TW201946994A - Adhesive sheet which is a heat-peelable adhesive tape including a substrate and an adhesive layer - Google Patents
Adhesive sheet which is a heat-peelable adhesive tape including a substrate and an adhesive layer Download PDFInfo
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- TW201946994A TW201946994A TW108115530A TW108115530A TW201946994A TW 201946994 A TW201946994 A TW 201946994A TW 108115530 A TW108115530 A TW 108115530A TW 108115530 A TW108115530 A TW 108115530A TW 201946994 A TW201946994 A TW 201946994A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明係關於一種黏著片。The present invention relates to an adhesive sheet.
作為於製造電子零件之步驟等中以將被加工品暫時固定為目的而使用之黏著帶,已知有於暫時固定時表現黏著性且於無需固定之情況下藉由加熱而表現剝離性之類此種易剝離性之黏著帶(例如,專利文獻1)。此種黏著帶通常具備基材及設置於基材上之黏著劑層。又,於製造上述黏著帶之情形時,將基材與黏著劑層積層而形成積層體後,存在該積層體被供於檢查步驟、黏著劑層加工步驟之情況。此種步驟中大多採用利用搬送輥搬送長條狀之上述積層體之所謂卷對卷(roll to roll)製程。此時,存在因與搬送輥等之接觸而產生摩擦熱,導致黏著劑層之特性發生變質。
[先前技術文獻]
[專利文獻]It is known as an adhesive tape used for the purpose of temporarily fixing a processed product in the steps of manufacturing electronic parts, etc., that exhibits adhesiveness during temporary fixation and peelability by heating without fixing. Such an easily peelable adhesive tape (for example, Patent Document 1). Such an adhesive tape usually includes a substrate and an adhesive layer provided on the substrate. In addition, in the case of manufacturing the above-mentioned adhesive tape, after the base material and the adhesive are laminated to form a laminated body, the laminated body may be used in an inspection step and an adhesive layer processing step. In such a step, a so-called roll-to-roll process in which the above-mentioned laminated body is conveyed by a conveying roller is mostly used. At this time, frictional heat is generated due to contact with the conveying roller or the like, and the characteristics of the adhesive layer are deteriorated.
[Prior technical literature]
[Patent Literature]
[專利文獻1]日本專利特開2001-131507號公報[Patent Document 1] Japanese Patent Laid-Open No. 2001-131507
[發明所欲解決之問題][Problems to be solved by the invention]
本發明係為了解決上述先前之問題而成者,其目的在於提供一種黏著片,其係具備具有基材與黏著劑層之熱剝離型黏著帶者,且黏著劑層不易受到自基材側施加之熱之影響,即便供於卷對卷製程,黏著劑層亦不易變質。
[解決問題之技術手段]The present invention has been made in order to solve the foregoing problems, and an object thereof is to provide an adhesive sheet having a heat-peeling type adhesive tape having a substrate and an adhesive layer, and the adhesive layer is not easily applied from the substrate side. The influence of the heat, even if used in the roll-to-roll process, the adhesive layer is not easy to deteriorate.
[Technical means to solve the problem]
本發明之黏著片依序具備:第1黏著劑層、第1基材、第2黏著劑層及第2基材,該第1黏著劑層及第1基材構成熱剝離型黏著帶,該第2黏著劑層及該第2基材構成積層部分A,該積層部分A以可自該熱剝離型黏著帶剝離之方式配置。
於一實施形態中,上述積層部分A之厚度為10 μm以上。
於一實施形態中,上述第2黏著劑層之凝膠分率為20重量%~100重量%。
於一實施形態中,將上述積層部分A在100℃下加熱30分鐘後對於聚對苯二甲酸乙二酯膜之黏著力A2相對於該積層部分A對於聚對苯二甲酸乙二酯膜之常態黏著力A1為10倍以下。
於一實施形態中,上述積層部分A對於聚對苯二甲酸乙二酯膜之常態黏著力A1為0.05 N/20 mm~5 N/20 mm。
根據本發明之另一態樣,提供一種熱剝離型黏著帶之搬送方法。該搬送方法係具備第1基材與第1黏著劑層之熱剝離型黏著帶之搬送方法,且該搬送方法包括:將積層部分A積層於該第1基材側,將附積層部分A之熱剝離型黏著帶進行搬送。
[發明之效果]The adhesive sheet of the present invention includes a first adhesive layer, a first substrate, a second adhesive layer, and a second substrate in this order. The first adhesive layer and the first substrate constitute a heat-peelable adhesive tape. The second adhesive layer and the second base material constitute a laminated portion A, and the laminated portion A is disposed so as to be peelable from the heat-peelable adhesive tape.
In one embodiment, the thickness of the laminated portion A is 10 μm or more.
In one embodiment, the gel fraction of the second adhesive layer is 20% to 100% by weight.
In one embodiment, the adhesion force A2 of the laminated portion A to the polyethylene terephthalate film after being heated at 100 ° C. for 30 minutes relative to the laminated portion A to the polyethylene terephthalate film. The normal adhesive force A1 is 10 times or less.
In one embodiment, the normal adhesion A1 of the laminated portion A to the polyethylene terephthalate film is 0.05 N / 20 mm to 5 N / 20 mm.
According to another aspect of the present invention, a method for transferring a heat-peelable adhesive tape is provided. The transfer method is a transfer method of a heat-peeling type adhesive tape including a first substrate and a first adhesive layer, and the transfer method includes: laminating a laminated portion A on the first substrate side, and laminating a laminated portion A The heat-peelable adhesive tape is conveyed.
[Effect of the invention]
根據本發明,能夠提供一種黏著片,其係具備具有基材與黏著劑層之熱剝離型黏著帶者,且黏著劑層不易受到自基材側施加之熱之影響,即便供於卷對卷製程,黏著劑層亦不易變質。According to the present invention, it is possible to provide an adhesive sheet having a heat-peeling type adhesive tape having a substrate and an adhesive layer, and the adhesive layer is not easily affected by the heat applied from the substrate side, even if it is provided for roll-to-roll In the manufacturing process, the adhesive layer is not easy to deteriorate.
A. 黏著片之整體構成
圖1係本發明之一實施形態之黏著片之概略剖視圖。黏著片100依序具備:第1黏著劑層11、第1基材12、第2黏著劑層21及第2基材22。第1黏著劑層11及第1基材12構成熱剝離型黏著帶10。第2黏著劑層21及第2基材22構成積層部分A20。積層部分A20以可自熱剝離型黏著帶10剝離之方式配置。雖未圖示,但黏著片亦可進而包含任意適當之其他層。 A. The overall composition of the adhesive sheet
FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention. The adhesive sheet 100 includes a first adhesive layer 11, a first substrate 12, a second adhesive layer 21, and a second substrate 22 in this order. The first adhesive layer 11 and the first base material 12 constitute a heat-peelable adhesive tape 10. The second adhesive layer 21 and the second base material 22 constitute a laminated portion A20. The laminated part A20 is arrange | positioned so that it may peel from the thermal peeling-type adhesive tape 10. Although not shown, the adhesive sheet may further include any appropriate other layers.
於本發明中,藉由在熱剝離型黏著帶10之第1基材12側具備積層部分A20,可保護第1黏著劑層11免受自第1基材12側(實質上為積層部分A20側)施加之熱。更具體而言,於需要將熱剝離型黏著帶10供於卷對卷製程(例如,黏著劑層面之檢查、黏著劑層面之加工等)之情形時,將熱剝離型黏著帶10以附有配置於第1基材12側之積層部分A20之熱剝離型黏著帶10(即,黏著片100)之形式供於該製程,藉此可保護第1黏著劑層11免於因與搬送輥之摩擦等影響導致溫度上升。於經由特定之步驟而完成熱剝離型黏著帶10之情形時,積層部分A20被剝離,熱剝離型黏著帶10例如可作為電子零件製造步驟中之暫時固定用帶而使用。根據本發明,藉由具備以可剝離之方式積層之積層部分A20,可防止熱剝離型黏著帶10之黏著劑層(即,第1黏著劑層)之熱劣化,並且可作為熱剝離型黏著帶10,製成符合實際用途之適當之厚度。熱剝離型黏著帶10在供於使用之前之期間可以附積層部分A20之熱剝離型黏著帶10(即,黏著片100)之形式來保管。In the present invention, by providing a build-up portion A20 on the first base material 12 side of the heat-peelable pressure-sensitive adhesive tape 10, the first adhesive layer 11 can be protected from the first base material 12 side (substantially the build-up portion A20). Side) Heat applied. More specifically, when it is necessary to supply the heat-peelable adhesive tape 10 to a roll-to-roll process (for example, inspection of the adhesive layer, processing of the adhesive layer, etc.), the heat-peelable adhesive tape 10 is attached with The form of the heat-peeling type adhesive tape 10 (that is, the adhesive sheet 100) of the laminated portion A20 disposed on the first substrate 12 side is provided for this process, thereby protecting the first adhesive layer 11 from being caused by contact with the transfer roller. Effects such as friction cause temperature rise. When the heat-peelable adhesive tape 10 is completed through a specific step, the laminated portion A20 is peeled off, and the heat-peelable adhesive tape 10 can be used, for example, as a temporary fixing tape in the manufacturing process of an electronic component. According to the present invention, by providing the build-up portion A20 which is laminated in a peelable manner, it is possible to prevent thermal deterioration of the adhesive layer (that is, the first adhesive layer) of the heat-peelable pressure-sensitive adhesive tape 10 and can be used as a heat-peelable type of adhesive. The band 10 is made to a suitable thickness according to the actual use. The heat-peelable pressure-sensitive adhesive tape 10 may be stored in the form of the heat-peelable pressure-sensitive adhesive tape 10 (that is, the adhesive sheet 100) of the buildup portion A20 before being used.
於一實施形態中,上述黏著片可以長條狀提供。In one embodiment, the adhesive sheet may be provided in a strip shape.
B.熱剝離型黏著帶
熱剝離型黏著帶具有藉由加熱而使黏著力降低或消失之特徵。作為此種熱剝離型黏著帶之形態,並無特別限定,例如可列舉具有包含熱膨脹性微小球之黏著劑層之帶、具有可加熱硬化之黏著劑層之帶等。使用上述熱剝離型黏著帶作為例如電子零件(例如陶瓷電容器)之加工時、加工物之暫時固定用片材之情形時,對該加工物實施特定之加工時,表現暫時固定所需之黏著性,在加工後將熱剝離型黏著帶自加工物剝離時,藉由加熱,使黏著力降低或消失,表現出良好之剝離性。於一實施形態中,熱剝離型黏著帶具備基材(第1基材)、及包含黏著劑A與熱膨脹性微小球之黏著劑層(第1黏著劑層)。以下,作為熱剝離型黏著帶之代表例,對具有包含熱膨脹性微小球之第1黏著劑層之熱剝離型黏著帶進行說明。
B. Thermal peeling type adhesive tape
The heat-peeling type adhesive tape has a characteristic of reducing or disappearing the adhesive force by heating. The form of such a heat-peelable adhesive tape is not particularly limited, and examples thereof include a tape having an adhesive layer containing thermally expandable microspheres, and a tape having a heat-curable adhesive layer. When using the heat-peelable pressure-sensitive adhesive tape, for example, when processing electronic parts (such as ceramic capacitors) or when temporarily fixing a processed product, when performing specific processing on the processed product, the adhesiveness required for temporary fixing is exhibited When the heat-peeling type adhesive tape is peeled from the processed object after processing, the adhesive force is reduced or disappeared by heating to show good peelability. In one embodiment, the heat-peelable pressure-sensitive adhesive tape includes a substrate (first substrate) and an adhesive layer (first adhesive layer) containing an adhesive A and a thermally expandable microsphere. Hereinafter, as a representative example of the heat-peelable pressure-sensitive adhesive tape, a heat-peelable pressure-sensitive adhesive tape having a first adhesive layer containing thermally expandable microspheres will be described.
第1黏著劑層中之熱膨脹性微小球於特定溫度下能夠發泡。對於此種包含熱膨脹性微小球之黏著劑層,藉由加熱,使熱膨脹性微小球發泡,從而在黏著面(即第1黏著劑層表面)產生凹凸,黏著力降低或消失。The thermally expandable microspheres in the first adhesive layer can foam at a specific temperature. For such an adhesive layer containing heat-expandable microspheres, the heat-expandable microspheres are foamed by heating, thereby causing unevenness on the adhesive surface (that is, the surface of the first adhesive layer), and the adhesive force is reduced or disappeared.
上述熱剝離型黏著帶對於聚對苯二甲酸乙二酯膜(例如,厚度25 μm)之黏著力(加熱前)較佳為0.1 N/20 mm以上,更佳為1.0 N/20 mm~50 N/20 mm,進而較佳為2.0 N/20 mm~20 N/20 mm。若為此種範圍,則例如能夠獲得作為電子零件之製造中使用之暫時固定用片材有用之熱剝離型黏著帶。本說明書中黏著力係指藉由在23℃之環境下依據JIS Z 0237:2000之方法(貼合條件:2kg輥往返1次、剝離速度:300 mm/分鐘、剝離角度180°)所測得之黏著力。The adhesive force (before heating) of the heat-peelable adhesive tape to a polyethylene terephthalate film (for example, 25 μm in thickness) is preferably 0.1 N / 20 mm or more, and more preferably 1.0 N / 20 mm to 50 N / 20 mm, more preferably 2.0 N / 20 mm to 20 N / 20 mm. Within this range, for example, a heat-peelable pressure-sensitive adhesive tape useful as a sheet for temporary fixing used in the manufacture of electronic parts can be obtained. Adhesive force in this specification is measured by a method in accordance with JIS Z 0237: 2000 at 23 ° C (adhesion conditions: 2 kg roller reciprocating once, peeling speed: 300 mm / min, peeling angle 180 °) Adhesion.
將上述熱剝離型黏著帶之黏著面貼合於聚對苯二甲酸乙二酯膜並加熱後之黏著力較佳為0.2 N/20 mm以下,更佳為0.1 N/20 mm以下。本說明書中,對熱剝離型黏著帶之加熱係指熱膨脹性微小球膨脹或發泡從而使黏著力降低之溫度、時間下之加熱。該加熱例如為在70℃~270℃下進行1分鐘~10分鐘之加熱。The adhesive force of the heat-peelable adhesive tape on the polyethylene terephthalate film is preferably 0.2 N / 20 mm or less, and more preferably 0.1 N / 20 mm or less. In the present specification, the heating of the heat-peelable adhesive tape refers to heating at a temperature and time where the thermally expandable microspheres expand or foam to reduce the adhesive force. This heating is, for example, heating at 70 ° C to 270 ° C for 1 minute to 10 minutes.
上述熱剝離型黏著帶之厚度較佳為30 μm~500 μm,更佳為40 μm~300 μm。The thickness of the thermal peeling type adhesive tape is preferably 30 μm to 500 μm, and more preferably 40 μm to 300 μm.
B-1. 第1黏著劑層
上述第1黏著劑層之厚度較佳為1 μm~30 μm,更佳為1 μm~20 μm,進而較佳為1 μm~10 μm。若為此種範圍,則可獲得能夠防止被黏著體之位置偏移及向第1黏著劑層沈入之熱剝離型黏著帶。構成黏著片之各層之厚度可使用規尺、游標卡尺、測微計來測定。又,亦可使用電子顯微鏡、光學顯微鏡、原子力顯微鏡等顯微鏡。進而,可根據組成之不同來判別鄰接之層之界面並測定各層之厚度。作為界面之判別方法,例如可列舉拉曼光譜分析、紅外分光分析、X射線光電子光譜分析等分光分析;基質輔助雷射脫附游離飛行時間質譜儀(MALDI-TOFMS)、或飛行時間二次離子質譜儀(TOF-SIMS)等質量分析等方法。B-1. First adhesive layer The thickness of the first adhesive layer is preferably 1 μm to 30 μm, more preferably 1 μm to 20 μm, and even more preferably 1 μm to 10 μm. Within this range, a heat-peelable pressure-sensitive adhesive tape capable of preventing positional displacement of the adherend and sinking into the first adhesive layer can be obtained. The thickness of each layer constituting the adhesive sheet can be measured using a ruler, a vernier caliper, and a micrometer. Microscopes such as an electron microscope, an optical microscope, and an atomic force microscope can also be used. Furthermore, the interface of adjacent layers can be discriminated according to the difference in composition, and the thickness of each layer can be measured. Examples of interface discrimination methods include Raman spectroscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy; matrix-assisted laser desorption free time-of-flight mass spectrometer (MALDI-TOFMS) or time-of-flight secondary ions Mass spectrometer (TOF-SIMS) and other mass analysis methods.
上述第1黏著劑層於25℃下之藉由奈米壓痕法獲得之彈性模數較佳為未達100 MPa,更佳為0.1 MPa~50 MPa,進而較佳為0.1 MPa~10 MPa。若為此種範圍,則可獲得能夠防止被黏著體之位置偏移及向第1黏著劑層沈入之熱剝離型黏著帶。藉由奈米壓痕法獲得之彈性模數係指在負荷時、卸載時連續地對將壓頭壓入至試樣(例如黏著面)時對壓頭之負荷載重及壓入深度進行測定,由獲得之負荷載重-壓入深度曲線所求出之彈性模數。於本說明書中,藉由奈米壓痕法獲得之彈性模數係指將測定條件設為載重:1 mN、負荷、卸載速度:0.1 mN/s、保持時間:1 s並以上述方式測得之彈性模數。再者,於第1黏著劑層包含熱膨脹性微小球之情形時,第1黏著劑層之藉由奈米壓痕法獲得之彈性模數為選擇不存在熱膨脹性微小球之部分並藉由上述測定方法測得之彈性模數。The elastic modulus of the first adhesive layer obtained by the nanoindentation method at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and still more preferably 0.1 MPa to 10 MPa. Within this range, a heat-peelable pressure-sensitive adhesive tape capable of preventing positional displacement of the adherend and sinking into the first adhesive layer can be obtained. The elastic modulus obtained by the nanoindentation method refers to the continuous measurement of the load and indentation depth of the indenter when the indenter is pressed into the sample (such as the adhesive surface) under load and unloading. Elastic modulus obtained from the obtained load-indentation depth curve. In this specification, the elastic modulus obtained by the nanoindentation method means that the measurement conditions are set to load: 1 mN, load, unloading speed: 0.1 mN / s, holding time: 1 s and measured in the manner described above. Modulus of elasticity. When the first adhesive layer includes thermally expandable microspheres, the elastic modulus of the first adhesive layer obtained by the nanoindentation method is to select a portion where no thermally expandable microspheres are present and use the above measurement. The elastic modulus measured by the method.
(黏著劑A)
作為構成上述第1黏著劑層之黏著劑A,只要可獲得本發明之效果,則可使用任意適當之黏著劑。於一實施形態中,作為上述黏著劑A,使用硬化型黏著劑,較佳使用活性能量線硬化型黏著劑。於另一實施形態中,作為上述黏著劑A,使用感壓型黏著劑。作為感壓型黏著劑,例如可列舉丙烯酸系黏著劑、橡膠系黏著劑等。(Adhesive A)
As the adhesive A constituting the first adhesive layer, any appropriate adhesive can be used as long as the effect of the present invention can be obtained. In one embodiment, as the adhesive A, a hardening type adhesive is used, and an active energy ray hardening type adhesive is preferably used. In another embodiment, a pressure-sensitive adhesive is used as the adhesive A. Examples of the pressure-sensitive adhesive include acrylic adhesives and rubber-based adhesives.
(活性能量線硬化型黏著劑)
作為構成上述活性能量線硬化型黏著劑之樹脂材料,例如可列舉紫外線硬化系統(加藤清視著,綜合技術中心出版,(1989))、光硬化技術(技術情報協會編(2000))、日本專利特開2003-292916號公報、日本專利4151850號等中記載之樹脂材料。更具體而言,可列舉包含作為母劑之聚合物及活性能量線反應性化合物(單體或低聚物)之樹脂材料(R1)、包含活性能量線反應性聚合物之樹脂材料(R2)等。(Active energy ray hardening adhesive)
Examples of the resin material constituting the active energy ray-curable adhesive include an ultraviolet curing system (Kato Kiyoshi, published by the Comprehensive Technology Center, (1989)), a photocuring technique (Technical Information Association (2000)), Japan Resin materials described in Patent Publication No. 2003-292916, Japanese Patent No. 4151850, and the like. More specifically, a resin material (R1) containing a polymer as a base agent and an active energy ray reactive compound (monomer or oligomer), and a resin material (R2) containing an active energy ray reactive polymer may be mentioned. Wait.
作為上述作為母劑之聚合物,例如可列舉:天然橡膠、聚異丁烯橡膠、苯乙烯・丁二烯橡膠、苯乙烯・異戊二烯・苯乙烯嵌段共聚物橡膠、再生橡膠、丁基橡膠、聚異丁烯橡膠、腈橡膠(NBR)等橡膠系聚合物;矽酮系聚合物;丙烯酸系聚合物等。該等聚合物可單獨使用或組合使用2種以上。Examples of the polymer used as the base agent include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, and butyl rubber. , Polyisobutylene rubber, nitrile rubber (NBR) and other rubber-based polymers; silicone polymers; acrylic polymers. These polymers can be used alone or in combination of two or more.
作為上述活性能量線反應性化合物,例如可列舉具有複數個丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之官能基之光反應性單體或低聚物。其中,較佳為使用具有乙烯性不飽和官能基之化合物,更佳為使用具有乙烯性不飽和官能基之(甲基)丙烯酸系化合物。具有乙烯性不飽和官能基之化合物由於利用紫外線容易生成自由基,因此,若使用該化合物,則可形成能以短時間硬化之第1黏著劑層。又,若使用具有乙烯性不飽和官能基之(甲基)丙烯酸系化合物,則可形成於硬化後具有適度硬度(具體而言為熱膨脹性微小球可良好地發泡之硬度)之黏著劑層。作為光反應性單體或低聚物之具體例,可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(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、聚乙二醇二(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯系化合物等含(甲基)丙烯醯基之化合物;該含(甲基)丙烯醯基化合物之二~五聚物等。該等化合物可單獨使用或組合使用2種以上。Examples of the active energy ray-reactive compound include a photoreactive monomer having a plurality of functional groups having a carbon-carbon multiple bond, such as acrylfluorenyl, methacrylfluorenyl, vinyl, allyl, and ethynyl. Or oligomers. Among them, a compound having an ethylenically unsaturated functional group is preferably used, and a (meth) acrylic compound having an ethylenically unsaturated functional group is more preferably used. Since a compound having an ethylenically unsaturated functional group easily generates radicals by using ultraviolet rays, if the compound is used, a first adhesive layer that can harden in a short time can be formed. In addition, if a (meth) acrylic compound having an ethylenically unsaturated functional group is used, an adhesive layer having a moderate hardness (specifically, a hardness in which the thermally expandable microspheres can foam well) can be formed after curing. . Specific examples of the photoreactive monomer or oligomer include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and pentaerythritol tri (meth) acrylic acid. Ester, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, (meth) acrylate urethane-based compounds and other compounds containing (meth) acrylfluorenyl groups; the Contains (meth) acrylic fluorenyl-based compounds pentamers, etc. These compounds can be used alone or in combination of two or more.
又,作為上述活性能量線反應性化合物,亦可使用環氧化丁二烯、甲基丙烯酸縮水甘油酯、丙烯醯胺、乙烯基矽氧烷等單體;或由該單體構成之低聚物。包含該等化合物之樹脂材料(R1)可利用紫外線、電子束等高能量線而硬化。In addition, as the active energy ray reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinylsiloxane; or oligomers composed of the monomers can also be used. . The resin material (R1) containing these compounds can be hardened by high energy rays such as ultraviolet rays and electron beams.
進而,作為上述活性能量線反應性化合物,可使用鎓鹽等有機鹽類與分子內具有複數個雜環之化合物之混合物。關於該混合物,藉由活性能量線(例如,紫外線、電子束)之照射,有機鹽裂解而生成離子,其成為起始種而引起雜環之開環反應,可形成三維網狀結構。作為上述有機鹽類,例如可列舉碘鎓鹽、鏻鹽、銻鹽、鋶鹽、硼酸鹽等。作為上述分子內具有複數個雜環之化合物中之雜環,可列舉環氧乙烷、氧雜環丁烷、氧雜環戊烷(oxolane)、環硫乙烷、氮丙啶等。Further, as the active energy ray-reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule can be used. Regarding this mixture, by irradiation of active energy rays (for example, ultraviolet rays, electron beams), organic salts are cleaved to generate ions, which become the starting species and cause ring-opening reactions of heterocycles to form a three-dimensional network structure. Examples of the organic salts include iodonium salts, sulfonium salts, antimony salts, sulfonium salts, and borate salts. Examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, oxetane, oxolane, ethanesulfide, and aziridine.
上述包含作為母劑之聚合物與活性能量線反應性化合物之樹脂材料(R1)中,活性能量線反應性化合物之含有比率相對於作為母劑之聚合物100重量份,較佳為0.1重量份~500重量份,更佳為1重量份~300重量份,進而較佳為10重量份~200重量份。In the above-mentioned resin material (R1) containing the polymer as the mother agent and the active energy ray reactive compound, the content ratio of the active energy ray reactive compound is preferably 0.1 part by weight relative to 100 parts by weight of the polymer as the mother agent. ~ 500 parts by weight, more preferably 1 to 300 parts by weight, and still more preferably 10 to 200 parts by weight.
作為上述活性能量線反應性聚合物,例如可列舉具有丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之活性能量線反應性官能基之聚合物。較佳為使用具有乙烯性不飽和官能基之化合物(聚合物),更佳為使用具有丙烯醯基或甲基丙烯醯基之(甲基)丙烯酸系聚合物。作為具有活性能量線反應性官能基之聚合物之具體例,可列舉由多官能(甲基)丙烯酸酯構成之聚合物等。Examples of the active energy ray-reactive polymer include polymerization of an active energy ray-reactive functional group having a carbon-carbon multiple bond, such as an acryl group, a methacryl group, a vinyl group, an allyl group, or an ethynyl group. Thing. It is preferable to use a compound (polymer) having an ethylenically unsaturated functional group, and it is more preferable to use a (meth) acrylic polymer having an acrylfluorene group or a methacrylfluorene group. Specific examples of the polymer having an active energy ray-reactive functional group include a polymer composed of a polyfunctional (meth) acrylate and the like.
包含上述活性能量線反應性聚合物之樹脂材料(R2)亦可進而含有上述活性能量線反應性化合物(單體或低聚物)。The resin material (R2) containing the active energy ray reactive polymer may further contain the active energy ray reactive compound (monomer or oligomer).
上述活性能量線硬化型黏著劑可藉由活性能量線之照射而硬化。上述熱剝離型黏著帶中,在使黏著劑A硬化前貼合被黏著體後,照射活性能量線而使黏著劑A硬化,藉此能夠密接該被黏著體。作為活性能量線,例如可列舉:γ射線、紫外線、可見光線、紅外線(熱射線)、射頻波、α射線、β射線、電子束、電漿流、電離射線、粒子射線等。活性能量線之波長、照射量等條件可根據使用之樹脂材料之種類等來設定為任意適當之條件。例如,可照射照射量10~1000 mJ/cm2 之紫外線,使黏著劑A硬化。The above-mentioned active energy ray-curable adhesive can be hardened by irradiation with active energy rays. In the heat-peelable pressure-sensitive adhesive tape, after the adherend is adhered before the adhesive A is cured, the active energy ray is irradiated to harden the adhesive A, whereby the adherend can be closely adhered. Examples of active energy rays include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio frequency waves, alpha rays, beta rays, electron beams, plasma flow, ionizing rays, and particle rays. The conditions such as the wavelength and irradiation amount of the active energy ray can be set to any appropriate conditions depending on the type of the resin material used and the like. For example, it is possible to irradiate ultraviolet rays with an irradiation amount of 10 to 1000 mJ / cm 2 to harden the adhesive A.
(丙烯酸系黏著劑)
作為上述丙烯酸系黏著劑,例如可列舉:將使用1種或2種以上之(甲基)丙烯酸烷基酯作為單體成分之丙烯酸系聚合物(均聚物或共聚物)作為基礎聚合物之丙烯酸系黏著劑等。作為(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)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(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、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯。其中,可較佳地使用具有碳數4~18之直鏈狀或支鏈狀烷基之(甲基)丙烯酸烷基酯。(Acrylic Adhesive)
Examples of the acrylic adhesive include acrylic polymer (homopolymer or copolymer) using one or two or more alkyl (meth) acrylates as monomer components as a base polymer. Acrylic adhesives, etc. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( Butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, hex (meth) acrylate Ester, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) ) Isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Tridecyl ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, C1-20 alkyl (meth) acrylates, such as octadecyl (meth) acrylate, undecyl (meth) acrylate, and eicosyl (meth) acrylate. Among them, an alkyl (meth) acrylate having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used.
為了實現凝集力、耐熱性、交聯性等之改質,上述丙烯酸系聚合物根據需要可包含和能夠與上述(甲基)丙烯酸烷基酯共聚合之其他單體成分相對應之單元。作為此種單體成分,例如可列舉:丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、巴豆酸等含羧基單體;馬來酸酐、伊康酸酐等酸酐單體;(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌、乙烯基吡、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基嗎啉、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯基系單體;丙烯腈、甲基丙烯腈等氰基丙烯酸酯單體;(甲基)丙烯酸縮水甘油酯等含環氧基丙烯酸系單體;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、矽酮(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體;己二醇二(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、三羥甲基丙烷三(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、環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯等多官能單體;異戊二烯、丁二烯、異丁烯等烯烴系單體;乙烯基醚等乙烯基醚系單體等。該等單體成分可單獨使用或組合使用2種以上。In order to improve the cohesive force, heat resistance, and crosslinkability, the acrylic polymer may include a unit corresponding to other monomer components that can be copolymerized with the alkyl (meth) acrylate, as necessary. Examples of such monomer components include carboxyl-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, iconic acid, maleic acid, fumaric acid, and crotonic acid; Anhydride monomers, such as Iconic anhydride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, (meth) acrylic acid Hydroxyl octyl ester, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate and other hydroxyl-containing monomers; styrene sulfonic acid, allyl Sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acrylamidonaphthalene Sulfonic group-containing monomers such as sulfonic acid; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxymethyl (N-substituted) fluorenamide-based monomers such as (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N (meth) acrylic acid, N-dimethylaminoethyl, (methyl) (Meth) acrylic acid amine alkyl ester monomers such as tert-butylamino ethyl methacrylate; methethyl (meth) acrylate, ethoxy ethyl (meth) acrylate, etc. ) Alkoxyalkyl acrylate monomers; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide Maleimide monomers such as imine; N-methyl Ikonimide, N-ethyl Ikonimide, N-butyl Ikonimide, N-octyl Ikonimide Amine, N-2-ethylhexyl Ikonimide, N-cyclohexyl Ikonimide, N-Lauryl Ikonimide, and other Ikonimide monomers; N- (methyl) Acrylic acid oxymethylene succinimide, N- (meth) acryl fluorenyl-6-oxohexamethylene succinimide, N- (meth) acryl fluorenyl-8-oxyoctamethylene Succinimide-based monomers such as succinimide; vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, ethylene Is pyrimidine, vinyl piperazine, vinylpyridine, vinylpyrrole, vinylimidazole, vinyloxazole, vinyl? , Vinyl monomers such as N-vinylcarboxamides, styrene, α-methylstyrene, N-vinyl caprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxyethylene glycol (meth) acrylate Diol-based acrylate monomers such as methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate, etc. Acrylic monomers such as rings, halogen atoms, and silicon atoms; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylic acid Ester, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (methyl) Base) polyfunctional monomers such as acrylate, epoxy acrylate, polyester acrylate, acrylic urethane; isoprene, butadiene , Isobutylene and other olefinic monomers; vinyl ether vinyl ether-based monomers. These monomer components can be used individually or in combination of 2 or more types.
(橡膠系黏著劑)
作為上述橡膠系黏著劑,例如可列舉將天然橡膠;聚異戊二烯橡膠、苯乙烯・丁二烯(SB)橡膠、苯乙烯・異戊二烯(SI)橡膠、苯乙烯・異戊二烯・苯乙烯嵌段共聚物(SIS)橡膠、苯乙烯・丁二烯・苯乙烯嵌段共聚物(SBS)橡膠、苯乙烯・乙烯・丁烯・苯乙烯嵌段共聚物(SEBS)橡膠、苯乙烯・乙烯・丙烯・苯乙烯嵌段共聚物(SEPS)橡膠、苯乙烯・乙烯・丙烯嵌段共聚物(SEP)橡膠、再生橡膠、丁基橡膠、聚異丁烯、該等之改性體等合成橡膠等作為基礎聚合物之橡膠系黏著劑。(Rubber-based adhesive)
Examples of the rubber-based adhesive include natural rubber; polyisoprene rubber, styrene-butadiene (SB) rubber, styrene-isoprene (SI) rubber, and styrene-isoprene Styrene · styrene block copolymer (SIS) rubber, styrene · butadiene · styrene block copolymer (SBS) rubber, styrene · ethylene · butene · styrene block copolymer (SEBS) rubber, Styrene, ethylene, propylene, and styrene block copolymer (SEPS) rubber, styrene, ethylene, and propylene block copolymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, and modified materials thereof Rubber-based adhesives such as synthetic rubber as the base polymer.
(添加劑)
上述黏著劑A根據需要可包含任意適當之添加劑。作為該添加劑,例如可列舉:起始劑、交聯劑、黏著賦予劑、塑化劑、顏料、染料、填充劑、防老化劑、導電材、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。(additive)
The said adhesive agent A can contain arbitrary appropriate additives as needed. Examples of the additives include initiators, crosslinking agents, adhesion-imparting agents, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, Peeling modifiers, softeners, surfactants, flame retardants, antioxidants, etc.
(熱膨脹性微小球)
於一實施形態中,上述第1黏著劑層包含熱膨脹性微小球。包含熱膨脹性微小球之第1黏著劑層藉由加熱而使熱膨脹性微小球膨脹或發泡,結果在黏著面產生凹凸,使黏著力降低或消失。若使用具備此種第1黏著劑層之熱剝離型黏著帶作為暫時固定材料,則能夠容易地剝離暫時固定後之被黏著體。(Thermally expandable microspheres)
In one embodiment, the first adhesive layer includes thermally expandable microspheres. The first adhesive layer containing the heat-expandable microspheres expands or foams by heating to expand the heat-expandable microspheres. As a result, unevenness is generated on the adhesive surface, and the adhesive force is reduced or disappeared. When a heat-peeling type adhesive tape having such a first adhesive layer is used as a temporary fixing material, the adherend after the temporary fixing can be easily peeled off.
作為上述熱膨脹性微小球,只要為藉由加熱可膨脹或發泡之微小球,則可使用任意適當之熱膨脹性微小球。作為上述熱膨脹性微小球,例如可使用使藉由加熱容易膨脹之物質內包於具有彈性之殼內而得之微小球。此種熱膨脹性微小球可藉由任意適當之方法、例如凝聚法、界面聚合法等來製造。As the thermally expandable microspheres, any appropriate thermally expandable microspheres can be used as long as they are expandable or foamable microspheres by heating. As the thermally expandable microspheres, for example, microspheres obtained by encapsulating a substance that is easily expanded by heating in a shell having elasticity can be used. Such thermally expandable microspheres can be produced by any appropriate method, such as a coacervation method and an interfacial polymerization method.
作為藉由加熱而容易膨脹之物質,例如可列舉:丙烷、丙烯、丁烯、正丁烷、異丁烷、異戊烷、新戊烷、正戊烷、正己烷、異己烷、庚烷、辛烷、石油醚、甲烷之鹵化物、四烷基矽烷等低沸點液體;藉由熱分解而氣化之偶氮二甲醯胺等。Examples of substances that can be easily expanded by heating include propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, heptane, Low boiling point liquids such as octane, petroleum ether, halides of methane, and tetraalkylsilane; azodimethoxamine gasified by thermal decomposition.
作為構成上述殼之物質,例如可列舉:由丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈、富馬腈等腈單體;丙烯酸、甲基丙烯酸、伊康酸、馬來酸、富馬酸、檸康酸等羧酸單體;偏二氯乙烯;乙酸乙烯酯;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、丙烯酸β-羧基乙酯等(甲基)丙烯酸酯;苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯單體;丙烯醯胺、取代丙烯醯胺、甲基丙烯醯胺、取代甲基丙烯醯胺等醯胺單體等構成之聚合物。由該等單體構成之聚合物可為均聚物,亦可為共聚物。作為該共聚物,例如可列舉偏二氯乙烯-甲基丙烯酸甲酯-丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈-甲基丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丙烯腈-甲基丙烯腈-伊康酸共聚物等。Examples of the material constituting the shell include: nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, and Ikon Acid, maleic acid, fumaric acid, citraconic acid and other carboxylic acid monomers; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, beta β -(Meth) acrylates such as carboxyethyl esters; styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; acrylamide, substituted acrylamide, methacrylamide, substituted methacryl A polymer composed of an ammonium monomer such as amidine. The polymer composed of these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and methyl methacrylate-acrylonitrile copolymer. , Acrylonitrile-methacrylonitrile-itaconic acid copolymer, etc.
作為上述熱膨脹性微小球,亦可使用無機系發泡劑或有機系發泡劑。作為無機系發泡劑,例如可列舉:碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、硼氫化鈉、各種疊氮化物類等。又,作為有機系發泡劑,例如可列舉:三氯單氟甲烷、二氯單氟甲烷等氯氟化烷烴系化合物;偶氮雙異丁腈、偶氮二甲醯胺、偶氮二羧酸鋇等偶氮系化合物;對甲苯磺醯肼、二苯基碸-3,3'-二磺醯肼、4,4'-氧雙(苯磺醯肼)、烯丙基雙(磺醯肼)等肼系化合物;對甲苯基磺醯胺基脲、4,4'-氧雙(苯磺醯胺基脲)等胺基脲系化合物;5-嗎啉基-1,2,3,4-噻三唑等三唑系化合物;N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺等N-亞硝基系化合物等。As the thermally expandable microspheres, an inorganic foaming agent or an organic foaming agent may be used. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and various azides. Examples of the organic blowing agent include chlorofluorinated alkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethylformamide, and azodicarboxylate. Azo compounds such as barium acid; p-toluenesulfonylhydrazine, diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis (benzenesulfonylhydrazine), allylbis (sulfonium Hydrazine) and other hydrazine-based compounds; p-tolylsulfonamidourea, 4,4'-oxobis (benzenesulfonamidourea) and other aminourea-based compounds; 5-morpholinyl-1,2,3, Triazole compounds such as 4-thiatriazole; N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroso-p-xylylenediamine N-nitroso compounds such as amines.
上述熱膨脹性微小球亦可使用市售品。作為市售品之熱膨脹性微小球之具體例,可列舉:松本油脂製藥股份有限公司製造之商品名「Matsumoto Microsphere」(等級:F-30、F-30D、F-36D、F-36LV、F-50、F-50D、F-65、F-65D、FN-100SS、FN-100SSD、FN-180SS、FN-180SSD、F-190D、F-260D、F-2800D)、Japan Fillite公司製造之商品名「Expancel」(等級:053-40、031-40、920-40、909-80、930-120)、吳羽化學工業股份有限公司製造之「DAIFOAM」(等級:H750、H850、H1100、S2320D、S2640D、M330、M430、M520)、積水化學工業股份有限公司製造之「ADVANCELL」(等級:EML101、EMH204、EHM301、EHM302、EHM303、EM304、EHM401、EM403、EM501)等。As the thermally expandable microsphere, a commercially available product may be used. Specific examples of commercially available thermally expandable microspheres include the product name "Matsumoto Microsphere" (grades: F-30, F-30D, F-36D, F-36LV, F -50, F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), products made by Japan Fillite Name "Expancel" (Class: 053-40, 031-40, 920-40, 909-80, 930-120), "DAIFOAM" (Class: H750, H850, H1100, S2320D) manufactured by Wu Yu Chemical Industry Co., Ltd. , S2640D, M330, M430, M520), "ADVANCELL" (Grade: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501) manufactured by Sekisui Chemical Industry Co., Ltd.
上述熱膨脹性微小球之加熱前之粒徑較佳為0.5 μm~80 μm,更佳為5 μm~45 μm,進而較佳為10 μm~20 μm,尤佳為10 μm~15 μm。因此,用平均粒徑來說明上述熱膨脹性微小球之加熱前之粒子尺寸時,較佳為6 μm~45 μm,更佳為15 μm~35 μm。上述粒徑及平均粒徑係藉由雷射散射法中之粒度分佈測定法所求出之值。The particle diameter of the thermally expandable microspheres before heating is preferably 0.5 μm to 80 μm, more preferably 5 μm to 45 μm, still more preferably 10 μm to 20 μm, and even more preferably 10 μm to 15 μm. Therefore, when the average particle diameter is used to describe the particle size of the thermally expandable microspheres before heating, it is preferably 6 μm to 45 μm, and more preferably 15 μm to 35 μm. The particle diameter and the average particle diameter are values obtained by a particle size distribution measurement method in a laser scattering method.
上述熱膨脹性微小球較佳為具有在體積膨脹率較佳為成為5倍以上、更佳為成為7倍以上、進而較佳為成為10倍以上之前不會破裂之適度之強度。於使用此種熱膨脹性微小球之情形時,藉由加熱處理,能夠效率良好地降低黏著力。The thermally expandable microspheres preferably have a moderate strength that does not break until the volume expansion rate is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more. When such a thermally expandable microsphere is used, it is possible to efficiently reduce the adhesive force by heat treatment.
上述第1黏著劑層中之熱膨脹性微小球之含有比率可根據所需之黏著力之降低性等來適當地設定。熱膨脹性微小球之含有比率相對於形成第1黏著劑層之基礎聚合物100重量份,例如為1重量份~150重量份,較佳為10重量份~130重量份,進而較佳為25重量份~100重量份。The content ratio of the heat-expandable microspheres in the first adhesive layer can be appropriately set depending on the required reduction of the adhesive force and the like. The content ratio of the heat-expandable microspheres is 100 parts by weight with respect to 100 parts by weight of the base polymer forming the first adhesive layer, for example, 1 to 150 parts by weight, preferably 10 to 130 parts by weight, and more preferably 25 parts by weight Parts ~ 100 parts by weight.
B-2. 第1基材
作為上述第1基材,例如可列舉:樹脂片、不織布、紙、金屬箔、織布、橡膠片、發泡片、該等之積層體(特別是包含樹脂片之積層體)等。作為構成樹脂片之樹脂,例如可列舉:聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳族聚醯胺)、聚醯亞胺(PI)、聚氯乙烯(PVC)、聚苯硫醚(PPS)、氟系樹脂、聚醚醚酮(PEEK)等。作為不織布,可列舉包含馬尼拉麻之不織布等由具有耐熱性之天然纖維獲得之不織布;聚丙烯樹脂不織布、聚乙烯樹脂不織布、酯系樹脂不織布等合成樹脂不織布等。B-2. First substrate As the first substrate, for example, resin sheet, non-woven fabric, paper, metal foil, woven fabric, rubber sheet, foamed sheet, laminates of these (especially including resin sheet) Laminated body) and so on. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene (PE). ), Polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamide (aromatic polyamide), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine-based resin, polyetheretherketone (PEEK), and the like. Examples of the nonwoven fabric include nonwoven fabrics obtained from natural fibers having heat resistance such as nonwoven fabric including Manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabric, polyethylene resin nonwoven fabric, and ester resin nonwoven fabric.
關於上述第1基材之厚度,可根據所需之強度或柔軟性、以及使用目的等,設定為任意適當之厚度。基材之厚度較佳為1000 μm以下,更佳為1 μm~1000 μm,進而較佳為1 μm~500 μm、尤佳為3 μm~300 μm,最佳為5 μm~250 μm。The thickness of the first substrate can be set to any appropriate thickness according to the required strength or flexibility, the purpose of use, and the like. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, even more preferably 3 μm to 300 μm, and most preferably 5 μm to 250 μm.
上述第1基材亦可實施表面處理。作為表面處理,例如可列舉:電暈處理、鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離輻射線處理、利用底塗劑之塗佈處理等。若進行此種表面處理,則可提高第1黏著劑層與基材之密接性。特別是利用有機塗佈材料之塗佈處理就提高密接性、並且在剝離時第1黏著劑層不易發生固著破壞之方面而言較佳。表面處理層可形成於第1黏著劑層側之面。The first substrate may be surface-treated. Examples of the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment using a primer. Such surface treatment can improve the adhesion between the first adhesive layer and the substrate. In particular, a coating treatment using an organic coating material is preferable in terms of improving the adhesion and preventing the first adhesive layer from being easily damaged when peeling. The surface treatment layer may be formed on a surface on the side of the first adhesive layer.
作為上述有機塗佈材料,例如可列舉:塑膠硬塗材料II(CMC出版、(2004))中記載之材料。較佳使用胺基甲酸酯系聚合物,更佳為使用聚丙烯酸胺基甲酸酯、聚酯胺基甲酸酯或該等之前驅物。其原因在於:對基材之塗敷・塗佈簡便,並且工業上能夠選擇多種物質,且可廉價地獲得。該胺基甲酸酯系聚合物例如為包含異氰酸酯單體與含醇羥基之單體(例如,含羥基之丙烯酸系化合物或含羥基之酯化合物)之反應混合物的聚合物。有機塗佈材料亦可包含聚胺等鏈延長劑、防老化劑、氧化穩定劑等作為任意之添加劑。有機塗敷層之厚度並無特別限定,例如適宜為0.1 μm~10 μm左右,較佳為0.1 μm~5 μm左右,更佳為0.5 μm~5 μm左右。有機塗敷層例如可對上述有機塗佈材料使用任意適當之印刷法等來形成。Examples of the organic coating material include materials described in Plastic Hard Coating Material II (CMC Publication, (2004)). It is preferable to use a urethane-based polymer, and it is more preferable to use a polyacrylate urethane, a polyester urethane, or a precursor thereof. The reason is that the application and application of the base material are simple, industrially, a variety of substances can be selected, and they can be obtained at low cost. The urethane-based polymer is, for example, a polymer containing a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl-containing acrylic compound or a hydroxyl-containing ester compound). The organic coating material may contain a chain extender such as a polyamine, an aging inhibitor, an oxidation stabilizer, and the like as optional additives. The thickness of the organic coating layer is not particularly limited. For example, it is preferably about 0.1 μm to 10 μm, preferably about 0.1 μm to 5 μm, and more preferably about 0.5 μm to 5 μm. The organic coating layer can be formed using, for example, any appropriate printing method on the organic coating material.
B-3. 中間層
熱剝離型黏著帶亦可於上述第1黏著劑層與第1基材之間進而具備中間層。作為構成上述中間層之材料,例如可列舉矽酮系聚合物、環氧系聚合物、聚碳酸酯系聚合物、乙烯基系聚合物、丙烯酸系聚合物、胺基甲酸酯系聚合物、聚酯系聚合物、聚烯烴系聚合物、聚醯胺系聚合物、聚醯亞胺系聚合物、不飽和烴系聚合物等聚合物材料。若使用該等聚合物材料,則適宜選擇單體種類、交聯劑、聚合度等,從而能夠容易地形成具有上述彈性模數之中間層。上述聚合物材料可單獨使用或組合使用2種以上。B-3. The intermediate layer heat-peelable pressure-sensitive adhesive tape may further include an intermediate layer between the first adhesive layer and the first substrate. Examples of the material constituting the intermediate layer include silicone polymers, epoxy polymers, polycarbonate polymers, vinyl polymers, acrylic polymers, urethane polymers, and the like. Polymer materials such as polyester-based polymers, polyolefin-based polymers, polyamide-based polymers, polyimide-based polymers, and unsaturated hydrocarbon-based polymers. If such a polymer material is used, the type of monomer, the cross-linking agent, the degree of polymerization, and the like are appropriately selected so that an intermediate layer having the above-mentioned elastic modulus can be easily formed. These polymer materials may be used alone or in combination of two or more.
於一實施形態中,作為構成上述中間層之材料,使用藉由活性能量線之照射而可硬化之樹脂材料。若使用藉由活性能量線之照射而可硬化之樹脂材料,則於適當之時機照射活性能量線,從而能夠使中間層之彈性模數提高,並且彈性模數之調整亦變容易。若利用此種材料形成中間層,則於黏著片之貼附時,彈性較低且柔軟性較高,處理性優異,在貼附後,藉由照射活性能量線,能夠獲得可調整為上述範圍之彈性模數之黏著片。In one embodiment, as the material constituting the intermediate layer, a resin material that can be hardened by irradiation with active energy rays is used. If a resin material that can be hardened by irradiation with active energy rays is used, the active energy rays are irradiated at an appropriate timing, so that the elastic modulus of the intermediate layer can be improved, and the adjustment of the elastic modulus becomes easy. If an intermediate layer is formed using such a material, the elasticity is low, the flexibility is high, and the handleability is excellent when the adhesive sheet is attached. After the attachment, the active energy ray can be irradiated to obtain the adjustable range. The elastic modulus of the adhesive sheet.
作為藉由活性能量線之照射而可硬化之樹脂材料,例如可列舉:上述B-1項中說明之包含作為母劑之聚合物與活性能量線反應性化合物(單體或低聚物)之樹脂材料(R1)、包含活性能量線反應性聚合物之樹脂材料(R2)等。於一實施形態中,對於作為中間層之材料所使用之樹脂材料(R1)中之活性能量線反應性化合物,可使用具有乙烯性不飽和官能基之化合物。又,於一實施形態中,作為樹脂材料(R2)中之活性能量線反應性聚合物,可使用具有乙烯性不飽和官能基之化合物(聚合物)。Examples of the resin material that can be hardened by irradiation with active energy rays include, for example, those described in the above item B-1, which include a polymer as a base agent and an active energy ray-reactive compound (monomer or oligomer). Resin material (R1), resin material (R2) containing an active energy ray reactive polymer, and the like. In one embodiment, as the active energy ray reactive compound in the resin material (R1) used as the material of the intermediate layer, a compound having an ethylenically unsaturated functional group can be used. Moreover, in one embodiment, as the active energy ray reactive polymer in the resin material (R2), a compound (polymer) having an ethylenically unsaturated functional group can be used.
又,作為構成上述中間層之材料,可使用由乙烯-乙酸乙烯酯共聚物、聚丙烯系樹脂、聚醯胺系樹脂等熱塑性樹脂構成之熱熔系樹脂。As the material constituting the intermediate layer, a hot-melt resin made of a thermoplastic resin such as an ethylene-vinyl acetate copolymer, a polypropylene-based resin, or a polyamide-based resin can be used.
上述中間層可根據需要進而包含任意適當之添加劑。作為該添加劑,例如可列舉:起始劑、交聯劑、黏著賦予劑、塑化劑、顏料、染料、填充劑、防老化劑、導電材、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。The intermediate layer may further include any appropriate additive as necessary. Examples of the additives include initiators, crosslinking agents, adhesion-imparting agents, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, Peeling modifiers, softeners, surfactants, flame retardants, antioxidants, etc.
中間層之厚度較佳為1 μm~200 μm,更佳為5 μm~50 μm,進而較佳為10 μm~40 μm。The thickness of the intermediate layer is preferably 1 μm to 200 μm, more preferably 5 μm to 50 μm, and still more preferably 10 μm to 40 μm.
C. 積層部分 A
如上所述,積層部分A具備第2黏著劑層及第2基材。黏著劑層通常導熱性低於基材。本發明中,利用包含此種黏著劑層(第2黏著劑層)之積層部分A來保護熱剝離型黏著帶,因此可防止第1黏著劑層(熱剝離型黏著帶所具有之黏著劑層)之熱劣化。
C. Layer A
As described above, the laminated portion A includes the second adhesive layer and the second substrate. The adhesive layer is generally less thermally conductive than the substrate. In the present invention, since the laminated portion A including such an adhesive layer (second adhesive layer) is used to protect the heat-peelable adhesive tape, the first adhesive layer (the adhesive layer of the heat-peelable adhesive tape) can be prevented. ) 'S thermal degradation.
上述積層部分A對於聚對苯二甲酸乙二酯膜(例如,厚度50 μm)之黏著力A1(常態黏著力A1)較佳為0.04 N/20 mm~10 N/20 mm,更佳為0.05 N/20 mm~5 N/20 mm,進而較佳為0.08 N/20 mm~4.5 N/20 mm,進而較佳為0.1 N/20 mm~2.5 N/20 mm,尤佳為0.15 N/20 mm~1.2 N/20 mm。若為此種範圍,則可獲得將黏著片(即,上述熱剝離型黏著帶與積層部分A之積層體)供於特定步驟時積層部分A不易自熱剝離型黏著帶剝離、並且在特定之步驟後可容易地將無需之積層部分A自熱剝離型黏著帶剝離之黏著片。The adhesion A1 (normal adhesion A1) of the laminated portion A to a polyethylene terephthalate film (for example, 50 μm in thickness) is preferably 0.04 N / 20 mm to 10 N / 20 mm, and more preferably 0.05. N / 20 mm ~ 5 N / 20 mm, further preferably 0.08 N / 20 mm ~ 4.5 N / 20 mm, further preferably 0.1 N / 20 mm ~ 2.5 N / 20 mm, particularly preferably 0.15 N / 20 mm ~ 1.2 N / 20 mm. Within this range, it is possible to obtain an adhesive sheet (that is, a laminated body of the above-mentioned heat-peelable adhesive tape and the laminated portion A) in a specific step when the laminated portion A is not easily peeled from the heat-peelable adhesive tape, After the step, the unnecessary laminated layer A can be easily peeled off from the heat-adhesive type adhesive tape.
將上述積層部分A在100℃下加熱30分鐘後對於聚對苯二甲酸乙二酯膜(例如,厚度50 μm)之黏著力A2(加熱後黏著力A2)較佳為0.05 N/20 mm~10.0 N/20 mm,更佳為0.08 N/20 mm~5.0 N/20 mm,進而較佳為0.10 N/20 mm~1.5 N/20 mm。若為此種範圍,則積層部分A即便在將黏著片供於特定之步驟時該黏著片溫度上升,亦可具有所需之剝離力。再者,上述加熱後黏著力係在上述溫度下加熱後,第2黏著劑層溫度降低至23℃時之在23℃環境下之黏著力。After the laminated part A is heated at 100 ° C. for 30 minutes, the adhesive force A2 (adhesive force A2 after heating) on the polyethylene terephthalate film (for example, 50 μm in thickness) is preferably 0.05 N / 20 mm ~ 10.0 N / 20 mm, more preferably 0.08 N / 20 mm to 5.0 N / 20 mm, and still more preferably 0.10 N / 20 mm to 1.5 N / 20 mm. If it is this range, the laminated part A can have a required peeling force even if the temperature of the adhesive sheet rises when the adhesive sheet is supplied to a specific step. In addition, the adhesive force after heating is the adhesive force at 23 ° C when the temperature of the second adhesive layer is reduced to 23 ° C after heating at the above temperature.
上述加熱後黏著力A2相對於上述常態黏著力A1較佳為10倍以下,更佳為5倍以下,進而較佳為0.001倍~2.5倍,尤佳為0.001倍~1.8倍。若為此種範圍,則積層部分A即便在將黏著片供於特定之步驟時該黏著片溫度上升,亦可具有所需之剝離力。The above-mentioned heating adhesion A2 is preferably 10 times or less, more preferably 5 times or less, more preferably 0.001 times to 2.5 times, and even more preferably 0.001 times to 1.8 times, compared to the normal state adhesion A1. If it is this range, the laminated part A can have a required peeling force even if the temperature of the adhesive sheet rises when the adhesive sheet is supplied to a specific step.
上述積層部分A之厚度較佳為10 μm以上,更佳為20 μm以上,進而較佳為30 μm以上,尤佳為50 μm~500 μm,最佳為50 μm~300 μm。若積層部分A之厚度為10 μm以上,則能夠顯著地防止第1黏著劑層之熱劣化。The thickness of the laminated part A is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, particularly preferably 50 μm to 500 μm, and most preferably 50 μm to 300 μm. When the thickness of the laminated portion A is 10 μm or more, thermal degradation of the first adhesive layer can be significantly prevented.
C-1. 第2黏著劑層
上述第2黏著劑層之厚度較佳為1 μm~100 μm,更佳為5 μm~80 μm,進而較佳為5 μm~50 μm。若為此種範圍,則能夠顯著地防止第1黏著劑層之熱劣化。C-1. Second adhesive layer The thickness of the second adhesive layer is preferably 1 μm to 100 μm, more preferably 5 μm to 80 μm, and still more preferably 5 μm to 50 μm. Within this range, thermal degradation of the first adhesive layer can be significantly prevented.
上述第2黏著劑層代表性的是包含以特定之聚合物為基礎聚合物之黏著劑B。作為上述黏著劑B,亦較佳為使用感壓型黏著劑。作為第2黏著劑層中使用之感壓型黏著劑,例如可列舉丙烯酸系黏著劑、橡膠系黏著劑、乙烯基烷基醚系黏著劑、矽酮系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、胺基甲酸酯系黏著劑、苯乙烯-二烯嵌段共聚物系黏著劑等。其中,較佳為丙烯酸系黏著劑或矽酮系黏著劑。再者,上述黏著劑可單獨使用或組合使用2種以上。The second adhesive layer is typically an adhesive B containing a specific polymer as a base polymer. As the adhesive B, it is also preferable to use a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive used in the second adhesive layer include an acrylic adhesive, a rubber adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polymer. Amine-based adhesives, urethane-based adhesives, styrene-diene block copolymer-based adhesives, and the like. Among them, an acrylic adhesive or a silicone adhesive is preferred. In addition, the said adhesive can be used individually or in combination of 2 or more types.
作為第2黏著劑層中所含有之丙烯酸系黏著劑,例如使用上述B-1項中說明之黏著劑。As the acrylic pressure-sensitive adhesive contained in the second pressure-sensitive adhesive layer, for example, the pressure-sensitive adhesive described in the above item B-1 is used.
作為第2黏著劑層中所含有之矽酮系黏著劑,可使用任意適當之黏著劑。作為上述矽酮系黏著劑,例如可較佳地使用將包含有機聚矽氧烷之矽酮橡膠或矽酮樹脂等作為基礎聚合物之矽酮系黏著劑。作為構成矽酮系黏著劑之基礎聚合物,可使用將上述矽酮橡膠或矽酮樹脂交聯而獲得之基礎聚合物。再者,本說明書中,「矽酮橡膠」與「矽酮樹脂」之區別係依據「技術资讯協會 黏著劑(膜・帶)之材料設計及功能性賦予 第1版 2009年9月30日 222~228頁」。即,「矽酮橡膠」係指由二有機矽氧烷(D單元)構成之直鏈結構之矽酮,該矽酮橡膠具有例如10000 Pa・s左右之黏度。「矽酮樹脂」係指包含三有機半矽氧烷(triorganosilhemioxane,M單元)及矽酸酯(Q單元)、且具有支鏈結構之矽酮。As the silicone-based adhesive contained in the second adhesive layer, any appropriate adhesive can be used. As the silicone-based adhesive, for example, a silicone-based adhesive using a silicone rubber or silicone resin containing an organic polysiloxane as a base polymer can be preferably used. As the base polymer constituting the silicone-based adhesive, a base polymer obtained by crosslinking the above-mentioned silicone rubber or silicone resin can be used. In addition, in this specification, the difference between "silicone rubber" and "silicone resin" is based on the material design and functionality of the "Technical Information Association Adhesive (Film / Tape)" First Edition September 30, 2009 222 ~ 228 pages ". That is, "silicone rubber" refers to a silicone having a linear structure composed of diorganosiloxane (D unit), and the silicone rubber has a viscosity of about 10,000 Pa · s, for example. A "silicone resin" refers to a silicone having a branched structure including triorganosilhemioxane (M unit) and silicate (Q unit).
上述第2黏著劑層之凝膠分率較佳為20重量%~100重量%,更佳為30重量%~99重量%,進而較佳為50重量%~99重量%。若為此種範圍,則加熱後之黏著力上升得以抑制,能夠構成剝離性優異之積層部分A。凝膠分率係如下方式進行測定。
<凝膠分率測定方法>
取樣第2黏著劑層約0.1g並準確稱量(試樣之重量),將該樣品用網狀片(商品名「NTF-1122」、日東電工股份有限公司製造)包裹後,於約50 ml之甲苯中在室溫下浸漬1週。然後,將溶劑不溶成分(網狀片之內容物)自甲苯中取出,在70℃下乾燥約2小時,稱量乾燥後之溶劑不溶成分(浸漬、乾燥後之重量),藉由下述式(a)算出凝膠分率(重量%)。
凝膠分率(重量%)=[(浸漬、乾燥後之重量)/(試樣之重量)]×100 (a)The gel fraction of the second adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 99% by weight, and still more preferably 50% by weight to 99% by weight. If it is this range, the increase of the adhesive force after heating can be suppressed, and the laminated part A which is excellent in peelability can be comprised. The gel fraction was measured as follows.
<Method for measuring gel fraction>
A sample of about 0.1 g of the second adhesive layer was sampled and accurately weighed (the weight of the sample). The sample was wrapped in a mesh sheet (trade name "NTF-1122", manufactured by Nitto Denko Corporation), and then packed in about 50 ml. The toluene was immersed at room temperature for 1 week. Then, the solvent-insoluble component (the content of the mesh sheet) was taken out from toluene, and dried at 70 ° C for about 2 hours. The solvent-insoluble component (the weight after impregnation and drying) after drying was weighed, and the following formula was used: (a) Calculate the gel fraction (% by weight).
Gel fraction (% by weight) = [(Weight after dipping and drying) / (Weight of sample)] × 100 (a)
構成上述黏著劑B之基礎聚合物較佳為具有OH基或COOH基。其原因在於:若使用此種基礎聚合物,則能夠使用交聯劑來調整上述凝膠分率。The base polymer constituting the adhesive B preferably has an OH group or a COOH group. The reason is that if such a base polymer is used, the above-mentioned gel fraction can be adjusted using a crosslinking agent.
C-2. 第2基材
作為上述第2基材,例如可列舉樹脂片、不織布、紙、金屬箔、織布、橡膠片、發泡片、該等之積層體(特別是包含樹脂片之積層體)等。較佳為樹脂片。作為構成樹脂片之樹脂,例如可列舉聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳族聚醯胺)、聚醯亞胺(PI)、聚氯乙烯(PVC)、聚苯硫醚(PPS)、氟系樹脂、聚醚醚酮(PEEK)等。其中,較佳為PET或PI。C-2. Second substrate As the second substrate, for example, resin sheets, non-woven fabrics, paper, metal foil, woven fabrics, rubber sheets, foamed sheets, laminates of these (especially those containing resin sheets) Laminated body) and so on. A resin sheet is preferred. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene (PE). , Polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamine (aromatic polyamine), polyimide ( PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine-based resin, polyetheretherketone (PEEK), and the like. Among them, PET or PI is preferred.
上述第2基材之厚度較佳為8 μm~400 μm,更佳為15 μm~300 μm,尤佳為25 μm~200 μm。若為此種範圍,則能夠顯著地防止第1黏著劑層之熱劣化。The thickness of the second substrate is preferably 8 μm to 400 μm, more preferably 15 μm to 300 μm, and even more preferably 25 μm to 200 μm. Within this range, thermal degradation of the first adhesive layer can be significantly prevented.
上述第2基材亦可實施表面處理。作為表面處理,例如可列舉上述B-2項中說明之處理。表面處理層可形成於第2黏著劑層側之面。The second substrate may be surface-treated. Examples of the surface treatment include the treatment described in the above item B-2. The surface treatment layer may be formed on a surface on the side of the second adhesive layer.
D. 黏著片之製造方法
本發明之黏著片可藉由任意適當之方法來製造。於一實施形態中,形成熱剝離型黏著帶後,以於該熱剝離型黏著帶之第1基材之與第1黏著劑層相反側經由第2黏著劑層積層第2基材之方式,貼合積層部分A,藉此能夠製造上述黏著片。
D. Manufacturing method of adhesive sheet
The adhesive sheet of the present invention can be produced by any appropriate method. In one embodiment, after forming the heat-peelable adhesive tape, the second base material is laminated on the second base material via the second adhesive layer on the opposite side of the first base material of the heat-peelable adhesive tape, By laminating the laminated portion A, the above-mentioned adhesive sheet can be manufactured.
上述熱剝離型黏著帶可藉由任意適當之方法來製造。關於上述熱剝離型黏著帶,例如可列舉如下方法:於第1基材上直接塗敷包含形成第1黏著劑層之黏著劑A(形成包含熱膨脹性微小球之第1黏著劑層之情形時,進而包含熱膨脹性微小球)之黏著劑層形成用組合物A之方法;或將在任意適當之基體上塗敷黏著劑層形成用組合物A而形成之塗敷層轉印至第1基材之方法等。黏著劑層形成用組合物A可包含任意適當之溶劑。又,於形成包含熱膨脹性微小球之第1黏著劑層之情形時,藉由包含黏著劑A之組合物形成黏著劑塗敷層後,在該黏著劑塗敷層上撒落熱膨脹性微小球後,使用層壓機等,將該熱膨脹性微小球埋入該塗敷層中,形成包含熱膨脹性微小球之第1黏著劑層。The heat-peelable pressure-sensitive adhesive tape can be produced by any appropriate method. The heat-peeling type adhesive tape can be exemplified by a method in which the first substrate is directly coated with an adhesive A that includes a first adhesive layer (when a first adhesive layer including a thermally expandable microsphere is formed). Method further comprising a composition A for forming an adhesive layer containing thermally expandable microspheres); or transferring a coating layer formed by applying the composition A for forming an adhesive layer on any appropriate substrate to a first substrate Methods, etc. The composition A for forming an adhesive layer may contain any appropriate solvent. In the case where the first adhesive layer containing the thermally expandable microspheres is formed, after the adhesive coating layer is formed from the composition containing the adhesive A, the thermally expandable microspheres are scattered on the adhesive coating layer. Then, using a laminator or the like, the heat-expandable microspheres are embedded in the coating layer to form a first adhesive layer containing the heat-expandable microspheres.
黏著劑層形成用組合物A中之熱膨脹性微小球之含有比率相對於黏著劑層形成用組合物之固體成分重量,較佳為5重量%~95重量%,更佳為10重量%~70重量%,進而較佳為10重量%~50重量%。The content ratio of the thermally expandable microspheres in the composition A for forming an adhesive layer is preferably 5 to 95% by weight, and more preferably 10 to 70% by weight relative to the weight of the solid content of the composition for forming an adhesive layer. % By weight, more preferably 10% by weight to 50% by weight.
上述積層部分A可藉由任意適當之方法來製造。關於上述積層部分A,例如可列舉如下方法:於第2基材上直接塗敷包含形成第2黏著劑層之黏著劑B之黏著劑層形成用組合物B之方法;或將在任意適當之基體上塗敷黏著劑層形成用組合物B而形成之塗敷層轉印至第2基材之方法等。黏著劑層形成用組合物B可包含任意適當之溶劑。The laminated portion A can be produced by any appropriate method. Regarding the above-mentioned laminated portion A, for example, a method of directly applying an adhesive layer-forming composition B including an adhesive B forming a second adhesive layer on a second substrate, or any appropriate method A method of transferring the coating layer formed by applying the adhesive layer-forming composition B on a substrate to a second substrate, and the like. The composition B for forming an adhesive layer may contain any appropriate solvent.
作為上述各組合物之塗敷方法,可採用任意適當之塗敷方法。例如,可於塗佈後進行乾燥而形成各層。作為塗佈方法,例如可列舉:使用多重塗佈機(multi-coater)、模嘴塗佈機、凹版塗佈機、敷料器等之塗佈方法。作為乾燥方法,例如可列舉自然乾燥、加熱乾燥等。加熱乾燥之情形時之加熱溫度根據作為乾燥對象之物質之特性,可設定為任意適當之溫度。As a coating method of each of the above-mentioned compositions, any appropriate coating method can be adopted. For example, each layer can be formed by drying after coating. Examples of the coating method include coating methods using a multi-coater, a die coater, a gravure coater, and an applicator. Examples of the drying method include natural drying and heat drying. In the case of heating and drying, the heating temperature can be set to any appropriate temperature according to the characteristics of the substance to be dried.
E. 熱剝離型黏著帶之搬送方法
本發明之熱剝離型黏著帶之搬送方法為上述熱剝離型黏著帶之搬送方法,其包括:將積層部分A積層於具備第1基材與第1黏著劑層之上述熱剝離型黏著帶之該第1基材側,將附積層部分A之熱剝離型黏著帶進行搬送。如上所述,積層部分A包含第2黏著劑層及第2基材。積層部分A係以於熱剝離型黏著帶之第1基材之與第1黏著劑層相反側經由第2黏著劑層積層第2基材之方式配置。
E. Method for conveying thermal peeling type adhesive tape
The transport method of the heat-peelable pressure-sensitive adhesive tape of the present invention is the above-mentioned method of transporting the heat-peelable pressure-sensitive adhesive tape. The first base material side carries a heat-peelable pressure-sensitive adhesive tape with a build-up portion A. As described above, the build-up portion A includes the second adhesive layer and the second substrate. The lamination part A is arrange | positioned so that the 2nd base material may be laminated | stacked via the 2nd adhesive agent on the opposite side of the 1st base material of a heat release type adhesive tape from a 1st adhesive agent layer.
於一實施形態中,上述搬送方法包括利用搬送輥將熱剝離型黏著帶(實質上為附積層部分A之熱剝離型黏著帶)進行搬送。附積層部分A之熱剝離型黏著帶較佳以積層部分A成為搬送輥側之方式被搬送。根據本發明之搬送方法,藉由使用積層部分A將熱剝離型黏著帶進行搬送,可保護第1黏著劑層免於因與搬送輥之摩擦等影響導致溫度上升。根據本發明,藉由具備以可剝離之方式積層之積層部分A20,可防止熱剝離型黏著帶之黏著劑層(即,第1黏著劑層)之劣化,並且可作為熱剝離型黏著帶,製成符合實際用途之適當之厚度。
[實施例]In one embodiment, the transfer method includes transferring a heat-peelable pressure-sensitive adhesive tape (substantially a heat-peelable pressure-sensitive adhesive tape with a build-up layer portion A) using a transfer roller. It is preferable that the heat-peeling type adhesive tape with the build-up part A is conveyed so that the build-up part A becomes a conveyance roller side. According to the conveying method of the present invention, by using the lamination section A to convey the heat-peeling type adhesive tape, the first adhesive layer can be protected from temperature rise due to the influence of friction with the conveying roller and the like. According to the present invention, by providing a build-up portion A20 laminated in a peelable manner, deterioration of the adhesive layer (that is, the first adhesive layer) of the heat-peeling type adhesive tape can be prevented, and it can be used as a heat-peeling type adhesive tape. It is made into a thickness suitable for practical use.
[Example]
以下,藉由實施例具體地對本發明進行說明,但本發明不受該等實施例之限定。實施例中之評價方法如下所述。又,實施例中,只要並無特別說明,則「份」及「%」為重量基準。Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. In the examples, unless otherwise specified, "parts" and "%" are based on weight.
[實施例1]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸=95重量份:5重量份)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)3重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(厚度:50 μm)上,以乾燥後之厚度成為5 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(厚度:38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:5 μm)/隔離膜)。[Example 1]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: 95 parts by weight of acrylic acid: 5 parts by weight) and 3 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (thickness: 50 μm) as a second substrate so that the thickness became 5 μm after drying, and dried to form a second adhesive layer. The PET release film (thickness: 38 μm) was bonded to the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).
[實施例2]
作為第2基材,使用聚醯亞胺膜(厚度:50 μm)代替PET膜(厚度:50 μm),除此以外,以與實施例1相同之方式獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:5 μm)/隔離膜)。[Example 2]
Except that a polyimide film (thickness: 50 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (second substrate ( Thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).
[實施例3]
作為第2基材,使用PET膜(厚度:25 μm)代替PET膜(厚度:50 μm),除此以外,以與實施例1相同之方式獲得積層部分A(第2基材(厚度:25 μm)/第2黏著劑層(厚度:5 μm)/隔離膜)。[Example 3]
Except that a PET film (thickness: 25 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (thickness: 25) was obtained in the same manner as in Example 1. μm) / second adhesive layer (thickness: 5 μm) / separator).
[實施例4]
作為第2基材,使用PET膜(厚度:100 μm)代替PET膜(厚度:50 μm),除此以外,以與實施例1相同之方式獲得積層部分A(第2基材(厚度:100 μm)/第2黏著劑層(厚度:5 μm)/隔離膜)。[Example 4]
Except that a PET film (thickness: 100 μm) was used as the second substrate instead of the PET film (thickness: 50 μm), a laminated portion A (second substrate (thickness: 100) was obtained in the same manner as in Example 1. μm) / second adhesive layer (thickness: 5 μm) / separator).
[實施例5]
將第2黏著劑層之厚度設為25 μm,除此以外,以與實施例1相同之方式獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:25 μm)/隔離膜)。[Example 5]
Except that the thickness of the second adhesive layer was set to 25 μm, a laminated portion A (second substrate (thickness: 50 μm)) / second adhesive layer (thickness: 25) was obtained in the same manner as in Example 1. μm) / separator).
[實施例6]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸羥基乙酯(重量比)=100:4)100重量份、異氰酸酯系交聯劑(Nippon Polyurethane Industry公司製造,商品名「CORONATE L」)2重量份、交聯促進劑(東曹股份有限公司製造,商品名「Triethylenediamine(TEDA)」)0.05重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(50 μm)上,以乾燥後之厚度成為10 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:10 μm)/隔離膜)。[Example 6]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: hydroxyethyl acrylate (weight ratio) = 100: 4), and an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry, trade name "CORONATE L") 2 parts by weight, 0.05 parts by weight of a crosslinking accelerator (manufactured by Tosoh Corporation, trade name "Triethylenediamine (TEDA)") and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (50 μm) as a second substrate so that the thickness became 10 μm after drying, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 10 μm) / separator).
[實施例7]
將丙烯酸系共聚物(丙烯酸丁酯:丙烯酸(重量比)=100:5)100重量份、異氰酸酯系交聯劑(Nippon Polyurethane Industry公司製造,商品名「CORONATE L」)2重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)0.5重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(50 μm)上,以乾燥後之厚度成為50 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:50 μm)/隔離膜)。[Example 7]
100 parts by weight of an acrylic copolymer (butyl acrylate: acrylic acid (weight ratio) = 100: 5), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry, trade name "CORONATE L"), and epoxy-based 0.5 parts by weight of a cross-linking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "TETRAD C") and toluene were mixed to prepare an adhesive solution. On the PET film (50 μm) as the second substrate, apply the above adhesive solution so that the thickness after drying becomes 50 μm and dry to form a second adhesive layer, and attach a PET release film (38 μm) Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 50 μm) / separator).
[實施例8]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸=95重量份:5重量份)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)5重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(50 μm)上,以乾燥後之厚度成為5 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:5 μm)/隔離膜)。[Example 8]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight) and 5 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was coated on a PET film (50 μm) as a second substrate so that the thickness became 5 μm after drying, and dried to form a second adhesive layer. A PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 5 μm) / separator).
[實施例9]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸=95重量份:5重量份)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)3重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(5 μm)上,以乾燥後之厚度成為3 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:5 μm)/第2黏著劑層(厚度:3 μm)/隔離膜)。[Example 9]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: 95 parts by weight of acrylic acid: 5 parts by weight) and 3 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (5 μm) as a second substrate so that the thickness after drying became 3 μm, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 5 μm) / second adhesive layer (thickness: 3 μm) / separator).
[實施例10]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸=95重量份:5重量份)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)0.6重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(50 μm)上,以乾燥後之厚度成為10 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:10 μm)/隔離膜)。[Example 10]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight) and 0.6 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was applied to a PET film (50 μm) as a second substrate so that the thickness became 10 μm after drying, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 10 μm) / separator).
[實施例11]
將第2黏著劑層之厚度設為50 μm,除此以外,以與實施例10相同之方式獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:50 μm)/隔離膜)。[Example 11]
Except that the thickness of the second adhesive layer was set to 50 μm, a laminated portion A (second substrate (thickness: 50 μm)) / second adhesive layer (thickness: 50) was obtained in the same manner as in Example 10. μm) / separator).
[實施例12]
將丙烯酸系共聚物(丙烯酸2-乙基己酯:丙烯酸=95重量份:5重量份)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD C」)6重量份及甲苯進行混合,製備黏著劑溶液。於作為第2基材之PET膜(50 μm)上,以乾燥後之厚度成為3 μm之方式塗佈上述黏著劑溶液並乾燥,形成第2黏著劑層,將PET隔離膜(38 μm)貼合於第2黏著劑層上,獲得積層部分A(第2基材(厚度:50 μm)/第2黏著劑層(厚度:3 μm)/隔離膜)。[Example 12]
100 parts by weight of an acrylic copolymer (2-ethylhexyl acrylate: acrylic acid = 95 parts by weight: 5 parts by weight), and 6 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C") Parts and toluene were mixed to prepare an adhesive solution. The above adhesive solution was coated on a PET film (50 μm) as a second substrate so that the thickness after drying became 3 μm, and dried to form a second adhesive layer, and a PET release film (38 μm) was pasted. Lamination was performed on the second adhesive layer to obtain a laminated portion A (second substrate (thickness: 50 μm) / second adhesive layer (thickness: 3 μm) / separator).
<評價>
將實施例中製作之積層部分A、及包含積層部分A和熱剝離型黏著帶之黏著片供於以下之評價。將結果示於表1。
又,將不含積層部分A而僅由熱剝離型黏著帶構成之黏著片供於(4)熱剝離型黏著帶之保護性評價,將其作為比較例1之結果。
(1)積層部分A(第2基材/第2黏著劑層)之常態黏著力
將實施例中製作之積層部分A(第2基材/第2黏著劑層)切斷成寬度:20 mm、長度:140 mm之尺寸,將隔離膜剝離後,於第2黏著劑層上依據JIS Z 0237(2000年)貼合作為被黏著體之聚對苯二甲酸乙二酯膜(商品名「Lumirror S-10」Toray公司製造;厚度:50 μm、寬度:20 mm)(具體而言,在溫度:23±2℃及濕度:65±5%RH之環境下使2 kg之輥往返1次進行壓接而貼合),製作評價用樣品。將該評價用樣品安裝至附有設定為23℃之恆溫槽之拉伸試驗機(島津製作所股份有限公司製造,商品名「Shimadzu Autograph AG-120kN」)上,放置30分鐘。放置後,測定在23℃之溫度下將被黏著體在剝離角度:180°、剝離速度(拉伸速度):300 mm/分鐘之條件下自積層部分A剝離時之載重,求出此時之凹凸平均載重(測定初期之峰頂除外之載重之凹凸平均值),將該凹凸平均載重作為積層部分A之黏著力(N/20 mm寬度)。< Evaluation >
The laminated part A produced in the Example and the adhesive sheet containing the laminated part A and the heat-peeling type adhesive tape were evaluated for the following evaluation. The results are shown in Table 1.
Moreover, the adhesive sheet which consists only of a heat release type adhesive tape without the laminated part A was provided for the protective evaluation of (4) heat release type adhesive tape, and this was made into the result of the comparative example 1.
(1) Normal adhesion of the laminated part A (second substrate / second adhesive layer) Cut the laminated portion A (second substrate / second adhesive layer) produced in the example into a width: 20 mm 、 Length: 140 mm. After peeling the release film, adhere to the second adhesive layer according to JIS Z 0237 (2000) to form a polyethylene terephthalate film (brand name “Lumirror”). S-10 "manufactured by Toray; thickness: 50 μm, width: 20 mm) (Specifically, a 2 kg roller is reciprocated once in an environment of temperature: 23 ± 2 ° C and humidity: 65 ± 5% RH Pressure-bonding and bonding) to prepare a sample for evaluation. This sample for evaluation was attached to a tensile tester (made by Shimadzu Corporation, trade name "Shimadzu Autograph AG-120kN") with a thermostatic bath set at 23 ° C, and left for 30 minutes. After standing, the load at the time of peeling of the adherend at 23 ° C under the conditions of peeling angle: 180 °, peeling speed (stretching speed): 300 mm / min was measured, and the weight at this time was determined. Concave-convex average load (average of concavities and convexities of loads other than the peak at the beginning of the measurement), and the average uneven-convex load was used as the adhesion force (N / 20 mm width) of the laminated portion A.
(2)積層部分A(第2基材/第2黏著劑層)之加熱後黏著力
以與上述(1)相同之方式製作評價用樣品。
將評價用樣品於100℃下加熱30分鐘,然後,在23℃環境下放置30分鐘。其後,將評價用樣品安裝至附有設定為23℃之恆溫槽之拉伸試驗機(商品名「Shimadzu Autograph AG-120kN」,島津製作所股份有限公司製造)上,放置30分鐘。放置後,測定於23℃之溫度下將被黏著體在剝離角度:180°、剝離速度(拉伸速度):300 mm/分鐘之條件下自積層部分A剝離時之載重,求出此時之凹凸平均載重(測定初期之峰頂除外之載重之凹凸平均值),將該凹凸平均載重作為積層部分A之黏著力(N/20 mm寬度)。
又,基於測定值,按照以下之基準評價積層部分A之剝離性。再者,此處之剝離性於實際使用之情形時,可相當於將由熱剝離型黏著帶與積層部分A構成之黏著片供於卷對卷製程,受到由與搬送輥之摩擦等影響導致溫度上升後之剝離性。
:加熱後黏著力為5.0 N/20 mm以下
Δ:加熱後黏著力超過5.0 N/20 mm(2) The adhesive force after heating of the laminated portion A (second substrate / second adhesive layer) was prepared in the same manner as in (1) above.
The sample for evaluation was heated at 100 ° C for 30 minutes, and then left to stand in an environment of 23 ° C for 30 minutes. Thereafter, the sample for evaluation was attached to a tensile tester (trade name "Shimadzu Autograph AG-120kN", manufactured by Shimadzu Corporation) with a thermostat set at 23 ° C, and left for 30 minutes. After standing, the load at the time of peeling of the adherend at 23 ° C under the conditions of peeling angle: 180 °, peeling speed (stretching speed): 300 mm / min was measured, and the weight at this time was determined. Concave-convex average load (average of concavities and convexities of loads other than the peak at the beginning of the measurement), and the average uneven-convex load was used as the adhesion force (N / 20 mm width) of the laminated portion A.
In addition, based on the measured values, the peelability of the laminated portion A was evaluated according to the following criteria. In addition, when the peelability here is actually used, it may be equivalent to supplying a pressure-sensitive adhesive sheet composed of a heat-peeling type adhesive tape and the laminated part A to a roll-to-roll process, and the temperature may be affected by the friction with the transfer roller. Peelability after rising.
: Adhesion after heating is 5.0 N / 20 mm or less Δ: Adhesion after heating exceeds 5.0 N / 20 mm
(3)第2黏著劑層之凝膠分率
取樣構成積層部分A之黏著劑層約0.1g並準確稱量(試樣之重量),將該樣品用網狀片(商品名「NTF-1122」、日東電工股份有限公司製造)包裹後,於約50 ml之甲苯中在室溫下浸漬1週。然後,將溶劑不溶成分(網狀片之內容物)自甲苯中取出,在70℃下乾燥約2小時,稱量乾燥後之溶劑不溶成分(浸漬、乾燥後之重量),藉由下述式(a)算出凝膠分率(重量%)。
凝膠分率(重量%)=[(浸漬、乾燥後之重量)/(試樣之重量)]×100 (a)(3) Take a sample of the gel fraction of the second adhesive layer to sample about 0.1 g of the adhesive layer that constitutes layer A and weigh it accurately (weight of the sample). Use a mesh sheet (trade name "NTF-1122") for this sample. ", Manufactured by Nitto Denko Co., Ltd.) After wrapping, immerse in about 50 ml of toluene at room temperature for 1 week. Then, the solvent-insoluble component (the content of the mesh sheet) was taken out from toluene, and dried at 70 ° C for about 2 hours. The solvent-insoluble component (the weight after impregnation and drying) after drying was weighed, and the following formula was used: (a) Calculate the gel fraction (% by weight).
Gel fraction (% by weight) = [(Weight after dipping and drying) / (Weight of sample)] × 100 (a)
(4)熱剝離型黏著帶之保護性評價
使用手壓輥,將實施例中製作之積層部分A貼合於由第1基材(PET膜、厚度:50 μm)、中間層及第1黏著劑層構成之熱剝離型黏著帶之第1基材面,獲得評價用黏著片(第1黏著劑層(熱剝離性)/中間層/第1基材/第2黏著劑層/第2基材)。再者,熱剝離型黏著帶係熱剝離型黏著帶係藉由以下所示之方法製作。
於丙烯酸系共聚物(丙烯酸丁酯:丙烯酸羥基乙酯=100重量份:3重量份)100重量份中調配萜酚系黏著賦予樹脂(商品名「YS Polystar T80」、YASUHARA CHEMICAL公司製造)30重量份、異氰酸酯系交聯劑(商品名「CORONATE L」,Nippon Polyurethane Industry公司製造)1重量份,加入甲苯,均勻地混合,製作黏著劑溶液,於PET基材(第1基材、厚度:50 μm)上以乾燥後之厚度成為20 μm之方式塗佈上述黏著劑溶液,形成中間層。
進而,於上述共聚物100重量份中均勻地混合異氰酸酯系交聯劑(商品名「CORONATE L」、Nippon Polyurethane Industry公司製造)1重量份、發泡劑(熱膨脹性微小球;商品名「Matsumoto Microsphere F-30D」、松本油脂製藥股份有限公司製造)50重量份、及甲苯並使該等溶解,將所得塗敷液以乾燥後之厚度成為30 μm之方式塗佈於PET基材隔離膜(38 μm)上,形成第1黏著劑層。將該黏著劑層轉印至上述中間層上,獲得上述熱剝離型黏著帶。
於下述條件下測定評價用樣品之第1黏著劑層之探針黏著力,將其值設為C0
。又,自評價用樣品之背面(第2基材)側在下述條件下進行加熱,測定加熱後之探針黏著力C。藉由式(C/C0
)×100算出探針黏著力殘留率。
於受到來自背面之熱之影響而使熱膨脹性微小球開始發泡之情形時,探針黏著力之值變小,隨之探針黏著力殘留率亦變小。因此,基於探針黏著力殘留率之大小,按照以下之基準評價黏著片中之熱剝離型黏著帶之保護性。
:探針黏著力殘留率為80%以上
Δ:探針黏著力殘留率為70%以上且未達80%
×:探針黏著力殘留率未達70%
再者,於比較例中,將如上所述製作之熱剝離型黏著帶直接作為評價用黏著帶,供於上述評價。
・加熱方法
以第2基材(比較例中為第1基材)成為加熱板側之方式載置於加熱至90℃之加熱板,進而自評價用黏著帶之上方以該帶均勻地接觸加熱板之方式載置玻璃之重物(140 mm×140 mm×10 mm)。維持該狀態20秒鐘,對評價用黏著帶進行加熱。
・探針黏著力測定方法
使用黏著試驗機TAC-II(RHESCA公司製造),於以下之條件下評價探針黏著力。將拔出時施加之峰值載重(gf)作為探針黏著力之值。
・金屬探針之直徑 10 mm
・探針之壓入速度 30 mm/分鐘
・載重 50gf
・壓入時間 0.5秒
・拔出速度 30 mm/分鐘(4) Evaluation of the protective property of the heat-peelable adhesive tape Using a hand roller, the laminated part A produced in the example was bonded to the first substrate (PET film, thickness: 50 μm), the intermediate layer, and the first adhesive layer. The first base material surface of the heat-peelable pressure-sensitive adhesive tape composed of an adhesive layer was obtained as an adhesive sheet for evaluation (first adhesive layer (thermal peelability) / intermediate layer / first substrate / second adhesive layer / second base). material). The heat-peelable pressure-sensitive adhesive tape system is produced by the following method.
30 parts by weight of 100% by weight of an acrylic copolymer (butyl acrylate: hydroxyethyl acrylate = 100 parts by weight: 3 parts by weight) is formulated with a terpene phenol-based adhesion-imparting resin (trade name "YS Polystar T80", manufactured by Yasuhara Chemical Co., Ltd.) Parts, 1 part by weight of isocyanate-based cross-linking agent (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry, Inc.), toluene was added thereto, and they were mixed uniformly to prepare an adhesive solution, which was applied to a PET substrate (first substrate, thickness: 50) μm) The above-mentioned adhesive solution was applied so that the thickness after drying became 20 μm to form an intermediate layer.
Furthermore, 1 part by weight of an isocyanate-based crosslinking agent (trade name "CORONATE L", manufactured by Nippon Polyurethane Industry) and a foaming agent (heat-expandable microsphere; trade name "Matsumoto Microsphere") were uniformly mixed with 100 parts by weight of the copolymer. F-30D ", manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd.) and 50 parts by weight of toluene, and dissolving them, and the obtained coating liquid was applied to a PET substrate release film (38 μm thickness after drying) μm) to form a first adhesive layer. The pressure-sensitive adhesive layer was transferred onto the intermediate layer to obtain the heat-peelable pressure-sensitive adhesive tape.
The probe adhesive force of the first adhesive layer of the sample for evaluation was measured under the following conditions, and the value was set to C 0 . The self-evaluation sample was heated on the back surface (second substrate) side under the following conditions, and the probe adhesion C after heating was measured. The probe adhesive force residual ratio was calculated by the formula (C / C 0 ) × 100.
When the thermally expandable microspheres start to foam due to the influence of the heat from the back surface, the value of the probe adhesive force becomes smaller, and the residual rate of the probe adhesive force becomes smaller. Therefore, based on the magnitude of the probe adhesion residual rate, the protective properties of the heat-peelable adhesive tape in the adhesive sheet were evaluated according to the following criteria.
: Probe adhesion residual rate is 80% or more Δ: Probe adhesion residual rate is 70% or more and less than 80%
×: Residual adhesion of probe is less than 70%
In the comparative example, the heat-peelable pressure-sensitive adhesive tape produced as described above was directly used as an evaluation tape, and was used for the above-mentioned evaluation.
・ Heating method: Place the second substrate (the first substrate in the comparative example) on the heating plate side and place it on a heating plate heated to 90 ° C, and then contact the tape evenly from above the adhesive tape for evaluation and heat it. Place the weight of the glass (140 mm × 140 mm × 10 mm) in the form of a plate. This state was maintained for 20 seconds, and the adhesive tape for evaluation was heated.
-Probe adhesion measurement method The adhesion tester TAC-II (manufactured by RHESCA) was used to evaluate the probe adhesion under the following conditions. The peak load (gf) applied at the time of extraction was taken as the value of the probe adhesion.
・ Metal probe diameter 10 mm
・ Pressing speed of probe: 30 mm / min ・ Load capacity: 50gf
・ Press-in time 0.5 seconds ・ Pull-out speed 30 mm / min
(5)積層部分A之穩定性評價
以與上述(4)相同之方式製作評價用黏著帶。
將評價用黏著帶切割成20 mm×100 mm之尺寸。將短條狀之評價用黏著帶以積層部分A側成為內側之方式相對於長度方向彎成一半後,拉伸至原本之狀態。
藉由目視觀察折痕部分,按照以下之基準進行評價。
:於熱剝離型黏著帶之第1基材面與積層部分A之第2黏著劑層面之間未確認到隆起
Δ:於第1基材面與第2黏著劑層之間確認到一部分隆起,但實用上可容許
×:於第1基材面與第2黏著劑層之間確認到實用上不被容許之程度之隆起(5) Evaluation of stability of laminated layer A In the same manner as in (4) above, an adhesive tape for evaluation was produced.
The adhesive tape for evaluation was cut into a size of 20 mm × 100 mm. The short strip-shaped adhesive tape for evaluation was bent in half with respect to the longitudinal direction so that the side of the laminated portion A was inward, and then stretched to the original state.
The crease portion was visually observed and evaluated according to the following criteria.
: No bulge was confirmed between the first base material surface of the heat-peelable pressure-sensitive adhesive tape and the second adhesive layer of the laminated portion A. A bulge was confirmed between the first base material surface and the second adhesive layer, but Practically tolerable ×: A bulge of a degree not practically acceptable was confirmed between the first substrate surface and the second adhesive layer
[表1]
10‧‧‧熱剝離型黏著帶10‧‧‧Heat release type adhesive tape
11‧‧‧第1黏著劑層 11‧‧‧The first adhesive layer
12‧‧‧第1基材 12‧‧‧ the first substrate
20‧‧‧積層部分A 20‧‧‧Laminated part A
21‧‧‧第2黏著劑層 21‧‧‧Second adhesive layer
22‧‧‧第2基材 22‧‧‧ 2nd substrate
100‧‧‧黏著片 100‧‧‧ Adhesive sheet
圖1係本發明之一實施形態之黏著片之概略剖視圖。FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention.
Claims (10)
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JP2018095561A JP7133355B2 (en) | 2018-05-17 | 2018-05-17 | Adhesive sheet |
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Cited By (2)
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US11478567B2 (en) | 2015-11-24 | 2022-10-25 | University Of Washington | Photosensitive medical tape |
US11878499B2 (en) | 2019-06-28 | 2024-01-23 | University Of Washington | Apparatus, system, and method for activating a low-adhesion state of thermal-sensitive tape |
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CN116368199A (en) * | 2020-12-07 | 2023-06-30 | 日东电工株式会社 | Pressure-sensitive adhesive sheet |
JP2023039829A (en) * | 2021-09-09 | 2023-03-22 | 日東電工株式会社 | Adhesive sheet for temporarily fixing electronic component |
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JP5258128B2 (en) * | 2001-01-24 | 2013-08-07 | 日東電工株式会社 | Manufacturing method of heat-peelable pressure-sensitive adhesive sheet |
JP4381860B2 (en) * | 2004-03-24 | 2009-12-09 | 日東電工株式会社 | Method and apparatus for separating reinforcing plate fixed to reinforced semiconductor wafer |
JP5362332B2 (en) * | 2008-11-19 | 2013-12-11 | 日東電工株式会社 | Surface protection sheet and use thereof |
JP5631690B2 (en) * | 2010-10-15 | 2014-11-26 | セイコーインスツル株式会社 | Adhesive label, production method and production apparatus |
JP6000958B2 (en) * | 2011-09-20 | 2016-10-05 | 日東電工株式会社 | Heat-peelable pressure-sensitive adhesive sheet for cutting electronic components and electronic component cutting method |
US20150299521A1 (en) * | 2012-11-02 | 2015-10-22 | Nitto Denko Corporation | Thermally debondable tape |
CN107075323A (en) * | 2014-11-13 | 2017-08-18 | Dic株式会社 | Double-sided adhesive tape, article and separation method |
CN104629639B (en) * | 2015-01-26 | 2019-04-23 | 东莞市华诚宇丰电子科技有限公司 | A kind of hot soarfing is from interim positioning film |
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US11478567B2 (en) | 2015-11-24 | 2022-10-25 | University Of Washington | Photosensitive medical tape |
US11878499B2 (en) | 2019-06-28 | 2024-01-23 | University Of Washington | Apparatus, system, and method for activating a low-adhesion state of thermal-sensitive tape |
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