TW201631085A - Double-sided adhesive sheet for surface protective panels, and surface protective panel - Google Patents
Double-sided adhesive sheet for surface protective panels, and surface protective panel Download PDFInfo
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- TW201631085A TW201631085A TW104142422A TW104142422A TW201631085A TW 201631085 A TW201631085 A TW 201631085A TW 104142422 A TW104142422 A TW 104142422A TW 104142422 A TW104142422 A TW 104142422A TW 201631085 A TW201631085 A TW 201631085A
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
本發明係關於一種表面保護面板用雙面黏接片以及表面保護面板；特別關於一種黏貼於行動電子機器的顯示器面表面而使用的表面保護面板以及該表面保護面板用的雙面黏接片。 The present invention relates to a double-sided adhesive sheet for a surface protection panel and a surface protection panel; and more particularly to a surface protection panel for use in adhering to a display surface of a mobile electronic device and a double-sided adhesive sheet for the surface protection panel.
近來急速普及中的智慧型手機或平板終端等行動電子機器，於顯示器搭載了觸控式面板，藉由手指於顯示器表面的頂層玻璃接觸而進行操作。與此相同，以手指於頂層玻璃接觸的操作方法容易造成頂層玻璃受損，此外，電子機器的顯示器上由於外部光線的反射，使其於室外的能見度極低。 Recently, mobile electronic devices such as smart phones or tablet terminals that are rapidly gaining popularity have been equipped with a touch panel on the display, and are operated by touching the top glass of the display surface with a finger. Similarly, the operation of the finger on the top glass is liable to cause damage to the top glass. In addition, the visibility of the external display is extremely low due to the reflection of external light.
為了解決上述問題，普遍係以透明硬化塗佈層或防眩光硬化塗佈層在聚對酞酸乙二酯薄膜等之上形成的光學片，利用黏接劑黏貼於頂層玻璃。 In order to solve the above problems, an optical sheet formed on a polyethylene terephthalate film or the like by a transparent hard coating layer or an anti-glare hardening coating layer is generally adhered to the top glass by an adhesive.
但就智慧型手機或平板終端等頂層玻璃而言，為了防止來自外部的衝擊導致觸控式面板或液晶模組等破損，一般會使用化學強化玻璃，但若受到預計以上的衝擊，即使是化學強化玻璃也會破損。因此，為了抑制頂層玻璃的破損，最終消費者自己或行動電子機器周邊機器銷售者等，提出於頂層玻璃的表面追加黏貼保護玻璃，一部份正市售中。 However, in the case of a top glass such as a smart phone or a tablet terminal, chemically strengthened glass is generally used to prevent damage from a touch panel or a liquid crystal module due to an external impact, but even if it is subjected to an expected impact, even chemistry The tempered glass will also be damaged. Therefore, in order to suppress the damage of the top glass, the consumer himself or the seller of the mobile electronic peripheral machine, etc., proposed to attach the protective glass to the surface of the top glass, and some of them are on the market.
但玻璃板等硬質物類貼合的情況下，由於難以使該等彎曲，兩者之間容易留下氣泡。尤其若不使用專用貼合機等而以手工作業貼合，頂層玻璃和保護玻璃之間殘存大量氣泡，顯示器的能見度因而變得低落。此外，硬質物類剝離的情況下，也因為難以使該等彎曲，因而難以進行剝離。因此，由於貼合失誤等需進行再度貼合時，從頂層玻璃剝離保護玻璃之際，根據情況之不同，有造成保護玻璃碎裂的疑慮。 However, when a hard substance such as a glass plate is bonded, it is difficult to bend the same, and air bubbles are likely to remain between the two. In particular, if a large amount of air bubbles remain between the top glass and the cover glass without using a special laminating machine or the like, the visibility of the display becomes low. Further, in the case where the hard substance is peeled off, it is also difficult to bend the hard material, and thus it is difficult to perform the peeling. Therefore, when the cover glass is peeled off and the like, the protective glass is peeled off from the top glass, depending on the situation, there is a concern that the protective glass is broken.
此處專利文獻1中，揭示了用於大型顯示器之平板顯示器的透明緩衝積層體。另外，專利文獻2中，揭示了具有紫外線硬化性黏接劑層2層以上的層間用黏接片，以及使用其之透明積層體。 Patent Document 1 herein discloses a transparent buffer laminated body for a flat panel display of a large display. Further, Patent Document 2 discloses an interlayer adhesive sheet having two or more layers of an ultraviolet curable adhesive layer, and a transparent laminate using the same.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利公開2001-266759號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-266759
[專利文獻2]日本專利公開2012-31416號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-31416
專利文獻1中所記載的透明緩衝積層體，是以平板顯示器的製造製程之一環積層而成，並非考慮到透過最終消費者手工作業之積層。因此，透過前面所述之手工作業進行黏貼以及剝離時之問題仍然存在。 The transparent buffer laminated body described in Patent Document 1 is formed by laminating one of the manufacturing processes of the flat panel display, and is not considered to be a laminate which is manually operated by the final consumer. Therefore, the problem of sticking and peeling through the manual work described above still exists.
此外，專利文獻2中所記載的透明積層體使用上述層間用黏接片，將玻璃板類、玻璃板和合成樹脂板，或合成樹脂板類積層，使黏接劑層紫外線硬化而成。此透明積層體紫 外線硬化前的黏接劑層，藉由具有所設定的黏彈性特性，得以獲得無氣泡的積層外觀。因此，黏接劑層紫外線硬化後，重新黏貼時難以使其不產生氣泡。此外，最終消費者自己亦難以進行紫外線照射。 In the transparent laminate described in Patent Document 2, the above-mentioned interlayer adhesive sheet is used, and a glass plate, a glass plate, a synthetic resin plate, or a synthetic resin plate is laminated to cure the adhesive layer by ultraviolet rays. This transparent laminated body purple The adhesive layer before the external line hardening has a set-up viscoelastic property to obtain a bubble-free laminated appearance. Therefore, after the adhesive layer is cured by ultraviolet rays, it is difficult to prevent bubbles from being generated when re-adhering. In addition, it is difficult for the end consumers themselves to perform ultraviolet radiation.
本發明係有鑒於上述問題而完成，目的在於提供即使透過最終消費者進行手工作業時，黏貼於顯示器時難以留下氣泡，且易於從顯示器剝離的表面保護面板用雙面黏接片以及表面保護面板。 The present invention has been made in view of the above problems, and an object thereof is to provide a double-sided adhesive sheet for a surface protection panel and surface protection which is difficult to leave air bubbles when adhered to a display, and which is easily peeled off from the display even when manually operated by a final consumer. panel.
為了達成上述目的，第一，本發明提供一種用於行動電子機器的顯示器面表面的表面保護面板用雙面黏接片(發明1)，其特徵在於：具有透明樹脂薄膜，和於上述透明樹脂薄膜的一面積層的以丙烯酸類黏接劑構成的丙烯酸類黏接劑層，和於上述透明樹脂薄膜的另一面積層的以聚矽氧類黏接劑構成的聚矽氧類黏接劑層。上述丙烯酸類黏接劑於23℃的耗損正切係0.3~1.0，上述丙烯酸類黏接劑層的厚度係25~100μm，上述聚矽氧類黏接劑層對於無鹼玻璃的黏接力係10~300mN/25mm。 In order to achieve the above object, a first aspect of the present invention provides a double-sided adhesive sheet for a surface protection panel for use in a surface of a display of a mobile electronic device (Invention 1), comprising: a transparent resin film, and the above transparent resin An acrylic adhesive layer composed of an acrylic adhesive in one area of the film, and a polyoxygenated adhesive layer composed of a polyoxyloxy adhesive in another area layer of the transparent resin film. The acrylic adhesive has a loss tangent of 0.3 to 1.0 at 23 ° C, a thickness of the acrylic adhesive layer of 25 to 100 μm, and a bonding force of the polyfluorene adhesive layer to an alkali-free glass. 300mN/25mm.
另外，本發明專利說明書中所謂的「行動電子機器的顯示器面表面」，意指行動電子機器的顯示器上之顯示面的表面，即，外露給觀看該顯示器者(最終消費者)的表面。 Further, the term "display surface of a mobile electronic device" as used in the specification of the present invention means a surface of a display surface on a display of a mobile electronic device, that is, a surface exposed to a person (final consumer) who views the display.
透過上述發明(發明1)所涉及的表面保護面板用雙面黏接片，於上述丙烯酸類黏接劑層積層透明硬質板構成表面保護面板。此表面保護面板即使透過最終消費者的手工作業， 於行動電子機器的顯示器面表面黏貼時亦難留下氣泡，此外，重新黏貼時，可輕易地將表面保護面板從顯示器剝離。 According to the double-sided adhesive sheet for a surface protection panel according to the invention (Invention 1), the surface protective panel is formed of the acrylic adhesive layer laminated transparent hard plate. This surface protection panel, even through the manual work of the final consumer, It is also difficult to leave air bubbles when the surface of the display surface of the mobile electronic device is pasted, and the surface protection panel can be easily peeled off from the display when re-adhering.
上述發明(發明1)中，藉由於上述丙烯酸類黏接劑層積層透明硬質板構成表面保護面板，上述表面保護面板透過上述聚矽氧類黏接劑層黏貼於行動電子機器的顯示器面表面為佳(發明2)。 In the above invention (Invention 1), the surface protective panel is formed by the acrylic adhesive layer laminated transparent hard plate, and the surface protective panel is adhered to the surface of the display surface of the mobile electronic device through the polyoxynoxy adhesive layer. Good (Invention 2).
上述發明(發明1、2)中，上述聚矽氧類黏接劑層的厚度係5~100μm為佳(發明3)。 In the above inventions (Inventions 1 and 2), the thickness of the polyoxymethylene-based adhesive layer is preferably 5 to 100 μm (Invention 3).
上述發明(發明1~3)中，上述透明樹脂薄膜係聚對酞酸乙二酯薄膜為佳(發明4)。 In the above invention (Inventions 1 to 3), the transparent resin film is preferably a polyethylene terephthalate film (Invention 4).
上述發明(發明1~4)中，上述透明樹脂薄膜的厚度係12~100μm為佳(發明5)。 In the above invention (Inventions 1 to 4), the thickness of the transparent resin film is preferably from 12 to 100 μm (Invention 5).
上述發明(發明1~5)中，上述透明樹脂薄膜的的霧度係1.5%以下為佳(發明6)。 In the above invention (Inventions 1 to 5), the haze of the transparent resin film is preferably 1.5% or less (Invention 6).
上述發明(發明1~6)中，上述表面保護面板用雙面黏接片的霧度係2.0%以下為佳(發明7)。 In the above invention (Inventions 1 to 6), the haze of the double-sided adhesive sheet for a surface protection panel is preferably 2.0% or less (Invention 7).
第二，本發明提供一種表面保護面板(發明8)，其特徵在於：具有上述表面保護面板用雙面黏接片(發明1~7)，和於上述表面保護面板用雙面黏接片的上述丙烯酸類黏接劑層上積層的透明硬質板，可用於行動電子機器的顯示器面表面。 Secondly, the present invention provides a surface protection panel (Invention 8), comprising: the double-sided adhesive sheet for the surface protection panel (Inventions 1 to 7), and the double-sided adhesive sheet for the surface protection panel The transparent hard board laminated on the above acrylic adhesive layer can be used for the display surface of a mobile electronic device.
上述發明(發明8)中，上述透明硬質板係玻璃板、聚碳酸酯板或丙烯酸樹脂板為佳(發明9)。 In the above invention (Invention 8), the transparent hard plate-based glass plate, the polycarbonate plate or the acrylic plate is preferable (Invention 9).
透過本發明所涉及的表面保護面板用雙面黏接片以及表面保護面板，即使透過最終消費者進行手工作業，黏貼於顯示器時難以留下氣泡，從顯示器剝離時亦可輕易地剝離。 According to the double-sided adhesive sheet for a surface protection panel and the surface protection panel according to the present invention, even if it is manually handled by the final consumer, it is difficult to leave air bubbles when adhered to the display, and it can be easily peeled off when peeled off from the display.
1‧‧‧(表面保護面板用)雙面黏接片 1‧‧‧ (for surface protection panels) double-sided adhesive sheets
11‧‧‧透明樹脂薄膜 11‧‧‧Transparent resin film
12‧‧‧丙烯酸類黏接劑層 12‧‧‧Acrylic adhesive layer
13‧‧‧聚矽氧類黏接劑層 13‧‧‧Polyoxygen adhesive layer
2a、2b‧‧‧剝離片 2a, 2b‧‧‧ peeling tablets
3‧‧‧剝離片附著雙面黏接片 3‧‧‧ peeling sheet attached to double-sided adhesive sheet
4‧‧‧透明硬質板 4‧‧‧Transparent hardboard
5‧‧‧表面保護面板 5‧‧‧Surface protection panel
6‧‧‧顯示器 6‧‧‧ display
[圖1]本發明之其一實施形態所涉及的表面保護面板用雙面黏接片之剖面圖。 Fig. 1 is a cross-sectional view showing a double-sided adhesive sheet for a surface protection panel according to an embodiment of the present invention.
[圖2]本發明之其一實施形態所涉及的表面保護面板之剖面圖。 Fig. 2 is a cross-sectional view showing a surface protection panel according to an embodiment of the present invention.
[圖3]本發明之其一實施形態所涉及的表面保護面板黏貼於顯示器表面的積層體之剖面圖。 Fig. 3 is a cross-sectional view showing a laminated body in which a surface protection panel according to an embodiment of the present invention is adhered to a surface of a display.
以下對於本發明之實施形態進行說明。 Embodiments of the present invention will be described below.
〔表面保護面板用雙面黏接片〕 [Double-sided adhesive sheet for surface protection panel]
如圖1所示，使本實施形態所涉及的表面保護面板用雙面黏接片(以下亦簡稱為「雙面黏接片」)1和2張剝離片2a、2b的剝離面接觸，夾層於該2張剝離片2a、2b，將以剝離片2a、雙面黏接片1，以及剝離片2b形成的積層體，以下稱為剝離片附著雙面黏接片3。 As shown in Fig. 1, the double-sided adhesive sheet for a surface protection panel according to the present embodiment (hereinafter also referred to simply as "double-sided adhesive sheet") 1 and the peeling surfaces of the two release sheets 2a and 2b are brought into contact with each other. In the two release sheets 2a and 2b, a laminate formed of the release sheet 2a, the double-sided adhesive sheet 1, and the release sheet 2b, hereinafter referred to as a release sheet, is attached to the double-sided adhesive sheet 3.
本實施形態中，上述剝離片2a、2b並非必須構成要素，使用雙面黏接片1時會剝離．去除。此外，本發明專利說明書中所謂的剝離片之剝離面，意指剝離片中具有剝離性的面，經剝離處理的面以及未經剝離處理但呈現剝離性的面皆包含於此。 In the present embodiment, the release sheets 2a and 2b are not essential components, and are peeled off when the double-sided adhesive sheet 1 is used. Remove. Further, the release surface of the release sheet in the specification of the present invention means a surface having peeling property in the release sheet, and the surface subjected to the release treatment and the surface which is not peeled off but exhibiting releasability are included.
本實施形態所涉及的雙面黏接片1，，具有作為所謂的芯材的透明樹脂薄膜11，和於透明樹脂薄膜11的一面上積層的以丙烯酸類黏接劑構成的丙烯酸類黏接劑層12，和於透明樹脂薄膜11的另一面上積層的以聚矽氧類黏接劑構成的聚矽氧類黏接劑層13。 The double-sided adhesive sheet 1 according to the present embodiment has a transparent resin film 11 as a so-called core material, and an acrylic adhesive composed of an acrylic adhesive layer laminated on one surface of the transparent resin film 11. The layer 12 and the polyoxynoxy-based adhesive layer 13 made of a polyoxyl-based adhesive laminated on the other surface of the transparent resin film 11 are provided.
本實施形態所涉及的雙面黏接片1中，丙烯酸類黏接劑在23℃的耗損正切係0.3~1.0，丙烯酸類黏接劑層12的厚度係25~100μm，聚矽氧類黏接劑層13對於無鹼玻璃的黏接力係10~300mN/25mm。此外，上述耗損正切可透過後面將敘述的測試例中例示的動態黏彈性測量儀器測量。另外，上述黏接力的具體測量方法如後面將敘述的測試例所示。 In the double-sided adhesive sheet 1 according to the present embodiment, the acrylic adhesive has a loss tangent of 0.3 to 1.0 at 23 ° C, and the thickness of the acrylic adhesive layer 12 is 25 to 100 μm, and the polyoxynitride is bonded. The adhesion of the agent layer 13 to the alkali-free glass is 10 to 300 mN/25 mm. Further, the above-described loss tangent can be measured by a dynamic viscoelasticity measuring instrument exemplified in the test examples which will be described later. In addition, the specific measurement method of the above-mentioned adhesive force is shown in the test example which will be described later.
本實施形態所涉及的雙面黏接片1可如以下理想地使用。即，如圖2所示，藉由於上述丙烯酸類黏接劑層12積層透明硬質板4構成表面保護面板5，所獲得的表面保護面板5如圖3所示，透過上述聚矽氧類黏接劑層13，黏貼至外露於行動電子機器的顯示器6(通常係頂層玻璃)的最終消費者所觀看的表面。 The double-sided adhesive sheet 1 according to the present embodiment can be preferably used as follows. That is, as shown in FIG. 2, the surface protective panel 5 is formed by laminating the transparent hard plate 4 with the acrylic adhesive layer 12, and the obtained surface protective panel 5 is bonded through the above-mentioned polyoxygen oxide as shown in FIG. The layer 13 is adhered to the surface viewed by the end consumer exposed to the display 6 of the mobile electronic device (usually the top glass).
此處，本實施形態所涉及的雙面黏接片1，於透明樹脂薄膜11的一面上具有丙烯酸類黏接劑層12，另一面上具有聚矽氧類黏接劑層13，同時，藉由丙烯酸類黏接劑在23℃時的耗損正切、丙烯酸類黏接劑層12的厚度，以及聚矽氧類黏接劑層13對於無鹼玻璃的黏接力皆介於上述範圍，即使透過最終消費者進行手工作業，表面保護面板5黏貼於行動電子機器的顯示器6時亦難以留下氣泡，另外，重新黏貼時，表面 保護面板5可輕易地從顯示器6剝離。 Here, the double-sided adhesive sheet 1 according to the present embodiment has the acrylic adhesive layer 12 on one surface of the transparent resin film 11, and the polyoxynoxy adhesive layer 13 on the other surface. The loss tangent of the acrylic adhesive at 23 ° C, the thickness of the acrylic adhesive layer 12, and the adhesion of the polyoxynoxy adhesive layer 13 to the alkali-free glass are all in the above range, even though the final When the consumer performs manual work, it is difficult to leave air bubbles when the surface protection panel 5 is attached to the display 6 of the mobile electronic device, and when re-adhering, the surface The protective panel 5 can be easily peeled off from the display 6.
1.雙面黏接片 1. Double-sided adhesive sheet
(1)透明樹脂薄膜 (1) Transparent resin film
本實施形態所涉及的雙面黏接片1，因具有作為芯材的透明樹脂薄膜11而具有硬度，使其處理性變得優良。 The double-sided adhesive sheet 1 according to the present embodiment has hardness by having the transparent resin film 11 as a core material, and the handleability thereof is excellent.
就透明樹脂薄膜11而言，可舉例：聚對酞酸乙二酯、聚(對酞酸丁二酯)、聚萘二甲酸乙二酯等以聚酯形成的聚酯薄膜；聚氨酯薄膜、聚乙烯薄膜、聚丙烯薄膜、三乙酸纖維素等纖維素薄膜；聚氯乙烯薄膜、聚氯乙烯亞乙烯薄膜、聚乙烯醇薄膜、乙烯/乙酸乙烯酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、丙烯酸樹脂薄膜、降莰烯類樹脂薄膜、環烯樹脂薄膜等塑膠薄膜；該等2種以上的積層體等。塑膠薄膜係單軸拉伸或雙軸拉伸者皆可。該等中，又以聚酯薄膜較佳，尤其從處理性、加工性等觀點來看，聚對酞酸乙二酯薄膜較佳。 The transparent resin film 11 can be exemplified by a polyester film formed of a polyester such as polyethylene terephthalate, poly(p-butyl phthalate) or polyethylene naphthalate; a polyurethane film and a poly Cellulose film such as vinyl film, polypropylene film, cellulose triacetate; polyvinyl chloride film, polyvinyl vinylene film, polyvinyl alcohol film, ethylene/vinyl acetate film, polystyrene film, polycarbonate A plastic film such as a film, an acrylic resin film, a norbornene resin film or a cycloolefin resin film; or two or more kinds of laminates. The plastic film can be uniaxially stretched or biaxially stretched. Among these, a polyester film is preferable, and a polyethylene terephthalate film is preferable from the viewpoints of handleability and processability.
上述透明樹脂薄膜11中，為了達成提升鄰接的聚矽氧類黏接劑層13以及/或與丙烯酸類黏接劑層12的附著性等目的，可根據所需，於單面或雙面上透過氧化法等進行表面處理或底漆處理。就上述氧化法而言，可舉例：電暈放電處理、電漿放電處理、鉻氧化處理(濕式)、火焰處理、熱風處理、臭氧‧紫外線照射處理等。該等表面處理法雖可根據塑膠薄膜的種類適當地選擇，一般而言，使用電暈放電處理法在效果以及操作性方面較佳。 In order to achieve the purpose of improving the adhesion of the adjacent polyoxynitride-based adhesive layer 13 and/or the acrylic adhesive layer 12, the transparent resin film 11 may be provided on one or both sides as needed. Surface treatment or primer treatment by oxidation or the like. Examples of the above oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. These surface treatment methods can be appropriately selected depending on the type of the plastic film. In general, the corona discharge treatment method is preferable in terms of effect and workability.
透明樹脂薄膜11的厚度從雙面黏接片1的處理性之觀點看來，較佳係12~100μm，更佳係20~90μm，特佳係 30~70μm。透明樹脂薄膜11的厚度若係12μm以上，則可發揮所設定的硬度，獲得優良的處理性。此外，透明樹脂薄膜11的厚度若係100μm以下，雙面黏接片1(剝離片附著雙面黏接片3)的加工性(特別係衝孔加工性)會變得更為優良。 The thickness of the transparent resin film 11 is preferably from 12 to 100 μm, more preferably from 20 to 90 μm, from the viewpoint of handleability of the double-sided adhesive sheet 1. 30~70μm. When the thickness of the transparent resin film 11 is 12 μm or more, the set hardness can be exhibited, and excellent handleability can be obtained. In addition, when the thickness of the transparent resin film 11 is 100 μm or less, the workability (especially, punching workability) of the double-sided adhesive sheet 1 (the release sheet adheres to the double-sided adhesive sheet 3) is further improved.
透明樹脂薄膜11的霧度(以JIS K7136：2000為基準測量的值)較佳係1.5%以下，更佳係1.0%以下，特佳係0.5%以下。透明樹脂薄膜11的霧度若係1.5%以下，使雙面黏接片1的霧度(後面將敘述)變低，可實現高透明性，而可得到適合作為行動電子機器的顯示器表面用表面保護面板。 The haze of the transparent resin film 11 (value measured based on JIS K7136:2000) is preferably 1.5% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less. When the haze of the transparent resin film 11 is 1.5% or less, the haze of the double-sided adhesive sheet 1 (described later) is lowered, and high transparency can be achieved, and a surface for a display surface suitable as a mobile electronic device can be obtained. Protect the panel.
(2)丙烯酸類黏接劑層 (2) Acrylic adhesive layer
丙烯酸類黏接劑層12在23℃時的耗損正切(tanδ)下限值係0.3以上，較佳係0.35以上，更佳係0.4以上。丙烯酸類黏接劑層12的耗損正切下限值若係0.3以上，對於行動電子機器的顯示器6黏貼時便難以留下氣泡。另一方面，丙烯酸類黏接劑層12在23℃時的耗損正切上限值係1.0以下，較佳係0.8以下，更佳係0.6以下。丙烯酸類黏接劑層12的耗損正切上限值若係1.0以下，不僅可抑制丙烯酸類黏接劑層12中的黏接劑滲出，同時使刮痕等外觀缺點變得難以發生。 The lower limit of the loss tangent (tan δ) of the acrylic adhesive layer 12 at 23 ° C is 0.3 or more, preferably 0.35 or more, more preferably 0.4 or more. When the loss tangent lower limit value of the acrylic adhesive layer 12 is 0.3 or more, it is difficult to leave air bubbles when the display 6 of the mobile electronic device is pasted. On the other hand, the upper limit of the loss tangent of the acrylic adhesive layer 12 at 23 ° C is 1.0 or less, preferably 0.8 or less, more preferably 0.6 or less. When the loss tangent upper limit of the acrylic adhesive layer 12 is 1.0 or less, it is possible to suppress not only the bleeding of the adhesive in the acrylic adhesive layer 12 but also the appearance defects such as scratches.
此外，丙烯酸類黏接劑層12的厚度下限值係25μm以上，較佳係30μm以上，更佳係35μm以上。丙烯酸類黏接劑層12的厚度下限值若係25μm以上，對於行動電子機器的顯示器6黏貼時便難以留下氣泡。另一方面，丙烯酸類黏接劑層12的厚度上限值係100μm以下，較佳係80μm以下，更佳係60μm以下。丙烯酸類黏接劑層12的厚度上限值若係100μm以 下，便可抑制從丙烯酸類黏接劑層12滲出黏接劑，亦可維持良好外觀。 Further, the lower limit of the thickness of the acrylic adhesive layer 12 is 25 μm or more, preferably 30 μm or more, and more preferably 35 μm or more. When the thickness lower limit of the acrylic adhesive layer 12 is 25 μm or more, it is difficult to leave air bubbles when the display 6 of the mobile electronic device is pasted. On the other hand, the upper limit of the thickness of the acrylic adhesive layer 12 is 100 μm or less, preferably 80 μm or less, and more preferably 60 μm or less. The upper limit of the thickness of the acrylic adhesive layer 12 is 100 μm. Then, the adhesion of the adhesive from the acrylic adhesive layer 12 can be suppressed, and a good appearance can be maintained.
丙烯酸類黏接劑層12係以丙烯酸類黏接劑構成，較佳係以可滿足上述耗損正切的丙烯酸類黏接劑構成。丙烯酸類黏接劑含有(甲基)丙烯酸酯聚合物(a)較佳，更佳係該(甲基)丙烯酸酯聚合物(a)含有透過架橋劑(b)架橋而成物。這種丙烯酸類黏接劑容易滿足上述耗損正切。此外，本發明專利說明書中所謂(甲基)丙烯酸酯，意指丙烯酸酯以及異丁烯酸酯全部，其他類似用語亦同。另外，「聚合物」中亦包含「共聚物」的概念。 The acrylic adhesive layer 12 is made of an acrylic adhesive, and is preferably made of an acrylic adhesive which satisfies the above-described loss tangent. The acrylic adhesive preferably contains a (meth) acrylate polymer (a), and more preferably the (meth) acrylate polymer (a) contains a bridging agent (b) bridged. Such an acrylic adhesive easily satisfies the above-described loss tangent. Further, the term "(meth)acrylate" in the specification of the present invention means all of acrylate and methacrylate, and other similar terms are also the same. In addition, the concept of "copolymer" is also included in "polymer".
(甲基)丙烯酸酯聚合物(a)作為構成該聚合物的單體，含有烷基碳數係1~20的(甲基)丙烯酸烷酯為佳，藉此，所獲得的黏接劑便可發揮理想的黏接性。另外，(甲基)丙烯酸酯聚合物(a)係烷基的碳數係1~20的(甲基)丙烯酸烷酯和具有可與架橋劑(b)反應的官能基之單體(含反應性官能基單體)，根據所需使用的其他單體之共聚物更佳。 The (meth) acrylate polymer (a) preferably contains, as a monomer constituting the polymer, an alkyl (meth) acrylate having an alkyl carbon number of 1 to 20, whereby the obtained binder is used. It can achieve the desired adhesion. Further, the (meth) acrylate polymer (a) is an alkyl group having 1 to 20 carbon atoms and a monomer having a functional group reactive with the bridging agent (b) (including a reaction) The functional functional monomer) is preferably a copolymer of other monomers to be used.
就烷基的碳數係1~20的(甲基)丙烯酸烷酯而言，可舉例：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕櫚酯、(甲基)丙烯酸十八酯等。其中，從使黏接性更為提升之觀點來看，使用烷基的碳數係1~8的(甲基)丙烯酸烷酯較佳，使用(甲基)丙烯酸甲酯、(甲 基)丙烯酸正丁酯，以及(甲基)丙烯酸2-乙基己酯則更佳。此外，該等可1種單獨使用，亦可組合2種以上使用。 Examples of the (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms of the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. N-butyl acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylate N-decyl ester, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, octadecyl (meth)acrylate, and the like. Among them, from the viewpoint of improving the adhesion, it is preferred to use an alkyl (meth) acrylate having a carbon number of 1 to 8 in an alkyl group, and to use methyl (meth) acrylate. The base is n-butyl acrylate, and 2-ethylhexyl (meth)acrylate is more preferred. In addition, these may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(a)作為構成該聚合物的單體單位，含有烷基碳數係1~20的(甲基)丙烯酸烷酯40~99質量%較佳，更佳係含有50~90質量%，特佳係含有75~85質量%。 The (meth) acrylate polymer (a) preferably contains 40 to 99% by mass of an alkyl (meth) acrylate having an alkyl carbon number of 1 to 20 as a monomer unit constituting the polymer, and more preferably contains 50 to 90% by mass, and particularly good for 75 to 85% by mass.
就上述含反應性官能基單體而言，可舉例分子內含有羥基的單體(含羥基單體)、分子內含有羧基的單體(含羧基單體)、分子內含有胺基的單體(含胺基單體)等。該等單體可1種單獨使用，亦可組合2種以上使用。 The above-mentioned reactive functional group-containing monomer may, for example, be a monomer having a hydroxyl group in the molecule (a hydroxyl group-containing monomer), a monomer having a carboxyl group in the molecule (a carboxyl group-containing monomer), or a monomer having an amine group in the molecule. (Amine-containing monomer) and the like. These monomers may be used alone or in combination of two or more.
就含羥基單體而言，可舉例：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丁酯、(甲基)丙烯酸4-羥丁酯等(甲基)丙烯酸羥烷基酯。其中，從所獲得的(甲基)丙烯酸酯聚合物(A)中的與羥基之架橋劑(b)的反應性，以及與其他單體之共聚合性之觀點來看，(甲基)丙烯酸2-羥乙酯或(甲基)丙烯酸4-羥丁酯較佳。該等可1種單獨使用，亦可組合2種以上使用。 As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or (meth)acrylic acid 2 can be exemplified. a hydroxyalkyl (meth)acrylate such as hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. Among them, (meth)acrylic acid from the viewpoint of reactivity with the hydroxyl group bridging agent (b) in the obtained (meth)acrylate polymer (A) and copolymerization with other monomers 2-Hydroxyethyl ester or 4-hydroxybutyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.
就含羧基單體而言，可舉例：丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、伊康酸、焦檸檬酸等乙烯性不飽和羧基酸。其中，以所獲得的(甲基)丙烯酸酯聚合物(a)中的與羧基之架橋劑(b)的反應性，以及與其他單體之共聚合性的觀點來看，丙烯酸為佳。該等可1種單獨使用，亦可組合2種以上使用。 The carboxyl group-containing monomer may, for example, be an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or pyroic acid. Among them, acrylic acid is preferred from the viewpoint of reactivity with the carboxyl group-trapping agent (b) in the obtained (meth)acrylate polymer (a) and copolymerization with other monomers. These may be used alone or in combination of two or more.
就含胺基單體而言，可舉例：(甲基)丙烯酸胺乙酯、(甲基)丙烯酸正丁胺乙基酯等。該等可1種單獨使用，亦可組合2種以上使用。 The amine group-containing monomer may, for example, be aminoethyl (meth)acrylate or n-butylamine (meth)acrylate. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(a)作為構成該聚合物的單體單位，含有含反應性官能基單體1~40質量%較佳，更佳係含有10~35質量%，特佳係含有15~25質量%。 The (meth) acrylate polymer (a) is preferably a monomer unit constituting the polymer, and preferably contains 1 to 40% by mass of the reactive functional group-containing monomer, more preferably 10 to 35% by mass, particularly preferably Contains 15 to 25% by mass.
就上述其他單體而言，可舉例：(甲基)丙烯酸甲氧基酯、(甲基)烯丙酸乙氧乙酯等(甲基)丙烯酸烷氧基烷基酯；(甲基)丙烯酸環己酯等具有脂肪族環的(甲基)丙烯酸酯；丙烯醯胺、甲基丙烯醯胺等非架橋性的丙烯醯胺；(甲基)丙烯酸N,N-二甲胺基、(甲基)丙烯酸N,N-二甲胺丙基等具有非架橋性的3級胺基的(甲基)丙烯酸酯；乙酸乙烯酯、苯乙烯等。該等單體可1種單獨使用，亦可組合2種以上使用。 With respect to the above other monomers, (meth)acrylic acid methoxide, (meth)acrylic acid ethoxyethyl ester (meth)acrylic acid alkoxyalkyl ester; (meth)acrylic acid (meth) acrylate having an aliphatic ring such as cyclohexyl ester; non-branching acrylamide such as acrylamide or methacrylamide; N,N-dimethylamino group (meth) acrylate, (A) (meth) acrylate having a non-branching grade 3 amine group such as N,N-dimethylaminopropyl acrylate; vinyl acetate, styrene, and the like. These monomers may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(a)的聚合狀態可係隨機共聚物，亦可係嵌段共聚物。 The polymerization state of the (meth) acrylate polymer (a) may be a random copolymer or a block copolymer.
(甲基)丙烯酸酯聚合物(a)的重量平均分子量較佳係30萬~100萬，更佳係40萬~90萬，特佳係50萬~70萬。此外，本發明專利說明書中的重量平均分子量，係以凝膠滲透層析(GPC)術所測量的標準聚苯乙烯換算值。 The weight average molecular weight of the (meth) acrylate polymer (a) is preferably from 300,000 to 1,000,000, more preferably from 400,000 to 900,000, and particularly preferably from 500,000 to 700,000. Further, the weight average molecular weight in the specification of the present invention is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
(甲基)丙烯酸酯聚合物(a)的重量平均分子量若係30萬以上，丙烯酸類黏接劑層12的耐久性會變得優秀。此外，(甲基)丙烯酸酯聚合物(a)的重量平均分子量若係100萬以下，即可獲得良好的塗層性。 When the weight average molecular weight of the (meth) acrylate polymer (a) is 300,000 or more, the durability of the acrylic adhesive layer 12 is excellent. Further, when the weight average molecular weight of the (meth) acrylate polymer (a) is 1,000,000 or less, good coating properties can be obtained.
另外，上述丙烯酸類黏接劑中，(甲基)丙烯酸酯聚 合物(a)可1種單獨使用，亦可組合2種以上使用。 In addition, among the above acrylic adhesives, (meth) acrylate polymerization The compound (a) may be used alone or in combination of two or more.
就架橋劑(b)而言，可與(甲基)丙烯酸酯聚合物(a)所具有與反應性官能基反應者為佳，可舉例：異氰酸鹽類架橋劑、環氧樹脂類架橋劑、胺類架橋劑、三聚氰胺類架橋劑、氮環丙烷類架橋劑、聯氨類架橋劑、醛類架橋劑、二氫(口咢)唑類架橋劑、金屬烷氧化物類架橋劑、金屬鉗合物類架橋劑、金屬鹽類架橋劑、銨鹽類架橋劑等。上述中，(甲基)丙烯酸酯聚合物(a)所具有的反應性官能基係羥基的狀況下，使用與羥基反應性優秀的異氰酸鹽類架橋劑較佳；(甲基)丙烯酸酯聚合物(a)所具有的反應性官能基係羧基的情況下，使用與羧基反應性優秀的環氧樹脂類架橋劑為佳。另外，架橋劑(b)可1種單獨使用，亦可組合2種以上使用。 In the case of the bridging agent (b), it is preferred to react with the reactive functional group of the (meth) acrylate polymer (a), and examples thereof include an isocyanate bridging agent and an epoxy resin bridge. Agent, amine bridging agent, melamine bridging agent, nitrogen cyclopropane bridging agent, hydrazine bridging agent, aldehyde bridging agent, dihydro(ortho)azole bridging agent, metal alkoxide bridging agent, metal Clamp-type bridging agent, metal salt bridging agent, ammonium salt bridging agent, etc. In the above, in the case where the reactive functional group of the (meth) acrylate polymer (a) is a hydroxyl group, an isocyanate bridging agent excellent in reactivity with a hydroxyl group is preferably used; (meth) acrylate When the reactive functional group of the polymer (a) is a carboxyl group, an epoxy resin bridging agent excellent in reactivity with a carboxyl group is preferably used. In addition, the bridging agent (b) may be used alone or in combination of two or more.
異氰酸鹽類架橋劑(C)至少包含聚異氰酸鹽化合物。就聚異氰酸鹽化合物而言，可舉例：二異氰酸甲苯酯、二苯甲烷二異氰酸酯、二甲苯二異氰酸鹽等芳香族聚異氰酸鹽；環己烷二異氰酸鹽等脂肪族等脂肪族聚異氰酸鹽；異佛酮二異氰酸鹽、添氫二苯甲烷二異氰酸酯等脂環族聚異氰酸鹽等，以及與該等縮二脲體、三聚異氰酸體、或乙二醇、丙二醇、新戊二醇、三羥甲丙烷、篦蔴油等含低分子活性氫化合物的反應物之加成物等。其中從和羥基的反應性觀點來看，三羥甲丙烷變性芳香族聚異氰酸鹽，特別係三羥甲丙烷變性二異氰酸甲苯酯以及三羥甲丙烷變性二甲苯二異氰酸鹽更佳。 The isocyanate bridging agent (C) contains at least a polyisocyanate compound. The polyisocyanate compound may, for example, be an aromatic polyisocyanate such as toluene diisocyanate, diphenylmethane diisocyanate or xylene diisocyanate; cyclohexane diisocyanate Aliphatic polyisocyanates such as aliphatic; alicyclic polyisocyanates such as isophorone diisocyanate, hydrogen diphenylmethane diisocyanate, etc., and trimerization and trimerization An isocyanate or an adduct of a reactant containing a low molecular weight active hydrogen compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Among them, trimethylolpropane-denatured aromatic polyisocyanate, especially trimethylolpropane-denatured toluene diisocyanate and trimethylolpropane-denatured xylene diisocyanate, from the viewpoint of reactivity with a hydroxyl group Better.
就環氧樹脂類架橋劑而言，可舉例：1,3-雙(N,N-二縮水甘油氨甲基)環己烷、N,N,N’,N’-四縮水甘油基-m-苯二 甲胺、乙二醇二縮水甘油醚、1,6-二醇二縮水甘油醚、三羥甲基丙烷二縮水甘油醚、二縮水甘油基、縮水甘油胺等。 As the epoxy resin bridging agent, for example, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m can be exemplified. -Benzene Methylamine, ethylene glycol diglycidyl ether, 1,6-diol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl group, glycidylamine, and the like.
架橋劑(b)的使用量相對於(甲基)丙烯酸酯聚合物(a)100質量份，較佳係0.001~10質量份，更佳係0.01~1.5質量份，特佳係0.1~1.0質量份。架橋劑(b)的使用量若過量，丙烯酸類黏接劑在23℃的耗損正切會有變得過小的傾向。 The amount of the bridging agent (b) to be used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass based on 100 parts by mass of the (meth) acrylate polymer (a). Share. If the amount of the bridging agent (b) used is excessive, the loss tangent of the acrylic adhesive at 23 ° C tends to be too small.
就構成聚合物的單體單位而言，包含含反應性官能基單體的(甲基)丙烯酸酯聚合物(a)和含有架橋劑(b)的黏接性組成物若加熱，架橋劑(b)會與構成(甲基)丙烯酸酯聚合物(a)的含反應性官能基單體之反應性官能基反應。據此，透過架橋劑(b)使(甲基)丙烯酸酯聚合物(a)形成架橋的構造，可提升所獲得的黏接劑層之凝聚力，更進一步提升強度以及耐久性。 The monomeric unit constituting the polymer, if the (meth) acrylate polymer (a) containing the reactive functional group-containing monomer and the adhesive composition containing the bridging agent (b) are heated, the bridging agent ( b) reacting with a reactive functional group of a reactive functional group-containing monomer constituting the (meth) acrylate polymer (a). According to this, the structure in which the (meth) acrylate polymer (a) is bridged by the bridging agent (b) can enhance the cohesive force of the obtained adhesive layer, and further improve the strength and durability.
上述丙烯酸類黏接劑中可根據需求添加平常使用的各種添加劑，可舉例：折射率調整劑、抗靜電劑、賦黏劑、矽烷耦合劑、抗氧化劑、紫外線吸收劑、光穩定劑、軟化劑、填充劑等。 The above-mentioned acrylic adhesive may be added with various additives which are usually used according to requirements, and examples thereof include a refractive index adjuster, an antistatic agent, a tackifier, a decane coupling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a softener. , fillers, etc.
形成丙烯酸類黏接劑層12時，將丙烯酸類黏接劑以及根據所需含有溶劑的塗佈溶液塗佈於塗佈對象(例如剝離片2b的剝離面)，之後加熱處理形成塗膜。形成的塗膜在不需要養生期的情況下，可直接作為丙烯酸類黏接劑層12，在需要養生期的情況下，則經過養生期後成為丙烯酸類黏接劑層12。 When the acrylic adhesive layer 12 is formed, an acrylic adhesive and a coating solution containing a solvent as required are applied to a coating target (for example, a peeling surface of the release sheet 2b), and then heat-treated to form a coating film. The formed coating film can be directly used as the acrylic adhesive layer 12 without requiring a curing period, and when it is required to have a curing period, it becomes the acrylic adhesive layer 12 after the curing period.
上述加熱處理亦可兼作使塗佈溶液的稀釋溶劑等揮發時的乾燥處理。在進行加熱處理的情況下，加熱溫度較佳係50~150℃，更佳係70~120℃。另外，加熱時間較佳係30 秒鐘~10分鐘，更佳係50秒鐘~2分鐘。加熱處理後根據所需，可於常溫(例如：23℃、50%RH)中靜置養生期1~2週左右。 The heat treatment may also serve as a drying treatment when volatilizing a solvent or the like of the coating solution. In the case of heat treatment, the heating temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. In addition, the heating time is preferably 30 Seconds ~ 10 minutes, more preferably 50 seconds ~ 2 minutes. After the heat treatment, if necessary, the body can be allowed to stand at room temperature (for example, 23 ° C, 50% RH) for about 1 to 2 weeks.
上述丙烯酸類黏接劑含有含反應性官能基的(甲基)丙烯酸酯聚合物(a)以及架橋劑(b)的情況下，以上述加熱處理，透過架橋劑(b)使(甲基)丙烯酸酯聚合物(a)形成架橋的構造。 When the acrylic adhesive contains a reactive functional group-containing (meth)acrylate polymer (a) and a bridging agent (b), the heat treatment is carried out by a bridging agent (b). The acrylate polymer (a) forms a bridging structure.
此處，丙烯酸類黏接劑層12的黏接面(透明樹脂薄膜11的反面)之以JIS Z0237：2009為基準的無鹼玻璃黏接力較佳係0.5N/25mm以上，更佳係1N/25mm以上，特佳係5N/25mm以上。上述黏接力若係0.5N/25mm以上，則使用表面保護面板5時，丙烯酸類黏接劑層12和透明硬質板4的界面上，可防發生意外的剝離。此外，丙烯酸類黏接劑層12的黏接面因不需再剝離性，上述黏接力的上限雖無特別限制，但考慮到處理容易性等時，上限值係80N/25mm左右。 Here, the adhesion of the acrylic-based adhesive layer 12 (the reverse side of the transparent resin film 11) based on JIS Z0237:2009 is preferably 0.5 N/25 mm or more, more preferably 1 N/ 25mm or more, especially good 5N/25mm or more. When the adhesion is 0.5 N/25 mm or more, when the surface protective panel 5 is used, accidental peeling can be prevented at the interface between the acrylic adhesive layer 12 and the transparent hard plate 4. In addition, the upper limit of the adhesive force is not particularly limited, and the upper limit of the adhesive force is not particularly limited, but the upper limit is about 80 N/25 mm in consideration of ease of handling and the like.
(3)聚矽氧類黏接劑層 (3) Polyoxylized adhesive layer
聚矽氧類黏接劑層13對於無鹼玻璃的黏接力下限值係10mN/25mm以上，較佳係20mN/25mm以上，更佳係30mN/25mm以上。聚矽氧類黏接劑層13的黏接力下限值若係10mN/25mm以上，則可維持良好的行動電子機器與顯示器6的附著性，並可抑制經過一段時間後發生浮起或氣泡。另一方面，聚矽氧類黏接劑層13對於無鹼玻璃的黏接力上限值係300mN/25mm以下，較佳係250mN/25mm以下，更佳係200mN/25mm以下。聚矽氧類黏接劑層13的黏接力上限值若 係300mN/25mm以下，則於行動電子機器的顯示器6黏貼的表面保護面板5便可簡單地於該顯示器6再次剝離，並可輕鬆地重新黏貼。 The lower limit of the adhesion strength of the polyoxynoxy adhesive layer 13 to the alkali-free glass is 10 mN/25 mm or more, preferably 20 mN/25 mm or more, more preferably 30 mN/25 mm or more. When the lower limit of the adhesive strength of the polyoxygen-based adhesive layer 13 is 10 mN/25 mm or more, the adhesion between the mobile electronic device and the display 6 can be maintained, and floating or bubbles can be suppressed from occurring after a certain period of time. On the other hand, the upper limit of the adhesion strength of the polyoxynoxy-based adhesive layer 13 to the alkali-free glass is 300 mN/25 mm or less, preferably 250 mN/25 mm or less, more preferably 200 mN/25 mm or less. The upper limit of the adhesion force of the polyoxygen adhesive layer 13 is When the thickness is 300 mN/25 mm or less, the surface protection panel 5 adhered to the display 6 of the mobile electronic device can be easily peeled off again from the display 6, and can be easily reattached.
此外，聚矽氧類黏接劑層13的厚度下限值較佳係5μm以上，更佳係20μm以上，特佳係30μm以上。聚矽氧類黏接劑層13的厚度下限值若係5μm以上，則可發揮所需黏接力，並可確保與行動電子機器的顯示器6之附著性。另一方面，聚矽氧類黏接劑層13的厚度上限值較佳係100μm以下，更佳係70μm以下，特佳係50μm以下。聚矽氧類黏接劑層13的厚度上限值若係100μm以下，則可有效防止製造過程所導致的殘留溶劑或氣泡混入，使黏接力呈現優良的穩定性以及光學特性。 Further, the lower limit of the thickness of the polyoxymethylene-based adhesive layer 13 is preferably 5 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more. When the thickness lower limit of the polyoxygen-based adhesive layer 13 is 5 μm or more, the desired adhesive force can be exhibited, and the adhesion to the display 6 of the mobile electronic device can be ensured. On the other hand, the upper limit of the thickness of the polyoxynoxy adhesive layer 13 is preferably 100 μm or less, more preferably 70 μm or less, and particularly preferably 50 μm or less. When the upper limit of the thickness of the polyoxygen-based adhesive layer 13 is 100 μm or less, it is possible to effectively prevent the residual solvent or bubbles from being mixed in the manufacturing process, and the adhesion is excellent in stability and optical characteristics.
藉由使聚矽氧類黏接劑層13的黏接力以及厚度各介於上述範圍內，使表面保護面板5自行動電子機器的顯示器6再次剝離時更加容易。 By making the adhesion force and the thickness of the polyoxynitride-based adhesive layer 13 within the above range, it is easier to peel off the surface protection panel 5 from the display 6 of the mobile electronic device.
聚矽氧類黏接劑層13係以聚矽氧類黏接劑構成，以可滿足上述黏接力的聚矽氧類黏接劑構成為佳。就聚矽氧類黏接劑而言，有機聚矽醚，特別係含有附加型有機聚矽醚(之硬化物)為佳。這種聚矽氧類黏接劑容易滿足上述的黏接力，且加工性亦優秀。 The polyoxo-based adhesive layer 13 is composed of a polyoxymethylene-based adhesive, and is preferably composed of a polyoxyl-based adhesive which satisfies the above-mentioned adhesive force. In the case of a polyoxymethylene-based adhesive, the organic polyanthracene, particularly containing an additional type of organopolyether (hardened product), is preferred. Such a polyoxygen-based adhesive easily satisfies the above-mentioned adhesive force and is excellent in workability.
附加型有機聚矽醚係以矽氧烷鍵為主骨架的含烯基有機聚矽醚和有機氫聚矽氧烷反應所獲得者為佳。 The additional type of organopolyfluorene ether is preferably obtained by reacting an alkenyl group-containing polyorganoether having a siloxane chain as a main skeleton and an organohydrogenpolyoxyalkylene.
以矽氧烷鍵為主骨架的含烯基有機聚矽醚係以下列平均單位式(1)所顯示的化合物，另外，分子中至少具有2 個烯基的化合物為佳。 The alkenyl group-containing polyorganoether having a siloxane chain as a main skeleton is a compound represented by the following average unit formula (1), and has at least 2 in the molecule. Alkenyl compounds are preferred.
R1 aSiO(4-a)/2．．．(1) R 1 a SiO (4-a)/2 . . . (1)
(式中R1係相同或相異的碳數1~12，較佳係1~8的非取代或取代的1價碳氫化合物，a係介於1.5~2.8，較佳係介於1.8~2.5，更佳係介於1.95~2.05之範圍的正數。) (wherein R 1 is the same or different carbon number of 1 to 12, preferably 1 to 8 of unsubstituted or substituted monovalent hydrocarbons, a is between 1.5 and 2.8, preferably between 1.8 and 2.8 2.5, a better number of positive numbers between 1.95 and 2.05.)
就上述以R1顯示的矽原子鍵結之非或取代的1價碳氫化合物而言，可舉例：乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基、辛烯基等烯基；甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等烷基；苯基、甲苯基、茬基、萘基等芳基、苄基、苯乙基、苯丙基等芳烷基或該等基的氫原子的一部份或全部；氟、溴、氯等鹵素原子；以氰基取代者，可舉例：氯甲基、氯丙基、溴乙基、三氟丙基、氰乙基等。從以烯基硬化時間短暫，以及生產性的觀點來看，乙烯基為佳。 With respect to the above-mentioned non- or substituted monovalent hydrocarbon bonded with a ruthenium atom shown by R 1 , a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and a ring may be exemplified. Alkenyl, octenyl and the like alkenyl; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl An alkyl group such as a fluorenyl group or a fluorenyl group; an aryl group such as a phenyl group, a tolyl group, a fluorenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; or a part of a hydrogen atom of the group; Or all; a halogen atom such as fluorine, bromine or chlorine; and a cyano group substituted by chloromethyl, chloropropyl, bromoethyl, trifluoropropyl or cyanoethyl. Vinyl is preferred from the viewpoint of short-term hardening of the alkenyl group and productivity.
有機氫聚矽氧烷的分子中具有SiH基，藉由上述有機聚矽醚的烯基和有機氫聚矽氧烷的SiH反應，兩者進行附加反應，而獲得附加型有機聚矽醚。 The organohydrogen polyoxyalkylene has an SiH group in the molecule, and an additional reaction is carried out by reacting an alkenyl group of the above organic polyfluorene ether with an organic hydrogen polyoxyalkylene to obtain an additional type of organopolydecene ether.
由於附加型有機聚矽醚在鉑催化劑的存在下可良好地硬化，上述聚矽氧黏接劑含有鉑催化劑為佳。就鉑催化劑而言，可舉例：鉑黑、鹽化第二鉑、氯鉑酸、氯鉑酸和1價乙醇的反應物，氯鉑酸和烯烴類的錯合物則可舉例鉑雙乙醯乙酸等。 Since the additional type organopolyether can be well cured in the presence of a platinum catalyst, the above-mentioned polyoxynene binder preferably contains a platinum catalyst. In the case of a platinum catalyst, for example, a reaction product of platinum black, a second platinum salt, a chloroplatinic acid, a chloroplatinic acid, and a monovalent ethanol, and a complex of chloroplatinic acid and an olefin may be exemplified by platinum diacetamidine. Acetic acid, etc.
上述聚矽氧黏接劑中的鉑催化劑之含有量相對於附加型有機聚矽醚100質量份，較佳係含有0.01~3質量份， 更佳係含有0.05~2質量份。藉由鉑催化劑的含有量介於上述範圍內，便可不妨礙塗層，使附加型有機聚矽醚硬化而形成聚矽氧類黏接劑層13。 The content of the platinum catalyst in the polyoxygen oxide adhesive is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the additional type organic polyterpene ether. More preferably, it contains 0.05 to 2 parts by mass. When the content of the platinum catalyst is within the above range, the additional type organic polydecene ether can be cured without interfering with the coating layer to form the polyoxynoxy adhesive layer 13.
附加型有機聚矽醚中，在不損害本發明的目的之範圍內，為了提升黏接力，使其含有分子中含有3官能性或4官能性的矽氧烷單位之有機聚矽醚(聚矽氧樹脂)為佳。 In the additional type of organic polyanthracene, in order to enhance the adhesion, the organic polyethylene ether containing a trifunctional or tetrafunctional siloxane unit having a molecular weight in the molecule is contained. Oxygen resin) is preferred.
上述聚矽氧黏接劑中的包含3官能性或4官能性的矽氧烷單位之有機聚矽醚的含有量，相對於附加型有機聚矽醚100質量份，較佳係含有0~100質量份，更佳係含有5~70質量份，特佳係含有10~50質量份。包含3官能性或4官能性的矽氧烷單位之有機聚矽醚的含有量若過多，聚矽氧類黏接劑層13的黏接力會上升，而有再剝離性低落的疑慮。 The content of the organopolyxanthene containing a trifunctional or tetrafunctional siloxane unit in the polyoxygenated adhesive is preferably from 0 to 100 based on 100 parts by mass of the additional organopolyether. The mass fraction is preferably 5 to 70 parts by mass, and the particularly preferred one is 10 to 50 parts by mass. If the content of the organopolydecene ether containing a trifunctional or tetrafunctional siloxane unit is too large, the adhesive strength of the polyoxygen-based adhesive layer 13 rises, and there is a concern that the re-peelability is lowered.
形成聚矽氧類黏接劑層13時，例如，附加型有機聚矽醚和根據需求包含3官能性或4官能性的矽氧烷單位的有機聚矽醚與鉑催化劑，以甲基乙基酮、甲苯、乙酸乙酯、二甲苯等溶劑稀釋為10~60質量%左右的塗佈溶液，塗佈於塗佈對象(例如：透明樹脂薄膜11或剝離片2a的剝離面)後，加熱使其硬化即可。加熱溫度係90~180℃左右為佳，加熱時間則係1~5分鐘左右為佳。 When forming the polyoxynoxy adhesive layer 13, for example, an additional type of organopolydecene ether and an organopolyetherether containing a trifunctional or tetrafunctional siloxane unit as required, and a platinum catalyst, methylethyl A coating solution having a solvent such as ketone, toluene, ethyl acetate or xylene diluted to about 10 to 60% by mass is applied to a coating target (for example, a peeling surface of the transparent resin film 11 or the release sheet 2a), and then heated. It can be hardened. The heating temperature is preferably about 90 to 180 ° C, and the heating time is preferably about 1 to 5 minutes.
(4)雙面黏接片之物理性質 (4) Physical properties of double-sided adhesive sheets
本實施形態所涉及的雙面黏接片1的霧度(以JIS K7136：2000為基準測量的值)較佳係2.0%以下，更佳係1.5%以下，特佳係1.0%以下。雙面黏接片1的霧度若係2.0%以下，則可獲得透明性高且適合作為行動電子機器的顯示器表面用 表面保護面板。 The haze (value measured based on JIS K7136:2000) of the double-sided adhesive sheet 1 according to the present embodiment is preferably 2.0% or less, more preferably 1.5% or less, and particularly preferably 1.0% or less. When the haze of the double-sided adhesive sheet 1 is 2.0% or less, high transparency can be obtained and it is suitable for use as a display surface of a mobile electronic device. Surface protection panel.
2.剝離片 2. Stripping sheet
就剝離片2a、2b而言，並無特別限制，可使用眾所皆知的塑膠薄膜，可舉例：聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對酞酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚(對酞酸丁二酯)薄膜、聚氨酯薄膜、乙烯/乙酸乙烯酯薄膜、離子聚合物樹脂薄膜、乙烯．(甲基)丙烯酸共聚物薄膜、乙烯．(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。此外，亦可使用該等架橋薄膜，另外，該等積層薄膜亦佳。 The release sheets 2a and 2b are not particularly limited, and a well-known plastic film can be used, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethylpentene. Alkene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly(p-butyl phthalate) film, polyurethane film, ethylene/vinyl acetate Ester film, ionic polymer resin film, ethylene. (Meth)acrylic copolymer film, ethylene. (Meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, and the like. In addition, these bridge films can also be used, and these laminated films are also preferred.
上述剝離片2a、2b的剝離面(特別係和雙面黏接片1接觸的面)中，上述剝離片2b的剝離面經剝離處理尤佳(作為剝離片2a，使用未經剝離處理的原本塑膠薄膜亦佳)。就剝離處理中所使用的剝離劑而言，可舉例：醇酸類、聚矽氧類、氟類、不飽和聚酯類、聚烯烴類、蠟類剝離劑等。此外，將剝離片2a、2b中剝離片剝離力大的一邊作為重剝離型剝離片，另一邊剝離片剝離力小的作為輕剝離型剝離片為佳。 In the peeling surface of the peeling sheets 2a and 2b (particularly the surface in contact with the double-sided adhesive sheet 1), the peeling surface of the peeling sheet 2b is preferably subjected to a peeling treatment (as the peeling sheet 2a, the original peeling treatment is used) Plastic film is also good). The release agent used in the release treatment may, for example, be an alkyd, a polyfluorene, a fluorine, an unsaturated polyester, a polyolefin, a wax release agent or the like. In addition, it is preferable that the peeling sheet 2a and 2b have a large peeling force on one side as a heavy peeling type peeling sheet, and the other peeling sheet has a small peeling force as a light peeling type peeling sheet.
對於剝離片2a、2b的厚度雖無特別限制，通常係20~150μm左右。 The thickness of the release sheets 2a and 2b is not particularly limited, but is usually about 20 to 150 μm.
3.剝離片附著雙面黏接片之製造 3. Fabrication of peeling sheet attached double-sided adhesive sheet
就剝離片附著雙面黏接片3之其一製造例而言，於剝離片2b的剝離面形成丙烯酸類黏接劑層12，之後，於該丙烯酸類黏接劑層12貼合透明樹脂薄膜11。接著，於此透明樹脂薄膜 11的外露面上形成聚矽氧類黏接劑層13，之後，在該聚矽氧類黏接劑層13上，使剝離片2a的剝離面與其接觸貼合剝離片2a，獲得剝離片附著雙面黏接片3。此製造例中，丙烯酸類黏接劑層12的形成和聚矽氧類黏接劑層13的形成可交替進行。 In the manufacturing example in which the release sheet is attached to the double-sided adhesive sheet 3, the acrylic adhesive layer 12 is formed on the release surface of the release sheet 2b, and then the transparent resin film is bonded to the acrylic adhesive layer 12. 11. Next, the transparent resin film A polyoxymethylene-based adhesive layer 13 is formed on the exposed surface of the layer 11, and then the release surface of the release sheet 2a is brought into contact with the release sheet 2a on the polyoxynitride-based adhesive layer 13, and the release sheet is attached. Double-sided adhesive sheet 3. In this production example, the formation of the acrylic adhesive layer 12 and the formation of the polyoxygen-based adhesive layer 13 can be alternately performed.
另外，就剝離片附著雙面黏接片3的另一製造例而言，於剝離片2a的剝離面上形成聚矽氧類黏接劑層13後，在聚矽氧類黏接劑層13外露面貼合透明樹脂薄膜11，以此作為第1積層體。另一方面，於剝離片2b的剝離面上形成丙烯酸類黏接劑層12，以此作為第2積層體。接著，使第1積層體的透明樹脂薄膜11和第2積層體的丙烯酸類黏接劑層12接觸，黏貼第1積層體和第2積層體，獲得剝離片附著雙面黏接片3。上述第1積層體的製造中，聚矽氧類黏接劑層13亦可於透明樹脂薄膜11側形成。另外，上述製造例中，丙烯酸類黏接劑層12的形成和聚矽氧類黏接劑層13的形成可交替進行。 Further, in another production example in which the release sheet is adhered to the double-sided adhesive sheet 3, after the polysilicon-based adhesive layer 13 is formed on the release surface of the release sheet 2a, the polyoxynitride-based adhesive layer 13 is formed. The transparent resin film 11 was bonded to the exposed surface as the first laminate. On the other hand, the acrylic adhesive layer 12 is formed on the peeling surface of the release sheet 2b, and this is used as the second laminated body. Then, the transparent resin film 11 of the first laminate is brought into contact with the acrylic adhesive layer 12 of the second laminate, and the first laminate and the second laminate are adhered to obtain the release sheet adhered to the double-sided adhesive sheet 3. In the production of the first layered body, the polyoxynoxy adhesive layer 13 may be formed on the side of the transparent resin film 11. Further, in the above production example, the formation of the acrylic adhesive layer 12 and the formation of the polyoxygen-based adhesive layer 13 may be alternately performed.
〔表面保護面板〕 [surface protection panel]
本實施形態所涉及的表面保護面板5如圖2所示，上述雙面黏接片1和該雙面黏接片1的丙烯酸類黏接劑層12上，具有積層的透明硬質板4而構成。此外，如圖2所示，亦可於聚矽氧類黏接劑層13中的透明樹脂薄膜11側之反側積層剝離片2a。 As shown in FIG. 2, the surface protection panel 5 according to the present embodiment has a laminated transparent hard plate 4 on the double-sided adhesive sheet 1 and the acrylic adhesive layer 12 of the double-sided adhesive sheet 1. . Further, as shown in FIG. 2, the release sheet 2a may be laminated on the side opposite to the side of the transparent resin film 11 in the polyoxynitride-based adhesive layer 13.
1.透明硬質板 1. Transparent hard board
透明硬質板4係在行動電子機器的顯示器6受到衝擊的情況下，為保護該顯示器6不碎裂而存在，通常以JIS K7127：1999為基準所測量的楊氏模數係10GPa以上。就本實施形態中的透 明硬質板4而言，透明性以及強度優秀的玻璃板、聚碳酸酯板、丙烯酸樹脂板等皆為理想的例子。該等中，從耐久性的觀點來看，玻璃板較佳，更佳係以強化玻璃形成的玻璃板，特佳係以化學強化玻璃(透過化學處理，於表面形成壓縮應力層的玻璃)形成的玻璃板。 When the display 6 of the mobile electronic device is subjected to an impact, the transparent hard plate 4 is present to protect the display 6 from chipping, and the Young's modulus is usually 10 GPa or more measured based on JIS K7127:1999. In this embodiment, In the case of the bright hard plate 4, a glass plate, a polycarbonate plate, an acrylic plate, and the like which are excellent in transparency and strength are preferable examples. Among these, from the viewpoint of durability, a glass plate is preferable, and a glass plate formed of tempered glass is more preferable, and a chemically strengthened glass (glass which is chemically treated to form a compressive stress layer on the surface) is formed. Glass plate.
透明硬質板4的厚度較佳係0.1~5mm，更佳係0.3~3mm，特佳係0.5~2mm。透明硬質板4的厚度若係0.1mm以上，則會變得即使施予衝擊亦難以碎裂。此外，透明硬質板4的厚度若係5mm以下，則可防止表面保護面板5變得過重，更進一步抑制表面保護面板5黏貼的行動電子機器變重。 The thickness of the transparent hard plate 4 is preferably 0.1 to 5 mm, more preferably 0.3 to 3 mm, and particularly preferably 0.5 to 2 mm. When the thickness of the transparent hard plate 4 is 0.1 mm or more, it becomes difficult to be broken even if an impact is applied. Further, when the thickness of the transparent hard plate 4 is 5 mm or less, the surface protection panel 5 can be prevented from becoming excessively heavy, and the mobile electronic device to which the surface protection panel 5 is adhered can be further suppressed from becoming heavy.
2.表面保護面板之製造方法 2. Method for manufacturing surface protection panel
本實施形態所涉及的表面保護面板5製造時，自前面所述之剝離片附著雙面黏接片3剝離剝離片2b，於外露的丙烯酸類黏接劑層12貼合透明硬質板4。 In the manufacture of the surface protection panel 5 according to the present embodiment, the release sheet 2b is peeled off from the release sheet attached to the above-mentioned release sheet, and the transparent rigid sheet 4 is bonded to the exposed acrylic adhesive layer 12.
3.表面保護面板之使用方法 3. How to use the surface protection panel
本實施形態所涉及的表面保護面板5使用時，如圖3所示，由聚矽氧類黏接劑層13剝離剝離片2a，使外露的聚矽氧類黏接劑層13接觸行動電子機器的顯示器6(通常係頂層玻璃)之外露給最終消費者觀看的表面上，將表面保護面板5壓於顯示器6以進行黏貼，此作業可由最終消費者進行手工作業。 When the surface protection panel 5 according to the present embodiment is used, as shown in FIG. 3, the release sheet 2a is peeled off by the polyoxygen-based adhesive layer 13, and the exposed polyoxygen-based adhesive layer 13 is brought into contact with the mobile electronic device. The display 6 (usually the top glass) is exposed to the surface viewed by the end consumer, and the surface protection panel 5 is pressed against the display 6 for bonding, which can be manually performed by the final consumer.
此時，表面保護面板5具有按順序積層透明硬質板4、丙烯酸類黏接劑層12、透明樹脂薄膜11，以及聚矽氧類黏接劑層13而形成的構成，同時，藉由丙烯酸類黏接劑在23℃的耗損正切、丙烯酸類黏接劑層12的厚度，以及聚矽氧類 黏接劑層13對於無鹼玻璃的黏接力皆介於前面所述之範圍內，即使透過最終消費者進行手工作業，亦可抑制聚矽氧類黏接劑層13和顯示器6之間留下氣泡的情況。此外，黏貼於顯示器6的表面保護面板5即使在重新黏貼等情況下，表面保護面板5仍可輕易地從顯示器6剝離。 At this time, the surface protective panel 5 has a structure in which the transparent hard plate 4, the acrylic adhesive layer 12, the transparent resin film 11, and the polyoxygen-based adhesive layer 13 are laminated in this order, and at the same time, by acrylic Loss tangent of the adhesive at 23 ° C, thickness of the acrylic adhesive layer 12, and polyfluorene oxide The adhesion of the adhesive layer 13 to the alkali-free glass is within the range described above, and even if the manual operation by the final consumer is performed, the adhesion between the polyoxyl-based adhesive layer 13 and the display 6 can be suppressed. The case of bubbles. Further, the surface protection panel 5 adhered to the display 6 can be easily peeled off from the display 6 even in the case of re-adhesive or the like.
以上說明的實施形態，係為了便於理解本發明而記載，當不能以此限定本發明實施之範圍，因此，屬於上述實施形態中記載的各元素之技術性範圍內的所有設計變更或均等物，皆應仍屬本發明專利涵蓋之範圍內。 The embodiments described above are described in order to facilitate the understanding of the present invention, and are not intended to limit the scope of the present invention. Therefore, all design changes or equivalents within the technical scope of each element described in the above embodiments are All should remain within the scope of the invention patent.
例如，可省略剝離片附著雙面黏接片3中的剝離片2a、2b其中任一邊，另外，雙面黏接片1中的透明樹脂薄膜11和丙烯酸類黏接劑層12之間，以及/或透明樹脂薄膜11和聚矽氧類黏接劑層13之間，亦可存在其他層。 For example, it is possible to omit the peeling sheet from adhering to either one of the release sheets 2a, 2b in the double-sided adhesive sheet 3, and further, between the transparent resin film 11 and the acrylic adhesive layer 12 in the double-sided adhesive sheet 1, and There may be other layers between the transparent resin film 11 and the polyoxygen-based adhesive layer 13.
(實施例) (Example)
以下，透過實施例等進一步對本發明進行具體說明，但本發明的範圍並不受這些實施例等限制。 Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited by the examples and the like.
〔實施例1〕 [Example 1]
將丙烯酸正丁酯60質量份、丙烯酸甲酯20質量份，以及丙烯酸2-羥乙酯20質量份共聚合，調製(甲基)丙烯酸酯聚合物。此(甲基)丙烯酸酯聚合物的分子量以後面將敘述的方法測得之重量平均分子量係60萬。 60 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized to prepare a (meth) acrylate polymer. The molecular weight of the (meth) acrylate polymer measured by a method described later is 600,000.
從上述所獲得的(甲基)丙烯酸酯聚合物100質量份(固體含量換算；以下相同)和作為異氰酸鹽類架橋劑的三羥甲基丙烷變性二異氰酸甲苯(Nippon Polyurethane Industry Co.,Ltd.製，Coronate L)0.3質量份混合後充分攪拌，以甲基乙基酮稀釋後，獲得固體含量濃度係30質量%的丙烯酸類黏接劑塗佈液。 100 parts by mass of the (meth) acrylate polymer obtained above (in terms of solid content; the same applies hereinafter) and trimethylolpropane-denatured toluene diisocyanate as an isocyanate-type bridging agent (Nippon Polyurethane Industry) Co., Ltd., manufactured by Co., Ltd., Co., Ltd., 0.3 parts by mass, mixed well, and stirred with methyl ethyl ketone to obtain an acrylic adhesive coating liquid having a solid content concentration of 30% by mass.
將所獲得的丙烯酸類黏接劑塗佈液，於聚對酞酸乙二酯薄膜的單面以聚矽氧類剝離劑剝離處理過的剝離片(Lintec Corporation.製，RL-1，厚度：38μm)之剝離處理面，以刀式塗佈機塗佈後，於90℃使其乾燥1分鐘，形成厚度係50μm的丙烯酸類黏接劑層。 The obtained acrylic adhesive coating liquid was peeled off by a polyphthalic acid release agent on one side of a polyethylene terephthalate film (Lintec Corporation, RL-1, thickness: The release-treated surface of 38 μm) was applied by a knife coater, and then dried at 90 ° C for 1 minute to form an acrylic adhesive layer having a thickness of 50 μm.
接著，於上述丙烯酸類黏接劑層，作為透明樹脂薄膜，貼合聚對酞酸乙二酯薄膜(Toyobo Co.,Ltd.製，Cosmo Shine PET50A4300，厚度：50μm)，獲得以透明樹脂薄膜/丙烯酸類黏接劑層/剝離片所形成的積層體。 Next, a polyethylene terephthalate film (Cosmo Shine PET 50A4300, thickness: 50 μm, manufactured by Toyobo Co., Ltd.) was attached as a transparent resin film to the above-mentioned acrylic adhesive layer to obtain a transparent resin film/ A laminate formed of an acrylic adhesive layer/release sheet.
另一方面，將利用以矽氧烷鍵為主骨架的含乙烯基有機聚矽醚，以及有機氫聚矽氧烷形成的附加型有機聚矽醚(Shin-Etsu Chemical Co.,Ltd.製，KS-847H)100質量份，和包含3官能性或4官能性的矽氧烷單位的有機聚矽醚(聚矽氧樹脂；Dow Corning Toray Co.,Ltd.製，SD-4584)25質量份，以及鉑催化劑(Dow Corning Toray Co.,Ltd.製，SRX-212 CATAAKYST)0.6質量份混合後充分攪拌，以甲基乙基酮稀釋後，獲得固體含量濃度係25質量%的聚矽氧類黏接劑塗佈液。 On the other hand, an additional type of organic polyanthracene (Shin-Etsu Chemical Co., Ltd., which is made of a vinyl-containing organic polyfluorene ether having a ruthenium oxide bond as a main skeleton, and an organic hydrogen polyoxyalkylene oxide, will be used. KS-847H) 100 parts by mass, and 25 parts by mass of an organic polyanthracene (polyoxyxylene resin; manufactured by Dow Corning Toray Co., Ltd., SD-4584) containing a trifunctional or tetrafunctional siloxane unit And 0.6 parts by mass of a platinum catalyst (manufactured by Dow Corning Toray Co., Ltd., SRX-212 CATAAKYST), and thoroughly stirred, and after being diluted with methyl ethyl ketone, a polyfluorene oxide having a solid content concentration of 25% by mass was obtained. Adhesive coating solution.
將獲得的聚矽氧類黏接劑塗佈液，於上述積層體的透明樹脂薄膜上，以刀式塗佈機塗佈後，在90℃中使其乾燥1分鐘，形成厚度係35μm的聚矽氧類黏接劑層。之後，於聚矽氧類黏接劑層的外露面，作為剝離片，貼合未經剝離處理或 易黏著處理的未處理PET薄膜(Toray Industries Inc.製，Lumirror T60，厚度：50μm)，獲得以剝離片/丙烯酸類黏接劑層/透明樹脂薄膜/聚矽氧類黏接劑層/剝離片形成的剝離片附著雙面黏接片。 The obtained polyoxo-based adhesive coating liquid was applied onto the transparent resin film of the laminate described above by a knife coater, and then dried at 90 ° C for 1 minute to form a poly 35 μm thick layer. Oxide adhesive layer. After that, on the exposed surface of the polyoxyl-based adhesive layer, as a release sheet, the bonding is not peeled off or Untreated PET film which is easily adhered (manufactured by Toray Industries Inc., Lumirror T60, thickness: 50 μm), obtained as a release sheet/acrylic adhesive layer/transparent resin film/polyoxygenated adhesive layer/release sheet The formed release sheet is attached to the double-sided adhesive sheet.
〔實施例2〕 [Example 2]
丙烯酸類黏接劑塗佈液調製時，除了異氰酸鹽類類架橋劑的配合量變更為0.8質量份以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 In the preparation of the acrylic adhesive coating liquid, the release sheet adhered to the double-sided adhesive sheet in the same manner as in Example 1 except that the blending amount of the isocyanate-based bridging agent was changed to 0.8 parts by mass.
〔實施例3〕 [Example 3]
除了丙烯酸類黏接劑層的厚度變更為30μm以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 The peeling sheet adhered to the double-sided adhesive sheet was produced in the same manner as in Example 1 except that the thickness of the acrylic adhesive layer was changed to 30 μm.
〔實施例4〕 [Example 4]
聚矽氧類黏接劑塗佈液的調製中，除了包含3官能性或4官能性的矽氧烷單位的有機聚矽醚之配合量變更為40質量份以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 In the preparation of the polyoxymethylene-based adhesive coating liquid, the amount of the organopolydecene ether containing a trifunctional or tetrafunctional siloxane unit is changed to 40 parts by mass, and the others are the same as in the first embodiment. The double-sided adhesive sheet is attached to the peeling sheet.
〔實施例5〕 [Example 5]
除了聚矽氧類黏接劑層的厚度變更為50μm以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 The release sheet adhered to the double-sided adhesive sheet in the same manner as in Example 1 except that the thickness of the polyoxymethylene-based adhesive layer was changed to 50 μm.
〔比較例1〕 [Comparative Example 1]
丙烯酸類黏接劑塗佈液的調製中，除了異氰酸鹽類架橋劑的配合量變更為2.0質量份以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 In the preparation of the acrylic adhesive coating liquid, the release sheet adhered to the double-sided adhesive sheet in the same manner as in Example 1 except that the amount of the isocyanate-based bridging agent was changed to 2.0 parts by mass.
〔比較例2〕 [Comparative Example 2]
除了丙烯酸類黏接劑層的厚度變更為10μm以外，其餘皆 與實施例1一致以製造剝離片附著雙面黏接片。 Except that the thickness of the acrylic adhesive layer was changed to 10 μm, In the same manner as in Example 1, a release sheet was attached to the double-sided adhesive sheet.
〔比較例3〕 [Comparative Example 3]
聚矽氧類黏接劑塗佈液的調製中，除了包含3官能性或4官能性的矽氧烷單位之有機聚矽醚的配合量變更為80質量份以外，其餘皆與實施例1一致以製造剝離片附著雙面黏接片。 In the preparation of the polyoxo-based adhesive coating liquid, the amount of the organopolydecene ether containing a trifunctional or tetrafunctional siloxane unit is changed to 80 parts by mass, and the others are the same as in the first embodiment. The double-sided adhesive sheet is attached to the peeling sheet.
此處，前述重量平均分子量(Mw)，係利用凝膠滲透層析儀(GPC)，根據以下條件測量(GPC測量)之標準聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a standard polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) according to the following conditions (GPC measurement).
<測量條件> <Measurement conditions>
．GPC測量儀器：Tosoh Corporation製，HLC-8020 . GPC measuring instrument: manufactured by Tosoh Corporation, HLC-8020
．GPC管柱(以下列順序通過)：Tosoh Corporation製 . GPC column (passed in the following order): manufactured by Tosoh Corporation
TSK guard column HXL-H TSK guard column HXL-H
TSK gel GMHXL(×2) TSK gel GMHXL (×2)
TSK gel G2000HXL TSK gel G2000HXL
．測量溶劑：四氫呋喃 . Measuring solvent: tetrahydrofuran
．測量溫度：40℃ . Measuring temperature: 40 ° C
〔測試例1〕(耗損正切之測量) [Test Example 1] (Measurement of loss tangent)
將實施例以及比較例中調製的丙烯酸類黏接劑塗佈液，於聚對酞酸乙二酯薄膜的單面經聚矽氧類剝離劑剝離處理的剝離片(Lintec Corporation.製，RL-1，厚度：38μm)之剝離處理面，以刀式塗佈機塗佈後，於90℃使其乾燥1分鐘，形成厚度係25μm的丙烯酸類黏接劑層。將此丙烯酸類黏接劑層多次積層，同時進行衝孔加工，製造直徑8mm、厚度3mm的測試片。對於獲得的測試片，以扭轉剪切法依以下條件測量耗損正切， 結果如表1所示。 The acrylic adhesive coating liquid prepared in the examples and the comparative examples was peeled off from the polyethylene terephthalate film by one side of the polyethylene terephthalate film (Lintec Corporation, RL- The peel-treated surface of 1, thickness: 38 μm was applied by a knife coater, and then dried at 90 ° C for 1 minute to form an acrylic adhesive layer having a thickness of 25 μm. This acrylic adhesive layer was laminated several times and punched at the same time to produce a test piece having a diameter of 8 mm and a thickness of 3 mm. For the obtained test piece, the loss tangent was measured by the torsional shear method according to the following conditions, The results are shown in Table 1.
．動態黏彈性測量儀器：Rheomtric公司製，DYNAMIC ANALYZER RDA II . Dynamic viscoelastic measuring instrument: DYNAMIC ANALYZER RDA II, manufactured by Rheomtric
．頻率：1Hz . Frequency: 1Hz
．溫度：23℃ . Temperature: 23 ° C
〔測試例2〕(黏接力之測量) [Test Example 2] (Measurement of adhesion)
於實施例以及比較例中製造的剝離片附著雙面黏接片上，剝離丙烯酸類黏接劑層的剝離片，於外露的丙烯酸類黏接劑層貼合聚對酞酸乙二酯薄膜(Toray Industries Inc.製，PET25 S10，厚度：25μm)，得到以聚對酞酸乙二酯薄膜/丙烯酸類黏接劑層/透明樹脂薄膜/聚矽氧類黏接劑層/剝離片所形成的積層體。將獲得的積層體裁切為25mm×250mm大小，以此作為樣本。 The release sheets produced in the examples and the comparative examples were attached to the double-sided adhesive sheets, the release sheets of the acrylic adhesive layer were peeled off, and the polyethylene terephthalate film was bonded to the exposed acrylic adhesive layer (Toray). Manufactured by Industries Inc., PET25 S10, thickness: 25 μm), laminated with polyethylene terephthalate film/acrylic adhesive layer/transparent resin film/polyoxygenated adhesive layer/release sheet body. The obtained laminate was cut into a size of 25 mm × 250 mm as a sample.
於23℃、50%RH的環境中，從上述樣本剝離剝離片，將外露的聚矽氧類黏接劑層對無鹼玻璃(Corning Incorporated製，Eagle XG)利用2kg的橡膠輥黏貼後靜置24小時。 The peeling sheet was peeled off from the sample in an environment of 23° C. and 50% RH, and the exposed polyoxynoxy adhesive layer was adhered to an alkali-free glass (Eagle XG, manufactured by Corning Incorporated) using a 2 kg rubber roller, and then allowed to stand. 24 hours.
之後，利用萬用型張力試驗機(Orientec Co.,Ltd.製，Tensilon UTM-4-100)，以JIS Z0237：2009為基準，在剝離速度300mm/min、剝離角度180°的條件下，測量聚矽氧類黏接劑層的黏接力(mN/25mm)，結果如表1所示。 After that, the measurement was carried out under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180° using a universal tension tester (Tensilon UTM-4-100, manufactured by Orientec Co., Ltd.) based on JIS Z0237:2009. The adhesion of the polyxylene adhesive layer (mN/25mm), the results are shown in Table 1.
〔測試例3〕(霧度之測量) [Test Example 3] (Measurement of haze)
對於實施例以及比較例中使用的透明樹脂薄膜，以及實施例和比較例中製造的剝離片附著雙面黏接片上，剝離2張剝離片的雙面黏接片(丙烯酸類黏接劑層/透明樹脂薄膜/聚矽氧類 黏接劑層)入射光後，使用霧度計(Nippon Denshoku Industries Co.,Ltd.製，NDH2000)，以JIS K7136：2000為基準測量個別的霧度(%)，結果如表1所示。 The transparent resin film used in the examples and the comparative examples, and the release sheets produced in the examples and the comparative examples were attached to the double-sided adhesive sheet, and the double-sided adhesive sheets of the two release sheets were peeled off (acrylic adhesive layer/ Transparent resin film / polyfluorene After the incident light, the individual haze (%) was measured using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000) based on JIS K7136:2000. The results are shown in Table 1.
〔測試例4〕(氣泡殘留評價) [Test Example 4] (bubble residue evaluation)
於實施例以及比較例中製造的剝離片附著雙面黏接片剝離丙烯酸類黏接劑層的剝離片，將外露的丙烯酸類黏接劑層，以貼合機貼合於大小係70mm×140mm的化學強化玻璃板(Corning Incorporated.製，Gorilla玻璃，厚度：1.1mm，楊氏模數：72GPa)，獲得剝離片附著的表面保護面板。 The release sheet produced in the examples and the comparative examples was adhered to the double-sided adhesive sheet to peel off the release sheet of the acrylic adhesive layer, and the exposed acrylic adhesive layer was attached to the size system by a bonding machine of 70 mm × 140 mm. A chemically strengthened glass plate (manufactured by Corning Incorporated., Gorilla glass, thickness: 1.1 mm, Young's modulus: 72 GPa) was used to obtain a surface protective panel to which a release sheet was attached.
接著從剝離片附著的表面保護面板之聚矽氧類黏接劑層剝離剝離片，將外露的聚矽氧類黏接劑層，以手工作業貼合於大小係70mm×150mm的鹼石灰玻璃(Central Glass Co.,Ltd.製，厚度：1.1mm)，此時表面保護面板的聚矽氧類黏接劑層和鹼石灰玻璃之間，沒有留下氣泡的情況下，判斷為氣泡殘留評價良好(○)；有留下氣泡的情況下，則判斷為氣泡殘留評價不良(×)。此外，此氣泡殘留評價中，評價者3人個別進行上述貼合作業，3人皆無留下氣泡的情況下，判斷為評價良好(○)，只要有1人留下氣泡，則不受限於其他評價者的結果，判斷為評價不良(×)，結果如表1所示。 Then, the release sheet is peeled off from the polyoxyl-based adhesive layer of the surface protection panel to which the release sheet is attached, and the exposed polyoxymethylene-based adhesive layer is manually bonded to a soda lime glass having a size of 70 mm × 150 mm ( Manufactured by Central Glass Co., Ltd., thickness: 1.1 mm). At this time, when there is no air bubble between the polyxylene-based adhesive layer of the surface protective panel and the soda-lime glass, it is judged that the bubble residue evaluation is good. (○); When there is a bubble left, it is judged that the bubble residual evaluation is poor (×). In addition, in the evaluation of the bubble residue, three of the evaluators individually performed the above-mentioned bonding work, and when three people did not leave a bubble, it was judged that the evaluation was good (○), and as long as one person left the bubble, it was not limited. The results of other evaluators were judged to be poor evaluation (x), and the results are shown in Table 1.
〔測試例5〕(再剝離性之評價) [Test Example 5] (Evaluation of re-peelability)
測試例4中製造的表面保護面板以及鹼石灰玻璃的積層體(化學強化玻璃板/丙烯酸類黏接劑層/透明樹脂薄膜/聚矽氧類黏接劑層/鹼石灰玻璃)之聚矽氧類黏接劑層和鹼石灰玻璃的界面上，以手工作業剝離表面保護面板(化學強化玻璃板/丙烯酸 類黏接劑層/透明樹脂薄膜/聚矽氧類黏接劑層)和鹼石灰玻璃。此時，剝離時毫無問題之情況下，判斷為再剝離性良好(○)； 化學強化玻璃板或鹼石灰玻璃碎裂或無法剝離的情況下，判斷為再剝離性不良(×)，結果如表1所示。 The surface protective panel manufactured in Test Example 4 and the laminated body of the soda-lime glass (chemically strengthened glass plate/acrylic adhesive layer/transparent resin film/polyoxygenated adhesive layer/soda lime glass) Adhesive peeling surface protection panel (chemically strengthened glass plate/acrylic acid) by manual work on the interface between the adhesive layer and the soda lime glass Type of adhesive layer/transparent resin film/polyoxygenated adhesive layer) and soda lime glass. At this time, when there is no problem in peeling, it is judged that the removability is good (○); When the chemically strengthened glass plate or the soda lime glass was broken or could not be peeled off, it was judged that the removability was poor (x), and the results are shown in Table 1.
由表1可得知，實施例中獲得的表面保護面板即使進行手工作業，黏貼時亦難以留下氣泡，亦易於剝離。 As can be seen from Table 1, even if the surface protection panel obtained in the examples was manually handled, it was difficult to leave air bubbles when pasted, and it was easy to peel off.
(產業上之可利用性) (industrial availability)
本發明所涉及的表面保護面板用雙面黏接片以及表面保護面板，例如，係用於保護智慧型手機或平板終端等機器上之顯示器的表面保護面板，適合作為最終消費者進行黏貼．剝離作業的表面保護面板。 The double-sided adhesive sheet for a surface protection panel and the surface protection panel according to the present invention are, for example, a surface protection panel for protecting a display on a machine such as a smart phone or a tablet terminal, and are suitable for sticking as an end consumer. Surface protection panel for peeling work.
Claims (9)
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| PCT/JP2014/084184 WO2016103372A1 (en) | 2014-12-24 | 2014-12-24 | Double-sided adhesive sheet for surface protective panels, and surface protective panel |
| WOPCT/JP2014/084184 | 2014-12-24 |
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| TWI741038B (en) * | 2016-10-03 | 2021-10-01 | 日商陶氏東麗股份有限公司 | Photo-curable liquid silicone composition and cured product thereof |
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| TWI741038B (en) * | 2016-10-03 | 2021-10-01 | 日商陶氏東麗股份有限公司 | Photo-curable liquid silicone composition and cured product thereof |
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