TW202113000A - Adhesive sheet material having excellent stretchability and maintaining good stretchability even when repeated stretch operations are performed - Google Patents
Adhesive sheet material having excellent stretchability and maintaining good stretchability even when repeated stretch operations are performed Download PDFInfo
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- 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
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
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- 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
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- 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
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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- 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
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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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- 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
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- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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- C09J2425/00—Presence of styrenic polymer
- C09J2425/006—Presence of styrenic polymer in the substrate
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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Abstract
Description
本發明係關於一種黏著片材。The present invention relates to an adhesive sheet.
半導體晶圓、各種封裝體類等之電子零件材料有在以大徑之狀態製造後，切斷分離(切割)為元件小片(晶片)並且被逐個拾取並移至安裝步驟的情況。此時，通常被加工物以貼附於黏著片材之狀態被供於各步驟，在拾取晶片時，為了擴大晶片間隔，使黏著片材伸長(擴展步驟)。因此，以如上所述之方式使用之黏著片材所具備之基材大多使用伸長性優異之聚氯乙烯膜(專利文獻1、2)。Electronic component materials such as semiconductor wafers and various packages are sometimes cut and separated (diced) into small component pieces (chips) after being manufactured in a large-diameter state, and they are picked up one by one and moved to the mounting step. At this time, the workpiece is usually supplied to each step in a state of being attached to the adhesive sheet. When the wafer is picked up, the adhesive sheet is extended (expansion step) in order to increase the gap between the wafers. Therefore, a polyvinyl chloride film with excellent extensibility is often used as a base material of an adhesive sheet used as described above (Patent Documents 1 and 2).
在從黏著片材拾取複數個晶片之一部分並保管餘下之晶片之情形時，從保管性之觀點出發，要求黏著片材在伸長後恢復。但是，先前之黏著片材(例如，以聚氯乙烯膜為基材之黏著片材)之恢復性(收縮性)不充分，特別是將固定在1張黏著片材上之晶片分複數次拾取之情形時，有難以使用之問題。 [先前技術文獻] [專利文獻]When picking up a part of a plurality of wafers from the adhesive sheet and storing the remaining wafers, from the viewpoint of storage ability, the adhesive sheet is required to recover after being stretched. However, the recoverability (shrinkage) of the previous adhesive sheet (for example, an adhesive sheet with a polyvinyl chloride film as the base material) is insufficient, especially when the chip fixed on one adhesive sheet is picked up several times In this case, there is a problem that it is difficult to use. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特開2001-207140號公報 [專利文獻2]日本專利特開2010-260893號公報[Patent Document 1] Japanese Patent Laid-Open No. 2001-207140 [Patent Document 2] Japanese Patent Laid-Open No. 2010-260893
[發明所欲解決之問題][The problem to be solved by the invention]
本發明係為了解決上述先前之問題而完成者，其目的在於提供一種可供於電子零件材料之固定之黏著片材，其伸縮性優異，並且即使進行反覆之伸縮操作亦能維持良好之伸縮性。 [解決問題之技術手段]The present invention was completed in order to solve the above-mentioned previous problems, and its purpose is to provide an adhesive sheet that can be used for fixing electronic component materials, which has excellent stretchability and can maintain good stretchability even if repeated stretch operations are performed . [Technical means to solve the problem]
本發明之黏著片材具備：基材、及配置於該基材之至少單側之黏著劑層，該基材包含選自由聚胺基甲酸酯系樹脂、苯乙烯系彈性體及丙烯系彈性體所組成之群中之至少1種。 一個實施方式中，上述基材包含脂肪酸醯胺。 一個實施方式中，相對於上述基材100重量份，上述脂肪酸醯胺之含有比率為0.001重量份～10重量份。 一個實施方式中，上述黏著劑層包含丙烯酸系黏著劑。 一個實施方式中，上述丙烯酸系黏著劑包含如下丙烯酸系聚合物，上述丙烯酸系聚合物包含源自具有極性官能基之單體之結構單元。 一個實施方式中，相對於上述丙烯酸系聚合物100重量份，上述具有極性官能基之單體之含有比率為0.01重量份～40重量份。 一個實施方式中，上述具有極性官能基之單體為(甲基)丙烯酸。 一個實施方式中，相對於上述(甲基)丙烯酸系聚合物100重量份，上述(甲基)丙烯酸之含有比率為1重量份～20重量份。 [發明之效果]The adhesive sheet of the present invention includes: a substrate and an adhesive layer disposed on at least one side of the substrate, the substrate including a polyurethane resin, a styrene elastomer, and an acrylic elastomer At least one of the group consisting of body. In one embodiment, the above-mentioned base material contains fatty acid amides. In one embodiment, the content ratio of the fatty acid amide is 0.001 parts by weight to 10 parts by weight relative to 100 parts by weight of the substrate. In one embodiment, the adhesive layer contains an acrylic adhesive. In one embodiment, the acrylic adhesive includes an acrylic polymer, and the acrylic polymer includes a structural unit derived from a monomer having a polar functional group. In one embodiment, the content ratio of the monomer having the polar functional group is 0.01 to 40 parts by weight relative to 100 parts by weight of the acrylic polymer. In one embodiment, the above-mentioned monomer having a polar functional group is (meth)acrylic acid. In one embodiment, the content ratio of the (meth)acrylic acid is 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylic polymer. [Effects of Invention]
根據本發明，可提供一種可供於電子零件材料之固定之黏著片材，其伸縮性優異，並且即使進行反覆之伸縮操作亦能維持良好之伸縮性。According to the present invention, it is possible to provide an adhesive sheet that can be used for fixing electronic component materials, which has excellent stretchability and maintains good stretchability even if repeated stretch operations are performed.
A. 黏著片材之概要
圖1為本發明之較佳之實施方式之黏著片材之概略剖視圖。黏著片材100具備：基材10、及配置於基材10之至少單側之黏著劑層20。基材10包含聚胺基甲酸酯系樹脂、苯乙烯系彈性體或丙烯系彈性體。該等可單獨使用或組合2種以上使用。本發明中，藉由由此種材料構成基材，從而可提供伸縮性優異、並且即使進行反覆之伸縮操作亦能維持良好之伸縮性之黏著片材。例如，將配置於黏著片材上之複數個晶片分複數次進行拾取之情形時，若使用本發明之黏著片材，則在拾取時能夠使該黏著片材伸長，從而良好地拾取一部分晶片，其後，黏著片材收縮恢復從而實現良好之保管性。又，即使反覆進行此種操作之情形時，亦會表現出伸縮性、維持良好之拾取性及保管性。 A. Outline of Adhesive Sheet Fig. 1 is a schematic cross-sectional view of an adhesive sheet according to a preferred embodiment of the present invention. The
本發明之黏著片材以伸長前之黏著片材片為基準，在23℃之環境下、在施加張力而使黏著片材伸長150%之狀態下保持5分鐘並釋放張力時之尺寸恢復率(以下，亦簡稱為恢復率)較佳為80%以上、更佳為82%以上、進而較佳為85%以上。該恢復率越大越佳，上限值例如為95%(較佳為98%)。本說明書中，恢復率係藉由下述之方法來測定。 對寬度10 mm、長度100 mm之黏著片材片，在長度方向記錄初始評價點間距離L0 ＝50 mm之標線。以夾頭間距離70 mm安裝於拉伸試驗機，以拉伸速度300 mm/分鐘使其伸長至150%(例如，夾頭間距離：145 mm)，保持伸長狀態5分鐘後，測定伸長評價點間距離L1 。其後釋放張力並測定5分鐘後之評價點間距離L，藉由下式求出恢復率(%)。 恢復率(%)＝{(伸長評價點間距離L1 －評價點間距離L)/(伸長評價點間距離L1 －初始評價點間距離L0 )}×100 上述恢復率例如可藉由適當地選擇構成基材之樹脂種類、調整該樹脂之結構(例如聚胺基甲酸酯膜)、PP彈性體膜、St彈性體膜等來控制。The adhesive sheet of the present invention is based on the adhesive sheet sheet before elongation, and the dimensional recovery rate when the adhesive sheet is stretched 150% by applying tension under an environment of 23°C for 5 minutes and the tension is released ( Hereinafter, also referred to simply as the recovery rate) is preferably 80% or more, more preferably 82% or more, and still more preferably 85% or more. The larger the recovery rate, the better, and the upper limit is, for example, 95% (preferably 98%). In this manual, the recovery rate is measured by the following method. For an adhesive sheet with a width of 10 mm and a length of 100 mm, a mark line with the distance L 0 between the initial evaluation points of 50 mm is recorded in the length direction. Install it on a tensile testing machine with a distance between the chucks of 70 mm, extend it to 150% at a tensile speed of 300 mm/min (for example, the distance between the chucks: 145 mm), keep the elongation state for 5 minutes, and measure the elongation evaluation The distance between the points L 1 . After that, the tension is released and the distance L between the evaluation points after 5 minutes is measured, and the recovery rate (%) is obtained by the following formula. Recovery rate (%)={(distance between elongation evaluation points L 1 －distance between evaluation points L)/(distance between elongation evaluation points L 1 －distance between initial evaluation points L 0 )}×100 The above recovery rate can be, for example, Appropriate selection of the type of resin constituting the substrate, adjustment of the structure of the resin (for example, polyurethane film), PP elastomer film, St elastomer film, etc. are controlled.
本發明之黏著片材對聚矽氧鏡面晶圓(例如，厚度20 μm)之黏著力較佳為0.1 N/20 mm以上、更佳為0.5 N/20 mm～20 N/20 mm、進而較佳為0.8 N/20 mm～15 N/20 mm。若為此種範圍，則例如能夠得到作為電子零件之製造中使用之臨時固定用片材有用之黏著片材。係指在23℃之環境下、藉由基於JIS Z 0237：2000之方法(貼合條件：2 kg輥往返1次、剝離速度：300 mm/分鐘、剝離角度90°)測定之黏著力。The adhesive force of the adhesive sheet of the present invention to a polysilicon mirror wafer (for example, a thickness of 20 μm) is preferably 0.1 N/20 mm or more, more preferably 0.5 N/20 mm-20 N/20 mm, and more Preferably, it is 0.8 N/20 mm～15 N/20 mm. If it is such a range, for example, an adhesive sheet useful as a temporary fixing sheet used in the manufacture of electronic parts can be obtained. It refers to the adhesive force measured by the method based on JIS Z 0237:2000 (laminating conditions: 2 kg roller reciprocating once, peeling speed: 300 mm/min, peeling angle 90°) under an environment of 23°C.
本發明之黏著片材之厚度較佳為30 μm～500 μm、更佳為40 μm～300 μm、進而較佳為50 μm～200 μm。The thickness of the adhesive sheet of the present invention is preferably 30 μm to 500 μm, more preferably 40 μm to 300 μm, and still more preferably 50 μm to 200 μm.
本發明之黏著片材在23℃下之斷裂伸長率較佳為100%以上、更佳為250%以上、進而較佳為400%～1000%、尤佳為500%～900%。上述斷裂伸長率可依據JIS K 7113進行測定。The elongation at break of the adhesive sheet of the present invention at 23° C. is preferably 100% or more, more preferably 250% or more, further preferably 400% to 1000%, particularly preferably 500% to 900%. The above-mentioned elongation at break can be measured in accordance with JIS K 7113.
本發明之黏著片材在23℃下之25%模數較佳為1 N/10 mm～100 N/10 mm、更佳為1.5 N/10 mm～50 N/10 mm、進而較佳為2 N/10 mm～20 N/10 mm。一個實施方式中，本發明之黏著片材在23℃下之25%模數為20 N/10 mm以下。若為此種範圍，則可得到良好之擴展性。25%模數之測定方法如下。 ＜25%模數測定方法＞ 將黏著片材切斷成寬度10 mm、長度100 mm之尺寸，以夾頭間距離成為50 mm之方式安裝於附恆溫槽之拉伸試驗機，以拉伸速度：300 mm/分鐘沿長度方向對黏著片材進行拉伸，將伸長25%時之應力作為25%模數(N/10 mm)。The 25% modulus of the adhesive sheet of the present invention at 23°C is preferably 1 N/10 mm to 100 N/10 mm, more preferably 1.5 N/10 mm to 50 N/10 mm, and more preferably 2 N/10 mm～20 N/10 mm. In one embodiment, the 25% modulus of the adhesive sheet of the present invention at 23° C. is 20 N/10 mm or less. If it is in this range, good scalability can be obtained. The measuring method of 25% modulus is as follows. ＜25% modulus measuring method＞ Cut the adhesive sheet into a size of 10 mm in width and 100 mm in length, and install it on a tensile testing machine with a constant temperature bath so that the distance between the chucks becomes 50 mm. The tensile speed: 300 mm/min along the length direction The adhesive sheet is stretched, and the stress at 25% elongation is taken as the 25% modulus (N/10 mm).
上述黏著片材只要可得到本發明之效果，則可進而具備任意適當之其他層。又，亦可提供在直到黏著片材供於實用前之期間將隔離膜配置於黏著劑層上從而保護黏著劑層的附隔離膜之黏著片材。The above-mentioned pressure-sensitive adhesive sheet may further include any appropriate other layer as long as the effect of the present invention can be obtained. In addition, it is also possible to provide an adhesive sheet with a release film to protect the adhesive layer by disposing the release film on the adhesive layer during the period until the adhesive sheet is used for practical use.
B. 基材 如上所述，作為構成上述基材之材料，使用聚胺基甲酸酯系樹脂、苯乙烯系彈性體或丙烯系彈性體。 B. Substrate As described above, as the material constituting the aforementioned substrate, polyurethane-based resin, styrene-based elastomer, or acrylic-based elastomer is used.
上述聚胺基甲酸酯系樹脂係指具有胺基甲酸酯鍵之樹脂，亦包含丙烯酸系樹脂-聚胺基甲酸酯共聚物、或聚酯-聚胺基甲酸酯共聚物。聚胺基甲酸酯系樹脂代表性而言係藉由使多元醇與多異氰酸酯反應來得到。作為多元醇，只要在分子中具有2個以上羥基，則無特別限定，可使用任意適當之多元醇。例如，可列舉聚丙烯酸系多元醇、聚酯多元醇、聚醚多元醇等。其中較佳為聚酯多元醇或聚醚多元醇，若使用該等多元醇，則本發明之效果變得更顯著。上述多元醇可單獨使用或組合2種以上使用。The above-mentioned polyurethane-based resin refers to a resin having a urethane bond, and also includes an acrylic resin-urethane copolymer or a polyester-urethane copolymer. The polyurethane resin is typically obtained by reacting a polyol and a polyisocyanate. The polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and any appropriate polyol can be used. For example, polyacrylic polyol, polyester polyol, polyether polyol, etc. can be mentioned. Among them, polyester polyols or polyether polyols are preferred. If these polyols are used, the effect of the present invention becomes more remarkable. The above-mentioned polyols can be used alone or in combination of two or more kinds.
上述聚丙烯酸系多元醇代表性而言係藉由使(甲基)丙烯酸酯與具有羥基之單體共聚來獲得。作為(甲基)丙烯酸酯，例如，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯等。作為具有羥基之單體，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2-羥基戊酯等(甲基)丙烯酸之羥基烷基酯；甘油、三羥甲基丙烷等多元醇之(甲基)丙烯酸單酯；N-羥甲基(甲基)丙烯醯胺等。該等可單獨使用或組合2種以上使用。The above-mentioned polyacrylic polyol is typically obtained by copolymerizing (meth)acrylate and a monomer having a hydroxyl group. Examples of (meth)acrylates include methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2 (meth)acrylate -Hydroxyalkyl esters of (meth)acrylic acid such as hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, etc.; of polyols such as glycerol and trimethylolpropane ( Meth) acrylic acid monoester; N-methylol (meth)acrylamide and the like. These can be used individually or in combination of 2 or more types.
上述聚丙烯酸系多元醇除上述單體成分以外可共聚有其他單體。作為其他單體，只要可共聚，則可使用任意適當之單體。具體而言，可列舉(甲基)丙烯酸等不飽和單羧酸；馬來酸等不飽和二羧酸以及其酐及單酯或二酯類；(甲基)丙烯腈等不飽和腈類；(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺等不飽和醯胺類；乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；甲基乙烯基醚等乙烯基醚類；乙烯、丙烯等α-烯烴類；氯乙烯、偏二氯乙烯等鹵化α,β-不飽和脂肪族單體；苯乙烯、α-甲基苯乙烯等α,β-不飽和芳香族單體等。該等可單獨使用或組合2種以上使用。The above-mentioned polyacrylic polyol may be copolymerized with other monomers in addition to the above-mentioned monomer components. As the other monomer, any appropriate monomer can be used as long as it can be copolymerized. Specifically, unsaturated monocarboxylic acids such as (meth)acrylic acid; unsaturated dicarboxylic acids such as maleic acid and anhydrides and monoesters or diesters thereof; unsaturated nitriles such as (meth)acrylonitrile; Unsaturated amides such as (meth)acrylamide and N-methylol(meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether ; Α-olefins such as ethylene and propylene; halogenated α, β-unsaturated aliphatic monomers such as vinyl chloride and vinylidene chloride; α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene Wait. These can be used individually or in combination of 2 or more types.
上述聚酯多元醇代表性而言係藉由使多元酸成分與多元醇成分反應來獲得。作為多元酸成分，例如，可列舉鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、聯苯二羧酸、四氫鄰苯二甲酸等芳香族二羧酸；草酸、琥珀酸、丙二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、十二烷二羧酸、十八烷二羧酸、酒石酸、烷基琥珀酸、亞麻油酸、馬來酸、富馬酸、中康酸、檸康酸、伊康酸等脂肪族二羧酸；六氫鄰苯二甲酸、四氫鄰苯二甲酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸等脂環式二羧酸；或該等之酸酐、烷基酯、醯鹵等反應性衍生物等。該等可單獨使用或組合2種以上使用。The above-mentioned polyester polyol is typically obtained by reacting a polyacid component and a polyol component. Examples of polybasic acid components include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. , Biphenyl dicarboxylic acid, tetrahydrophthalic acid and other aromatic dicarboxylic acids; oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decane Diacid, decane dicarboxylic acid, dodecane dicarboxylic acid, octadecane dicarboxylic acid, tartaric acid, alkyl succinic acid, linoleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, Aliphatic dicarboxylic acids such as itaconic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Carboxylic acid; or reactive derivatives such as acid anhydrides, alkyl esters, and halides. These can be used individually or in combination of 2 or more types.
作為上述多元醇成分，可列舉乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、戊二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1-甲基-1,3-丁二醇、2-甲基-1,3-丁二醇、1-甲基-1,4-戊二醇、2-甲基-1,4-戊二醇、1,2-二甲基-新戊二醇、2,3-二甲基-新戊二醇、1-甲基-1,5-戊二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、1,2-二甲基丁二醇、1,3-二甲基丁二醇、2,3-二甲基丁二醇、1,4-二甲基丁二醇、二乙二醇、三乙二醇、聚乙二醇、二丙二醇、聚丙二醇、1,4-環己烷二甲醇、1,4-環己二醇、雙酚A、雙酚F、氫化雙酚A、氫化雙酚F等。該等可單獨使用或組合2種以上使用。As the above-mentioned polyol component, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1 ,6-Hexanediol, 1,8-octanediol, 1,10-decanediol, 1-methyl-1,3-butanediol, 2-methyl-1,3-butanediol, 1 -Methyl-1,4-pentanediol, 2-methyl-1,4-pentanediol, 1,2-dimethyl-neopentyl glycol, 2,3-dimethyl-neopentyl glycol , 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-dimethylbutanediol , 1,3-dimethylbutanediol, 2,3-dimethylbutanediol, 1,4-dimethylbutanediol, diethylene glycol, triethylene glycol, polyethylene glycol, two Propylene glycol, polypropylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, etc. These can be used individually or in combination of 2 or more types.
上述聚醚多元醇代表性而言係藉由使環氧烷開環聚合並與多元醇加成來獲得。作為多元醇，例如，可列舉乙二醇、二乙二醇、丙二醇、二丙二醇、甘油、三羥甲基丙烷等。作為環氧烷，例如，可列舉環氧乙烷、環氧丙烷、環氧丁烷、環氧苯乙烷、四氫呋喃等。該等可單獨使用或組合2種以上使用。The above-mentioned polyether polyol is typically obtained by ring-opening polymerization of alkylene oxide and addition with polyol. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and the like. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, and the like. These can be used individually or in combination of 2 or more types.
作為上述多異氰酸酯，例如，可列舉四亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、1,4-丁烷二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2-甲基戊烷-1,5-二異氰酸酯、3-甲基戊烷-1,5-二異氰酸酯等脂肪族二異氰酸酯；異佛爾酮二異氰酸酯、氫化苯二甲基二異氰酸酯、4,4'-環己基甲烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基伸環己基二異氰酸酯、1,3-雙(異氰酸根合甲基)環己烷等脂環族二異氰酸酯；甲伸苯基二異氰酸酯、2,2'-二苯基甲烷二異氰酸酯、2,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基二甲基甲烷二異氰酸酯、4,4'-二苄基二異氰酸酯、1,5-萘二異氰酸酯、苯二甲基二異氰酸酯、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯等芳香族二異氰酸酯；二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、α,α,α,α-四甲基苯二甲基二異氰酸酯等芳香脂肪族二異氰酸酯等。該等可單獨使用或組合2種以上使用。As the polyisocyanate, for example, tetramethylene diisocyanate, dodecane diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene Methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1 , 5-diisocyanate and other aliphatic diisocyanates; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methyl isocyanate Cyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane and other alicyclic diisocyanates; phenylmethylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4 '-Diphenylmethane Diisocyanate, 4,4'-Diphenylmethane Diisocyanate, 4,4'-Diphenyldimethylmethane Diisocyanate, 4,4'-Dibenzyl Diisocyanate, 1,5 -Naphthalene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and other aromatic diisocyanates; dialkyl diphenylmethane diisocyanate, tetraalkyl Aromatic aliphatic diisocyanates such as diphenylmethane diisocyanate, α,α,α,α-tetramethylxylylene diisocyanate, etc. These can be used individually or in combination of 2 or more types.
上述聚胺基甲酸酯系樹脂之重量平均分子量較佳為5000～600000、進而較佳為10000～400000。上述聚胺基甲酸酯系樹脂之酸值較佳為10以上、進而較佳為10～50、尤佳為20～45。再者，本說明書中，重量平均分子量可藉由GPC(溶劑：THF)進行測定。The weight average molecular weight of the polyurethane-based resin is preferably 5,000 to 600,000, and more preferably 10,000 to 400,000. The acid value of the polyurethane resin is preferably 10 or more, more preferably 10-50, and particularly preferably 20-45. In addition, in this specification, the weight average molecular weight can be measured by GPC (solvent: THF).
作為上述苯乙烯系彈性體，例如，可列舉苯乙烯・丁二烯・苯乙烯三嵌段共聚物彈性體(SBS)、苯乙烯・異戊二烯・苯乙烯三嵌段共聚物彈性體(SIS)、苯乙烯-乙烯・丁烯共聚物彈性體(SEB)、苯乙烯-乙烯・丙烯共聚物彈性體(SEP)、苯乙烯-乙烯・丁烯-苯乙烯共聚物彈性體(SEBS)、苯乙烯-乙烯・丁烯-乙烯共聚物彈性體(SEBC)、氫化苯乙烯・丁二烯彈性體(HSBR)、苯乙烯-乙烯・丙烯-苯乙烯共聚物彈性體(SEPS)、苯乙烯-乙烯・乙烯・丙烯-苯乙烯共聚物彈性體(SEEPS)、苯乙烯-丁二烯・丁烯-苯乙烯共聚物彈性體(SBBS)等。其中較佳為SIS、SEBS。As the above-mentioned styrene elastomer, for example, styrene, butadiene, styrene triblock copolymer elastomer (SBS), styrene, isoprene, styrene triblock copolymer elastomer ( SIS), styrene-ethylene·butene copolymer elastomer (SEB), styrene-ethylene·propylene copolymer elastomer (SEP), styrene-ethylene·butene-styrene copolymer elastomer (SEBS), Styrene-ethylene·butene-ethylene copolymer elastomer (SEBC), hydrogenated styrene·butadiene elastomer (HSBR), styrene-ethylene·propylene-styrene copolymer elastomer (SEPS), styrene- Ethylene, ethylene, propylene-styrene copolymer elastomer (SEEPS), styrene-butadiene, butene-styrene copolymer elastomer (SBBS), etc. Among them, SIS and SEBS are preferred.
上述苯乙烯系彈性體中，源自苯乙烯之結構單元之含有比率較佳為30重量%以下、更佳為20重量%以下。若為此種範圍，則能夠得到伸縮性優異之黏著片材。In the above-mentioned styrene-based elastomer, the content ratio of the styrene-derived structural unit is preferably 30% by weight or less, more preferably 20% by weight or less. If it is such a range, an adhesive sheet excellent in stretchability can be obtained.
上述苯乙烯系彈性體之重量平均分子量較佳為1萬～50萬、更佳為5萬～30萬。若為此種範圍，則能夠得到伸縮性優異之黏著片材。The weight average molecular weight of the styrene-based elastomer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000. If it is such a range, an adhesive sheet excellent in stretchability can be obtained.
上述丙烯系彈性體為包含源自丙烯之結構單元之彈性體，一個實施方式中，為包含源自丙烯之結構單元之共聚物。上述丙烯系彈性體中，源自丙烯之結構單元之含有比率較佳為30重量%～90重量%、更佳為50重量%～90重量%。若為此種範圍，則能夠得到伸縮性優異之黏著片材。The above-mentioned propylene-based elastomer is an elastomer containing a propylene-derived structural unit, and in one embodiment, is a copolymer containing a propylene-derived structural unit. In the above-mentioned propylene-based elastomer, the content ratio of the propylene-derived structural unit is preferably 30% by weight to 90% by weight, more preferably 50% by weight to 90% by weight. If it is such a range, an adhesive sheet excellent in stretchability can be obtained.
作為構成上述丙烯系彈性體之其他共聚成分，例如，可列舉源自乙烯、1-丁烯、2-甲基丙烯、1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯等單體之結構單元。其中，較佳為乙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯等，尤佳為乙烯、1-丁烯。該等可單獨使用或組合2種以上使用。一個實施方式中，上述丙烯系彈性體包含源自乙烯之結構單元。上述丙烯系彈性體中，源自乙烯之結構單元之含有比率較佳為5重量%～20重量%、更佳為8重量%～15重量%。As other copolymerization components constituting the above-mentioned propylene-based elastomer, for example, those derived from ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, and 1-hexene can be cited. , 4-methyl-1-pentene, 1-octene and other monomer structural units. Among them, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc. are preferred, and ethylene and 1-butene are particularly preferred. These can be used individually or in combination of 2 or more types. In one embodiment, the above-mentioned propylene-based elastomer contains a structural unit derived from ethylene. In the above-mentioned propylene-based elastomer, the content ratio of the ethylene-derived structural unit is preferably 5 wt% to 20 wt%, more preferably 8 wt% to 15 wt%.
丙烯系彈性體之重量平均分子量較佳為1萬～50萬、更佳為5萬～30萬。若為此種範圍，則能夠得到伸縮性優異之黏著片材。The weight average molecular weight of the propylene-based elastomer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000. If it is such a range, an adhesive sheet excellent in stretchability can be obtained.
一個實施方式中，上述基材為單層構成。In one embodiment, the above-mentioned substrate has a single-layer structure.
另一實施方式中，上述基材為多層構成。基材為多層構成之情形時，較佳為構成基材之層中至少1層如上所述包含聚胺基甲酸酯系樹脂、苯乙烯系彈性體或丙烯系彈性體。包含聚胺基甲酸酯系樹脂、苯乙烯系彈性體或丙烯系彈性體之層之合計厚度相對於基材之總厚較佳為50%以上、更佳為70%以上。In another embodiment, the above-mentioned substrate has a multilayer structure. When the substrate has a multilayer structure, it is preferable that at least one of the layers constituting the substrate contains a polyurethane-based resin, a styrene-based elastomer, or an acrylic-based elastomer as described above. The total thickness of the layers containing polyurethane resin, styrene elastomer, or acrylic elastomer is preferably 50% or more, more preferably 70% or more with respect to the total thickness of the substrate.
一個實施方式中，上述基材包含脂肪酸醯胺。藉由含有脂肪酸醯胺，能夠得到具有適度之滑動性之基材。具備包含脂肪酸醯胺之基材之黏著片材之搬送性優異，又，對擴展器之平台之抓力優異、在擴展步驟中能夠良好伸長。上述基材為多層構成、並且在基材之單側配置有黏著劑層之情形時，較佳為至少在位於黏著劑層之相反側之該基材之最外層含有脂肪酸醯胺。In one embodiment, the above-mentioned base material contains fatty acid amides. By containing fatty acid amide, a base material with moderate sliding properties can be obtained. The adhesive sheet with a base material containing fatty acid amides has excellent transportability, and also has excellent grip on the platform of the expander, and can stretch well during the expansion step. When the substrate is of a multilayer structure and an adhesive layer is arranged on one side of the substrate, it is preferable that at least the outermost layer of the substrate located on the opposite side of the adhesive layer contains fatty acid amides.
作為脂肪酸醯胺，例如，可列舉月桂酸醯胺、棕櫚酸醯胺、硬脂酸醯胺、山萮酸醯胺、油酸醯胺、芥酸醯胺、羥基硬脂酸醯胺等單醯胺類、伸乙基雙月桂酸醯胺、伸乙基雙硬脂酸醯胺、伸乙基雙羥基硬脂酸醯胺、伸乙基雙山萮酸醯胺、六亞甲基雙硬脂酸醯胺、伸乙基雙油酸醯胺、六亞甲基雙油酸醯胺等。構成脂肪酸醯胺系潤滑劑之脂肪酸之碳數較佳為12以上、更佳為12～30、進而較佳為14～28。Examples of fatty acid amides include lauric acid amides, palmitic acid amides, stearic acid amides, behenic acid amides, oleic acid amides, erucic acid amides, and hydroxystearate amides. Amines, ethylenebislaurate, ethylenebisstearate, ethylenebishydroxystearate, ethylenebisbehenate, hexamethylene bisstearate Acid amide, ethylene dioleic acid amide, hexamethylene dioleic acid amide, etc. The carbon number of the fatty acid constituting the fatty acid amide-based lubricant is preferably 12 or more, more preferably 12-30, and still more preferably 14-28.
一個實施方式中，相對於基材100重量份，脂肪酸醯胺之含有比率較佳為0.001重量份～10重量份、更佳為0.01重量份～3重量份。In one embodiment, the content ratio of the fatty acid amide is preferably 0.001 parts by weight to 10 parts by weight, more preferably 0.01 parts by weight to 3 parts by weight, relative to 100 parts by weight of the substrate.
一個實施方式中，上述基材為多層構成、並且在基材之單側配置有黏著劑層之情形時，位於黏著劑層之相反側之該基材之最外層中之脂肪酸醯胺之含有比率相對於該最外層100重量份較佳為0.001重量份～10重量份、更佳為0.01重量份～3重量份。In one embodiment, when the substrate has a multilayer structure and an adhesive layer is arranged on one side of the substrate, the content ratio of the fatty acid amide in the outermost layer of the substrate on the opposite side of the adhesive layer It is preferably 0.001 parts by weight to 10 parts by weight, more preferably 0.01 parts by weight to 3 parts by weight relative to 100 parts by weight of the outermost layer.
上述基材以伸長前為基準，在23℃之環境下、在施加張力而使基材伸長150%之狀態下保持5分鐘並釋放張力時之恢復率較佳為80%以上、更佳為82%以上、進而較佳為85%以上。該恢復率越大越佳，上限值例如為95%(較佳為98%)。The above-mentioned substrate is based on the pre-extension, and the recovery rate is preferably 80% or more, more preferably 82% when the substrate is stretched 150% by applying tension for 5 minutes under an environment of 23°C and the tension is released. % Or more, more preferably 85% or more. The larger the recovery rate, the better, and the upper limit is, for example, 95% (preferably 98%).
上述基材在23℃下之斷裂伸長率較佳為10%以上、更佳為250%以上、進而較佳為250%～1000%、尤佳為250%～800%。The elongation at break of the substrate at 23° C. is preferably 10% or more, more preferably 250% or more, still more preferably 250% to 1000%, particularly preferably 250% to 800%.
上述基材在23℃下之25%模數較佳為1 N/10 mm～100 N/10 mm、更佳為2 N/10 mm～60 N/10 mm、進而較佳為3 N/10 mm～30 N/10 mm。一個實施方式中，基材在23℃下之25%模數為30 N/10 mm以下。若為此種範圍，則可得到良好之擴展性。The 25% modulus of the substrate at 23°C is preferably 1 N/10 mm to 100 N/10 mm, more preferably 2 N/10 mm to 60 N/10 mm, and more preferably 3 N/10 mm～30 N/10 mm. In one embodiment, the 25% modulus of the substrate at 23° C. is 30 N/10 mm or less. If it is in this range, good scalability can be obtained.
上述基材之依據JIS K 6253測定之硬度較佳為80 A～100 A、更佳為85 A～95 A。若為此種範圍，則可得到良好之擴展性。一個實施方式中，使用上述聚胺基甲酸酯系樹脂作為構成基材之材料，該基材之上述硬度為80 A～100 A(較佳為85 A～95 A)。若如此，則本發明之效果變得顯著。The hardness of the base material measured in accordance with JIS K 6253 is preferably 80 A to 100 A, more preferably 85 A to 95 A. If it is in this range, good scalability can be obtained. In one embodiment, the above-mentioned polyurethane resin is used as the material constituting the substrate, and the above-mentioned hardness of the substrate is 80 A to 100 A (preferably 85 A to 95 A). If so, the effect of the present invention becomes remarkable.
上述基材之厚度可根據期望之強度或柔軟性、以及使用目的等而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～500 μm、進而較佳為1 μm～300 μm、尤佳為3 μm～200 μm、最佳為5 μm～100 μm。The thickness of the above-mentioned base material can be set to any appropriate thickness according to the desired strength or flexibility, purpose of use, and the like. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 500 μm, still more preferably 1 μm to 300 μm, particularly preferably 3 μm to 200 μm, most preferably 5 μm to 100 μm.
上述基材相對於至少一面之SUS304板之動摩擦力較佳為0.1 N～7.0 N、更佳為0.1 N～5.0 N、進而較佳為0.1 N～3.0 N。具備動摩擦係數為此種範圍之基材之黏著片材之搬送性優異，又，對擴展器之平台之抓力優異，在擴展步驟中能夠良好地伸長。The dynamic friction force of the substrate with respect to at least one side of the SUS304 plate is preferably 0.1 N to 7.0 N, more preferably 0.1 N to 5.0 N, and still more preferably 0.1 N to 3.0 N. The adhesive sheet having a substrate with a dynamic friction coefficient in this range has excellent transportability, and has excellent grip on the platform of the extender, and can stretch well during the expansion step.
C. 黏著劑層 上述黏著劑層由任意適當之黏著劑構成。作為黏著劑，可列舉丙烯酸系黏著劑、聚矽氧系黏著劑、乙烯基烷基醚系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、胺基甲酸酯系黏著劑、氟系黏著劑、苯乙烯-二烯嵌段共聚物系黏著劑、活性能量線硬化型黏著劑等。一個實施方式中，使用丙烯酸系黏著劑。 C. Adhesive layer The above-mentioned adhesive layer is composed of any suitable adhesive. Examples of adhesives include acrylic adhesives, silicone adhesives, vinyl alkyl ether adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, fluorine Adhesives, styrene-diene block copolymer adhesives, active energy ray-curable adhesives, etc. In one embodiment, an acrylic adhesive is used.
作為上述丙烯酸系黏著劑，例如，可列舉以使用1種或2種以上(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)作為基礎聚合物的丙烯酸系黏著劑等。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，可良好地使用具有碳數為4～18之直鏈狀或支鏈狀之烷基之(甲基)丙烯酸烷基酯。As the above-mentioned acrylic adhesive, for example, an acrylic polymer (homopolymer or copolymer) that uses one or more (meth)acrylic acid alkyl esters as a monomer component is used as a base polymer. Department of adhesives, etc. As specific examples of the alkyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate Base) butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate , 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, ten (meth)acrylate Trialkyl ester, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, ( C1-20 alkyl (meth)acrylates such as stearyl meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and the like. Among them, alkyl (meth)acrylates having a linear or branched alkyl group having 4 to 18 carbon atoms can be used satisfactorily.
相對於丙烯酸系聚合物100重量份，源自(甲基)丙烯酸烷基酯之結構單元之含有比率較佳為50重量份、更佳為60重量份以上、進而較佳為70重量份以上、尤佳為80重量份～97重量份。With respect to 100 parts by weight of the acrylic polymer, the content ratio of the structural unit derived from the alkyl (meth)acrylate is preferably 50 parts by weight, more preferably 60 parts by weight or more, and still more preferably 70 parts by weight or more, Particularly preferably, it is from 80 parts by weight to 97 parts by weight.
出於凝集力、耐熱性、交聯性等之改性之目的，上述丙烯酸系聚合物根據需要可包含對應於可與上述(甲基)丙烯酸烷基酯共聚之其他單體的單元。作為此種單體，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-二甲基胺基乙酯、(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-氧代六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧代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、乙烯基哌𠯤、乙烯基吡𠯤、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基嗎啉、N-乙烯基羧酸醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯系單體；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、聚矽氧(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。該等單體可單獨使用或組合2種以上使用。For the purpose of modification of cohesive force, heat resistance, crosslinkability, etc., the acrylic polymer may contain units corresponding to other monomers copolymerizable with the alkyl (meth)acrylate as needed. Examples of such monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride, Iconic anhydride and other acid anhydride monomers; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxy(meth)acrylate Hydroxy-containing monomers such as octyl ester, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc.; styrene sulfonic acid, allyl sulfonic acid Acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide propanesulfonic acid, (meth)acrylic acid sulfopropyl, (meth)acrylamide-2-methylpropanesulfonic acid Acid and other sulfonic acid group-containing monomers; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol( (N-substituted) amide-based monomers such as meth)acrylamide, N-methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, N,N (meth)acrylic acid -Aminoalkyl (meth)acrylate monomers such as dimethylaminoethyl and tert-butylaminoethyl (meth)acrylate; methoxyethyl (meth)acrylate, (meth) Yl) ethoxyethyl acrylate and other (meth) alkoxyalkyl acrylate monomers; N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl horse Maleimines such as lyimines and N-phenylmaleimines; N-methylikonimines, N-ethylikonimines, N-butylikon Ikonimines, N-octyl Ikonimines, N-2-Ethylhexyl Ikonimines, N-cyclohexyl Ikonimines, N-Lauryl Ikonimines, etc. Imine-based monomer; N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxohexamethylene succinimide, N-( Succinimidyl monomers such as meth)acryloyl-8-oxoctamethylene succinimidyl; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrole Pyridone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperidine, vinyl pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl morpholine, N-vinyl carboxylate Vinyl monomers such as amides, styrene, α-methylstyrene, and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; (meth)acrylic acid shrinkage Epoxy-containing acrylic monomers such as glycerides; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, (meth)acrylic acid Methoxy polypropylene glycol ester and other glycol-based acrylate monomers; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane (meth)acrylate, etc. have heterocycles, halogen atoms, Acrylic monomers such as silicon atoms; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Multifunctional monomers such as acrylates, epoxy acrylates, polyester acrylates, and acrylic urethanes; olefin monomers such as isoprene, butadiene, and isobutylene; vinyl ethers such as vinyl ethers Body and so on. These monomers can be used individually or in combination of 2 or more types.
一個實施方式中，上述丙烯酸系聚合物包含源自具有極性官能基之單體之結構單元。基材包含脂肪酸醯胺之情形時，若使用包含源自具有極性官能基之單體之結構單元之丙烯酸系聚合物，則能夠防止脂肪酸醯胺向黏著劑層之轉移，能夠得到耐久性優異之黏著片材。相對於丙烯酸系聚合物100重量份，源自具有極性官能基之單體之結構單元之含有比率較佳為0.01重量份～40重量份、更佳為1重量份～30重量份、進而較佳為2重量份～20重量份、尤佳為3重量份～15重量份。作為上述極性官能基，例如，可列舉羧基、羥基等。In one embodiment, the above-mentioned acrylic polymer contains a structural unit derived from a monomer having a polar functional group. When the base material contains fatty acid amides, if acrylic polymers containing structural units derived from monomers with polar functional groups are used, the fatty acid amides can be prevented from being transferred to the adhesive layer, and an excellent durability can be obtained. Adhesive sheet. Relative to 100 parts by weight of the acrylic polymer, the content ratio of the structural unit derived from the monomer having a polar functional group is preferably 0.01 part by weight to 40 parts by weight, more preferably 1 part by weight to 30 parts by weight, and still more preferably It is 2 parts by weight to 20 parts by weight, particularly preferably 3 parts by weight to 15 parts by weight. As said polar functional group, a carboxyl group, a hydroxyl group, etc. are mentioned, for example.
一個實施方式中，作為具有極性官能基之單體，可使用(甲基)丙烯酸。該實施方式中，相對於丙烯酸系聚合物100重量份，源自(甲基)丙烯酸之結構單元之含有比率較佳為1重量份～40重量份、更佳為1重量份～20重量份、進而較佳為1重量份～10重量份。In one embodiment, (meth)acrylic acid can be used as a monomer having a polar functional group. In this embodiment, relative to 100 parts by weight of the acrylic polymer, the content ratio of the structural unit derived from (meth)acrylic acid is preferably 1 part by weight to 40 parts by weight, more preferably 1 part by weight to 20 parts by weight, More preferably, it is 1 part by weight to 10 parts by weight.
上述黏著劑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 above-mentioned adhesive may contain any appropriate additives as required. Examples of the additives include initiators, crosslinking agents, adhesion-imparting agents, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, and peeling agents. Regulators, softeners, surfactants, flame retardants, antioxidants, etc.
一個實施方式中，上述黏著劑包含交聯劑。In one embodiment, the adhesive includes a crosslinking agent.
作為上述交聯劑，例如，可列舉異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、以及脲系交聯劑、金屬烷醇鹽系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。其中較佳為異氰酸酯系交聯劑或環氧系交聯劑。Examples of the above-mentioned crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, and metal alkoxide-based crosslinking agents. Linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, azoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent Wait. Among them, an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent is preferred.
作為上述異氰酸酯系交聯劑之具體例，可列舉伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族多異氰酸酯類；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類；2,4-甲伸苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類；三羥甲基丙烷/甲伸苯基二異氰酸酯三聚物加成物(Nippon Polyurethane Industry公司製造、商品名「CORONATE L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(Nippon Polyurethane Industry公司製造、商品名「CORONATE HL」)、六亞甲基二異氰酸酯之異氰脲酸酯體(Nippon Polyurethane Industry公司製造、商品名「CORONATE HX」)等異氰酸酯加成物；等。異氰酸酯系交聯劑之含量可根據期望之黏著力、黏著劑層之彈性等設定為任意適當之量，相對於基礎聚合物100重量份，代表性而言為0.1重量份～20重量份，更佳為0.5重量份～10重量份。Specific examples of the above-mentioned isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone Alicyclic isocyanates such as diisocyanates; aromatic isocyanates such as 2,4-methylenephenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/ Phenylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "CORONATE L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Industry) Manufacture, trade name "CORONATE HL"), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "CORONATE HX") and other isocyanate adducts; etc. The content of the isocyanate-based crosslinking agent can be set to any appropriate amount according to the desired adhesive force, the elasticity of the adhesive layer, etc., relative to 100 parts by weight of the base polymer, typically 0.1 to 20 parts by weight, more It is preferably 0.5 parts by weight to 10 parts by weight.
作為前述環氧系交聯劑，例如，可列舉N,N,N',N'-四縮水甘油基間苯二胺、二縮水甘油基苯胺、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷(三菱瓦斯化學公司製造、商品名「TETRAD C」)、1,6-己二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 1600」)、新戊二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 1500NP」)、乙二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 40E」)、丙二醇二縮水甘油醚(共榮社化學公司製造、商品名「Epolight 70P」)、聚乙二醇二縮水甘油醚(日本油脂公司製造、商品名「EPIOL E-400」)、聚丙二醇二縮水甘油醚(日本油脂公司製造、商品名「EPIOL P-200」)、山梨糖醇聚縮水甘油醚(Nagase ChemteX公司製造、商品名「DENACOL EX-611」)、甘油聚縮水甘油醚(Nagase ChemteX公司製造、商品名「DENACOL EX-314」)、季戊四醇聚縮水甘油醚、聚甘油聚縮水甘油醚(Nagase ChemteX公司製造、商品名「DENACOL EX-512」)、山梨糖醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、三(2-羥基乙基)異氰脲酸三縮水甘油酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚、分子內具有2個以上環氧基之環氧系樹脂等。環氧系交聯劑之含量可根據期望之黏著力、黏著劑層之彈性等而設定為任意適當之量，相對於基礎聚合物100重量份，代表性而言為0.01重量份～10重量份、更佳為0.03重量份～5重量份。As the epoxy-based crosslinking agent, for example, N,N,N',N'-tetraglycidyl m-phenylenediamine, diglycidyl aniline, 1,3-bis(N,N-glycidyl (Methylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1600") , Neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Company, trade name "Epolight 1500NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Company, trade name "Epolight 40E"), propylene glycol two Glycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., brand name "Epolight 70P"), polyethylene glycol diglycidyl ether (manufactured by Nippon Oil & Fat Co., Ltd., brand name "EPIOL E-400"), polypropylene glycol diglycidyl ether ( Nippon Oil & Fat Co., Ltd., brand name "EPIOL P-200"), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX, brand name "DENACOL EX-611"), glycerol polyglycidyl ether (manufactured by Nagase ChemteX, product Name "DENACOL EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "DENACOL EX-512"), sorbitan polyglycidyl ether, trimethylol Propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris (2-hydroxyethyl) isocyanurate triglycidyl ester, resorcinol diglycidyl ether, double Phenol-S-diglycidyl ether, epoxy resin with two or more epoxy groups in the molecule, etc. The content of the epoxy-based crosslinking agent can be set to any appropriate amount according to the desired adhesive force, the elasticity of the adhesive layer, etc., with respect to 100 parts by weight of the base polymer, typically 0.01 parts by weight to 10 parts by weight , More preferably, it is 0.03 parts by weight to 5 parts by weight.
上述黏著劑層之厚度較佳為1 μm～50 μm、更佳為1 μm～30 μm、進而較佳為2 μm～20 μm。The thickness of the adhesive layer is preferably 1 μm to 50 μm, more preferably 1 μm to 30 μm, and still more preferably 2 μm to 20 μm.
上述黏著劑層之基於奈米壓痕法之彈性模數較佳為0.005～5 MPa、更佳為0.01～2 MPa。若為此種範圍，則能夠形成不易阻礙基材之伸縮性之黏著劑層，本發明之效果更顯著。又，可形成具有適當之黏著力之黏著劑層。上述彈性模數例如可藉由黏著劑層中包含之黏著劑之組成；成為黏著劑之基礎聚合物之樹脂材料之種類、分子量、交聯度等來調整。再者，基於奈米壓痕法之彈性模數係在負載時、卸載時連續測定在將壓頭壓入試樣(不存在熱膨脹性微球之部位)時對壓頭之負載載荷與壓入深度，根據得到之負載載荷-壓入深度曲線來求出。本說明書中，基於奈米壓痕法之彈性模數係測定條件設為載荷：1 mN、負載/卸載速度：0.1 mN/s、保持時間：1 s、環境溫度：23℃並如上所述地測定之彈性模數。The elastic modulus of the adhesive layer based on the nanoindentation method is preferably 0.005 to 5 MPa, more preferably 0.01 to 2 MPa. If it is in this range, an adhesive layer that does not easily hinder the stretchability of the base material can be formed, and the effect of the present invention is more remarkable. In addition, an adhesive layer with appropriate adhesive force can be formed. The above-mentioned elastic modulus can be adjusted by, for example, the composition of the adhesive contained in the adhesive layer; the type, molecular weight, and degree of crosslinking of the resin material used as the base polymer of the adhesive. Furthermore, the modulus of elasticity based on the nanoindentation method is to continuously measure the load and indentation depth of the indenter when the indenter is pressed into the sample (the part where there are no thermally expandable microspheres) during loading and unloading. , Calculated according to the obtained load-indentation depth curve. In this manual, the measurement conditions of the elastic modulus system based on the nanoindentation method are set as load: 1 mN, load/unload speed: 0.1 mN/s, holding time: 1 s, ambient temperature: 23°C and as described above The measured modulus of elasticity.
D. 黏著片材之製造方法 本發明之黏著片材可藉由任意適當之方法來製造。本發明之黏著片材可在基材上形成黏著劑層而得到。作為黏著劑層之形成方法，例如，可列舉在基材上塗佈黏著劑之方法、將在任意適當之膜上塗佈黏著劑而形成之塗佈層轉印至中間層之方法等。 D. Manufacturing method of adhesive sheet The adhesive sheet of the present invention can be manufactured by any appropriate method. The adhesive sheet of the present invention can be obtained by forming an adhesive layer on a substrate. As a method of forming the adhesive layer, for example, a method of applying an adhesive on a substrate, a method of transferring a coating layer formed by applying an adhesive on any appropriate film to an intermediate layer, and the like can be cited.
作為上述黏著劑之塗佈方法，可採用任意適當之塗佈方法。例如，可在塗佈後進行乾燥而形成各層。作為塗佈方法，例如，可列舉使用多層塗佈機(Multi Coater)、模塗機、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。As the coating method of the above-mentioned adhesive, any suitable coating method can be adopted. For example, drying can be performed after coating to form each layer. As the coating method, for example, a coating method using a multi-layer coater (Multi Coater), a die coater, a gravure coater, an applicator, and the like can be cited. As a drying method, natural drying, heat drying, etc. are mentioned, for example.
E. 用途 本發明之黏著片材在製造電子零件時可良好地作為用以將電子零件材料進行臨時固定之片材使用。一個實施方式中，本發明之黏著片材可用作晶片拾取用之黏著片材。可用作將電子零件材料切斷時之臨時固定片材。作為該電子零件材料，例如，可列舉半導體晶片、LED晶片、陶瓷電容器等。 [實施例] E. Application The adhesive sheet of the present invention can be used as a sheet for temporarily fixing the materials of electronic parts when manufacturing electronic parts. In one embodiment, the adhesive sheet of the present invention can be used as an adhesive sheet for chip pickup. It can be used as a temporary fixing sheet when cutting electronic parts materials. Examples of materials for this electronic component include semiconductor wafers, LED wafers, ceramic capacitors, and the like. [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限定。實施例中之評價方法如下。再者，下述評價中，使用將隔離膜剝離之黏著片材。又，實施例中，只要無特別說明，則「份」及「%」為重量基準。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. In addition, in the following evaluation, the adhesive sheet which peeled a separator was used. In addition, in the examples, unless otherwise specified, "parts" and "%" are based on weight.
(1)恢復率 對寬度10 mm、長度100 mm之黏著片材片，在長度方向記錄初始評價點間距離L0 ＝50 mm之標線。在23℃之環境溫度下、以夾頭間距離70 mm安裝於拉伸試驗機，以拉伸速度300 mm/分鐘使其伸長至150%(夾頭間距離：145 mm)，保持伸長狀態5分鐘後，測定伸長評價點間距離L1 。其後釋放張力，測定5分鐘後之評價點間距離L，藉由下式求出恢復率(%)。 恢復率(%)＝{(伸長評價點間距離L1 －評價點間距離L)/(伸長評價點間距離L1 －初始評價點間距離L0 )}×100 恢復率係對特定方向I及與該方向I正交之方向II之2種取樣進行測定。 又，在40℃之環境溫度下、藉由上述之方法使黏著片材伸縮並求出恢復率。(1) Recovery rate For an adhesive sheet with a width of 10 mm and a length of 100 mm, record the marking line with the distance L 0 =50 mm between the initial evaluation points in the length direction. Installed on a tensile testing machine at an ambient temperature of 23°C with a distance between the chucks of 70 mm, stretched to 150% (distance between the chucks: 145 mm) at a tensile speed of 300 mm/min, and maintained the extended state 5 After minutes, the distance L 1 between the elongation evaluation points was measured. After that, the tension was released, the distance L between the evaluation points after 5 minutes was measured, and the recovery rate (%) was obtained by the following formula. Recovery rate (%) = {(distance between elongation evaluation points L 1 －distance between evaluation points L)/(distance between elongation evaluation points L 1 －distance between initial evaluation points L 0 )}×100 The recovery rate is relative to a specific direction I And two kinds of sampling in the direction II orthogonal to the direction I for measurement. In addition, at an ambient temperature of 40°C, the adhesive sheet was expanded and contracted by the above-mentioned method, and the recovery rate was obtained.
(2)動摩擦力 將黏著帶以基材膜面朝上之方式貼附於工作台上，在其上以與基材膜面接觸之方式放置SUS304板(重量200 g、63 mm×63 mm)，使SUS304板在基材膜面上移動(100 mm/分鐘)，測量此時產生之平均載荷(N)，將其作為動摩擦力。(2) Dynamic friction Attach the adhesive tape to the workbench with the substrate film surface facing up, and place a SUS304 plate (weight 200 g, 63 mm×63 mm) on it so that the SUS304 plate is in contact with the substrate film surface. The substrate film surface moves (100 mm/min), and the average load (N) generated at this time is measured and used as the dynamic friction force.
[實施例1] 製備包含由丙烯酸2-乙基己酯(2EHA)/丙烯酸(AA)＝90/10(重量比)構成之丙烯酸系聚合物100重量份、多異氰酸酯系交聯劑(商品名「CORONATE L」、Nippon Polyurethane Industry公司製造)5重量份、縮水甘油胺系交聯劑(商品名「TETRAD-C」、三菱瓦斯化學公司製造)0.05重量份、及乙酸乙酯的黏著劑。將該黏著劑塗佈於對單面用聚矽氧進行了剝離處理之厚度38 μm之聚酯膜(商品名：MRF、三菱化學聚酯股份有限公司製造)之剝離處理面，以120℃加熱2分鐘，形成厚度20 μm之黏著劑層。繼而，將該黏著劑層面轉印至作為基材之含有0.1重量份硬脂酸醯胺之聚胺基甲酸酯系膜A(厚度：70 μm、大石產業公司製造)，在50℃下保存48小時，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Example 1] The preparation contains 100 parts by weight of acrylic polymer composed of 2-ethylhexyl acrylate (2EHA)/acrylic acid (AA)=90/10 (weight ratio), polyisocyanate-based crosslinking agent (trade name "CORONATE L", Nippon Polyurethane Industry Co., Ltd.) 5 parts by weight, glycidylamine-based crosslinking agent (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.05 parts by weight, and an ethyl acetate adhesive. This adhesive was applied to the peel-off treated surface of a 38 μm thick polyester film (trade name: MRF, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) that was peeled off with silicone on one side, and heated at 120°C In 2 minutes, an adhesive layer with a thickness of 20 μm is formed. Then, the adhesive layer was transferred to a polyurethane-based film A (thickness: 70 μm, manufactured by Dashi Sangyo Co., Ltd.) containing 0.1 parts by weight of amide stearate as a substrate, and stored at 50°C For 48 hours, an adhesive sheet was obtained. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[實施例2] 作為基材，使用聚胺基甲酸酯系膜B(厚度：60 μm、Nihon Matai公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Example 2] As the base material, a polyurethane-based film B (thickness: 60 μm, manufactured by Nihon Matai Co., Ltd.) was used. Except for this, the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[實施例3] 作為基材，使用含有0.05重量份硬脂酸醯胺之聚丙烯系彈性體(PP彈性體)膜(厚度：100 μm、日東電工公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Example 3] As the substrate, a polypropylene elastomer (PP elastomer) film (thickness: 100 μm, manufactured by Nitto Denko Corporation) containing 0.05 parts by weight of amide stearate was used. Obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[實施例4] 作為基材，使用由聚乙烯(PE；厚度：10 μm)/苯乙烯系彈性體(St彈性體；厚度：60 μm)膜/聚乙烯(厚度：10 μm)構成之積層體(厚度：80 μm、Nihon Matai公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Example 4] As the substrate, a laminate (thickness: 80 μm) composed of polyethylene (PE; thickness: 10 μm)/styrene-based elastomer (St elastomer; thickness: 60 μm) film/polyethylene (thickness: 10 μm) was used. μm, manufactured by Nihon Matai Co.), except for this, the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[實施例5] 作為基材，使用由乙烯乙酸乙烯酯共聚物膜(EVA；厚度：10 μm)/苯乙烯系彈性體膜(厚度：60 μm)/乙烯乙酸乙烯酯共聚物膜(厚度：10 μm)構成之積層體(厚度：80 μm、Nihon Matai公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Example 5] As the base material, an ethylene vinyl acetate copolymer film (EVA; thickness: 10 μm)/styrene-based elastomer film (thickness: 60 μm)/ethylene vinyl acetate copolymer film (thickness: 10 μm) was used. Except for the laminate (thickness: 80 μm, manufactured by Nihon Matai), the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[比較例1] 作為基材，使用含有0.7重量份硬脂酸醯胺之聚氯乙烯膜(PVC；厚度：70 μm、DiaPlus公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Comparative Example 1] As the base material, a polyvinyl chloride film (PVC; thickness: 70 μm, manufactured by DiaPlus Corporation) containing 0.7 parts by weight of amide stearate was used. Except for this, the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[比較例2] 作為基材，使用聚乙烯膜(PE；厚度：100 μm、日東電工公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Comparative Example 2] As the base material, a polyethylene film (PE; thickness: 100 μm, manufactured by Nitto Denko Corporation) was used. Except for this, the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[比較例3] 作為基材，使用由聚丙烯膜(PP；厚度：55 μm)/聚乙烯膜(PE；厚度：25 μm)構成之積層體(厚度：80 μm、大倉工業公司製造)，除此以外，與實施例1同樣地實施，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Comparative Example 3] As the base material, a laminate (thickness: 80 μm, manufactured by Okura Kogyo Co., Ltd.) composed of polypropylene film (PP; thickness: 55 μm)/polyethylene film (PE; thickness: 25 μm) was used. Example 1 was implemented in the same manner, and an adhesive sheet was obtained. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[比較例4] 作為基材，使用乙烯乙酸乙烯酯共聚物膜(厚度：100 μm、日東電工公司製造)，除此以外，與實施例1同樣地操作，得到黏著片材。 將得到之黏著片材供於上述(1)及(2)之評價。將結果示於表1。[Comparative Example 4] As the base material, an ethylene vinyl acetate copolymer film (thickness: 100 μm, manufactured by Nitto Denko Corporation) was used. Except for this, the same procedure as in Example 1 was carried out to obtain an adhesive sheet. The obtained adhesive sheet was used for the evaluation of (1) and (2) above. The results are shown in Table 1.
[表1]
10:基材 20:黏著劑層 100:黏著片材10: Substrate 20: Adhesive layer 100: Adhesive sheet
圖1為本發明之一個實施方式之黏著片材之概略剖視圖。Fig. 1 is a schematic cross-sectional view of an adhesive sheet according to an embodiment of the present invention.
10:基材 10: Substrate
20:黏著劑層 20: Adhesive layer
100:黏著片材 100: Adhesive sheet
Claims (8)
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| JP2019-143868 | 2019-08-05 | ||
| JP2019143868A JP2021024949A (en) | 2019-08-05 | 2019-08-05 | Pressure sensitive adhesive sheet |
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| TW202113000A true TW202113000A (en) | 2021-04-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6269640A (en) * | 1985-09-24 | 1987-03-30 | Nippon Carbide Ind Co Ltd | Adhesive film for wafer dicing |
| WO1991002377A1 (en) * | 1989-08-01 | 1991-02-21 | Mitsui Toatsu Chemicals, Incorporated | Film for wafer processing |
| JP3081113B2 (en) * | 1994-08-12 | 2000-08-28 | 株式会社クラレ | Thermoplastic polymer composition |
| JP3029102B1 (en) * | 1998-10-20 | 2000-04-04 | 和泰股▲ふん▼有限公司 | Elastic nonwoven composition |
| JP2001207140A (en) | 2000-01-26 | 2001-07-31 | Sumitomo Bakelite Co Ltd | Adhesive tape for processing semiconductor wafer |
| JP4463399B2 (en) * | 2000-08-23 | 2010-05-19 | 日東電工株式会社 | Medical adhesive tape or sheet, and emergency bandage |
| JP2003049132A (en) * | 2001-08-06 | 2003-02-21 | Nitto Denko Corp | Surface protecting sheet |
| JP4286043B2 (en) * | 2003-03-31 | 2009-06-24 | ロンシール工業株式会社 | Wafer dicing adhesive tape |
| JP2005029907A (en) * | 2003-07-08 | 2005-02-03 | Kanebo Ltd | Stretchable nonwoven fabric, method for producing the same and pressure-sensitive adhesive sheet using the same |
| JP5140910B2 (en) * | 2005-08-30 | 2013-02-13 | 住友ベークライト株式会社 | Film base and adhesive tape for semiconductor wafer processing |
| WO2010001959A1 (en) * | 2008-07-03 | 2010-01-07 | 電気化学工業株式会社 | Pressure-sensitive adhesive film, laminate using the pressure-sensitive adhesive film and method for protecting molded article |
| JP2010260893A (en) | 2009-04-30 | 2010-11-18 | Nitto Denko Corp | Laminated film and method for producing semiconductor device |
| KR20150099769A (en) * | 2012-12-28 | 2015-09-01 | 린텍 가부시키가이샤 | Dicing-sheet substrate film and dicing sheet |
| JP6107230B2 (en) * | 2013-02-28 | 2017-04-05 | 住友ベークライト株式会社 | Dicing film |
| KR102528636B1 (en) * | 2016-06-30 | 2023-05-03 | 린텍 가부시키가이샤 | Sheet for semiconductor processing |
| JP6807234B2 (en) * | 2017-01-10 | 2021-01-06 | 日東電工株式会社 | Adhesive sheet |
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