acrylic polymer (A) used in the present invention does not directly contact the line containing the metal or metal oxide. Corrosion, etc., can impart the characteristics that the adhesive composition of the present invention does not cause the resistance value of the line to change over a long period of time.

此外，本發明所使用之(甲基)丙烯酸系聚合物(A)，其重量平均分子量係5萬以上未達40萬，較佳為於20萬至38萬之範圍內。 Further, the (meth)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 200,000 to 380,000.

以往所使用之黏著劑，係使用重量平均分子量為40萬至160萬左右的高分子量之丙烯酸系聚合物，但本發明如上所述，係使用重量平均分子量較以往低之(甲基)丙烯酸系聚合物(A)作為(甲基)丙烯酸系聚合物，藉此黏著劑變得質地較軟且段差順應性變得良好，此外，貼附採用該黏著劑組成物之黏著片時，變得不易捲入氣泡。再者，溶劑中之固形分可保持高濃度，而以一次塗裝步驟即可塗成足夠厚度，塗裝性亦優異。又，即使使用重量平均分子量為未達5萬之(甲基)丙烯酸系聚合物(A)，仍無法得到充分的凝聚力。而且重量平均分子量為40萬以上時，不僅形態順應性不充分，當水分滲入後會難以將之排出，而成為後述白化的原因。 A conventionally used adhesive is a high molecular weight acrylic polymer having a weight average molecular weight of about 400,000 to about 1.6 million. However, as described above, the present invention uses a (meth)acrylic acid having a lower weight average molecular weight than conventional ones. When the polymer (A) is a (meth)acrylic polymer, the adhesive becomes soft in texture and the stepwise compliance becomes good, and when the adhesive sheet using the adhesive composition is attached, it becomes difficult. Entrap into the bubble. Further, the solid content in the solvent can be maintained at a high concentration, and can be applied to a sufficient thickness in a single coating step, and the coating property is also excellent. Further, even if a (meth)acrylic polymer (A) having a weight average molecular weight of less than 50,000 is used, sufficient cohesive force cannot be obtained. Further, when the weight average molecular weight is 400,000 or more, not only the form conformability is insufficient, but also it is difficult to discharge the water after it has penetrated, which causes whitening to be described later.

本發明中，(甲基)丙烯酸系聚合物(A)以Fox方程式求 得之玻璃轉移溫度(Tg)，通常為-70℃至0℃，較佳為於-70℃至-30℃之範圍內。藉由使用具有此種玻璃轉移溫度(Tg)之(甲基)丙烯酸系聚合物(A)，可得到於常溫具有優異的接著強度之黏著劑組成物。 In the present invention, the (meth)acrylic polymer (A) is obtained by the Fox equation. The resulting glass transition temperature (Tg) is usually from -70 ° C to 0 ° C, preferably from -70 ° C to -30 ° C. By using the (meth)acrylic polymer (A) having such a glass transition temperature (Tg), an adhesive composition having excellent adhesion strength at normal temperature can be obtained.

<(甲基)丙烯酸系聚合物(A)之製造方法> <Method for Producing (Meth)Acrylic Polymer (A)>

上述(甲基)丙烯酸系聚合物(A)雖可藉由公知方法製造，惟較佳為藉由溶液聚合而製造。溶液聚合中，聚合溶劑係可使用例如乙酸乙酯、甲基乙基酮、甲苯、丙酮等。 The (meth)acrylic polymer (A) can be produced by a known method, but it is preferably produced by solution polymerization. In the solution polymerization, for example, ethyl acetate, methyl ethyl ketone, toluene, acetone or the like can be used as the polymerization solvent.

具體而言，係依上述所說明之比例裝入於反應容器內裝入聚合溶劑、原料單體，在氮氣等惰性氣體環境下添加聚合起始劑，將反應溫度加熱至50至90℃左右，使其反應4至20小時。 Specifically, the polymerization solvent and the raw material monomer are charged in a reaction container at a ratio described above, and a polymerization initiator is added in an inert gas atmosphere such as nitrogen to heat the reaction temperature to about 50 to 90 ° C. Allow to react for 4 to 20 hours.

用於溶液聚合之反應起始劑，可列舉如偶氮系起始劑、過氧化物系起始劑。相對於原料單體100重量份，該等反應起始劑通常係使用0.01至5重量份範圍內之量。此外，上述聚合反應中，亦可適宜地追加添加聚合起始劑、鏈轉移劑、原料單體、溶劑。 The reaction initiator used for the solution polymerization may, for example, be an azo initiator or a peroxide initiator. The reaction initiators are usually used in an amount ranging from 0.01 to 5 parts by weight based on 100 parts by weight of the raw material monomers. Further, in the above polymerization reaction, a polymerization initiator, a chain transfer agent, a raw material monomer, and a solvent may be added as appropriate.

如上述條件中，所得之(甲基)丙烯酸系聚合物(A)的重量平均分子量，係可依照公知技術，藉由調整使用溶劑的種類及量、聚合起始劑的種類及量、反應時間、反應溫度等反應條件而進行調控。 In the above conditions, the weight average molecular weight of the obtained (meth)acrylic polymer (A) can be adjusted according to a known technique, by adjusting the kind and amount of the solvent to be used, the type and amount of the polymerization initiator, and the reaction time. The reaction conditions such as the reaction temperature are adjusted.

[(B)交聯劑] [(B) Crosslinker]

本發明之黏著劑組成物復含有交聯劑(B)。交聯劑(B)之例，可列舉如異氰酸酯系交聯劑、金屬螯合物系交聯劑 等，從高溫環境下之耐久性之觀點來看，較佳為異氰酸酯系交聯劑。 The adhesive composition of the present invention further contains a crosslinking agent (B). Examples of the crosslinking agent (B) include an isocyanate crosslinking agent and a metal chelate crosslinking agent. From the viewpoint of durability in a high temperature environment, an isocyanate crosslinking agent is preferred.

前述異氰酸酯系交聯劑之例，可列舉如二異氰酸甲苯酯(tolylenediisocyanate)、二異氰酸伸茬酯、二異氰酸氯伸苯酯、二異氰酸六亞甲酯、二異氰酸四亞甲酯、異佛酮二異氰酸酯、經氫化之二苯基甲烷二異氰酸酯等分子中具有二個以上異氰酸酯基化合物(以下，亦將上述所例示之化合物稱為「異氰酸酯化合物」)：上述異氰酸酯化合物與三羥甲基丙烷、新戊四醇等多元醇進行加成反應之化合物或與上述異氰酸酯化合物之三聚異氰酸酯(isocyanurate)化合物及縮二脲型化合物、以及使上述異氰酸酯化合物與公知之聚醚多元醇或聚酯多元醇、丙烯酸多元醇、丁二烯多元醇、聚異戊二烯等進行加成反應之胺酯預聚物型之在分子內具有二個以上異氰酸酯基的化合物。 Examples of the above-mentioned isocyanate crosslinking agent include tolylene diisocyanate, diisocyanate diisocyanate, phenyl diphenyl phthalate, hexamethylene diisocyanate, and diiso isocyanate. The tetramethylene cyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate or the like has two or more isocyanate group-containing compounds (hereinafter, the above-exemplified compound is also referred to as "isocyanate compound"): a compound in which an isocyanate compound is subjected to an addition reaction with a polyhydric alcohol such as trimethylolpropane or neopentyl alcohol, or an isocyanurate compound and a biuret-type compound with the above isocyanate compound, and a known isocyanate compound. a compound having two or more isocyanate groups in a molecule, which is an amine ester prepolymer type which is subjected to an addition reaction, such as a polyether polyol or a polyester polyol, an acrylic polyol, a butadiene polyol, or a polyisoprene. .

該等之中，就可提高對被黏著物的從順性以減低貼合時之泡體捲入，並可抑制於高溫之排氣之點而言，係以二異氰酸伸茬酯及其三羥甲基丙烷加成物、以及二異氰酸六亞甲酯之三聚異氰酸酯化合物為較佳，此外，就可提高貼附面之段差順應性，使耐熱發泡性良好之點而言，係以二異氰酸六亞甲酯及其三羥甲基丙烷加成物為較佳。 Among these, it is possible to improve the compliance of the adherend to reduce the entrapment of the foam at the time of bonding, and to suppress the exfoliation of the high temperature, and the diisocyanate and A trimeric isocyanate compound of a trimethylolpropane adduct and a hexamethylene diisocyanate is preferred, and a stepwise compliance of the adhesion surface can be improved, and the heat-resistant foaming property is improved. Preferably, hexamethylene diisocyanate and its trimethylolpropane adduct are preferred.

以上所說明之交聯劑(B)，係可單獨使用1種或將2種以上組合使用。 The crosslinking agent (B) described above may be used alone or in combination of two or more.

藉由調配前述交聯劑(B)，會提升本發明黏著劑組成物之凝聚力，而即使於貼附時捲入少許氣泡，也可抑制該氣 泡之膨脹，發揮優異的耐熱發泡性。 By blending the aforementioned crosslinking agent (B), the cohesive force of the adhesive composition of the present invention is enhanced, and the gas can be suppressed even if a small amount of bubbles are caught in the attachment. The expansion of the bubble exerts excellent heat-resistant foaming properties.

[黏著劑組成物] [Adhesive composition]

本發明之黏著劑係藉由將上述(甲基)丙烯酸系聚合物(A)，與相對於該(甲基)丙烯酸系聚合物(A))100重量份通常為0.1至2重量份、較佳為0.1至1重量份之交聯劑(B)，以及進一步視所需之其他成分進行調配而得。 The adhesive of the present invention is usually 0.1 to 2 parts by weight, based on 100 parts by weight of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (A). It is preferably 0.1 to 1 part by weight of the crosslinking agent (B), and further prepared according to other components required.

前述之其他成分，可列舉如抗氧化劑、光安定劑、金屬抗蝕劑、賦黏劑、塑化劑、抗靜電劑、交聯促進劑、重工(rework)劑等。該等成分係可於不損及本發明黏著劑組成物之效果的範圍，進行調配。 Examples of the other components mentioned above include an antioxidant, a photostabilizer, a metal resist, an adhesive, a plasticizer, an antistatic agent, a crosslinking accelerator, a rework agent, and the like. These components can be formulated without affecting the effects of the adhesive composition of the present invention.

以此種方式得到的黏著劑組成物係與公知的黏著劑相同，經溶劑稀釋為適當的濃度後，藉由進行塗裝、乾燥，而可用於各種構件之接著。於溶劑中，含有本發明所使用之(甲基)丙烯酸系聚合物(A)及交聯劑(B)、以及其他成分之塗佈溶液，由於(甲基)丙烯酸系聚合物(A)的重量平均分子量(Mw)低，故可使用乙酸乙酯、甲基乙基酮、丙酮、甲苯等溶劑，將不揮發成分的濃度調整為所期望的濃度。 The adhesive composition obtained in this manner is the same as a known adhesive, and after being diluted to a suitable concentration by a solvent, it can be applied to various members by coating and drying. A coating solution containing the (meth)acrylic polymer (A), the crosslinking agent (B), and other components used in the present invention in a solvent, due to the (meth)acrylic polymer (A) Since the weight average molecular weight (Mw) is low, a solvent such as ethyl acetate, methyl ethyl ketone, acetone or toluene can be used to adjust the concentration of the nonvolatile component to a desired concentration.

因此，藉由使用本發明之黏著劑組成物，可容易地使塗裝後黏著劑的厚度成為所期望的厚度。尤其是可以本發明之黏著劑組成物容易地調製不揮發成分含量高之溶液，例如可調整不揮發成分為10至70%、較佳為30至60%之範圍內，因而可以較少塗佈次數形成所期望的厚度之黏著劑層。此外，藉由如此使用不揮發成分含量高之溶液，塗裝/乾燥後的塗膜之整平(Leveling)性提高，另外，乾燥時間 亦縮短而作業性提高。另外，因為揮發溶劑量較少，對環境造成的負擔亦變小。 Therefore, by using the adhesive composition of the present invention, the thickness of the post-coating adhesive can be easily made into a desired thickness. In particular, the adhesive composition 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%, and thus can be coated less. The number of times the adhesive layer of the desired thickness is formed. In addition, by using a solution having a high content of nonvolatile components, the leveling property of the coating film after coating/drying is improved, and drying time is also increased. It is also shortened and the workability is improved. In addition, since the amount of the volatile solvent is small, the burden on the environment is also small.

因為該黏著劑組成物係如上所述，係耐熱發泡性、耐濕熱安定性及段差順應性優異，而即使與包含金屬或金屬氧化物之線路直接接觸亦不對該等造成腐蝕，故可適合使用於構成觸控面板之層合體之透明導電膜等導電膜的貼合。 Since the adhesive composition is excellent in heat-resistant foaming property, moist heat stability, and step compliance as described above, it does not corrode even if it is in direct contact with a wire containing a metal or a metal oxide, so it is suitable. The bonding of a conductive film such as a transparent conductive film constituting a laminate of a touch panel.

[黏著片] [Adhesive sheet]

本發明之黏著片，通常係將不揮發成分經調整為10至70%、較佳係經調整為30至60%之黏著劑組成物的塗佈液，塗佈於表面經剝離處理之基材(例：剝離處理PET等)的表面，以成為乾燥厚度於10至1000μm之範圍內的厚度，較佳係以成為25至500μm之範圍內的厚度之方式進行塗佈，去除溶劑後，於所形成之黏著劑層的表面貼附表面經剝離處理之保護膜，通常係於0至50℃之溫度進行1日至10日熟成而得。 The adhesive sheet of the present invention is usually a coating liquid of an adhesive composition having a nonvolatile content adjusted to 10 to 70%, preferably 30 to 60%, and applied to a surface-treated substrate. (Example: peeling treatment PET or the like), the surface is formed to have a dry thickness in the range of 10 to 1000 μm, preferably coated to a thickness in the range of 25 to 500 μm, and after removing the solvent, The surface of the formed adhesive layer is subjected to a release-treated protective film, which is usually obtained by aging at a temperature of 0 to 50 ° C for 1 to 10 days.

以此種方式得到的黏著片之黏著劑層的膠體分率，通常為50至80%、較佳為60至70%之範圍內，而具有優異的凝聚力，可有效地抑制發泡。又，本發明之膠體分率係以以下所述方式求得。 The adhesive fraction of the adhesive sheet obtained in this manner is usually in the range of 50 to 80%, preferably 60 to 70%, and has excellent cohesive force, and can effectively suppress foaming. Further, the colloid fraction of the present invention was obtained in the following manner.

採取約0.1g於23℃熟成7天後之黏著劑層試樣至採樣瓶、加入乙酸乙酯30cc並震盪4小時後，將該試樣瓶之內容物以網眼數200的不鏽鋼製金屬網過濾，將金屬網上的殘留物於100℃乾燥2小時，測定乾燥重量，並藉由下 式算出膠體分率。 After taking about 0.1 g of the adhesive layer sample which was cooked at 23 ° C for 7 days to the sampling bottle, adding 30 cc of ethyl acetate and shaking for 4 hours, the contents of the sample bottle were made of stainless steel metal mesh with a mesh number of 200. Filtration, drying the residue on the metal mesh at 100 ° C for 2 hours, measuring the dry weight, and by the next The colloid fraction was calculated by the formula.

膠體分率(%)=(乾燥重量/採取的試樣重量)×100 Colloid fraction (%) = (dry weight / sample weight taken) × 100

[觸控面板用層合體] [Layer for Touch Panel]

以此種方式得到的黏著片，進一步界定之，則指形成於該基材上之黏著劑層，係可對各種構件進行貼附，尤其是適於貼合不同種構件之觸控面板用層合體的貼附。 The adhesive sheet obtained in this manner is further defined as an adhesive layer formed on the substrate, which can be attached to various members, in particular, a layer for a touch panel suitable for bonding different kinds of members. Fitted attachment.

如第1圖及第2圖所示，就觸控面板單元而言，係有電阻膜式觸控面板單元(參照第1圖)、與靜電容量式觸控面板單元(第2圖參照)。 As shown in FIGS. 1 and 2, the touch panel unit is provided with a resistive touch panel unit (see FIG. 1) and a capacitive touch panel unit (see FIG. 2).

第1圖係表示電阻膜式觸控面板單元10-1之例。 Fig. 1 shows an example of a resistive film type touch panel unit 10-1.

如第1圖所示，電阻膜式觸控面板單元10-1係藉由以貼合劑30形成間隙34之方式，貼合上部層合體11-1與下部層合體13-1而形成，並於間隙34內配置有用以確保有效的間隙寬度之間隔件32。 As shown in FIG. 1, the resistive touch panel unit 10-1 is formed by bonding the upper laminate 11-1 and the lower laminate 13-1 so that the gap 34 is formed by the bonding agent 30, and A spacer 32 is provided within the gap 34 to ensure an effective gap width.

上部層合體11-1中，朝向間隙34配置有包含金屬或是金屬氧化物之透明導電膜27-1。此透明導電膜27-1係以、ITO(銦錫氧化物)、ATO(銻錫氧化物)氧化錫等具有透明性之導電材料所形成，通常係如第1圖所示，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)或玻璃等透明構件所構成之上部電極支撐物25-1的表面。 In the upper laminate 11-1, a transparent conductive film 27-1 containing a metal or a metal oxide is disposed toward the gap 34. The transparent conductive film 27-1 is formed of a transparent conductive material such as ITO (indium tin oxide) or ATO (antimony tin oxide) tin oxide, and is usually formed as shown in FIG. A transparent member such as polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) or glass constitutes the surface of the upper electrode support 25-1.

上部層合體11-1之最表面係配置有表面支撐物21-1，該表面支撐物21-1通常係如高透明性的玻璃之透明構件或是聚碳酸酯(PC)、聚對苯二甲酸乙二酯(PET)、聚甲 基丙烯酸甲酯(PMMA)、等透明薄膜。 The outermost surface of the upper laminate 11-1 is provided with a surface support 21-1, which is usually a transparent member of glass having high transparency or polycarbonate (PC) or polyparaphenylene. Ethylene formate (PET), polymethyl A transparent film such as methyl acrylate (PMMA).

為了接著上述表面支撐物21-1與上部電極支撐物25-1，係形成有含本發明黏著劑組成物之黏著劑層23-1。 In order to continue the surface support 21-1 and the upper electrode support 25-1, an adhesive layer 23-1 containing the adhesive composition of the present invention is formed.

此外，於下部層合體13-1中，相同地朝向間隙34形成有金屬或是金屬氧化物之透明導電膜27-2、此透明導電膜27-2係以ITO、ATO、氧化錫等具有透明性之導電材料所形成，通常係如第1圖所示，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)等透明薄膜或玻璃等透明構件所構成之下部電極支撐物25-2的表面。 Further, in the lower laminate 13-1, a transparent conductive film 27-2 of a metal or a metal oxide is formed in the same manner toward the gap 34, and the transparent conductive film 27-2 is transparent with ITO, ATO, tin oxide, or the like. The conductive material is usually formed as a transparent film made of polyethylene terephthalate (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA) as shown in Fig. 1. Or a transparent member such as glass constitutes the surface of the lower electrode support 25-2.

於下部層合體13-1之最深部中，係以面對於平板顯示器(Flat-Panel Display；FPD)的表面之方式形成有深部的表面支撐物21-2，此深部的表面支撐物21-2係以如玻璃之透明構件或聚碳酸酯(PC)、聚對苯二甲酸乙二酯(PET)、聚甲基丙烯酸甲酯(PMMA)等透明薄膜等高透明性的構件所形成。 In the deepest portion of the lower laminate 13-1, a deep surface support 21-2 is formed in such a manner as to face the surface of a flat panel display (FPD), and the deep surface support 21-2 It is formed of a transparent member such as glass or a highly transparent member such as a transparent film such as polycarbonate (PC), polyethylene terephthalate (PET) or polymethyl methacrylate (PMMA).

下部層合體13-1中，係形成有用以接著深部的表面支撐物21-2與下部電極支撐物25-2之含本發明黏著劑之黏著劑層23-2。 In the lower laminate 13-1, an adhesive layer 23-2 containing the adhesive of the present invention, which is followed by a deep surface support 21-2 and a lower electrode support 25-2, is formed.

此外，亦有使用本發明之黏著劑組成物作為貼合劑30之情形。 Further, there is also a case where the adhesive composition of the present invention is used as the bonding agent 30.

又，上述透明導電膜27-1、27-2形成有電路，係藉由從表面支撐物21-1之上以手指等施加壓力，使被施加壓力的部分之間隙34消失而使透明導電膜27-1及27-2進行接 觸並通電，以感測加壓部分之方式所形成。 Further, the transparent conductive films 27-1 and 27-2 are formed with a circuit, and a pressure is applied from the surface support 21-1 by a finger or the like, and the gap 34 of the portion to which the pressure is applied is eliminated to make the transparent conductive film. 27-1 and 27-2 are connected The contact is energized and formed by sensing the pressurized portion.

電阻膜式觸控面板單元10-1中，表面支撐物21-1之厚度通常為25至2000μm，上部透明導電膜27-1之厚度通常為10至100nm，上部電極支撐物25-1厚度通常為25至2000μm。層合該等之黏著劑層23-1之厚度如上所述，通常於10至1000μm之範圍內，較佳為於25至500μm之範圍內。 In the resistive film type touch panel unit 10-1, the thickness of the surface support 21-1 is usually 25 to 2000 μm, the thickness of the upper transparent conductive film 27-1 is usually 10 to 100 nm, and the thickness of the upper electrode support 25-1 is usually It is 25 to 2000 μm. The thickness of the adhesive layer 23-1 laminated is as described above, and is usually in the range of 10 to 1000 μm, preferably in the range of 25 to 500 μm.

相同地，在電阻膜式觸控面板單元中，深部的支撐物21-2之厚度通常為25至2000μm，下部透明導電膜27-2之厚度通常為10至100nm，上部電極支撐物25-2之厚度通常為25至2000μm。層合該等之黏著劑層23-2之厚度如上所述，通常於10至1000μm之範圍內，較佳為於25至500μm之範圍內。 Similarly, in the resistive film type touch panel unit, the thickness of the deep support 21-2 is usually 25 to 2000 μm, and the thickness of the lower transparent conductive film 27-2 is usually 10 to 100 nm, and the upper electrode support 25-2 The thickness is usually 25 to 2000 μm. The thickness of the adhesive layer 23-2 laminated is as described above, and is usually in the range of 10 to 1000 μm, preferably in the range of 25 to 500 μm.

此外，電阻膜式觸控面板單元10-1中，形成於中央的間隙30之寬度，通常於1至2000μm之範圍內。 Further, in the resistive film type touch panel unit 10-1, the width of the gap 30 formed at the center is usually in the range of 1 to 2000 μm.

另一方面，就一般而言，靜電容量式觸控面板單元10-2大多具有將上部層合體15-1與下部層合體15-2配置為夾置玻璃、聚碳酸酯(PC)等高透明性構件所構成之中央支撐物60之構造。 On the other hand, in general, the capacitive touch panel unit 10-2 has a high transparency in which the upper laminate 15-1 and the lower laminate 15-2 are disposed so as to sandwich glass or polycarbonate (PC). The construction of the central support 60 formed by the structural members.

靜電容量式觸控面板10-2之上部層合體15-1中，係配置有接觸中央支撐物60之透明導電膜57-1，最表面配置有保護玻璃或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)等光穿透性構件所構成之表面支撐物51-1。並以接著該透明1導電膜57-1與表面 支撐物51-1之方式配置有含本發明黏著劑組成物之黏著劑層53-1，而該黏著劑層53-1係與透明導電膜57-1直接接觸。 In the upper laminated body 15-1 of the capacitive touch panel 10-2, a transparent conductive film 57-1 contacting the central support 60 is disposed, and the outermost surface is provided with a protective glass or polyethylene terephthalate. Surface support 51-1 composed of a light-transmitting member such as (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA). And then the transparent 1 conductive film 57-1 and the surface The adhesive layer 53-1 containing the adhesive composition of the present invention is disposed in the manner of the support 51-1, and the adhesive layer 53-1 is in direct contact with the transparent conductive film 57-1.

另一方面，靜電容量式觸控面板單元10-2之下部層合體15-2中，係配置有接觸中央支撐物60之透明導電膜57-2，並於最深部配置有保護玻璃或是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)等光穿透性構件所構成之表面支撐物51-2。並以接著該透明導電膜57-2與最深部的表面支撐物51-2之方式配置有含本發明黏著劑組成物之黏著劑層53-2，而該黏著劑層53-2係與透明導電膜57-2直接接觸。 On the other hand, in the lower laminate 15-2 of the capacitive touch panel unit 10-2, a transparent conductive film 57-2 contacting the central support 60 is disposed, and a protective glass is disposed at the deepest portion or A surface support 51-2 composed of a light-transmitting member such as polyethylene terephthalate (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA). The adhesive layer 53-2 containing the adhesive composition of the present invention is disposed in the manner of the transparent conductive film 57-2 and the deepest surface support 51-2, and the adhesive layer 53-2 is transparent. The conductive film 57-2 is in direct contact.

靜電容量式觸控面板單元10-2中，最深部的表面支撐物51-2係以與平板顯示器相對之方式配置。 In the electrostatic capacitance type touch panel unit 10-2, the deepest surface support 51-2 is disposed to face the flat panel display.

上述靜電容量式觸控面板單元10-2中，上部層合體15-1之厚度通常為175至3000μm、上部透明電極膜57-1之厚度通常為10至100nm，接著兩者之黏著劑層53-1之厚度係如上述，通常10至1000μm。此外，下部層合體15-2中，下部透明導電膜57-2之厚度通常為10至100nm，最深部的表面支撐物51-2之厚度通常為25至2000μm，接著兩者之黏著劑層53-2之厚度係如上述，通常10至1000μm。此外，位於上述上部層合體15-1與下部層合體15-2之間的中央支撐物60之厚度，通常於25至1000μm之範圍內。 In the above electrostatic capacitance type touch panel unit 10-2, the thickness of the upper laminate 15-1 is usually 175 to 3000 μm, and the thickness of the upper transparent electrode film 57-1 is usually 10 to 100 nm, and then the adhesive layer 53 of the two is used. The thickness of -1 is as described above, usually 10 to 1000 μm. Further, in the lower laminate 15-2, the thickness of the lower transparent conductive film 57-2 is usually 10 to 100 nm, and the thickness of the surface support 51-2 at the deepest portion is usually 25 to 2000 μm, followed by the adhesive layer 53 of both. The thickness of -2 is as described above, usually 10 to 1000 μm. Further, the thickness of the central support 60 located between the upper laminate 15-1 and the lower laminate 15-2 is usually in the range of 25 to 1000 μm.

又，透明導電膜57-1及57-2係有電路形成。此外， 第2圖所示之靜電容量式觸控面板單元10-2中，藉由將上部層合體15-1及下部層合體15-2分別獨立地作為於X軸方向及Y軸方向設置的二系列電路，即可省略上部層合體15-1或是下部層合體15-2中之一者。 Further, the transparent conductive films 57-1 and 57-2 are formed by circuits. In addition, In the capacitance type touch panel unit 10-2 shown in FIG. 2, the upper laminate 15-1 and the lower laminate 15-2 are independently provided as two series in the X-axis direction and the Y-axis direction. In the circuit, one of the upper laminate 15-1 or the lower laminate 15-2 can be omitted.

靜電容量式觸控面板中，係藉由讀取因手指接觸觸控面板單元10-2的表面所造成的接觸部分之靜電容量變化，以感測接觸位置。 In the electrostatic capacitance type touch panel, the contact position is sensed by reading a change in electrostatic capacitance of a contact portion caused by a finger contacting the surface of the touch panel unit 10-2.

如上所述觸控面板單元中，會在例如在第2圖之A所表示的邊緣部的表面支撐物51-1之與黏著劑層53-1接觸之面施行框緣印刷。該框緣印刷部分係擴大表示於第3圖。第3圖中，係以編號62表示框緣印刷部分。該框緣印刷部分62的厚度(t0)通常為10至50μm，其剖面幾乎形成為矩形。黏著劑層53-1係藉由將上述本發明之黏著片貼附於表面支撐物51-1所形成，故黏著片所形成之黏著劑層若為硬質而缺乏形態順應性，則會如第4a圖所示，導致在框緣印刷部分62之末端部且為與表面支撐物51-1之間，形成黏著劑層53-1與表面支撐物51-1及框緣印刷部分62的邊緣部中之任一者皆未接觸的空隙64該部分原本應如第4b圖所示，不形成空隙64而於表面支撐物51-1及框緣印刷部分62的邊緣部密著有黏著劑層53-1。 In the touch panel unit as described above, frame edge printing is performed on the surface of the surface support 51-1 at the edge portion indicated by A in Fig. 2, which is in contact with the adhesive layer 53-1. The frame printed portion is enlarged and shown in Fig. 3. In Fig. 3, the frame print portion is indicated by reference numeral 62. The frame edge printed portion 62 has a thickness (t 0 ) of usually 10 to 50 μm, and its cross section is formed almost in a rectangular shape. The adhesive layer 53-1 is formed by attaching the above-mentioned adhesive sheet of the present invention to the surface support 51-1, so that if the adhesive layer formed of the adhesive sheet is hard and lacks form conformability, it will be as 4a, the edge portion of the adhesive layer 53-1 and the surface support 51-1 and the frame print portion 62 is formed between the end portion of the frame print portion 62 and the surface support 51-1. The void 64 which is not in contact with any of the portions 64 should be formed as shown in Fig. 4b, and the adhesive layer 53 is adhered to the edge portions of the surface support 51-1 and the frame print portion 62 without forming the void 64. -1.

然而，就如以往之以重量平均分子量為40萬至160萬的丙烯酸系聚合物為基底材料(base)之黏著劑而言，黏著劑層的形狀無法隨此種極為微細的形態變化進行變化，而會導致形成空隙64。 However, as in the case of conventional adhesives having an acrylic polymer having a weight average molecular weight of 400,000 to 1,600,000 as a base material, the shape of the adhesive layer cannot be changed in accordance with such extremely fine morphological changes. This will result in the formation of voids 64.

構成以表面支撐物、黏著劑層及透明導電膜(亦有具有支撐物者)層合之本發明之觸控面板用層合體的黏著劑層53-1，係藉由使用具有如上述之特定組成、重量平均分子量(Mw)為5萬以上未達40萬之(甲基)丙烯酸系聚合物(A)，使其藉由交聯劑(B)進行交聯而達成優異的凝聚力，同時具有非常優異的形態順應性，而於框緣印刷部分62之周邊未形成空隙64。。 The adhesive layer 53-1 of the laminate for a touch panel of the present invention laminated with a surface support, an adhesive layer, and a transparent conductive film (also having a support) is used by using the above-mentioned specific a (meth)acrylic polymer (A) having a composition and a weight average molecular weight (Mw) of 50,000 or more and less than 400,000, which is crosslinked by a crosslinking agent (B) to achieve excellent cohesive force, and has Very excellent form compliance, and no voids 64 are formed in the periphery of the frame edge printing portion 62. .

此外，本發明之觸控面板用層合體若如第5圖所示，使用如聚碳酸酯(PC)之容易發生排氣的構件作為支撐物51-2時，則有例如以耐熱試驗條件80℃之條件進行試驗，即會由支撐物發生排氣而使得在支撐物與黏著劑層之間產生氣泡66之情形。此外，即使使用不發生排氣之支撐物，仍會有在支撐物與黏著劑層接著時捲入泡體68之情形，而該氣泡若因溫度變化而成長即成為發泡之原因。 Further, when the laminate for a touch panel of the present invention is used as a support 51-2 such as polycarbonate (PC) as shown in Fig. 5, for example, it is subjected to heat resistance test conditions 80. The test was carried out under the conditions of °C, that is, the support was vented to cause bubbles 66 to be generated between the support and the adhesive layer. Further, even if a support that does not generate exhaust gas is used, there is a case where the support body and the adhesive layer are wound into the bubble body 68, and if the bubble grows due to temperature change, it becomes a cause of foaming.

本發明之黏著劑組成物係具有特定之組成，係使用重量平均分子量(Mw)5萬以上未達40萬之(甲基)丙烯酸系聚合物(A)，並藉由交聯劑(B)將之進行交聯，故具有非常高的凝聚力，可藉由高凝聚力而抑制如上述之排氣造成的發泡及捲入的氣泡成長造成的發泡。因此，本發明之觸控面板用層合體可達成幾乎觀察不到如上所述之發泡。 The adhesive composition of the present invention has a specific composition, and a (meth)acrylic polymer (A) having a weight average molecular weight (Mw) of not less than 50,000 and less than 400,000 is used, and a crosslinking agent (B) is used. Since it is cross-linked, it has a very high cohesive force, and it is possible to suppress foaming due to foaming due to the above-described exhaust gas and growth of the entrapped air bubbles by high cohesive force. Therefore, the laminate for a touch panel of the present invention can achieve almost no foaming as described above.

此外，就觸控面板用層合體而言，若將構件放置於耐久試驗條件(例如，85℃、85%)，則會有如第6圖所示，由支撐物側及末端部滲入水分之情形。雖然於高溫條件下，已滲入的水分並不會析出，但溫度若是下降，所滲入的水 分會析出，並形成目視可見的大小之液滴，故觸控面板用層合體會白化、霧度會顯著劣化。 In addition, in the laminate for a touch panel, if the member is placed under endurance test conditions (for example, 85 ° C, 85%), as shown in Fig. 6, the water is infiltrated from the support side and the end portion. . Although the water that has penetrated does not precipitate under high temperature conditions, if the temperature is lowered, the water infiltrated The fractions are precipitated and formed into droplets of a visible size, so that the laminate for the touch panel is whitened and the haze is significantly deteriorated.

然而，形成本發明觸控面板用層合體之黏著劑層係藉由具有特定之組成，而非常不易從支撐物層或末端部滲入水分，極不易發生白化現象造成之霧度劣化。 However, the adhesive layer forming the laminate for a touch panel of the present invention has a specific composition, and it is extremely difficult to infiltrate moisture from the support layer or the end portion, and the haze which is less likely to cause whitening is deteriorated.

此外，本發明之黏著劑組成物中實質上未含酸性基，故即使該黏著劑組成物直接接觸金屬或是金屬氧化物之透明導電膜、透明電極膜之電阻值變化最大仍為10%左右，此變化量係在驅動觸控面板方面完全不造成問題之量。 In addition, the adhesive composition of the present invention does not substantially contain an acidic group, so even if the adhesive composition directly contacts the metal or the metal oxide, the transparent conductive film and the transparent electrode film have a maximum change in resistance value of about 10%. This amount of change is not a problem in driving the touch panel at all.

如上所述，本發明之觸控面板用層合體，係採用含有具有特定組成之重量平均分子量5萬以上未達40萬之(甲基)丙烯酸系聚合物(A)、與交聯劑(B)之黏著劑組成物作為黏著劑，以黏著支撐物與透明導電性膜，其係具有優異的形態順應性，而在形成於邊緣部之框緣印刷部分不形成空隙，此外，可抑制因捲入及因排氣造成的兩種發泡，此外，由於無水分之浸入，故黏著劑層也不會白化而發生霧度劣化之問題。 As described above, the laminate for a touch panel of the present invention is a (meth)acrylic polymer (A) having a weight average molecular weight of 50,000 or more and having a specific composition of less than 400,000, and a crosslinking agent (B). The adhesive composition is used as an adhesive to adhere the support to the transparent conductive film, which has excellent form conformability, and does not form voids in the printing portion formed at the edge of the edge portion, and can suppress the volume Both the foaming and the two types of foaming due to the exhaust gas are caused by the absence of moisture, so that the adhesive layer is not whitened and the haze is deteriorated.

(實施例) (Example)

其次，係以本發明之實施例進一步詳細地說明本發明，惟本發明並不限定於該等實施例。 The invention is further described in detail by way of examples of the invention, but the invention is not limited thereto.

藉由以下所示方法，進行黏著劑的物性之測定及評估。 The measurement and evaluation of the physical properties of the adhesive were carried out by the method shown below.

[測定方法] [test methods] <水蒸氣穿透率> <Water vapor transmission rate>

依照JIS Z 0208之「防濕包裝材料之穿透濕度試驗方 法」進行測定。 According to JIS Z 0208, "Penetration test method for moisture-proof packaging materials" The method is measured.

具體而言，於所欲測定的各個單體製造重量平均分子量50萬之均聚物，以乾燥後之厚度成為50μm之方式塗裝於經剝離處理之聚對苯二甲酸乙二酯(PET)薄膜上，並用80℃之乾燥機使其乾燥2分鐘，得到黏著片。於黏著片的黏著劑面貼合濾紙後，將經剝離處理之PET薄膜剝離，以黏著面覆於放有吸濕劑之專用圓筒的筒口並加以固定，於40℃，90%RH環境下靜置48小時，而由吸濕劑之質量變化算出水蒸氣穿透率。 Specifically, a homopolymer having a weight average molecular weight of 500,000 is produced for each monomer to be measured, and is applied to the release-treated polyethylene terephthalate (PET) so as to have a thickness of 50 μm after drying. The film was dried by a dryer at 80 ° C for 2 minutes to obtain an adhesive sheet. After adhering the filter paper to the adhesive surface of the adhesive sheet, the peeled PET film is peeled off, and the adhesive surface is covered on the nozzle of the special cylinder with the moisture absorbent, and fixed at 40 ° C, 90% RH environment. After standing for 48 hours, the water vapor transmission rate was calculated from the change in the mass of the moisture absorbent.

WVTR(g/m2‧日)=質量變化(g)/(透濕面積(m2)×時間(日)) WVTR (g/m 2 ‧ day) = mass change (g) / (moisture permeability area (m 2 ) × time (day))

<重量平均分子量> <weight average molecular weight>

用膠體滲透層析(Gel Permeation Chromatography，GPC)、求得標準聚苯乙烯換算之重量平均分子量(Mw)及數量平均分子量(Mn)。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined by gel permeation chromatography (GPC).

測定條件 Measuring condition

裝置：HLC-8120(TOSOH股份有限公司製) Device: HLC-8120 (manufactured by TOSOH Co., Ltd.)

管柱：G7000HXL(TOSOH股份有限公司製)GMHXL(TOSOH股份有限公司製)G2500HXL(TOSOH股份有限公司製) Pipe column: G7000HXL (manufactured by TOSOH Co., Ltd.) GMHXL (manufactured by TOSOH Co., Ltd.) G2500HXL (manufactured by TOSOH Co., Ltd.)

試樣濃度：1.5mg/ml(以四氫呋喃稀釋) Sample concentration: 1.5 mg/ml (diluted with tetrahydrofuran)

移動相溶劑：四氫呋喃 Mobile phase solvent: tetrahydrofuran

流速：1.0ml/分鐘 Flow rate: 1.0ml/min

管柱溫度：40℃ Column temperature: 40 ° C

<濕熱白化性> <Damp heat whitening>

將裁切為50mm×60mm之實施例及比較例所得到的黏著片(黏著劑層之厚度50μm)貼附於經異丙醇擦拭之聚碳酸酯板，於50℃×5 atm以高壓釜(autoclave)進行處理20分鐘。其次，於室溫靜置1小時後，在85℃，85%RH環境下放置500小時，並在23℃，65%RH靜置1小時後，使用霧度計HM-150(村上色彩研究所股份有限公司製)依照JIS K 7361測定霧度，評估黏著劑層之白化。 The adhesive sheets obtained by the examples and the comparative examples cut into 50 mm × 60 mm (the thickness of the adhesive layer of 50 μm) were attached to a polycarbonate sheet wiped with isopropyl alcohol, and autoclaved at 50 ° C × 5 atm ( Autoclave) for 20 minutes. Next, after standing at room temperature for 1 hour, it was allowed to stand at 85 ° C, 85% RH for 500 hours, and after standing at 23 ° C, 65% RH for 1 hour, using a haze meter HM-150 (Murata Color Research Institute) Co., Ltd.) The haze of the adhesive layer was evaluated by measuring the haze according to JIS K 7361.

<發泡性> <foaming property>

將裁切為50mm×60mm之實施例及比較例所得到的黏著片(黏著劑層之厚度50μm)貼附於經異丙醇擦拭之聚碳酸酯板，於50℃×5 atm以高壓釜進行處理20分鐘。其次，於室溫靜置1小時後，在85℃，85%RH環境下放置500小時，並在23℃，65%RH靜置1小時後，以目視確認黏著劑層有無發泡。評估基準係如以下所示。 The adhesive sheets (thickness of the adhesive layer 50 μm) obtained by the examples and the comparative examples cut into 50 mm × 60 mm were attached to a polycarbonate sheet wiped with isopropyl alcohol, and were autoclaved at 50 ° C × 5 atm. Handle for 20 minutes. Next, after standing at room temperature for 1 hour, it was allowed to stand at 85 ° C, 85% RH for 500 hours, and after standing at 23 ° C and 65% RH for 1 hour, the presence or absence of foaming of the adhesive layer was visually confirmed. The evaluation criteria are as follows.

(評估)　　　(內容) (assessment) (content)

○：無法以目視確認於黏著劑層之氣泡。 ○: Bubbles in the adhesive layer could not be visually confirmed.

△：可以目視確認少許氣泡。 △: A small amount of bubbles can be visually confirmed.

×：可確認到大的氣泡。此外，黏著劑層從基材或黏附物浮起。 ×: A large bubble can be confirmed. In addition, the adhesive layer floats from the substrate or the adhesive.

<ITO腐蝕性> <ITO Corrosivity>

將實施例及比較例所得到的黏著片裁切為10mm×60mm，貼附至裁切為10mm×100mm之ITO蒸鍍PET薄膜，於50℃×5 atm以高壓釜進行處理20分鐘。其次，於室溫靜置1小時後，在60℃，90%RH環境下放置500小時、並在 23℃，65%RH靜置1小時後，測定ITO蒸鍍薄膜之電阻值，與事先測定之耐久試驗前的電阻值相比較，求得電阻值之變化率。又，電阻值之測定值係使用試驗機(三和電氣計器股份有限公司製，Digital Multimeter PC510)。 The adhesive sheets obtained in the examples and the comparative examples were cut into 10 mm × 60 mm, attached to an ITO vapor-deposited PET film cut to 10 mm × 100 mm, and treated in an autoclave at 50 ° C × 5 atm for 20 minutes. Next, after standing at room temperature for 1 hour, it was allowed to stand at 60 ° C, 90% RH for 500 hours, and After standing at 23 ° C and 65% RH for 1 hour, the resistance value of the ITO vapor-deposited film was measured, and the rate of change of the resistance value was determined in comparison with the resistance value before the endurance test measured in advance. Further, the measured value of the resistance value was a test machine (Digital Multimeter PC510, manufactured by Sanwa Electric Co., Ltd.).

<塗裝性> <paintability>

將實施例及比較例所得到的黏著劑組成物以乾燥後厚度成為200μm之方式塗裝至厚度38μm之聚對苯二甲酸乙二酯(PET)薄膜，以80℃乾燥2分鐘後，以目視確認塗膜表面。 The adhesive composition obtained in the examples and the comparative examples was applied to a polyethylene terephthalate (PET) film having a thickness of 38 μm so as to have a thickness of 200 μm after drying, and dried at 80 ° C for 2 minutes, and visually observed. Confirm the surface of the coating film.

○：塗膜表面光滑而無氣泡或粗糙 ○: The surface of the coating film is smooth without bubbles or roughness

×：塗膜表面可見到氣泡或粗糙 ×: Bubbles or roughness are visible on the surface of the coating film.

[製造例1] [Manufacturing Example 1]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物1。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 1 having a weight average molecular weight of 300,000.

[製造例2] [Manufacturing Example 2]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反 應裝置中，裝入丙烯酸月桂酯(LA)80重量份、丙烯酸正丁酯(BA)11重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 With a blender, reflux condenser, thermometer and nitrogen inlet tube In the apparatus, 80 parts by weight of lauryl acrylate (LA), 11 parts by weight of n-butyl acrylate (BA), 7 parts by weight of 2-hydroxyethyl acrylate (2-HEA), and 2 parts by weight of acrylamide (AM) were charged. The solvent, 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.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物2。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 2 having a weight average molecular weight of 300,000.

[製造例3] [Manufacturing Example 3]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入甲基丙烯酸月桂酯(LMA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 lauryl methacrylate (LMA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate ( 7 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物3。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 3 having a weight average molecular weight of 300,000.

[製造例4] [Manufacturing Example 4]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸環己酯(CHA)60重量份、丙烯酸正 丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 cyclohexyl acrylate (CHA) was charged, and acrylic acid was added. 31 parts by weight of butyl ester (BA), 7 parts by weight of 2-hydroxyethyl acrylate (2-HEA), 2 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc), and methyl ethyl ketone ( 20 parts by weight of MEK), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物4。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 4 having a weight average molecular weight of 300,000.

[製造例5] [Manufacturing Example 5]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸苯氧基乙酯(POA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 phenoxyethyl acrylate (POA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate were charged. 7 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.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物5。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 5 having a weight average molecular weight of 300,000.

[製造例6] [Manufacturing Example 6]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸2-乙基己酯(2-EHA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7 重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of 2-ethylhexyl acrylate (2-EHA), 31 parts by weight of n-butyl acrylate (BA), and 2-acrylic acid in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube Hydroxyethyl ester (2-HEA) 7 Parts 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.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物6。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 6 having a weight average molecular weight of 300,000.

[製造例7] [Manufacturing Example 7]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)32.9重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)0.1重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 32.9 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 0.1 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 to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物7。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 7 having a weight average molecular weight of 300,000.

[製造例8] [Manufacturing Example 8]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)28重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)5重量份、乙酸乙酯(EtAc)100重量份及甲基 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 lauryl acrylate (LA), 28 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 7 parts by weight, 5 parts by weight of acrylamide (AM), 100 parts by weight of ethyl acetate (EtAc) and methyl 20 parts by weight of ethyl ketone (MEK) was heated to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物8。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 8 having a weight average molecular weight of 300,000.

[製造例9] [Manufacturing Example 9]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯酸二甲基胺基乙酯(DMAEA)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 2 parts by weight of dimethylaminoethyl acrylate (DMAEA), 100 parts by weight of ethyl acetate (EtAc) and 20 parts by weight of methyl ethyl ketone (MEK), and the temperature is raised to 70 while introducing nitrogen gas. °C.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物9。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 9 having a weight average molecular weight of 300,000.

[製造例10] [Manufacturing Example 10]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、正乙烯吡咯啶酮(n-VP)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫 至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 2 parts by weight of n-vinylpyrrolidone (n-VP), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), and heated while introducing nitrogen gas Up to 70 ° C.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物10。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 10 having a weight average molecular weight of 300,000.

[製造例11] [Manufacturing Example 11]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯嗎啉(ACMO)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 2 parts by weight of propylene morpholine (ACMO), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物11。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 11 having a weight average molecular weight of 300,000.

[製造例12] [Manufacturing Example 12]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)37.5重量份、丙烯酸2-羥基乙酯(2-HEA)0.5重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 lauryl acrylate (LA), 37.5 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 0.5 parts 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), and the temperature is raised while introducing nitrogen gas. 70 ° C.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物12。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 12 having a weight average molecular weight of 300,000.

[製造例13] [Manufacturing Example 13]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)28重量份、丙烯酸2-羥基乙酯(2-HEA)10重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 lauryl acrylate (LA), 28 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 10 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物13。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 13 having a weight average molecular weight of 300,000.

[製造例14] [Manufacturing Example 14]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、及甲基乙基酮(MEK)120重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 2 parts by weight of acrylamide (AM), and 120 parts by weight of methyl ethyl ketone (MEK), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮 環境下於70℃進行聚合反應5小時。 Next, 0.2 parts by weight of azobisisobutyronitrile (AIBN) was added in the nitrogen The polymerization was carried out at 70 ° C for 5 hours under the environment.

反應結束後，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量10萬之丙烯酸系聚合物14。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 14 having a weight average molecular weight of 100,000.

[製造例15] [Manufacturing Example 15]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)110重量份及甲基乙基酮(MEK)10重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 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 the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量40萬之丙烯酸系聚合物15。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 15 having a weight average molecular weight of 400,000.

[製造例16] [Manufacturing Example 16]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸甲酯(MA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 methyl acrylate (MA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 7 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固 形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物16。 After the reaction was completed, the reaction solution was diluted with ethyl acetate (EtAc) to adjust the solid. The component concentration was 30%, and an acrylic polymer 16 having a weight average molecular weight of 300,000 was obtained.

[製造例17] [Manufacturing Example 17]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸乙酯(EA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 ethyl acrylate (EA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 7 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物17。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 17 having a weight average molecular weight of 300,000.

[製造例18] [Manufacturing Example 18]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸正丁酯(BA)91重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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, 91 parts by weight of n-butyl acrylate (BA), 7 parts by weight of 2-hydroxyethyl acrylate (2-HEA), and acrylamide ( 2 parts by weight of AM, 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物18。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 18 having a weight average molecular weight of 300,000.

[製造例19] [Manufacturing Example 19]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)45重量份、丙烯酸正丁酯(BA)46重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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, 45 parts by weight of lauryl acrylate (LA), 46 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 7 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物19。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 19 having a weight average molecular weight of 300,000.

[製造例20] [Manufacturing Example 20]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)30重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、丙烯酸(AA)1重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 30 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 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), while introducing nitrogen gas Warm to 70 °C.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物20。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 20 having a weight average molecular weight of 300,000.

[製造例21] [Manufacturing Example 21]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)2重量份、及乙酸乙酯(EtAc)120重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 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.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量50萬之丙烯酸系聚合物21。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 21 having a weight average molecular weight of 500,000.

[製造例22] [Manufacturing Example 22]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)31重量份、丙烯酸2-羥基乙酯(2-HEA)7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 lauryl acrylate (LA), 31 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 2 parts by weight of acrylamide (AM), and 180 parts by weight of methyl ethyl ketone (MEK), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量3萬之丙烯酸系聚合物22。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 22 having a weight average molecular weight of 30,000.

[製造例23] [Manufacturing Example 23]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁 酯(BA)33重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA) and butyl acrylate in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 33 parts by weight of ester (BA), 7 parts by weight of 2-hydroxyethyl acrylate (2-HEA), 100 parts by weight of ethyl acetate (EtAc), and 20 parts by weight of methyl ethyl ketone (MEK), and heated while introducing nitrogen gas. Up to 70 ° C.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物23。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 23 having a weight average molecular weight of 300,000.

[製造例24] [Manufacturing Example 24]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)26重量份、丙烯酸2-羥基乙酯(2-HEA)7重量份、丙烯醯胺(AM)7重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至50℃。 60 parts by weight of lauryl acrylate (LA), 26 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube) HEA) 7 parts by weight, 7 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 to 50 ° C while introducing nitrogen gas.

其次，加入0.6重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應8小時。 Next, 0.6 parts by weight of azobisisobutyronitrile (AIBN) was added, and polymerization was carried out at 70 ° C for 8 hours under a nitrogen atmosphere.

反應結束後，以己烷(HEX)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物24。 After completion of the reaction, the reaction liquid was diluted with hexane (HEX) to adjust the solid content concentration to 30% to obtain an acrylic polymer 24 having a weight average molecular weight of 300,000.

[製造例25] [Manufacturing Example 25]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)38重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(MEK)20重量份，一邊導入氮氣一邊昇溫至70℃。 60 parts by weight of lauryl acrylate (LA), 38 parts by weight of n-butyl acrylate (BA), and 2 parts by weight of acrylamide (AM) were placed in a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. 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.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物25。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 25 having a weight average molecular weight of 300,000.

[製造例26] [Manufacturing Example 26]

在具備攪拌機、回流冷凝器、溫度計及氮導入管之反應裝置中，裝入丙烯酸月桂酯(LA)60重量份、丙烯酸正丁酯(BA)27重量份、丙烯酸2-羥基乙酯(2-HEA)11重量份、丙烯醯胺(AM)2重量份、乙酸乙酯(EtAc)100重量份及甲基乙基酮(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 lauryl acrylate (LA), 27 parts by weight of n-butyl acrylate (BA), and 2-hydroxyethyl acrylate (2- HEA) 11 parts 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), and the temperature was raised to 70 ° C while introducing nitrogen gas.

其次，加入0.2重量份之偶氮雙異丁腈(AIBN)，在氮環境下於70℃進行聚合反應5小時。 Next, 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，以乙酸乙酯(EtAc)稀釋反應液，調整固形分濃度為30%，得到重量平均分子量30萬之丙烯酸系聚合物26。 After completion of the reaction, the reaction liquid was diluted with ethyl acetate (EtAc) to adjust the solid content concentration to 30% to obtain an acrylic polymer 26 having a weight average molecular weight of 300,000.

[實施例1] [Example 1]

對於100重量份之製造例1所得之丙烯酸系聚合物1，混合三羥甲基丙烷加成型二異氰酸伸茬酯之TAKENATE D-110N(三井化學公司製)0.4重量份(固形分)作為交聯劑，得到黏著劑組成物。 For 100 parts by weight of the acrylic polymer 1 obtained in Production Example 1, 0.4 parts by weight (solid content) of TAKENATE D-110N (manufactured by Mitsui Chemicals, Inc.) containing trimethylolpropane and diisocyanate was added as A crosslinking agent to obtain an adhesive composition.

將所得到的黏著劑組成物，以乾燥後之厚度成為50μm之方式塗裝覦經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，去除溶劑並形成黏著劑層。將 經剝離處理之PET薄膜貼合在相對於與黏著劑層之PET薄膜相接之面的表面，並於23℃，65%環境下進行熟化(aging)7天，得到黏著片。 The obtained adhesive composition was applied onto a peeled polyethylene terephthalate (PET) film by drying to a thickness of 50 μm, and dried at 80 ° C for 2 minutes to remove the solvent and form. Adhesive layer. will 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 carried out for 7 days at 23 ° C in a 65% environment to obtain an adhesive sheet.

[實施例2] [Embodiment 2]

除了使用100重量份之製造例2所得之丙烯酸系聚合物2，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 obtained in Production Example 2 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例3] [Example 3]

除了使用100重量份之製造例3所得之丙烯酸系聚合物3，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 obtained in Production Example 3 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例4] [Example 4]

除了使用100重量份之製造例4所得之丙烯酸系聚合物4，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 obtained in Production Example 4 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例5] [Example 5]

除了使用100重量份之製造例5所得之丙烯酸系聚合物5，以取代100重量份之丙烯酸系聚合物以外，與實施例1以相同方式，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 5 obtained in Production Example 5 was used instead of 100 parts by weight of the acrylic polymer.

[實施例6] [Embodiment 6]

除了使用100重量份之製造例6所得之丙烯酸系聚合物6，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 6 obtained in Production Example 6 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例7] [Embodiment 7]

除了使用100重量份之製造例7所得之丙烯酸系聚合物7，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 7 obtained in Production Example 7 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例8] [Embodiment 8]

除了使用100重量份之製造例8所得之丙烯酸系聚合物8，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 8 obtained in Production Example 8 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例9] [Embodiment 9]

除了使用100重量份之製造例9所得之丙烯酸系聚合物9，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 9 obtained in Production Example 9 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例10] [Embodiment 10]

除了使用100重量份之製造例10所得之丙烯酸系聚合物10，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 10 obtained in Production Example 10 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例11] [Example 11]

除了使用100重量份之製造例11所得之丙烯酸系聚合物11，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 11 obtained in Production Example 11 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例12] [Embodiment 12]

除了使用100重量份之製造例12所得之丙烯酸系聚合物12，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 12 obtained in Production Example 12 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例13] [Example 13]

除了使用100重量份之製造例13所得之丙烯酸系聚合物13，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 13 obtained in Production Example 13 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例14] [Embodiment 14]

除了使用100重量份之製造例14所得之丙烯酸系聚合物14，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 14 obtained in Production Example 14 was used instead of 100 parts by weight of the acrylic polymer 1.

[實施例15] [Example 15]

除了使用100重量份之製造例15所得之丙烯酸系聚合物15，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 15 obtained in Production Example 15 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例1] [Comparative Example 1]

除了使用100重量份之製造例16所得之丙烯酸系聚合物16，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 16 obtained in Production Example 16 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例2] [Comparative Example 2]

除了使用100重量份之製造例17所得之丙烯酸系聚合物17，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 17 obtained in Production Example 17 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例3] [Comparative Example 3]

除了使用100重量份之製造例18所得之丙烯酸系聚合物18，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 18 obtained in Production Example 18 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例4] [Comparative Example 4]

除了使用100重量份之製造例19所得之丙烯酸系聚合物19，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 19 obtained in Production Example 19 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例5] [Comparative Example 5]

除了使用100重量份之製造例20所得之丙烯酸系聚合物20，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 20 obtained in Production Example 20 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例6] [Comparative Example 6]

除了使用100重量份之，製造例21所得之丙烯酸系聚合物21，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 21 obtained in Production Example 21 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例7] [Comparative Example 7]

除了使用100重量份之製造例22所得之丙烯酸系聚合物22，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 22 obtained in Production Example 22 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例8] [Comparative Example 8]

除了使用100重量份之製造例23所得之丙烯酸系聚合物23，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 23 obtained in Production Example 23 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例9] [Comparative Example 9]

除了使用100重量份之製造例24所得之丙烯酸系聚合物24，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 24 obtained in Production Example 24 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例10] [Comparative Example 10]

除了使用100重量份之製造例25所得之丙烯酸系聚合物25，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 25 obtained in Production Example 25 was used instead of 100 parts by weight of the acrylic polymer 1.

[比較例11] [Comparative Example 11]

除了使用100重量份之製造例26所得之丙烯酸系聚合物26，以取代100重量份之丙烯酸系聚合物1以外，與實施例1以相同方式，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 26 obtained in Production Example 26 was used instead of 100 parts by weight of the acrylic polymer 1.

表2中之代稱係如以下所示。 The nomenclature in Table 2 is as follows.

LA．．．丙烯酸月桂酯 LA. . . Lauryl acrylate

LMA．．．甲基丙烯酸月桂酯 LMA. . . Lauryl methacrylate

CHA．．．丙烯酸環己酯 CHA. . . Cyclohexyl acrylate

POA．．．丙烯酸苯氧基乙酯 POA. . . Phenoxyethyl acrylate

2EHA．．．丙烯酸2-乙基己酯 2EHA. . . 2-ethylhexyl acrylate

MA．．．丙烯酸甲酯 MA. . . Methyl acrylate

EA．．．丙烯酸乙酯 EA. . . Ethyl acrylate

BA．．．丙烯酸丁酯 BA. . . Butyl acrylate

2-HEA．．．丙烯酸2-羥基乙酯 2-HEA. . . 2-hydroxyethyl acrylate

AA．．．丙烯酸 AA. . . acrylic acid

DMAEA．．．丙烯酸二甲基胺基乙基甲酯 DMAEA. . . Dimethylaminoethyl acrylate

AM．．．丙烯醯胺 AM. . . Acrylamide

n-VP．．．正乙烯吡咯啶酮 n-VP. . . Vinylpyrrolidone

ACMO．．．丙烯醯嗎啉 ACMO. . . Propylene morpholine

D-110N．．．二異氰酸伸茬酯之三羥甲基丙烷加成物(三井化學公司製) D-110N. . . Trimethylolpropane adduct of diisocyanate diacetate (manufactured by Mitsui Chemicals, Inc.)

此外，表2中，Mw的單位為萬。以聚合所使用之全部單體為100重量份。 In addition, in Table 2, the unit of Mw is 10,000. 100 parts by weight of all the monomers used for the polymerization.

10-1‧‧‧電阻膜式觸控面板單元 10-1‧‧‧Resistive film type touch panel unit

10-2‧‧‧靜電容量式觸控面板單元 10-2‧‧‧Electrostatic touch panel unit

11-1‧‧‧上部層合體 11-1‧‧‧Upper laminate

13-1‧‧‧下部層合體 13-1‧‧‧Lower laminate

15-1‧‧‧上部層合體 15-1‧‧‧Upper laminate

15-2‧‧‧下部層合體 15-2‧‧‧Lower laminate

21-1‧‧‧表面支撐物 21-1‧‧‧Surface support

21-2‧‧‧深部的表面支撐物 21-2‧‧‧Deep surface support

23-1、23-2‧‧‧黏著劑層 23-1, 23-2‧‧‧Adhesive layer

25-1‧‧‧上部電極支撐物 25-1‧‧‧Upper electrode support

25-2‧‧‧下部電極支撐物 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‧‧‧間隔件 32‧‧‧ spacers

34‧‧‧間隙 34‧‧‧ gap

51-1、51-2‧‧‧表面支撐物 51-1, 51-2‧‧‧ surface support

53-1、53-2‧‧‧黏著劑層 53-1, 53-2‧‧‧Adhesive layer

57-1、57-2‧‧‧透明導電膜 57-1, 57-2‧‧‧ Transparent conductive film

60‧‧‧中央支撐物 60‧‧‧ central support

62‧‧‧框緣印刷部分 62‧‧‧ frame printing section

64‧‧‧空隙 64‧‧‧ gap

66‧‧‧氣泡 66‧‧‧ bubbles

68‧‧‧泡體 68‧‧‧ bubble

第1圖係表示組裝有本發明之觸控面板用層合體之電阻膜式觸控面板之觸控面板單元之例的示意性剖面圖。 1 is a schematic cross-sectional view showing an example of a touch panel unit in which a resistive film type touch panel of a touch panel for a touch panel of the present invention is incorporated.

第2圖係表示組裝有本發明之觸控面板用層合體之靜電容量式觸控面板之觸控面板單元之例的示意性剖面圖。 2 is a schematic cross-sectional view showing an example of a touch panel unit of a capacitance type touch panel in which the laminate for a touch panel of the present invention is incorporated.

第3圖係示意性表示靜電容量式觸控面板之末端部之構成例的剖面圖。 Fig. 3 is a cross-sectional view schematically showing a configuration example of a distal end portion of a capacitance type touch panel.

第4圖(a)及(b)係表示對於形成在觸控面板之末端部之框緣印刷部分的黏著片之黏著狀態的示意性剖面圖。 Fig. 4 (a) and (b) are schematic cross-sectional views showing an adhesive state of an adhesive sheet formed on a printing portion of a frame edge of a distal end portion of a touch panel.

第5圖係用以說明觸控面板用層合體所發生之發泡狀態的剖面圖。 Fig. 5 is a cross-sectional view for explaining a foaming state of a laminate for a touch panel.

第6圖係用以說明觸控面板用層合體所發生之白化現象的剖面圖。 Fig. 6 is a cross-sectional view for explaining a whitening phenomenon occurring in a laminate for a touch panel.

10-2‧‧‧靜電容量式觸控面板單元 10-2‧‧‧Electrostatic touch panel unit

15-1‧‧‧上部層合體 15-1‧‧‧Upper laminate

15-2‧‧‧下部層合體 15-2‧‧‧Lower laminate

51-1、51-2‧‧‧表面支撐物 51-1, 51-2‧‧‧ surface support

53-1、53-2‧‧‧黏著劑層 53-1, 53-2‧‧‧Adhesive layer

57-1、57-2‧‧‧透明導電膜 57-1, 57-2‧‧‧ Transparent conductive film

60‧‧‧中央支撐物 60‧‧‧ central support

Claims (17)

一種黏著劑組成物，係用於貼合導電膜，其含有丙烯酸系聚合物(A)與交聯劑(B)，該丙烯酸系聚合物(A)係將包含下述成分(a-1)、(a-2)及(a-3)之單體共聚合而得之實質上不具有酸性基，且重量平均分子量為5萬以上未達40萬者；以全部單體為100重量%計，(a-1)(甲基)丙烯酸烷基酯，將其重量平均分子量50萬的均聚物以圓筒法測定，於40℃ 90%RH的水蒸氣穿透率為500g/m2‧日以下者：50重量%以上，(a-2)具有羥基之單體：0.5至10重量%，(a-3)含氮單體：0.1至5重量%。 An adhesive composition for bonding a conductive film comprising an acrylic polymer (A) and a crosslinking agent (B), the acrylic polymer (A) comprising the following component (a-1) The monomers of (a-2) and (a-3) are copolymerized to have substantially no acidic groups, and the weight average molecular weight is 50,000 or more and less than 400,000; and the total monomer is 100% by weight. (a-1) alkyl (meth)acrylate, which has a weight average molecular weight of 500,000 homopolymer measured by a cylinder method, and has a water vapor permeability of 500 g/m 2 at 40 ° C 90% RH. The following: 50% by weight or more, (a-2) a monomer having a hydroxyl group: 0.5 to 10% by weight, and (a-3) a nitrogen-containing monomer: 0.1 to 5% by weight. 如申請專利範圍第1項所述之黏著劑組成物，其中，形成前述(甲基)丙烯酸系聚合物(A)之(a-2)具有羥基的單體係含羥基之(甲基)丙烯酸酯。 The adhesive composition according to claim 1, wherein the (meth)acrylic polymer (A) (a-2) has a hydroxyl group-containing monohydroxy group-containing (meth)acrylic acid. ester. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中，形成前述(甲基)丙烯酸系聚合物(A)之(甲基)丙烯酸烷基酯(a-1)係具有脂肪族環或芳香族環。 The adhesive composition according to claim 1 or 2, wherein the alkyl (meth)acrylate (a-1) having the (meth)acrylic polymer (A) is formed Aliphatic or aromatic ring. 如申請專利範圍第3項所述之黏著劑組成物，其中，前述脂肪族環及芳香族環係單環結構。 The adhesive composition according to claim 3, wherein the aliphatic ring and the aromatic ring are monocyclic structures. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中，前述(甲基)丙烯酸烷基酯(a-1)的烷基之碳數為8至22。 The adhesive composition according to claim 1 or 2, wherein the alkyl group of the alkyl (meth)acrylate (a-1) has a carbon number of 8 to 22. 如申請專利範圍第5項所述之黏著劑組成物，其中，前 述(甲基)丙烯酸烷基酯(a-1)的烷基之碳數為10至22。 An adhesive composition as described in claim 5, wherein the former The alkyl group of the alkyl (meth)acrylate (a-1) has a carbon number of 10 to 22. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中，前述黏著劑組成物係與金屬或金屬氧化物直接接觸之靜電容量式觸控面板用之黏著劑組成物。 The adhesive composition according to the first or second aspect of the invention, wherein the adhesive composition is an adhesive composition for a capacitive touch panel in direct contact with a metal or a metal oxide. 一種黏著片，其係具有基材、與層合於該基材上之包含申請專利範圍第1項至第7項中任一項所述之黏著劑組成物的黏著劑層。 An adhesive sheet comprising a substrate, and an adhesive layer comprising the adhesive composition according to any one of claims 1 to 7 laminated on the substrate. 如申請專利範圍第8項所述之黏著片，其中，前述基材係經施行剝離處理之保護膜(cover film)。 The adhesive sheet according to claim 8, wherein the substrate is a cover film subjected to a release treatment. 一種觸控面板用層合體，係將表面支撐物，包含申請專利範圍第1項至第7項中任一項所述之黏著劑組成物之黏著劑層，包含金屬、金屬氧化物或是附電極支撐物的金屬或金屬氧化物之透明導電膜，依上述順序層合而成。 A laminate for a touch panel, comprising a surface support, comprising an adhesive layer of an adhesive composition according to any one of claims 1 to 7, comprising a metal, a metal oxide or a coating A transparent conductive film of a metal or metal oxide of the electrode support is laminated in the above-described order. 如申請專利範圍第10項所述之觸控面板用層合體，其中，前述黏著劑層之厚度係10至1000μm。 The laminate for a touch panel according to claim 10, wherein the thickness of the adhesive layer is 10 to 1000 μm. 如申請專利範圍第10項或第11項所述之觸控面板用層合體，其中，前述觸控面板用層合體係形成靜電容量式觸控面板之構件者。 The laminate for a touch panel according to the invention of claim 10, wherein the laminate system for a touch panel forms a member of a capacitive touch panel. 如申請專利範圍第10項或第11項所述之觸控面板用層合體，其係在前述表面支撐物之與前述黏著劑層相對之面的邊緣部進行框緣印刷。 The laminate for a touch panel according to claim 10, wherein the edge of the surface support opposite to the adhesive layer is edge-printed. 如申請專利範圍第13項所述之觸控面板用層合體，其中，前述框緣印刷之厚度係於10至50μm之範圍內。 The laminate for a touch panel according to claim 13, wherein the thickness of the frame printing is in the range of 10 to 50 μm. 如申請專利範圍第10項或第11項所述之觸控面板用層合體，其中，前述透明導電膜係使用ITO或是ATO作為金屬氧化物之配線圖案，該配線圖案係直接接觸前述黏著劑層。 The laminate for a touch panel according to claim 10, wherein the transparent conductive film uses ITO or ATO as a wiring pattern of a metal oxide, and the wiring pattern directly contacts the adhesive. Floor. 如申請專利範圍第10項或第11項所述之觸控面板用層合體，其中，前述表面支撐物之厚度係於25至2000μm之範圍內。 The laminate for a touch panel according to claim 10, wherein the thickness of the surface support is in the range of 25 to 2000 μm. 如申請專利範圍第10項至或第11項所述之觸控面板用層合體，其中，前述透明導電膜之厚度係於10至100nm之範圍內。 The laminate for a touch panel according to claim 10, wherein the thickness of the transparent conductive film is in the range of 10 to 100 nm.
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