TWI513786B - Non-crosslinking adhesive composition and adhesive sheet - Google Patents

Non-crosslinking adhesive composition and adhesive sheet Download PDF

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Publication number
TWI513786B
TWI513786B TW103107658A TW103107658A TWI513786B TW I513786 B TWI513786 B TW I513786B TW 103107658 A TW103107658 A TW 103107658A TW 103107658 A TW103107658 A TW 103107658A TW I513786 B TWI513786 B TW I513786B
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meth
acrylate
adhesive composition
adhesive
adhesion
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TW103107658A
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TW201439256A (en
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Satoru Kawata
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • 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
    • 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
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)

Description

非交聯性黏著組成物及黏著片Non-crosslinking adhesive composition and adhesive sheet 技術領域Technical field

本發明是有關於一種黏著片，其用在搬運、加工偏光板、液晶面板或顯示器用玻璃基板等光學構件或是半導體晶圓或半導體封裝體等電子零件時，黏貼於該等構件上以保其等免於刮傷、破損或污染之用途等。The present invention relates to an adhesive sheet for use in transporting, processing an optical member such as a polarizing plate, a liquid crystal panel or a glass substrate for a display, or an electronic component such as a semiconductor wafer or a semiconductor package, and adhering to the members to protect They are free from scratches, breakage or contamination.

背景技術Background technique

為了於搬運時或加工時保護而免於刮傷、破損或污染，光學構件或電子零件一般會進行黏貼黏著片。構成被黏著體的光學構件或電子零件從表面平滑者到粗面者，存在有各式各樣者，黏著片必須對該等之表面良好地黏合，且於結束搬運、加工時必須剝離且黏著劑不會殘留於被黏著體。In order to protect against scratching, breakage or contamination during handling or during processing, optical components or electronic components are generally adhered to the adhesive sheet. There are various types of optical members or electronic components constituting the adherend from the surface smoother to the rough surface. The adhesive sheet must be well bonded to the surface, and must be peeled off and adhered at the end of handling and processing. The agent does not remain in the adherend.

作為對各種構件之表面保護片，目前揭示有經久之黏著力變化優異之表面保護片(專利文獻1)。然而，專利文獻1所揭示之表面保護片具有黏著劑硬且對表面粗糙之被黏著體無法良好地黏合之問題。As a surface protection sheet for various members, a surface protection sheet excellent in adhesion change over a long period of time has been disclosed (Patent Document 1). However, the surface protection sheet disclosed in Patent Document 1 has a problem that the adhesive is hard and the adherend which is rough on the surface cannot be adhered well.

又，作為使用在矽晶圓之加工之黏著片，目前揭 示有具有優異之拾取性之黏著片(專利文獻2)。然而，由於專利文獻2所揭示之黏著片含有低分子成分，因此，會有於矽晶圓之切塊中晶片自黏著片剝離並飛散之情形，或是來自黏著劑之污染物殘留於矽晶圓之情形。Also, as an adhesive sheet used in the processing of tantalum wafers, it is currently disclosed. An adhesive sheet having excellent pick-up property is shown (Patent Document 2). However, since the adhesive sheet disclosed in Patent Document 2 contains a low molecular component, there is a case where the wafer is peeled off and scattered from the adhesive sheet in the dicing of the enamel wafer, or a contaminant from the adhesive remains in the twin crystal. The situation of the circle.

先行技術文獻Advanced technical literature 專利文獻Patent literature

專利文獻1：日本專利公開公報特開2010-42580號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2010-42580

專利文獻2：日本專利公開公報特開2008-60434號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-60434

發明揭示Invention

本發明是用以解決前述習知課題而完成，目的在提供一種黏著片，其無論對光學構件或電子零件等平滑表面或粗糙表面，密接性皆不會變化而可良好地黏合，且剝離時黏著劑不會殘留於被黏著體。The present invention has been made to solve the above-mentioned conventional problems, and an object of the invention is to provide an adhesive sheet which can be adhered well without peeling on a smooth surface or a rough surface such as an optical member or an electronic component, and is peeled off. The adhesive does not remain in the adherend.

為了達成前述目的，提供以下發明。In order to achieve the aforementioned object, the following invention is provided.

(1)一種非交聯性黏著組成物，其以(甲基)丙烯酸酯共聚物作為主成分，且前述(甲基)丙烯酸酯共聚物之重量平均分子量為70萬~200萬且分散度為5以下，而且未具有會與異氰酸酯系硬化劑或環氧系硬化劑反應之官能基。(1) A non-crosslinkable adhesive composition comprising a (meth) acrylate copolymer as a main component, and the (meth) acrylate copolymer has a weight average molecular weight of 700,000 to 2,000,000 and a dispersion degree of 5 or less, and does not have a functional group which will react with an isocyanate type hardener or an epoxy type hardener.

(2)如(1)之非交聯性黏著組成物，其中會與異氰酸酯系硬化劑或環氧系硬化劑反應之前述官能基為羧基或羥基。(2) The non-crosslinkable adhesive composition according to (1), wherein the aforementioned functional group which reacts with the isocyanate-based curing agent or the epoxy-based curing agent is a carboxyl group or a hydroxyl group.

(3)一種黏著片，係將如(1)或(2)之非交聯性黏著組成物積層於基材膜之至少單面而成者，且對表面粗度Rz為5μm之被黏著體之黏著力(A1)與對表面粗度Rz為0.5μm之被黏著體之黏著力(A2)滿足以下關係，即：A1/A2=0.8~1.2。(3) An adhesive sheet obtained by laminating a non-crosslinkable adhesive composition of (1) or (2) on at least one side of a base film, and an adherend having a surface roughness Rz of 5 μm. The adhesion (A1) and the adhesion (A2) to the adherend having a surface roughness Rz of 0.5 μm satisfy the following relationship: A1/A2 = 0.8 to 1.2.

藉由使用本發明之黏著片，密接性不會因被黏著體之表面粗度而變化，且可在剝離時不使黏著劑殘留於被黏著體。By using the adhesive sheet of the present invention, the adhesion is not changed by the surface roughness of the adherend, and the adhesive can be prevented from remaining on the adherend at the time of peeling.

1‧‧‧黏著片1‧‧‧Adhesive film

3‧‧‧基材膜3‧‧‧Base film

5‧‧‧非交聯性黏著組成物層5‧‧‧ Non-crosslinking adhesive composition layer

圖1是顯示本實施形態之黏著片1之截面圖。Fig. 1 is a cross-sectional view showing the adhesive sheet 1 of the present embodiment.

用以實施發明之形態Form for implementing the invention

以下，根據圖式，詳細地說明本發明之實施形態。Hereinafter, embodiments of the present invention will be described in detail based on the drawings.

圖1是顯示本實施形態之黏著片1之截面圖。黏著片1具有基材膜3及設置於基材膜3上之非交聯性黏著組成物層5。以下，說明各層之構造。Fig. 1 is a cross-sectional view showing the adhesive sheet 1 of the present embodiment. The adhesive sheet 1 has a base film 3 and a non-crosslinkable adhesive composition layer 5 provided on the base film 3. Hereinafter, the structure of each layer will be described.

<基材膜><Substrate film>

前述基材膜並無特殊之限制，可自以往公知之樹脂膜中適當地選擇、使用。具體而言，可列舉如：像是聚乙烯、聚丙烯、乙烯-丙烯共聚物及聚丁烯之聚烯烴、像是乙烯-醋酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物及乙烯-(甲基)丙烯酸酯共聚物之乙烯共聚物、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚甲基丙烯酸甲酯等之工程塑膠、軟質聚氯乙烯、半硬質聚氯乙烯、聚酯、聚胺基 甲酸酯、聚醯胺、聚醯亞胺天然橡膠及合成橡膠等之高分子材料。又，亦可為混合選自於該等群中之2種以上者或複層化者，且可依照與黏著組成物之接著性任意地選擇。The base film is not particularly limited, and can be appropriately selected and used from a conventionally known resin film. Specific examples thereof include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene, such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and ethylene. -Ethylene copolymer of (meth) acrylate copolymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate, etc., engineering plastic, soft polychlorinated Ethylene, semi-rigid polyvinyl chloride, polyester, polyamine Polymer materials such as formate, polyamide, polyamide, and synthetic rubber. Further, it may be a mixture of two or more types or stratified persons selected from the group, and may be arbitrarily selected in accordance with the adhesion to the adhesive composition.

前述基材膜之厚度並無特殊之限制，可依照使用目的適當地決定。一般為30~500μm，且宜為50~200μm。The thickness of the base film is not particularly limited and may be appropriately determined depending on the purpose of use. It is generally 30 to 500 μm, and preferably 50 to 200 μm.

<非交聯性黏著組成物><non-crosslinking adhesive composition>

積層於基材膜表面之非交聯性黏著組成物是以(甲基)丙烯酸酯共聚物作為主成分，且前述(甲基)丙烯酸酯共聚物之重量平均分子量為70萬~200萬且分散度為5以下，而且未具有會與異氰酸酯系硬化劑或環氧系硬化劑反應之官能基。另，「(甲基)丙烯酸」是指丙烯酸及/或甲基丙烯酸。又，所謂「主成分」是指非交聯性黏著組成物中的(甲基)丙烯酸酯共聚物之比例為50~100質量%，且該比例宜為80~100質量%。The non-crosslinkable adhesive composition laminated on the surface of the base film is a (meth) acrylate copolymer as a main component, and the weight average molecular weight of the (meth) acrylate copolymer is 700,000 to 2,000,000 and dispersed. The degree is 5 or less, and does not have a functional group which will react with an isocyanate type hardener or an epoxy type hardener. Further, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. In addition, the "main component" means that the ratio of the (meth) acrylate copolymer in the non-crosslinkable adhesive composition is 50 to 100% by mass, and the ratio is preferably 80 to 100% by mass.

舉例言之，構成本實施形態之(甲基)丙烯酸酯共聚物之單體成分可列舉如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸s-丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十五酯、(甲基) 丙烯酸十六酯、(甲基)丙烯酸十七酯、(甲基)丙烯酸十八酯等之(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯等之(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苯酯等之(甲基)丙烯酸芳基酯或(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸乙氧乙酯等之(甲基)丙烯酸烷氧基烷基酯及丙烯腈或甲基丙烯腈等之腈系單體等。(甲基)丙烯酸酯可單獨或組合2種以上來使用。For example, examples of the monomer component constituting the (meth) acrylate copolymer of the present embodiment include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl methacrylate, butyl (meth) acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (A) Ethyl acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, eleven (meth) acrylate, dodecyl (meth) acrylate, Tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (methyl) (meth)acrylic acid naphthyl ester such as hexadecyl acrylate, heptadecylate (meth) acrylate, octadecyl (meth) acrylate or the like; cyclohexyl (meth) acrylate a (meth)acrylic acid alkoxylate such as phenyl (meth)acrylate or methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate. An alkyl ester, a nitrile monomer such as acrylonitrile or methacrylonitrile, or the like. The (meth) acrylate may be used singly or in combination of two or more.

本實施形態之(甲基)丙烯酸酯共聚物未具有會 與異氰酸酯系硬化劑或環氧系硬化劑反應之官能基，因此，在未使用(甲基)丙烯酸等之含羧基單體，或(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸-6-羥己酯、(甲基)丙烯酸-8-羥辛酯、(甲基)丙烯酸-10-羥癸酯、(甲基)丙烯酸-12-羥月桂酯等之含羥基單體下即可聚合。即，意指本實施形態之(甲基)丙烯酸酯共聚物之酸值(JIS K0070中和滴定法)為0.1mgKOH/g以下，且羥值(JIS K0070中和滴定法)為0.1mgKOH/g以下。The (meth) acrylate copolymer of the present embodiment does not have a meeting a functional group reactive with an isocyanate-based curing agent or an epoxy-based curing agent. Therefore, a carboxyl group-containing monomer such as (meth)acrylic acid or 2-hydroxyethyl (meth)acrylate or (meth) is not used. 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, (meth)acrylic acid- The hydroxyl group-containing monomer such as 10-hydroxydecyl ester or (meth)acrylic acid-12-hydroxylauryl ester can be polymerized. In other words, the acid value (JIS K0070 neutralization titration method) of the (meth) acrylate copolymer of the present embodiment is 0.1 mgKOH/g or less, and the hydroxyl value (JIS K0070 neutralization titration method) is 0.1 mgKOH/g. the following.

舉例言之，異氰酸酯硬化劑可列舉如：甲苯二異 氰酸酯、氯伸苯基二異氰酸酯、六亞甲基二異氰酸酯、四亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、苯二甲基二異氰酸酯、二苯甲烷二異氰酸酯、加氫二苯甲烷二異氰酸酯等之異氰酸酯單體以及將該等異氰酸酯單體與三羥甲基丙烷等加成之加成物系異氰酸酯化合物；使三聚異氰酸酯化物、縮二脲型化合物進而是公知之聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇或聚異戊二烯多元醇等加成反應之胺基甲酸酯預聚合物型之異氰酸酯等。For example, an isocyanate hardener can be exemplified by: toluene dimer Cyanate ester, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane An isocyanate monomer such as a diisocyanate or an addition isocyanate compound obtained by adding such an isocyanate monomer to trimethylolpropane or the like; and a trimeric isocyanate compound and a biuret type compound are further known as a polyether polyol. And a urethane prepolymer type isocyanate which is an addition reaction such as a polyester polyol, an acrylic polyol, a polybutadiene polyol or a polyisoprene polyol.

舉例言之，環氧系硬化劑可列舉如：乙二醇二環 氧丙基醚、聚乙二醇二環氧丙基醚、丙三醇二環氧丙基醚、丙三醇三環氧丙基醚、1,6-己二醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、二環氧丙基苯胺、N,N,N’,N’-四環氧丙基-m-伸茬二胺、1,3-雙(N,N-二環氧丙基胺甲基)環己烷、N,N,N’,N’-四環氧丙基胺基苯甲烷、三環氧丙基三聚異氰酸酯、m-N,N-二環氧丙基胺苯基環氧丙基醚、N,N-二環氧丙基甲苯胺及N,N-二環氧丙基苯胺等。For example, an epoxy-based hardener may be exemplified by ethylene glycol bicyclo Oxypropyl propyl ether, polyethylene glycol diepoxypropyl ether, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, Trimethylolpropane triepoxypropyl ether, diepoxypropyl aniline, N,N,N',N'-tetraepoxypropyl-m-extension diamine, 1,3-double (N, N-diepoxypropylamine methyl)cyclohexane, N,N,N',N'-tetraepoxypropylaminophenylmethane, triepoxypropyl trimer isocyanate, mN,N-bicyclic Oxypropylamine phenylepoxypropyl ether, N,N-diepoxypropyltoluamide, N,N-diepoxypropylaniline, and the like.

本實施形態之(甲基)丙烯酸酯共聚物之重量平 均分子量(Mw)為70萬~200萬，且更宜為100~150萬。當重量平均分子量小於70萬時，會有剝離時黏著劑殘留於被黏著體之情形，當大於200萬時，對表面粗糙之被黏著體之密接性會明顯地降低，且密接性會因被黏著體之表面粗度而變化。The weight of the (meth) acrylate copolymer of this embodiment is flat The average molecular weight (Mw) is 700,000 to 2,000,000, and more preferably 100 to 1.5 million. When the weight average molecular weight is less than 700,000, the adhesive remains in the adherend when peeling off. When it is more than 2 million, the adhesion to the surface of the adhered body is remarkably lowered, and the adhesion is caused by the adhesion. The surface of the adhesive changes in thickness.

又，本實施形態之(甲基)丙烯酸酯共聚物之分散 度為5以下，且更宜為2.5~4。在此，所謂分散度是以數量平均分子量(Mn)除重量平均分子量(Mw)之值。當分散度大於5時，低分子成分對密接性之貢獻會變大，且剝離時黏著劑殘留於被黏著體之情形，或密接性因被黏著體之表面粗度而變化。又，分散度可藉由聚合方法、條件或聚合物之精製來降低，然而，由於生產成本會上升，因此，宜為2.5以上。另，重量平均分子量(Mw)及數量平均分子量(Mn)是藉由凝膠滲透層析法(GPC)所測定之聚苯乙烯換算分子量。Further, the dispersion of the (meth) acrylate copolymer of the present embodiment The degree is 5 or less, and more preferably 2.5 to 4. Here, the degree of dispersion is a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). When the degree of dispersion is more than 5, the contribution of the low molecular component to the adhesion is increased, and the adhesive remains in the adherend during peeling, or the adhesion changes due to the surface roughness of the adherend. Further, the degree of dispersion can be lowered by the polymerization method, the conditions, or the purification of the polymer. However, since the production cost rises, it is preferably 2.5 or more. Further, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-converted molecular weights measured by gel permeation chromatography (GPC).

本實施形態之(甲基)丙烯酸酯共聚物之製造方 法可藉由以往公知之手法來製造。舉例言之，可適當地選擇溶液聚合法、懸浮聚合法、塊狀聚合法、沉澱聚合法、乳化聚合法等之自由基聚合法。其中，由於乳化聚合法可製造分子量高且分散度狹小之聚合物，因此更為理想。自由基聚合起始劑可使用偶氮系、過氧化物系之各種公知者。Manufacturer of the (meth) acrylate copolymer of the present embodiment The method can be manufactured by a conventionally known method. For example, a radical polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, a precipitation polymerization method, an emulsion polymerization method, or the like can be appropriately selected. Among them, the emulsion polymerization method is preferable because it can produce a polymer having a high molecular weight and a small dispersion. As the radical polymerization initiator, various known examples of azo-based or peroxide-based compounds can be used.

非交聯性黏著組成物除了屬於主成分之(甲基) 丙烯酸酯共聚物之外，亦可於未脫離本發明之目的之範圍含有任意之適切添加劑。舉例言之，可列舉如：紫外線硬化樹脂、光聚合起始劑、紫外線吸收劑、黏著賦予劑、硬化劑、可塑劑、抗氧化劑、防帶電劑、聚合抑制劑、矽烷耦合劑、有機或無機填充劑等。Non-crosslinking adhesive composition except for the main component (methyl) In addition to the acrylate copolymer, any suitable additive may be contained in a range not departing from the object of the present invention. For example, examples thereof include an ultraviolet curing resin, a photopolymerization initiator, an ultraviolet absorber, an adhesion-imparting agent, a hardener, a plasticizer, an antioxidant, an antistatic agent, a polymerization inhibitor, a decane coupling agent, and an organic or inorganic agent. Filler, etc.

前述紫外線硬化樹脂是使用在藉由紫外線照射 使本發明之非交聯性黏著組成物硬化並輕易地進行剝離之情形。紫外線硬化樹脂並無特殊之限制，舉例言之，可列舉如：胺基甲酸酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯等。The aforementioned ultraviolet curing resin is used by ultraviolet irradiation The non-crosslinkable adhesive composition of the present invention is cured and easily peeled off. The ultraviolet curable resin is not particularly limited, and examples thereof include, for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether ( Methyl) acrylate or the like.

於藉由紫外線照射使本發明之非交聯性黏著組 成物硬化時，會添加光聚合起始劑。光聚合起始劑並無特殊之限制，舉例言之，可列舉如：安息香異丙醚、安息香異丁醚、二苯基酮、米其勒酮、氯噻噸酮、十二烷基噻噸酮、二甲基噻噸酮、二乙基噻噸酮、苄基二甲基縮酮、α-羥環己基苯基酮、2-羥甲基苯基丙烷等。Non-crosslinking adhesive group of the present invention by ultraviolet irradiation When the object hardens, a photopolymerization initiator is added. The photopolymerization initiator is not particularly limited, and examples thereof include benzoin isopropyl ether, benzoin isobutyl ether, diphenyl ketone, misch ketone, chlorothioxanthone, and dodecyl thioxanthene. Ketone, dimethyl thioxanthone, diethyl thioxanthone, benzyl dimethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl propane, and the like.

又，本發明之非交聯性黏著組成物可積層於基材 膜之至少單面而使用作為黏著片，且黏著片對被黏著體之 表面粗度Rz為5.0μm之被黏著體之黏著力(A1)與對表面粗度Rz為0.5μm之被黏著體之黏著力(A2)宜滿足以下關係。Moreover, the non-crosslinkable adhesive composition of the present invention can be laminated on a substrate At least one side of the film is used as an adhesive sheet, and the adhesive sheet is adhered to the body. The adhesive force (A1) of the adherend having a surface roughness Rz of 5.0 μm and the adhesive force (A2) of the adherend having a surface roughness Rz of 0.5 μm should preferably satisfy the following relationship.

A1/A2=0.8~1.2A1/A2=0.8~1.2

藉由滿足前式，黏著片無論被黏著體之表面粗度皆可獲得良好之密接性。By satisfying the front type, the adhesive sheet can obtain good adhesion regardless of the surface roughness of the adherend.

非交聯性黏著組成物之厚度可依照使用目的或黏著力適當地決定。一般為1~300μm，且宜為3~50μm。The thickness of the non-crosslinkable adhesive composition can be appropriately determined depending on the purpose of use or adhesion. It is generally 1 to 300 μm, and preferably 3 to 50 μm.

<黏著片之製造方法><Method of Manufacturing Adhesive Sheet>

黏著片之製造方法並無特殊之限制，可自以往公知之塗抹方法中選擇。舉例言之，可列舉如：逆轉塗佈、凹版印刷塗佈等之輥塗法、旋轉塗佈法、網版塗佈法、噴注塗佈法、浸漬法、噴霧法等。在塗佈非交聯性黏著組成物之溶液後，藉由於乾燥步驟中將溶劑或水揮發，製得預定厚度之非交聯性黏著組成物層。又，亦可直接塗抹於基材膜上，且亦可於脫模片上塗佈非交聯性黏著組成物後，轉印至基材膜。The manufacturing method of the adhesive sheet is not particularly limited, and can be selected from previously known smearing methods. For example, a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a spray coating method, a dipping method, a spray method, or the like can be given. After coating the solution of the non-crosslinkable adhesive composition, a non-crosslinkable adhesive composition layer having a predetermined thickness is obtained by volatilizing the solvent or water in the drying step. Further, it may be applied directly onto the substrate film, and the non-crosslinkable adhesive composition may be applied onto the release sheet and then transferred to the substrate film.

(本實施形態之效果)(Effect of this embodiment)

藉由使用本實施形態之黏著片，無論對光學構件或電子零件等平滑之表面或粗糙之表面，密接性皆不會變化而可良好地黏合。By using the adhesive sheet of the present embodiment, the surface of the smooth surface or the rough surface such as the optical member or the electronic component can be adhered without any change in adhesion.

又，藉由使用本實施形態之黏著片，可使黏著劑不會殘留於被黏著體而剝離。Further, by using the adhesive sheet of the present embodiment, the adhesive can be peeled off without remaining on the adherend.

實施例Example

其次，為了使本實施形態之效果更明確化，詳細 地說明實施例及比較例，然而，本發明並不限於該等實施例。Next, in order to make the effect of the embodiment more clear, detailed The examples and comparative examples are described, however, the invention is not limited to the embodiments.

<實施例1><Example 1>

[非交聯性黏著組成物之製造][Manufacture of non-crosslinking adhesive composition]

(1)丙烯酸酯共聚物之調製(1) Modulation of acrylate copolymer

於具備溫度計、攪拌裝置之聚合反應器中，注入水、丙烯酸乙酯、丙烯酸丁酯、丙烯腈及月桂硫酸鈉作為乳化劑，且2度進行真空化及氮置換而充分地除去氧。然後，加入氫過氧化異丙苯與甲醛次硫酸鈉，且於常壓下以溫度30℃開始乳化聚合，並反應至聚合轉化率到達95%為止。藉由氯化鈣溶液，將所製得之乳化聚合液凝固，且水洗、乾燥後，製得重量平均分子量70萬、分散度(Mw/Mn)2.5之丙烯酸酯共聚物。由於實施例1之丙烯酸酯共聚物之單體成分為丙烯酸乙酯、丙烯酸丁酯與丙烯腈，因此，於表1中，揭示為EA/BA/AN。In a polymerization reactor equipped with a thermometer and a stirring device, water, ethyl acrylate, butyl acrylate, acrylonitrile, and sodium lauryl sulfate were injected as an emulsifier, and vacuuming and nitrogen substitution were performed at 2 degrees to sufficiently remove oxygen. Then, cumene hydroperoxide and sodium sulfoxylate formaldehyde were added, and emulsion polymerization was started at a temperature of 30 ° C under normal pressure, and the reaction was carried out until the polymerization conversion ratio reached 95%. The obtained emulsion polymerization liquid was solidified by a calcium chloride solution, washed with water, and dried to obtain an acrylate copolymer having a weight average molecular weight of 700,000 and a degree of dispersion (Mw/Mn) of 2.5. Since the monomer component of the acrylate copolymer of Example 1 was ethyl acrylate, butyl acrylate and acrylonitrile, it is disclosed in Table 1 as EA/BA/AN.

(2)重量平均分子量及分散度之測定(2) Determination of weight average molecular weight and dispersion

藉由GPC(凝膠滲透層析)法之下述條件來測定。It was measured by the following conditions of the GPC (gel permeation chromatography) method.

分析裝置：東曹(TOSOH)製，HLC-8120GPCAnalytical device: Tosoh (TOSOH), HLC-8120GPC

管柱：東曹製，G7000HXL+GMHXL+GMHXLPipe column: Tosoh system, G7000HXL+GMHXL+GMHXL

管柱尺寸：各7.8mm□×30cm計90cmColumn size: 7.8mm □ x 30cm, 90cm

管柱溫度：40℃Column temperature: 40 ° C

流速：0.8ml/min.Flow rate: 0.8ml/min.

注入量：100μlInjection volume: 100μl

溶析液：四氫呋喃Lysate: tetrahydrofuran

檢測器：示差折射計Detector: differential refractometer

標準試料：聚苯乙烯Standard sample: polystyrene

[黏著片之作成][Adhesive film creation]

藉由醋酸乙酯，將所製得之丙烯酸酯共聚物溶解，且於厚度100μm之基材膜(東麗(TORAY)公司製LUMIRROR U34)上，將相對於丙烯酸酯共聚物100重量份而摻合硬化劑(日本聚胺基甲酸酯公司製CORONATE L)1重量份之非交聯性黏著組成物塗佈成構成厚度10μm，並作成黏著片。The obtained acrylate copolymer was dissolved by ethyl acetate, and was mixed with 100 parts by weight of the acrylate copolymer on a base film having a thickness of 100 μm (LUMIRROR U34 manufactured by Toray Co., Ltd.). 1 part by weight of a non-crosslinkable adhesive composition of a curing agent (CORONATE L manufactured by Nippon Polyurethane Co., Ltd.) was applied to have a thickness of 10 μm, and an adhesive sheet was prepared.

<實施例2~5、比較例1~4><Examples 2 to 5, Comparative Examples 1 to 4>

相對於實施例1，將使用在丙烯酸酯共聚物之製造之單體成分如表1所示般變更。又，變更聚合條件使所製得之丙烯酸酯共聚物之重量平均分子量(Mw)與分散度(Mw/Mn)變成如表1。除了該等之外，亦包含硬化劑，作成與實施例1相同而作成黏著劑組成物、黏著片。The monomer component used in the production of the acrylate copolymer was changed as shown in Table 1 with respect to Example 1. Further, the polymerization conditions were changed so that the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the obtained acrylate copolymer were as shown in Table 1. In addition to these, a curing agent was also contained, and an adhesive composition and an adhesive sheet were prepared in the same manner as in Example 1.

針對藉由前述實施例及比較例所製得之黏著片，進行以下評價。表1顯示結果。The following evaluations were made for the adhesive sheets prepared by the foregoing Examples and Comparative Examples. Table 1 shows the results.

(酸值測定方法)(acid value determination method)

藉由如下述所示根據JISK0070之中和滴定法來測定。首先，於三角燒瓶量取試料。其次，加入丙酮100ml及酚酞溶液數滴作為指示劑，並充分地搖勻，直到水浴上試料完全溶解為止。其次，以0.1mol/l氫氧化鉀乙醇溶液滴定，並將指示劑之淺紅色持續30秒鐘時作成終點。又，藉由下式算出酸值。It was measured by the JIS K0070 neutralization titration method as shown below. First, the sample was weighed in a conical flask. Next, 100 ml of acetone and a few drops of phenolphthalein solution were added as an indicator, and shaken well until the sample on the water bath was completely dissolved. Next, the solution was titrated with a 0.1 mol/l potassium hydroxide ethanol solution, and the light red color of the indicator was continued for 30 seconds to form an end point. Further, the acid value was calculated by the following formula.

A=B×f×5.611/S 式(1)A=B×f×5.611/S (1)

(然而，式(1)中，A：酸值(mgKOH/g)，B：使用在滴定之0.1mol/l氫氧化鉀乙醇溶液之量(ml)，f：0.1mol/l氫氧化鉀乙醇溶液之係數(濃度校正係數)，S：試料之質量(g))(However, in the formula (1), A: acid value (mgKOH/g), B: used in a titration of 0.1 mol/l potassium hydroxide ethanol solution (ml), f: 0.1 mol/l potassium hydroxide ethanol Coefficient of solution (concentration correction factor), S: mass of sample (g))

(羥值測定方法)(Method for measuring hydroxyl value)

藉由如下述所示根據JISK0070之中和滴定法來測定。首先，於量瓶100ml取入醋酸酐25g，並加入吡啶而將全量作成100ml，且充分地搖勻而製作乙醯化試藥。乙醯化試藥作成不會與濕氣、二氧化碳及酸之蒸氣接觸，並保存於褐色瓶。其次，於平底燒瓶量取試料，並使用移液吸管，將乙醯化試藥5ml加入其中。其次，將小漏斗放置於燒瓶口，並將底部約1cm浸漬於溫度95~100℃之甘油浴中而加熱。為了防止燒瓶頸承受甘油浴之熱而溫度上升，將中間穿設有圓孔之厚紙圓板蓋在燒瓶頸之根部。又，1小時後，自甘油浴取出燒瓶，且放冷後自漏斗加入水1ml並搖動而分解醋酸酐。再者，為了完全地進行分解，再度將燒瓶於甘油浴中加熱10分鐘，且放冷後藉由乙醇5ml清洗漏斗及燒瓶之壁部。加入酚酞溶液數滴作為指示劑，並以0.5mol/l氫氧化鉀乙醇溶液滴定，且將指示劑之淺紅色持續約30秒鐘時作成終點。與前述相同，未放入試料而進行對照試驗。又，藉由下式算出羥值。It was measured by the JIS K0070 neutralization titration method as shown below. First, 25 g of acetic anhydride was taken in 100 ml of a measuring flask, and pyridine was added thereto to make 100 ml of the whole amount, and the mixture was thoroughly shaken to prepare an acetamidine reagent. The acetaminophen test preparation is not in contact with moisture, carbon dioxide and acid vapor, and is stored in a brown bottle. Next, the sample was weighed in a flat-bottomed flask, and 5 ml of an acetamidine reagent was added thereto using a pipette pipette. Next, a small funnel was placed in the mouth of the flask, and the bottom was immersed in a glycerin bath at a temperature of 95 to 100 ° C for about 1 cm to be heated. In order to prevent the boiling bottleneck from being heated by the glycerin bath and the temperature rises, a thick paper circular plate with a round hole in the middle is placed over the root of the bottle neck. Further, after 1 hour, the flask was taken out from the glycerin bath, and after allowing to cool, 1 ml of water was added from the funnel and shaken to decompose acetic anhydride. Further, in order to completely decompose, the flask was again heated in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall portion of the flask were washed with 5 ml of ethanol. A few drops of the phenolphthalein solution were added as an indicator, and titrated with a 0.5 mol/l potassium hydroxide ethanol solution, and the light red of the indicator was continued for about 30 seconds to form an end point. In the same manner as described above, a control test was carried out without placing a sample. Further, the hydroxyl value was calculated by the following formula.

A=((B-C)×f×28.05/S)+D 式(2)A=((B-C)×f×28.05/S)+D (2)

(然而，式(2)中，A：羥值(mgKOH/g)，B：使用在對照試驗之0.5mol/l氫氧化鉀乙醇溶液之量(ml)，C：使用在滴定之0.5mol/l氫氧化鉀乙醇溶液之量(ml)，f：0.5mol/l氫氧 化鉀乙醇溶液之係數(濃度校正係數)，S：試料之質量(g)，D：酸值(mgKOH/g))(However, in the formula (2), A: hydroxyl value (mgKOH/g), B: amount of 0.5 mol/l potassium hydroxide ethanol solution used in the control test (ml), C: used in the titration of 0.5 mol/ l The amount of potassium hydroxide ethanol solution (ml), f: 0.5mol / l oxyhydrogen Coefficient of potassium solution in ethanol (concentration correction factor), S: mass of sample (g), D: acid value (mgKOH/g)

(黏著力之測定方法)(Method for measuring adhesion)

(1)對表面粗度Rz=5μm之被黏著體之黏著力(A1)(1) Adhesion to the adherend of surface roughness Rz=5 μm (A1)

自各黏著片採集寬度25mm×長度300mm之試驗片3片，並將該等黏貼於業已研磨成構成表面粗度Rz=5μm之SUS304鋼板(厚度1.5mm~2.0mm)上後，施加2kg之橡膠輥往復3次而壓接，並放置1小時後，使用測定值納入其容量之15~85%之範圍適合於JIS B 7721之拉伸試驗機，並測定黏著力。剝離角度作成180度，剝離速度作成300mm/min。測定環境是調製成23℃、50%RH。Three pieces of test piece having a width of 25 mm and a length of 300 mm were collected from each of the adhesive sheets, and the same was applied to a SUS304 steel plate (thickness: 1.5 mm to 2.0 mm) which had been ground to have a surface roughness of Rz = 5 μm, and then a rubber roller of 2 kg was applied. After reciprocating three times and crimping, and after standing for one hour, the measurement value was included in the range of 15 to 85% of the capacity, which was suitable for the tensile tester of JIS B 7721, and the adhesion was measured. The peeling angle was made 180 degrees, and the peeling speed was made to 300 mm/min. The measurement environment was prepared at 23 ° C and 50% RH.

(2)對表面粗度Rz=0.5μm之被黏著體之黏著力(A2)(2) Adhesion to the adherend with surface roughness Rz = 0.5 μm (A2)

自各黏著片採集寬度25mm×長度300mm之試驗片3片，並將該等黏貼於業已研磨成構成表面粗度Rz=0.5μm之SUS304鋼板(厚度1.5mm~2.0mm)上後，施加2kg之橡膠輥往復3次而壓接，並放置1小時後，使用測定值納入其容量之15~85%之範圍適合於JIS B 7721之拉伸試驗機，並測定黏著力。剝離角度作成180度，剝離速度作成300mm/min。測定環境是調製成23℃、50%RH。3 pieces of test piece having a width of 25 mm and a length of 300 mm were collected from each of the adhesive sheets, and these were adhered to a SUS304 steel plate (thickness: 1.5 mm to 2.0 mm) which had been ground to have a surface roughness of Rz = 0.5 μm, and then 2 kg of rubber was applied. The roller was reciprocated three times and crimped, and after standing for one hour, the measurement was carried out in a range of 15 to 85% of its capacity, which was suitable for a tensile tester of JIS B 7721, and the adhesion was measured. The peeling angle was made 180 degrees, and the peeling speed was made to 300 mm/min. The measurement environment was prepared at 23 ° C and 50% RH.

(被黏著體選擇性之評價方法)(Method of evaluation of adhesion selectivity)

如前述般測定的黏著力A1、A2滿足A1/A2=0.8~1.2之關係時作成○，未滿足時作成×。When the adhesion forces A1 and A2 measured as described above satisfy the relationship of A1/A2=0.8 to 1.2, ○ is formed, and when it is not satisfied, ○ is formed.

(被黏著體上之殘膠之評價方法)(Evaluation method of residual glue on the adhesive body)

測定前述A1、A2之黏著力時，藉由目視，評價膠帶剝離後SUS板上有無殘膠。將SUS板上無殘膠時作成○，將有殘膠時作成×。When the adhesion of the above A1 and A2 was measured, the presence or absence of residual glue on the SUS plate after tape peeling was evaluated by visual observation. When the SUS plate has no residual glue, it is made into ○, and when there is residual glue, it is made into ×.

EA：丙烯酸乙酯，BA：丙烯酸丁酯，AN：丙烯腈，EA: ethyl acrylate, BA: butyl acrylate, AN: acrylonitrile,

MEA：丙烯酸2-甲氧乙酯，2HEA：丙烯酸2-羥乙酯MEA: 2-methoxyethyl acrylate, 2HEA: 2-hydroxyethyl acrylate

實施例1~5、比較例1~3之丙烯酸酯共聚物之酸值為0.1mgKOH/g以下，羥值為0.1mgKOH/g以下。The acrylate copolymers of Examples 1 to 5 and Comparative Examples 1 to 3 had an acid value of 0.1 mgKOH/g or less and a hydroxyl value of 0.1 mgKOH/g or less.

比較例4之丙烯酸酯聚合物係具有羥基以作為與異氰酸酯系硬化劑或環氧硬化劑反應之官能基者，且羥值為5.0mgKOH/g。The acrylate polymer of Comparative Example 4 had a hydroxyl group as a functional group reactive with an isocyanate-based curing agent or an epoxy curing agent, and had a hydroxyl value of 5.0 mgKOH/g.

又，由表1可知，將下述非交聯性黏著組成物積層於基材膜單面而成之黏著片(實施例1~5)對表面粗度不同的被黏著體皆可良好地黏合，且剝離時被黏著體上亦無殘膠，即：前述黏著片係以(甲基)丙烯酸酯共聚物作為主成分，且前述(甲基)丙烯酸酯共聚物之重量平均分子量為70萬~200萬且分散度為5以下，並且未具有會與異氰酸酯系硬化劑或環氧系硬化劑反應之官能基。Further, as is clear from Table 1, the adhesive sheets (Examples 1 to 5) in which the following non-crosslinkable adhesive composition was laminated on one surface of the base film were adhered well to the adherends having different surface roughness. And the adhesive sheet is free from residual glue, that is, the adhesive sheet is composed of a (meth) acrylate copolymer as a main component, and the weight average molecular weight of the (meth) acrylate copolymer is 700,000~ 2 million and having a degree of dispersion of 5 or less, and having no functional group which will react with an isocyanate-based curing agent or an epoxy-based curing agent.

另一方面，當丙烯酸酯共聚物之重量平均分子量 為50萬時(比較例1)，雖然被黏著體選擇性良好，然而，被黏著體上觀察到殘膠。一般認為這是因為分子量低，因此，低分子成分構成殘膠之故。On the other hand, when the weight average molecular weight of the acrylate copolymer At 500,000 hours (Comparative Example 1), although the adhesion to the adherend was good, the residual glue was observed on the adherend. It is generally considered that this is because the molecular weight is low, and therefore, the low molecular component constitutes a residual rubber.

又，當丙烯酸酯共聚物之重量平均分子量為210 萬時(比較例2)，雖然未觀察到殘膠，然而，被黏著體選擇性惡化。一般認為這是因為分子量高，且對粗糙之表面之密接性惡化之故。Also, when the weight average molecular weight of the acrylate copolymer is 210 In 10,000 (Comparative Example 2), although no residual glue was observed, the adhesion was selectively deteriorated. This is considered to be because the molecular weight is high and the adhesion to the rough surface is deteriorated.

再者，當丙烯酸酯共聚物之分散度為6時(比較例 3)，被黏著體選擇性惡化，且被黏著體上亦觀察到殘膠。 一般認為這是非交聯性黏著組成物之低分子成分造成不良影響。Furthermore, when the dispersion degree of the acrylate copolymer is 6, (Comparative Example) 3) The adhesion was selectively deteriorated, and the residual glue was also observed on the adherend. This is generally considered to be an adverse effect of the low molecular component of the non-crosslinking adhesive composition.

又，當丙烯酸酯共聚物之單體成分使用丙烯酸2- 羥乙酯，且具有羥基以作為與異氰酸酯系硬化劑或環氧硬化劑反應之官能基時(比較例4)，雖然被黏著體上未觀察到殘膠，然而，被黏著體選擇性惡化。一般認為這是因為進行與硬化劑之交聯反應，且對粗糙面之密接性明顯地降低之故。Also, when the monomer component of the acrylate copolymer uses acrylic acid 2- When hydroxyethyl ester has a hydroxyl group as a functional group reactive with an isocyanate-based curing agent or an epoxy curing agent (Comparative Example 4), although no residual glue is observed on the adherend, the viscosity of the adherend is deteriorated. This is considered to be because the crosslinking reaction with the hardener is carried out, and the adhesion to the rough surface is remarkably lowered.

以上，一面參照附圖，一面說明本發明之較佳實 施形態，然而，本發明並不限於前述例子。若為該發明所屬技術領域中具有通常知識者，則顯然可於本發明所揭示之技術思想之範疇內思及各種變更例或修正例，並了解該等當然亦屬於本發明之技術範圍。The above is a better description of the present invention with reference to the accompanying drawings. However, the present invention is not limited to the foregoing examples. It is obvious that various modifications and alterations can be made within the scope of the technical idea of the invention, and it is obvious that these are also within the technical scope of the present invention.

1‧‧‧黏著片1‧‧‧Adhesive film

3‧‧‧基材膜3‧‧‧Base film

5‧‧‧非交聯性黏著組成物層5‧‧‧ Non-crosslinking adhesive composition layer

Claims (3)

一種非交聯性黏著組成物，其以(甲基)丙烯酸酯共聚物作為主成分，且前述(甲基)丙烯酸酯共聚物之重量平均分子量為70萬~200萬且分散度為2.5~4，並且未具有會與異氰酸酯系硬化劑或環氧系硬化劑反應之官能基。 A non-crosslinkable adhesive composition comprising a (meth) acrylate copolymer as a main component, and the (meth) acrylate copolymer has a weight average molecular weight of 700,000 to 2,000,000 and a dispersion of 2.5 to 4 And does not have a functional group which will react with an isocyanate-based hardener or an epoxy-based hardener. 如請求項1之非交聯性黏著組成物，其中會與異氰酸酯系硬化劑或環氧系硬化劑反應之前述官能基為羧基或羥基。 The non-crosslinkable adhesive composition of claim 1, wherein the aforementioned functional group which reacts with the isocyanate-based curing agent or the epoxy-based curing agent is a carboxyl group or a hydroxyl group. 一種黏著片，係將如請求項1或2之非交聯性黏著組成物積層於基材膜之至少單面而成者，且其對表面粗度Rz為5μm之被黏著體之黏著力(A1)與對表面粗度Rz為0.5μm之被黏著體之黏著力(A2)滿足以下關係，即：A1/A2=0.8~1.2。 An adhesive sheet obtained by laminating at least one side of a base film, such as the non-crosslinkable adhesive composition of claim 1 or 2, and having an adhesion to an adherend having a surface roughness Rz of 5 μm ( A1) The adhesion (A2) to the adherend having a surface roughness Rz of 0.5 μm satisfies the following relationship: A1/A2 = 0.8 to 1.2.
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