TW202136450A - Double-sided pressure-sensitive adhesive tape - Google Patents
Double-sided pressure-sensitive adhesive tape Download PDFInfo
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- TW202136450A TW202136450A TW109141637A TW109141637A TW202136450A TW 202136450 A TW202136450 A TW 202136450A TW 109141637 A TW109141637 A TW 109141637A TW 109141637 A TW109141637 A TW 109141637A TW 202136450 A TW202136450 A TW 202136450A
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- adhesive tape
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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
- C09J7/26—Porous or cellular plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/348—Hydroxycarboxylic acids
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
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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
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- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- 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
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- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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Abstract
Description
本發明係關於一種兩面黏著帶。The present invention relates to a double-sided adhesive tape.
黏著帶被廣泛地用作固定電子零件之用途。具體而言,例如於電視、監視器等顯示裝置中,為了將表面之蓋板固定於殼體而使用黏著帶。此種黏著帶例如以邊框狀等形狀配置於顯示畫面之周邊而使用。Adhesive tapes are widely used for fixing electronic parts. Specifically, for example, in display devices such as televisions and monitors, adhesive tapes are used in order to fix the surface cover to the housing. Such an adhesive tape is used, for example, which is arranged in a frame shape or the like on the periphery of the display screen.
近年來,追求設計感或功能性,結果使得電視、監視器等顯示裝置不斷窄邊框化,人們對無邊框之顯示裝置之期待亦不斷提高。於以往之顯示裝置之製造中,亦有時會藉由嵌入或螺固將蓋板固定於殼體,但於不斷窄邊框化之顯示裝置,難以進行嵌入或螺固,故而對利用黏著帶進行固定之需求越來越高,黏著帶亦不斷薄型化及窄幅化。In recent years, the pursuit of design or functionality has resulted in display devices such as televisions and monitors becoming narrower, and people’s expectations for bezel-less display devices have also been increasing. In the manufacture of display devices in the past, sometimes the cover plate is fixed to the housing by embedding or screwing. However, it is difficult to embed or screw the display device with narrower frames. Therefore, the use of adhesive tape is The demand for fixation is getting higher and higher, and the adhesive tape is becoming thinner and narrower.
作為可於此種顯示裝置使用之黏著帶,例如於專利文獻1及2中記載有一種撞擊吸收帶,其於基材層之至少單面積層一體化有丙烯酸系黏著劑層,該基材層為具有特定之交聯度及氣泡之縱橫比的交聯聚烯烴系樹脂發泡片。
[先前技術文獻]
[專利文獻]As an adhesive tape that can be used in such a display device, for example,
專利文獻1:日本特開2009-242541號公報 專利文獻2:日本特開2009-258274號公報Patent Document 1: Japanese Patent Application Publication No. 2009-242541 Patent Document 2: Japanese Patent Application Publication No. 2009-258274
[發明所欲解決之課題][The problem to be solved by the invention]
然而,電視、監視器等顯示裝置不斷大型化,蓋板、殼體等被固定構件之重量亦不斷增加。因此,於剪切方向上對黏著帶施加較以往更大之非常大的載重,於薄型且窄幅地使用黏著帶之情形時,尤其會產生如下問題:因運送時之掉落等導致受到撞擊,從而產生基材之層間破壞或黏著帶之剝離。 又,隨著大型化,顯示裝置亦容易產生顯示不均。為了減少顯示不均,黏著帶尤其是黏著帶之基材必須具有可釋放應力之適度之柔軟性。進而,近年來,電子零件有價格變高之傾向,因此要求例如於固定零件時產生不良情況之情形等能夠對零件進行二次加工。作為對零件進行二次加工之方法之一,例如可使用如下方法:利用切刀刃將黏著帶之發泡體基材撕掉,使層間破壞而將零件拆卸下。於此種情形時,亦要求基材不過硬,具有適度之柔軟性。 此處,為了可承受因運送時之掉落等導致之撞擊,必須提高基材之強度,而另一方面,為了減少顯示不均及易撕,必須提高基材之柔軟性。然而,基材之強度與柔軟性為相反之性質,因此難以兼顧該兩者。 本發明之目的在於提供一種兩面黏著帶,其耐掉落撞擊性優異,可減少顯示裝置之顯示不均,自被接著體剝離時能容易地撕掉發泡體基材。 [解決課題之技術手段]However, display devices such as televisions and monitors have continued to increase in size, and the weight of fixed components such as covers and housings has also increased. Therefore, in the shearing direction, a larger and very large load is applied to the adhesive tape than before. When the adhesive tape is used in a thin and narrow width, the following problems especially occur: impact due to falling during transportation, etc. , Resulting in interlayer failure of the substrate or peeling of the adhesive tape. In addition, as the size of the display device increases, display unevenness is also likely to occur. In order to reduce display unevenness, the adhesive tape, especially the base material of the adhesive tape, must have moderate flexibility that can release stress. Furthermore, in recent years, electronic components have tended to increase in price, and therefore, it is required that, for example, when a problem occurs when fixing the components, it is required to be able to perform secondary processing on the components. As one of the methods for secondary processing of parts, for example, the following method can be used: using a cutting blade to tear off the foam base material of the adhesive tape to break the interlayer and disassemble the part. In this case, it is also required that the substrate is not too hard and has moderate flexibility. Here, in order to withstand the impact caused by dropping during transportation, the strength of the substrate must be increased. On the other hand, in order to reduce display unevenness and easy tearing, the flexibility of the substrate must be increased. However, the strength and flexibility of the substrate are opposite properties, so it is difficult to balance the two. The object of the present invention is to provide a double-sided adhesive tape that has excellent drop impact resistance, can reduce display unevenness of the display device, and can easily tear off the foam substrate when peeled from the adherend. [Technical means to solve the problem]
本發明係一種兩面黏著帶,其係具有發泡體基材及積層於上述發泡體基材兩側之黏著劑層者,上述發泡體基材之氣泡體積分率為40體積%以上75體積%以下,剪切斷裂強度為200 N/inch2 以上500 N/inch2 以下。 以下,對本發明進行詳細說明。The present invention is a double-sided adhesive tape, which has a foam base material and adhesive layers laminated on both sides of the foam base material. The foam base material has a bubble volume fraction of 40% by volume or more. Volume% or less, the shear breaking strength is 200 N/inch 2 or more and 500 N/inch 2 or less. Hereinafter, the present invention will be described in detail.
本發明人等對於具有發泡體基材及積層於該發泡體基材兩側之黏著劑層之兩面黏著帶,使用X射線CT(X-ray Computed Tomography;電腦斷層攝影法)裝置及圖像解析軟體對發泡體基材之氣泡結構進行分析,對氣泡結構對兩面黏著帶之性能造成之影響進行了研究。其結果,本發明人發現等藉由將發泡體基材之氣泡體積分率調整為特定範圍,進而將發泡體基材之剪切斷裂強度調整為特定範圍,可提高發泡體基材之強度與柔軟性兩者。發現藉此可獲得耐掉落撞擊性優異、可減少顯示裝置之顯示不均、自被接著體剝離時能容易地撕掉發泡體基材之兩面黏著帶,從而完成了本發明。The inventors of the present invention used X-ray CT (X-ray Computed Tomography; computer tomography) equipment and drawings for the adhesive tape on both sides of the foam substrate and the adhesive layer laminated on both sides of the foam substrate. The image analysis software analyzes the bubble structure of the foam substrate, and studies the influence of the bubble structure on the performance of the adhesive tape on both sides. As a result, the inventors found that by adjusting the bubble volume fraction of the foam substrate to a specific range, and then adjusting the shear breaking strength of the foam substrate to a specific range, the foam substrate can be improved. Both the strength and flexibility. It has been found that excellent drop impact resistance can be obtained, the display unevenness of the display device can be reduced, and the adhesive tape on both sides of the foam substrate can be easily torn off when peeling from the adherend, and the present invention has been completed.
本發明之兩面黏著帶具有發泡體基材及積層於上述發泡體基材兩側之黏著劑層。 上述發泡體基材具有適度之柔軟性,故而可釋放應力。藉由具有上述發泡體基材,兩面黏著帶之應力緩和性提高。The double-sided adhesive tape of the present invention has a foam base material and an adhesive layer laminated on both sides of the foam base material. The above-mentioned foam substrate has moderate flexibility, so it can relieve stress. By having the above-mentioned foam base material, the stress relaxation properties of the double-sided adhesive tape are improved.
上述發泡體基材之氣泡體積分率之下限為40體積%,上限為75體積%。藉由將上述氣泡體積分率調整為上述範圍,可提高上述發泡體基材之強度與柔軟性兩者,而同時兼顧該兩者。 若上述氣泡體積分率為40體積%以上,則上述發泡體基材可具有適度之柔軟性,因此可減少顯示裝置之顯示不均,將兩面黏著帶自被接著體剝離時能容易地撕掉上述發泡體基材。若上述氣泡體積分率為75體積%以下,則可抑制上述發泡體基材之強度過度降低,因此可提高兩面黏著帶之耐掉落撞擊性。又,若上述氣泡體積分率為75體積%以下,則亦容易確保上述發泡體基材之防塵性及防水性。上述氣泡體積分率之較佳下限為42體積%,較佳之上限為70體積%,更佳之下限為46體積%,更佳之上限為67體積%,進而較佳之下限為48體積%,進而較佳之上限為63體積%,尤佳之下限為50體積%,尤佳之上限為60體積%。 再者,氣泡體積分率係使用X射線CT裝置及圖像解析軟體,藉由下述式(1)算出。 氣泡體積分率(體積%)=氣泡體積/發泡體基材之體積×100 (1) 式(1)中,氣泡體積係指測定對象試樣之發泡體基材所含之全部氣泡之體積的合計。The lower limit of the bubble volume fraction of the foam substrate is 40% by volume, and the upper limit is 75% by volume. By adjusting the bubble volume fraction to the above range, both the strength and flexibility of the foam base material can be improved, while taking into account both. If the bubble volume fraction is 40% by volume or more, the foam base material can have moderate flexibility, so the display unevenness of the display device can be reduced, and the double-sided adhesive tape can be easily torn off when peeling off the adherend. Remove the above-mentioned foam substrate. If the bubble volume fraction is 75% by volume or less, the strength of the foam base material can be suppressed from excessively decreasing, and therefore the drop impact resistance of the double-sided adhesive tape can be improved. In addition, if the bubble volume fraction is 75% by volume or less, it is easy to ensure the dustproofness and waterproofness of the foam base material. The lower limit of the above-mentioned bubble volume fraction is preferably 42% by volume, the upper limit is preferably 70% by volume, the lower limit is more preferably 46% by volume, the upper limit is more preferably 67% by volume, and the lower limit is more preferably 48% by volume, and more preferably The upper limit is 63% by volume, the lower limit is particularly preferably 50% by volume, and the upper limit is particularly preferably 60% by volume. In addition, the bubble volume fraction is calculated by the following formula (1) using an X-ray CT device and image analysis software. Volume fraction of bubbles (vol%) = volume of bubbles/volume of foam substrate×100 (1) In formula (1), the bubble volume refers to the total volume of all the bubbles contained in the foam base material of the sample to be measured.
上述發泡體基材之氣泡之長徑分佈的平均值及標準偏差並無特別限定,氣泡之長徑分佈之平均值的較佳上限為55 μm,氣泡之長徑分佈之標準偏差的較佳上限為30 μm。 藉由將上述長徑分佈之平均值及標準偏差調整為上述範圍,將氣泡大小及氣泡大小之變動抑制在一定程度以下,可進一步提高上述發泡體基材之強度與柔軟性兩者。其結果,可提高兩面黏著帶之耐掉落撞擊性,又,可減少顯示裝置之顯示不均,並且將兩面黏著帶自被接著體剝離時能容易地撕掉上述發泡體基材。 又,若氣泡過大或氣泡大小存在變動,則於薄型且窄幅地使用兩面黏著帶之情形時,尤其會於上述發泡體基材中局部存在強度特別低之部位,因運送時之掉落等導致受到撞擊,從而以上述部位為起點而產生上述發泡體基材之層間破壞或兩面黏著帶之剝離。藉由將上述長徑分佈之平均值及標準偏差調整為上述範圍,將氣泡大小及氣泡大小之變動抑制在一定程度以下,可抑制局部存在強度特別低之部位,提高兩面黏著帶之耐掉落撞擊性。The average value and standard deviation of the long-diameter distribution of the foam substrate are not particularly limited. The upper limit of the average value of the long-diameter distribution of the bubbles is preferably 55 μm, and the standard deviation of the long-diameter distribution of the bubbles is better. The upper limit is 30 μm. By adjusting the average value and standard deviation of the above-mentioned long-diameter distribution to the above-mentioned range, the variation of the bubble size and the bubble size is suppressed to a certain level or less, and both the strength and flexibility of the foam base material can be further improved. As a result, the drop impact resistance of the double-sided adhesive tape can be improved, and the display unevenness of the display device can be reduced, and the foam substrate can be easily torn off when the double-sided adhesive tape is peeled from the adherend. In addition, if the bubbles are too large or the size of the bubbles fluctuates, when the double-sided adhesive tape is used in a thin and narrow width, there are particularly low-strength parts in the foam base material, which may drop during transportation. It may be impacted, and the foam base material may be broken or peeled off of the adhesive tape on both sides from the above-mentioned location as a starting point. By adjusting the average value and standard deviation of the above-mentioned long-diameter distribution to the above-mentioned range, the bubble size and the variation of the bubble size can be suppressed below a certain level, and the presence of particularly low-strength parts can be suppressed, and the drop resistance of the double-sided adhesive tape can be improved. Impact.
上述長徑分佈之平均值之更佳上限為53 μm,進而較佳之上限為51 μm,進而更佳之上限為49 μm。上述長徑分佈之平均值之下限並無特別限定,亦取決於上述發泡體基材之氣泡體積分率及厚度而決定,但實際上之下限為10 μm。 上述長徑分佈之標準偏差之更佳上限為28 μm,進而較佳之上限為27 μm,進而更佳之上限為24 μm。上述長徑分佈之標準偏差之下限並無特別限定,越小,氣泡大小越不存在變動,故而較佳,實際上之下限為5 μm。 再者,氣泡之長徑分佈之平均值及標準偏差,係使用X射線CT裝置及圖像解析軟體求出氣泡之長徑分佈,根據所得之長徑分佈算出平均值及標準偏差。A more preferable upper limit of the average value of the aforementioned long diameter distribution is 53 μm, a still more preferable upper limit is 51 μm, and a still more preferable upper limit is 49 μm. The lower limit of the average value of the aforementioned long-diameter distribution is not particularly limited, and is also determined depending on the cell volume fraction and thickness of the aforementioned foam base material, but the lower limit is actually 10 μm. A more preferable upper limit of the standard deviation of the aforementioned long diameter distribution is 28 μm, a further preferable upper limit is 27 μm, and a still more preferable upper limit is 24 μm. The lower limit of the standard deviation of the above-mentioned long-diameter distribution is not particularly limited. The smaller the size of the bubble, the less there is a change in the size of the bubble, so it is preferable. In fact, the lower limit is 5 μm. Furthermore, the average and standard deviation of the long-diameter distribution of the bubbles are obtained by using the X-ray CT device and image analysis software to obtain the long-diameter distribution of the bubbles, and the average and standard deviation are calculated based on the obtained long-diameter distribution.
上述發泡體基材之氣泡之連泡率並無特別限定,於上述發泡體基材為聚胺酯發泡體之情形時,氣泡之連泡率較佳上限為95體積%。一般而言,聚胺酯發泡體採用連泡結構,連泡率成為接近100體積%之值。因此,於上述發泡體基材為聚胺酯發泡體之情形時,具有上述範圍之連泡率意指於聚胺酯發泡體中連泡率較低,獨立氣泡較多。 藉由將上述連泡率調整為上述範圍,增加獨立氣泡,可進一步提高聚胺酯發泡體之強度與柔軟性兩者。其結果,可提高兩面黏著帶之耐掉落撞擊性,又,可減少顯示裝置之顯示不均,並且將兩面黏著帶自被接著體剝離時能容易地撕掉上述發泡體基材。 又,藉由將上述連泡率調整為上述範圍,增加獨立氣泡,可抑制如上述之局部存在強度特別低之部位,使兩面黏著帶之耐掉落撞擊性提高。The continuous cell rate of the foam substrate is not particularly limited. When the foam substrate is a polyurethane foam, the cell continuous cell rate is preferably 95% by volume. Generally speaking, polyurethane foam adopts a continuous foam structure, and the continuous foam rate becomes a value close to 100% by volume. Therefore, when the above-mentioned foam substrate is a polyurethane foam, the continuous foam rate having the above range means that the continuous foam rate in the polyurethane foam is low and there are many independent cells. By adjusting the above-mentioned continuous foam ratio to the above-mentioned range and increasing independent cells, both the strength and flexibility of the polyurethane foam can be further improved. As a result, the drop impact resistance of the double-sided adhesive tape can be improved, and the display unevenness of the display device can be reduced, and the foam substrate can be easily torn off when the double-sided adhesive tape is peeled from the adherend. In addition, by adjusting the continuous bubble ratio to the above range and increasing the number of independent bubbles, it is possible to suppress the local presence of particularly low-strength parts as described above, and to improve the drop impact resistance of the double-sided adhesive tape.
上述連泡率之更佳上限為93體積%,進而較佳之上限為91體積%。上述連泡率之下限並無特別限定,聚胺酯發泡體之連泡率之一般下限為90體積%。 再者,氣泡之連泡率係使用X射線CT裝置及圖像解析軟體,藉由下述式(2)算出。 連泡率(體積%)=連通氣泡體積/氣泡體積×100 (2) 式(2)中,連通氣泡體積係指測定對象試樣之發泡體基材所含之全部連通之氣泡其體積的合計,氣泡體積係指測定對象試樣之發泡體基材所含之全部氣泡之體積的合計。The more preferable upper limit of the continuous foam rate is 93% by volume, and the more preferable upper limit is 91% by volume. The lower limit of the continuous foam rate is not particularly limited, and the general lower limit of the continuous foam rate of the polyurethane foam is 90% by volume. Furthermore, the continuous bubble rate of bubbles is calculated by the following formula (2) using an X-ray CT device and image analysis software. Continuous bubble rate (vol%) = connected bubble volume/bubble volume×100 (2) In formula (2), the volume of connected cells refers to the total volume of all connected cells contained in the foam substrate of the sample to be measured, and the volume of cells refers to the volume contained in the foam substrate of the sample to be measured The total volume of all bubbles.
上述發泡體基材之氣泡之扁率並無特別限定,較佳之上限為0.2。藉由將上述扁率調整為上述範圍,可使對自所有角度掉落之撞擊緩和更均勻,可提高兩面黏著帶之耐掉落撞擊性。The flatness of the bubbles of the foam substrate is not particularly limited, and the preferred upper limit is 0.2. By adjusting the flatness to the above range, the impact of falling from all angles can be alleviated more uniformly, and the drop impact resistance of the two-sided adhesive tape can be improved.
上述扁率之更佳上限為0.18,進而較佳之上限為0.16,進而更佳之上限為0.14。上述扁率之下限並無特別限定,越接近0,氣泡越接近真球,對自所有角度掉落之撞擊緩和變得更均勻,故而較佳,實際上之下限為0.05。The more preferable upper limit of the flatness is 0.18, the more preferable upper limit is 0.16, and the more preferable upper limit is 0.14. The lower limit of the flatness is not particularly limited. The closer it is to 0, the closer the bubble is to the real ball, and the more uniform the impact of falling from all angles will be relieved. Therefore, it is preferable. In fact, the lower limit is 0.05.
上述發泡體基材之氣泡之縱橫比並無特別限定,較佳之上限為1.5。藉由將上述縱橫比調整為上述範圍,可使對自所有角度掉落之撞擊緩和變得更均勻,可提高兩面黏著帶之耐掉落撞擊性。The aspect ratio of the bubbles of the foam substrate is not particularly limited, and the preferred upper limit is 1.5. By adjusting the aspect ratio to the above range, the impact of falling from all angles can be alleviated more uniformly, and the drop impact resistance of the two-sided adhesive tape can be improved.
上述縱橫比之更佳上限為1.1,進而較佳之上限為1.09,進而更佳之上限為1.07。上述縱橫比之下限並無特別限定,越接近1,氣泡越接近真圓,對自所有角度掉落之撞擊緩和變得更均勻,故而較佳,實際上之下限為1.01。 再者,氣泡之縱橫比及扁率係使用X射線CT裝置及圖像解析軟體,藉由下述式(3)及(4)算出。 縱橫比=x/y (3) 扁率={(x+y)/2-z}/z (4) (x=長徑,y=中徑,z=短徑,x≧y≧z)The more preferable upper limit of the above aspect ratio is 1.1, the more preferable upper limit is 1.09, and the more preferable upper limit is 1.07. The lower limit of the aspect ratio is not particularly limited. The closer it is to 1, the closer the bubble is to a true circle, and the impact of falling from all angles becomes more uniform. Therefore, it is preferable. In practice, the lower limit is 1.01. Furthermore, the aspect ratio and oblateness of the bubbles are calculated by the following formulas (3) and (4) using an X-ray CT device and image analysis software. Aspect ratio = x/y (3) Flat rate = {(x+y)/2-z}/z (4) (X=long diameter, y=medium diameter, z=short diameter, x≧y≧z)
上述X射線CT裝置及上述圖像解析軟體並無特別限定,使用上述X射線CT裝置及上述圖像解析軟體之分析更詳細而言,例如以如下方式進行。 藉由X射線CT裝置(例如,大和科學公司製造,「TDM1000H-II(2K)」,解像度1.5 μm/1像素左右)對切斷發泡體基材所得之測定樣品之中心部進行拍攝,獲得長度1.5 mm、寬度1.2 mm、高度0.3 mm之長方體狀3D圖像。對於所獲得之圖像,藉由圖像解析軟體(例如,FEI公司製造,「Avizo9.2.0」)進行雜訊去除及二值化,求出表示發泡體基材之氣泡結構之各數值(氣泡體積分率、氣泡之長徑分佈之平均值及標準偏差、氣泡之連泡率、氣泡之縱橫比及氣泡之扁率等)。使用Mo作為X射線源,使用透鏡(L0270),於分級(binning)2、曝光時間10秒、拍攝張數1200張之條件下進行拍攝。 於圖像解析時,首先,藉由中值濾波器(Median Filter)(Neighborhood值 26)功能去除雜訊。然後,利用交互閾值(Interactive Thresholding)功能進行二值化。閾值設為256階調中之90。於二值化後之圖像中,氣泡為獨立氣泡還是為連泡,係根據像素之連續部分有無中斷來判斷。又,於計算長徑、中徑、短徑時,首先,利用接點將氣泡彼此分割,求出氣泡之重心。繼而,設定與該重心相同之位置具有重心且內接於氣泡之長方體,針對正交之3邊之長度,自較長者起分別設為長徑、中徑、短徑。再者,此時,將長徑未達10 μm之氣泡排除在外。The X-ray CT apparatus and the image analysis software are not particularly limited, and the analysis using the X-ray CT apparatus and the image analysis software is more detailed, for example, as follows. Use an X-ray CT device (for example, "TDM1000H-II (2K)" manufactured by Yamato Scientific Co., Ltd., with a resolution of about 1.5 μm/1 pixel) to photograph the center of the measurement sample obtained by cutting the foam substrate. A rectangular 3D image with a length of 1.5 mm, a width of 1.2 mm, and a height of 0.3 mm. For the obtained image, noise removal and binarization are performed by image analysis software (for example, "Avizo9.2.0" made by FEI), and the values representing the bubble structure of the foam substrate are calculated ( The bubble volume fraction, the average and standard deviation of the bubble's long-diameter distribution, the bubble's continuous bubble rate, the bubble's aspect ratio, and the bubble's flatness, etc.). Use Mo as the X-ray source, use a lens (L0270), and shoot under the conditions of binning, exposure time of 10 seconds, and number of shots of 1200. In image analysis, first, use the Median Filter (Neighborhood value 26) function to remove noise. Then, use the interactive threshold (Interactive Thresholding) function for binarization. The threshold is set to 90 out of 256 tones. In the binarized image, whether the bubble is an independent bubble or a continuous bubble is determined based on whether the continuous part of the pixel is interrupted. In addition, when calculating the long diameter, the middle diameter, and the short diameter, first, the bubbles are separated from each other by the contacts, and the center of gravity of the bubbles is obtained. Then, a rectangular parallelepiped with a center of gravity at the same position as the center of gravity and inscribed in the bubble is set, and the length of the three orthogonal sides is set as the long diameter, the middle diameter, and the short diameter from the longer one. In addition, at this time, air bubbles with a major diameter of less than 10 μm are excluded.
將表示上述發泡體基材之氣泡結構之各數值(氣泡體積分率、氣泡之長徑分佈之平均值及標準偏差、氣泡之連泡率、氣泡之縱橫比及氣泡之扁率等)調整為上述範圍之方法並無特別限定。 例如,於上述發泡體基材為聚胺酯發泡體之情形時,調整胺酯樹脂組成物中之聚異氰酸酯及多元醇之種類及含量、向胺酯樹脂組成物混合空氣、氮等時之條件、將胺酯樹脂組成物加熱硬化時之反應條件等即可。其中,例如較佳為如下方法:藉由增加胺酯樹脂組成物中之聚異氰酸酯之含量而提高樹脂之流動性等,緩慢進行胺酯化反應,藉此生成更均勻大小之氣泡而調整氣泡結構。 更具體而言,上述氣泡體積分率可藉由改變胺酯樹脂組成物中之聚異氰酸酯及多元醇之種類及含量、以及發泡條件而進行調整。即便於原料相同之情形時,亦可藉由改變向胺酯樹脂組成物混合空氣、氮等時之條件、將胺酯樹脂組成物加熱硬化時之反應條件等而進行調整。又,上述氣泡之長徑分佈之平均值及標準偏差可藉由緩慢進行胺酯化反應而進行調整,藉此使之變小。Adjust the numerical values (the volume fraction of the bubbles, the average value and standard deviation of the long-diameter distribution of the bubbles, the continuous bubble rate of the bubbles, the aspect ratio of the bubbles and the flatness of the bubbles, etc.) representing the bubble structure of the above-mentioned foam substrate The method within the above range is not particularly limited. For example, when the aforementioned foam substrate is polyurethane foam, adjust the type and content of polyisocyanate and polyol in the urethane resin composition, and adjust the conditions when air and nitrogen are mixed into the urethane resin composition , The reaction conditions when the urethane resin composition is heated and hardened. Among them, for example, the following method is preferred: by increasing the content of polyisocyanate in the urethane resin composition to improve the fluidity of the resin, the amine esterification reaction is slowly carried out, thereby generating more uniformly sized bubbles and adjusting the bubble structure . More specifically, the above-mentioned bubble volume fraction can be adjusted by changing the type and content of polyisocyanate and polyol in the urethane resin composition, and the foaming conditions. Even when the raw materials are the same, it can be adjusted by changing the conditions when air, nitrogen, etc. are mixed with the urethane resin composition, and the reaction conditions when the urethane resin composition is heated and hardened. In addition, the average value and standard deviation of the long-diameter distribution of the above-mentioned bubbles can be adjusted by slowly carrying out the amine esterification reaction, thereby making it smaller.
上述發泡體基材可為單層結構,亦可為多層結構。 上述發泡體基材並無特別限定,例如可列舉:聚胺酯發泡體、聚烯烴發泡體、丙烯酸發泡體等。其中,就具有適度之柔軟性,容易調整氣泡結構之方面而言,較佳為聚胺酯發泡體。The aforementioned foam substrate may have a single-layer structure or a multilayer structure. The said foam base material is not specifically limited, For example, a polyurethane foam, a polyolefin foam, an acrylic foam, etc. are mentioned. Among them, a polyurethane foam is preferred in terms of moderate flexibility and easy adjustment of the cell structure.
作為上述聚胺酯發泡體,例如可列舉由含有聚異氰酸酯及多元醇之胺酯樹脂組成物構成之聚胺酯發泡體。此種聚胺酯發泡體可藉由將上述胺酯樹脂組成物加熱硬化而製造。 上述聚異氰酸酯並無特別限定,可列舉一般之聚胺酯發泡體所使用之芳香族聚異氰酸酯或脂肪族聚異氰酸酯。其中,較佳為1分子中具有2個異氰酸基(isocyanate group)之芳香族二異氰酸酯或脂肪族二異氰酸酯。As said polyurethane foam, the polyurethane foam which consists of a urethane resin composition containing a polyisocyanate and a polyol is mentioned, for example. Such a polyurethane foam can be manufactured by heating and hardening the said urethane resin composition. The above-mentioned polyisocyanate is not particularly limited, and an aromatic polyisocyanate or aliphatic polyisocyanate used in general polyurethane foams can be mentioned. Among them, it is preferably an aromatic diisocyanate or an aliphatic diisocyanate having two isocyanate groups in one molecule.
藉由使上述聚異氰酸酯為上述芳香族二異氰酸酯或脂肪族二異氰酸酯,上述聚胺酯發泡體之交聯度不會過度提高,玻璃轉移點(Tg)會變得較低,因此成為容易伸長之發泡體,且強度與柔軟性變高。 作為上述芳香族二異氰酸酯或脂肪族二異氰酸酯,具體而言,例如可列舉:4,4'-二苯基甲烷二異氰酸酯、二異氰酸甲苯酯、1,6-六亞甲基二異氰酸酯、1,5-萘二異氰酸酯、對伸苯基二異氰酸酯、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、4,4'-二環己基甲烷二異氰酸酯、間二甲苯二異氰酸酯、六亞甲基二異氰酸酯、氫化MDI、異佛爾酮二異氰酸酯等。再者,4,4'-二苯基甲烷二異氰酸酯一般亦被稱為「MDI」或「2核體單體MDI」。其中,就容易獲得柔軟性優異之聚胺酯發泡體之方面而言,較佳為4,4'-二苯基甲烷二異氰酸酯(MDI)。該等芳香族二異氰酸酯或脂肪族二異氰酸酯可單獨使用,亦可併用兩種以上。By making the above-mentioned polyisocyanate the above-mentioned aromatic diisocyanate or aliphatic diisocyanate, the degree of cross-linking of the above-mentioned polyurethane foam will not be excessively increased, and the glass transition point (Tg) will become lower, so it becomes easy to elongate. The foam has high strength and flexibility. As the above-mentioned aromatic diisocyanate or aliphatic diisocyanate, specifically, for example, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-Naphthalene diisocyanate, p-phenylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, m-xylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI, isophorone diisocyanate, etc. Furthermore, 4,4'-diphenylmethane diisocyanate is also generally referred to as "MDI" or "2-nucleus monomer MDI". Among them, 4,4'-diphenylmethane diisocyanate (MDI) is preferable in terms of easily obtaining a polyurethane foam having excellent flexibility. These aromatic diisocyanates or aliphatic diisocyanates may be used alone, or two or more of them may be used in combination.
上述聚異氰酸酯亦可於1分子中具有3個以上之異氰酸基。作為此種聚異氰酸酯,例如可舉聚合MDI等。作為上述聚異氰酸酯,進而亦可舉具有異氰酸基之胺酯預聚物等。該等聚異氰酸酯可單獨使用,亦可併用兩種以上。The above-mentioned polyisocyanate may have 3 or more isocyanate groups in one molecule. As such a polyisocyanate, polymeric MDI etc. are mentioned, for example. As said polyisocyanate, the urethane prepolymer etc. which have an isocyanate group can also be mentioned further. These polyisocyanates may be used alone, or two or more of them may be used in combination.
上述多元醇並無特別限定,可列舉一般之聚胺酯發泡體所使用之多元醇。具體而言,例如可列舉:聚醚多元醇、聚酯多元醇、聚醚酯多元醇等。又,作為上述多元醇,亦可列舉:3官能聚醚多元醇、甘油、三羥甲基丙烷等。該等多元醇可單獨使用,亦可併用兩種以上。 上述聚醚多元醇並無特別限定,例如可舉聚丙二醇(PPG)等。上述聚酯多元醇並無特別限定,可使用由多元醇成分與酸成分構成之聚酯多元醇。The above-mentioned polyol is not particularly limited, and examples thereof include polyols used in general polyurethane foams. Specifically, for example, polyether polyol, polyester polyol, polyether ester polyol, and the like can be cited. Moreover, as said polyol, trifunctional polyether polyol, glycerol, trimethylolpropane, etc. can also be mentioned. These polyols may be used alone, or two or more of them may be used in combination. The said polyether polyol is not specifically limited, For example, polypropylene glycol (PPG) etc. are mentioned. The above-mentioned polyester polyol is not particularly limited, and a polyester polyol composed of a polyol component and an acid component can be used.
上述多元醇較佳含有短鏈二醇。 藉由上述多元醇含有上述短鏈二醇,而使上述聚胺酯發泡體之強度變高。因此,即便於為了生成更均勻大小之氣泡來調整氣泡結構,例如藉由增加上述胺酯樹脂組成物中之上述聚異氰酸酯之含量而提高樹脂之流動性等,以緩慢進行胺酯化反應的情形時,亦可抑制上述聚胺酯發泡體之強度過度降低。 作為上述短鏈二醇,例如可列舉:1,5-戊二醇、1,6-六亞甲基二醇(1,6-hexamethylene diol)、新戊二醇、乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、新戊二醇等。該等短鏈二醇可單獨使用,亦可併用兩種以上。其中,就容易獲得高強度之聚胺酯發泡體之方面而言,較佳為1,5-戊二醇或1,6-六亞甲基二醇。又,就容易降低上述連泡率之方面而言,較佳為新戊二醇。The above-mentioned polyol preferably contains a short-chain diol. When the polyol contains the short-chain diol, the strength of the polyurethane foam is increased. Therefore, even in the case of adjusting the bubble structure in order to generate more uniformly sized bubbles, for example, by increasing the content of the polyisocyanate in the urethane resin composition to improve the fluidity of the resin, the amine esterification reaction proceeds slowly. In this case, it is also possible to suppress the excessive decrease in the strength of the above-mentioned polyurethane foam. Examples of the above-mentioned short-chain diols include: 1,5-pentanediol, 1,6-hexamethylene diol (1,6-hexamethylene diol), neopentyl glycol, ethylene glycol, and diethylene glycol. Alcohol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, etc. These short-chain diols may be used alone, or two or more of them may be used in combination. Among them, in terms of easily obtaining a high-strength polyurethane foam, 1,5-pentanediol or 1,6-hexamethylene glycol is preferred. In addition, in terms of easily reducing the above-mentioned continuous foam rate, neopentyl glycol is preferred.
上述多元醇之重量平均分子量並無特別限定,較佳之下限為500,較佳之上限為5000。若上述多元醇之重量平均分子量為500以上,則上述聚胺酯發泡體可具有適度之柔軟性。若上述多元醇之重量平均分子量為5000以下,則可抑制上述聚胺酯發泡體之強度過度降低。上述多元醇之重量平均分子量之更佳下限為700,更佳之上限為2000,進而較佳之下限為800,進而較佳之上限為1500。 再者,多元醇之重量平均分子量例如可於製備試樣之四氫呋喃溶液後,使用GPC裝置(例如,東曹公司製造,製品名「HLC-8220」,管柱:TSKgelSurper HZM-N(4根))測定。於GPC測定中,作為測定條件,例如可採用40℃、流量0.5 mL/min。The weight average molecular weight of the polyol is not particularly limited, and the preferred lower limit is 500, and the preferred upper limit is 5,000. If the weight average molecular weight of the polyol is 500 or more, the polyurethane foam may have moderate flexibility. If the weight average molecular weight of the polyol is 5000 or less, the strength of the polyurethane foam can be prevented from being excessively reduced. A more preferable lower limit of the weight average molecular weight of the polyol is 700, a more preferable upper limit is 2,000, a still more preferable lower limit is 800, and a more preferable upper limit is 1,500. Furthermore, the weight average molecular weight of the polyol can be used, for example, after preparing the tetrahydrofuran solution of the sample, using a GPC device (for example, manufactured by Tosoh Corporation, product name "HLC-8220", column: TSKgelSurper HZM-N (4)) ) Determination. In the GPC measurement, as the measurement conditions, for example, 40°C and a flow rate of 0.5 mL/min can be adopted.
上述胺酯樹脂組成物中之上述聚異氰酸酯之異氰酸酯指數並無特別限定,較佳之下限為70,較佳之上限為120。 異氰酸酯指數係指異氰酸酯與含活性氫之化合物之反應中的異氰酸酯當量相關之指數。於異氰酸酯指數未達100情形時,意指羥基等反應基與異氰酸基相比過剩,於異氰酸酯指數超過100之情形時,意指異氰酸基與羥基等反應基相比過剩。 若上述異氰酸酯指數為70以上,則藉由上述聚異氰酸酯所進行之交聯變得充分,容易調整氣泡結構,故而上述聚胺酯發泡體可具有適度之密度,強度與柔軟性變高。若上述異氰酸酯指數為120以下,則上述聚胺酯發泡體之交聯度不會過度提高,玻璃轉移點(Tg)會變得較低,故而成為容易伸長之發泡體,且強度與柔軟性變高。The isocyanate index of the polyisocyanate in the urethane resin composition is not particularly limited, and the preferred lower limit is 70, and the preferred upper limit is 120. The isocyanate index refers to the index related to the isocyanate equivalent in the reaction of isocyanate and active hydrogen-containing compound. When the isocyanate index is less than 100, it means that the reactive group such as a hydroxyl group is excessive compared to the isocyanate group, and when the isocyanate index exceeds 100, it means that the isocyanate group is excessive compared to the reactive group such as a hydroxyl group. If the isocyanate index is 70 or more, the crosslinking by the polyisocyanate becomes sufficient and the cell structure is easily adjusted. Therefore, the polyurethane foam can have an appropriate density and increase strength and flexibility. If the isocyanate index is 120 or less, the degree of crosslinking of the polyurethane foam will not increase excessively, and the glass transition point (Tg) will become lower, so it becomes a foam that is easy to elongate, and its strength and flexibility are reduced. high.
上述胺酯樹脂組成物中之上述聚異氰酸酯之含量並無特別限定,例如較佳藉由增加上述胺酯樹脂組成物中之上述聚異氰酸酯之含量而提高樹脂之流動性等,以緩慢進行胺酯化反應,藉此生成更均勻大小之氣泡來調整氣泡結構。 上述聚異氰酸酯之含量相對於上述多元醇100重量%,較佳之下限為5重量%,較佳之上限為30重量%。若上述聚異氰酸酯之含量為5重量%以上,則可緩慢進行胺酯化反應而生成更均勻大小之氣泡,故而容易調整氣泡結構,上述聚胺酯發泡體之強度與柔軟性變高。若上述聚異氰酸酯之含量為30重量%以下,則上述聚胺酯發泡體之交聯度不會過度提高,玻璃轉移點(Tg)會變得較低,故而成為容易伸長之發泡體,且強度與柔軟性變高。上述聚異氰酸酯之含量之更佳下限為15重量%、更佳之上限為25重量%。The content of the polyisocyanate in the urethane resin composition is not particularly limited. For example, it is preferable to increase the fluidity of the resin by increasing the content of the polyisocyanate in the urethane resin composition to slow the urethane resin composition. Chemical reaction, thereby generating more uniformly sized bubbles to adjust the bubble structure. The content of the polyisocyanate relative to 100% by weight of the polyol has a preferred lower limit of 5% by weight, and a preferred upper limit of 30% by weight. If the content of the polyisocyanate is more than 5% by weight, the amination reaction can proceed slowly to generate more uniformly sized bubbles, so it is easy to adjust the bubble structure, and the strength and flexibility of the polyurethane foam become higher. If the content of the polyisocyanate is 30% by weight or less, the degree of crosslinking of the polyurethane foam will not be excessively increased, and the glass transition point (Tg) will become lower, so it becomes a foam that is easy to elongate and has strength. And flexibility becomes higher. The lower limit of the content of the polyisocyanate is more preferably 15% by weight, and the upper limit is more preferably 25% by weight.
上述胺酯樹脂組成物視需要亦可含有觸媒。 作為上述觸媒,例如可列舉:有機錫化合物、有機鋅化合物、有機鎳化合物、有機鐵化合物、金屬觸媒、三級胺系觸媒、有機酸鹽等。其中,較佳為有機錫化合物。該等觸媒可單獨使用,亦可併用兩種以上。 上述觸媒之添加量並無特別限定,相對於上述多元醇100重量份,較佳之下限為0.05重量份,較佳之上限為5.0重量份,更佳之上限為4.0重量份。The said urethane resin composition may contain a catalyst as needed. Examples of the above-mentioned catalyst include organic tin compounds, organic zinc compounds, organic nickel compounds, organic iron compounds, metal catalysts, tertiary amine catalysts, organic acid salts, and the like. Among them, organotin compounds are preferred. These catalysts may be used alone, or two or more of them may be used in combination. The amount of the catalyst added is not particularly limited. Relative to 100 parts by weight of the polyol, the lower limit is preferably 0.05 parts by weight, the upper limit is preferably 5.0 parts by weight, and the upper limit is more preferably 4.0 parts by weight.
作為上述有機錫化合物,例如可列舉:辛酸亞錫、二乙酸二丁基錫、二月桂酸二丁基錫等。作為上述有機鋅化合物,例如可舉:辛酸鋅等。作為上述有機鎳化合物,例如可列舉:乙醯乙酸鎳、二乙醯乙酸鎳等。作為上述有機鐵化合物,例如可舉:乙醯乙酸鐵等。作為上述金屬觸媒,例如可列舉:乙酸鈉等鹼金屬或鹼土類金屬之烷氧化物、苯氧化物等。作為上述三級胺系觸媒,例如可列舉:三乙胺、三伸乙二胺、N-甲基嗎福林二甲胺甲基苯酚、咪唑、1,8-二吖雙環[5.4.0]十一烯等。As said organotin compound, stannous octoate, dibutyl tin diacetate, dibutyl tin dilaurate, etc. are mentioned, for example. As said organozinc compound, zinc caprylate etc. are mentioned, for example. As said organic nickel compound, nickel acetylacetate, nickel diacetylacetate, etc. are mentioned, for example. Examples of the above-mentioned organic iron compound include iron acetyl acetate and the like. Examples of the metal catalyst include alkoxides and phenoxides of alkali metals or alkaline earth metals such as sodium acetate. Examples of the tertiary amine catalyst include: triethylamine, triethylenediamine, N-methylmorphine dimethylamine methylphenol, imidazole, 1,8-diazebicyclo[5.4.0 ] Undecene etc.
上述胺酯樹脂組成物視需要亦可含有發泡劑。 作為上述發泡劑,可列舉一般之聚胺酯發泡體所使用之發泡劑。具體而言,例如可列舉:水、戊烷、環戊烷、己烷、環己烷、二氯甲烷、二氧化碳等。 上述發泡劑之添加量並無特別限定,設為適宜之量,但於上述發泡劑為水之情形時,通常相對於上述多元醇100重量份,為0.1~3重量份左右。The said urethane resin composition may contain a foaming agent as needed. As the above-mentioned foaming agent, foaming agents used for general polyurethane foams can be cited. Specifically, for example, water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide and the like can be cited. The addition amount of the foaming agent is not particularly limited and is set to an appropriate amount, but when the foaming agent is water, it is usually about 0.1 to 3 parts by weight with respect to 100 parts by weight of the polyol.
上述胺酯樹脂組成物視需要亦可含有泡沫穩定劑。 作為上述泡沫穩定劑,例如可列舉:二甲基矽氧烷、聚醚二甲基矽氧烷、苯基甲基矽氧烷等矽酮系泡沫穩定劑。其中,較佳為聚醚二甲基矽氧烷。聚醚二甲基矽氧烷中,更佳為二甲基聚矽氧烷與聚醚之嵌段共聚物。該等泡沫穩定劑可單獨使用,亦可併用兩種以上。 上述泡沫穩定劑之添加量並無特別限定,相對於上述多元醇100重量份,較佳之下限為0.2重量份,較佳之上限為7重量份,更佳之下限為0.4重量份,更佳之上限為5重量份。The above-mentioned urethane resin composition may contain a foam stabilizer as needed. Examples of the aforementioned foam stabilizer include silicone-based foam stabilizers such as dimethylsiloxane, polyether dimethylsiloxane, and phenylmethylsiloxane. Among them, polyether dimethylsiloxane is preferred. Among the polyether dimethylsiloxane, a block copolymer of dimethylpolysiloxane and polyether is more preferred. These foam stabilizers may be used alone, or two or more of them may be used in combination. The addition amount of the foam stabilizer is not particularly limited. Relative to 100 parts by weight of the polyol, the lower limit is preferably 0.2 parts by weight, the upper limit is preferably 7 parts by weight, the lower limit is more preferably 0.4 parts by weight, and the upper limit is more preferably 5 parts by weight. Parts by weight.
上述胺酯樹脂組成物,視需要亦可含有紫外線吸收劑、抗氧化劑、有機填充劑、無機填充劑、著色劑等於聚胺酯發泡體之製造中一般使用之添加劑。The above-mentioned urethane resin composition may contain ultraviolet absorbers, antioxidants, organic fillers, inorganic fillers, and colorants as required, which are the same as additives generally used in the production of polyurethane foams.
作為製造上述聚胺酯發泡體之方法,例如可列舉如下方法(機械絲線法(mechanical floss method))等:於脫模襯墊或樹脂膜之表面塗佈將空氣、氮等機械地混合而起泡之胺酯樹脂組成物(液體),並將所塗佈之胺酯樹脂組成物加熱硬化,藉此製造發泡體。又,可列舉如下方法(化學發泡法)等:使上述聚異氰酸酯與用以形成上述聚胺酯發泡體之原料進行反應而產生氣體。其中,較佳為機械絲線法。藉由機械絲線法所獲得之聚胺酯發泡體相較於藉由化學發泡法所獲得之聚胺酯發泡體,更容易成為高密度,且氣泡結構更容易變得微細且均勻。As a method of producing the above polyurethane foam, for example, the following method (mechanical floss method) etc. can be cited: the surface of the release liner or the resin film is coated and air, nitrogen, etc. are mechanically mixed to foam The urethane resin composition (liquid), and the applied urethane resin composition is heated and hardened to produce a foam. Moreover, the following method (chemical foaming method) etc. are mentioned, and the said polyisocyanate and the raw material for forming the said polyurethane foam are made to react, and a gas is generated. Among them, the mechanical wire method is preferred. Compared with the polyurethane foam obtained by the chemical foaming method, the polyurethane foam obtained by the mechanical thread method is easier to become high density, and the bubble structure is easier to become fine and uniform.
作為上述聚烯烴發泡體,例如可列舉由聚乙烯系樹脂、聚丙烯系樹脂、聚丁二烯系樹脂等樹脂構成之發泡體。其中,就容易獲得柔軟之聚烯烴發泡體之方面而言,較佳為聚乙烯系樹脂。As said polyolefin foam, the foam which consists of resins, such as a polyethylene resin, a polypropylene resin, a polybutadiene resin, etc. is mentioned, for example. Among them, a polyethylene-based resin is preferred in terms of easily obtaining a flexible polyolefin foam.
上述發泡體基材之剪切斷裂強度之下限為200 N/inch2 ,上限為500 N/inch2 。若上述剪切斷裂強度為200 N/inch2 以上,則上述發泡體基材之強度變得充分高,兩面黏著帶之耐掉落撞擊性提高。若上述剪切斷裂強度為500 N/inch2 以下,則可抑制上述發泡體基材之柔軟性過度降低,故而可減少顯示裝置之顯示不均,將兩面黏著帶自被接著體剝離時能容易地撕掉上述發泡體基材。上述剪切斷裂強度之較佳下限為220 N/inch2 ,較佳之上限為470 N/inch2 ,更佳之下限為240 N/inch2 ,更佳之上限為450 N/inch2 ,進而較佳之下限為270 N/inch2 ,進而較佳之上限為415 N/inch2 。The lower limit of the shear rupture strength of the foam substrate is 200 N/inch 2 , and the upper limit is 500 N/inch 2 . If the shear rupture strength is 200 N/inch 2 or more, the strength of the foam base material becomes sufficiently high, and the drop impact resistance of the double-sided adhesive tape is improved. If the shear rupture strength is 500 N/inch 2 or less, the flexibility of the foam base material can be prevented from being excessively reduced, so the display unevenness of the display device can be reduced, and the double-sided adhesive tape can be peeled off from the adherend. The aforementioned foam substrate is easily torn off. The preferred lower limit of the above-mentioned shear rupture strength is 220 N/inch 2 , the preferred upper limit is 470 N/inch 2 , the more preferred lower limit is 240 N/inch 2 , the more preferred upper limit is 450 N/inch 2 , and the more preferred lower limit It is 270 N/inch 2 , and the more preferable upper limit is 415 N/inch 2 .
再者,剪切斷裂強度可藉由以下方法測定。
圖1中示出表示剪切斷裂強度之測定方法之示意圖。首先,將兩面黏著帶之尺寸25 mm×25 mm之試驗片18及2片尺寸125 mm×50 mm、厚度2 mm之SUS板19如圖1所示進行積層。於5 kg、10秒之條件下使用重物壓接該積層體,然後靜置24小時,製作經由試驗片18貼合有2片SUS板19之試驗用樣品。將該試驗用樣品其中之一SUS板19加以固定後,於23℃之條件下,將另一SUS板19之上方一方沿與SUS板之積層方向垂直之方向(圖中箭頭方向)以12.7 mm/min之條件進行拉伸,測定試驗片18斷裂時施加於試驗片18之力(斷裂點強度)。再者,試驗片18斷裂,意指發泡體基材發生層間破壞。
上述發泡體基材之剪切斷裂強度,可藉由改變胺酯樹脂組成物中之聚異氰酸酯及多元醇之種類及含量而進行調整。即便於原料相同之情形時,亦可藉由將氣泡體積分率、氣泡之長徑分佈之平均值及標準偏差等設定為合適之範圍而進行調整。Furthermore, the shear breaking strength can be measured by the following method.
Fig. 1 shows a schematic diagram showing the method of measuring the shear breaking strength. First, a
上述發泡體基材之25%抗壓強度並無特別限定,較佳之下限為0.015 MPa,較佳之上限為0.08 MPa。若上述25%抗壓強度為0.015 MPa以上,則上述發泡體基材之強度變得充分高,兩面黏著帶之耐掉落撞擊性提高。若上述25%抗壓強度為0.08 MPa以下,則可抑制上述發泡體基材之柔軟性過度降低,故而可良好地壓接兩面黏著帶,可減少顯示裝置之顯示不均,將兩面黏著帶自被接著體剝離時能容易地撕掉上述發泡體基材。上述25%抗壓強度之更佳下限為0.02 MPa,更佳之上限為0.07 MPa,進而較佳之下限為0.025 MPa,進而較佳之上限為0.065 MPa,進而更佳之下限為0.03 MPa,進而更佳之上限為0.06 MPa。 再者,25%抗壓強度可藉由依據JIS K 6254:2010進行測定而求出。 上述發泡體基材之25%抗壓強度,可藉由改變胺酯樹脂組成物中之聚異氰酸酯及多元醇之種類及含量而進行調整。即便於原料相同之情形時,亦可藉由將氣泡體積分率、氣泡之長徑分佈之平均值及標準偏差等設定為合適之範圍而進行調整。The 25% compressive strength of the foam substrate is not particularly limited, and the preferred lower limit is 0.015 MPa, and the preferred upper limit is 0.08 MPa. If the 25% compressive strength is 0.015 MPa or more, the strength of the foam base material becomes sufficiently high, and the drop impact resistance of the double-sided adhesive tape is improved. If the 25% compressive strength is 0.08 MPa or less, the flexibility of the foam substrate can be prevented from being excessively reduced, so the adhesive tape on both sides can be pressed well, and the display unevenness of the display device can be reduced. The above-mentioned foam base material can be easily torn off when peeling from the adherend. A more preferable lower limit of the 25% compressive strength is 0.02 MPa, a more preferable upper limit is 0.07 MPa, a still more preferable lower limit is 0.025 MPa, a still more preferable upper limit is 0.065 MPa, a still more preferable lower limit is 0.03 MPa, and a more preferable upper limit is 0.06 MPa. Furthermore, the 25% compressive strength can be obtained by measuring in accordance with JIS K 6254:2010. The 25% compressive strength of the aforementioned foam substrate can be adjusted by changing the type and content of polyisocyanate and polyol in the urethane resin composition. Even when the raw materials are the same, it can be adjusted by setting the bubble volume fraction, the average value and standard deviation of the bubble's long-diameter distribution, etc., to an appropriate range.
上述發泡體基材之玻璃轉移點並無特別限定,較佳之下限為-30℃,較佳之上限為30℃。若上述發泡體基材之玻璃轉移點為-30℃以上,則上述發泡體基材顯示良好之低反彈性,可緩和應力。若上述發泡體基材之玻璃轉移點為30℃以下,則上述發泡體基材可具有適度之柔軟性,又,成為容易伸長之發泡體,且強度與柔軟性變高。上述發泡體基材之玻璃轉移點之更佳下限為-25℃,更佳之上限為20℃。
再者,玻璃轉移點可使用黏彈性測定裝置(例如,Rheometrics公司製造之「Rheometrics Dynamic Analyze RDA-700」),於測定溫度-30~100℃、升溫速度3℃/min、頻率1 Hz之條件下求出。The glass transition point of the foam substrate is not particularly limited, and the preferred lower limit is -30°C, and the preferred upper limit is 30°C. If the glass transition point of the foam substrate is -30°C or higher, the foam substrate exhibits good low resilience and can relax stress. If the glass transition point of the foam base material is 30°C or less, the foam base material can have moderate flexibility, become a foam that is easy to extend, and increase the strength and flexibility. A more preferable lower limit of the glass transition point of the foam substrate is -25°C, and a more preferable upper limit is 20°C.
Furthermore, the glass transition point can be measured using a viscoelasticity measuring device (for example, "Rheometrics Dynamic Analyze RDA-700" manufactured by Rheometrics) under the conditions of measuring temperature -30~100℃,
上述發泡體基材之厚度並無特別限定,較佳之下限為100 μm,較佳之上限為1000 μm。若上述發泡體基材之厚度為100 μm以上,則上述發泡體基材可具有適度之柔軟性。若上述發泡體基材之厚度為1000 μm以下,則可抑制氣泡大小之變動,又,可抑制因運送時之掉落等導致受到撞擊而使上述發泡體基材伸長斷裂。上述發泡體基材之厚度之更佳下限為150 μm,更佳之上限為950 μm,進而較佳之下限為300 μm,進而較佳之上限為750 μm,進而更佳之下限為450 μm,進而更佳之上限為700 μm。 再者,發泡體基材之厚度可使用針盤式厚度規(例如,三豐公司製造,「ABS數位式指示器」)測定。The thickness of the aforementioned foam substrate is not particularly limited, and the preferred lower limit is 100 μm, and the preferred upper limit is 1000 μm. If the thickness of the foam substrate is 100 μm or more, the foam substrate may have moderate flexibility. If the thickness of the foam base material is 1000 μm or less, the change in the size of the bubbles can be suppressed, and the foam base material can be prevented from being stretched and broken due to impact due to falling during transportation or the like. A more preferable lower limit of the thickness of the aforementioned foam substrate is 150 μm, a more preferable upper limit is 950 μm, a still more preferable lower limit is 300 μm, a still more preferable upper limit is 750 μm, and a more preferable lower limit is 450 μm, and still more preferably The upper limit is 700 μm. Furthermore, the thickness of the foam substrate can be measured using a dial-type thickness gauge (for example, "ABS digital indicator" manufactured by Mitutoyo Corporation).
本發明之兩面黏著帶亦可進而於上述發泡體基材之至少單側具有樹脂片。藉由使用上述樹脂片,可抑制操作時上述發泡體基材伸長斷裂,且可對兩面黏著帶賦予二次加工性。 上述樹脂片可積層於上述發泡體基材之單側,亦可積層於兩側。 構成上述樹脂片之樹脂並無特別限定,例如可列舉:聚對苯二甲酸乙二酯等聚酯系樹脂、丙烯酸系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、聚氯乙烯、環氧樹脂、矽氧樹脂、酚樹脂、聚醯亞胺、聚酯、聚碳酸酯等。其中,就柔軟性優異之方面而言,較佳為丙烯酸系樹脂、聚乙烯系樹脂、聚丙烯系樹脂、聚酯系樹脂。聚酯系樹脂中,較佳為聚對苯二甲酸乙二酯。The double-sided adhesive tape of the present invention may further have a resin sheet on at least one side of the above-mentioned foam base material. By using the above-mentioned resin sheet, the expansion and fracture of the above-mentioned foam base material during handling can be suppressed, and secondary workability can be imparted to the double-sided adhesive tape. The said resin sheet may be laminated on one side of the said foam base material, and may be laminated on both sides. The resin constituting the resin sheet is not particularly limited, and examples include polyester resins such as polyethylene terephthalate, acrylic resins, polyethylene resins, polypropylene resins, polyvinyl chloride, and epoxy resins. , Silicone resin, phenol resin, polyimide, polyester, polycarbonate, etc. Among them, in terms of excellent flexibility, acrylic resins, polyethylene resins, polypropylene resins, and polyester resins are preferred. Among polyester resins, polyethylene terephthalate is preferred.
又,構成上述樹脂片之樹脂亦可為熱塑性樹脂。上述熱塑性樹脂並無特別限定,例如可列舉:苯乙烯系(共)聚合物、烯烴系(共)聚合物、氯乙烯系(共)聚合物、聚醚酯系三嵌段系(共)聚合物、聚酯系(共)聚合物、胺酯系(共)聚合物、醯胺系(共)聚合物、丙烯酸系(共)聚合物等。其中,就可發揮作為彈性體之強度、伸長率、柔軟性、自黏著性,可發揮優異之二次加工性,且同時進一步提高樹脂片與發泡體基材之密接性之觀點而言,上述熱塑性樹脂較佳為丙烯酸系(共)聚合物、苯乙烯系(共)聚合物或烯烴系(共)聚合物。進而,更佳為丙烯酸系(共)聚合物或苯乙烯系(共)聚合物,進而較佳為苯乙烯系(共)聚合物。In addition, the resin constituting the above-mentioned resin sheet may be a thermoplastic resin. The above-mentioned thermoplastic resin is not particularly limited. For example, styrene-based (co)polymers, olefin-based (co)polymers, vinyl chloride-based (co)polymers, and polyetherester-based triblock-based (co)polymers can be mentioned. Materials, polyester-based (co)polymers, urethane-based (co)polymers, amide-based (co)polymers, acrylic (co)polymers, etc. Among them, in terms of the strength, elongation, flexibility, and self-adhesiveness of an elastomer, excellent secondary processability, and at the same time, the adhesiveness of the resin sheet and the foam substrate can be further improved. The above-mentioned thermoplastic resin is preferably an acrylic (co)polymer, a styrene (co)polymer, or an olefin (co)polymer. Furthermore, an acrylic (co)polymer or a styrene (co)polymer is more preferable, and a styrene (co)polymer is still more preferable.
於構成上述樹脂片之樹脂為熱塑性樹脂之情形時,上述樹脂片之拉伸彈性模數較佳為200 MPa以下。藉由使用拉伸彈性模數為200 MPa以下之柔軟之樹脂,而確保兩面黏著帶整體之柔軟性,容易將兩面黏著帶捲繞為捲筒狀,操作性顯著提高。 再者,拉伸彈性模數可藉由依據JIS K 7161之方法測定。具體而言,例如使用例如高分子計器公司製造之沖裁刀「拉伸1號型啞鈴狀」等,將樹脂片沖裁成啞鈴狀而製作試驗片。對於所獲得之試驗片之拉伸彈性模數,例如使用島津製作所公司製造之「Autograph AGS-X」等,以拉伸速度100 mm/min測定。根據1~3%之應變間之拉伸強度的斜率算出拉伸彈性模數。When the resin constituting the resin sheet is a thermoplastic resin, the tensile modulus of the resin sheet is preferably 200 MPa or less. By using a soft resin with a tensile elastic modulus of 200 MPa or less, the overall flexibility of the double-sided adhesive tape is ensured, and the double-sided adhesive tape is easily wound into a roll shape, which significantly improves the operability. Furthermore, the tensile modulus of elasticity can be measured by a method based on JIS K 7161. Specifically, for example, the resin sheet is punched into a dumbbell shape by using, for example, a punching knife "stretched No. 1 dumbbell shape" manufactured by Polymer Meter Co., Ltd. to prepare a test piece. For the tensile elastic modulus of the obtained test piece, for example, using "Autograph AGS-X" manufactured by Shimadzu Corporation, etc., it is measured at a tensile speed of 100 mm/min. Calculate the tensile modulus of elasticity based on the slope of the tensile strength between 1% and 3% of the strain.
於上述樹脂片積層於上述發泡體基材兩側之情形時,構成至少一樹脂片之樹脂較佳為熱塑性樹脂。即,本發明之兩面黏著帶較佳具有由熱塑性樹脂構成之樹脂片。 本發明之兩面黏著帶具有積層於上述發泡體基材第1面之第1樹脂片、及積層於上述發泡體基材第2面之第2樹脂片,選自由上述第1樹脂片及上述第2樹脂片組成之群中之至少一者較佳為由熱塑性樹脂構成之樹脂片。When the resin sheet is laminated on both sides of the foam base material, the resin constituting at least one resin sheet is preferably a thermoplastic resin. That is, the double-sided adhesive tape of the present invention preferably has a resin sheet made of a thermoplastic resin. The double-sided adhesive tape of the present invention has a first resin sheet laminated on the first surface of the foam substrate and a second resin sheet laminated on the second surface of the foam substrate, selected from the first resin sheet and At least one of the group consisting of the second resin sheet is preferably a resin sheet made of a thermoplastic resin.
上述樹脂片之厚度並無特別限定,較佳之下限為10 μm,較佳之上限為100 μm。若上述樹脂片之厚度為10 μm以上,則即便於拉伸上述樹脂片時,上述樹脂片亦不易斷裂。若上述樹脂片之厚度為100 μm以下,則可抑制對被接著體之追隨性之降低。上述樹脂片之厚度之更佳下限為15 μm,更佳之上限為80 μm,進而較佳之下限為20 μm,進而較佳之上限為60 μm,進而更佳之下限為25 μm,進而更佳之上限為50 μm。The thickness of the above resin sheet is not particularly limited, and the preferred lower limit is 10 μm, and the preferred upper limit is 100 μm. If the thickness of the resin sheet is 10 μm or more, the resin sheet is not easily broken even when the resin sheet is stretched. If the thickness of the above-mentioned resin sheet is 100 μm or less, the decrease in the followability to the adherend can be suppressed. A more preferable lower limit of the thickness of the resin sheet is 15 μm, a more preferable upper limit is 80 μm, a still more preferable lower limit is 20 μm, a still more preferable upper limit is 60 μm, an even more preferable lower limit is 25 μm, and a more preferable upper limit is 50 μm.
上述樹脂片亦可進行著色。藉由將上述樹脂片著色,可對兩面黏著帶賦予遮光性。 將上述樹脂片著色之方法並無特別限定,例如可列舉:將碳黑、氧化鈦等粒子或微細氣泡揑合至構成上述樹脂片之樹脂之方法、於上述樹脂片之表面塗佈油墨之方法等。The above-mentioned resin sheet may also be colored. By coloring the above-mentioned resin sheet, light-shielding properties can be imparted to the double-sided adhesive tape. The method of coloring the resin sheet is not particularly limited, and examples include: a method of kneading particles or fine bubbles such as carbon black and titanium oxide into the resin constituting the resin sheet, a method of coating ink on the surface of the resin sheet, etc. .
積層於上述發泡體基材兩側之黏著劑層可為相同之組成,亦可為分別不同之組成。 上述黏著劑層並無特別限定,例如可列舉由丙烯酸黏著劑、橡膠系黏著劑、胺酯黏著劑、矽酮系黏著劑等構成之黏著劑層。其中,就容易調節黏著力,對光、熱、水分等相對穩定,且可應用於各種被接著體之方面而言,較佳為由含有丙烯酸共聚物及黏著賦予劑之丙烯酸黏著劑構成之黏著劑層。The adhesive layers laminated on both sides of the foam substrate may have the same composition or different compositions. The above-mentioned adhesive layer is not particularly limited, and examples thereof include adhesive layers composed of acrylic adhesives, rubber-based adhesives, urethane adhesives, silicone-based adhesives, and the like. Among them, in terms of easy adjustment of adhesive force, relatively stable to light, heat, moisture, etc., and can be applied to various substrates, the adhesive is preferably composed of an acrylic adhesive containing an acrylic copolymer and an adhesion imparting agent Agent layer.
上述丙烯酸共聚物係使單體混合物共聚而獲得者。要使上述單體混合物共聚而獲得上述丙烯酸共聚物,只要使上述單體混合物於聚合起始劑之存在下進行自由基反應即可。作為使上述單體混合物進行自由基反應之方法即聚合方法,可使用先前公知之方法,例如可列舉:溶液聚合(沸點聚合或恆溫聚合)、乳化聚合、懸浮聚合、塊狀聚合等。作為使上述單體混合物進行自由基反應時之反應方式,例如可列舉:活性自由基聚合、游離自由基聚合等。The acrylic copolymer is obtained by copolymerizing a monomer mixture. To copolymerize the above-mentioned monomer mixture to obtain the above-mentioned acrylic copolymer, it is only necessary to subject the above-mentioned monomer mixture to a radical reaction in the presence of a polymerization initiator. As a method of radically reacting the monomer mixture, that is, a polymerization method, a conventionally known method can be used, and examples thereof include solution polymerization (boiling point polymerization or isothermal polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization. Examples of the reaction method when the monomer mixture is subjected to a radical reaction include living radical polymerization, free radical polymerization, and the like.
上述丙烯酸共聚物之重量平均分子量(Mw)相對於數量平均分子量(Mn)之比(分子量分佈,Mw/Mn)並無特別限定,較佳之下限為1.05,較佳之上限為5.0。若上述分子量分佈(Mw/Mn)處於上述範圍內,則低分子量成分等之含量會變少,故而上述黏著劑層之凝聚力提高,兩面黏著帶之耐掉落撞擊性提高。上述分子量分佈(Mw/Mn)之更佳上限為3.0,進而較佳之上限為2.5,尤佳之上限為2.3。為了將上述分子量分佈(Mw/Mn)調整為上述範圍,只要調整聚合起始劑、聚合溫度等聚合條件即可。 再者,數量平均分子量(Mn)及重量平均分子量(Mw)係指利用GPC(Gel Permeation Chromatography:凝膠滲透層析法)所獲得之標準聚苯乙烯換算之分子量。GPC中例如可使用2690 Separations Model(Waters公司製造)等。又,亦可使用GPC裝置(例如,東曹公司製造,製品名「HLC-8220」,管柱:TSKgelSurper HZM-N(4根))等,作為溶劑,可使用四氫呋喃,作為測定條件,例如可採用40℃、流量0.5 mL/min。The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer (molecular weight distribution, Mw/Mn) is not particularly limited, and the preferred lower limit is 1.05, and the preferred upper limit is 5.0. If the above-mentioned molecular weight distribution (Mw/Mn) is within the above-mentioned range, the content of low-molecular-weight components and the like will decrease, so the cohesive force of the above-mentioned adhesive layer will increase, and the drop impact resistance of the double-sided adhesive tape will increase. A more preferable upper limit of the aforementioned molecular weight distribution (Mw/Mn) is 3.0, a further preferable upper limit is 2.5, and a particularly preferable upper limit is 2.3. In order to adjust the above-mentioned molecular weight distribution (Mw/Mn) to the above-mentioned range, it is only necessary to adjust the polymerization conditions such as the polymerization initiator and the polymerization temperature. Furthermore, the number average molecular weight (Mn) and weight average molecular weight (Mw) refer to the molecular weight in terms of standard polystyrene obtained by GPC (Gel Permeation Chromatography). For GPC, for example, 2690 Separations Model (manufactured by Waters Corporation) or the like can be used. In addition, a GPC device (for example, manufactured by Tosoh Corporation, product name "HLC-8220", column: TSKgelSurper HZM-N (4)), etc. can also be used. As a solvent, tetrahydrofuran can be used as the measurement conditions. For example, Use 40℃, flow rate 0.5 mL/min.
於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以下之情形時,上述丙烯酸共聚物較佳含有來自丙烯酸-2-乙基己酯之構成單元。 於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以下之情形時,上述來自丙烯酸-2-乙基己酯之構成單元之含量並無特別限定,較佳之下限為80重量%,較佳之上限為98重量%。若上述構成單元之含量為80重量%以上,則上述丙烯酸共聚物之玻璃轉移點降低,上述黏著劑層之對被接著體之潤濕性變高,兩面黏著帶之耐掉落撞擊性提高。若上述構成單元之含量為98重量%以下,則上述黏著劑層之凝聚力提高,兩面黏著帶之耐掉落撞擊性提高。上述構成單元之含量之更佳下限為90重量%,更佳之上限為97重量%。When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or less, the acrylic copolymer preferably contains a structural unit derived from 2-ethylhexyl acrylate. When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or less, the content of the structural unit derived from 2-ethylhexyl acrylate is not particularly limited, and the lower limit is preferably 80% by weight, more preferably The upper limit is 98% by weight. If the content of the structural unit is 80% by weight or more, the glass transition point of the acrylic copolymer decreases, the wettability of the adhesive layer to the adherend increases, and the drop impact resistance of the double-sided adhesive tape improves. If the content of the above-mentioned structural unit is 98% by weight or less, the cohesive force of the above-mentioned adhesive layer is improved, and the drop impact resistance of the double-sided adhesive tape is improved. A more preferable lower limit of the content of the above-mentioned structural unit is 90% by weight, and a more preferable upper limit is 97% by weight.
於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以上之情形時,上述丙烯酸共聚物較佳含有來自具有碳數4以下之烷基之(甲基)丙烯酸烷基酯的構成單元。於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以上之情形時,上述具有碳數4以下之烷基之(甲基)丙烯酸烷基酯並無特別限定。作為上述具有碳數4以下之烷基之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯等。其中,較佳為(甲基)丙烯酸乙酯及(甲基)丙烯酸正丁酯,更佳為該等之丙烯酸酯。該等具有碳數4以下之烷基之(甲基)丙烯酸烷基酯可單獨使用,亦可併用兩種以上。When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or more, the acrylic copolymer preferably contains a structural unit derived from an alkyl (meth)acrylate having an alkyl group with a carbon number of 4 or less. When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or more, the alkyl (meth)acrylate having an alkyl group with a carbon number of 4 or less is not particularly limited. Examples of the alkyl (meth)acrylate having an alkyl group having 4 or less carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, ( Isopropyl meth)acrylate, n-butyl (meth)acrylate, etc. Among them, ethyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and these acrylates are more preferred. These alkyl (meth)acrylates having an alkyl group with a carbon number of 4 or less may be used alone, or two or more of them may be used in combination.
於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以上之情形時,上述來自具有碳數4以下之烷基之(甲基)丙烯酸烷基酯的構成單元其含量並無特別限定,較佳之下限為40重量%,較佳之上限為80重量%。若上述構成單元之含量為40重量%以上,則上述黏著劑層之凝聚力提高,兩面黏著帶之耐掉落撞擊性提高。若上述構成單元之含量為80重量%以下,則可抑制上述黏著劑層之對被接著體之潤濕性過度降低,兩面黏著帶之耐掉落撞擊性提高。When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or more, the content of the structural unit derived from the alkyl (meth)acrylate having an alkyl group with a carbon number of 4 or less is not particularly limited. A preferable lower limit is 40% by weight, and a preferable upper limit is 80% by weight. If the content of the above-mentioned structural unit is 40% by weight or more, the cohesive force of the above-mentioned adhesive layer is improved, and the drop impact resistance of the double-sided adhesive tape is improved. If the content of the structural unit is 80% by weight or less, the wettability of the adhesive layer to the adherend can be prevented from being excessively reduced, and the drop and impact resistance of the double-sided adhesive tape can be improved.
於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以上之情形時,上述丙烯酸共聚物亦較佳含有來自丙烯酸-2-乙基己酯之構成單元。 於上述丙烯酸共聚物之分子量分佈(Mw/Mn)為2.5以上之情形時,上述來自丙烯酸-2-乙基己酯之構成單元之含量並無特別限定,較佳之下限為10重量%,較佳之上限為40重量%。若上述構成單元之含量為10重量%以上,則上述黏著劑層之凝聚力提高,兩面黏著帶之耐掉落撞擊性提高。若上述構成單元之含量為40重量%以下,則可抑制上述黏著劑層之凝聚力過度降低,兩面黏著帶之耐掉落撞擊性提高。When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or more, the acrylic copolymer preferably also contains structural units derived from 2-ethylhexyl acrylate. When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is 2.5 or more, the content of the structural unit derived from 2-ethylhexyl acrylate is not particularly limited, and the lower limit is preferably 10% by weight, more preferably The upper limit is 40% by weight. If the content of the above-mentioned structural unit is 10% by weight or more, the cohesive force of the above-mentioned adhesive layer is improved, and the drop impact resistance of the double-sided adhesive tape is improved. If the content of the above-mentioned structural unit is 40% by weight or less, the cohesive force of the above-mentioned adhesive layer can be suppressed from excessively decreasing, and the drop and impact resistance of the double-sided adhesive tape can be improved.
上述丙烯酸共聚物視需要,亦可含有除上述來自丙烯酸-2-乙基己酯之構成單元及上述來自具有碳數4以下之烷基之(甲基)丙烯酸烷基酯之構成單元以外的來自可共聚之其他聚合性單體之構成單元。 作為上述可共聚之其他聚合性單體,例如可列舉:具有碳數13~18之烷基之(甲基)丙烯酸烷基酯、官能性單體等。 作為上述具有碳數13~18之烷基之(甲基)丙烯酸烷基酯,例如可列舉:甲基丙烯酸十三烷基酯、(甲基)丙烯酸硬脂酯等。作為上述官能性單體,例如可列舉:(甲基)丙烯酸羥基烷基酯、甘油二甲基丙烯酸酯、(甲基)丙烯酸環氧丙酯、異氰酸2-甲基丙烯醯氧基乙酯、(甲基)丙烯酸、伊康酸、順丁烯二酸酐 、巴豆酸、順丁烯二酸、富馬酸等。 該等可共聚之其他聚合性單體可單獨使用,亦可併用兩種以上。其中,就藉由與交聯劑形成交聯結構而容易調整上述黏著劑層之凝膠分率之方面而言,較佳為具有如羥基或羧基之類的極性官能基之官能性單體,更佳為具有羥基之官能性單體。即,上述丙烯酸共聚物較佳含有羥基。If necessary, the acrylic copolymer may also contain other than the structural unit derived from the 2-ethylhexyl acrylate and the structural unit derived from the alkyl (meth)acrylate having an alkyl group with a carbon number of 4 or less. The constituent unit of other polymerizable monomers that can be copolymerized. As said other polymerizable monomer which can be copolymerized, the alkyl (meth)acrylate which has a C13-18 alkyl group, a functional monomer, etc. are mentioned, for example. Examples of the alkyl (meth)acrylate having an alkyl group having 13 to 18 carbon atoms include tridecyl methacrylate, stearyl (meth)acrylate, and the like. As the above-mentioned functional monomer, for example, hydroxyalkyl (meth)acrylate, glycerol dimethacrylate, glycidyl (meth)acrylate, 2-methacryloxyethyl isocyanate, Esters, (meth)acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid, fumaric acid, etc. These copolymerizable other polymerizable monomers may be used alone or in combination of two or more kinds. Among them, in terms of easily adjusting the gel fraction of the adhesive layer by forming a crosslinking structure with a crosslinking agent, a functional monomer having a polar functional group such as a hydroxyl group or a carboxyl group is preferred, More preferably, it is a functional monomer having a hydroxyl group. That is, the above-mentioned acrylic copolymer preferably contains a hydroxyl group.
上述丙烯酸共聚物之重量平均分子量(Mw)較佳下限為30萬,較佳之上限為200萬。若上述重量平均分子量為30萬以上,則上述黏著劑層成為適度之硬度而凝聚力變得充分,黏著力變高。若上述重量平均分子量為200萬以下,則上述黏著劑層之黏著力變得充分。上述重量平均分子量之更佳下限為50萬,更佳之上限為140萬。為了將上述重量平均分子量調整為上述範圍,只要調整聚合起始劑、聚合溫度等聚合條件即可。The preferred lower limit of the weight average molecular weight (Mw) of the acrylic copolymer is 300,000, and the preferred upper limit is 2 million. If the weight average molecular weight is 300,000 or more, the adhesive layer has an appropriate hardness, the cohesive force becomes sufficient, and the adhesive force becomes high. If the weight average molecular weight is 2 million or less, the adhesive force of the adhesive layer becomes sufficient. A more preferable lower limit of the above-mentioned weight average molecular weight is 500,000, and a more preferable upper limit is 1.4 million. In order to adjust the said weight average molecular weight to the said range, what is necessary is just to adjust polymerization conditions, such as a polymerization initiator and a polymerization temperature.
作為上述聚合起始劑,例如可列舉有機過氧化物、偶氮化合物等。 作為上述有機過氧化物,例如可列舉:1,1-雙(三級己基過氧)-3,3,5-三甲基環己烷、過氧異丁酸三級己酯、過氧異丁酸三級丁酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧)己烷、過氧-2-乙基己酸三級己酯、過氧-2-乙基己酸三級丁酯、過氧異丁酸三級丁酯、過氧-3,5,5-三甲基己酸三級丁酯、過氧月桂酸三級丁酯等。 上述偶氮化合物若為一般用於自由基聚合者,則並無特別限定。作為上述偶氮化合物,例如可列舉:2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、1,1-偶氮雙(環己烷-1-羰腈(carbonitrile))、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、4,4'-偶氮雙(4-氰基戊酸)、二甲基-2,2'-偶氮雙(2-甲基丙酸酯)、二甲基-1,1'-偶氮雙(1-環己烷羧酸酯)、2,2'-偶氮雙{2-甲基-N-[1,1'-雙(羥基甲基)-2-羥基乙基]丙醯胺}、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2'-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺]、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙{2-[1-(2-羥基乙基)-2-咪唑啉-2-基]丙烷}二鹽酸鹽、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2'-偶氮雙(2-甲脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙醯脒(methyl propione amidine)]四水合物、2,2'-偶氮雙(1-亞胺基-1-吡咯烷基(pyrrolidino)-2-甲基丙烷)二鹽酸鹽、2,2'-偶氮雙(2,4,4-三甲基戊烷)等。 又,作為上述聚合起始劑,使活性自由基聚合開始之聚合起始劑並無特別限定,較佳為有機碲聚合起始劑。 該等聚合起始劑可單獨使用,亦可併用兩種以上。As said polymerization initiator, an organic peroxide, an azo compound, etc. are mentioned, for example. As the above-mentioned organic peroxides, for example, 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane, tertiary hexyl peroxyisobutyrate, and isopropyl peroxy Tertiary butyl butyrate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, tertiary hexyl peroxy-2-ethylhexanoate, peroxy Tertiary butyl 2-ethylhexanoate, tertiary butyl peroxyisobutyrate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, etc. . The above-mentioned azo compound is not particularly limited as long as it is generally used for radical polymerization. As the above-mentioned azo compound, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis( 2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis(cyclohexane-1 -Carbonitrile), 1-[(1-cyano-1-methylethyl)azo]carboxamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl Group-2,2'-azobis(2-methylpropionate), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), 2,2'-azo Bis{2-methyl-N-[1,1'-bis(hydroxymethyl)-2-hydroxyethyl]propanamide}, 2,2'-azobis[2-methyl-N-( 2-Hydroxyethyl) propanamide], 2,2'-azobis[N-(2-propenyl)-2-methyl propanamide], 2,2'-azobis(N-butyl 2-methylpropanamide), 2,2'-azobis(N-cyclohexyl-2-methylpropanamide), 2,2'-azobis[2-(2-imidazoline) -2-yl)propane]dihydrochloride, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(2-carboxamidinopropane) dihydrochloride, 2,2'- Azobis[N-(2-carboxyethyl)-2-methyl propione amidine] tetrahydrate, 2,2'-azobis(1-imino-1-pyrrolidine) (Pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis(2,4,4-trimethylpentane), etc. In addition, as the polymerization initiator, the polymerization initiator that initiates the living radical polymerization is not particularly limited, but an organic tellurium polymerization initiator is preferred. These polymerization initiators may be used alone, or two or more of them may be used in combination.
於使上述單體混合物進行自由基反應時,亦可使用分散穩定劑。作為上述分散穩定劑,例如可列舉:聚乙烯吡咯啶酮、聚乙烯醇、甲基纖維素、乙基纖維素、聚(甲基)丙烯酸、聚(甲基)丙烯酸酯、聚乙二醇等。When the monomer mixture is subjected to a radical reaction, a dispersion stabilizer may also be used. Examples of the dispersion stabilizer include: polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, ethylcellulose, poly(meth)acrylic acid, poly(meth)acrylate, polyethylene glycol, etc. .
於使上述單體混合物進行自由基反應時使用聚合溶劑之情形時,該聚合溶劑並無特別限定。作為上述聚合溶劑,例如可使用:己烷、環己烷、辛烷、甲苯、二甲苯等非極性溶劑。又,作為上述聚合溶劑,例如可使用:水、甲醇、乙醇、丙醇、丁醇、丙酮、甲基乙基酮、甲基異丁基酮、四氫呋喃、二烷、N,N-二甲基甲醯胺等高極性溶劑。該等聚合溶劑可單獨使用,亦可併用兩種以上。就聚合速度之觀點而言,聚合溫度較佳為0~110℃。When a polymerization solvent is used when the monomer mixture is subjected to a radical reaction, the polymerization solvent is not particularly limited. As the polymerization solvent, for example, non-polar solvents such as hexane, cyclohexane, octane, toluene, and xylene can be used. In addition, as the above-mentioned polymerization solvent, for example, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, two Highly polar solvents such as alkane and N,N-dimethylformamide. These polymerization solvents may be used alone, or two or more of them may be used in combination. From the viewpoint of the polymerization rate, the polymerization temperature is preferably 0 to 110°C.
作為上述黏著賦予劑,例如可列舉:松香系樹脂、松香酯系樹脂、氫化松香系樹脂、萜烯系樹脂、萜烯酚(terpene phenol)樹脂、薰草哢-茚系樹脂、脂環族飽和烴系樹脂、C5系石油樹脂、C9系石油樹脂、C5-C9共聚系石油樹脂等。該等黏著賦予劑可單獨使用,亦可併用兩種以上。其中,較佳為松香系樹脂或萜烯系樹脂,更佳為含有羥基之松香系樹脂或含有羥基之萜烯系樹脂。Examples of the above-mentioned adhesion imparting agent include rosin resins, rosin ester resins, hydrogenated rosin resins, terpene resins, terpene phenol resins, lavender-indene resins, and alicyclic saturated resins. Hydrocarbon resins, C5 petroleum resins, C9 petroleum resins, C5-C9 copolymerized petroleum resins, etc. These adhesion-imparting agents may be used alone, or two or more of them may be used in combination. Among them, rosin-based resins or terpene-based resins are preferred, and hydroxyl-containing rosin-based resins or hydroxyl-containing terpene-based resins are more preferred.
上述黏著賦予劑之軟化溫度較佳下限為70℃,較佳上限為170℃。若上述軟化溫度為70℃以上,則可抑制上述黏著劑層變得過軟而兩面黏著帶之耐掉落撞擊性降低。若上述軟化溫度為170℃以下,則上述黏著劑層之對被接著體之潤濕性變高,兩面黏著帶之耐掉落撞擊性提高。上述軟化溫度之更佳下限為120℃。 再者,所謂軟化溫度,係指藉由JIS K2207環球法所測定之軟化溫度。The preferred lower limit of the softening temperature of the adhesion imparting agent is 70°C, and the preferred upper limit is 170°C. If the softening temperature is 70° C. or higher, the adhesive layer can be prevented from becoming too soft and the drop impact resistance of the double-sided adhesive tape is reduced. If the softening temperature is 170° C. or lower, the wettability of the adhesive layer to the adherend becomes higher, and the drop impact resistance of the double-sided adhesive tape is improved. The lower limit of the above softening temperature is more preferably 120°C. Furthermore, the so-called softening temperature refers to the softening temperature measured by the JIS K2207 ring and ball method.
上述黏著賦予劑之羥值較佳下限為25,較佳上限為160。若上述羥值處於上述範圍內,則上述黏著劑層之對被接著體之潤濕性變高,兩面黏著帶之耐掉落撞擊性提高。上述羥值之更佳下限為30,更佳上限為150。 再者,羥值可藉由JIS K1557(鄰苯二甲酸酐法)測定。The preferred lower limit of the hydroxyl value of the adhesion imparting agent is 25, and the preferred upper limit is 160. If the hydroxyl value is within the above range, the wettability of the adhesive layer to the adherend becomes higher, and the drop impact resistance of the double-sided adhesive tape is improved. A more preferable lower limit of the above hydroxyl value is 30, and a more preferable upper limit is 150. Furthermore, the hydroxyl value can be measured by JIS K1557 (phthalic anhydride method).
上述黏著賦予劑之含量並無特別限定,相對於上述丙烯酸共聚物100重量份,較佳之下限為10重量份,較佳之上限為60重量份。若上述黏著賦予劑之含量為10重量份以上,則上述黏著劑層之黏著力變高。若上述黏著賦予劑之含量為60重量份以下,則可抑制上述黏著劑層變得過硬而黏著力降低。The content of the adhesion imparting agent is not particularly limited. With respect to 100 parts by weight of the acrylic copolymer, the lower limit is preferably 10 parts by weight, and the upper limit is preferably 60 parts by weight. If the content of the adhesive agent is 10 parts by weight or more, the adhesive force of the adhesive agent layer becomes higher. If the content of the adhesive imparting agent is 60 parts by weight or less, the adhesive layer can be prevented from becoming too hard and reducing the adhesive force.
上述黏著劑層較佳藉由添加交聯劑而於構成上述黏著劑層之樹脂(例如上述丙烯酸共聚物、上述黏著賦予劑等)之主鏈間形成有交聯結構。藉由調整上述交聯劑之種類及量,容易調整上述黏著劑層之凝膠分率。 上述交聯劑並無特別限定,例如可列舉:異氰酸酯系交聯劑、氮丙啶系交聯劑、環氧系交聯劑、金屬螯合物型交聯劑等。其中,較佳為異氰酸酯系交聯劑。 上述交聯劑之添加量相對於上述丙烯酸共聚物100重量份,較佳之下限為0.01重量份,較佳之上限為10重量份,更佳之下限為0.1重量份,更佳之上限為3重量份。The adhesive layer is preferably added with a cross-linking agent to form a cross-linked structure between the main chains of the resin (for example, the acrylic copolymer, the adhesive imparting agent, etc.) constituting the adhesive layer. By adjusting the type and amount of the crosslinking agent, it is easy to adjust the gel fraction of the adhesive layer. The said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned. Among them, isocyanate-based crosslinking agents are preferred. With respect to 100 parts by weight of the acrylic copolymer, the preferred lower limit of the crosslinking agent is 0.01 parts by weight, the more preferred upper limit is 10 parts by weight, the more preferred lower limit is 0.1 parts by weight, and the more preferred upper limit is 3 parts by weight.
為了提高黏著力,上述黏著劑層亦可含有矽烷偶合劑。上述矽烷偶合劑並無特別限定,例如可列舉:環氧基矽烷類、丙烯酸矽烷類、甲基丙烯酸矽烷類、胺基矽烷類、異氰酸酯矽烷類等。In order to improve the adhesive force, the above-mentioned adhesive layer may also contain a silane coupling agent. The said silane coupling agent is not specifically limited, For example, epoxy silanes, acrylic silanes, methacrylic silanes, amino silanes, isocyanate silanes, etc. are mentioned.
為了賦予遮光性,上述黏著劑層亦可含有著色材料。上述著色材料並無特別限定,例如可列舉:碳黑、苯胺黑、氧化鈦等。其中,就相對廉價且化學性質穩定之方面而言,較佳為碳黑。In order to provide light-shielding properties, the adhesive layer may contain a coloring material. The said coloring material is not specifically limited, For example, carbon black, aniline black, titanium oxide, etc. are mentioned. Among them, carbon black is preferred in terms of being relatively inexpensive and chemically stable.
上述黏著劑層之凝膠分率並無特別限定,較佳之下限為1重量%,較佳之上限為90重量%。若上述凝膠分率為1重量%以上,則上述黏著劑層之凝聚力提高,兩面黏著帶之耐掉落撞擊性提高。若上述凝膠分率為90重量%以下,則可抑制上述黏著劑層之對被接著體之潤濕性過度降低,兩面黏著帶之耐掉落撞擊性提高。上述凝膠分率之更佳下限為20重量%,更佳之上限為70重量%,進而較佳之下限為30重量%,進而較佳之上限為50重量%。 再者,黏著劑層之凝膠分率可藉由以下方法測定。 將兩面黏著帶裁切成50 mm×100 mm之平面長方形狀,製作試驗片。將試驗片於23℃浸漬在乙酸乙酯中24小時,然後自乙酸乙酯中取出,於110℃之條件下乾燥1小時。測定乾燥後之試驗片之重量,利用下述式(5)算出凝膠分率。再者,於試驗片未積層用以保護黏著劑層之脫模膜。 凝膠分率(重量%)=100×(W2 -W0 )/(W1 -W0 ) (5) (W0 :基材重量,W1 :浸漬前之試驗片重量,W2 :浸漬、乾燥後之試驗片重量)The gel fraction of the adhesive layer is not particularly limited, and the preferred lower limit is 1% by weight, and the preferred upper limit is 90% by weight. If the gel fraction is 1% by weight or more, the cohesive force of the adhesive layer is improved, and the drop impact resistance of the double-sided adhesive tape is improved. If the gel fraction is 90% by weight or less, the wettability of the adhesive layer to the adherend can be prevented from being excessively reduced, and the drop impact resistance of the double-sided adhesive tape can be improved. The lower limit of the gel fraction is more preferably 20% by weight, the upper limit is more preferably 70% by weight, the lower limit is still more preferably 30% by weight, and the upper limit is more preferably 50% by weight. Furthermore, the gel fraction of the adhesive layer can be measured by the following method. Cut the adhesive tape on both sides into a flat rectangular shape of 50 mm×100 mm to make a test piece. The test piece was immersed in ethyl acetate at 23°C for 24 hours, then taken out from the ethyl acetate, and dried at 110°C for 1 hour. The weight of the test piece after drying is measured, and the gel fraction is calculated using the following formula (5). Furthermore, the release film for protecting the adhesive layer was not laminated on the test piece. Gel fraction (weight%)=100×(W 2 -W 0 )/(W 1 -W 0 ) (5) (W 0 : weight of substrate, W 1 : weight of test piece before immersion, W 2 : Weight of test piece after immersion and drying)
上述黏著劑層之厚度並無特別限定,單側之黏著劑層之厚度較佳下限為20 μm,較佳上限為100 μm。若上述黏著劑層之厚度為20 μm以上,則上述黏著劑層之黏著力變得充分。若上述黏著劑層之厚度為100 μm以下,則上述發泡體基材之應力緩和性亦可充分有助於作為兩面黏著帶整體之應力緩和性。上述黏著劑層之厚度更佳下限為25 μm,更佳之上限為80 μm,進而較佳之下限為30 μm,進而較佳之上限為70 μm,進而更佳之下限為35 μm,進而更佳之上限為65 μm。 再者,黏著劑層之厚度可使用針盤式厚度規(例如,三豐公司製造,「ABS數位式指示器」)測定。The thickness of the adhesive layer is not particularly limited. The thickness of the adhesive layer on one side preferably has a lower limit of 20 μm and a preferably upper limit of 100 μm. If the thickness of the adhesive layer is 20 μm or more, the adhesive force of the adhesive layer becomes sufficient. If the thickness of the adhesive layer is 100 μm or less, the stress relaxation properties of the foam base material can also sufficiently contribute to the stress relaxation properties of the entire double-sided adhesive tape. The lower limit of the thickness of the adhesive layer is more preferably 25 μm, more preferably upper limit is 80 μm, still more preferably lower limit is 30 μm, still more preferably upper limit is 70 μm, still more preferably lower limit is 35 μm, and still more preferably upper limit is 65 μm. Furthermore, the thickness of the adhesive layer can be measured using a dial-type thickness gauge (for example, "ABS digital indicator" manufactured by Mitutoyo Corporation).
本發明之兩面黏著帶之厚度並無特別限定,較佳之下限為100 μm,較佳之上限為1200 μm。若上述厚度為100 μm以上,則兩面黏著帶之黏著力變得充分,又,應力緩和性亦變得充分。若上述厚度為1200 μm以下,則可實現藉由兩面黏著帶所進行之充分之接著及固定。上述厚度之更佳下限為250 μm,更佳之上限為900 μm,進而較佳之下限為350 μm,進而較佳之上限為700 μm,進而更佳之下限為400 μm,進而更佳之上限為650 μm。The thickness of the double-sided adhesive tape of the present invention is not particularly limited, and the preferred lower limit is 100 μm, and the preferred upper limit is 1200 μm. If the above-mentioned thickness is 100 μm or more, the adhesive force of the double-sided adhesive tape becomes sufficient, and the stress relaxation property becomes sufficient. If the above thickness is 1200 μm or less, sufficient bonding and fixation can be achieved by the double-sided adhesive tape. A more preferable lower limit of the aforementioned thickness is 250 μm, a more preferable upper limit is 900 μm, a still more preferable lower limit is 350 μm, an even more preferable upper limit is 700 μm, an even more preferable lower limit is 400 μm, and a more preferable upper limit is 650 μm.
本發明之兩面黏著帶之構成並無特別限定,可於上述發泡體基材之表面上積層有上述黏著劑層,亦可於上述發泡體基材與上述黏著劑層之間積層有上述樹脂片。The structure of the double-sided adhesive tape of the present invention is not particularly limited. The adhesive layer may be laminated on the surface of the foam substrate, or the adhesive layer may be laminated between the foam substrate and the adhesive layer. Resin sheet.
作為本發明之兩面黏著帶之製造方法,例如可舉如下方法。 首先,向丙烯酸共聚物、視需要之黏著賦予劑、交聯劑等添加溶劑,製作黏著劑A之溶液,將該黏著劑A之溶液塗佈於發泡體基材之表面,將溶液中之溶劑完全乾燥去除,形成黏著劑層A。其次,將脫模膜以脫模膜之脫模處理面與黏著劑層A對向之狀態重疊於所形成之黏著劑層A上。 其次,準備與上述脫模膜不同之脫模膜,於該脫模膜之脫模處理面塗佈黏著劑B之溶液,將溶液中之溶劑完全乾燥去除,藉此製作於脫模膜之表面形成有黏著劑層B之積層膜。將所獲得之積層膜以黏著劑層B與發泡體基材之背面對向之狀態重疊於形成有黏著劑層A之發泡體基材之背面,製作積層體。繼而,藉由橡膠輥等對上述積層體進行加壓。藉此,可獲得於發泡體基材兩側具有黏著劑層,且黏著劑層之表面由脫模膜覆蓋之兩面黏著帶。As a manufacturing method of the double-sided adhesive tape of this invention, the following methods are mentioned, for example. First, add a solvent to the acrylic copolymer, the adhesive imparting agent, crosslinking agent, etc. as necessary to prepare a solution of adhesive A, apply the solution of adhesive A to the surface of the foam substrate, and apply the The solvent is completely dried and removed, forming an adhesive layer A. Next, the release film is superimposed on the formed adhesive layer A in a state where the release treatment surface of the release film faces the adhesive layer A. Next, prepare a release film different from the above-mentioned release film, apply a solution of adhesive B to the release treatment surface of the release film, and completely dry and remove the solvent in the solution, thereby making it on the surface of the release film A laminated film with adhesive layer B is formed. The obtained laminated film was superimposed on the back surface of the foam base material on which the adhesive layer A was formed in a state where the adhesive layer B and the back surface of the foam base material were opposed to each other to produce a laminated body. Then, the laminate is pressurized by a rubber roller or the like. Thereby, a double-sided adhesive tape with adhesive layers on both sides of the foam base material and the surface of the adhesive layer covered by the release film can be obtained.
又,亦可以相同之要領製作2組積層膜,將該等積層膜以使積層膜之黏著劑層與發泡體基材對向之狀態分別重疊於發泡體基材兩側而製作積層體,藉由橡膠輥等對該積層體進行加壓。藉此,可獲得於發泡體基材兩側具有黏著劑層,且黏著劑層之表面由脫模膜覆蓋之兩面黏著帶。In addition, two sets of laminated films can be produced in the same way, and the laminated films are superimposed on both sides of the foam base material in a state where the adhesive layer of the laminated film and the foam base material are opposed to each other to produce a laminated body. , The laminate is pressurized with a rubber roller or the like. Thereby, a double-sided adhesive tape with adhesive layers on both sides of the foam base material and the surface of the adhesive layer covered by the release film can be obtained.
本發明之兩面黏著帶之用途並無特別限定,例如可用於電子機器中之零件固定。上述電子機器並無特別限定,例如可列舉:電視、監視器、可攜式電子機器、車載用電子機器等。 其中,本發明之兩面黏著帶可適用於電視、監視器等顯示裝置,尤其是相對大型之顯示裝置中之零件固定,具體而言,例如於上述顯示裝置中用以將表面之蓋板固定於殼體。本發明之兩面黏著帶由於耐掉落撞擊性優異,可減少顯示裝置之顯示不均,故而即便於相對大型之顯示裝置中利用窄幅之兩面黏著帶固定零件的情形時,亦適用。本發明之兩面黏著帶可為窄幅,其寬度並無特別限定,較佳之下限為1000 μm,較佳之上限為10000 μm,更佳之下限為1500 μm,更佳之上限為5000 μm。該等用途中之本發明之兩面黏著帶的形狀並無特別限定,可列舉:長方形、邊框狀、圓形、橢圓形、圓環型等。 又,本發明之兩面黏著帶亦可用於車輛用內飾、家電(例如TV、空調、冰箱等)之內外飾等。 [發明之效果]The use of the double-sided adhesive tape of the present invention is not particularly limited. For example, it can be used for fixing parts in electronic equipment. The above-mentioned electronic equipment is not particularly limited, and examples thereof include televisions, monitors, portable electronic equipment, and in-vehicle electronic equipment. Among them, the double-sided adhesive tape of the present invention can be applied to display devices such as televisions, monitors, etc., especially for fixing parts in relatively large display devices. Specifically, for example, in the above-mentioned display device, it is used to fix the surface cover to case. The double-sided adhesive tape of the present invention has excellent drop and impact resistance and can reduce display unevenness of the display device. Therefore, it is applicable even when parts are fixed by narrow-width double-sided adhesive tapes in relatively large display devices. The double-sided adhesive tape of the present invention can be narrow, and its width is not particularly limited. The lower limit is preferably 1000 μm, the upper limit is preferably 10000 μm, the lower limit is more preferably 1500 μm, and the upper limit is more preferably 5000 μm. The shape of the double-sided adhesive tape of the present invention in these applications is not particularly limited, and examples thereof include rectangular, frame-shaped, circular, elliptical, ring-shaped, and the like. In addition, the double-sided adhesive tape of the present invention can also be used for interior and exterior decoration of vehicles, home appliances (such as TVs, air conditioners, refrigerators, etc.). [Effects of Invention]
若根據本發明,可提供一種耐掉落撞擊性優異、可減少顯示裝置之顯示不均、自被接著體剝離時能容易地撕掉發泡體基材之兩面黏著帶。According to the present invention, it is possible to provide a double-sided adhesive tape that has excellent drop impact resistance, can reduce display unevenness of the display device, and can easily tear off the foam substrate when peeling from the adherend.
以下,列舉實施例對本發明之態樣更詳細地進行說明,但本發明不僅限定於該等實施例。Hereinafter, examples of the present invention will be described in more detail, but the present invention is not limited to these examples.
(聚胺酯發泡體1-1(PU1-1)之製造) 作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,5-戊二醇10重量份。於多元醇之合計100重量份添加胺觸媒(Dabco LV33,Sankyo Air Product公司製造)0.7重量份、泡沫穩定劑(SZ5740M,Toray Dow Corning公司製造)1重量份,進行攪拌。向其中投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為85。然後,以成為0.2 g/cm3 之方式與氮氣混合攪拌,獲得混入有微細氣泡之溶液。使用敷料器,將該溶液以規定厚度塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上,使發泡體原料進行反應,而獲得聚胺酯發泡體。 對聚胺酯發泡體之剪切斷裂強度、25%抗壓強度及厚度進行測定。 藉由X射線CT裝置(大和科學公司製造,「TDM1000H-II(2K)」,解像度1.5 μm/1像素左右)對切斷聚胺酯發泡體所得之測定樣品之中心部進行拍攝,獲得長度1.5 mm、寬度1.2 mm、高度0.3 mm之長方體狀3D圖像。對於所獲得之圖像,藉由圖像解析軟體(FEI公司製造,「Avizo9.2.0」)進行雜訊去除及二值化,求出氣泡體積分率、氣泡之長徑分佈之平均值及標準偏差、氣泡之連泡率、氣泡之縱橫比及氣泡之扁率。(Production of Polyurethane Foam 1-1 (PU1-1)) As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 10 parts by weight of 1,5-pentanediol were used. To a total of 100 parts by weight of the polyol, 0.7 parts by weight of an amine catalyst (Dabco LV33, manufactured by Sankyo Air Products) and 1 part by weight of a foam stabilizer (SZ5740M, manufactured by Toray Dow Corning) were added and stirred. Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was put into it to adjust the isocyanate index to 85. Then, it was mixed and stirred with nitrogen so as to become 0.2 g/cm 3 to obtain a solution mixed with fine bubbles. Using an applicator, the solution was applied to a PET separator (manufactured by Nippa, V-2) with a thickness of 50 μm in a predetermined thickness, and the foam raw materials were reacted to obtain a polyurethane foam. Measure the shear breaking strength, 25% compressive strength and thickness of polyurethane foam. An X-ray CT device (manufactured by Yamato Scientific Co., "TDM1000H-II (2K)", with a resolution of about 1.5 μm/1 pixel) was used to photograph the center of the measurement sample obtained by cutting the polyurethane foam to obtain a length of 1.5 mm , A rectangular 3D image with a width of 1.2 mm and a height of 0.3 mm. For the obtained image, noise removal and binarization are performed with image analysis software (manufactured by FEI, "Avizo 9.2.0"), and the bubble volume fraction, the average value and standard of bubble length distribution are calculated. Deviation, continuous bubble rate of bubbles, aspect ratio of bubbles and flatness of bubbles.
(聚胺酯發泡體1-2(PU1-2)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,5-戊二醇5重量份、1,6-六亞甲基二醇5重量份。 [2]投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為85。(Manufacture of polyurethane foam 1-2 (PU1-2)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 5 parts by weight of 1,5-pentanediol, and 5 parts by weight of 1,6-hexamethylene glycol were used. [2] Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was added to adjust the isocyanate index to 85.
(聚胺酯發泡體1-3(PU1-3)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,5-戊二醇5重量份、新戊二醇5重量份。(Manufacture of polyurethane foam 1-3 (PU1-3)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 5 parts by weight of 1,5-pentanediol, and 5 parts by weight of neopentyl glycol were used.
(聚胺酯發泡體2(PU2)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)85重量份、1,6-六亞甲基二醇3重量份、新戊二醇3重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為90。(Manufacture of polyurethane foam 2 (PU2)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 85 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 3 parts by weight of 1,6-hexamethylene glycol, 3 parts by weight of neopentyl glycol, and ε-caprolactone were used 9 parts by weight. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 90.
(聚胺酯發泡體3-1(PU3-1)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)91重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為100。 [3]調整所混合之氮氣,並變更將混入有微細氣泡之溶液塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上時的厚度(變薄)。(Manufacture of polyurethane foam 3-1 (PU3-1)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 91 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 9 parts by weight of ε-caprolactone were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 100. [3] Adjust the mixed nitrogen and change the thickness (thinner) when the solution mixed with fine bubbles is applied to a 50 μm thick PET separator (manufactured by Nippa, V-2).
(聚胺酯發泡體3-2(PU3-2)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)91重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為100。(Manufacture of polyurethane foam 3-2 (PU3-2)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 91 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 9 parts by weight of ε-caprolactone were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 100.
(聚胺酯發泡體3-3(PU3-3)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)91重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為100。 [3]調整所混合之氮氣,並變更將混入有微細氣泡之溶液塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上時的厚度(變厚)。(Manufacture of polyurethane foam 3-3 (PU3-3)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 91 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 9 parts by weight of ε-caprolactone were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 100. [3] Adjust the mixed nitrogen and change the thickness (thickness) when the solution mixed with fine bubbles is applied to a 50 μm thick PET separator (manufactured by Nippa, V-2).
(聚胺酯發泡體4(PU4)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,5-戊二醇5重量份、1,6-六亞甲基二醇5重量份。 [2]投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為75。(Manufacture of polyurethane foam 4 (PU4)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 5 parts by weight of 1,5-pentanediol, and 5 parts by weight of 1,6-hexamethylene glycol were used. [2] Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was added to adjust the isocyanate index to 75.
(聚胺酯發泡體5(PU5)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,6-六亞甲基二醇10重量份。 [2]投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為95。(Manufacture of polyurethane foam 5 (PU5)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 10 parts by weight of 1,6-hexamethylene glycol were used. [2] Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was added to adjust the isocyanate index to 95.
(聚胺酯發泡體6(PU6)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)90重量份、1,5-戊二醇10重量份。 [2]投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為70。(Manufacture of polyurethane foam 6 (PU6)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 90 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 10 parts by weight of 1,5-pentanediol were used. [2] Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was added to adjust the isocyanate index to 70.
(聚胺酯發泡體7(PU7)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)91重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為110。(Manufacture of polyurethane foam 7 (PU7)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 91 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 9 parts by weight of ε-caprolactone were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 110.
(聚胺酯發泡體8(PU8)之製造) 除下述方面以外,以與聚胺酯發泡體3-1(PU3-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)91重量份、ε-己內酯9重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為85。(Manufacture of polyurethane foam 8 (PU8)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 3-1 (PU3-1). [1] As the polyol, 91 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000) and 9 parts by weight of ε-caprolactone were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 85.
(聚胺酯發泡體9(PU9)之製造) 除下述方面以外,以與聚胺酯發泡體8(PU8)之製造相同之方式獲得聚胺酯發泡體。 [1]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為90。(Manufacture of polyurethane foam 9 (PU9)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 8 (PU8). [1] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 90.
(聚胺酯發泡體10(PU10)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]投入聚異氰酸酯(2核體單體MDI,東曹公司製造)以將異氰酸酯指數調整為70。 [2]調整所混合之氮氣,並變更將混入有微細氣泡之溶液塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上時的厚度(變厚)。(Manufacture of polyurethane foam 10 (PU10)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] Polyisocyanate (2-core monomer MDI, manufactured by Tosoh Corporation) was added to adjust the isocyanate index to 70. [2] Adjust the mixed nitrogen and change the thickness (thickness) when the solution mixed with fine bubbles is applied to a 50 μm thick PET separator (manufactured by Nippa, V-2).
(聚胺酯發泡體11(PU11)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)30重量份、聚丙二醇(PPG)(重量平均分子量3100)60重量份、1,5-戊二醇10重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為65。 [3]調整所混合之氮氣,並變更將混入有微細氣泡之溶液塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上時的厚度(變厚)。(Manufacture of polyurethane foam 11 (PU11)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 30 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 60 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 3100), and 10 parts by weight of 1,5-pentanediol were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 65. [3] Adjust the mixed nitrogen and change the thickness (thickness) when the solution mixed with fine bubbles is applied to a 50 μm thick PET separator (manufactured by Nippa, V-2).
(聚胺酯發泡體12(PU12)之製造) 除下述方面以外,以與聚胺酯發泡體1-1(PU1-1)之製造相同之方式獲得聚胺酯發泡體。 [1]作為多元醇,使用聚丙二醇(PPG)(重量平均分子量1000)20重量份、聚丙二醇(PPG)(重量平均分子量3100)70重量份、1,5-戊二醇10重量份。 [2]投入聚異氰酸酯(聚合MDI,東曹公司製造)以將異氰酸酯指數調整為65。 [3]調整所混合之氮氣,並變更將混入有微細氣泡之溶液塗佈於厚度50 μm之PET隔片(Nippa製造,V-2)上時的厚度(變厚)。(Manufacture of polyurethane foam 12 (PU12)) Except for the following points, a polyurethane foam was obtained in the same manner as the production of polyurethane foam 1-1 (PU1-1). [1] As the polyol, 20 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 1000), 70 parts by weight of polypropylene glycol (PPG) (weight average molecular weight 3100), and 10 parts by weight of 1,5-pentanediol were used. [2] Put polyisocyanate (polymeric MDI, manufactured by Tosoh Corporation) to adjust the isocyanate index to 65. [3] Adjust the mixed nitrogen and change the thickness (thickness) when the solution mixed with fine bubbles is applied to a 50 μm thick PET separator (manufactured by Nippa, V-2).
(聚乙烯發泡體1(PE1)) 作為聚乙烯發泡體,使用XLIM#15003(積水化學工業公司製造)。(Polyethylene foam 1 (PE1)) As the polyethylene foam, XLIM#15003 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used.
(黏著劑I之製造(自由基聚合)) 向具備溫度計、攪拌機、冷卻管之反應器添加乙酸乙酯52重量份,進行氮氣置換後,對反應器進行加熱而開始回流。乙酸乙酯沸騰之後,於30分鐘後投入作為聚合起始劑之偶氮二異丁腈0.08重量份。歷時1小時30分鐘向其中均勻且緩慢地滴加單體混合物(丙烯酸丁酯(BA)60重量份、丙烯酸2-乙基己酯(2EHA)36.9重量份、丙烯酸(AAc)3重量份及丙烯酸2-羥基乙酯(2HEA)0.1重量份),使之進行反應。滴加結束30分鐘後添加偶氮二異丁腈0.1重量份,進而使之進行5小時聚合反應,向反應器內添加乙酸乙酯進行稀釋,且同時進行冷卻,藉此獲得含丙烯酸共聚物之溶液。(Manufacture of Adhesive I (radical polymerization)) 52 parts by weight of ethyl acetate was added to a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after nitrogen replacement, the reactor was heated to start reflux. After the ethyl acetate boiled, 0.08 parts by weight of azobisisobutyronitrile as a polymerization initiator was added 30 minutes later. The monomer mixture (60 parts by weight of butyl acrylate (BA), 36.9 parts by weight of 2-ethylhexyl acrylate (2EHA), 3 parts by weight of acrylic acid (AAc) and acrylic acid were added uniformly and slowly over a period of 1 hour and 30 minutes. 2-hydroxyethyl (2HEA) 0.1 parts by weight) to react. After 30 minutes from the end of the dropping, 0.1 parts by weight of azobisisobutyronitrile was added, and the polymerization reaction was carried out for 5 hours. Ethyl acetate was added to the reactor for dilution and cooling at the same time, thereby obtaining the acrylic acid-containing copolymer. Solution.
求出所獲得之丙烯酸共聚物之重量平均分子量(Mw)及分子量分佈(Mw/Mn)。具體而言,係利用四氫呋喃(THF)將所獲得之含丙烯酸共聚物之溶液稀釋50倍而獲得稀釋液,利用過濾器(材質:聚四氟乙烯,孔徑:0.2 μm)對該稀釋液進行過濾。將所獲得之濾液供給至凝膠滲透層析儀(Waters公司製造,2690 Separations Model),於樣品流量1毫升/min、管柱溫度40℃之條件下進行GPC測定,測定丙烯酸共聚物之聚苯乙烯換算分子量,求出重量平均分子量及分子量分佈(Mw/Mn)。重量平均分子量為100萬,分子量分佈(Mw/Mn)為2.6。作為管柱,使用GPC KF-806L(昭和電工公司製造),作為檢測器,使用示差折射計。Determine the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained acrylic copolymer. Specifically, the obtained acrylic copolymer-containing solution was diluted 50 times with tetrahydrofuran (THF) to obtain a diluted solution, and the diluted solution was filtered with a filter (material: polytetrafluoroethylene, pore size: 0.2 μm) . The obtained filtrate was supplied to a gel permeation chromatograph (2690 Separations Model, manufactured by Waters), and GPC measurement was performed under the conditions of a sample flow rate of 1 ml/min and a column temperature of 40°C to determine the polystyrene of the acrylic copolymer The molecular weight is converted into ethylene, and the weight average molecular weight and molecular weight distribution (Mw/Mn) are determined. The weight average molecular weight is 1 million, and the molecular weight distribution (Mw/Mn) is 2.6. As the column, GPC KF-806L (manufactured by Showa Denko Corporation) was used, and as the detector, a differential refractometer was used.
對於所獲得之含丙烯酸共聚物之溶液的非揮發成分100重量份,添加乙酸乙酯並進行攪拌,添加交聯劑(異氰酸酯系交聯劑,Coronate L-55E,東曹公司製造)5重量份、黏著賦予劑之合計30重量份並進行攪拌,獲得非揮發成分30重量%之黏著劑I。作為黏著賦予劑,使用氫化松香系樹脂(軟化點100℃,羥值40 mgKOH/g)10重量份、松香酯系樹脂(軟化點150℃,羥值40 mgKOH/g)10重量份、萜烯酚系樹脂(軟化點150℃,羥值40 mgKOH/g)10重量份。To 100 parts by weight of the non-volatile components of the obtained acrylic copolymer-containing solution, ethyl acetate was added and stirred, and 5 parts by weight of a crosslinking agent (isocyanate-based crosslinking agent, Coronaate L-55E, manufactured by Tosoh Corporation) was added 1. A total of 30 parts by weight of the adhesive imparting agent is stirred to obtain an adhesive I with 30% by weight of non-volatile content. As an adhesion imparting agent, 10 parts by weight of hydrogenated rosin resin (softening point 100°C, hydroxyl value 40 mgKOH/g), 10 parts by weight of rosin ester resin (softening point 150°C, hydroxyl value 40 mgKOH/g), terpene Phenolic resin (softening point 150°C, hydroxyl value 40 mgKOH/g) 10 parts by weight.
(實施例1~12、比較例1~5)
將黏著劑I塗佈於支持層1(樹脂片),於100℃乾燥5分鐘,藉此形成厚度20 μm之黏著劑層1。使發泡體基材之單面壓接於該黏著劑層1,製作支持層1與發泡體基材經由黏著劑層1積層之積層體。作為支持層1(樹脂片),使用聚對苯二甲酸乙二酯(PET)(X30,東麗公司製造,厚度50 μm)。繼而,使支持層2(樹脂片)熱熔接於發泡體基材之另一面,製作依序積層有支持層1、黏著劑層1、發泡體基材、支持層2之積層體。作為支持層2(樹脂片),使用由丙烯酸系樹脂(LA2250,可樂麗公司製造,厚度50 μm)或胺酯系嵌段共聚物(TPU)構成之片(1198ATR,BASF公司製造,厚度20 μm)。
繼而,準備厚度150 μm之脫模紙,於該脫模紙之脫模處理面塗佈黏著劑I,於100℃乾燥5分鐘,藉此形成厚度50 μm、55 μm或60 μm之黏著劑層2。使該黏著劑層2與積層於發泡體基材之支持層1(樹脂片)之表面貼合。繼而,按照相同之要領,於發泡體基材之相反之支持層2(樹脂片)的表面亦貼合與上述黏著劑層2相同構成之黏著劑層3。然後,藉由在40℃加熱48小時而進行靜置。藉此,獲得由脫模紙覆蓋之兩面黏著帶。
再者,支持層2(樹脂片)之拉伸彈性模數分別為10 MPa、108 MPa。(Examples 1 to 12, Comparative Examples 1 to 5)
The adhesive I was coated on the support layer 1 (resin sheet) and dried at 100° C. for 5 minutes, thereby forming the
將所獲得之兩面黏著帶裁切成50 mm×100 mm之平面長方形,製作試驗片,將試驗片於23℃浸漬於乙酸乙酯中24小時,然後自乙酸乙酯取出,於110℃之條件下乾燥1小時。測定乾燥後之試驗片之重量,利用下述式(5)算出黏著劑層之凝膠分率,結果黏著劑層之凝膠分率為42重量%。 凝膠分率(重量%)=100×(W2 -W0 )/(W1 -W0 ) (5) (W0 :基材重量,W1 :浸漬前之試驗片重量,W2 :浸漬、乾燥後之試驗片重量)The obtained double-sided adhesive tape was cut into a 50 mm×100 mm flat rectangle to make a test piece. The test piece was immersed in ethyl acetate at 23°C for 24 hours, and then taken out from ethyl acetate at 110°C. Dry for 1 hour. The weight of the test piece after drying was measured, and the gel fraction of the adhesive layer was calculated using the following formula (5). As a result, the gel fraction of the adhesive layer was 42% by weight. Gel fraction (weight%)=100×(W 2 -W 0 )/(W 1 -W 0 ) (5) (W 0 : weight of substrate, W 1 : weight of test piece before immersion, W 2 : Weight of test piece after immersion and drying)
<評價> 對實施例、比較例中所獲得之兩面黏著帶進行以下之評價。將結果示於表1~2。<Evaluation> The following evaluations were performed on the double-sided adhesive tapes obtained in Examples and Comparative Examples. The results are shown in Tables 1-2.
(1)二次加工(層間撕掉試驗)
圖2示出表示兩面黏著帶之層間撕掉試驗之示意圖。圖2(a)係前視圖,圖2(b)係側視圖。將兩面黏著帶之尺寸50 mm×5 mm之試驗片2及2片尺寸100 mm×20 mm、厚度2 mm之PC板1如圖2所示進行積層。於5 kg、10秒之條件下使用重物壓接該積層體,然後放置24小時,製作經由試驗片2貼合有2片PC板1之撕掉試驗用樣品。將該撕掉試驗用樣品其中一PC板加以固定後,自試驗片2之下方勾掛不鏽鋼製之金屬絲3(0.3,TRUSCO公司製造之「TYWS-03」),沿著圖2之箭頭方向於300 mm/min之條件下進行拉伸。對利用金屬絲3撕掉試驗片2之基材層間時之試驗力進行測定。將試驗力未達10 N/5 mm之情形表示為◎,試驗力為10 N/5 mm以上且未達15 N/5 mm之情形表示為〇,試驗力為15 N/5 mm以上之情形則表示為×。(1) Secondary processing (interlayer tear test) Figure 2 shows a schematic diagram showing the interlayer tear test of the double-sided adhesive tape. Figure 2 (a) is a front view, and Figure 2 (b) is a side view. Laminate the two-sided adhesive tape 50 mm × 5
(2)耐掉落撞擊(翻滾試驗)
圖3示出表示兩面黏著帶之翻滾試驗用樣品之示意圖。利用尺寸55 mm×65 mm、厚度10 mm、重量42 g之PMMA板5與尺寸70 mm×130 mm、厚度2 mm、重量137 g之SUS板4夾住兩面黏著帶之長邊23 mm×短邊13.3 mm、寬度3.2 mm之邊框狀試驗片6,如圖3所示進行積層。於5 kg、10秒之條件下使用重物壓接該積層體,然後放置24小時,製作經由試驗片6貼合有PMMA板5與SUS板4之翻滾試驗用樣品。將翻滾試驗用樣品放入翻滾試驗機(新榮電子計測器公司製造,TDR-1000A-SC01),以10次掉落/min之頻度反覆施加自各種角度之掉落撞擊。測定直至兩面黏著帶斷裂而翻滾試驗用樣品分離為止之掉落次數。將掉落次數為30次以上之情形表示為◎,掉落次數為10次以上且未達30次之情形表示為〇,掉落次數未達10次之情形則表示為×。(2) Resistance to falling and impact (rolling test)
Fig. 3 shows a schematic diagram showing a sample for a roll test of a double-sided adhesive tape. Use
(3)顯示不均(面起伏試驗)
圖4示出表示兩面黏著帶之面起伏試驗之示意圖。圖4(a)為俯視圖,圖4(b)為剖視圖。於尺寸256 mm×182 mm、厚度4 mm之玻璃板10上,隔開15 mm間隔積層寬度15 mm、厚度50 μm之黑色單面遮光帶8,製作階差。同樣地,於玻璃板10上積層寬度15 mm、厚度100 μm之黑色單面遮光帶9,製作階差。自該等階差之上方,將兩面黏著帶之寬度10 mm之試驗片7積層於玻璃板10的4邊。於試驗片7上積層尺寸256 mm×182 mm、厚度1 mm之玻璃板12,經由試驗片7使玻璃板10與玻璃板12貼合。進而,於玻璃板12上積層厚度100 μm之黑色單面遮光帶13,獲得面起伏試驗用樣品。依據JIS B0601:2001,對於面起伏試驗用樣品中之210 mm×105 mm之測定區域11,使用雷射顯微鏡(其恩斯公司製造,VR-3000型)測定表面粗糙度之最大高度Sz。將最大高度Sz未達120 μm之情形表示為◎,最大高度Sz為120 μm以上且未達200 μm之情形表示為〇,最大高度Sz為200 μm以上之情形則表示為×。(3) Uneven display (surface fluctuation test)
Fig. 4 shows a schematic diagram showing the surface undulation test of the double-sided adhesive tape. Fig. 4(a) is a top view, and Fig. 4(b) is a cross-sectional view. On a
[表1]
[表2]
若根據本發明,可提供一種耐掉落撞擊性優異、可減少顯示裝置之顯示不均、自被接著體剝離時能容易地撕掉發泡體基材之兩面黏著帶。According to the present invention, it is possible to provide a double-sided adhesive tape that has excellent drop impact resistance, can reduce display unevenness of the display device, and can easily tear off the foam substrate when peeling from the adherend.
1:PC板 2:試驗片(兩面黏著帶) 3:金屬絲 4:SUS板 5:PMMA板 6:邊框狀試驗片(兩面黏著帶) 7:試驗片(兩面黏著帶) 8:黑色單面遮光帶(寬度15 mm、厚度50μm) 9:黑色單面遮光帶(寬度15 mm、厚度100μm) 10:玻璃板 11:測定區域 12:玻璃板 13:黑色單面遮光帶 18:試驗片(兩面黏著帶) 19:SUS板1: PC board 2: Test piece (adhesive tape on both sides) 3: wire 4: SUS board 5: PMMA board 6: Frame-shaped test piece (adhesive tape on both sides) 7: Test piece (adhesive tape on both sides) 8: Black single-sided shading tape (width 15 mm, thickness 50μm) 9: Black single-sided shading tape (width 15 mm, thickness 100μm) 10: Glass plate 11: Measurement area 12: glass plate 13: Black single-sided shading tape 18: Test piece (adhesive tape on both sides) 19: SUS board
[圖1]係表示剪切斷裂強度之測定方法之示意圖。 [圖2]係表示兩面黏著帶之層間撕掉試驗之示意圖。 [圖3]係表示兩面黏著帶之翻滾試驗用樣品之示意圖。 [圖4]係表示兩面黏著帶之面起伏試驗之示意圖。[Figure 1] is a schematic diagram showing the method of measuring shear breaking strength. [Figure 2] is a schematic diagram showing the interlayer tear test of the adhesive tape on both sides. [Fig. 3] is a schematic diagram showing the sample for the roll test of the double-sided adhesive tape. [Figure 4] is a schematic diagram showing the surface undulation test of the double-sided adhesive tape.
Claims (13)
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US3993833A (en) * | 1976-01-19 | 1976-11-23 | Minnesota Mining And Manufacturing Company | Polyurethane foam-backed pressure-sensitive adhesive tape |
JP2009242541A (en) | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Impact-absorbing tape |
JP5249625B2 (en) | 2008-04-15 | 2013-07-31 | 積水化学工業株式会社 | Adhesive sheet for display device front plate |
KR20150060085A (en) * | 2013-11-25 | 2015-06-03 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Double coated tape exhibiting improved reworkable capability |
DE112015000743T5 (en) * | 2014-02-11 | 2016-12-29 | Rogers Corporation | Double-sided adhesive tape, method of manufacture, method of use, and articles assembled therefrom |
JP6424034B2 (en) * | 2014-07-18 | 2018-11-14 | 積水化学工業株式会社 | Adhesive sheet for electronic equipment |
EP3385315B1 (en) * | 2015-11-30 | 2020-10-07 | Sekisui Chemical Co., Ltd. | Polyolefin resin foam sheet and adhesive tape |
JP6687515B2 (en) * | 2016-01-21 | 2020-04-22 | 積水化学工業株式会社 | Double-sided adhesive tape |
WO2018168750A1 (en) * | 2017-03-15 | 2018-09-20 | 積水化学工業株式会社 | Double-sided pressure-sensitive adhesive tape |
CN110023439B (en) * | 2017-03-29 | 2022-05-24 | 积水化学工业株式会社 | Double-sided adhesive tape |
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