[go: up one dir, main page]

TWI719080B - Adhesive sheet and adhesive sheet with release film - Google Patents

Adhesive sheet and adhesive sheet with release film Download PDF

Info

Publication number
TWI719080B
TWI719080B TW105138382A TW105138382A TWI719080B TW I719080 B TWI719080 B TW I719080B TW 105138382 A TW105138382 A TW 105138382A TW 105138382 A TW105138382 A TW 105138382A TW I719080 B TWI719080 B TW I719080B
Authority
TW
Taiwan
Prior art keywords
adhesive
meth
adhesive sheet
acrylate
less
Prior art date
Application number
TW105138382A
Other languages
Chinese (zh)
Other versions
TW201720892A (en
Inventor
鈴木立也
重富清惠
中山純一
Original Assignee
日商日東電工股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日東電工股份有限公司 filed Critical 日商日東電工股份有限公司
Publication of TW201720892A publication Critical patent/TW201720892A/en
Application granted granted Critical
Publication of TWI719080B publication Critical patent/TWI719080B/en

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/005—Presence of polyester in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種包含黏著劑層之黏著片材。上述黏著片材具有第1面及第2面。上述第1面係由上述黏著劑層之一表面構成之第1黏著面。上述第1黏著面之十點平均粗糙度為1000 nm以下。上述黏著劑層於100℃下之儲存彈性模數為0.08 MPa以上。The present invention provides an adhesive sheet containing an adhesive layer. The said adhesive sheet has a 1st surface and a 2nd surface. The first surface is a first adhesive surface formed by one surface of the adhesive layer. The ten-point average roughness of the first adhesive surface is 1000 nm or less. The storage elastic modulus of the adhesive layer at 100°C is above 0.08 MPa.

Description

黏著片材及附剝離膜之黏著片材Adhesive sheet and adhesive sheet with release film

本發明係關於一種黏著片材及附剝離膜之黏著片材。The present invention relates to an adhesive sheet and an adhesive sheet with a release film.

一般而言，黏著劑(亦稱為感壓接著劑。以下相同)具有如下性質：於室溫附近之溫度區域內呈現柔軟之固體(黏彈性體)之狀態，可藉由壓力而簡單地接著於被接著體。有效利用該性質，黏著劑典型而言以包含該黏著劑之層之黏著片材之形態被廣泛利用於家電製品至汽車、OA(Office Automation，辦公自動化)設備等各種產業領域。 黏著片材中有對黏著面(黏著劑層之表面)要求高度之平滑性者。作為此種黏著片材之一例，可列舉面向光學用途之黏著片材。 作為關於防止黏著劑層表面產生凹凸之技術文獻，可列舉日本專利申請公開2014-189778號公報。國際公開第2014/156335號係關於具有表面平滑性較高之剝離膜之雙面黏著片材之技術文獻。Generally speaking, adhesives (also called pressure-sensitive adhesives. The same below) have the following properties: they are soft and solid (viscoelastic) in a temperature region near room temperature, and can be easily bonded by pressure. To be followed by the body. To make effective use of this property, adhesives are typically used in various industrial fields such as home appliances, automobiles, and OA (Office Automation) equipment, typically in the form of an adhesive sheet containing the adhesive layer. Among the adhesive sheets, there are those that require a high degree of smoothness on the adhesive surface (the surface of the adhesive layer). As an example of such an adhesive sheet, an adhesive sheet for optical applications can be cited. As a technical document about preventing unevenness on the surface of the adhesive layer, Japanese Patent Application Publication No. 2014-189778 can be cited. International Publication No. 2014/156335 is a technical document on a double-sided adhesive sheet with a release film with high surface smoothness.

一般而言，自流通之方便或生產性等觀點考慮，多數情況下黏著片材(特別是工業用之黏著片材)係製造成長條之帶狀之黏著片材捲繞成螺旋狀之形態、或相對較大面積之片狀之形態。其後，在最終貼附於各個被接著體之前之期間，可對黏著片材實施各種各樣之加工或處理。作為該加工或處理之例，可列舉藉由沖裁或切斷等使黏著片材之外形適合被接著體之形狀之加工、或者將黏著片材製備成適合於貼附至被接著體之作業之效率化或高精度化之形態之處理等。 於此種加工或處理之過程中，有時更換保護黏著片材之黏著面之剝離膜。即，有時自黏著片材之黏著面上去除一剝離膜，於藉此露出之黏著面上貼合另一剝離膜之剝離面。因此，存在於即將貼附於被接著體之前之黏著片材之黏著面上之剝離膜可為與在最初製造該黏著片材時存在於該黏著面上之剝離膜不同之剝離膜。隨著近年來之光學製品之多樣化、小型化、大畫面化、設計性之提高等，有在所製造之黏著片材貼附於被接著體之前之期間更換黏著面上之剝離膜之機會或其必要性增加之傾向。然而，如上所述，由於黏著劑為黏彈性體，故而即便為最初以具有高平滑之黏著面之方式製造之黏著片材，亦可能因其後之處理而導致黏著面之平滑性降低(粗化)。例如，若將保護高平滑之黏著面之剝離膜更換為另一剝離膜，則有時會因更換之剝離膜而導致上述黏著面之平滑性降低。 因此，本發明之目的在於提供一種具有高平滑之黏著面且該黏著面之平滑性不易受損之黏著片材。相關之其他目的在於提供一種於此種黏著片材之黏著面上具有剝離膜之附剝離膜之黏著片材。 本發明者等人發現：對於具有高平滑之黏著面之黏著片材，藉由著眼於構成該高平滑之黏著面之黏著劑層之100℃儲存彈性模數(100℃下之儲存彈性模數)而可解決上述課題，從而完成了本發明。 根據本說明書，提供一種黏著片材，其包含黏著劑層。上述黏著片材具有第1面及第2面。上述第1面係由上述黏著劑層之一表面構成之第1黏著面。上述第1黏著面之十點平均粗糙度(RzA1 )為約1000 nm以下。上述黏著劑層之100℃儲存彈性模數(G'100 )為約0.08 MPa以上。此種黏著片材由於具有高平滑之第1黏著面且構成該第1黏著面之黏著劑層之G'100 較高，故而有上述第1黏著面之平滑性不易受損之傾向。因此，上述黏著片材適合於需要高平滑之黏著面之用途(例如光學用途)。 此處揭示之技術之一態樣中，上述黏著劑層之100℃儲存彈性模數(G'100 )為該黏著劑層之23℃儲存彈性模數(23℃下之儲存彈性模數；G'23 )之約35%以上。即，上述黏著劑層之100℃/23℃儲存彈性模數比(G'100 /G'23 )為約35%以上。若利用具有此種黏著劑層之黏著片材，則有較佳地兼顧維持第1黏著面之平滑性之性能與室溫下之貼附作業性之傾向。G'100 /G'23 之上限並無特別限定，通常為約100%以下。 此處揭示之技術之一態樣中，上述黏著劑層之23℃儲存彈性模數(G'23 )未達約0.30 MPa。具有此種黏著劑層之黏著片材有於室溫下顯示出良好之初期接著性之傾向。 此處揭示之技術之一態樣中，上述黏著片材之上述第2面為第2黏著面。即，該態樣之黏著片材構成為上述第1面及上述第2面均為黏著面之雙面黏著片材。此種雙面黏著片材可以例如構件之接合或固定等目的而較佳地使用。一態樣中，上述第2黏著面之十點平均粗糙度(RzA2 )可為約2000 nm以下(較佳為約1000 nm以下)。具有此種第2黏著面之雙面黏著片材適合於需要高平滑之黏著面之用途。 此處揭示之技術之一態樣中，上述第2面可為由上述黏著劑層之另一表面構成之第2黏著面。即，上述黏著劑層之一表面及另一表面分別構成黏著片材之第1黏著面及第2黏著面。該態樣之黏著片材由於結構簡單，故而適合於光學特性(例如透明性)之提高。一態樣中，上述第2黏著面之該第2黏著面之十點平均粗糙度(RzA2 )可為約2000 nm以下(例如約1000 nm以下)。此種黏著片材由於具有高平滑之第2黏著面且構成上述第2黏著面之黏著劑層之G'100 較高，故而有該第2面之平滑性不易受損之傾向。因此適合於需要高平滑之黏著面之用途。 又，根據本說明書，提供一種附剝離膜之黏著片材，其包含此處揭示之任一黏著片材、及配置於該黏著片材之第1黏著面上之第1剝離膜。構成此種附剝離膜之黏著片材之黏著片材可以如下態樣較佳地使用：根據所需經過將上述第1剝離膜更換為其他剝離膜(更換貼附)之過程而貼附於被接著體。 如此，第1黏著面上具有第1剝離膜之附剝離膜之黏著片材較佳為上述第1剝離膜之與上述第1黏著面接觸之剝離面之十點平均粗糙度(RzR1 )與上述第1黏著面之十點平均粗糙度(RzA1 )之差為250 nm以內。即，|RzR1 －RzA1 |較佳為250 nm以下。此種附剝離膜之黏著片材由於第1剝離膜之剝離面與第1黏著面之密接性良好，故而有外觀品質優異之傾向。以下，有時將與第1黏著面接觸之剝離面稱為「第1剝離面」。又，有時將與第2黏著面接觸之剝離面稱為「第2剝離面」。 又，根據本說明書，提供一種附剝離膜之黏著片材，其包含此處揭示之任一雙面黏著片材、配置於該黏著片材之第1黏著面上之第1剝離膜及配置於該黏著片材之第2黏著面上之第2剝離膜。構成此種附剝離膜之黏著片材之雙面黏著片材可以如下態樣較佳地使用：根據所需經過將上述第1剝離膜及上述第2剝離膜之一者或兩者更換為其他剝離膜之過程而貼附於被接著體。 如此，包含雙面黏著片材、第1剝離膜及第2剝離膜之附剝離膜之黏著片材(附剝離膜之雙面黏著片材)於較佳之一態樣中可上述第1剝離膜之第1剝離面之十點平均粗糙度(RzR1 )與上述第1黏著面之十點平均粗糙度(RzA1 )之差為250 nm以內，且上述第2剝離膜之第2剝離面之十點平均粗糙度(RzR2 )與上述第2黏著面之十點平均粗糙度(RzA2 )之差為250 nm以內。即，可|RzR1 －RzA1 |為250 nm以下，且|RzR2 －RzA2 |為250 nm以內。該態樣之附剝離膜之黏著片材由於第1剝離膜之剝離面與第1黏著面之密接性及第2剝離膜之剝離面與第2黏著面之密接性均良好，故而有外觀品質優異之傾向。Generally speaking, considering the convenience of self-distribution or productivity, in most cases the adhesive sheet (especially the industrial adhesive sheet) is made into a long strip of adhesive sheet wound into a spiral shape, Or a relatively large area of flake form. After that, various processes or treatments can be applied to the adhesive sheet during the period before it is finally attached to each adherend. As an example of this processing or treatment, processing to adapt the outer shape of the adhesive sheet to the shape of the adherend by punching or cutting, or the operation of preparing the adhesive sheet to be suitable for attachment to the adherend The processing of the form of efficiency or high precision, etc. In the process of such processing or treatment, sometimes the peeling film that protects the adhesive surface of the adhesive sheet is replaced. That is, sometimes a release film is removed from the adhesive surface of the adhesive sheet, and the release surface of another release film is attached to the adhesive surface exposed thereby. Therefore, the release film present on the adhesive surface of the adhesive sheet immediately before being attached to the adherend may be a release film different from the release film present on the adhesive surface when the adhesive sheet is initially manufactured. With the diversification, miniaturization, large screen, and improvement of design of optical products in recent years, there is an opportunity to replace the release film on the adhesive surface during the period before the manufactured adhesive sheet is attached to the adherend. Or its tendency to increase in necessity. However, as described above, since the adhesive is a viscoelastic body, even if it is an adhesive sheet that is initially manufactured with a highly smooth adhesive surface, the subsequent processing may cause the smoothness of the adhesive surface to decrease (thick化). For example, if a peeling film that protects a highly smooth adhesive surface is replaced with another peeling film, the replacement of the peeling film may cause the smoothness of the adhesive surface to decrease. Therefore, the object of the present invention is to provide an adhesive sheet having a highly smooth adhesive surface and the smoothness of the adhesive surface is not easily impaired. Related other objects are to provide an adhesive sheet with a release film having a release film on the adhesive surface of the adhesive sheet. The inventors found that for an adhesive sheet with a highly smooth adhesive surface, by focusing on the 100°C storage elastic modulus (the storage elastic modulus at 100°C) of the adhesive layer constituting the highly smooth adhesive surface ) The above-mentioned problems can be solved, and the present invention has been completed. According to this specification, an adhesive sheet is provided, which includes an adhesive layer. The said adhesive sheet has a 1st surface and a 2nd surface. The first surface is a first adhesive surface formed by one surface of the adhesive layer. The ten-point average roughness (Rz A1 ) of the first adhesive surface is about 1000 nm or less. The storage elastic modulus (G' 100 ) of the adhesive layer at 100° C. is about 0.08 MPa or more. Such adhesive sheets because of a high smoothness of the surface and the first adhesive constituting the adhesive layer G of the first adhesive surface of the '100 high, and therefore tends to smoothness of the first adhesive surface of the easily damaged. Therefore, the above-mentioned adhesive sheet is suitable for applications that require a highly smooth adhesive surface (such as optical applications). In one aspect of the technology disclosed here, the 100°C storage elastic modulus of the adhesive layer (G' 100 ) is the 23°C storage elastic modulus of the adhesive layer (the storage elastic modulus at 23°C; G) '23 ) about 35% or more. That is, the 100°C/23°C storage modulus ratio (G' 100 /G' 23 ) of the adhesive layer is about 35% or more. If an adhesive sheet with such an adhesive layer is used, there is a tendency to better balance the performance of maintaining the smoothness of the first adhesive surface and the sticking workability at room temperature. G '100 / G' 23 of the upper limit is not particularly limited, is generally about 100% or less. In one aspect of the technology disclosed here, the storage elastic modulus (G' 23 ) of the adhesive layer at 23° C. does not reach about 0.30 MPa. Adhesive sheets with such an adhesive layer tend to show good initial adhesion at room temperature. In one aspect of the technique disclosed here, the second surface of the adhesive sheet is a second adhesive surface. That is, the adhesive sheet of this aspect is configured as a double-sided adhesive sheet in which the first surface and the second surface are both adhesive surfaces. Such a double-sided adhesive sheet can be preferably used for purposes such as joining or fixing of members. In one aspect, the ten-point average roughness (Rz A2 ) of the second adhesive surface may be about 2000 nm or less (preferably about 1000 nm or less). The double-sided adhesive sheet with such a second adhesive surface is suitable for applications requiring a highly smooth adhesive surface. In one aspect of the technology disclosed herein, the second surface may be a second adhesive surface formed by the other surface of the adhesive layer. That is, one surface and the other surface of the adhesive layer constitute the first adhesive surface and the second adhesive surface of the adhesive sheet, respectively. The adhesive sheet of this aspect is suitable for the improvement of optical properties (such as transparency) due to its simple structure. In one aspect, the ten-point average roughness (Rz A2 ) of the second adhesive surface of the second adhesive surface may be about 2000 nm or less (for example, about 1000 nm or less). Such adhesive sheets because of a high smoothness of the surface and the second adhesive constituting the adhesive layer G of the second adhesive surface of the '100 high, therefore there is a tendency that the smoothness of the second surface of the easily damaged. Therefore, it is suitable for applications that require a highly smooth adhesive surface. Furthermore, according to this specification, an adhesive sheet with a release film is provided, which includes any of the adhesive sheets disclosed herein and a first release film disposed on the first adhesive surface of the adhesive sheet. The adhesive sheet constituting the adhesive sheet with the release film can be preferably used in the following manner: according to need, the first release film is replaced with another release film (replacement) and attached to the substrate. Follow the body. Thus, the adhesive sheet with release film having the first release film on the first adhesive surface is preferably the ten-point average roughness (Rz R1 ) of the release surface of the first release film in contact with the first adhesive surface and The ten-point average roughness (Rz A1 ) difference of the above-mentioned first adhesive surface is within 250 nm. That is, |Rz R1- Rz A1 | is preferably 250 nm or less. Since the adhesive sheet with a release film has good adhesion between the release surface of the first release film and the first adhesive surface, the appearance quality tends to be excellent. Hereinafter, the peeling surface in contact with the first adhesive surface may be referred to as the "first peeling surface". In addition, the peeling surface in contact with the second adhesive surface is sometimes referred to as the "second peeling surface". In addition, according to this specification, an adhesive sheet with a release film is provided, which includes any double-sided adhesive sheet disclosed herein, a first release film arranged on the first adhesive surface of the adhesive sheet, and The second release film on the second adhesive surface of the adhesive sheet. The double-sided adhesive sheet constituting the adhesive sheet with release film can be preferably used as follows: one or both of the above-mentioned first release film and the above-mentioned second release film are replaced with other ones as required The process of peeling off the film is attached to the adherend. In this way, an adhesive sheet with a release film (a double-sided adhesive sheet with a release film) including a double-sided adhesive sheet, a first release film and a second release film can be the above-mentioned first release film in a preferred aspect The difference between the ten-point average roughness (Rz R1 ) of the first peeling surface and the ten-point average roughness (Rz A1 ) of the first adhesive surface is within 250 nm, and the difference between the second peeling surface of the second peeling film The difference between the ten-point average roughness (Rz R2 ) and the ten-point average roughness (Rz A2 ) of the second adhesive surface is within 250 nm. That is, |Rz R1- Rz A1 | can be 250 nm or less, and |Rz R2- Rz A2 | can be 250 nm or less. The adhesive sheet with release film of this aspect has good appearance quality due to the good adhesion between the release surface of the first release film and the first adhesive surface and the adhesion between the release surface of the second release film and the second adhesive surface. The tendency of excellence.

以下，說明本發明之較佳之實施形態。再者，對於除本說明書中特別提及之事項以外之實施本發明所必需之事項，業者可基於本說明書中所記載之關於發明之實施之提示及申請時之技術常識而理解。本發明可基於本說明書中所揭示之內容及該領域中之技術常識而實施。又，以下之圖式中，有時對發揮相同作用之構件、部位標附相同符號而進行說明，且有時省略或簡化重複之說明。又，圖式中所記載之實施形態為了清楚地說明本發明而進行示意化，並不一定正確地表示實際所提供之製品之尺寸或縮尺。 本說明書中，「黏著劑」係指如上所述具有如下性質之材料：於室溫附近之溫度區域內呈現柔軟之固體(黏彈性體)之狀態，可藉由壓力而簡單地接著於被接著體。此處所謂之黏著劑如「C. A. Dahlquist, "Adhesion：Fundamental and Practice", McLaren & Sons, (1966) P. 143」中所定義，一般而言，可為具有滿足複拉伸彈性模數E*(1 Hz)＜107 dyne/cm2 之性質之材料(典型而言，於25℃下具有上述性質之材料)。 本說明書中，「黏著面」係指基於JIS Z0237(2004)，將SUS304不鏽鋼板作為被接著體，於23℃之測定環境下使2 kg之輥往復1次而壓接於上述被接著體後30分鐘後，於拉伸速度300 mm/分鐘之條件下沿180度方向剝離時的剝離強度為0.1 N/20 mm以上之面。本說明書中，「非黏著面」係指不屬於上述黏著面之面，典型而言，係指上述剝離強度未達0.1 N/20 mm之面。於23℃之測定環境下使2 kg之輥往復1次而壓接於SUS304不鏽鋼板時不貼附於該不鏽鋼板之面(實質上不顯示黏著性之面)係此處所謂之非黏著面之概念中包含之典型例。 ＜黏著片材＞ 此處揭示之黏著片材形成為具有第1面及第2面之片狀(為包含帶狀等長條狀之形態之含義)。上述黏著片材至少包含黏著劑層。此處揭示之黏著片材可僅由黏著劑層構成，亦可包含黏著劑層以外之構成要素而構成。 此處揭示之黏著片材之第1面成為由上述黏著劑層之一表面構成之黏著面(第1黏著面)。上述黏著片材之第2面可為黏著面，亦可為非黏著面。一態樣之黏著片材中，該黏著片材之第2面成為由上述黏著劑層之另一表面構成之黏著面(第2黏著面)。即，一黏著劑層之一表面及另一表面分別構成黏著片材之第1黏著面及第2黏著面。將該態樣之黏著片材之一構成例示於圖1。 圖1所示之黏著片材1係包含黏著劑層11之無基材之雙面黏著片材。黏著片材1之第1面1A係由黏著劑層11之一表面11A構成之第1黏著面，黏著片材1之第2面1B係由黏著劑層11之另一表面11B構成之第2黏著面。黏著劑層11可為單層結構，亦可為2層以上之包含副黏著劑層之多層結構。構成上述多層結構之各副黏著劑層之構成(材質、厚度等)可相同，亦可不同。就生產性或透明性之觀點而言，可較佳地採用黏著劑層11為單層結構之態樣。 此處，無基材之雙面黏著片材係指於第1黏著面與第2黏著面之間不包含非剝離性之支持基材之雙面黏著片材。上述支持基材係指能夠獨立地維持形狀之基材。又，非剝離性之支持基材係指在使用包含該支持基材之黏著片材期間不意圖與黏著劑層分離之支持基材。 如例如圖1所示，使用前(即，貼附於被接著體之前)之黏著片材1可為第1黏著面1A及第2黏著面1B分別由第1剝離膜21及第2剝離膜22保護之形態。與第1黏著面11A接觸之第1剝離膜21之表面21A及與第2黏著面11B接觸之第2剝離膜22之表面22A均為剝離面(剝離性之表面，即能夠自該表面剝離上述黏著劑層之表面)。此種形態之黏著片材1亦可理解為包含該黏著片材1、使表面(第1剝離面)21A抵接於其第1黏著面11A而配置之第1剝離膜21及使表面(第2剝離面)22A抵接於其第2黏著面12A而配置之第2剝離膜22之附剝離膜之黏著片材(附剝離膜之雙面黏著片材)100之構成要素。附剝離膜之黏著片材100亦可為捲繞成螺旋狀之形態。作為使用前之黏著片材1之其他形態，可例示如下之形態：省略圖1所示之剝離膜22，將表面21A及背面21B均為剝離面之剝離膜21與黏著片材1重疊而捲繞成螺旋狀，藉此使第2黏著面11B抵接於剝離膜21之背面21B。 將第2面為非黏著面之黏著片材之一構成例示於圖2。圖2所示之黏著片材2構成為包含具有第1面15A之支持基材15及配置於該支持基材15之第1面15A上之黏著劑層11之附基材之單面黏著片材。此處，支持基材15之第1面15A為非剝離性之表面、即非剝離面。黏著片材2之第1面2A係由黏著劑層11之一表面11A構成之第1黏著面，黏著片材2之第2面2B係由支持基材15之第2面15B構成之非黏著面。第2面15B可為剝離面，亦可為非剝離面。 如例如圖2所示，使用前之黏著片材2可為由第1剝離膜21保護第1黏著面11A之形態。此種形態之黏著片材2亦可理解為包含該黏著片材2、使表面(第1剝離面)21A抵接於其第1黏著面11A而配置之第1剝離膜21之附剝離膜之黏著片材(附剝離膜之單面黏著片材)200之構成要素。附剝離膜之黏著片材200亦可為捲繞成螺旋狀之形態。 作為此處揭示之黏著片材之其他構成例，可列舉：具備第1面及第2面均為非剝離性之支持基材，且於該支持基材之上述第1面具有第1黏著劑層，於該支持基材之上述第2面具有第2黏著劑層之附基材之雙面黏著片材之構成。關於此種附基材之雙面黏著片材，該雙面黏著片材之第1面成為由上述第1黏著劑層之表面構成之第1黏著面，該雙面黏著片材之第2面成為由上述第2黏著劑層之表面構成之第2黏著面。第1黏著劑層與第2黏著劑層之組成及構成可相同，組成及構成之一者或兩者亦可不同。作為第1黏著劑層與第2黏著劑層之組成相同且構成不同之態樣之例，可列舉：第1黏著劑層與第2黏著劑層為由相同組成之黏著劑組合物構成之厚度不同之黏著劑層之態樣。第1黏著劑層及第2黏著劑層可分別獨立地為單層結構，亦可為2層以上之包含副黏著劑層之多層結構。就生產性或透明性之觀點而言，可較佳地採用第1黏著劑層及第2黏著劑層均為單層結構之態樣。 使用前之附基材之雙面黏著片材可與圖1所示之無基材之雙面黏著片材1同樣地，為第1黏著面(第1黏著劑層之表面)及第2黏著面分別由第1剝離膜及第2剝離膜保護之形態。此種形態之附基材之雙面黏著片材亦可理解為包含該黏著片材、第1剝離膜及第2剝離膜之附剝離膜之黏著片材之構成要素。該附剝離膜之黏著片材亦可為捲繞成螺旋狀之形態。又，使用前之附基材之雙面黏著片材亦可為將雙面為剝離面之剝離膜與黏著片材重疊並捲繞成螺旋狀之形態。 於如上述之附基材之單面黏著片材或附基材之雙面黏著片材般包含支持基材之形態之黏著片材中，該支持基材之材質並無特別限定。作為支持基材，例如可使用塑膠膜、紙、織布、不織布、橡膠片材、發泡體片材、金屬箔、玻璃、該等之複合體等。對於支持基材中設置黏著劑層之面，亦可實施底塗劑之塗佈、電暈放電處理、電漿處理等表面處理。再者，本說明書中，塑膠膜典型而言為非多孔質之片材，為不同於例如不織布(即，不包含不織布)之概念。 一態樣中，作為上述支持基材，就易於實現高平滑之第1黏著面等而言，可較佳地採用各種塑膠膜。作為塑膠膜之材料，例如可列舉：聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等聚酯系樹脂、三乙醯纖維素等纖維素樹脂、乙酸酯系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、環狀聚烯烴樹脂(降異

Figure 105138382-A0304-03-0013-01
烯系樹脂等)、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂、該等之混合物等。其中，作為較佳之材料，可列舉：聚酯系樹脂、纖維素樹脂、聚醯亞胺系樹脂及聚醚碸系樹脂。用於支持基材之塑膠膜中，可與後述剝離膜基材用之塑膠膜同樣地調配公知之添加劑。較佳為具有透明性之塑膠膜。 支持基材之厚度並無特別限定，可根據目的而適當選擇。一態樣中，支持基材之厚度可為約10 μm～約500 μm，通常宜為約10 μm～約300 μm。一態樣中，可較佳地採用厚度約15 μm～約200 μm之支持基材(例如，上述透明塑膠膜)。 (十點平均粗糙度) 此處揭示之黏著片材較佳為第1黏著面之十點平均粗糙度(RzA1 )為約1000 nm以下。具有此種第1黏著面之黏著片材適合於要求高平滑之黏著面之用途。例如，可以第1黏著面貼附於光學構件之態樣較佳地使用。就提供更高平滑之黏著面之觀點而言，RzA1 可較佳為約700 nm以下、更佳為約500 nm以下、進而較佳為約300 nm以下(例如約200 nm以下)。RzA1 之下限並無特別限定。一態樣中，可將RzA1 設為約30 nm以上(例如約50 nm以上)。 此處，本說明書中，所謂十點平均粗糙度，在無特別說明之情況下，係指使用非接觸式之表面粗糙度測定裝置所獲得之十點平均粗糙度。作為非接觸式之表面粗糙度測定裝置，使用光干涉方式之表面粗糙度測定裝置。作為具體之測定裝置，可使用Veeco公司製造之Wyko NT-9100或其相當品。具體之測定操作及測定條件可依據後述實施例中記載之測定條件設定、或者以可獲得與依據該測定條件之情形同等或對應之結果之方式設定。十點平均粗糙度係針對藉由上述表面粗糙度測定所獲得之粗糙度曲線，測定自最高之峰頂至第10位為止之峰頂之標高(Yp1～Yp10)及自最低之谷底至第10位為止之谷底之標高(Yv1～Yv10)，求出上述Yp1～Yp10與上述Yv1～Yv10之各差量之絕對值之平均值。 於此處揭示之黏著片材為雙面黏著片材(即，具有第1黏著面及第2黏著面之黏著片材)之形態之情形時，第2黏著面之十點平均粗糙度(RzA2 )並無特別限定。較佳之一態樣中，RzA2 可設為約2000 nm以下(典型而言，為約1000 nm以下，較佳為約700 nm以下，更佳為約500 nm以下，進而較佳為約300 nm以下，例如約200 nm以下)。RzA2 之下限並無特別限定。一態樣中，可將RzA2 設為約30 nm以上(例如約50 nm以上)。第2黏著面可為一表面構成第1黏著面之黏著劑層中之另一表面，亦可為與構成第1黏著劑層之黏著劑層不同之黏著劑層之表面。 (儲存彈性模數) 此處揭示之黏著片材較佳為構成第1黏著面之黏著劑層之100℃儲存彈性模數(G'100 )為約0.08 MPa以上。具有此種黏著劑層之黏著片材在製造該黏著片材後第1黏著面之平滑性不易受損。例如，在製造黏著片材後至該黏著片材貼附於被接著體之期間，即便將第1黏著面上之剝離膜更換為平滑性更低者，亦有抑制上述第1黏著面之平滑性降低之傾向。可認為其原因在於：更換(更換貼附)暫且製造之黏著片材之剝離膜後的黏著劑層之變形以低速進行時，可根據該黏著劑層之100℃儲存彈性模數適當地掌握針對低速下之塑性變形之黏著劑層之行為(時間-溫度換算法則)，藉由將上述100℃儲存彈性模數設為特定值以上，可高效率地實現不易發生因更換剝離膜而導致之第1黏著面之平滑性降低之黏著片材。 此處揭示之技術中，G'100 可為約0.09 MPa以上，可為約0.10 MPa以上，亦可為約0.11 MPa以上(例如約0.12 MPa以上)。藉由提高G'100 ，有更好地維持第1黏著面之平滑性之傾向。G'100之上限並無特別限定，例如可設為約1.5 MPa以下(典型而言為約1.0 MPa以下)。就對被接著體之密接性等觀點而言，G'100 通常宜為未達約0.50 MPa，較佳為未達約0.40 MPa，更佳為未達約0.30 MPa。G'100 可藉由黏著劑層之組成(例如，該黏著劑層中所含之聚合物之組成或分子量、交聯之態樣、交聯密度、是否使用添加劑及使用時之使用量)或製造方法等而進行調節。 此處揭示之技術之一態樣中，可將構成黏著片材之第1黏著面之黏著劑層之23℃儲存彈性模數(G'23 )設為未達約0.30 MPa。具有此種黏著劑層之黏著片材有於室溫下對被接著體顯示出良好之初期接著性之傾向。該情況就黏著片材之貼附作業性(例如，作業效率或貼附精度)等觀點而言較佳。一態樣中，G'23 可設為約0.29 MPa以下，可為約0.27 MPa以下，亦可為約0.25 MPa以下。藉由降低G'23 ，有黏著片材之初期接著性提高之傾向。G'23 之下限並無特別限定，例如可為約0.05 MPa以上。就易於兼顧特定以上之G'100之觀點而言，通常G'23 宜為約0.08 MPa以上，較佳為約0.10 MPa以上，更佳為約0.15 MPa以上(例如約0.17 MPa以上)。G'23 可藉由黏著劑層之組成或製造方法等而進行調節。 再者，此處揭示之技術中，作為黏著劑層之100℃儲存彈性模數(G'100 )及23℃儲存彈性模數(G'23 )，可使用藉由構成該黏著劑層之黏著劑之動態黏彈性測定而獲得之100℃及23℃之儲存彈性模數之值。作為具體之測定裝置，可使用TA Instruments公司製造之ARES或其相當品。具體之測定操作及測定條件可依據後述實施例中記載之測定條件設定，或者以可獲得與依據該測定條件之情形同等或對應之結果之方式設定。 此處揭示之技術可以構成第1黏著面之黏著劑層之100℃/23℃儲存彈性模數比(G'100 /G'23 )超過約30%(例如約31%以上)之態樣較佳地實施。就更佳地兼顧維持第1黏著面之平滑性之性能與室溫下之貼附作業性之觀點而言，G'100 /G'23 可設為約35%以上，可為約40%以上，亦可為約50%以上(例如約55%以上)。G'100 /G'23 之上限並無特別限定，通常為約100%以下，典型而言為未達約100%。就進一步提高室溫下之貼附作業性之觀點而言，G'100 /G'23 可設為約90%以下，亦可設為約80%以下(例如約70%以下)。一態樣中，可將G'100 /G'23 設為約35%～約50%。此種黏著劑層有易於形成高平滑之第1黏著面之傾向。 此處揭示之技術之一態樣中，構成第1黏著面之黏著劑層之100℃儲存彈性模數(G'100 )相對於該黏著劑層之厚度(TA1 )之比可為約9 MPa/mm以下。具備如此G'100 /TA1 為特定值以下之黏著劑層之黏著片材有與G'100 /TA1 更大之黏著劑層相比，長期來看顯示出良好之密接性之傾向，故而較佳。例如，若利用G'100 為約0.08 MPa以上(典型而言為約0.08 MPa以上且未達約0.50 MPa)且G'100 /TA1 為約9 MPa/mm以下之黏著劑層，則可實現如下之黏著片材：即便將第1黏著面上之剝離膜更換為平滑性更低者，該第1黏著面之平滑性亦不易受損，且對被接著體之長期之密接性優異。就獲得更良好之效果之觀點而言，一態樣中，可將G'100 /TA1 設為約7.0 MPa/mm以下。此處揭示之技術可以例如G'100 /TA1 為約5.0 MPa/mm以下(例如約3.0 MPa/mm以下)之態樣較佳地實施。G'100 /TA1 之下限並無特別限定，通常適宜設為約0.1 MPa/mm以上。 此處揭示之技術中，構成第1黏著面之黏著劑層之厚度(TA1 )並無特別限定。TA1 可為例如約1 μm～約500 μm(典型而言為約1 μm～約250 μm)。一態樣中，TA1 可為約5 μm以上，亦可為約15 μm以上。若TA1 變大，則有由將第1黏著面上之剝離膜更換為平滑性較低者而導致之該第1黏著面之平滑性降低變得易於進行之傾向。因此，應用此處揭示之技術而抑制第1黏著面之平滑性降低之意義更為重大。就該觀點而言，此處揭示之技術可以TA1 超過約20 μm(更佳為約25 μm以上，進而較佳為約30 μm以上，例如約40 μm以上)之態樣較佳地實施。又，若TA1 變小，則有第1黏著面之平滑性對黏著片材整體之特性造成之影響變得更大之傾向。就該觀點而言，此處揭示之技術可以TA1 為約250 μm以下(更佳為約150 μm以下，例如約100 μm以下)之態樣較佳地實施。一態樣中，TA1 亦可為約60 μm以下(例如約50 μm以下)。 此處揭示之技術之一態樣中，構成第1黏著面之黏著劑層之23℃儲存彈性模數(G'23 )相對於該黏著劑層之厚度(TA1 )之比可未達約10 MPa/mm。具備如此G'23 /TA1 未達特定值之黏著劑層之黏著片材有與G'23 /TA1 更大之黏著劑層相比，對被接著體顯示出更良好之初期接著性之傾向。例如，若利用G'100 為約0.08 MPa以上(典型而言為約0.08 MPa以上且未達約0.50 MPa)且G'23 /TA1 未達約10 MPa/mm之黏著劑層，則可實現如下之黏著片材：即便將第1黏著面上之剝離膜更換為平滑性更低者，該第1黏著面之平滑性亦不易受損，且對被接著體之初期接著性良好。就獲得更良好之效果之觀點而言，一態樣中，可將G'23 /TA1 設為約8.0 MPa/mm以下。此處揭示之技術可以例如G'23 /TA1 為約6.0 MPa/mm以下(例如約5.0 MPa/mm以下)之態樣較佳地實施。G'23 /TA1 之下限並無特別限定，通常適宜設為約0.2 MPa/mm以上。 於此處揭示之黏著片材為雙面黏著片材之形態之情形時，上述第2黏著面可為構成第1黏著面之黏著劑層之另一表面。由於此種態樣之雙面黏著片材(無基材之雙面黏著片材)之結構簡單，故而適合於光學特性(例如透明性)之提高。又，第2黏著面亦可為與構成第1黏著面之黏著劑層不同之黏著劑層、即第2黏著劑層之表面。此種態樣之雙面黏著片材典型而言為附基材之雙面黏著片材之形態，根據第1黏著劑層與第2黏著劑層之組成或構成之組合及支持基材之選擇而可實現多種多樣之性能。雖並無特別限定，但於一態樣中，第2黏著劑層可以滿足上文關於第1黏著劑層所述之各種特性(例如，G'100 、G'23 、G'100 /G'23 、TA1 、G'100 /TA1 、G'23 /TA1 、霧度值等)之1種或2種以上之方式構成。 ＜黏著劑＞ 此處揭示之技術中，構成黏著劑層之黏著劑之種類並無特別限定。例如可為包含選自丙烯酸系黏著劑、橡膠系黏著劑(天然橡膠系、合成橡膠系、該等之混合系等)、聚矽氧系黏著劑、聚酯系黏著劑、胺基甲酸酯系黏著劑、聚醚系黏著劑、聚醯胺系黏著劑、氟系黏著劑等公知之各種黏著劑中之1種或2種以上之黏著劑而構成之黏著劑層。此處，丙烯酸系黏著劑係指將(甲基)丙烯酸系聚合物作為基礎聚合物(聚合物成分中之主成分、即含量超過50質量%之成分)之黏著劑。橡膠系黏著劑及其他黏著劑亦為相同之含義。就透明性或耐候性等觀點而言，作為較佳之黏著劑層，可列舉丙烯酸系黏著劑之含有比率為50重量%以上、更佳為70重量%以上、進而較佳為90重量%以上之黏著劑層。丙烯酸系黏著劑之含有比率可超過98重量%，亦可為實質上由丙烯酸系黏著劑構成之黏著劑層。 此處，本說明書中，「(甲基)丙烯酸」係指包括丙烯酸及甲基丙烯酸之含義。同樣地，「(甲基)丙烯醯基」係指包括丙烯醯基及甲基丙烯醯基之含義，「(甲基)丙烯酸酯」係指包括丙烯酸酯及甲基丙烯酸酯之含義。 又，本說明書中，(甲基)丙烯酸系聚合物係指包含(甲基)丙烯酸系單體作為構成該(甲基)丙烯酸系聚合物之單體成分之聚合物。即，係指包含源自(甲基)丙烯酸系單體之單體單元之聚合物。此處，(甲基)丙烯酸系單體係指於1分子中具有至少1個(甲基)丙烯醯基之單體。 雖並無特別限定，但此處揭示之技術之一態樣中，上述黏著劑層可使用包含構成(甲基)丙烯酸系聚合物之單體成分之黏著劑組合物而較佳地製備。以下，有時將此種黏著劑組合物稱為「(甲基)丙烯酸系黏著劑組合物」。此處，「構成(甲基)丙烯酸系聚合物之單體成分」係指於由(甲基)丙烯酸系黏著劑組合物獲得之黏著劑中，構成(甲基)丙烯酸系聚合物之單體成分。上述單體成分於(甲基)丙烯酸系黏著劑組合物中可作為未反應單體(即，以聚合性官能基未反應之原料單體之形態)含有，亦可以聚合物之形態(即，作為單體單元)含有，亦可以該等兩者之形態含有。 ＜單體成分＞ 此處揭示之技術之一態樣中，上述黏著劑層可使用包含以下之(A)成分作為構成上述(甲基)丙烯酸系聚合物之單體成分之黏著劑組合物而形成。較佳之一態樣中，上述黏著劑層可使用下述(甲基)丙烯酸系黏著劑組合物而較佳地形成，上述(甲基)丙烯酸系黏著劑組合物至少包含以下之(A)成分、視需要進而包含以下之(B)成分及以下之(C)成分之一者或兩者作為構成上述(甲基)丙烯酸系聚合物之單體成分。 ((A)成分) 上述(A)成分係在酯末端具有碳數2～18之烷基之(甲基)丙烯酸烷基酯。以下，有時將在酯末端具有碳數為X以上且Y以下之烷基之(甲基)丙烯酸烷基酯表述為「(甲基)丙烯酸CX-Y 烷基酯」。(甲基)丙烯酸C2-18 烷基酯中之C2-18 烷基之結構並無特別限定，可使用上述烷基為直鏈者及為支鏈者中之任一種。作為(A)成分，可單獨使用此種(甲基)丙烯酸C2-18 烷基酯中之1種或者組合使用2種以上。 作為在酯末端具有直鏈烷基之(甲基)丙烯酸C2-18 烷基酯，可列舉：(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯、(甲基)丙烯酸正十五烷基酯、(甲基)丙烯酸正十六烷基酯、(甲基)丙烯酸正十七烷基酯及(甲基)丙烯酸正十八烷基酯。又，作為在酯末端具有支鏈烷基之(甲基)丙烯酸C3-18 烷基酯，可例示：(甲基)丙烯酸異丙酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸第三戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸異己酯、(甲基)丙烯酸異庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸2-丙基庚酯、(甲基)丙烯酸異十一烷基酯、(甲基)丙烯酸異十二烷基酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸異肉豆蔻基酯、(甲基)丙烯酸異十五烷基酯、(甲基)丙烯酸異十六烷基酯、(甲基)丙烯酸異十七烷基酯、(甲基)丙烯酸異硬脂基酯等。此處揭示之技術可以(A)成分包含選自丙烯酸C4-9 烷基酯中之1種或2種以上之態樣較佳地實施。作為丙烯酸C4-9 烷基酯之較佳例，可列舉：丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸異辛酯及丙烯酸異壬酯。 ((B)成分) 上述(B)成分為脂環式單體。於將該(B)成分與上述(A)成分組合而使用之態樣中，可較佳地實現平衡良好地兼顧此處揭示之較佳之儲存彈性模數與其他黏著性能(例如，對被接著體之接著性)之黏著劑層。 作為脂環式單體，可無特別限定地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有含脂環結構之基者。作為(B)成分，可單獨使用此種脂環式單體中之1種或者組合使用2種以上。此處，「含脂環結構之基」係指包含至少一個脂環結構之部分。又，「脂環結構」係指不具有芳香族性之飽和或不飽和之碳環結構。本說明書中，有時將含脂環結構之基簡稱為「脂環式基」。作為脂環式基之較佳例，可列舉包含脂環結構之烴基或烴氧基。 作為此處揭示之技術中較佳之脂環式單體之例，可列舉具有脂環式基及(甲基)丙烯醯基之脂環式(甲基)丙烯酸酯。作為脂環式(甲基)丙烯酸酯之具體例，可列舉：(甲基)丙烯酸環丙酯、(甲基)丙烯酸環丁酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸環庚酯、(甲基)丙烯酸環辛酯、(甲基)丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯、(甲基)丙烯酸二環戊酯等、以及下述化學式所示之HPMPA、TMA-2、HCPA等。
Figure 02_image001
脂環式單體中之脂環式基(脂環式(甲基)丙烯酸酯之情形時，自該脂環式(甲基)丙烯酸酯中去除(甲基)丙烯醯基所得之部分)之碳數並無特別限定。例如，可使用脂環式基之碳數為4～24(較佳為5～18、更佳為5～12)之脂環式單體。其中，較佳為丙烯酸環己酯(CHA)、甲基丙烯酸環己酯、丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯(IBXA)及甲基丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯，更佳為CHA及IBXA，尤佳為CHA。 ((C)成分) 上述(C)成分為具有羥基及羧基中之至少任一者之單體。 作為含羥基單體，可無特別限制地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有羥基者。含羥基單體可單獨使用1種或者組合使用2種以上。作為含羥基單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯等(甲基)丙烯酸羥基烷基酯；(甲基)丙烯酸(4-羥基甲基環己基)甲酯等(甲基)丙烯酸羥基烷基環烷烴酯。除此之外，可列舉：羥基乙基(甲基)丙烯醯胺、烯丙醇、2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚等。該等之中，較佳為(甲基)丙烯酸羥基烷基酯。例如可較佳地使用具有碳數2～6之羥基烷基之(甲基)丙烯酸羥基烷基酯。較佳之一態樣中，可將選自丙烯酸2-羥基乙酯(2HEA)、甲基丙烯酸2-羥基乙酯、丙烯酸4-羥基丁酯(4HBA)及甲基丙烯酸4-羥基丁酯中之1種或2種以上用作含羥基單體。此處揭示之技術之較佳態樣中使用之含羥基單體可為單獨之4HBA、單獨之2HEA、或者4HBA與2HEA之組合。 作為含羧基單體，可無特別限制地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有羧基者。含羧基單體可單獨使用1種或者組合使用2種以上。作為含羧基單體之例，可列舉：丙烯酸、甲基丙烯酸、巴豆酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯等乙烯性不飽和單羧酸；衣康酸、馬來酸、富馬酸、檸康酸等乙烯性不飽和二羧酸；該等之金屬鹽(例如鹼金屬鹽)；馬來酸酐、衣康酸酐等上述乙烯性不飽和二羧酸之酐等。該等之中，較佳為丙烯酸、甲基丙烯酸，尤佳為丙烯酸。 此處揭示之技術可以(C)成分包含含羥基單體之態樣較佳地實施。即，較佳為(C)成分僅包含含羥基單體、或者包含含羥基單體及含羧基單體。於(C)成分包含含羥基單體及含羧基單體之情形時，含羥基單體於(C)成分整體中所占之比率較佳為超過約50重量%，更佳為約80重量%以上(例如約90重量%以上)。增加含羥基單體於(C)成分中所占之比率就降低由羧基導致之金屬腐蝕等之觀點等而言較佳。此處揭示之技術可以單體成分實質上不含含羧基單體之態樣較佳地實施。例如，可將含羧基單體於單體成分中所占之比率設為未達約1重量%、較佳為未達約0.5重量%、更佳為未達約0.2重量%。 上述(A)成分於單體成分整體中所占之比率並無特別限定。就易於獲得G'100 及G'100 /G'23 中之一者或兩者成為較佳值之黏著劑層等而言，上述(A)成分之比率宜為約90重量%以下，較佳為約85重量%以下，更佳為約70重量%以下。較佳之一態樣中，亦可將上述(A)成分之比率設為約60重量%以下(進而為約50重量%以下，例如未達約50重量%)。又，就對被接著體之初期接著性等觀點而言，上述(A)成分之比率較佳為約30重量%以上，更佳為約35重量%以上。一態樣中，可將(A)成分於單體成分整體中所占之比率設為例如30～70重量%左右。 於包含(B)成分作為上述單體成分之情形時，(B)成分於單體成分整體中所占之比率並無特別限定。就易於獲得G'100 及G'100 /G'23 中之一者或兩者成為較佳值之黏著劑層等而言，上述(B)成分之比率通常宜為約3重量%以上，較佳為約5重量%以上，更佳為約8重量%以上(例如約10重量%以上)。又，就對被接著體之初期接著性等觀點而言，上述(B)成分之比率宜為約65重量%以下，較佳為約60重量%以下，更佳為約55重量%以下(進而為約50重量%以下，例如未達約50重量%)。較佳之一態樣中，可將(B)成分於單體成分整體中所占之比率設為約15重量%以上，可設為約20重量%以上，亦可設為約25重量%以上、進而約30重量%以上(例如約35重量%以上)。一態樣中，可將(B)成分於單體成分整體中所占之比率設為例如20～50重量%左右。 於包含(C)成分作為上述單體成分之情形時，(C)成分於單體成分整體中所占之比率並無特別限定。就對被接著體之初期接著性等觀點而言，上述(C)成分之比率典型而言為約3重量%以上，較佳為約5重量%以上，更佳為約8重量%以上(例如約10重量%以上)。又，就易於獲得G'100 及G'100 /G'23 中之一者或兩者成為較佳值之黏著劑層等而言，上述(C)成分之比率較佳為約35重量%以下，更佳為約30重量%以下，進而較佳為約25重量%以下。一態樣中，可將上述(C)成分之比率設為例如15～30重量%左右。 (任意單體) 此處揭示之技術中之單體成分亦可含有除上述之(A)成分、(B)成分及(C)成分以外之單體(以下亦稱為「任意單體」)。 作為此種任意單體之例，可列舉含環狀氮單體或含環狀醚基單體等含雜環單體。此種含雜環單體與上述(B)成分同樣地可有助於實現平衡良好地兼顧此處揭示之較佳之儲存彈性模數與其他黏著性能或其他特性之黏著劑層。又，亦可有助於提高黏著劑之接著力或凝聚力。含雜環單體可單獨使用1種或者組合使用2種以上。 作為含環狀氮單體，可無特別限制地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有環狀氮結構者。環狀氮結構較佳為於環狀結構內具有氮原子者。作為含環狀氮單體，例如可列舉：N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺、甲基乙烯基吡咯啶酮等內醯胺系乙烯基單體；2-乙烯基-2-
Figure 105138382-A0304-12-0015-1
唑啉、2-乙烯基-5-甲基-2-
Figure 105138382-A0304-12-0015-1
唑啉、2-異丙烯基-2-
Figure 105138382-A0304-12-0015-1
唑啉之類的含
Figure 105138382-A0304-12-0015-1
唑啉基之單體；乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌
Figure 105138382-A0304-12-0020-4
、乙烯基吡
Figure 105138382-A0304-12-0020-4
、乙烯基吡咯、乙烯基咪唑、乙烯基
Figure 105138382-A0304-12-0020-6
啉等具有含氮雜環之乙烯系單體等。作為含環狀氮單體之其他例，可列舉含有
Figure 105138382-A0304-12-0020-6
啉環、哌啶環、吡咯啶環、哌
Figure 105138382-A0304-12-0020-4
環、氮丙啶環等含氮雜環之(甲基)丙烯酸系單體。具體而言，可列舉：N-丙烯醯基
Figure 105138382-A0304-12-0020-6
啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯啶、N-丙烯醯基氮丙啶等。上述含環狀氮單體之中，就凝聚性等觀點而言，較佳為內醯胺系乙烯基單體，更佳為N-乙烯基吡咯啶酮。 作為具有環狀醚基之單體，可無特別限制地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有環氧基或氧雜環丁烷基等環狀醚基者。作為含環氧基之單體，例如可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚等。作為含氧雜環丁烷基之單體，例如可列舉：(甲基)丙烯酸3-氧雜環丁基甲酯、(甲基)丙烯酸3-甲基-氧雜環丁基甲酯、(甲基)丙烯酸3-乙基-氧雜環丁基甲酯、(甲基)丙烯酸3-丁基-氧雜環丁基甲酯、(甲基)丙烯酸3-己基-氧雜環丁基甲酯等。 作為上述任意單體之其他例，可列舉不屬於(A)成分之(甲基)丙烯酸烷基酯、即烷基之碳數為1或為19以上(例如19～24)之(甲基)丙烯酸烷基酯。作為此種(甲基)丙烯酸烷基酯之具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸正十九烷基酯、(甲基)丙烯酸異十九烷基酯、(甲基)丙烯酸正二十烷基酯、(甲基)丙烯酸異二十烷基酯等。該等可單獨使用1種或者組合使用2種以上。 作為上述任意單體之其他例，可列舉含有除羥基及羧基以外之官能基之單體。此種含官能基單體可以向(甲基)丙烯酸系聚合物中導入交聯點或者提高(甲基)丙烯酸系聚合物之凝聚力為目的而使用。作為含官能基單體，可列舉：例如(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等含醯胺基之單體；例如丙烯腈、甲基丙烯腈等含氰基之單體；例如苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸等含磺酸基之單體；例如丙烯醯基磷酸2-羥基乙酯等含磷酸基之單體；例如二丙酮(甲基)丙烯醯胺、二丙酮(甲基)丙烯酸酯、乙烯基甲基酮、乙醯乙酸乙烯酯等含酮基之單體；例如異氰酸2-(甲基)丙烯醯氧基乙酯等含異氰酸酯基之單體；例如(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基之單體；例如3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷等含烷氧基矽烷基之單體等。該等可單獨使用1種或者組合使用2種以上。 此處揭示之技術中之單體成分中，以調整(甲基)丙烯酸系聚合物之Tg或提高凝聚力等為目的，作為上述任意單體，亦可包含能夠與上述(A)、(B)、(C)成分共聚之除上述例示以外之共聚性單體。作為此種共聚性單體，可列舉：例如乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯；例如苯乙烯、取代苯乙烯(α-甲基苯乙烯等)、乙烯基甲苯等芳香族乙烯基化合物；例如(甲基)丙烯酸芳酯(例如(甲基)丙烯酸苯酯)、(甲基)丙烯酸芳氧基烷基酯(例如(甲基)丙烯酸苯氧基乙酯)、(甲基)丙烯酸芳基烷基酯(例如(甲基)丙烯酸苄酯)等含芳香族性環之(甲基)丙烯酸酯；例如乙烯、丙烯、異戊二烯、丁二烯、異丁烯等烯烴系單體；例如氯乙烯、偏二氯乙烯等含氯單體；例如甲基乙烯基醚、乙基乙烯基醚等乙烯基醚系單體；以及在使乙烯基聚合而成之單體末端具有自由基聚合性乙烯基之巨單體等。該等可單獨使用1種或者組合使用2種以上。 該等任意單體之使用量並無特別限定，可適當決定。通常，任意單體之合計使用量適宜設為未達單體成分之約50重量%，較佳為設為約30重量%以下，更佳為設為約20重量%以下。此處揭示之技術可以任意單體之合計使用量為單體成分之約10重量%以下(例如約5重量%以下)之態樣較佳地實施。於使用任意單體之情形時，就適當地發揮提高接著力或凝聚力之效果之觀點而言，適宜將該任意單體之使用量設為單體成分之約0.5重量%以上，較佳為設為約0.8重量%以上。又，此處揭示之技術亦可以實質上不使用任意單體之態樣(例如，任意單體之使用量為單體成分之約0.3重量%以下，典型而言為約0.1重量%以下之態樣)較佳地實施。 上述之(A)成分、(B)成分、(C)成分及任意單體典型而言為單官能單體。上述單體成分中，除了此種單官能單體以外，以調整黏著劑層之儲存彈性模數等為目的，可視需要含有適當量之多官能單體。此處，本說明書中，單官能單體係指僅具有1個(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基(典型而言為自由基聚合性官能基)之單體。相對於此，多官能單體如下所述係指具有至少2個此種聚合性官能基之單體。 (多官能單體) 多官能單體係具有至少2個(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基(典型而言為自由基聚合性官能基)之單體。作為多官能單體之例，可列舉：乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯等多元醇與(甲基)丙烯酸之酯；(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯基苯、環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯等。作為該等中之較佳例，可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。其中，作為較佳例，可列舉1,6-己二醇二(甲基)丙烯酸酯。多官能性單體可單獨使用1種或者組合使用2種以上。就反應性等觀點而言，通常較佳為具有2個以上丙烯醯基之多官能單體。 多官能單體之使用量並無特別限定，可以達成該多官能單體之使用目的之方式適當地設定。就平衡良好地兼顧此處揭示之較佳之儲存彈性模數與其他黏著性能或其他特性之觀點而言，一態樣中，多官能單體之使用量可設為上述單體成分之約3重量%以下，較佳為約2重量%以下，更佳為約1重量%以下(例如約0.5重量%以下)。使用多官能單體之情形時之使用量之下限大於0重量%即可，並無特別限定。通常藉由將多官能單體之使用量設為單體成分之約0.001重量%以上(例如約0.01重量%以上)，可適當地發揮該多官能單體之使用效果。 雖並無特別限定，但(A)成分、(B)成分及(C)成分之合計量於上述單體成分整體中所占之比率典型而言為超過約50重量%，較佳為約70重量%以上，更佳為約80重量%以上，進而較佳為約90重量%以上。此處揭示之技術可以上述合計量之比率為約95重量%以上(例如約99重量%以上)之態樣較佳地實施。上述合計量之比率亦可為100重量%。此處揭示之技術可以上述合計量於上述單體成分整體中所占之比率為99.999重量%以下(例如99.99重量%以下)之態樣較佳地實施。 雖並無特別限定，但就黏著片材之接著性或低溫特性等觀點而言，與上述單體成分之組成相對應之共聚物之Tg較佳為約-20℃以下，更佳為約-25℃以下。又，就易於獲得G'100 及G'100 /G'23 中之一者或兩者成為較佳值之黏著劑層等而言，上述共聚物之Tg宜為約-55℃以上，較佳為約-50℃以上，更佳為約-45℃以上。此處揭示之技術亦可以上述共聚物之Tg為約-40℃以上(例如約-35℃以上)之態樣較佳地實施。 此處，與單體成分之組成相對應之共聚物之Tg係指基於上述單體成分之組成由Fox公式求出之Tg。Fox公式如下所示係共聚物之Tg、與構成該共聚物之單體分別均聚而成之均聚物之玻璃轉移溫度Tgi之關係式。 1/Tg＝Σ(Wi/Tgi) 再者，於上述Fox公式中，Tg表示共聚物之玻璃轉移溫度(單位：K)，Wi表示該共聚物中之單體i之重量分率(重量基準之共聚比率)，Tgi表示單體i之均聚物之玻璃轉移溫度(單位：K)。但是，本說明書中，Tg之計算僅考慮單官能單體而進行。因此，於單體成分包含多官能單體之情形時，將該單體成分中包含之單官能單體之合計量設為100重量%，基於各單官能單體之均聚物之Tg及該單官能單體相對於上述合計量之重量分率而算出Tg。 作為計算Tg時使用之均聚物之玻璃轉移溫度，使用公知資料中記載之值。例如關於以下列舉之單體，該單體之均聚物之玻璃轉移溫度使用以下之值。 丙烯酸正丁酯                             -55℃ 丙烯酸2-乙基己酯                      -70℃ 丙烯酸環己酯                             15℃ 丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯                94℃ 丙烯酸2-羥基乙酯                      -15℃ 丙烯酸4-羥基丁酯                      -40℃ 丙烯酸                                       106℃ 甲基丙烯酸                                228℃ 關於上述例示以外之單體之均聚物之玻璃轉移溫度，使用「Polymer Handbook」(第3版，John Wiley & Sons, Inc，1989年)中記載之數值。關於該文獻中記載有多種數值之單體，採用最高值。 關於上述「Polymer Handbook」中亦未記載均聚物之玻璃轉移溫度之單體，使用藉由以下之測定方法所獲得之值(參照日本專利申請公開2007-51271號公報)。具體而言，向具備溫度計、攪拌機、氮氣導入管及回流冷卻管之反應器中投入單體100重量份、偶氮雙異丁腈0.2重量份及作為聚合溶劑之乙酸乙酯200重量份，一面流通氮氣一面攪拌1小時。如此去除聚合體系內之氧氣後，升溫至63℃並使其反應10小時。繼而，冷卻至室溫，獲得固形物成分濃度為33重量%之均聚物溶液。將該均聚物溶液流延塗佈於剝離膜上，進行乾燥而製作厚度約2 mm之試驗樣品(片狀之均聚物)。將該試驗樣品沖裁成直徑7.9 mm之圓盤狀，用平行板夾持，使用黏彈性試驗裝置(TA Instruments公司製造，ARES)，一面賦予頻率為1 Hz之剪切應變，一面於-70～150℃之溫度區域內以5℃/分鐘之升溫速度利用剪切模式測定黏彈性，將tanδ(損耗正切)之峰頂溫度設為玻璃轉移溫度。 ＜黏著劑組合物＞ 此處揭示之黏著劑層可使用以聚合物、未聚合物(即，聚合性官能基為未反應之形態)或者該等之混合物之形態包含如上所述之組成之單體成分之黏著劑組合物而形成。上述黏著劑組合物可為如下各種形態：於有機溶劑中包含黏著劑(黏著成分)之形態之組合物(溶劑型黏著劑組合物)；黏著劑分散於水性溶劑中之形態之組合物(水分散型黏著劑組合物)；以利用紫外線或放射線等活性能量線進行硬化而形成黏著劑之方式製備之組合物(活性能量線硬化型黏著劑組合物)；於加熱熔融狀態下進行塗敷並冷卻至室溫附近時會形成黏著劑之熱熔型黏著劑組合物等。 此處，本說明書中，「活性能量線」係指具有能夠引起聚合反應、交聯反應、起始劑之分解等化學反應之能量之能量線。此處所謂之活性能量線之例中包含紫外線、可見光線、紅外線之類的光；或者α射線、β射線、γ射線、電子束、中子束、X射線之類的放射線等。 上述黏著劑組合物典型而言以聚合物之形態包含該組合物之單體成分中之至少一部分(可為單體之種類之一部分，亦可為分量之一部分)。形成上述聚合物時之聚合方法並無特別限定，可適當採用先前公知之各種聚合方法。例如，可適當採用溶液聚合、乳液聚合、塊狀聚合等熱聚合(典型而言，於熱聚合起始劑之存在下進行)；照射紫外線等光而進行之光聚合(典型而言，於光聚合起始劑之存在下進行)；照射β射線、γ射線等放射線而進行之放射線聚合等。其中，較佳為光聚合。該等聚合方法中，聚合之態樣並無特別限定，可適當選擇先前公知之單體供給方法、聚合條件(溫度、時間、壓力、光照射量、放射線照射量等)、單體以外之使用材料(聚合起始劑、界面活性劑等)等而進行。 聚合時，可根據聚合方法或聚合態樣等而使用公知或慣用之光聚合起始劑或熱聚合起始劑。此種聚合起始劑可單獨使用1種或者適當組合使用2種以上。 作為光聚合起始劑，並無特別限定，例如可使用縮酮系光聚合起始劑、苯乙酮系光聚合起始劑、安息香醚系光聚合起始劑、醯基氧化膦系光聚合起始劑、α-酮醇系光聚合起始劑、芳香族磺醯氯系光聚合起始劑、光活性肟系光聚合起始劑、安息香系光聚合起始劑、苯偶醯系光聚合起始劑、二苯甲酮系光聚合起始劑、9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
系光聚合起始劑等。 縮酮系光聚合起始劑之具體例包括2,2-二甲氧基-1,2-二苯基乙烷-1-酮(例如，BASF公司製造之商品名「Irgacure 651」)等。 苯乙酮系光聚合起始劑之具體例包括1-羥基環己基-苯基-酮(例如，BASF公司製造之商品名「Irgacure 184」)、4-苯氧基二氯苯乙酮、4-第三丁基-二氯苯乙酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮(例如，BASF公司製造之商品名「Irgacure 2959」)、2-羥基-2-甲基-1-苯基-丙烷-1-酮(例如，BASF公司製造之商品名「Darocure 1173」)、甲氧基苯乙酮等。 安息香醚系光聚合起始劑之具體例包括安息香甲醚、安息香乙醚、安息香丙醚、安息香異丙醚、安息香異丁醚等安息香醚及茴香醚甲醚(anisole methyl ether)等經取代之安息香醚。 醯基氧化膦系光聚合起始劑之具體例包括雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(例如，BASF公司製造之商品名「Irgacure 819」)、雙(2,4,6-三甲基苯甲醯基)-2,4-二正丁氧基苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦(例如，BASF公司製造之商品名「Lucirin TPO」)、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦等。 α-酮醇系光聚合起始劑之具體例包括2-甲基-2-羥基苯丙酮、1-[4-(2-羥基乙基)苯基]-2-甲基丙烷-1-酮等。芳香族磺醯氯系光聚合起始劑之具體例包括2-萘磺醯氯等。光活性肟系光聚合起始劑之具體例包括1-苯基-1,1-丙二酮-2-(O-乙氧基羰基)肟等。安息香系光聚合起始劑之具體例包括安息香等。苯偶醯系光聚合起始劑之具體例包括苯偶醯等。 二苯甲酮系光聚合起始劑之具體例包括二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮、聚乙烯基二苯甲酮、α-羥基環己基苯基酮等。 9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
系光聚合起始劑之具體例包括9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2-氯-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2-甲基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2,4-二甲基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、異丙基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2,4-二氯-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2,4-二乙基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、異丙基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、2,4-二異丙基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
、十二烷基-9-氧硫
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
等。 作為熱聚合起始劑，並無特別限定，例如可使用偶氮系聚合起始劑、過氧化物系起始劑、由過氧化物與還原劑之組合形成之氧化還原系起始劑、經取代之乙烷系起始劑等。更具體而言，可例示：例如2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)、2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙脒]水合物等偶氮系起始劑；例如過硫酸鉀、過硫酸銨等過硫酸鹽；過氧化苯甲醯、氫過氧化第三丁基、過氧化氫等過氧化物系起始劑；例如經苯基取代之乙烷等經取代之乙烷系起始劑；例如過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉之組合等氧化還原系起始劑等，但不限定於該等。再者，熱聚合可於例如20～100℃(典型而言為40～80℃)左右之溫度下較佳地實施。 此種熱聚合起始劑或光聚合起始劑之使用量可設為與聚合方法或聚合態樣等相對應之通常之使用量，並無特別限定。例如，相對於聚合對象之單體100重量份，可使用聚合起始劑約0.001～5重量份(典型而言為約0.01～2重量份，例如為約0.01～1重量份)。 (包含單體成分之聚合物及未聚合物之黏著劑組合物) 較佳之一態樣之黏著劑組合物包含單體混合物之聚合反應物，上述單體混合物包含該組合物之至少一部分單體成分(原料單體)。典型而言，以聚合物之形態包含上述單體成分之一部分，以未聚合物(未反應之單體)之形態包含剩餘部分。上述單體混合物之聚合反應物可藉由使該單體混合物至少部分聚合而製備。 上述聚合反應物較佳為上述單體混合物之部分聚合物。此種部分聚合物為源自上述單體混合物之聚合物與未反應之單體之混合物，典型而言，呈現漿液狀(有黏性之液狀)。以下，有時將上述性狀之部分聚合物稱為「單體漿液」或簡稱為「漿液」。 獲得上述聚合反應物時之聚合方法並無特別限定，可適當地選擇使用如上所述之各種聚合方法。就效率或簡便性之觀點而言，可較佳地採用光聚合法。若利用光聚合，則藉由光之照射量(光量)等聚合條件，可容易地控制上述單體混合物之聚合轉化率。 上述部分聚合物中之單體混合物之聚合轉化率(單體轉化率，monomer conversion)並無特別限定。上述聚合轉化率可設為例如約70重量%以下，較佳為設為約60重量%以下。就包含上述部分聚合物之黏著劑組合物之製備容易性或塗敷性等觀點而言，通常上述聚合轉化率宜為約50重量%以下，較佳為約40重量%以下(例如約35重量%以下)。聚合轉化率之下限並無特別限定，典型而言為約1重量%以上，通常適宜設為約5重量%以上。 包含上述單體混合物之部分聚合物之黏著劑組合物例如可藉由利用適當之聚合方法(例如光聚合法)使包含全部原料單體之單體混合物進行部分聚合而容易地獲得。包含上述部分聚合物之黏著劑組合物中可調配視需要使用之其他成分(例如光聚合起始劑、多官能單體、交聯劑、後述丙烯酸系低聚物等)。調配此種其他成分之方法並無特別限定，例如可使其預先含有於上述單體混合物中，亦可添加至上述部分聚合物中。 又，此處揭示之黏著劑組合物亦可為包含單體成分(原料單體)中之一部分種類之單體之單體混合物之完全聚合物溶解於剩餘種類之單體或其部分聚合物中之形態。此種形態之黏著劑組合物亦包括於包含單體成分之聚合物及未聚合物之黏著劑組合物之例中。再者，本說明書中，「完全聚合物」係指聚合轉化率超過95重量%。 作為如此由包含單體成分之聚合物及未聚合物之黏著劑組合物形成黏著劑時之硬化方法(聚合方法)，可較佳地採用光聚合法。關於包含藉由光聚合法製備之聚合反應物之黏著劑組合物，尤佳為採用光聚合法作為其硬化方法。藉由光聚合法獲得之聚合反應物已經包含光聚合起始劑，因此使包含該聚合反應物之黏著劑組合物進一步硬化而形成黏著劑時，即便不追加新的光聚合起始劑亦能夠進行光硬化。或者，亦可為於藉由光聚合法製備之聚合反應物中視需要追加光聚合起始劑而獲得之組成之黏著劑組合物。追加之光聚合起始劑可與用於製備聚合反應物之光聚合起始劑相同，亦可不同。藉由光聚合以外之方法製備之黏著劑組合物可藉由添加光聚合起始劑而成為光硬化性。光硬化性之黏著劑組合物具有即便係較厚之黏著劑層亦可容易地形成之優點。較佳之一態樣中，由黏著劑組合物形成黏著劑時之光聚合可藉由紫外線照射而進行。紫外線照射可使用公知之高壓水銀燈、低壓水銀燈、金屬鹵化物燈等。 (以完全聚合物之形態包含單體成分之黏著劑組合物) 較佳之另一態樣之黏著劑組合物以完全聚合物之形態包含該劑組合物之單體成分。此種黏著劑組合物可為例如於有機溶劑中包含作為單體成分之完全聚合物之(甲基)丙烯酸系聚合物之溶劑型黏著劑組合物、上述(甲基)丙烯酸系聚合物分散於水性溶劑中而成之水分散型黏著劑組合物等形態。 (交聯劑) 此處揭示之黏著劑組合物可含有交聯劑。作為交聯劑，可使用黏著劑之領域中公知或慣用之交聯劑。例如可列舉：環氧系交聯劑、異氰酸酯系交聯劑、聚矽氧系交聯劑、
Figure 105138382-A0304-12-0015-1
唑啉系交聯劑、氮丙啶系交聯劑、矽烷系交聯劑、烷基醚化三聚氰胺系交聯劑、金屬螯合物系交聯劑等。該等可單獨使用1種或者組合使用2種以上。 交聯劑之含量(於包含2種以上之交聯劑之情形時為其等之合計量)並無特別限定。就實現平衡良好地發揮接著力或凝聚力等黏著特性之黏著劑之觀點而言，相對於黏著劑組合物中所含之單體成分100重量份，交聯劑之含量通常適宜設為約5重量份以下，較佳為設為約0.001～5重量份，更佳為設為約0.001～4重量份，進而較佳為設為約0.001～3重量份。或者，亦可為不含如上所述之交聯劑之黏著劑組合物。 ((甲基)丙烯酸系低聚物) 就提高接著力等觀點而言，此處揭示之黏著劑組合物中可含有(甲基)丙烯酸系低聚物。作為(甲基)丙烯酸系低聚物，較佳為使用Tg比與上述單體成分之組成相對應之共聚物之Tg(典型而言，大致對應於由黏著劑組合物形成之黏著劑中所含之(甲基)丙烯酸系聚合物之Tg)高之聚合物。藉由含有(甲基)丙烯酸系低聚物，可提高黏著劑之接著力。 上述(甲基)丙烯酸系低聚物較理想為Tg為約0℃以上且約300℃以下，較佳為約20℃以上且約300℃以下，進而較佳為約40℃以上且約300℃以下。藉由使Tg為上述範圍內，可較佳地提高接著力。再者，(甲基)丙烯酸系低聚物之Tg和與上述單體成分之組成相對應之共聚物之Tg同樣地，係基於Fox公式計算之值。 (甲基)丙烯酸系低聚物之重量平均分子量(Mw)典型而言可為約1000以上且未達約30000，較佳為約1500以上且未達約20000，進而較佳為約2000以上且未達約10000。藉由使Mw為上述範圍內，可獲得良好之接著力或保持特性，故而較佳。(甲基)丙烯酸系低聚物之Mw可藉由凝膠滲透層析法(GPC)進行測定，並以標準聚苯乙烯換算之值之形式而求出。具體而言，東曹股份有限公司製造之HPLC8020中使用TSK gel GMH-H(20)×2根作為管柱，利用四氫呋喃溶劑於流速約0.5 ml/分鐘之條件下進行測定。 作為構成(甲基)丙烯酸系低聚物之單體，例如可列舉：(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)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(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)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯之類的(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯、(甲基)丙烯酸二環戊酯之類的(甲基)丙烯酸與脂環族醇之酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯之類的(甲基)丙烯酸芳酯；由萜烯化合物衍生物醇獲得之(甲基)丙烯酸酯等。此種(甲基)丙烯酸酯可單獨使用1種或者組合使用2種以上。 作為(甲基)丙烯酸系低聚物，就可進一步提高黏著劑層之接著性之觀點而言，較佳為包含以(甲基)丙烯酸異丁酯或(甲基)丙烯酸第三丁酯之類的烷基具有支鏈結構之(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯或(甲基)丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯、(甲基)丙烯酸二環戊酯之類的(甲基)丙烯酸與脂環式醇之酯；(甲基)丙烯酸苯酯或(甲基)丙烯酸苄酯之類的(甲基)丙烯酸芳酯等具有環狀結構之(甲基)丙烯酸酯為代表之具有體積相對較大之結構之丙烯酸系單體作為單體單元。又，於合成(甲基)丙烯酸系低聚物時或製作黏著劑層時採用紫外線之情形時，就不易引起聚合阻礙之觀點而言，較佳為具有飽和鍵者，可將烷基具有支鏈結構之(甲基)丙烯酸烷基酯、或者與脂環式醇之酯較佳地用作構成(甲基)丙烯酸系低聚物之單體。 就此種觀點而言，作為較佳之(甲基)丙烯酸系低聚物，例如可列舉：甲基丙烯酸二環戊酯(DCPMA)、甲基丙烯酸環己酯(CHMA)、甲基丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯(IBXMA)、丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯(IBXA)、丙烯酸二環戊酯(DCPA)、甲基丙烯酸1-金剛烷基酯(ADMA)、丙烯酸1-金剛烷基酯(ADA)各自之均聚物、以及CHMA與甲基丙烯酸異丁酯(IBMA)之共聚物、CHMA與IBXMA之共聚物、CHMA與丙烯醯基
Figure 105138382-A0304-12-0020-6
啉(ACMO)之共聚物、CHMA與二乙基丙烯醯胺(DEAA)之共聚物、ADA與甲基丙烯酸甲酯(MMA)之共聚物、DCPMA與IBXMA之共聚物、DCPMA與MMA之共聚物等。 於此處揭示之黏著劑組合物中含有(甲基)丙烯酸系低聚物之情形時，其含量並無特別限定。就容易實現此處揭示之具有較佳之儲存彈性模數之黏著劑層之觀點而言，(甲基)丙烯酸系低聚物之含量通常相對於該黏著劑組合物中所含之單體成分100重量份，較佳為設為約20重量份以下，更佳為設為約15重量以下，進而較佳為設為約10重量份以下。此處揭示之技術亦可以不使用(甲基)丙烯酸系低聚物之態樣較佳地實施。 此外，此處揭示之黏著劑組合物可視需要含有於黏著劑之領域中公知之各種添加劑。例如可根據用途適當添加染料或顏料等著色劑、抗靜電劑、界面活性劑、塑化劑、黏著賦予樹脂、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機填充劑或有機填充劑、金屬粉、粒子狀物、箔狀物等。 此處揭示之技術中，作為用於形成黏著劑層之黏著劑組合物，可較佳地使用活性能量線硬化型黏著劑組合物(典型而言為光硬化型黏著劑組合物)。作為上述活性能量線硬化型黏著劑組合物，就環境衛生等觀點而言，較佳為實質上不含有機溶劑者。例如，較佳為有機溶劑之含量為約5重量%以下(更佳為約3重量%以下，例如約0.5重量%以下)之黏著劑組合物。又，如下所述，由於適合於形成使黏著劑組合物之液膜在一對剝離膜之剝離面間硬化之形態之黏著劑層，故而較佳為實質上不含溶劑(包含有機溶劑及水性溶劑之含義)之黏著劑組合物。例如，較佳為溶劑之含量為約5重量%以下(更佳為約3重量%以下，例如約0.5重量%以下)之黏著劑組合物。再者，此處溶劑係指於黏著劑層之形成過程中應去除之揮發性成分，即不意圖成為最終形成之黏著劑層之構成成分之揮發性成分。 ＜黏著片材之製造方法＞ 製造此處揭示之黏著片材之方法並無特別限定。例如，藉由將此處揭示之任一黏著劑組合物塗佈於剝離膜之剝離面上並使其乾燥或硬化而形成黏著劑層，可獲得包含該黏著劑層之無基材之雙面黏著片材。又，藉由將如此形成於剝離膜上之黏著劑層貼合(轉印)於支持基材之非剝離面上，可獲得附基材之單面黏著片材。作為製造附基材之單面黏著片材之其他方法，可列舉於支持基材之非剝離面直接塗佈黏著劑組合物並使其乾燥或硬化之方法。附基材之雙面黏著片材可藉由將形成於剝離膜上之黏著劑層轉印至支持基材之方法、或將黏著劑組合物直接塗佈於支持基材並使其乾燥或硬化之方法、或者組合該等之方法等而製造。 作為黏著劑組合物之塗佈方法，可使用先前公知之各種方法。具體而言，例如可列舉：輥式塗佈、接觸輥式塗佈、凹版塗佈、反向塗佈、輥式刷塗、噴霧塗佈、浸漬輥塗佈、棒式塗佈、刀式塗佈、氣刀塗佈、淋幕式塗佈、模唇塗佈、利用模嘴塗佈機等之擠出塗佈法等方法。 此處揭示之黏著片材可藉由如下方法而較佳地製造，該方法包括於剝離膜之剝離面上使黏著劑組合物之液膜乾燥或硬化而形成於上述剝離面上硬化之面為第1黏著面之黏著劑層。若利用該方法，則可藉由具有流動性之狀態之黏著劑組合物(液膜)與上述剝離面接觸並乾燥或硬化，而高精度地控制與該剝離面接觸而形成之黏著劑層表面之平滑性。例如，可藉由使用具備具有適當之平滑性之剝離面之剝離膜，而穩定地(再現性良好地)製造具有所期望之平滑性之第1黏著面。 此處揭示之黏著片材可藉由如下方法而較佳地製造，該方法包括使上述黏著劑組合物之液膜於一對剝離膜之剝離面間硬化而形成黏著劑層。該方法作為第1黏著面之十點平均粗糙度及第2黏著面之十點平均粗糙度均在此處揭示之較佳之範圍內之無基材之雙面黏著片材之製造方法較佳。又，藉由將如此獲得之無基材之雙面黏著片材貼合於支持基材之非剝離面，亦可較佳地用於製造附基材之單面黏著片材或附基材之雙面黏著片材。作為於一對剝離膜之剝離面間配置黏著劑組合物之液膜之方法，可採用如下方法，即，於第1剝離膜之剝離面塗佈液狀之黏著劑組合物，繼而於該黏著劑組合物之液膜上覆蓋第2剝離膜。作為其他方法，可列舉使剝離面相對向地向一對輥間供給第1剝離膜與第2剝離膜，並且向該等之剝離面之間供給液狀之黏著劑組合物之方法。再者，黏著劑組合物之塗佈較佳為於80℃以下進行，更佳為於60℃以下(例如40℃以下)進行。藉此，可抑制因剝離膜與黏著劑層之熱膨脹率不同所導致之黏著劑層之粗糙，形成平滑性更高之黏著面。 此處揭示之黏著劑層之凝膠分率並無特別限定，通常較佳為約99.5重量%以下，更佳為約20～99.5重量%，進而較佳為約50～99.5重量%。於上述黏著劑組合物含有交聯劑之情形時，可調整交聯劑之添加量，並且考慮交聯處理溫度或交聯處理時間之影響而控制凝膠分率。 雖並無特別限定，但構成此處揭示之黏著片材之黏著劑層較佳為厚度50 μm下之霧度值為2%以下。對於用於光學用途之黏著劑層，上述霧度值為2%以下特別有意義。黏著劑層之霧度值較佳為0～1.5%，更佳為0～1%。上述霧度值可將以厚度成為約50 μm之方式形成之黏著劑層貼附於鹼玻璃板之單面，使用霧度計而測定。作為霧度計，可使用村上色彩技術研究所製造之MR-100或其相當品。測定時，將貼附有黏著劑層之鹼玻璃板以該黏著劑層成為光源側之方式進行配置。於鹼玻璃本身具有霧度值之情形時，將自測定值減去鹼玻璃板本身之霧度值所得之值設為黏著劑層之霧度值。 ＜剝離膜＞ 此處揭示之技術中之剝離膜並無特別限定，可根據目的而適當選擇。可使用之剝離膜之非限定性之例包括：於剝離膜基材之一表面或兩表面具有剝離處理層，該剝離處理層之表面成為剝離面之剝離膜；及包含氟系聚合物(聚四氟乙烯等)或聚烯烴系樹脂(聚乙烯、聚丙烯等)之低接著性樹脂之剝離膜。作為上述剝離膜基材，可使用塑膠膜、紙(可為樹脂含浸紙或樹脂層壓紙)等。上述剝離處理層可為藉由剝離處理劑對上述剝離膜基材進行表面處理而形成者。作為剝離處理劑之例，可列舉：聚矽氧系剝離處理劑、長鏈烷基系剝離處理劑、氟系剝離處理劑、硫化鉬(IV)等。一態樣中，可較佳地採用具有基於聚矽氧系剝離處理劑之剝離處理層之剝離膜。 作為此處揭示之剝離膜，可較佳地採用於作為剝離膜基材之塑膠膜之表面具有剝離處理層者。構成此種塑膠膜之材料可自與作為用於支持基材之塑膠膜例示之材料相同之材料中任意地選擇。就尺寸穩定性或強度之觀點而言，可較佳地採用包含聚酯系樹脂膜(典型而言為聚對苯二甲酸乙二酯膜)之塑膠膜。較佳為至少於一部分之區域中具有透明性之塑膠膜。 此處揭示之技術中，用作上述之支持基材或剝離膜基材之塑膠膜可為未延伸膜、單軸延伸膜、雙軸延伸膜之任一種。又，上述塑膠膜可為單層結構，亦可為2層以上之包含副層之多層結構。上述塑膠膜中亦可調配抗氧化劑、抗老化劑、耐熱穩定劑、光穩定劑、紫外線吸收劑、顏料或染料等著色劑、潤滑劑、填充劑、抗靜電劑、成核劑等可用於黏著片材之支持基材或剝離膜基材之公知之添加劑。對於多層結構之塑膠膜，各添加劑可調配於全部之副層，亦可僅調配於一部分之副層。 作為此處揭示之技術中之剝離膜，可較佳地採用於塑膠膜(剝離膜基材)之表面具有剝離處理層，且不含粒子或含有直徑5 μm以下之粒子之剝離膜。剝離膜中所含之直徑超過5 μm之粒子(特別是無機粒子)可於該剝離膜之自由狀態下使剝離面之平滑性降低。又，含有直徑超過5 μm之粒子之剝離膜即便自由狀態下之平滑性較高，亦可能因該剝離膜之彎曲變形、拉伸變形、沿厚度方向之壓縮等而導致上述粒子自上述剝離膜突出，使剝離面之平滑性降低，進而使與該剝離面接觸之黏著面之平滑性降低。一態樣中，亦可使用實質上不含直徑超過5 μm之粒子之剝離膜、即除了不經意混入之雜質等以外不含直徑超過5 μm之粒子之剝離膜。 再者，上述直徑超過5 μm之粒子例如可為以潤滑劑、顏料、填充材料等為目的而可調配於剝離膜基材中之無機粒子。該無機粒子之非限定性之例中可包含二氧化矽、氧化鋁、高嶺土、滑石、雲母、碳酸鈣等。 剝離膜之厚度並無特別限定。就兼顧強度與柔軟性而言，通常可較佳地採用厚度為約10 μm～約500 μm左右之剝離膜。就抑制因經過剝離膜之外力而導致之黏著面之平滑性降低(例如，將附剝離膜之黏著片材捲繞成螺旋狀時可能混入之雜質隔著剝離膜被按壓於黏著面上而導致之平滑性降低)之觀點而言，剝離膜之厚度通常較佳為設為約20 μm以上，更佳為設為約25 μm以上(例如約30 μm以上)。又，就剝離膜本身或附剝離膜之黏著片材之操作性(例如易捲繞性)等觀點而言，剝離膜之厚度通常宜為約250 μm以下，較佳為約125 μm以下(例如約100 μm以下)，更佳為約80 μm以下。一態樣中，可較佳地使用厚度約75 μm以下(例如約50 μm以下)之剝離膜。 對於此處揭示之附剝離膜之黏著片材，抵接於黏著片材之第1黏著面之第1剝離膜之剝離面之十點平均粗糙度(RzR1 )可設為例如約2000 nm以下。就抑制該附剝離膜之黏著片材之保存中之第1黏著面之平滑性降低之觀點而言，RzR1 宜為約1500 nm以下，較佳為約1000 nm以下，更佳為約500 nm以下，進而較佳為約300 nm以下(例如約250 nm以下)。於上述第1黏著面為於第1剝離膜之剝離面上由液狀之黏著劑組合物形成之黏著劑層之表面之情形時，作為該第1剝離膜，較佳為使用RzR1 為約1200 nm以下(典型而言為約700 nm以下，更佳為約500 nm以下，進而較佳為約400 nm以下，例如約300 nm以下)者。RzR1 之下限並無特別限定。就第1剝離膜之製造容易性或操作性等觀點而言，一態樣中，可較佳地使用RzR1 為約50 nm以上(例如約100 nm以上)之第1剝離膜。 於此處揭示之附剝離膜之黏著片材為包含雙面黏著片材、第1剝離膜及第2剝離膜之附剝離膜之雙面黏著片材之形態之情形時，抵接於上述雙面黏著片材之第2黏著面之第2剝離膜之剝離面之十點平均粗糙度(RzR2 )並無特別限定，例如可為約3000 nm左右或其以上。一態樣中，可較佳地採用RzR2 未達約3000 nm(較佳為約2000 nm以下)之第2剝離膜。於第2黏著面之十點平均粗糙度RzA2 為1000 nm以下之態樣中，就抑制該第2黏著面之平滑性降低之觀點而言，RzR2 宜為約2000 nm以下(典型而言為約1500 nm以下，較佳為約1000 nm以下，更佳為約500 nm以下，進而較佳為約300 nm以下，例如約250 nm以下)。於上述第2黏著面為於第2剝離膜之剝離面上由液狀之黏著劑組合物形成之黏著劑層之表面之情形時，作為該第2剝離膜，較佳為使用RzR2 為約1200 nm以下(典型而言為約700 nm以下，更佳為約500 nm以下，進而較佳為約400 nm以下，例如約300 nm以下)者。RzR2 之下限並無特別限定。一態樣中，可較佳地使用RzR2 為約50 nm以上(例如約100 nm以上)之第2剝離膜。 此處揭示之技術中，構成附剝離膜之黏著片材之剝離膜之剝離面較佳為具有與該剝離面所抵接之黏著面之平滑性近似之平滑性。藉此，有更充分地抑制附剝離膜之黏著片材之保存中黏著面之平滑性變化，黏著片材之性能穩定性提高之傾向。於一態樣之附剝離膜之黏著片材中，第1黏著面與接觸於其之第1剝離面之十點平均粗糙度之差、即|RzR1 －RzA1 |可設為約300 nm以下(例如約250 nm以下)，較佳為約150 nm以下，更佳為約100 nm以下。又，就黏著片材之性能穩定性之觀點而言，較佳為第1黏著面之十點平均粗糙度小於第1剝離面之十點平均粗糙度。即，較佳為RzA1 ＜RzR1 ，滿足上述|RzR1 －RzA1 |之值及RzA1 ＜RzR1 之至少一者(較佳為兩者)之附剝離膜之黏著片材例如可藉由包括於構成該附剝離膜之黏著片材之第1剝離膜之剝離面上使黏著劑組合物之液膜乾燥或硬化之方法而較佳地製造。 於此處揭示之附剝離膜之黏著片材為包含雙面黏著片材、第1剝離膜及第2剝離膜之附剝離膜之雙面黏著片材之形態之情形時，一態樣中，第2黏著面與接觸於其之第2剝離面之十點平均粗糙度之差、即|RzR2 －RzA2 |可設為約300 nm以下(例如約250 nm以下)，較佳為約150 nm以下，更佳為約100 nm以下。又，就黏著片材之性能穩定性之觀點而言，較佳為第2黏著面之十點平均粗糙度小於第2剝離面之十點平均粗糙度。即，較佳為RzA2 ＜RzR2 。滿足上述|RzR2 －RzA2 |之值及RzA2 ＜RzR2 之至少一者(較佳為兩者)之附剝離膜之黏著片材例如可藉由如後所述包括於第1剝離膜之剝離面與第2剝離膜之剝離面之間使黏著劑組合物之液膜硬化之方法而較佳地製造。 構成附剝離膜之黏著片材之剝離膜之背面(即，與剝離面為相反側之表面)之平滑性並無特別限定。關於可捲繞成螺旋狀之附剝離膜之黏著片材，就防止上述捲繞之形態中由上述背面之凹凸引起之黏著面之平滑性降低之觀點而言，較佳為將剝離膜之背面之十點平均粗糙度設為約5000 nm以下(較佳為約4000 nm以下，例如約3000 nm以下)。 此處揭示之黏著片材(可為附剝離膜之黏著片材所包含之黏著片材。以下相同)可以於將該黏著片材貼附於被接著體之前之期間將第1黏著面上之剝離膜更換為其他剝離膜之態樣較佳地使用。以下，亦將更換之剝離膜稱為「更換膜」。更換膜之第1剝離面(即，接觸於第1黏著面而配置之剝離面)之十點平均粗糙度(RzE1 )並無特別限定，例如可為約50 nm以上(典型而言為約100 nm以上)。一態樣中，可較佳地採用RzE1 超過約250 nm(更佳為超過約500 nm，例如超過約700 nm)之更換膜。此處揭示之黏著片材於使用RzE1 為約1000 nm以上(進而為約1200 nm以上，例如約1500 nm以上)之更換膜之使用態樣中，亦可顯著地發揮抑制第1黏著面之平滑性降低之效果。RzE1 之上限並無特別限定。通常可較佳地使用RzE1 為約3000 nm以下(典型而言為約2000 nm以下)之更換膜。一態樣中，更換膜之RzE1 可為約1500 nm以下，亦可為約1000 nm以下。作為更換膜，可使用與更換前之剝離膜相同之構成(材質、厚度、表面粗糙度等)者，亦可使用不同之構成者。 較佳之一態樣中，作為更換膜，可採用RzE1 之值比更換前之剝離膜(可為剛製造之剝離膜)之第1剝離面之十點平均粗糙度(RzR1 )大者。一態樣中，可使用RzE1 /RzR1 為約2以上(較佳為約3以上)之更換膜。此處揭示之黏著片材例如於使用RzE1 /RzR1 為約5以上(進而為約7以上)之更換膜之使用態樣中，亦可顯著地發揮抑制第1黏著面之平滑性降低之效果。RzE1 /RzR1 之上限並無特別限定，通常適宜為約20以下(典型而言為約15以下，例如約10以下)。 ＜用途＞ 此處揭示之黏著劑層或黏著片材由於黏著面之平滑性較高且該黏著面之平滑性不易受損，故而適合於光學用途。例如，作為上述支持基材使用光學構件之黏著型光學構件有用。此種黏著型光學構件亦可理解為於此處揭示之任一雙面黏著片材之第1黏著面或第2黏著面上具有作為支持基材之光學構件之形態之附基材之單面黏著片材。較佳為於上述第2黏著面上具有光學構件之形態。該形態中，亦可構成於上述第1黏著面上具有剝離膜之附剝離膜之黏著型光學構件。 於使用光學膜作為上述光學構件之情形時，上述黏著型光學構件可用作附黏著劑層之光學膜。作為上述光學膜，可使用偏光板、相位差板、光學補償膜、亮度提高膜、硬塗(HC)膜、抗反射膜、衝擊吸收膜、防污膜、光致變色膜、調光膜、波長選擇吸收膜、波長轉換膜、進而將該等積層而成之膜等。此處揭示之黏著劑層或黏著片材亦適合於眼科領域之用途。又，本發明之黏著劑層或黏著片材不限定於如上所述之光學用途或眼科用途，例如可以通常之以防污膜、隔熱膜、緩衝吸收膜等作為支持體之黏著片材之形態應用於各種用途。 由本說明書所揭示之事項包括以下者。 (1)一種黏著片材，其係包含黏著劑層者，且 上述黏著片材具有第1面及第2面， 上述第1面係由上述黏著劑層之一表面構成之第1黏著面， 上述第1黏著面之十點平均粗糙度(RzA1 )為約1000 nm以下， 上述黏著劑層之100℃儲存彈性模數(G'100 )為約0.08 MPa以上。 (2)如上述(1)記載之黏著片材，其中上述黏著劑層之100℃儲存彈性模數(G'100 )相對於23℃儲存彈性模數(G'23 )之比為約35%以上。 (3)如上述(1)或(2)記載之黏著片材，其中上述黏著劑層之23℃儲存彈性模數(G'23 )未達約0.30 MPa。 (4)如上述(1)至(3)中任一項記載之黏著片材，其構成為上述第2面為第2黏著面之雙面黏著片材。 (5)如上述(4)記載之黏著片材，其中上述第2黏著面之十點平均粗糙度(RzA2 )為約2000 nm以下(例如約1000 nm以下)。 (6)如上述(4)或(5)記載之黏著片材，其中上述第2黏著面由上述黏著劑層之另一表面構成。 (7)如上述(4)至(6)中任一項記載之黏著片材，其中上述第1黏著面之十點平均粗糙度(RzA1 )及上述第2黏著面之十點平均粗糙度(RzA2 )中之任一者為約500 nm以下。 (8)如上述(4)至(7)中任一項記載之黏著片材，其中上述第1黏著面之十點平均粗糙度(RzA1 )及上述第2黏著面之十點平均粗糙度(RzA2 )均為約500 nm以下。 (9)如上述(4)至(8)中任一項記載之黏著片材，其中上述第1黏著面之十點平均粗糙度(RzA1 )與上述第2黏著面之十點平均粗糙度(RzA2 )之差(|RzA1 －RzA2 |)為約250 nm以下。 (10)如上述(1)至(9)中任一項記載之黏著片材，其中上述黏著片材為包含單層之黏著劑層之無基材之雙面黏著片材。 (11)如上述(1)至(10)中任一項記載之黏著片材，其中上述黏著劑層以超過該黏著劑層中所含之聚合物成分之50重量%之比率含有(甲基)丙烯酸系聚合物。 (12)如上述(11)記載之黏著片材，其中上述(甲基)丙烯酸系聚合物中，作為構成該(甲基)丙烯酸系聚合物之單體成分，包含以下之(A)成分： 在酯末端具有碳數2～18之烷基之(甲基)丙烯酸烷基酯。 (13)如上述(11)或(12)記載之黏著片材，其中上述(A)成分於上述單體成分整體中所占之比率為約30重量%～約70重量%。 (14)如上述(11)至(13)中任一項記載之黏著片材，其中上述(甲基)丙烯酸系聚合物中，作為構成該(甲基)丙烯酸系聚合物之單體成分，進而包含以下之(B)成分： 脂環式單體。 (15)如上述(11)至(14)中任一項記載之黏著片材，其中上述(B)成分為選自由(甲基)丙烯酸環丙酯、(甲基)丙烯酸環丁酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸環庚酯、(甲基)丙烯酸環辛酯、(甲基)丙烯酸異
Figure 105138382-A0304-03-0013-01
基酯、(甲基)丙烯酸二環戊酯所組成之群中之至少1種。 (16)如上述(11)至(15)中任一項記載之黏著片材，其中上述(B)成分於上述單體成分整體中所占之比率為約20重量%～約50重量%。 (17)如上述(11)至(16)中任一項記載之黏著片材，其中上述(甲基)丙烯酸系聚合物中，作為構成該(甲基)丙烯酸系聚合物之單體成分，進而包含以下之(C)成分： 具有羥基及羧基中之至少任一者之單體。 (18)如上述(11)至(17)中任一項記載之黏著片材，其中上述(C)成分於上述單體成分整體中所占之比率為約15重量%～約30重量%。 (19)如上述(11)至(18)中任一項記載之黏著片材，其中上述(甲基)丙烯酸系聚合物中，作為構成該(甲基)丙烯酸系聚合物之單體成分，進而包含多官能單體， 上述多官能單體於上述單體成分整體中所占之比率為約3重量%以下。 (20)如上述(11)至(19)中任一項記載之黏著片材，其中上述(甲基)丙烯酸系聚合物為上述單體成分之紫外線聚合物。 (21)一種黏著片材製造方法，其係製造如上述(11)至(20)中任一項記載之黏著片材之方法，且 包括使用以聚合物之形態包含上述單體成分之至少一部分之黏著劑組合物而形成上述黏著劑層。 (22)如上述(21)記載之黏著片材製造方法，其中形成上述黏著劑層包含於剝離膜之剝離面塗佈上述黏著劑組合物並於該剝離面上使上述黏著劑組合物乾燥或硬化。 (23)如上述(21)或(22)記載之黏著片材製造方法，其中上述黏著劑組合物之有機溶劑含量為約5重量%以下。 (24)如上述(21)至(23)中任一項記載之黏著片材製造方法，其中形成上述黏著劑層包括使上述黏著劑組合物之液膜於一對剝離膜之剝離面間硬化而形成上述黏著劑層。 (25)一種附剝離膜之黏著片材，其包含： 如上述(1)至(20)中任一項記載之黏著片材、及 配置於上述第1黏著面上之第1剝離膜。 (26)一種附剝離膜之黏著片材，其包含： 如上述(4)至(20)中任一項記載之黏著片材、 配置於上述第1黏著面上之第1剝離膜、及 配置於上述第2黏著面上之第2剝離膜。 (27)如上述(25)或(26)記載之附剝離膜之黏著片材，其中上述第1剝離膜與上述第1黏著面接觸之剝離面之十點平均粗糙度(RzR1 )與上述第1黏著面之十點平均粗糙度(RzA1 )之差為約250 nm以內。 (28)如上述(26)或(27)記載之附剝離膜之黏著片材，其滿足RzA1 ＜RzR1 及RzA2 ＜RzR2 。 (29)如上述(25)至(28)中任一項記載之附剝離膜之黏著片材，其中上述第1剝離膜包含選自由二氧化矽、氧化鋁、高嶺土、滑石、雲母及碳酸鈣所組成之群中之至少1種無機粒子。 (30)如上述(25)至(29)中任一項記載之附剝離膜之黏著片材，其中上述第1剝離膜之厚度為約10 μm以上且約500 μm以下(較佳為約20 μm以上且約100 μm以下，更佳為約25 μm以上且約80 μm以下)。 (31)一種黏著型光學構件，其包含： 如上述(4)至(20)中任一項記載之黏著片材、及 配置於上述黏著片材之第2黏著面上之光學構件。 (32)一種附黏著片材之物品之製造方法，其包括： 準備如上述(26)至(30)中任一項記載之附剝離膜之黏著片材； 自上述第1黏著面剝離上述第1剝離膜，於露出之上述第1黏著面貼合另一剝離膜之剝離面；及 將上述第2黏著面貼附於作為被接著體之物品。 (33)如上述(32)記載之附黏著片材之物品之製造方法，其中作為上述另一剝離膜，使用上述另一剝離膜之上述剝離面之十點平均粗糙度(RzE1 )大於上述第1剝離膜與上述第1黏著面接觸之剝離面之十點平均粗糙度(RzR1 )者。 [與相關申請案之相互參照] 本申請案主張基於2015年11月27日提出申請之日本專利申請案2015-232149號及2016年7月14日提出申請之日本專利申請案2016-139538號之優先權，且將該等申請案之全部內容作為參照而併入至本說明書中。 [實施例] 以下，說明與本發明相關之若干實施例，但並未意圖將本發明限定於該具體例中所示者。 ＜黏著劑組合物之製備＞ (黏著劑組合物C1) 將丙烯酸正丁酯40重量份、丙烯酸環己酯41重量份、丙烯酸4-羥基丁酯19重量份、作為光聚合起始劑之2,2-二甲氧基-1,2-二苯基乙烷-1-酮(BASF公司製造，商品名「Irgacure 651」)0.05重量份及1-羥基環己基-苯基-酮(BASF公司製造，商品名「Irgacure 184」)0.05重量份進行混合，於氮氣環境下照射紫外線而製作部分聚合物(單體漿液)。向所獲得之單體漿液中添加1,6-己二醇二丙烯酸酯0.1重量份，均勻混合而製備黏著劑組合物C1。 (黏著劑組合物C2～C4) 於黏著劑組合物C1之製備中，將1,6-己二醇二丙烯酸酯之添加量變更為黏著劑組合物C2中0.3重量份、黏著劑組合物C3中0.05重量份、黏著劑組合物C4中0重量份。其他方面以與黏著劑組合物C1之製備相同之方式製備黏著劑組合物C2～C4。 再者，該等黏著劑組合物C1～C4均為無溶劑型之組合物。具體而言，黏著劑組合物C1～C4中之溶劑之含量均未達5重量%，更詳細而言未達1重量%。 ＜黏著片材之製作＞ 準備：於厚度38 μm之聚對苯二甲酸乙二酯(PET)膜F1之單面具有基於聚矽氧系剝離處理劑A1之剝離處理層，剝離面(上述剝離處理層之表面)之十點平均粗糙度為211 nm之剝離膜R1；於厚度38 μm之PET膜F2之單面具有基於聚矽氧系剝離處理劑A1之剝離處理層，剝離面之十點平均粗糙度為1610 nm之剝離膜R2；及於上述PET膜F2之單面具有基於聚矽氧系剝離處理劑A2之剝離處理層，剝離面之十點平均粗糙度為1610 nm之剝離膜R3。剝離膜R3之剝離面以與剝離膜R1、R2之剝離面相比，自黏著劑層之剝離強度更高之方式形成。使用該等剝離膜，以下述方式製作黏著片材。 再者，上述剝離膜R1、R2、R3之各剝離面之十點平均粗糙度係以如下方式獲得之測定值：藉由用滴管滴加於載玻片S1112No.2(松浪硝子工業製造)上之1滴水使各剝離膜之背面(未經剝離處理之面)密接於上述載玻片而配置，除此以外，與後述第1黏著面之表面平滑性測定同樣地進行。 (實施例1) 將上述製備之黏著劑組合物C1塗佈於剝離膜R1之剝離面上，於該剝離面上形成上述黏著劑組合物之液膜。黏著劑組合物之塗佈量係以最終形成之黏著劑層之厚度成為50 μm之方式調整。繼而，於上述液膜上以該剝離膜R3之剝離面與上述液膜接觸之方式覆蓋剝離膜R3。藉此將上述液膜與氧氣隔斷。於如此使黏著劑組合物C1之液膜之雙面(第1面及第2面)分別接觸於剝離膜R1、R3之剝離面之狀態下，使用化學燈(東芝股份有限公司製造)照射360秒照度5 mW/cm2 之紫外線而進行聚合反應，藉此使上述液膜硬化而形成黏著劑層，獲得包含該黏著劑層(即，上述液膜之紫外線硬化物)之實施例1之黏著片材S1。黏著片材S1構成於該黏著片材S1之製作中使用之剝離膜R1、R3之剝離面分別抵接於第1面(第1黏著面)及第2面(第2黏著面)之附剝離膜之黏著片材。 再者，上述照度之值係利用峰感度波長約350 nm之工業用UV檢測器(TOPCON公司製造，商品名「UVR-T1」，受光部型號UD-T36)獲得之測定值。 (實施例2、3) 代替黏著劑組合物C1，分別使用黏著劑組合物C2、C3，除此以外，以與實施例1之黏著片材S1之製作相同之方式獲得實施例2、3之黏著片材S2、S3。黏著片材S2、S3構成於該等黏著片材之製作中使用之剝離膜R1、R3之剝離面分別抵接於第1黏著面及第2黏著面之附剝離膜之黏著片材。 (比較例1) 於實施例2之黏著片材S2之製作中，代替剝離膜R1而使用剝離膜R2。即，將黏著劑組合物C2塗佈於剝離膜R2之剝離面上而形成黏著劑組合物之液膜，於其液膜上以該剝離膜之剝離面與上述液膜接觸之方式覆蓋剝離膜R3。於如此使黏著劑組合物C2之液膜之雙面分別與剝離膜R2、R3之剝離面接觸之狀態下照射紫外線，除此以外，以與實施例2相同之方式獲得比較例1之黏著片材S4。黏著片材S4構成於該黏著片材S4之製作中使用之剝離膜R2、R3之剝離面分別抵接於第1黏著面及第2黏著面之附剝離膜之黏著片材。 (比較例2) 代替黏著劑組合物C1而使用黏著劑組合物C4，除此以外，以與實施例1之黏著片材S1之製作相同之方式獲得比較例2之黏著片材S5。黏著片材S5構成於該黏著片材S5之製作中使用之剝離膜R1、R3之剝離面分別抵接於第1黏著面及第2黏著面之附剝離膜之黏著片材。 各例之黏著片材於製造後以上述附剝離膜之黏著片材之形態在23℃、50%RH之環境下保存7天後，供於以下之測定及試驗。 ＜儲存彈性模數測定＞ 藉由重疊多張各例之黏著片材(厚度約50 μm之黏著劑層)而製作厚度約2 mm之黏著劑層。利用平行板夾持並固定將該黏著劑層沖裁成直徑7.9 mm之圓盤狀而獲得之試樣，藉由黏彈性試驗機(TA Instruments公司製造，ARES)於以下之條件下進行動態黏彈性測定，求出23℃儲存彈性模數(G'23 )及100℃儲存彈性模數(G'100 )。 ・測定模式：剪切模式 ・溫度範圍：-70℃～150℃ ・升溫速度：5℃/分鐘 ・測定頻率：1 Hz ＜初始構成中之第1黏著面之十點平均粗糙度＞ 在23℃、50%RH之環境下，去除各例之黏著片材之第2黏著面上之剝離膜，將露出之第2黏著面貼附於載玻片S1112No.2(松浪硝子工業製造)。繼而，將貼附於上述載玻片之黏著片材之第1黏著面上之剝離膜以約10 m/分鐘之剝離速度沿180度方向用手剝離，利用光干涉方式之表面粗糙度測定裝置(Veeco公司製造，Wyko NT-9100)測定藉此露出之第1黏著面之十點平均粗糙度。測定係自第1黏著面去除剝離膜後10分鐘以內進行。測定條件如下所述。 ・測定面積/次：622 μm×467 μm (物鏡：10倍、FOV(內部透鏡)：1.0倍) ・測定模式：VSI(Vertical Scan Interferometry，垂直掃描型干涉方式) ・背面掃描(back scan)：5 μm ・測定距離：10 μm ・閾值：0.1% ・掃描速度：1倍(Single scan) 自藉由測定而獲得之資料集中取測定面內之最高之峰，將其峰頂之標高記作H1。遮蔽H1周圍11×11像素之範圍，於該遮蔽之範圍以外取最高之峰，將其峰頂之標高記作H2。重複該操作而特定出H3～H10。如此求出自最高之峰至第10位之峰為止之標高(H1～H10)。以相同之方式，求出測定面內之自最低之谷至第10位之谷為止之谷底之標高(L1～L10)。根據該等之值，利用以下之公式算出Rz。式中，Hj 表示各峰頂之高度(標高)，Lj 表示各谷底之深度(標高)。 [數1]
Figure 02_image003
測定進行5次(即N＝5)，求出其等之平均值。 ＜剝離膜更換後之第1黏著面之十點平均粗糙度＞ (試驗例1) 在23℃、50%RH之環境下，自實施例1之黏著片材S1之第1黏著面以約10 m/分鐘之剝離速度沿180度方向用手剝離剝離膜R1。於藉此露出之第1黏著面立即使2 kg之輥以約300 mm/分鐘之移動速度往復1次而貼合另一剝離膜R1。如此將實施例1之保護黏著片材之第1黏著面之剝離膜R1更換為另一剝離膜R1(更換貼附)。將其在23℃、50%RH之環境下保持2小時後，以約10 m/分鐘之剝離速度沿180度方向用手剝離更換貼附之剝離膜R1，以與上述相同之方式對露出之第1黏著面之十點平均粗糙度進行測定。 (試驗例2) 於本試驗例中，將實施例2之黏著片材S2之第1黏著面上之剝離膜R1更換貼附為剝離膜R2。其他方面以與試驗例1相同之方式對去除更換貼附之剝離膜R2而露出之第1黏著面之十點平均粗糙度進行測定。 (試驗例3) 於本試驗例中，將實施例3之黏著片材S3之第1黏著面上之剝離膜R1更換貼附為剝離膜R2。其他方面以與試驗例1相同之方式對剝離更換貼附之剝離膜R2而露出之第1黏著面之十點平均粗糙度進行測定。 (試驗例4) 於本試驗例中，將比較例1之黏著片材S4之第1黏著面上之剝離膜R1更換貼附為剝離膜R2。其他方面以與試驗例1相同之方式對剝離更換貼附之剝離膜R2而露出之第1黏著面之十點平均粗糙度進行測定。 (試驗例5) 於本試驗例中，將比較例1之黏著片材S4之第1黏著面上之剝離膜R2更換貼附為剝離膜R1。其他方面以與試驗例1相同之方式對剝離更換貼附之剝離膜R1而露出之第1黏著面之十點平均粗糙度進行測定。 (試驗例6) 於本試驗例中，將比較例2之黏著片材S5之第1黏著面上之剝離膜R2更換貼附為其他剝離膜R2。其他方面以與試驗例1相同之方式對剝離更換貼附之剝離膜R2而露出之第1黏著面之十點平均粗糙度進行測定。 所獲得之結果示於表1。 [表1]
Figure 105138382-A0304-0001
 如表1所示，對於第1黏著面之十點平均粗糙度為1000 nm以下之黏著片材而言，確認到藉由將構成該第1黏著面之黏著劑層之100℃儲存彈性模數設為0.08 MPa以上，可顯著地抑制因更換剝離膜而導致之第1黏著面之平滑性降低。又，對於製造初始之構成中之第1黏著面之平滑性較低之黏著片材S4，即便其後將第1黏著面上之剝離膜更換為平滑性更高者，亦未發現第1黏著面之平滑性提高。 以上詳細說明了本發明之具體例，但該等僅為例示，並不對申請專利範圍進行限定。申請專利範圍中記載之技術包括對以上例示之具體例進行各種變化、變更而成者。Hereinafter, preferred embodiments of the present invention will be described. Furthermore, for the matters necessary to implement the present invention other than the matters specifically mentioned in this specification, the industry can understand based on the hints on the implementation of the invention described in this specification and the technical common sense at the time of application. The present invention can be implemented based on the content disclosed in this specification and common technical knowledge in the field. In addition, in the following drawings, members and parts that perform the same function may be described with the same reference numerals, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematic in order to clearly explain the present invention, and do not necessarily accurately represent the size or scale of the product actually provided. In this specification, "adhesive" refers to a material that has the following properties as described above: it presents a soft solid (viscoelastic body) state in a temperature region near room temperature, and can be easily adhered to by pressure. body. The so-called adhesive here is as defined in "CA Dahlquist, "Adhesion: Fundamental and Practice", McLaren & Sons, (1966) P. 143". Generally speaking, it can be a compound with a modulus of elasticity E* (1 Hz) Materials with properties of <10 7 dyne/cm 2 (typically, materials with the above properties at 25°C). In this manual, the "adhesive surface" refers to the SUS304 stainless steel plate as the adherend based on JIS Z0237 (2004), and the 2 kg roller is reciprocated once in a measuring environment at 23°C to be crimped on the adherend. After 30 minutes, the peel strength is 0.1 N/20 mm or more when peeling in the 180-degree direction under the condition of a tensile speed of 300 mm/min. In this manual, "non-adhesive surface" refers to the surface that does not belong to the above-mentioned adhesive surface. Typically, it refers to the surface whose peel strength does not reach 0.1 N/20 mm. The surface of the stainless steel plate that does not adhere to the stainless steel plate (the surface that does not substantially exhibit adhesiveness) is the so-called non-adhesive surface when the 2 kg roller is reciprocated once under the measuring environment of 23°C and crimped on the SUS304 stainless steel plate. The typical examples included in the concept. <Adhesive sheet> The adhesive sheet disclosed here is formed in a sheet shape having a first surface and a second surface (meaning that it includes a strip shape such as a strip shape). The above-mentioned adhesive sheet includes at least an adhesive layer. The adhesive sheet disclosed here may be composed of only the adhesive layer, or may include components other than the adhesive layer. The first surface of the adhesive sheet disclosed here becomes the adhesive surface (the first adhesive surface) constituted by one surface of the above-mentioned adhesive layer. The second surface of the adhesive sheet may be an adhesive surface or a non-adhesive surface. In one aspect of the adhesive sheet, the second surface of the adhesive sheet becomes the adhesive surface (second adhesive surface) constituted by the other surface of the above-mentioned adhesive layer. That is, one surface and the other surface of an adhesive layer constitute the first adhesive surface and the second adhesive surface of the adhesive sheet, respectively. An example of the configuration of an adhesive sheet of this aspect is shown in FIG. 1. The adhesive sheet 1 shown in FIG. 1 is a substrate-free double-sided adhesive sheet including an adhesive layer 11. The first surface 1A of the adhesive sheet 1 is the first adhesive surface formed by one surface 11A of the adhesive layer 11, and the second surface 1B of the adhesive sheet 1 is the second surface formed by the other surface 11B of the adhesive layer 11 Adhesive surface. The adhesive layer 11 may have a single-layer structure or a multi-layer structure including two or more secondary adhesive layers. The composition (material, thickness, etc.) of each auxiliary adhesive layer constituting the above-mentioned multilayer structure may be the same or different. From the viewpoint of productivity or transparency, the adhesive layer 11 may preferably be of a single-layer structure. Here, a double-sided adhesive sheet without a substrate refers to a double-sided adhesive sheet that does not include a non-peelable supporting substrate between the first adhesive surface and the second adhesive surface. The above-mentioned supporting substrate refers to a substrate capable of independently maintaining a shape. In addition, the non-peelable supporting substrate refers to a supporting substrate that is not intended to be separated from the adhesive layer during the use of the adhesive sheet containing the supporting substrate. For example, as shown in FIG. 1, the adhesive sheet 1 before use (that is, before being attached to the adherend) can have a first adhesive surface 1A and a second adhesive surface 1B composed of a first release film 21 and a second release film, respectively 22 The form of protection. The surface 21A of the first peeling film 21 in contact with the first adhesive surface 11A and the surface 22A of the second peeling film 22 in contact with the second adhesive surface 11B are both peelable surfaces (a peelable surface, that is, the surface can be peeled off from the surface). The surface of the adhesive layer). The adhesive sheet 1 of this form can also be understood as including the adhesive sheet 1, the first release film 21 arranged so that the surface (first release surface) 21A abuts on the first adhesive surface 11A and the surface (first release surface) 2Release surface) 22A is a component of the second release film 22 which is arranged in contact with the second adhesive surface 12A and is a component of the adhesive sheet with release film (double-sided adhesive sheet with release film) 100. The adhesive sheet 100 with a release film may also be in a spirally wound form. As another form of the adhesive sheet 1 before use, the following form can be exemplified: the peeling film 22 shown in FIG. 1 is omitted, and the peeling film 21 whose surface 21A and the back surface 21B are both peeling surfaces overlaps and rolls the adhesive sheet 1 By winding in a spiral shape, the second adhesive surface 11B abuts against the back surface 21B of the release film 21. An example of the configuration of an adhesive sheet with the second surface as a non-adhesive surface is shown in FIG. 2. The adhesive sheet 2 shown in FIG. 2 is configured as a single-sided adhesive sheet with a substrate including a supporting substrate 15 having a first side 15A and an adhesive layer 11 disposed on the first side 15A of the supporting substrate 15 material. Here, the first surface 15A of the support base 15 is a non-peelable surface, that is, a non-peelable surface. The first surface 2A of the adhesive sheet 2 is a first adhesive surface formed by one surface 11A of the adhesive layer 11, and the second surface 2B of the adhesive sheet 2 is a non-adhesive formed by the second surface 15B of the support base 15 surface. The second surface 15B may be a peeling surface or a non-peeling surface. For example, as shown in FIG. 2, the adhesive sheet 2 before use can be in a form in which the first adhesive surface 11A is protected by the first release film 21. The adhesive sheet 2 of this form can also be understood as including the adhesive sheet 2, the surface (first peeling surface) 21A abutting the first peeling film 21 of the first adhesive surface 11A with the peeling film The components of the adhesive sheet (single-sided adhesive sheet with release film) 200. The adhesive sheet 200 with a release film may also be in a spirally wound form. As another example of the structure of the adhesive sheet disclosed here, include: a support substrate with a non-peelable first surface and a second surface, and a first adhesive on the first surface of the support substrate The layer is a structure of a double-sided adhesive sheet with a substrate having a second adhesive layer on the second surface of the supporting substrate. Regarding the double-sided adhesive sheet with a substrate, the first side of the double-sided adhesive sheet becomes the first adhesive surface formed by the surface of the first adhesive layer, and the second side of the double-sided adhesive sheet It becomes the second adhesive surface constituted by the surface of the above-mentioned second adhesive layer. The composition and structure of the first adhesive layer and the second adhesive layer may be the same, and one or both of the composition and the structure may be different. As an example of the aspect in which the composition of the first adhesive layer and the second adhesive layer are the same but the composition is different, there can be mentioned: the first adhesive layer and the second adhesive layer have thicknesses composed of the adhesive composition of the same composition The appearance of different adhesive layers. The first adhesive layer and the second adhesive layer may each independently have a single-layer structure, or may have a multi-layer structure including two or more sub-adhesive layers. From the viewpoint of productivity or transparency, it is preferable to adopt the aspect in which both the first adhesive layer and the second adhesive layer have a single-layer structure. The double-sided adhesive sheet with a substrate before use can be the same as the double-sided adhesive sheet 1 without a substrate as shown in Fig. 1. It is the first adhesive surface (the surface of the first adhesive layer) and the second adhesive The surface is protected by the first release film and the second release film. The double-sided adhesive sheet with a base material of this form can also be understood as a constituent element of an adhesive sheet with a release film including the adhesive sheet, the first release film, and the second release film. The adhesive sheet with release film may also be in a spirally wound form. In addition, the double-sided adhesive sheet with a base material before use may be a form in which a release film and an adhesive sheet with a peeling surface on both sides are overlapped and wound into a spiral shape. In the adhesive sheet in the form of a supporting substrate, such as the single-sided adhesive sheet with a substrate or the double-sided adhesive sheet with a substrate, the material of the supporting substrate is not particularly limited. As the supporting substrate, for example, plastic film, paper, woven fabric, non-woven fabric, rubber sheet, foam sheet, metal foil, glass, composites of these, etc. can be used. For the surface of the support substrate where the adhesive layer is provided, surface treatments such as primer coating, corona discharge treatment, plasma treatment, etc. can also be implemented. Furthermore, in this specification, the plastic film is typically a non-porous sheet, which is a concept different from, for example, non-woven fabric (that is, non-woven fabric is not included). In one aspect, as the above-mentioned supporting substrate, various plastic films can be preferably used in terms of easily realizing a highly smooth first adhesive surface, etc. As the material of the plastic film, for example, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, cellulose resins such as triacetyl cellulose, acetate resins, and polyester resins can be cited. Resins, polyether-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyolefin-based resins, cyclic polyolefin resins
Figure 105138382-A0304-03-0013-01
Vinyl resins, etc.), (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide Series resins, mixtures of these, etc. Among them, preferred materials include polyester resins, cellulose resins, polyimide resins, and polyether turpentine resins. In the plastic film used to support the substrate, known additives can be blended in the same manner as the plastic film for the release film substrate described later. It is preferably a transparent plastic film. The thickness of the supporting substrate is not particularly limited, and can be appropriately selected according to the purpose. In one aspect, the thickness of the supporting substrate may be about 10 μm to about 500 μm, and usually preferably about 10 μm to about 300 μm. In one aspect, a supporting substrate with a thickness of about 15 μm to about 200 μm (for example, the above-mentioned transparent plastic film) can be preferably used. (Ten point average roughness) The adhesive sheet disclosed here preferably has the ten point average roughness (Rz A1 ) of the first adhesive surface of about 1000 nm or less. The adhesive sheet having such a first adhesive surface is suitable for applications requiring a highly smooth adhesive surface. For example, it can be preferably used in a state where the first adhesive surface is attached to the optical member. From the viewpoint of providing a smoother adhesive surface, Rz A1 may be preferably about 700 nm or less, more preferably about 500 nm or less, and even more preferably about 300 nm or less (for example, about 200 nm or less). The lower limit of Rz A1 is not particularly limited. In one aspect, Rz A1 can be set to about 30 nm or more (for example, about 50 nm or more). Here, in this specification, the ten-point average roughness refers to the ten-point average roughness obtained by using a non-contact surface roughness measuring device unless otherwise specified. As a non-contact surface roughness measuring device, a surface roughness measuring device of the optical interference method is used. As a specific measuring device, Wyko NT-9100 manufactured by Veeco Corporation or its equivalent can be used. The specific measurement operation and measurement conditions can be set in accordance with the measurement conditions described in the embodiments described later, or can be set in such a way that results equivalent to or corresponding to those based on the measurement conditions can be obtained. The ten-point average roughness is based on the roughness curve obtained by the above surface roughness measurement, measuring the elevation from the highest peak to the 10th peak (Yp1～Yp10) and from the lowest valley to the 10th For the elevation of the valley bottom up to the position (Yv1～Yv10), find the average of the absolute values of the differences between the above Yp1～Yp10 and the above Yv1～Yv10. When the adhesive sheet disclosed here is a double-sided adhesive sheet (ie, an adhesive sheet having a first adhesive surface and a second adhesive surface), the ten-point average roughness of the second adhesive surface (Rz A2 ) There is no particular limitation. In a preferred aspect, Rz A2 can be set to about 2000 nm or less (typically, about 1000 nm or less, preferably about 700 nm or less, more preferably about 500 nm or less, and more preferably about 300 nm. Below, for example, about 200 nm or less). The lower limit of Rz A2 is not particularly limited. In one aspect, Rz A2 can be set to about 30 nm or more (for example, about 50 nm or more). The second adhesive surface may be the other surface of the adhesive layer constituting the first adhesive surface, or the surface of an adhesive layer different from the adhesive layer constituting the first adhesive layer. (Storage Elastic Modulus) The adhesive sheet disclosed here preferably has a storage elastic modulus (G' 100 ) at 100° C. of about 0.08 MPa or more of the adhesive layer constituting the first adhesive surface. After the adhesive sheet having such an adhesive layer is manufactured, the smoothness of the first adhesive surface is not easily impaired. For example, after the adhesive sheet is manufactured until the adhesive sheet is attached to the adherend, even if the release film on the first adhesive surface is replaced with one with lower smoothness, the smoothness of the first adhesive surface is suppressed. Tendency to decrease sex. It can be considered that the reason is that: when the deformation of the adhesive layer after the release film of the temporarily manufactured adhesive sheet is replaced (replaced and attached) is performed at a low speed, the target can be properly grasped according to the 100°C storage elastic modulus of the adhesive layer The behavior of the plastically deformed adhesive layer at low speed (time-temperature conversion algorithm), by setting the above-mentioned storage elastic modulus at 100°C to a specific value or more, it is possible to efficiently realize that it is not easy to occur due to the replacement of the peeling film. 1 Adhesive sheet with reduced smoothness of the adhesive surface. The technology disclosed here in, G '100 may be less than about 0.09 MPa, may be less than about 0.10 MPa, may also be greater than about 0.11 MPa (e.g. above about 0.12 MPa). By improving G '100, tends to better maintain the smoothness of the first surface of the adhesive. The upper limit of G'100 is not particularly limited. For example, it can be about 1.5 MPa or less (typically, about 1.0 MPa or less). Next to it is the adhesion between the body of the other viewpoint, G '100 is less than of usually about 0.50 MPa, preferably less than about 0.40 MPa, more preferably less than about 0.30 MPa. G '100 may be composed by the adhesive layer (e.g., contained in the composition of the polymer of the adhesive agent layer or molecular weight, cross-linked state of the sample, the crosslinking density, if the amount of use and the use of additives), or The manufacturing method, etc. are adjusted. In one aspect of the technology disclosed here, the 23°C storage elastic modulus (G' 23 ) of the adhesive layer constituting the first adhesive surface of the adhesive sheet can be set to less than about 0.30 MPa. The adhesive sheet with such an adhesive layer tends to show good initial adhesion to the adherend at room temperature. This case is preferable from the viewpoint of the sticking workability of the adhesive sheet (for example, work efficiency or sticking accuracy). One aspect, G '23 may be set to be about 0.29 MPa or less, may be about 0.27 MPa or less, may also be from about 0.25 MPa or less. By reducing G '23, the initial adhesion tends to be improved sheet of the next. G '23 of the lower limit is not particularly limited, for example, less than about 0.05 MPa. View of the above it is easy to take into account the specific G'100, it is generally G '23 should be less than about 0.08 MPa, preferably less than about 0.10 MPa, more preferably less than about 0.15 MPa (e.g. above about 0.17 MPa). G '23 may be composed by the adhesive layer or the manufacturing method be adjusted. Furthermore, in the technology disclosed here, as the 100°C storage elastic modulus (G' 100 ) and 23°C storage elastic modulus (G' 23 ) of the adhesive layer, the adhesive layer can be used to form the adhesive The value of the storage elastic modulus at 100°C and 23°C obtained by measuring the dynamic viscoelasticity of the agent. As a specific measuring device, ARES manufactured by TA Instruments or its equivalent can be used. The specific measurement operation and measurement conditions can be set according to the measurement conditions described in the embodiments described later, or set in such a way that a result equivalent or corresponding to the situation based on the measurement conditions can be obtained. The technology disclosed here can make up the 100℃/23℃ storage elastic modulus ratio (G' 100 /G' 23 ) of the adhesive layer of the first adhesive surface more than about 30% (for example, about 31% or more). Implemented well. More preferably to maintain the balance between the smoothness of the surface of the adhesive properties of the first viewpoint of the workability at room temperature for purposes of attachment, G '100 / G' 23 may be set to more than about 35%, about 40% or more may be It can also be about 50% or more (for example, about 55% or more). G '100 / G' 23 of the upper limit is not particularly limited, is generally about 100% or less, in terms of typically less than about 100%. To further improve the workability of attaching the viewpoint at the temperature concerned, G '100 / G' 23 may be set to about 90% or less, it can be set to about 80% (e.g. about 70% or less). In one aspect, G'100 /G' 23 can be set to about 35% to about 50%. This type of adhesive layer tends to easily form a highly smooth first adhesive surface. In one aspect of the technology disclosed here, the ratio of the 100°C storage elastic modulus (G' 100 ) of the adhesive layer constituting the first adhesive surface to the thickness (T A1 ) of the adhesive layer may be about 9 Below MPa/mm. Have such a G '100 / T A1 and G have the adhesive sheet is a specific value or less of the adhesive agent layer' compared to 100 / T A1 of the adhesive layer is greater, it exhibits good long term tendency of adhesion, therefore Better. For example, when using a G '100 is greater than about 0.08 MPa (Typically less than about less than about 0.08 MPa and 0.50 MPa) and G' 100 / T A1 of about 9 MPa / mm or less of the adhesive layer, can be achieved The following adhesive sheet: Even if the release film on the first adhesive surface is replaced with one with lower smoothness, the smoothness of the first adhesive surface is not easily damaged, and the long-term adhesion to the adherend is excellent. From the viewpoint of obtaining a better effect, in one aspect, G'100 /T A1 can be set to approximately 7.0 MPa/mm or less. The techniques disclosed herein may be, for example, G '100 / T A1 (e.g. about 3.0 MPa / mm or less) of the aspect of the embodiment is preferably from about 5.0 MPa / mm or less. G '100 / T A1 of the lower limit is not particularly limited, but suitably is generally set to about 0.1 MPa / mm or more. In the technique disclosed here, the thickness (T A1 ) of the adhesive layer constituting the first adhesive surface is not particularly limited. T A1 may be, for example, about 1 μm to about 500 μm (typically, about 1 μm to about 250 μm). In one aspect, T A1 may be about 5 μm or more, or about 15 μm or more. If T A1 becomes larger, the reduction in the smoothness of the first adhesive surface due to the replacement of the release film on the first adhesive surface with one with lower smoothness tends to be easier. Therefore, the application of the technique disclosed here to suppress the decrease in the smoothness of the first adhesive surface is of even greater significance. From this point of view, the technology disclosed herein can be preferably implemented with T A1 exceeding about 20 μm (more preferably about 25 μm or more, and even more preferably about 30 μm or more, for example, about 40 μm or more). In addition, if T A1 becomes smaller, the smoothness of the first adhesive surface tends to have a greater influence on the characteristics of the entire adhesive sheet. From this point of view, the technology disclosed herein can be preferably implemented with T A1 of about 250 μm or less (more preferably about 150 μm or less, for example, about 100 μm or less). In one aspect, T A1 may be about 60 μm or less (for example, about 50 μm or less). In one aspect of the technology disclosed here, the ratio of the 23°C storage elastic modulus (G' 23 ) of the adhesive layer constituting the first adhesive surface to the thickness (T A1 ) of the adhesive layer may be less than approximately 10 MPa/mm. Have such a G '23 / T A1 less than the adhesive sheet of the adhesive layer has a certain value and G' compared to 23 / T A1 of the adhesive layer is greater, then the body of the show better adhesive property of the initial tendency. For example, when using a G '100 is greater than about 0.08 MPa (Typically less than about less than about 0.08 MPa and 0.50 MPa) and G' 23 / T A1 less than about 10 MPa / mm of the adhesive layer, can be achieved The following adhesive sheet: Even if the release film on the first adhesive surface is replaced with one with lower smoothness, the smoothness of the first adhesive surface is not easily impaired, and the initial adhesion to the adherend is good. From the viewpoint of obtaining a better effect, in one aspect, G'23 /T A1 can be set to approximately 8.0 MPa/mm or less. The techniques disclosed herein may be, for example, G '23 / T A1 is about 6.0 MPa / mm or less (e.g. about 5.0 MPa / mm or less) of the aspect of the preferred embodiment. G '23 / T A1 of the lower limit is not particularly limited, but suitably is generally set to about 0.2 MPa / mm or more. When the adhesive sheet disclosed here is in the form of a double-sided adhesive sheet, the second adhesive surface may be the other surface of the adhesive layer constituting the first adhesive surface. Due to the simple structure of the double-sided adhesive sheet (the double-sided adhesive sheet without substrate) of this aspect, it is suitable for the improvement of optical properties (such as transparency). In addition, the second adhesive surface may be an adhesive layer different from the adhesive layer constituting the first adhesive surface, that is, the surface of the second adhesive layer. This type of double-sided adhesive sheet is typically in the form of a double-sided adhesive sheet with a substrate, which is based on the composition or combination of the first adhesive layer and the second adhesive layer and the choice of the supporting substrate And can achieve a variety of performance. Although not particularly limited, but in one aspect, the second adhesive layer satisfy the various characteristics described above for the first adhesive layer of the (e.g., G '100, G' 23 , G '100 / G' configuration 23, T A1, G '100 / T A1, G' 23 / T A1, haze value, etc.) of one or two or more kinds of ways. <Adhesive> In the technique disclosed here, the type of adhesive constituting the adhesive layer is not particularly limited. For example, it can be selected from acrylic adhesives, rubber adhesives (natural rubber, synthetic rubber, mixed systems of these, etc.), silicone adhesives, polyester adhesives, and urethanes. Adhesive layer composed of one or two or more of various known adhesives such as adhesives, polyether adhesives, polyamide-based adhesives, and fluorine-based adhesives. Here, the acrylic adhesive refers to an adhesive that uses a (meth)acrylic polymer as a base polymer (the main component in the polymer component, that is, a component with a content of more than 50% by mass). Rubber adhesives and other adhesives also have the same meaning. From the viewpoint of transparency or weather resistance, as a preferable adhesive layer, the content of acrylic adhesive is 50% by weight or more, more preferably 70% by weight or more, and more preferably 90% by weight or more. Adhesive layer. The content ratio of the acrylic adhesive may exceed 98% by weight, or it may be an adhesive layer substantially composed of an acrylic adhesive. Here, in this specification, "(meth)acrylic acid" means including acrylic acid and methacrylic acid. Similarly, "(meth)acryloyl" means including acryloyl and methacryloyl, and "(meth)acrylate" means including acrylate and methacrylate. In this specification, the (meth)acrylic polymer refers to a polymer containing a (meth)acrylic monomer as a monomer component constituting the (meth)acrylic polymer. That is, it refers to a polymer containing monomer units derived from (meth)acrylic monomers. Here, the (meth)acrylic mono-system refers to a monomer having at least one (meth)acrylic acid group in one molecule. Although not particularly limited, in one aspect of the technique disclosed herein, the adhesive layer can be preferably prepared using an adhesive composition containing monomer components constituting a (meth)acrylic polymer. Hereinafter, such an adhesive composition may be referred to as a "(meth)acrylic adhesive composition". Here, the "monomer component constituting the (meth)acrylic polymer" refers to the monomer constituting the (meth)acrylic polymer in the adhesive obtained from the (meth)acrylic adhesive composition ingredient. The above-mentioned monomer components may be contained in the (meth)acrylic adhesive composition as unreacted monomers (that is, in the form of raw monomers with unreacted polymerizable functional groups), or may be in the form of polymers (that is, It is contained as a monomer unit), and may be contained in the form of both of these. <Monomer component> In one aspect of the technology disclosed here, the adhesive layer may use an adhesive composition containing the following (A) component as the monomer component constituting the (meth)acrylic polymer. form. In a preferred aspect, the adhesive layer can be preferably formed using the following (meth)acrylic adhesive composition, and the (meth)acrylic adhesive composition includes at least the following (A) component , If necessary, further include one or both of the following (B) component and the following (C) component as monomer components constituting the (meth)acrylic polymer. ((A) component) The said (A) component is an alkyl (meth)acrylate which has a C2-C18 alkyl group at the ester terminal. Hereinafter, the alkyl (meth)acrylate having an alkyl group having a carbon number of X or more and Y or less at the end of the ester may be expressed as "C XY alkyl (meth)acrylate". (Meth) acrylic acid C 2-18 alkyl esters of C 2-18 alkyl group of the structure is not particularly limited, and may be used by the above-described alkyl group is linear and branched to any one of who. As (A) component, 1 type of such (meth)acrylic acid C 2-18 alkyl ester can be used individually or in combination of 2 or more types. Examples of C 2-18 (meth)acrylic acid C 2-18 alkyl esters having a linear alkyl group at the end of the ester include ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate Ester, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, (meth) N-decyl acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate Base ester, n-pentadecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-heptadecyl (meth)acrylate and n-octadecyl (meth)acrylate . In addition, examples of the C 3-18 alkyl (meth)acrylate having a branched alkyl group at the end of the ester include isopropyl (meth)acrylate, tert-butyl (meth)acrylate, (meth) ) Isobutyl acrylate, isoamyl (meth)acrylate, tertiary amyl (meth)acrylate, neopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, 2-propylheptyl (meth)acrylate Esters, isundecyl (meth)acrylate, isododecyl (meth)acrylate, istridecyl (meth)acrylate, isomyristyl (meth)acrylate, ( Isopentadecyl meth)acrylate, isocetyl (meth)acrylate, isoteptadecyl (meth)acrylate, isostearyl (meth)acrylate, and the like. The technique disclosed here can be preferably implemented in a state where the component (A) contains one or more selected from C 4-9 alkyl acrylates. Preferred examples of C 4-9 alkyl acrylate include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate. ((B) component) The said (B) component is an alicyclic monomer. In the state where the component (B) and the component (A) are combined and used, a good balance can be achieved and the better storage elastic modulus disclosed herein and other adhesive properties (for example, to be adhered to Body adhesion) of the adhesive layer. As the alicyclic monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and an alicyclic structure-containing group can be used without particular limitation. As (B) component, 1 type of such alicyclic monomers can be used individually or in combination of 2 or more types. Here, "a group containing an alicyclic structure" refers to a portion containing at least one alicyclic structure. In addition, the "alicyclic structure" refers to a saturated or unsaturated carbocyclic structure without aromaticity. In this specification, the group containing an alicyclic structure may be abbreviated as "alicyclic group". As a preferable example of the alicyclic group, a hydrocarbyl group or hydrocarbyloxy group containing an alicyclic structure can be cited. As an example of a preferable alicyclic monomer in the technique disclosed herein, alicyclic (meth)acrylate having an alicyclic group and a (meth)acryloyl group can be cited. Specific examples of alicyclic (meth)acrylates include: cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and (meth)acrylate ring Hexyl ester, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, isopropyl (meth)acrylate
Figure 105138382-A0304-03-0013-01
Base ester, dicyclopentyl (meth)acrylate, etc., and HPMPA, TMA-2, HCPA, etc. represented by the following chemical formulas.
Figure 02_image001
The alicyclic group in the alicyclic monomer (in the case of alicyclic (meth)acrylate, the part obtained by removing the (meth)acryloyl group from the alicyclic (meth)acrylate) The carbon number is not particularly limited. For example, an alicyclic monomer having a carbon number of 4-24 (preferably 5-18, more preferably 5-12) of the alicyclic group can be used. Among them, preferred are cyclohexyl acrylate (CHA), cyclohexyl methacrylate, isoacrylate
Figure 105138382-A0304-03-0013-01
Base ester (IBXA) and methacrylic acid iso
Figure 105138382-A0304-03-0013-01
The base ester is more preferably CHA and IBXA, and particularly preferably CHA. ((C) component) The said (C) component is a monomer which has at least any one of a hydroxyl group and a carboxyl group. As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. The hydroxyl-containing monomer can be used individually by 1 type or in combination of 2 or more types. Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Hydroxybutyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylate Base) hydroxyalkyl (meth)acrylates such as 12-hydroxylauryl acrylate; hydroxyalkylcycloalkane (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. In addition, examples include: hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. . Among them, hydroxyalkyl (meth)acrylate is preferred. For example, a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms can be preferably used. In a preferred aspect, it can be selected from 2-hydroxyethyl acrylate (2HEA), 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate (4HBA), and 4-hydroxybutyl methacrylate. One type or two or more types are used as the hydroxyl-containing monomer. The hydroxyl-containing monomer used in the preferred aspect of the technology disclosed herein may be 4HBA alone, 2HEA alone, or a combination of 4HBA and 2HEA. As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and a carboxyl group can be used without particular limitation. A carboxyl group-containing monomer can be used individually by 1 type or in combination of 2 or more types. Examples of carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate; itaconic acid, Maleic acid, fumaric acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids; metal salts of these (such as alkali metal salts); maleic anhydride, itaconic anhydride and other ethylenically unsaturated dicarboxylic acids such as anhydrides Wait. Among them, acrylic acid and methacrylic acid are preferred, and acrylic acid is particularly preferred. The technique disclosed here can be preferably implemented in a state where the component (C) contains a hydroxyl-containing monomer. That is, it is preferable that the (C) component contains only a hydroxyl-containing monomer, or contains a hydroxyl-containing monomer and a carboxyl group-containing monomer. When the component (C) contains a hydroxyl-containing monomer and a carboxyl-containing monomer, the ratio of the hydroxyl-containing monomer to the entire component (C) is preferably more than about 50% by weight, more preferably about 80% by weight Above (for example, about 90% by weight or more). Increasing the ratio of the hydroxyl-containing monomer in the component (C) is preferable from the viewpoint of reducing metal corrosion caused by carboxyl groups. The technology disclosed herein can be implemented preferably in a state where the monomer component does not substantially contain a carboxyl group-containing monomer. For example, the ratio of the carboxyl group-containing monomer in the monomer component can be set to less than about 1% by weight, preferably less than about 0.5% by weight, and more preferably less than about 0.2% by weight. The ratio of the said (A) component in the whole monomer component is not specifically limited. It is easy to obtain 100 / G '23 in one or both of G' 100 and G 'in terms of the adhesive layer and the like become the preferred values, the ratio of component (A) of the above-described preferably about 90% by weight, preferably It is about 85% by weight or less, more preferably about 70% by weight or less. In a preferred aspect, the ratio of the above-mentioned component (A) can also be set to about 60% by weight or less (furthermore, about 50% by weight or less, for example, less than about 50% by weight). Moreover, from the viewpoint of the initial adhesiveness of the adherend, etc., the ratio of the component (A) is preferably about 30% by weight or more, and more preferably about 35% by weight or more. In one aspect, the ratio of the component (A) in the entire monomer component can be set to, for example, about 30 to 70% by weight. When the (B) component is included as the above-mentioned monomer component, the ratio of the (B) component in the entire monomer component is not particularly limited. It is easy to obtain 100 / G '23 in one or both of G' 100 and G 'in terms of the adhesive layer and the like become better value, (B) the ratio of the component is generally preferably about 3% by weight or more, more It is preferably about 5% by weight or more, more preferably about 8% by weight or more (for example, about 10% by weight or more). In addition, from the viewpoint of the initial adhesion of the adherend, the ratio of the component (B) is preferably about 65% by weight or less, preferably about 60% by weight or less, and more preferably about 55% by weight or less (furthermore It is about 50% by weight or less, for example, less than about 50% by weight). In a preferred aspect, the ratio of component (B) in the entire monomer component can be set to about 15% by weight or more, it can be set to about 20% by weight or more, or it can be set to about 25% by weight or more. Furthermore, about 30% by weight or more (for example, about 35% by weight or more). In one aspect, the ratio of the component (B) in the entire monomer component can be set to, for example, about 20 to 50% by weight. When the (C) component is included as the above-mentioned monomer component, the ratio of the (C) component in the entire monomer component is not particularly limited. From the viewpoint of the initial adhesion of the adherend, the ratio of the component (C) is typically about 3% by weight or more, preferably about 5% by weight or more, and more preferably about 8% by weight or more (for example About 10% by weight or more). Moreover, it is easy to obtain G '100 and G' 100 / G '23 in terms of one or both of the adhesive layer and the like become better value, (C) the ratio of the component is preferably above about 35 wt% or less , More preferably about 30% by weight or less, and still more preferably about 25% by weight or less. In one aspect, the ratio of the component (C) can be, for example, about 15 to 30% by weight. (Optional monomer) The monomer component in the technology disclosed here may also contain monomers other than the above-mentioned (A) component, (B) component and (C) component (hereinafter also referred to as "optional monomer") . Examples of such optional monomers include heterocyclic ring-containing monomers such as cyclic nitrogen-containing monomers or cyclic ether group-containing monomers. Such heterocyclic monomers, like the above-mentioned component (B), can help to achieve a well-balanced adhesive layer that takes into account the better storage elastic modulus disclosed herein and other adhesive properties or other characteristics. In addition, it can also help to improve the adhesion or cohesion of the adhesive. The heterocyclic ring-containing monomer may be used singly or in combination of two or more kinds. As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure is preferably one having a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include internal vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methyl vinylpyrrolidone; 2 -Vinyl-2-
Figure 105138382-A0304-12-0015-1
Oxazoline, 2-vinyl-5-methyl-2-
Figure 105138382-A0304-12-0015-1
Oxazoline, 2-isopropenyl-2-
Figure 105138382-A0304-12-0015-1
Containing oxazoline
Figure 105138382-A0304-12-0015-1
Monomers of oxazoline groups; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper
Figure 105138382-A0304-12-0020-4
Vinylpyridine
Figure 105138382-A0304-12-0020-4
, Vinyl pyrrole, vinyl imidazole, vinyl
Figure 105138382-A0304-12-0020-6
Vinyl monomers with nitrogen-containing heterocycles such as morpholines. As other examples of cyclic nitrogen-containing monomers, examples include
Figure 105138382-A0304-12-0020-6
Morpholine ring, piperidine ring, pyrrolidine ring, piper
Figure 105138382-A0304-12-0020-4
Nitrogen-containing heterocyclic (meth)acrylic monomers such as ring and aziridine ring. Specifically, can cite: N-acryloyl group
Figure 105138382-A0304-12-0020-6
Phylloline, N-acryloyl piperidine, N-methacryloyl piperidine, N-acryloyl pyrrolidine, N-acryloyl aziridine, etc. Among the above-mentioned cyclic nitrogen-containing monomers, from the viewpoint of cohesiveness and the like, a lactam-based vinyl monomer is preferred, and N-vinylpyrrolidone is more preferred. As a monomer having a cyclic ether group, a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group and an epoxy group or an oxetanyl group can be used without particular limitation. Those who are cyclic ether groups. Examples of epoxy-containing monomers include: glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-hydroxybutyl glycidyl (meth)acrylate Ether and so on. Examples of the oxetanyl group-containing monomer include: 3-oxetanyl methyl (meth)acrylate, 3-methyl-oxetanyl methyl (meth)acrylate, and (meth)acrylic acid 3-ethyl-oxetanyl methyl ester, 3-butyl-oxetanyl methyl (meth)acrylate, 3-hexyl-oxetanyl methyl (meth)acrylate, and the like. As other examples of any of the above-mentioned monomers, alkyl (meth)acrylates that are not component (A), that is, (methyl) whose alkyl group has 1 or 19 or more carbon atoms (e.g., 19-24) Alkyl acrylate. As specific examples of such alkyl (meth)acrylates, methyl (meth)acrylate, n-nonadecyl (meth)acrylate, isnonadecyl (meth)acrylate, N-eicosyl (meth)acrylate, isoeicosyl (meth)acrylate, etc. These can be used individually by 1 type or in combination of 2 or more types. As other examples of the above-mentioned arbitrary monomers, monomers containing functional groups other than a hydroxyl group and a carboxyl group can be cited. Such a functional group-containing monomer can be used for the purpose of introducing a crosslinking point into the (meth)acrylic polymer or improving the cohesive force of the (meth)acrylic polymer. Examples of functional group-containing monomers include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, etc. Monomers such as acrylonitrile, methacrylonitrile and other cyano group-containing monomers; such as styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid Monomers containing sulfonic acid groups; for example, monomers containing phosphoric acid groups such as 2-hydroxyethyl acryloyl phosphate; such as diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl Ketone group-containing monomers such as ketone, acetyl vinyl acetate, etc.; for example, isocyanate group-containing monomers such as 2-(meth)acryloxyethyl isocyanate; for example, (meth)acrylate methoxyethyl Ester, ethoxyethyl (meth)acrylate and other alkoxy-containing monomers; for example, 3-(meth)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl Triethoxysilane and other monomers containing alkoxysilyl groups. These can be used individually by 1 type or in combination of 2 or more types. Among the monomer components in the technology disclosed herein, for the purpose of adjusting the Tg of the (meth)acrylic polymer or improving the cohesive force, etc., any of the above-mentioned monomers may also include those capable of interacting with the above-mentioned (A) and (B). , (C) Copolymerizable monomers other than those exemplified above for copolymerization of component. Examples of such copolymerizable monomers include vinyl carboxylates such as vinyl acetate and vinyl propionate; and aromatic vinyls such as styrene, substituted styrene (α-methylstyrene, etc.), and vinyl toluene. Base compound; such as (meth) aryl acrylate (such as (meth) phenyl acrylate), (meth) aryloxyalkyl acrylate (such as (meth) phenoxy ethyl acrylate), (methyl) ) Arylalkyl acrylate (for example, benzyl (meth)acrylate) and other aromatic ring-containing (meth)acrylates; for example, olefinic monomers such as ethylene, propylene, isoprene, butadiene, isobutylene, etc. For example, chlorine-containing monomers such as vinyl chloride and vinylidene chloride; for example, vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; Macro monomers based on polymerizable vinyl groups, etc. These can be used individually by 1 type or in combination of 2 or more types. The usage amount of these arbitrary monomers is not specifically limited, It can determine suitably. Generally, the total usage amount of any monomer is suitably set to be less than about 50% by weight of the monomer components, preferably about 30% by weight or less, and more preferably about 20% by weight or less. The technique disclosed herein can be preferably implemented in a state where the total usage amount of any monomer is about 10% by weight or less (for example, about 5% by weight or less) of the monomer components. In the case of using arbitrary monomers, from the viewpoint of properly exerting the effect of improving adhesion or cohesion, it is appropriate to set the usage amount of the arbitrary monomer to about 0.5% by weight or more of the monomer component, and it is preferable to set It is about 0.8% by weight or more. In addition, the technology disclosed here can also be used without any monomer (for example, the amount of any monomer used is about 0.3% by weight or less of the monomer component, typically about 0.1% by weight or less. Like) is better implemented. The above-mentioned (A) component, (B) component, (C) component, and arbitrary monomers are typically monofunctional monomers. Among the above-mentioned monomer components, in addition to such a monofunctional monomer, for the purpose of adjusting the storage elastic modulus of the adhesive layer, etc., an appropriate amount of a polyfunctional monomer may be contained as needed. Here, in the present specification, a monofunctional monosystem refers to a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group (typically a radical polymerizable functional group) The monomer. In contrast, a polyfunctional monomer as described below means a monomer having at least two such polymerizable functional groups. (Multifunctional monomer) A multifunctional single system having at least two (meth)acrylic groups or vinyl groups and other polymerizable functional groups with unsaturated double bonds (typically radical polymerizable functional groups) body. Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate (Methyl)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate and other polyols and (meth)acrylate esters; (meth)acrylate allyl ester , Vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, etc. As preferable examples among these, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be mentioned. Among them, as a preferred example, 1,6-hexanediol di(meth)acrylate can be cited. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of reactivity and the like, a polyfunctional monomer having two or more acryl groups is generally preferred. The usage amount of the polyfunctional monomer is not particularly limited, and it can be appropriately set in a manner to achieve the purpose of use of the polyfunctional monomer. From the viewpoint of a good balance between the better storage elastic modulus disclosed here and other adhesive properties or other characteristics, in one aspect, the usage amount of the multifunctional monomer can be set to about 3 weight of the above monomer components % Or less, preferably about 2% by weight or less, more preferably about 1% by weight or less (for example, about 0.5% by weight or less). In the case of using a multifunctional monomer, the lower limit of the usage amount should be greater than 0% by weight, and there is no particular limitation. Generally, by setting the usage amount of the multifunctional monomer to about 0.001% by weight or more (for example, about 0.01% by weight or more) of the monomer components, the effect of using the multifunctional monomer can be appropriately exerted. Although not particularly limited, the ratio of the total amount of (A) component, (B) component and (C) component in the total monomer component is typically more than about 50% by weight, preferably about 70 % By weight or more, more preferably about 80% by weight or more, and still more preferably about 90% by weight or more. The technology disclosed herein can be preferably implemented in a state where the above-mentioned total ratio is about 95% by weight or more (for example, about 99% by weight or more). The ratio of the above total amount may also be 100% by weight. The technique disclosed here can be preferably implemented in a state where the ratio of the total amount of the total monomer component in the entire monomer component is 99.999% by weight or less (for example, 99.99% by weight or less). Although not particularly limited, from the viewpoint of adhesiveness of the adhesive sheet or low-temperature characteristics, the Tg of the copolymer corresponding to the composition of the above-mentioned monomer components is preferably about -20°C or less, more preferably about- Below 25°C. Moreover, it is easy to obtain 100 / G '23 in one or both of G' 100 and G 'in terms of the adhesive layer and the like become better value the Tg of the copolymer should be less than about -55 deg.] C, preferably It is about -50°C or higher, more preferably about -45°C or higher. The technology disclosed herein can also be preferably implemented in a state where the Tg of the above-mentioned copolymer is about -40°C or higher (for example, about -35°C or higher). Here, the Tg of the copolymer corresponding to the composition of the monomer component refers to the Tg obtained by the Fox formula based on the composition of the above monomer component. The Fox formula is shown as the relationship between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer formed by the homopolymerization of the monomers constituting the copolymer. 1/Tg=Σ(Wi/Tgi) Furthermore, in the above Fox formula, Tg represents the glass transition temperature of the copolymer (unit: K), and Wi represents the weight fraction of monomer i in the copolymer (weight basis The copolymerization ratio), Tgi represents the glass transition temperature of the homopolymer of monomer i (unit: K). However, in this specification, the calculation of Tg is performed considering only monofunctional monomers. Therefore, when the monomer component contains a polyfunctional monomer, the total amount of the monofunctional monomer contained in the monomer component is set to 100% by weight, based on the Tg of the homopolymer of each monofunctional monomer and the The Tg is calculated by the weight fraction of the monofunctional monomer with respect to the above-mentioned total amount. As the glass transition temperature of the homopolymer used when calculating Tg, the value described in the publicly known data is used. For example, regarding the monomers listed below, the following values are used for the glass transition temperature of the homopolymer of the monomer. N-Butyl acrylate -55℃ 2-ethylhexyl acrylate -70℃ Cyclohexyl acrylate 15℃ Isoacrylate
Figure 105138382-A0304-03-0013-01
Base ester 94°C 2-hydroxyethyl acrylate-15°C 4-hydroxybutyl acrylate-40°C acrylic acid 106°C methacrylic acid 228°C For the glass transition temperature of homopolymers of monomers other than those exemplified above, use "Polymer Handbook""(3rd edition, John Wiley & Sons, Inc, 1989). For monomers with multiple values recorded in this document, the highest value is used. Regarding the monomer that does not describe the glass transition temperature of the homopolymer in the above-mentioned "Polymer Handbook", the value obtained by the following measurement method is used (refer to Japanese Patent Application Publication No. 2007-51271). Specifically, 100 parts by weight of monomers, 0.2 parts by weight of azobisisobutyronitrile, and 200 parts by weight of ethyl acetate as a polymerization solvent were put into a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux cooling tube. Stir for 1 hour while flowing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63°C and allowed to react for 10 hours. Then, it was cooled to room temperature, and a homopolymer solution with a solid content concentration of 33% by weight was obtained. The homopolymer solution was cast-coated on a release film and dried to prepare a test sample (sheet-like homopolymer) with a thickness of about 2 mm. The test sample was punched into a disc shape with a diameter of 7.9 mm, clamped with parallel plates, and a viscoelastic test device (manufactured by TA Instruments, ARES) was used to impart a shear strain with a frequency of 1 Hz on one side and at -70 on the other side. Measure the viscoelasticity in a shear mode at a temperature range of ~150°C at a heating rate of 5°C/min, and set the peak top temperature of tanδ (loss tangent) as the glass transition temperature. <Adhesive composition> The adhesive layer disclosed here can be used in the form of polymer, unpolymer (that is, the polymerizable functional group is in an unreacted form), or a mixture of the above composition. The body composition is formed by the adhesive composition. The aforementioned adhesive composition can be in various forms as follows: a composition in the form of an organic solvent containing an adhesive (adhesive component) (solvent adhesive composition); a composition in the form of an adhesive dispersed in an aqueous solvent (water Dispersed adhesive composition); a composition prepared by curing with active energy rays such as ultraviolet rays or radiation to form an adhesive (active energy ray hardening adhesive composition); coating and melting under heating When cooled to around room temperature, a hot-melt adhesive composition, etc., will form an adhesive. Here, in this specification, "active energy rays" refer to energy rays having energy capable of causing chemical reactions such as polymerization reactions, crosslinking reactions, and decomposition of initiators. Examples of active energy rays referred to herein include light such as ultraviolet rays, visible rays, and infrared rays; or radiation rays such as α rays, β rays, γ rays, electron beams, neutron beams, and X rays. The above-mentioned adhesive composition typically contains at least a part of the monomer components of the composition in the form of a polymer (may be a part of the monomer type, or a part of the weight). The polymerization method when forming the above-mentioned polymer is not particularly limited, and various previously known polymerization methods can be suitably adopted. For example, thermal polymerization such as solution polymerization, emulsion polymerization, and bulk polymerization (typically carried out in the presence of a thermal polymerization initiator) can be suitably used; photopolymerization carried out by irradiating light such as ultraviolet rays (typically, in light In the presence of a polymerization initiator); radiation polymerization performed by irradiating radiation such as β-rays and γ-rays. Among them, photopolymerization is preferred. Among these polymerization methods, the state of polymerization is not particularly limited, and the previously known monomer supply method, polymerization conditions (temperature, time, pressure, light exposure, radiation exposure, etc.), use other than monomers can be appropriately selected Materials (polymerization initiators, surfactants, etc.) and the like. At the time of polymerization, a known or commonly used photopolymerization initiator or thermal polymerization initiator can be used according to the polymerization method, the polymerization state, and the like. Such a polymerization initiator can be used individually by 1 type or in combination of 2 or more types suitably. The photopolymerization initiator is not particularly limited. For example, a ketal-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, a benzoin ether-based photopolymerization initiator, and an phosphine oxide-based photopolymerization agent can be used. Initiator, α-ketol-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzalkonium-based photopolymerization initiator Polymerization initiator, benzophenone-based photopolymerization initiator, 9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
Department of photopolymerization initiator and so on. Specific examples of the ketal-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name "Irgacure 651" manufactured by BASF Corporation) and the like. Specific examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl-phenyl-ketone (for example, the trade name "Irgacure 184" manufactured by BASF), 4-phenoxydichloroacetophenone, 4 -Tertiary butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (for example, BASF The company’s brand name "Irgacure 2959"), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (for example, the brand name "Darocure 1173" manufactured by BASF), methoxy styrene Ketones and so on. Specific examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, and substituted benzoin such as anisole methyl ether ether. Specific examples of phosphine oxide-based photopolymerization initiators include bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide (for example, the trade name "Irgacure 819" manufactured by BASF), (2,4,6-trimethylbenzyl)-2,4-di-n-butoxyphenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide (e.g. , The trade name "Lucirin TPO" manufactured by BASF Corporation), bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, etc. Specific examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1-one Wait. Specific examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. Specific examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(O-ethoxycarbonyl)oxime and the like. Specific examples of the benzoin-based photopolymerization initiator include benzoin and the like. Specific examples of the benzyl-based photopolymerization initiator include benzyl and the like. Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and polyvinyl benzophenone. Ketones, α-hydroxycyclohexyl phenyl ketone, etc. 9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
Specific examples of the photopolymerization initiator include 9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2-Chloro-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2-Methyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2,4-Dimethyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, Isopropyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2,4-Dichloro-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2,4-Diethyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, Isopropyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, 2,4-Diisopropyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
, Dodecyl-9-oxysulfur
Figure 105138382-A0304-003-035-2
Figure 105138382-A0304-xxxx-3
Wait. The thermal polymerization initiator is not particularly limited. For example, an azo-based polymerization initiator, a peroxide-based initiator, a redox-based initiator formed by a combination of a peroxide and a reducing agent, and a thermal polymerization initiator can be used. Substituted ethane-based starter, etc. More specifically, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis( 2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-co Azodis (N,N'-dimethylisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate and other azo systems Initiators; for example, persulfates such as potassium persulfate and ammonium persulfate; peroxide-based initiators such as benzyl peroxide, t-butyl hydroperoxide, hydrogen peroxide, etc.; for example, ethyl substituted with phenyl Alkanes and other substituted ethane-based initiators; for example, redox initiators such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc., but are not limited to these. Furthermore, thermal polymerization can be preferably carried out at a temperature of about 20-100°C (typically 40-80°C), for example. The usage amount of such a thermal polymerization initiator or photopolymerization initiator can be set to a usual usage amount corresponding to the polymerization method or polymerization state, etc., and is not particularly limited. For example, about 0.001 to 5 parts by weight (typically about 0.01 to 2 parts by weight, for example, about 0.01 to 1 part by weight) of the polymerization initiator can be used with respect to 100 parts by weight of the monomer to be polymerized. (Polymer and unpolymerized adhesive composition containing monomer components) A preferred aspect of the adhesive composition includes a polymerization reaction product of a monomer mixture, and the monomer mixture includes at least a part of the monomer of the composition Ingredients (raw monomers). Typically, a part of the aforementioned monomer components is included in the form of a polymer, and the remainder is included in the form of an unpolymerized (unreacted monomer). The polymerization reactant of the aforementioned monomer mixture can be prepared by at least partially polymerizing the monomer mixture. The above-mentioned polymerization reactant is preferably a partial polymer of the above-mentioned monomer mixture. Such partial polymer is a mixture of polymer and unreacted monomer derived from the aforementioned monomer mixture, and is typically in the form of a slurry (liquid with viscosity). Hereinafter, some polymers of the above-mentioned properties are sometimes referred to as "monomer slurry" or simply "slurry". The polymerization method when obtaining the above-mentioned polymerization reaction product is not particularly limited, and various polymerization methods as described above can be appropriately selected and used. From the viewpoint of efficiency or simplicity, a photopolymerization method can be preferably used. If photopolymerization is used, the polymerization conversion rate of the above-mentioned monomer mixture can be easily controlled by polymerization conditions such as light irradiation amount (light amount). The polymerization conversion rate (monomer conversion) of the monomer mixture in the above-mentioned partial polymer is not particularly limited. The said polymerization conversion rate can be set to about 70 weight% or less, for example, Preferably it is set to about 60 weight% or less. From the viewpoints of ease of preparation or coating properties of the adhesive composition containing the above-mentioned partial polymer, generally the above-mentioned polymerization conversion rate is preferably about 50% by weight or less, preferably about 40% by weight or less (for example, about 35% by weight). %the following). The lower limit of the polymerization conversion rate is not particularly limited, but is typically about 1% by weight or more, and usually it is appropriately set to about 5% by weight or more. The adhesive composition containing the partial polymer of the above-mentioned monomer mixture can be easily obtained, for example, by partially polymerizing the monomer mixture including all the raw material monomers by an appropriate polymerization method (for example, a photopolymerization method). The adhesive composition containing the above-mentioned partial polymer may be equipped with other components (for example, photopolymerization initiator, multifunctional monomer, crosslinking agent, acrylic oligomer described later, etc.) as needed. The method of compounding such other components is not particularly limited. For example, it may be contained in the above-mentioned monomer mixture in advance, or may be added to the above-mentioned partial polymer. In addition, the adhesive composition disclosed herein may also be a monomer mixture containing a part of a monomer component (raw monomer). A complete polymer is dissolved in the remaining monomer or a part of the polymer. The form. Adhesive compositions of this form are also included in the examples of polymer and unpolymerized adhesive compositions containing monomer components. In addition, in this specification, "complete polymer" means that the polymerization conversion rate exceeds 95% by weight. As a curing method (polymerization method) when the adhesive composition is formed from a polymer containing a monomer component and an unpolymerized adhesive composition, a photopolymerization method can be preferably used. Regarding the adhesive composition containing the polymerization reactant prepared by the photopolymerization method, it is particularly preferable to adopt the photopolymerization method as the hardening method. The polymerization reaction product obtained by the photopolymerization method already contains a photopolymerization initiator. Therefore, when the adhesive composition containing the polymerization reaction product is further hardened to form an adhesive, it is possible to add a new photopolymerization initiator. Perform light hardening. Alternatively, it may also be an adhesive composition obtained by adding a photopolymerization initiator to the polymerization reaction prepared by the photopolymerization method as necessary. The additional photopolymerization initiator may be the same as or different from the photopolymerization initiator used to prepare the polymerization reactant. The adhesive composition prepared by a method other than photopolymerization can become photocurable by adding a photopolymerization initiator. The light-curable adhesive composition has the advantage that even a thicker adhesive layer can be easily formed. In a preferred aspect, the photopolymerization when forming the adhesive from the adhesive composition can be performed by ultraviolet irradiation. For ultraviolet irradiation, known high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, etc. can be used. (Adhesive composition containing monomer components in the form of a complete polymer) Another preferred adhesive composition includes the monomer components of the agent composition in the form of a complete polymer. Such an adhesive composition may be, for example, a solvent-based adhesive composition containing a (meth)acrylic polymer as a monomer component of a complete polymer in an organic solvent, and the above-mentioned (meth)acrylic polymer is dispersed in A water-dispersed adhesive composition in an aqueous solvent. (Crosslinking agent) The adhesive composition disclosed here may contain a crosslinking agent. As the crosslinking agent, a known or customary crosslinking agent in the field of adhesives can be used. Examples include: epoxy-based cross-linking agents, isocyanate-based cross-linking agents, silicone-based cross-linking agents,
Figure 105138382-A0304-12-0015-1
Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, metal chelate-based cross-linking agents, etc. These can be used individually by 1 type or in combination of 2 or more types. The content of the crosslinking agent (in the case of containing two or more crosslinking agents, the total amount thereof) is not particularly limited. From the viewpoint of realizing an adhesive that exhibits adhesive properties such as adhesion or cohesion in a well-balanced manner, the content of the crosslinking agent is usually about 5 parts by weight relative to 100 parts by weight of the monomer components contained in the adhesive composition It is preferably about 0.001 to 5 parts by weight, more preferably about 0.001 to 4 parts by weight, and still more preferably about 0.001 to 3 parts by weight. Alternatively, it may also be an adhesive composition that does not contain the above-mentioned crosslinking agent. ((Meth)acrylic oligomer) From the viewpoint of improving adhesive strength, etc., the adhesive composition disclosed here may contain a (meth)acrylic oligomer. As the (meth)acrylic oligomer, it is preferable to use the Tg of a copolymer having a Tg ratio corresponding to the composition of the above-mentioned monomer components (typically, roughly corresponding to the adhesive composition formed from the adhesive composition). Containing (meth)acrylic polymer has a high Tg) polymer. By containing (meth)acrylic oligomer, the adhesive strength of the adhesive can be improved. The above-mentioned (meth)acrylic oligomer preferably has a Tg of about 0°C or higher and about 300°C or lower, preferably about 20°C or higher and about 300°C or lower, and more preferably about 40°C or higher and about 300°C the following. By making Tg within the above-mentioned range, the adhesive force can be improved preferably. In addition, the Tg of the (meth)acrylic oligomer and the Tg of the copolymer corresponding to the composition of the above-mentioned monomer components are the values calculated based on the Fox formula. The weight average molecular weight (Mw) of the (meth)acrylic oligomer can typically be about 1,000 or more and less than about 30,000, preferably about 1,500 or more and less than about 20,000, and more preferably about 2,000 or more. Less than about 10,000. By making Mw within the above-mentioned range, good adhesive force or retention characteristics can be obtained, which is preferable. The Mw of the (meth)acrylic oligomer can be measured by gel permeation chromatography (GPC) and obtained as a value in terms of standard polystyrene. Specifically, HPLC8020 manufactured by Tosoh Co., Ltd. uses TSK gel GMH-H(20)×2 as the column, and the measurement is performed with a tetrahydrofuran solvent at a flow rate of about 0.5 ml/min. Examples of monomers constituting the (meth)acrylic oligomer include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate Ester, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate ) Isoamyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate , Nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, (meth) Alkyl (meth)acrylates such as dodecyl acrylate; cyclohexyl (meth)acrylate, isopropyl (meth)acrylate
Figure 105138382-A0304-03-0013-01
(Meth)acrylic acid and alicyclic alcohol esters such as dicyclopentyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate and the like (meth) Aromatic acrylate; (meth)acrylate obtained from terpene compound derivative alcohol, etc. Such (meth)acrylate can be used individually by 1 type or in combination of 2 or more types. As the (meth)acrylic oligomer, from the viewpoint of further improving the adhesiveness of the adhesive layer, it is preferable to include isobutyl (meth)acrylate or tertiary butyl (meth)acrylate. Alkyl (meth) acrylate with branched structure; cyclohexyl (meth) acrylate or isopropyl (meth) acrylate
Figure 105138382-A0304-03-0013-01
(Meth)acrylic acid and alicyclic alcohol esters such as dicyclopentyl (meth)acrylate; (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate (Meth)acrylic acid esters such as aryl acrylates and the like having a cyclic structure are represented by acrylic monomers with relatively large structures as monomer units. In addition, when the (meth)acrylic oligomer is synthesized or when ultraviolet rays are used in the production of the adhesive layer, it is less likely to cause polymerization inhibition. It is preferable to have a saturated bond, and the alkyl group may have a branch. The alkyl (meth)acrylate of the chain structure or the ester with an alicyclic alcohol is preferably used as the monomer constituting the (meth)acrylic oligomer. From this point of view, preferred (meth)acrylic oligomers include, for example, dicyclopentyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isomethacrylate
Figure 105138382-A0304-03-0013-01
Base ester (IBXMA), acrylic iso
Figure 105138382-A0304-03-0013-01
Base ester (IBXA), dicyclopentyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA) and their respective homopolymers, as well as CHMA and methacrylic acid Copolymer of isobutyl ester (IBMA), copolymer of CHMA and IBXMA, CHMA and acrylic acid base
Figure 105138382-A0304-12-0020-6
Copolymer of ACMO, Copolymer of CHMA and DEAA, Copolymer of ADA and Methyl Methacrylate (MMA), Copolymer of DCPMA and IBXMA, Copolymer of DCPMA and MMA Wait. When the adhesive composition disclosed here contains (meth)acrylic oligomer, its content is not particularly limited. From the viewpoint of easy realization of the adhesive layer with better storage elastic modulus disclosed here, the content of (meth)acrylic oligomer is generally relative to the monomer component contained in the adhesive composition. Parts by weight are preferably set to about 20 parts by weight or less, more preferably set to about 15 parts by weight or less, and still more preferably set to about 10 parts by weight or less. The technology disclosed here can also be implemented preferably without using (meth)acrylic oligomers. In addition, the adhesive composition disclosed herein may optionally contain various additives known in the field of adhesives. For example, coloring agents such as dyes or pigments, antistatic agents, surfactants, plasticizers, adhesion-imparting resins, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, and light stabilizers can be appropriately added according to the application. , UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. In the technique disclosed here, as the adhesive composition for forming the adhesive layer, an active energy ray-curable adhesive composition (typically, a light-curable adhesive composition) can be preferably used. As the above-mentioned active energy ray-curable adhesive composition, from the viewpoint of environmental sanitation and the like, it is preferably one that does not substantially contain an organic solvent. For example, it is preferably an adhesive composition in which the content of the organic solvent is about 5% by weight or less (more preferably about 3% by weight or less, for example, about 0.5% by weight or less). In addition, as described below, since it is suitable for forming an adhesive layer in a form in which the liquid film of the adhesive composition is hardened between the peeling surfaces of a pair of peeling films, it is preferably substantially free of solvents (including organic solvents and water-based The meaning of solvent) is the adhesive composition. For example, it is preferably an adhesive composition with a solvent content of about 5% by weight or less (more preferably about 3% by weight or less, for example, about 0.5% by weight or less). Furthermore, the solvent here refers to the volatile component that should be removed during the formation of the adhesive layer, that is, the volatile component that is not intended to be a constituent of the final formed adhesive layer. <The manufacturing method of the adhesive sheet> The method of manufacturing the adhesive sheet disclosed here is not specifically limited. For example, by coating any of the adhesive compositions disclosed herein on the peeling surface of the release film and drying or hardening to form an adhesive layer, a double-sided substrate-free substrate containing the adhesive layer can be obtained Adhesive sheet. In addition, by attaching (transferring) the adhesive layer formed on the release film on the non-release surface of the supporting substrate, a single-sided adhesive sheet with the substrate can be obtained. As another method of manufacturing a single-sided adhesive sheet with a substrate, a method of directly coating the adhesive composition on the non-peelable surface of the supporting substrate and drying or curing the adhesive composition can be cited. The double-sided adhesive sheet with substrate can be transferred by the method of transferring the adhesive layer formed on the release film to the supporting substrate, or the adhesive composition can be directly applied to the supporting substrate and dried or cured Method, or a combination of these methods, etc. As a coating method of the adhesive composition, various methods previously known can be used. Specifically, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating, knife coating Cloth, air knife coating, curtain coating, die lip coating, extrusion coating using die nozzle coating machine, etc. The adhesive sheet disclosed here can be preferably manufactured by a method including drying or hardening a liquid film of the adhesive composition on the peeling surface of the peeling film to form a hardened surface on the peeling surface: Adhesive layer of the first adhesive surface. Using this method, the adhesive composition (liquid film) in a fluid state can be brought into contact with the peeling surface and dried or hardened, and the surface of the adhesive layer formed in contact with the peeling surface can be controlled with high precision. The smoothness. For example, by using a peeling film having a peeling surface with appropriate smoothness, a first adhesive surface with desired smoothness can be manufactured stably (with good reproducibility). The adhesive sheet disclosed herein can be preferably manufactured by a method including hardening the liquid film of the adhesive composition between the peeling surfaces of a pair of peeling films to form an adhesive layer. This method is better as a method for manufacturing a substrate-free double-sided adhesive sheet in which the ten-point average roughness of the first adhesive surface and the ten-point average roughness of the second adhesive surface are both within the preferred range disclosed herein. In addition, by attaching the thus obtained double-sided adhesive sheet without substrate to the non-peelable surface of the supporting substrate, it can also be preferably used to manufacture a substrate-attached single-sided adhesive sheet or a substrate-attached single-sided adhesive sheet. Double-sided adhesive sheet. As a method of arranging a liquid film of the adhesive composition between the peeling surfaces of a pair of peeling films, the following method can be adopted. That is, a liquid adhesive composition is applied to the peeling surface of the first peeling film, and then the adhesive composition is applied. The liquid film of the agent composition is covered with a second release film. As another method, the method of supplying a 1st peeling film and a 2nd peeling film between a pair of rolls with peeling surfaces facing each other, and supplying a liquid adhesive composition between these peeling surfaces is mentioned. Furthermore, the application of the adhesive composition is preferably performed at 80°C or lower, and more preferably at 60°C or lower (for example, 40°C or lower). Thereby, the roughness of the adhesive layer caused by the difference in the thermal expansion rate of the release film and the adhesive layer can be suppressed, and a smoother adhesive surface can be formed. The gel fraction of the adhesive layer disclosed herein is not particularly limited, and is generally preferably about 99.5% by weight or less, more preferably about 20-99.5% by weight, and still more preferably about 50-99.5% by weight. In the case where the above-mentioned adhesive composition contains a cross-linking agent, the amount of the cross-linking agent added can be adjusted, and the gel fraction can be controlled in consideration of the effect of the cross-linking treatment temperature or the cross-linking treatment time. Although not particularly limited, the adhesive layer constituting the adhesive sheet disclosed herein preferably has a haze value of 2% or less at a thickness of 50 μm. For the adhesive layer used for optical applications, the above-mentioned haze value of 2% or less is particularly meaningful. The haze value of the adhesive layer is preferably 0 to 1.5%, more preferably 0 to 1%. The above-mentioned haze value can be measured by attaching an adhesive layer formed so that the thickness becomes about 50 μm on one side of an alkali glass plate and using a haze meter. As a haze meter, MR-100 manufactured by Murakami Color Technology Research Institute or its equivalent can be used. At the time of the measurement, the alkali glass plate to which the adhesive layer was attached was arranged so that the adhesive layer was on the light source side. When the alkali glass itself has a haze value, the value obtained by subtracting the haze value of the alkali glass plate itself from the measured value is the haze value of the adhesive layer. <Release film> The release film in the technique disclosed here is not particularly limited, and can be appropriately selected according to the purpose. Non-limiting examples of the release film that can be used include: a release film having a release treatment layer on one or both surfaces of the release film substrate, and the surface of the release treatment layer becomes a release film; and a release film containing a fluorine-based polymer (poly A release film of low-adhesive resin such as tetrafluoroethylene) or polyolefin resin (polyethylene, polypropylene, etc.). As the above-mentioned release film substrate, a plastic film, paper (may be resin impregnated paper or resin laminated paper), etc. can be used. The said peeling process layer may be formed by surface-treating the said peeling film base material by a peeling process agent. Examples of release treatment agents include silicone release treatment agents, long-chain alkyl release treatment agents, fluorine release treatment agents, molybdenum (IV) sulfide, and the like. In one aspect, a release film having a release treatment layer based on a silicone-based release treatment agent can be preferably used. As the release film disclosed here, it can be preferably used for those having a release treatment layer on the surface of the plastic film as the base material of the release film. The material constituting this plastic film can be arbitrarily selected from the same materials as those exemplified as the plastic film for supporting the base material. From the viewpoint of dimensional stability or strength, a plastic film containing a polyester resin film (typically a polyethylene terephthalate film) can be preferably used. Preferably, it is a plastic film having transparency in at least a part of the area. In the technology disclosed herein, the plastic film used as the above-mentioned supporting substrate or release film substrate may be any of unstretched film, uniaxially stretched film, and biaxially stretched film. In addition, the above-mentioned plastic film may have a single-layer structure, or a multi-layer structure including two or more layers including secondary layers. Antioxidants, anti-aging agents, heat-resistant stabilizers, light stabilizers, ultraviolet absorbers, pigments or dyes and other colorants, lubricants, fillers, antistatic agents, nucleating agents, etc. can also be formulated in the above plastic film. It can be used for adhesion. A well-known additive for the supporting substrate of the sheet or the substrate of the release film. For a plastic film with a multilayer structure, each additive can be deployed in all the secondary layers, or only in a part of the secondary layers. As the release film in the technique disclosed herein, a release film having a release treatment layer on the surface of a plastic film (release film base material) and containing no particles or particles with a diameter of 5 μm or less can be preferably used. Particles (especially inorganic particles) with a diameter of more than 5 μm contained in the release film can reduce the smoothness of the release surface in the free state of the release film. In addition, even if the release film containing particles with a diameter of more than 5 μm has high smoothness in the free state, the particles may be removed from the release film due to bending deformation, tensile deformation, and compression in the thickness direction of the release film. The protrusion reduces the smoothness of the peeling surface, and further reduces the smoothness of the adhesive surface in contact with the peeling surface. In one aspect, it is also possible to use a release film that does not substantially contain particles with a diameter of more than 5 μm, that is, a release film that does not contain particles with a diameter of more than 5 μm except for inadvertently mixed impurities. Furthermore, the above-mentioned particles with a diameter of more than 5 μm may be, for example, inorganic particles that can be formulated in the release film base material for the purpose of lubricants, pigments, fillers, and the like. Non-limiting examples of the inorganic particles may include silica, alumina, kaolin, talc, mica, calcium carbonate, and the like. The thickness of the release film is not particularly limited. In terms of both strength and flexibility, it is generally preferable to use a release film with a thickness of about 10 μm to about 500 μm. It suppresses the decrease in the smoothness of the adhesive surface caused by the external force of the peeling film (for example, when the adhesive sheet with the peeling film is wound into a spiral shape, the impurities that may be mixed in are pressed against the adhesive surface through the peeling film. From the viewpoint of reduction in smoothness), the thickness of the release film is usually preferably set to about 20 μm or more, and more preferably set to about 25 μm or more (for example, about 30 μm or more). In addition, from the viewpoint of the handling properties of the release film itself or the adhesive sheet with the release film (such as easy winding), the thickness of the release film is generally preferably about 250 μm or less, preferably about 125 μm or less (for example, About 100 μm or less), more preferably about 80 μm or less. In one aspect, a release film having a thickness of about 75 μm or less (for example, about 50 μm or less) can be preferably used. For the adhesive sheet with release film disclosed here, the ten-point average roughness (Rz R1 ) of the release surface of the first release film that abuts on the first adhesive surface of the adhesive sheet can be set to, for example, about 2000 nm or less . From the viewpoint of suppressing the decrease in the smoothness of the first adhesive surface during storage of the adhesive sheet with a release film, Rz R1 is preferably about 1500 nm or less, preferably about 1000 nm or less, and more preferably about 500 nm Hereinafter, it is more preferably about 300 nm or less (for example, about 250 nm or less). When the above-mentioned first adhesive surface is the surface of an adhesive layer formed of a liquid adhesive composition on the release surface of the first release film, as the first release film, it is preferable to use Rz R1 of about approx. 1200 nm or less (typically about 700 nm or less, more preferably about 500 nm or less, and still more preferably about 400 nm or less, for example, about 300 nm or less). The lower limit of Rz R1 is not particularly limited. From the viewpoints of ease of manufacture and handling of the first release film, in one aspect, the first release film having Rz R1 of about 50 nm or more (for example, about 100 nm or more) can be preferably used. When the adhesive sheet with a release film disclosed here is in the form of a double-sided adhesive sheet with a release film including a double-sided adhesive sheet, a first release film, and a second release film, it abuts against the above-mentioned double The ten-point average roughness (Rz R2 ) of the peeling surface of the second peeling film of the second adhesive surface of the surface-adhesive sheet is not particularly limited, and may be, for example, about 3000 nm or more. In one aspect, a second release film with Rz R2 less than about 3000 nm (preferably less than about 2000 nm) can be preferably used. In the aspect where the ten-point average roughness Rz A2 of the second adhesive surface is 1000 nm or less, from the viewpoint of suppressing the decrease in the smoothness of the second adhesive surface, Rz R2 is preferably about 2000 nm or less (typically It is about 1500 nm or less, preferably about 1000 nm or less, more preferably about 500 nm or less, and still more preferably about 300 nm or less, for example, about 250 nm or less). When the above-mentioned second adhesive surface is the surface of an adhesive layer formed of a liquid adhesive composition on the release surface of the second release film, it is preferable to use Rz R2 as the second release film. 1200 nm or less (typically about 700 nm or less, more preferably about 500 nm or less, and still more preferably about 400 nm or less, for example, about 300 nm or less). The lower limit of Rz R2 is not particularly limited. In one aspect, a second release film with Rz R2 of about 50 nm or more (for example, about 100 nm or more) can be preferably used. In the technique disclosed here, the peeling surface of the peeling film constituting the adhesive sheet with the peeling film preferably has a smoothness similar to the smoothness of the adhesive surface abutting the peeling surface. Thereby, there is a tendency to more fully suppress the change in the smoothness of the adhesive surface of the adhesive sheet with the release film during storage, and improve the performance stability of the adhesive sheet. In one aspect of an adhesive sheet with a release film, the ten-point average roughness difference between the first adhesive surface and the first release surface in contact with it, that is |Rz R1- Rz A1 | can be set to about 300 nm Or less (for example, about 250 nm or less), preferably about 150 nm or less, more preferably about 100 nm or less. In addition, from the viewpoint of performance stability of the adhesive sheet, it is preferable that the ten-point average roughness of the first adhesive surface is smaller than the ten-point average roughness of the first release surface. That is, Rz A1 <Rz R1 is preferably an adhesive sheet with a release film that satisfies the value of |Rz R1- Rz A1 | and at least one of Rz A1 <Rz R1 (preferably both), for example, It is preferably manufactured by a method including drying or hardening the liquid film of the adhesive composition on the release surface of the first release film constituting the adhesive sheet with release film. When the adhesive sheet with release film disclosed here is in the form of a double-sided adhesive sheet with a release film including a double-sided adhesive sheet, a first release film and a second release film, in the same aspect, The ten-point average roughness difference between the second adhesive surface and the second peeling surface in contact with it, that is |Rz R2- Rz A2 | can be set to about 300 nm or less (for example, about 250 nm or less), preferably about 150 nm or less, more preferably about 100 nm or less. In addition, from the viewpoint of performance stability of the adhesive sheet, it is preferable that the ten-point average roughness of the second adhesive surface is smaller than the ten-point average roughness of the second release surface. That is, Rz A2 <Rz R2 is preferable. An adhesive sheet with a release film satisfying at least one of the values of |Rz R2- Rz A2 | and Rz A2 <Rz R2 (preferably both) can be included in the first release film, for example, as described later It is preferably manufactured by the method of curing the liquid film of the adhesive composition between the peeling surface of the second peeling film and the peeling surface of the second peeling film. The smoothness of the back surface of the release film constituting the adhesive sheet with the release film (that is, the surface on the opposite side to the release surface) is not particularly limited. Regarding the adhesive sheet with a release film that can be wound into a spiral shape, from the viewpoint of preventing the reduction in the smoothness of the adhesive surface caused by the unevenness of the back surface in the above-mentioned winding form, it is preferable to make the back surface of the release film The ten-point average roughness is set to be about 5000 nm or less (preferably about 4000 nm or less, for example, about 3000 nm or less). The adhesive sheet disclosed here (which may be an adhesive sheet included in an adhesive sheet with a release film. The same applies below) can be applied to the first adhesive surface during the period before the adhesive sheet is attached to the adherend. It is better to use the state where the release film is replaced with another release film. Hereinafter, the replaced release film is also referred to as "replacement film". The ten-point average roughness (Rz E1 ) of the first peeling surface of the replacement film (ie, the peeling surface disposed in contact with the first adhesive surface) is not particularly limited, and may be, for example, about 50 nm or more (typically about about 50 nm). Above 100 nm). In one aspect, a replacement film with Rz E1 exceeding about 250 nm (more preferably more than about 500 nm, for example, more than about 700 nm) may be used. The adhesive sheet disclosed here can also significantly inhibit the first adhesive surface when using a replacement film with Rz E1 of about 1000 nm or more (and further about 1200 nm or more, for example, about 1500 nm or more). The effect of reduced smoothness. The upper limit of Rz E1 is not particularly limited. Generally, it is better to use a replacement film with an Rz E1 of about 3000 nm or less (typically about 2000 nm or less). In one aspect, the Rz E1 of the replacement film may be below about 1500 nm, or below about 1000 nm. As the replacement film, the same configuration (material, thickness, surface roughness, etc.) of the release film before replacement can be used, or a different configuration can be used. In a preferred aspect, as the replacement film, the value of Rz E1 may be larger than the ten-point average roughness (Rz R1 ) of the first peeling surface of the peeling film before replacement (which may be a peeling film that has just been manufactured). In one aspect, a replacement film with Rz E1 /Rz R1 of about 2 or more (preferably about 3 or more) can be used. The adhesive sheet disclosed here, for example, in the use of a replacement film with Rz E1 /Rz R1 of about 5 or more (and further about 7 or more), can also significantly suppress the reduction in the smoothness of the first adhesive surface. effect. The upper limit of Rz E1 /Rz R1 is not particularly limited, but it is usually about 20 or less (typically about 15 or less, for example, about 10 or less). <Use> The adhesive layer or adhesive sheet disclosed here is suitable for optical applications because the smoothness of the adhesive surface is high and the smoothness of the adhesive surface is not easily damaged. For example, an adhesive-type optical member using an optical member as the support base material is useful. Such an adhesive optical member can also be understood as a single side with a substrate with the form of supporting the optical member on the first or second adhesive surface of any double-sided adhesive sheet disclosed herein Adhesive sheet. Preferably, it has a form with an optical member on the said 2nd adhesive surface. In this aspect, an adhesive-type optical member with a release film which has a release film on the said 1st adhesive surface can also be comprised. In the case of using an optical film as the optical member, the adhesive optical member can be used as an optical film to which an adhesive layer is attached. As the above-mentioned optical film, a polarizing plate, a retardation film, an optical compensation film, a brightness enhancement film, a hard coat (HC) film, an anti-reflection film, an impact absorption film, an antifouling film, a photochromic film, a light-adjusting film, A wavelength selective absorption film, a wavelength conversion film, and a film formed by laminating these films, etc. The adhesive layer or adhesive sheet disclosed here is also suitable for use in the ophthalmology field. In addition, the adhesive layer or the adhesive sheet of the present invention is not limited to the optical or ophthalmic use as described above. For example, it may be an adhesive sheet with an antifouling film, a heat insulation film, a cushioning absorption film, etc. as a support. The form is used for various purposes. The matters disclosed in this manual include the following. (1) An adhesive sheet comprising an adhesive layer, and the adhesive sheet has a first surface and a second surface, and the first surface is a first adhesive surface formed by one surface of the adhesive layer, The ten-point average roughness (Rz A1 ) of the first adhesive surface is about 1000 nm or less, and the storage elastic modulus (G' 100 ) of the adhesive layer at 100° C. is about 0.08 MPa or more. (2) The adhesive sheet as described in (1) above, wherein the ratio of the storage elastic modulus (G' 100 ) at 100°C of the adhesive layer to the storage elastic modulus (G' 23 ) at 23°C is about 35% the above. (3) The adhesive sheet as described in (1) or (2) above, wherein the storage elastic modulus (G' 23 ) of the adhesive layer at 23° C. does not reach about 0.30 MPa. (4) The adhesive sheet described in any one of (1) to (3) above, which is configured as a double-sided adhesive sheet whose second surface is the second adhesive surface. (5) The adhesive sheet as described in (4) above, wherein the ten-point average roughness (Rz A2 ) of the second adhesive surface is about 2000 nm or less (for example, about 1000 nm or less). (6) The adhesive sheet according to (4) or (5) above, wherein the second adhesive surface is constituted by the other surface of the adhesive layer. (7) The adhesive sheet described in any one of (4) to (6) above, wherein the ten-point average roughness of the first adhesive surface (Rz A1 ) and the ten-point average roughness of the second adhesive surface Any one of (Rz A2 ) is about 500 nm or less. (8) The adhesive sheet described in any one of (4) to (7) above, wherein the ten-point average roughness of the first adhesive surface (Rz A1 ) and the ten-point average roughness of the second adhesive surface (Rz A2 ) are all about 500 nm or less. (9) The adhesive sheet described in any one of (4) to (8) above, wherein the ten-point average roughness (Rz A1 ) of the first adhesive surface and the ten-point average roughness of the second adhesive surface The difference of (Rz A2 ) (|Rz A1- Rz A2 |) is about 250 nm or less. (10) The adhesive sheet according to any one of (1) to (9) above, wherein the adhesive sheet is a substrate-free double-sided adhesive sheet including a single-layer adhesive layer. (11) The adhesive sheet according to any one of (1) to (10) above, wherein the adhesive layer contains (methyl) at a ratio exceeding 50% by weight of the polymer component contained in the adhesive layer ) Acrylic polymer. (12) The adhesive sheet according to (11) above, wherein the (meth)acrylic polymer includes the following (A) component as a monomer component constituting the (meth)acrylic polymer: An alkyl (meth)acrylate having an alkyl group having 2 to 18 carbon atoms at the end of the ester. (13) The adhesive sheet according to (11) or (12) above, wherein the ratio of the component (A) in the entire monomer component is about 30% by weight to about 70% by weight. (14) The adhesive sheet according to any one of (11) to (13) above, wherein in the (meth)acrylic polymer, as a monomer component constituting the (meth)acrylic polymer, It further contains the following (B) component: alicyclic monomer. (15) The adhesive sheet according to any one of (11) to (14) above, wherein the component (B) is selected from cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, ( Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, isopropyl (meth)acrylate
Figure 105138382-A0304-03-0013-01
At least one of the group consisting of dicyclopentyl (meth)acrylate and dicyclopentyl (meth)acrylate. (16) The adhesive sheet according to any one of (11) to (15) above, wherein the ratio of the component (B) in the entire monomer component is about 20% by weight to about 50% by weight. (17) The adhesive sheet according to any one of (11) to (16) above, wherein in the (meth)acrylic polymer, as a monomer component constituting the (meth)acrylic polymer, It further contains the following (C) component: a monomer having at least any one of a hydroxyl group and a carboxyl group. (18) The adhesive sheet according to any one of (11) to (17) above, wherein the ratio of the component (C) in the entire monomer component is about 15% by weight to about 30% by weight. (19) The adhesive sheet according to any one of (11) to (18) above, wherein in the (meth)acrylic polymer, as a monomer component constituting the (meth)acrylic polymer, Furthermore, it contains a polyfunctional monomer, and the ratio of the said polyfunctional monomer in the said whole monomer component is about 3 weight% or less. (20) The adhesive sheet according to any one of (11) to (19) above, wherein the (meth)acrylic polymer is an ultraviolet polymer of the monomer component. (21) A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet as described in any one of (11) to (20) above, and includes using at least a part of the monomer component in the form of a polymer The adhesive composition forms the above-mentioned adhesive layer. (22) The method for producing an adhesive sheet according to (21) above, wherein forming the adhesive layer comprises coating the adhesive composition on the release surface of the release film and drying the adhesive composition on the release surface or hardening. (23) The method for producing an adhesive sheet according to (21) or (22), wherein the organic solvent content of the adhesive composition is about 5 wt% or less. (24) The method for producing an adhesive sheet according to any one of (21) to (23) above, wherein forming the adhesive layer includes curing the liquid film of the adhesive composition between the peeling surfaces of a pair of peeling films And the above-mentioned adhesive layer is formed. (25) An adhesive sheet with a release film, comprising: the adhesive sheet described in any one of (1) to (20) above, and a first release film arranged on the first adhesive surface. (26) An adhesive sheet with a release film, comprising: the adhesive sheet as described in any one of (4) to (20) above, a first release film arranged on the first adhesive surface, and an arrangement The second release film on the second adhesive surface mentioned above. (27) The adhesive sheet with a release film as described in (25) or (26) above, wherein the ten-point average roughness (Rz R1 ) of the release surface of the first release film in contact with the first adhesive surface is the same as the above The ten-point average roughness (Rz A1 ) difference of the first adhesive surface is within about 250 nm. (28) The adhesive sheet with a release film as described in (26) or (27) above, which satisfies Rz A1 <Rz R1 and Rz A2 <Rz R2 . (29) The adhesive sheet with a peeling film as described in any one of (25) to (28) above, wherein the first peeling film is selected from the group consisting of silica, alumina, kaolin, talc, mica, and calcium carbonate At least one type of inorganic particle in the group consisting of. (30) The adhesive sheet with a release film according to any one of (25) to (29) above, wherein the thickness of the first release film is about 10 μm or more and about 500 μm or less (preferably about 20 μm or more and about 100 μm or less, more preferably about 25 μm or more and about 80 μm or less). (31) An adhesive-type optical member comprising: the adhesive sheet described in any one of (4) to (20) above, and an optical member arranged on the second adhesive surface of the adhesive sheet. (32) A method of manufacturing an article with an adhesive sheet, comprising: preparing the adhesive sheet with a release film as described in any one of (26) to (30) above; peeling the first adhesive sheet from the first adhesive surface 1 peeling film, sticking the peeling surface of another peeling film to the exposed first adhesive surface; and sticking the second adhesive surface to the article to be adhered. (33) The method for manufacturing an article with an adhesive sheet as described in (32) above, wherein as the other release film, the ten-point average roughness (Rz E1 ) of the release surface of the another release film is greater than the above The ten-point average roughness (Rz R1 ) of the peeling surface of the first peeling film in contact with the first adhesive surface. [Cross reference with related applications] This application is based on the Japanese Patent Application No. 2015-232149 filed on November 27, 2015 and the Japanese Patent Application No. 2016-139538 filed on July 14, 2016 Priority, and the entire contents of these applications are incorporated into this specification by reference. [Examples] Hereinafter, several examples related to the present invention will be described, but the present invention is not intended to be limited to those shown in this specific example. <Preparation of adhesive composition> (Adhesive composition C1) 40 parts by weight of n-butyl acrylate, 41 parts by weight of cyclohexyl acrylate, and 19 parts by weight of 4-hydroxybutyl acrylate were used as 2 of the photopolymerization initiators ,2-Dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF company, trade name "Irgacure 651") 0.05 parts by weight and 1-hydroxycyclohexyl-phenyl-ketone (BASF company Manufactured, trade name "Irgacure 184") 0.05 parts by weight were mixed, and ultraviolet rays were irradiated in a nitrogen atmosphere to prepare a partial polymer (monomer slurry). 0.1 parts by weight of 1,6-hexanediol diacrylate was added to the obtained monomer slurry, and the mixture was uniformly mixed to prepare an adhesive composition C1. (Adhesive composition C2～C4) In the preparation of adhesive composition C1, the addition amount of 1,6-hexanediol diacrylate was changed to 0.3 parts by weight in adhesive composition C2 and adhesive composition C3 0.05 parts by weight in the adhesive composition, 0 parts by weight in the adhesive composition C4. In other respects, adhesive compositions C2 to C4 were prepared in the same manner as the preparation of adhesive composition C1. Furthermore, the adhesive compositions C1 to C4 are all solvent-free compositions. Specifically, the content of the solvent in the adhesive compositions C1 to C4 does not reach 5% by weight, more specifically, it does not reach 1% by weight. <Production of Adhesive Sheet> Preparation: a polyethylene terephthalate (PET) film F1 with a thickness of 38 μm has a release treatment layer based on a silicone release treatment agent A1 on one side, and the release side (the above-mentioned release The surface of the treatment layer) has a release film R1 with an average roughness of 211 nm; on one side of the PET film F2 with a thickness of 38 μm, there is a release treatment layer based on the silicone release treatment agent A1. Ten points of the release surface Release film R2 with an average roughness of 1610 nm; and release film R3 with a release treatment layer based on silicone release treatment agent A2 on one side of the above-mentioned PET film F2, and a release film R3 with a ten-point average roughness of the release side of 1610 nm . The peeling surface of the peeling film R3 is formed in such a way that the peeling strength of the self-adhesive layer is higher than the peeling surface of the peeling films R1 and R2. Using these release films, an adhesive sheet was produced in the following manner. Furthermore, the ten-point average roughness of each peeling surface of the peeling film R1, R2, R3 is the measured value obtained by the following method: by dropping it on the glass slide S1112 No. 2 (manufactured by Songnang Glass Industry) with a dropper The above 1 drop of water was carried out in the same manner as the measurement of the surface smoothness of the first adhesive surface described later, except that the back surface (the surface without the peeling treatment) of each release film was placed in close contact with the above-mentioned slide glass. (Example 1) The adhesive composition C1 prepared above was coated on the peeling surface of the peeling film R1, and a liquid film of the adhesive composition was formed on the peeling surface. The coating amount of the adhesive composition is adjusted so that the thickness of the finally formed adhesive layer becomes 50 μm. Then, the peeling film R3 is covered on the said liquid film so that the peeling surface of this peeling film R3 may contact the said liquid film. In this way, the above-mentioned liquid film is blocked from oxygen. In such a state that the both sides (first side and second side) of the liquid film of the adhesive composition C1 are in contact with the peeling surfaces of the peeling films R1 and R3, a chemical lamp (manufactured by Toshiba Co., Ltd.) is used to irradiate 360 Ultraviolet rays with 5 mW/cm 2 per second illuminance are polymerized to harden the liquid film to form an adhesive layer, and the adhesive layer of Example 1 containing the adhesive layer (ie, the ultraviolet cured product of the liquid film) is obtained Sheet S1. The adhesive sheet S1 constitutes the peeling surfaces of the peeling films R1 and R3 used in the production of the adhesive sheet S1. The peeling surfaces of the peeling films abut on the first surface (first adhesive surface) and the second surface (second adhesive surface) respectively. Adhesive sheet of film. In addition, the above-mentioned illuminance values are measured values obtained by using an industrial UV detector (manufactured by TOPCON Corporation, trade name "UVR-T1", light-receiving part model UD-T36) with a peak sensitivity wavelength of about 350 nm. (Examples 2 and 3) Instead of the adhesive composition C1, the adhesive compositions C2 and C3 were used, respectively. Except for this, the production of the adhesive sheet S1 of Example 1 was performed in the same manner as that of Examples 2 and 3 Adhesive sheets S2 and S3. The adhesive sheets S2 and S3 constitute the adhesive sheets with the release films of the release films R1 and R3 used in the production of the adhesive sheets, respectively, abutting against the first adhesive surface and the second adhesive surface. (Comparative Example 1) In the production of the adhesive sheet S2 of Example 2, the release film R2 was used instead of the release film R1. That is, the adhesive composition C2 is coated on the peeling surface of the peeling film R2 to form a liquid film of the adhesive composition, and the peeling film is covered on the liquid film such that the peeling surface of the peeling film is in contact with the liquid film. R3. In this way, the both sides of the liquid film of the adhesive composition C2 were irradiated with ultraviolet rays in the state where the peeling surfaces of the release films R2 and R3 were respectively in contact with each other. Except for this, the adhesive sheet of Comparative Example 1 was obtained in the same manner as in Example 2.材S4. The adhesive sheet S4 constitutes an adhesive sheet with a release film of the release film R2 and R3 used in the production of the adhesive sheet S4, respectively, abutting against the first adhesive surface and the second adhesive surface. (Comparative Example 2) The adhesive composition C4 was used instead of the adhesive composition C1, and the adhesive sheet S5 of Comparative Example 2 was obtained in the same manner as the production of the adhesive sheet S1 of Example 1 except that the adhesive composition C4 was used. The adhesive sheet S5 constitutes an adhesive sheet with a release film of the release films R1 and R3 used in the production of the adhesive sheet S5, respectively, abutting against the first adhesive surface and the second adhesive surface. After the adhesive sheet of each example was manufactured in the form of the adhesive sheet with release film, it was stored for 7 days in an environment of 23° C. and 50% RH, and then used for the following measurements and tests. <Measurement of storage elastic modulus> An adhesive layer with a thickness of about 2 mm was produced by stacking multiple adhesive sheets (adhesive layer with a thickness of about 50 μm) of each example. The sample obtained by clamping and fixing the adhesive layer into a disc shape with a diameter of 7.9 mm is clamped and fixed by a parallel plate. The viscoelasticity testing machine (manufactured by TA Instruments, ARES) is used for dynamic adhesion under the following conditions The elasticity measurement was performed to determine the storage elastic modulus (G' 23 ) at 23°C and the storage elastic modulus (G' 100 ) at 100°C.・Measurement mode: Shear mode ・Temperature range: -70℃～150℃ ・Temperature rise rate: 5℃/min ・Measurement frequency: 1 Hz <The ten-point average roughness of the first adhesive surface in the initial configuration> At 23℃ , Under a 50%RH environment, remove the peeling film on the second adhesive surface of the adhesive sheet in each case, and attach the exposed second adhesive surface to the glass slide S1112 No.2 (manufactured by Songlang Glass Industry). Then, the peeling film attached to the first adhesive surface of the adhesive sheet of the glass slide was peeled off by hand along a 180 degree direction at a peeling speed of about 10 m/min, and a surface roughness measuring device using light interference method (Manufactured by Veeco, Wyko NT-9100) The ten-point average roughness of the first adhesive surface thus exposed was measured. The measurement was performed within 10 minutes after the peeling film was removed from the first adhesive surface. The measurement conditions are as follows.・Measurement area/time: 622 μm×467 μm (Objective lens: 10 times, FOV (internal lens): 1.0 times) ・Measurement mode: VSI (Vertical Scan Interferometry) ・Back scan: 5 μm ・Measuring distance: 10 μm ・Threshold: 0.1% ・Scan speed: 1 times (Single scan) Take the highest peak in the measurement surface from the data obtained by measurement, and record the height of the peak top as H1 . Cover the 11×11 pixels around H1, take the highest peak outside the covered range, and record the height of its peak as H2. Repeat this operation to specify H3～H10. In this way, the elevation (H1～H10) from the highest peak to the tenth peak is obtained. In the same way, find the elevation of the bottom of the valley from the lowest valley to the 10th valley in the measurement surface (L1～L10). Based on these values, use the following formula to calculate Rz. In the formula, H j represents the height (elevation) of each peak top, and L j represents the depth (elevation) of each valley bottom. [Number 1]
Figure 02_image003
The measurement was performed 5 times (that is, N=5), and the average value of the values was obtained. <The ten-point average roughness of the first adhesive surface after the peeling film was replaced> (Experimental example 1) In an environment of 23°C and 50% RH, the first adhesive surface of the adhesive sheet S1 of Example 1 is approximately 10 The peeling speed of m/min was used to peel the peeling film R1 by hand in the 180 degree direction. Immediately make a 2 kg roller reciprocate once at a moving speed of about 300 mm/min on the first adhesive surface exposed by this to bond another release film R1. In this way, the peeling film R1 that protects the first adhesive surface of the adhesive sheet of Example 1 was replaced with another peeling film R1 (replacement and attachment). After keeping it in an environment of 23°C and 50%RH for 2 hours, peel off the attached peeling film R1 by hand at a peeling speed of about 10 m/min in the direction of 180 degrees and replace the attached peeling film R1 in the same way as above. The ten-point average roughness of the first adhesive surface was measured. (Test Example 2) In this test example, the peeling film R1 on the first adhesive surface of the adhesive sheet S2 of Example 2 was replaced with a peeling film R2. In other respects, the ten-point average roughness of the first adhesive surface exposed by removing the peeling film R2 to be attached and replaced was measured in the same manner as in Test Example 1. (Test Example 3) In this test example, the peeling film R1 on the first adhesive surface of the adhesive sheet S3 of Example 3 was replaced with a peeling film R2. In other respects, the ten-point average roughness of the first adhesive surface exposed by peeling off and replacing the attached peeling film R2 was measured in the same manner as in Test Example 1. (Test Example 4) In this test example, the peeling film R1 on the first adhesive surface of the adhesive sheet S4 of Comparative Example 1 was replaced with a peeling film R2. In other respects, the ten-point average roughness of the first adhesive surface exposed by peeling off and replacing the attached peeling film R2 was measured in the same manner as in Test Example 1. (Test Example 5) In this test example, the peeling film R2 on the first adhesive surface of the adhesive sheet S4 of Comparative Example 1 was replaced with a peeling film R1. In other respects, the ten-point average roughness of the first adhesive surface exposed by peeling and replacing the attached peeling film R1 was measured in the same manner as in Test Example 1. (Test Example 6) In this test example, the peeling film R2 on the first adhesive surface of the adhesive sheet S5 of Comparative Example 2 was replaced with another peeling film R2. In other respects, the ten-point average roughness of the first adhesive surface exposed by peeling off and replacing the attached peeling film R2 was measured in the same manner as in Test Example 1. The results obtained are shown in Table 1. [Table 1]
Figure 105138382-A0304-0001
 As shown in Table 1, for the adhesive sheet with the ten-point average roughness of the first adhesive surface of 1000 nm or less, it was confirmed that the storage elastic modulus of the adhesive layer constituting the first adhesive surface at 100°C Setting it to 0.08 MPa or more can significantly suppress the decrease in the smoothness of the first adhesive surface due to the replacement of the release film. In addition, for the adhesive sheet S4 with the lower smoothness of the first adhesive surface in the initial configuration, even if the release film on the first adhesive surface was replaced with one with higher smoothness, the first adhesive was not found The smoothness of the surface is improved. The specific examples of the present invention have been described in detail above, but these are only examples and do not limit the scope of patent applications. The technology described in the scope of the patent application includes various changes and modifications to the specific examples illustrated above.

1‧‧‧黏著片材1A‧‧‧第1面(第1黏著面)1B‧‧‧第2面(第2黏著面)2‧‧‧黏著片材2A‧‧‧第1面(第1黏著面)2B‧‧‧第2面(非黏著面)11‧‧‧黏著劑層11A‧‧‧一表面11B‧‧‧另一表面15‧‧‧支持基材15A‧‧‧第1面15B‧‧‧第2面21‧‧‧第1剝離膜21A‧‧‧表面(第1剝離面)21B‧‧‧背面22‧‧‧第2剝離膜22A‧‧‧表面(第2剝離面)100‧‧‧附剝離膜之黏著片材200‧‧‧附剝離膜之黏著片材1‧‧‧Adhesive sheet 1A‧‧‧Side 1 (1st adhesive surface) 1B‧‧‧2nd (2nd adhesive surface) 2‧‧‧Adhesive sheet 2A‧‧‧1st surface (1st Adhesive surface) 2B‧‧‧Second surface (non-adhesive surface) 11‧‧‧Adhesive layer 11A‧‧‧One surface 11B‧‧‧The other surface 15‧‧‧Supporting base 15A‧‧‧The first side 15B ‧‧‧Second surface 21‧‧‧First release film 21A‧‧‧Surface (first release surface) 21B‧‧‧Back surface 22‧‧‧Second release film 22A‧‧‧Surface (second release surface) 100 ‧‧‧Adhesive sheet with release film 200‧‧‧Adhesive sheet with release film

圖1係表示包含一實施形態之黏著片材(無基材之雙面黏著片材)之附剝離膜之黏著片材之示意剖視圖。 圖2係表示包含其他實施形態之黏著片材(附基材之單面黏著片材)之附剝離膜之黏著片材之示意剖視圖。Fig. 1 is a schematic cross-sectional view of an adhesive sheet with a release film including an adhesive sheet (a double-sided adhesive sheet without a substrate) according to an embodiment. 2 is a schematic cross-sectional view showing an adhesive sheet with a release film including an adhesive sheet (single-sided adhesive sheet with a substrate) of another embodiment.

1‧‧‧黏著片材 1‧‧‧Adhesive sheet

1A‧‧‧第1面(第1黏著面) 1A‧‧‧Side 1 (Adhesive Surface 1)

1B‧‧‧第2面(第2黏著面) 1B‧‧‧Second surface (Second adhesive surface)

11‧‧‧黏著劑層 11‧‧‧Adhesive layer

11A‧‧‧一表面 11A‧‧‧One surface

11B‧‧‧另一表面 11B‧‧‧The other surface

21‧‧‧第1剝離膜 21‧‧‧The first peeling film

21A‧‧‧表面(第1剝離面) 21A‧‧‧Surface (the first peeling surface)

21B‧‧‧背面 21B‧‧‧Back

22‧‧‧第2剝離膜 22‧‧‧Second peeling film

22A‧‧‧表面(第2剝離面) 22A‧‧‧Surface (Second peeling surface)

100‧‧‧附剝離膜之黏著片材 100‧‧‧Adhesive sheet with peeling film

Claims (17)

一種黏著片材，其係包含黏著劑層者，且上述黏著片材具有第1面及第2面，上述第1面係由上述黏著劑層之一表面構成之第1黏著面，上述第1黏著面之十點平均粗糙度為30nm以上且1000nm以下，上述黏著劑層之100℃儲存彈性模數為0.08MPa以上且未滿0.50MPa，上述黏著劑層以超過該黏著劑層中所含之聚合物成分之50重量%之比率包含(甲基)丙烯酸系聚合物，上述(甲基)丙烯酸系聚合物進而包含15重量%以上且30重量%以下之具有羥基及羧基中之至少任一者之單體，作為構成該(甲基)丙烯酸系聚合物之單體成分。 An adhesive sheet comprising an adhesive layer, and the adhesive sheet has a first surface and a second surface, the first surface being a first adhesive surface formed by one surface of the adhesive layer, the first The ten-point average roughness of the adhesive surface is 30nm or more and 1000nm or less, the 100℃ storage elastic modulus of the adhesive layer is 0.08MPa or more and less than 0.50MPa, and the adhesive layer is more than that contained in the adhesive layer. The polymer component contains a (meth)acrylic polymer at a ratio of 50% by weight, and the (meth)acrylic polymer further contains 15% by weight or more and 30% by weight or less of at least any one of a hydroxyl group and a carboxyl group The monomers are used as monomer components constituting the (meth)acrylic polymer. 如請求項1之黏著片材，其中上述黏著劑層之100℃儲存彈性模數相對於23℃儲存彈性模數之比為35%以上。 Such as the adhesive sheet of claim 1, wherein the ratio of the 100°C storage elastic modulus of the above-mentioned adhesive layer to the 23°C storage elastic modulus is 35% or more. 如請求項1或2之黏著片材，其中上述黏著劑層之23℃儲存彈性模數未達0.30MPa。 Such as the adhesive sheet of claim 1 or 2, wherein the storage elastic modulus of the adhesive layer at 23°C does not reach 0.30 MPa. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系聚合物包含在酯末端具有碳數2~18之烷基之(甲基)丙烯酸烷基酯作為構成該(甲基)丙烯酸系聚合物之單體成分。 The adhesive sheet of claim 1 or 2, wherein the (meth)acrylic polymer includes an alkyl (meth)acrylate having an alkyl group with 2 to 18 carbon atoms at the end of the ester as constituting the (meth) The monomer component of acrylic polymer. 如請求項4之黏著片材，其中上述在酯末端具有碳數2~18之烷基之(甲基)丙烯酸烷基酯於上述單體成分整體中所占之比率為30重量%以上且70重量%以下。 The adhesive sheet of claim 4, wherein the ratio of the alkyl (meth)acrylate having an alkyl group with a carbon number of 2 to 18 at the end of the ester in the total monomer component is 30% by weight or more and 70 Weight% or less. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系聚合物進而包含脂環式單體作為構成該(甲基)丙烯酸系聚合物之單體成分。 The adhesive sheet of claim 1 or 2, wherein the (meth)acrylic polymer further includes an alicyclic monomer as a monomer component constituting the (meth)acrylic polymer. 如請求項1或2之黏著片材，其中上述脂環式單體於上述單體成分整體中所占之比率為20重量%以上且50重量%以下。 The adhesive sheet of claim 1 or 2, wherein the proportion of the alicyclic monomer in the entire monomer component is 20% by weight or more and 50% by weight or less. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系聚合物進而包含多官能單體作為構成該(甲基)丙烯酸系聚合物之單體成分，上述多官能單體於上述單體成分整體中所占之比率為超過0重量%且3重量%以下。 The adhesive sheet of claim 1 or 2, wherein the (meth)acrylic polymer further includes a multifunctional monomer as a monomer component constituting the (meth)acrylic polymer, and the multifunctional monomer is in the above The ratio of the total monomer component is more than 0% by weight and 3% by weight or less. 如請求項1或2之黏著片材，其中上述(甲基)丙烯酸系聚合物為上述單體成分之紫外線聚合物。 The adhesive sheet of claim 1 or 2, wherein the (meth)acrylic polymer is an ultraviolet polymer of the monomer component. 如請求項1或2之黏著片材，其中上述第2面為第2黏著面。 Such as the adhesive sheet of claim 1 or 2, wherein the second surface is the second adhesive surface. 如請求項10之黏著片材，其中上述第2黏著面之十點平均粗糙度為2000nm以下。 Such as the adhesive sheet of claim 10, wherein the ten-point average roughness of the second adhesive surface is 2000 nm or less. 如請求項11之黏著片材，其中上述第2黏著面之十點平均粗糙度為1000nm以下。 Such as the adhesive sheet of claim 11, wherein the ten-point average roughness of the second adhesive surface is 1000 nm or less. 如請求項10之黏著片材，其中上述第1黏著面之十點平均粗糙度及上述第2黏著面之十點平均粗糙度之任一者為30nm以上且500nm以下。 The adhesive sheet of claim 10, wherein any one of the ten-point average roughness of the first adhesive surface and the ten-point average roughness of the second adhesive surface is 30 nm or more and 500 nm or less. 如請求項10之黏著片材，其中上述第2黏著面由上述黏著劑層之另一表面構成。 The adhesive sheet of claim 10, wherein the second adhesive surface is constituted by the other surface of the adhesive layer. 一種附剝離膜之黏著片材，其包含：如請求項1至14中任一項之黏著片材、及配置於上述第1黏著面上之第1剝離膜。 An adhesive sheet with a release film, comprising: the adhesive sheet according to any one of claims 1 to 14 and a first release film arranged on the first adhesive surface. 如請求項15之附剝離膜之黏著片材，其中上述第2面為第2黏著面，上述附剝離膜之黏著片材進而包含配置於上述第2黏著面上之第2剝離膜。 The adhesive sheet with a release film of claim 15, wherein the second surface is a second adhesive surface, and the adhesive sheet with a release film further includes a second release film disposed on the second adhesive surface. 如請求項15或16之附剝離膜之黏著片材，其中上述第1剝離膜具有與上述第1黏著面接觸之剝離面，上述剝離面之十點平均粗糙度與上述第1黏著面之十點平均粗糙度之差為250nm以內。 The adhesive sheet with a release film of claim 15 or 16, wherein the first release film has a release surface in contact with the first adhesive surface, and the ten-point average roughness of the release surface is equal to ten of the first adhesive surface. The difference in point average roughness is within 250nm.
TW105138382A 2015-11-27 2016-11-23 Adhesive sheet and adhesive sheet with release film TWI719080B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015232149 2015-11-27
JP??2015-232149 2015-11-27
JP2016139538A JP6829960B2 (en) 2015-11-27 2016-07-14 Adhesive sheet and adhesive sheet with release film
JP??2016-139538 2016-07-14

Publications (2)

Publication Number Publication Date
TW201720892A TW201720892A (en) 2017-06-16
TWI719080B true TWI719080B (en) 2021-02-21

Family

ID=59059103

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105138382A TWI719080B (en) 2015-11-27 2016-11-23 Adhesive sheet and adhesive sheet with release film

Country Status (5)

Country Link
JP (1) JP6829960B2 (en)
KR (1) KR102370507B1 (en)
CN (1) CN107033793B (en)
HU (1) HUE056084T2 (en)
TW (1) TWI719080B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7166762B2 (en) * 2018-01-30 2022-11-08 日東電工株式会社 PSA SHEET, MANUFACTURING METHOD THEREOF, AND IMAGE DISPLAY DEVICE
KR102500919B1 (en) * 2018-02-05 2023-02-16 닛토덴코 가부시키가이샤 Adhesive sheet and peeling method for adhesive sheet
KR102751413B1 (en) * 2018-06-15 2025-01-07 린텍 가부시키가이샤 Adhesive sheet for device packaging, and method for manufacturing a device packaging body
JP7077519B2 (en) 2018-11-12 2022-05-31 エルジー・ケム・リミテッド Color conversion film, backlight unit and display device including this
JP7271219B2 (en) * 2019-02-25 2023-05-11 日東電工株式会社 Laminated sheet roll
KR102259294B1 (en) * 2019-09-08 2021-05-31 최문성 Leaflet applied reusable adhesive and method manufacturing the same
JP7624817B2 (en) * 2019-09-30 2025-01-31 日東電工株式会社 Laminated Sheet
WO2021193935A1 (en) * 2020-03-27 2021-09-30 リンテック株式会社 Sheet for production of semiconductor device and method for producing semiconductor chip with film-form adhesive
JP7614728B2 (en) * 2020-03-31 2025-01-16 日東電工株式会社 Adhesive sheet with release film
CN116731615A (en) * 2023-06-08 2023-09-12 宁波鑫智达新材料有限公司 Double-component acrylic adhesive and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1946821A (en) * 2004-02-27 2007-04-11 琳得科株式会社 Adhesive sheet
CN104073177A (en) * 2013-03-28 2014-10-01 琳得科株式会社 Double-sided adhesive sheet and roll thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009124133A (en) * 2007-10-23 2009-06-04 Hitachi Chem Co Ltd Adhesive member, semiconductor element mounting support member, and semiconductor device
JP2010229246A (en) * 2009-03-26 2010-10-14 Daio Paper Corp Pressure-sensitive adhesive sheet
DE102009031421A1 (en) * 2009-07-01 2011-01-05 Tesa Se Use of pressure-sensitive adhesive tapes
JP2013006892A (en) * 2011-06-22 2013-01-10 Nitto Denko Corp Optical double-sided pressure-sensitive adhesive sheet
JP6225025B2 (en) * 2011-08-03 2017-11-01 リンテック株式会社 Gas barrier pressure-sensitive adhesive sheet, method for producing the same, electronic member, and optical member
JP6001316B2 (en) * 2011-11-10 2016-10-05 日東電工株式会社 Adhesive sheet
JP6057600B2 (en) * 2012-08-09 2017-01-11 日東電工株式会社 Adhesive, adhesive layer, and adhesive sheet
JP6013092B2 (en) * 2012-09-06 2016-10-25 日東電工株式会社 Double-sided adhesive sheet
JP6105412B2 (en) * 2013-07-03 2017-03-29 早川ゴム株式会社 Adhesive tape for flat panel display
EP3106498B1 (en) * 2015-06-16 2021-08-11 Nitto Denko Corporation Pressure-sensitive adhesive composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1946821A (en) * 2004-02-27 2007-04-11 琳得科株式会社 Adhesive sheet
CN104073177A (en) * 2013-03-28 2014-10-01 琳得科株式会社 Double-sided adhesive sheet and roll thereof

Also Published As

Publication number Publication date
TW201720892A (en) 2017-06-16
KR102370507B1 (en) 2022-03-04
JP2017105974A (en) 2017-06-15
HUE056084T2 (en) 2022-01-28
CN107033793B (en) 2021-03-12
CN107033793A (en) 2017-08-11
KR20170062390A (en) 2017-06-07
JP6829960B2 (en) 2021-02-17

Similar Documents

Publication Publication Date Title
TWI719080B (en) Adhesive sheet and adhesive sheet with release film
JP6057600B2 (en) Adhesive, adhesive layer, and adhesive sheet
JP6722245B2 (en) Optical pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, optical member, and touch panel
JP6830753B2 (en) Methods for improving bending resistance of laminates, touch panels, laminate formation kits, and transparent conductive films
JP6782071B2 (en) Polarizing film with double-sided adhesive layer, its manufacturing method and image display device
KR102835405B1 (en) Laminated sheet
US20140272201A1 (en) Pressure-sensitive adhesive, pressure sensitive adhesive layer, pressure-sensitive adhesive sheet, and touch panel
CN106256840B (en) adhesive composition
US10836932B2 (en) Pressure-sensitive adhesive sheet and release film-supported pressure-sensitive adhesive sheet
JP6691813B2 (en) Adhesive composition
KR102799072B1 (en) Rolled-body of laminate sheet
JP2025109745A (en) Adhesive sheet and its use
JP2021008606A (en) Adhesive sheet and its use