TWI679113B - Surface-protective film and optical component attached with the same - Google Patents
Surface-protective film and optical component attached with the same Download PDFInfo
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- TWI679113B TWI679113B TW105106643A TW105106643A TWI679113B TW I679113 B TWI679113 B TW I679113B TW 105106643 A TW105106643 A TW 105106643A TW 105106643 A TW105106643 A TW 105106643A TW I679113 B TWI679113 B TW I679113B
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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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
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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
- B32B2551/00—Optical elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本發明提供一種表面保護膜及使用了該表面保護膜的光學元件,該表面保護膜可用於表面具有凹凸的光學用膜,對被黏附體的污染少,且對被黏附體的低污染性不發生經時變化,不會經時劣化而具有優異的剝離防靜電性能。所述表面保護膜(10)在由具有透明性的樹脂構成的基材膜(1)的一個面上,形成含有作為防靜電劑的離子化合物的黏結劑層(2),在黏結劑層(2)上貼合有具有剝離劑層(4)的剝離膜(5),所述剝離劑層(4)由鹼金屬鹽及矽氧樹脂類剝離劑構成,鹼金屬鹽成分從所述剝離膜轉印至所述黏結劑層的表面,從被黏附體上剝離所述黏結劑層時的剝離靜電壓降低。 The invention provides a surface protection film and an optical element using the surface protection film. The surface protection film can be used for an optical film with unevenness on the surface, and has less pollution to the adherend and low pollution to the adherend. It has excellent peeling and antistatic properties without changing with time. The surface protection film (10) forms a binder layer (2) containing an ionic compound as an antistatic agent on one surface of a substrate film (1) made of a transparent resin, and the binder layer ( 2) A release film (5) having a release agent layer (4) is bonded to the release agent layer (4), and the release agent layer (4) is composed of an alkali metal salt and a silicone resin-based release agent, and the alkali metal salt component is removed from the release film. The static voltage is reduced when the adhesive layer is transferred to the surface of the adhesive layer and the adhesive layer is peeled from the adherend.
Description
本發明係有關於一種表面保護膜,其貼合於偏光板(polarizing plate)、相位差板、顯示器用透鏡膜等光學元件(以下有時也稱作光學用膜)的表面。更詳細而言,本發明提供一種表面保護膜及貼合有該表面保護膜的光學元件,所述表面保護膜對被黏附體的污染少,並且不會經時劣化地具有優異的剝離防靜電性能。 The present invention relates to a surface protection film that is bonded to the surface of an optical element (hereinafter sometimes referred to as an optical film) such as a polarizing plate, a retardation plate, and a lens film for a display. In more detail, the present invention provides a surface protection film and an optical element to which the surface protection film is bonded. The surface protection film has less contamination of an adherend, and has excellent peeling and antistatic properties without deterioration over time. performance.
在製造、搬運偏光板、相位差板、顯示器用透鏡膜、防反射膜、硬塗膜、觸控面板用透明導電性膜等光學用膜及使用了它們的顯示器等光學產品時,在該光學用膜的表面貼合表面保護膜,以防止後續步驟中的表面污染和損傷。作為產品的光學用膜的外觀檢查為了節省剝下表面保護膜再進行貼合的時間,提高工作效率,有時也以表面保護膜貼合於光學用膜的狀態直接進行。 When manufacturing and transporting optical films such as polarizing plates, retardation plates, display lens films, anti-reflection films, hard coating films, and transparent conductive films for touch panels, and optical products such as displays using these, The surface of the film is adhered to a surface protection film to prevent surface contamination and damage in subsequent steps. In order to save the time of peeling off the surface protective film and then bonding, and improve the working efficiency, the visual inspection of the optical film as a product may be performed directly in a state where the surface protective film is bonded to the optical film.
長期以來,在光學產品的製造步驟中,為了防止損傷或污垢的附著,通常使用在基材膜的一個面上設有黏結劑層的表面保護膜。表面保護膜經由具有弱黏結力的黏結劑層貼 合於光學用膜上。將黏結劑層設為弱黏結力,是為了將使用過的表面保護膜從光學用膜的表面上剝離去除時,能夠容易剝離,且黏結劑不附著殘留在作為被黏附體的光學用膜產品上(即防止殘膠的產生)。 For a long time, in the manufacturing steps of optical products, in order to prevent damage or adhesion of dirt, a surface protective film having an adhesive layer provided on one surface of a base film is generally used. Surface protective film is applied via an adhesive layer with weak adhesion It is attached to the optical film. The reason why the adhesive layer has a weak adhesive force is that when the used surface protective film is peeled off from the surface of the optical film, it can be easily peeled off, and the adhesive does not remain on the optical film product as an adherend. (Ie prevent the generation of residual glue).
近年來,在液晶顯示面板的生產步驟中,如下現象雖然發生件數少,但還是存在:由於將貼合於光學用膜上的表面保護膜剝離去除時產生的剝離靜電壓而產生的用於控製液晶顯示面板的顯示畫面的驅動IC等電路元件被破壞、液晶分子的配向損壞的現象。 In recent years, in the production steps of liquid crystal display panels, although the number of occurrences is small, there are still the following phenomena: the peeling static voltage generated when the surface protective film bonded to the optical film is peeled off and removed A phenomenon in which circuit elements such as a driving IC that controls a display screen of a liquid crystal display panel is damaged, and alignment of liquid crystal molecules is damaged.
此外,為了降低液晶顯示面板的耗電,液晶材料的驅動電壓變低,驅動IC的破壞電壓也隨之變低。最近開始謀求使剝離靜電壓在+0.7kV~-0.7kV的範圍內。 In addition, in order to reduce the power consumption of the liquid crystal display panel, the driving voltage of the liquid crystal material is reduced, and the destruction voltage of the driving IC is also reduced accordingly. Recently, efforts have been made to make the peeling static voltage within a range of +0.7 kV to -0.7 kV.
此外,以往的偏光板是在由含浸有碘的聚乙烯醇(PVA)構成的偏光鏡(polarizer)的兩側,為了保護偏光鏡而用水性黏合劑黏合三乙醯纖維素膜(TAC膜)來製造偏光板的,但近年來,也開始使用如下偏光板:使用丙烯酸膜、環狀聚烯烴膜、聚酯膜代替TAC膜的偏光板;使用紫外線固化型黏合劑代替水性黏合劑的偏光板。偏光板的構成材料變化產生了以下問題:在剝離去除表面保護膜時產生的剝離靜電壓比使用以往構成的偏光板時增高。 In addition, conventional polarizers are composed of a polarizer made of polyvinyl alcohol (PVA) impregnated with iodine, and a triacetam cellulose film (TAC film) is bonded with a water-based adhesive to protect the polarizer. To manufacture polarizing plates, but in recent years, polarizing plates using acrylic films, cyclic polyolefin films, and polyester films instead of TAC films have also started to be used; polarizing plates using ultraviolet curing adhesives instead of water-based adhesives . A change in the constituent material of the polarizing plate causes a problem that the peeling static voltage generated when the surface protective film is peeled off is higher than that when a polarizing plate having a conventional structure is used.
此外,近年來隨著3D顯示器(立體顯示器)的普及,在偏振片等光學用膜的表面有時貼合有FPR(Film Patterned Retarder(圖案化相位差))膜。在將貼合於偏振片等光學用膜的表面的表面保護膜剝下後,貼合FPR膜。但是, 偏振片等光學用膜的表面若被用於表面保護膜的黏結劑或防靜電劑污染,則存在FPR膜難以黏接的問題。因此,對於該用途的表面保護膜,謀求一種對被黏附體的污染少的膜。 In addition, in recent years, with the spread of 3D displays (stereoscopic displays), FPR (Film Patterned Retarder) films are sometimes bonded to the surface of optical films such as polarizers. After peeling off the surface protection film attached to the surface of an optical film such as a polarizing plate, the FPR film was attached. but, If the surface of an optical film such as a polarizer is contaminated with an adhesive or an antistatic agent for a surface protection film, there is a problem that the FPR film is difficult to adhere. Therefore, for the surface protection film for this application, a film with less contamination to the adherend is required.
另一方面,在一些液晶面板製造商中,作為表面保護膜對被黏附體的污染性的評價方法,採用如下方法,先將貼合於偏振片等光學用膜的表面保護膜剝下,以混入有氣泡的狀態再次貼合,以規定條件進行加熱處理,然後,剝下表面保護膜,觀察被黏附體的表面。在這種評價方法中,即使被黏附體的表面污染為微量,若在混入氣泡的部分和表面保護膜的與黏結劑接觸的部分,被黏附體的表面污染有差別,則以氣泡痕跡(有時也稱為氣泡斑)的形式殘留。因此,作為這種對被黏附體的表面的污染性的評價方法,成為非常嚴格的評價方法。近年來謀求一種表面保護膜,該表面保護膜即使在由這種嚴格的評價方法所判定的結果中,在對被黏附體的表面的污染性上也不存在問題。 On the other hand, in some liquid crystal panel manufacturers, as a method for evaluating the contamination of a surface protection film to an adherend, the following method is used to peel off the surface protection film attached to an optical film such as a polarizing plate to The air bubbles were mixed again in a state where they were mixed, and heat treatment was performed under predetermined conditions. Then, the surface protective film was peeled off, and the surface of the adherend was observed. In this evaluation method, even if the surface of the adherend is contaminated in a small amount, if the surface contamination of the adherend differs between the part where the air bubbles are mixed and the part of the surface protective film that is in contact with the adhesive, the air bubble trace (with (Also known as bubble spots). Therefore, as an evaluation method of the contamination property to the surface of an adherend, it becomes a very strict evaluation method. In recent years, a surface protective film has been sought, and the surface protective film has no problem in the contamination of the surface of an adherend even in a result determined by such a strict evaluation method.
提出了如下一種表面保護膜:將表面保護膜從作為被黏附體的光學用膜上剝離時,為了防止因剝離靜電壓高導致的不良狀況,使用了將剝離靜電壓抑制為較低、含有防靜電劑的黏結劑層。 A surface protection film has been proposed. When the surface protection film is peeled off from an optical film as an adherend, in order to prevent an unfavorable condition caused by a high peeling static voltage, a low peeling static voltage is used and a protective film is used. Adhesive layer of electrostatic agent.
例如,在專利文獻1中,公開了一種表面保護膜,其使用了由烷基三甲基銨鹽、含有羥基的丙烯酸類聚合物、聚異氰酸酯構成的黏結劑。 For example, Patent Document 1 discloses a surface protective film using a binder composed of an alkyltrimethylammonium salt, a hydroxyl-containing acrylic polymer, and a polyisocyanate.
此外,在專利文獻2中,公開了一種黏結劑組合物及使用了該黏結劑組合物的黏結片類,所述黏結劑組合物由離子液體 及酸值為1.0以下的丙烯酸聚合物構成。 In addition, Patent Document 2 discloses an adhesive composition and an adhesive sheet using the adhesive composition. The adhesive composition is made of an ionic liquid. And an acrylic polymer having an acid value of 1.0 or less.
此外,在專利文獻3中,公開了一種黏結組合物及使用了該黏結組合物的表面保護膜,所述黏結組合物由丙烯酸聚合物、聚醚多元醇化合物、經陰離子吸附性化合物處理過的鹼金屬鹽構成。 In addition, Patent Literature 3 discloses an adhesive composition and a surface protection film using the adhesive composition, the adhesive composition being made of an acrylic polymer, a polyether polyol compound, or an anion-adsorbing compound treated Alkali metal salt composition.
此外,在專利文獻4中,公開了一種黏結劑組合物及使用了該黏結劑組合物的表面保護膜,所述黏結劑組合物由離子液體、鹼金屬鹽、玻璃轉移溫度為0℃以下的聚合物構成。 In addition, Patent Document 4 discloses an adhesive composition and a surface protective film using the adhesive composition. The adhesive composition is composed of an ionic liquid, an alkali metal salt, and a glass transition temperature of 0 ° C or lower. Polymer composition.
現有技術文獻 Prior art literature
專利文獻 Patent literature
專利文獻1:日本特開2005-131957號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2005-131957
專利文獻2:日本特開2005-330464號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2005-330464
專利文獻3:日本特開2005-314476號公報 Patent Document 3: Japanese Patent Application Laid-Open No. 2005-314476
專利文獻4:日本特開2006-152235號公報 Patent Document 4: Japanese Patent Application Laid-Open No. 2006-152235
在上述專利文獻1~4所述的表面保護膜中,在黏結劑層的內部添加有防靜電劑。因此,黏結劑層的厚度越厚,或者在貼合於被黏附體後時間越久,對於貼合了表面保護膜的被黏附體,有防靜電劑從黏結劑層向被黏附體轉移的量越多的趨勢。若向被黏附體轉移的防靜電劑的量變多,則有作為被黏附體的光學用膜的外觀品質下降、或是貼合FPR膜時FPR膜的黏合性降低的可能性。 In the surface protection films described in the aforementioned Patent Documents 1 to 4, an antistatic agent is added inside the adhesive layer. Therefore, the thicker the adhesive layer, or the longer it takes to adhere to the adherend, the greater the amount of antistatic agent transferred from the adhesive layer to the adherend for the adherend to which the surface protective film is attached. More trends. When the amount of the antistatic agent transferred to the adherend is increased, there is a possibility that the appearance quality of the optical film as an adherend is deteriorated, or the adhesiveness of the FPR film may be reduced when the FPR film is bonded.
如此,為了減少所述從黏結劑層向被黏附體轉移的防靜電劑的經時變化,若使黏結劑層的厚度變薄,則會產生別的問題。例如,存在如下問題:在用於防眩光用的經過防眩處理的偏振片等表面具有凹凸的光學用膜的情況下,黏結劑無法追隨光學用膜表面的凹凸而混入氣泡;由於光學用膜與黏結劑的黏合面積減少而使黏結力降低,在使用中表面保護膜翹起、脫落。 In this way, in order to reduce the change with time of the antistatic agent transferred from the adhesive layer to the adherend, if the thickness of the adhesive layer is made thinner, another problem occurs. For example, in the case of an optical film having unevenness on the surface such as an anti-glare polarizing plate used for anti-glare, the adhesive cannot follow the unevenness on the surface of the optical film and mix air bubbles; The adhesion area with the adhesive is reduced to reduce the adhesive force, and the surface protective film is lifted and peeled off during use.
此外,為了使從黏結劑層向被黏附體轉移的防靜電劑的經時變化減少,若減少向黏結劑層中添加的防靜電劑的添加量,則存在產生如下現象的危險性:剝離去除表面保護膜時產生的剝離靜電壓增高、驅動IC等電路元件被破壞的現象,或液晶分子的配向被破壞的現象。 In addition, in order to reduce the change with time of the antistatic agent transferred from the adhesive layer to the adherend, if the amount of the antistatic agent added to the adhesive layer is reduced, there is a risk of the following phenomenon: peeling and removing The phenomenon that the peeling static voltage increases during the surface protection film increases, the circuit elements such as the driver IC are destroyed, or the alignment of the liquid crystal molecules is destroyed.
本發明是鑑於上述情況而完成的,其技術問題在於提供一種表面保護膜及使用了該表面保護膜的光學元件,所述表面保護膜為一種用於光學用膜的表面保護膜,該表面保護膜即使對於表面上具有凹凸的光學用膜也能夠使用,對被黏附體的污染非常少,且對被黏附體的污染性不會經時變化,而且,即使替換偏光板的構成元件(TAC膜變更為丙烯酸膜或聚酯膜、水性黏合劑變更為紫外線固化型黏合劑),也能將剝離表面保護膜時的剝離靜電壓抑制為較低。 The present invention has been made in view of the above circumstances, and a technical problem thereof is to provide a surface protection film and an optical element using the surface protection film. The surface protection film is a surface protection film for an optical film. The surface protection The film can be used even for an optical film having unevenness on the surface, the pollution to the adherend is very small, and the contamination of the adherend does not change with time, and even if the component of the polarizing plate (TAC film) is replaced Changing to an acrylic film or a polyester film, and changing the water-based adhesive to a UV-curable adhesive) can also suppress the peeling static voltage when peeling the surface protective film to a low level.
為了解決所述技術問題,本申請發明人等進行了認真研究。 In order to solve the technical problem, the inventors of the present application have conducted earnest research.
首先,為了對被黏附體的污染少,且使污染性的經時變化小,需要減少推測為污染被黏附體的防靜電劑的添加量。但 是,在減少防靜電劑的添加量的情況下,將表面保護膜從被黏附體剝離時的剝離靜電壓會增高。於是,本申請發明人對於在不增加防靜電劑添加量的情況,將表面保護膜從被黏附體剝離時的剝離靜電壓抑制為較低的方法進行了研究。 First, in order to reduce the contamination of the adherend and to reduce the contamination change with time, it is necessary to reduce the amount of the antistatic agent presumed to contaminate the adherend. but When the amount of the antistatic agent is reduced, the peeling static voltage when the surface protective film is peeled from the adherend increases. Therefore, the inventors of the present application have studied a method of suppressing the peeling static voltage when the surface protective film is peeled from the adherend to be low without increasing the amount of the antistatic agent added.
對所述內容進行研究後,結果本申請發明人等發現,在黏結劑組合物中添加不污染被黏附體的程度的防靜電劑,在基材的一個面上塗佈、乾燥該黏結劑組合物,層疊黏結劑層後,向黏結劑層的表面賦予適量的防靜電劑。由此,能夠將表面保護膜從作為被黏附體的光學用膜上剝離時的剝離靜電壓抑制為較低,且難以污染被黏附體,從而完成了本發明。 After researching the content, the inventors of the present application found that an antistatic agent is added to the adhesive composition to a degree that does not contaminate the adherend, and the adhesive composition is coated and dried on one surface of the substrate. After the adhesive layer is laminated, an appropriate amount of an antistatic agent is applied to the surface of the adhesive layer. Accordingly, the peeling static voltage when the surface protective film is peeled from the optical film as an adherend can be suppressed to a low level, and it is difficult to contaminate the adherend, and the present invention has been completed.
本發明的表面保護膜的技術思想在於,透過塗佈、乾燥含有不污染被黏附體的程度的防靜電劑的黏結劑組合物,層疊黏結劑層後,賦予黏結劑層的表面適量的防靜電劑,在將對被黏附體的污染性抑制為低污染性的基礎上,將從作為被黏附體的光學用膜上剝離時的剝離靜電壓抑制為較低。 The technical idea of the surface protection film of the present invention is to apply and dry an adhesive composition containing an antistatic agent to a degree that does not contaminate the adherend, and after laminating the adhesive layer, give the surface of the adhesive layer an appropriate amount of antistatic. The agent suppresses the contamination property of the adherend to low contamination properties, and suppresses the peeling static voltage when peeling from the optical film as the adherend to be low.
為了解決上述技術問題,本發明提供一種表面保護膜,其特徵在於,在由具有透明性的樹脂構成的基材膜的一個面上,形成含有作為防靜電劑的離子化合物的黏結劑層,具有剝離劑層的剝離膜經由所述剝離劑層貼合在該黏結劑層上,所述剝離劑層含有鹼金屬鹽及矽氧樹脂類剝離劑,所述鹼金屬鹽的成分從所述剝離膜轉印至所述黏結劑層的表面,從被黏附體上剝離所述黏結劑層時的剝離靜電壓降低。 In order to solve the above-mentioned technical problems, the present invention provides a surface protection film characterized in that an adhesive layer containing an ionic compound as an antistatic agent is formed on one surface of a substrate film made of a resin having transparency, and The release film of the release agent layer is bonded to the adhesive layer via the release agent layer. The release agent layer contains an alkali metal salt and a silicone resin-based release agent, and components of the alkali metal salt are removed from the release film. The static voltage is reduced when the adhesive layer is transferred to the surface of the adhesive layer and the adhesive layer is peeled from the adherend.
此外,優選所述離子化合物不是鹼金屬鹽。 Furthermore, it is preferred that the ionic compound is not an alkali metal salt.
此外,優選所述黏結劑層由(甲基)丙烯酸酯共聚物交聯而成。 In addition, it is preferable that the adhesive layer is formed by crosslinking a (meth) acrylate copolymer.
此外,提供一種從作為被黏附體的光學用膜上剝離時的表面電勢(surface potential)為+0.7kV~-0.7kV的表面保護膜。 In addition, a surface protection film having a surface potential of +0.7 kV to -0.7 kV when peeled from an optical film as an adherend is provided.
此外,優選將所述剝離膜從所述黏結劑層上剝離時的剝離力為0.005~0.3N/50mm。 In addition, the peeling force when peeling the release film from the adhesive layer is preferably 0.005 to 0.3 N / 50 mm.
此外,本發明提供一種貼合有所述表面保護膜的光學元件。 The present invention also provides an optical element to which the surface protection film is bonded.
本發明的表面保護膜為用於光學用膜的表面保護膜,即使對表面具有凹凸的光學用膜也可使用。此外,本發明的表面保護膜對被黏附體的污染非常少,是一種對被黏附體的污染性不會經時變化的表面保護膜。更進一步,本發明能夠提供一種表面保護膜及使用了該保護膜的光學元件,本發明的表面保護膜即使是偏光板的構成元件發生變化(從TAC膜變為丙烯酸膜、環狀聚烯烴膜或聚酯膜,從水性黏合劑變為紫外線固化型黏合劑),仍將剝離表面保護膜時的剝離靜電壓抑制為較低。 The surface protective film of the present invention is a surface protective film for an optical film, and can be used even for an optical film having unevenness on the surface. In addition, the surface protection film of the present invention has very little pollution to the adherend, and is a surface protection film that does not change the contamination of the adherend with time. Furthermore, the present invention can provide a surface protection film and an optical element using the same. Even if the surface protection film of the present invention is a constituent element of a polarizing plate, it changes (from a TAC film to an acrylic film or a cyclic polyolefin film). Or polyester film, from an aqueous adhesive to an ultraviolet-curable adhesive), the peeling static voltage when the surface protective film is peeled off is still kept low.
根據本發明的表面保護膜,能夠降低從被黏附體剝離時產生的靜電的量,且剝離防靜電性能的經時變化及對被黏附體的污染少,因此能夠預期生產率的提高及成品率的提高。 According to the surface protection film of the present invention, the amount of static electricity generated when peeling from an adherend can be reduced, and the time-dependent change of the peeling antistatic performance and the pollution to the adherend are small. Therefore, an improvement in productivity and yield can be expected. improve.
1‧‧‧基材膜 1‧‧‧ substrate film
2‧‧‧黏結劑層 2‧‧‧ Adhesive layer
3‧‧‧樹脂膜 3‧‧‧ resin film
4‧‧‧剝離劑層 4‧‧‧ peeling agent layer
5‧‧‧剝離膜 5‧‧‧ peeling film
7‧‧‧防靜電劑 7‧‧‧Antistatic agent
8‧‧‧被黏附體(光學元件) 8‧‧‧ Adhered body (optical element)
10‧‧‧表面保護膜 10‧‧‧ surface protective film
11‧‧‧剝下剝離膜的表面保護膜 11‧‧‧ peel off the surface protection film of the release film
20‧‧‧貼合有表面保護膜的光學元件 20‧‧‧ Optical element with surface protection film
第1圖為本發明的表面保護膜的示意性剖面圖;第2圖為表示將剝離膜從本發明的表面保護膜上剝下的狀態的剖面圖;第3圖為表示將本發明的表面保護膜貼合於光學元件的一個實施例的剖面圖。 FIG. 1 is a schematic cross-sectional view of a surface protective film of the present invention; FIG. 2 is a cross-sectional view showing a state where a release film is peeled from the surface protective film of the present invention; and FIG. 3 is a view showing a surface of the present invention A cross-sectional view of one embodiment of a protective film bonded to an optical element.
以下,根據實施方式對本發明進行詳細說明。 Hereinafter, this invention is demonstrated in detail based on embodiment.
第1圖為本發明的表面保護膜的示意性剖面圖。該表面保護膜10在透明的基材膜1的一個面的表面上形成有含防靜電劑的黏結劑層2。在該黏結劑層2的表面上貼合有剝離膜5,所述剝離膜5在樹脂膜3的表面上形成了含有防靜電劑7的剝離劑層4。 FIG. 1 is a schematic cross-sectional view of a surface protection film of the present invention. This surface protection film 10 has an antistatic agent-containing adhesive layer 2 formed on one surface of a transparent base film 1. A release film 5 is laminated on the surface of the adhesive layer 2, and the release film 5 forms a release agent layer 4 containing an antistatic agent 7 on the surface of the resin film 3.
作為用於本發明的表面保護膜10的基材膜1,使用由具有透明性及可撓性的樹脂形成的基材膜。如此,能夠以表面保護膜貼合于作為被黏附體的光學元件上的狀態,進行光學元件的外觀檢查。用作基材膜1的由具有透明性的樹脂構成的膜適宜使用聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚間苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯等聚酯膜。除了聚酯膜之外,只要是具有所需強度、且具有光學特性的膜,也可以使用由其他樹脂構成的膜。基材膜1可以是無拉伸膜,也可以是經單軸或雙軸拉伸的膜。此外,也可以將拉伸膜(stretched film)的拉伸倍率、隨拉伸膜的結晶化而形成的軸方向的配向角度控製為特定的值。 As the base film 1 used for the surface protection film 10 of the present invention, a base film made of a resin having transparency and flexibility is used. In this manner, the appearance inspection of the optical element can be performed in a state where the surface protective film is bonded to the optical element as an adherend. As the film made of a transparent resin used as the base film 1, polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polyethylene terephthalate are suitably used. Polyester film such as butanediol diformate. In addition to a polyester film, a film made of another resin may be used as long as it has a desired strength and has optical characteristics. The base film 1 may be a non-stretched film, or may be a uniaxially or biaxially stretched film. The stretching ratio of the stretched film and the alignment angle in the axial direction formed by the crystallization of the stretched film may be controlled to specific values.
用於本發明的表面保護膜10的基材膜1的厚度沒有特別 的限定,例如,優選為12~100μm左右的厚度,若為20~75μm左右的厚度則便於操作,因此更優選。 The thickness of the base film 1 used for the surface protection film 10 of the present invention is not particularly limited For example, a thickness of about 12 to 100 μm is preferable, and a thickness of about 20 to 75 μm is preferable because it is easy to handle.
此外,可以根據需要,在基材膜1的形成有黏結劑層2的面的相反側面上,設置防止表面污染的防汙層、防靜電層、防損傷的硬塗層等。此外,在基材膜1的表面上可以施加經由電暈放電導致的表面改質、塗佈增黏塗劑等易黏合處理。 In addition, if necessary, an antifouling layer, an antistatic layer, a hard coat layer, or the like that prevents surface contamination can be provided on the opposite side of the surface on which the adhesive layer 2 is formed on the base film 1. In addition, the surface of the base film 1 may be subjected to an easy-adhesion treatment such as surface modification by corona discharge and application of a tackifier.
此外,用於本發明的表面保護膜10的黏結劑層2只要是黏合於被黏附體的表面,可在使用後簡單剝下,且難以污染被黏附體的黏結劑,則沒有特別的限定,若考慮貼合於光學用膜之後的耐久性等,通常使用由(甲基)丙烯酸酯共聚物交聯而成的黏結劑。 In addition, the adhesive layer 2 used in the surface protection film 10 of the present invention is not particularly limited as long as it is adhered to the surface of the adherend, can be easily peeled off after use, and it is difficult to contaminate the adherent of the adherend. In consideration of durability after bonding to an optical film, an adhesive obtained by crosslinking a (meth) acrylate copolymer is usually used.
作為(甲基)丙烯酸酯共聚物,可列舉出使正丁基丙烯酸酯、2-乙基己基丙烯酸酯、異辛基丙烯酸酯、異壬基丙烯酸酯等主要單體與丙烯腈、醋酸乙烯酯、甲基丙烯酸甲酯、丙烯酸乙酯等共聚單體、丙烯酸、甲基丙烯酸、羥基乙基丙烯酸酯、羥基丁基丙烯酸酯、甲基丙烯酸縮水甘油酯、N-羥甲基丙烯醯胺等官能性單體共聚而成的共聚物。(甲基)丙烯酸酯共聚物可以主要單體及其他單體均為(甲基)丙烯酸酯,作為主要單體之外的單體,可以含有1種或2種以上(甲基)丙烯酸酯以外的單體。 Examples of the (meth) acrylate copolymer include a main monomer such as n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate, and acrylonitrile and vinyl acetate. , Comonomers such as methyl methacrylate, ethyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxybutyl acrylate, glycidyl methacrylate, N-hydroxymethacrylamide, etc. Copolymer made from copolymerizing monomers. The (meth) acrylic acid ester copolymer may have both the main monomer and other monomers as (meth) acrylic acid esters. As a monomer other than the main monomer, it may contain one or two or more kinds of (meth) acrylic acid esters. Monomer.
此外,在(甲基)丙烯酸酯共聚物中,可以將含有聚氧化烯基的化合物共聚,也可將其混合。作為含有可共聚的聚氧化烯基的化合物,可列舉出聚乙二醇(400)單丙烯酸酯、聚乙二醇(400)單甲基丙烯酸酯,甲氧基聚乙二醇(400) 丙烯酸酯、甲氧基聚乙二醇(400)甲基丙烯酸酯、聚丙二醇(400)單丙烯酸酯、聚丙二醇(400)單甲基丙烯酸酯、甲氧基聚丙二醇(400)丙烯酸酯、甲氧基聚丙二醇(400)甲基丙烯酸酯等。透過使這些含有聚氧化烯基的單體與所述(甲基)丙烯酸酯共聚物的主要單體、官能性單體共聚,能夠得到由含有聚氧化烯基的共聚物形成的黏結劑。 In the (meth) acrylate copolymer, a compound containing a polyoxyalkylene group may be copolymerized or mixed. Examples of the compound containing a copolymerizable polyoxyalkylene group include polyethylene glycol (400) monoacrylate, polyethylene glycol (400) monomethacrylate, and methoxypolyethylene glycol (400). Acrylate, methoxy polyethylene glycol (400) methacrylate, polypropylene glycol (400) monoacrylate, polypropylene glycol (400) monomethacrylate, methoxy polypropylene glycol (400) acrylate, methyl Oxypolypropylene glycol (400) methacrylate and the like. By copolymerizing these polyoxyalkylene group-containing monomers with the main monomer and functional monomer of the (meth) acrylic acid ester copolymer, a binder composed of a polyoxyalkylene group-containing copolymer can be obtained.
作為可混合於(甲基)丙烯酸酯共聚物中的含有聚氧化烯基的化合物,優選為含有聚氧化烯基的(甲基)丙烯酸酯共聚物,更優選為含有聚氧化烯基的(甲基)丙烯酸類單體的聚合物,例如,可列舉出聚乙二醇(400)單丙烯酸酯、聚乙二醇(400)單甲基丙烯酸酯、甲氧基聚乙二醇(400)丙烯酸酯、甲氧基聚乙二醇(400)甲基丙烯酸酯、聚丙二醇(400)單丙烯酸酯、聚丙二醇(400)單甲基丙烯酸酯、甲氧基聚丙二醇(400)丙烯酸酯、甲氧基聚丙二醇(400)甲基丙烯酸酯等的聚合物。透過將這些含有聚氧化烯基的化合物與所述(甲基)丙烯酸酯共聚物混合,能夠獲得添加有含有聚氧化烯基的化合物的黏結劑。 The polyoxyalkylene group-containing compound that can be mixed in the (meth) acrylate copolymer is preferably a (meth) acrylate copolymer containing a polyoxyalkylene group, and more preferably a (meth) acrylate containing a polyoxyalkylene group. Polymer of acrylic monomers, for example, polyethylene glycol (400) monoacrylate, polyethylene glycol (400) monomethacrylate, and methoxypolyethylene glycol (400) acrylic acid Esters, methoxy polyethylene glycol (400) methacrylate, polypropylene glycol (400) monoacrylate, polypropylene glycol (400) monomethacrylate, methoxy polypropylene glycol (400) acrylate, methoxy Polymers such as polypropylene glycol (400) methacrylate. By mixing these polyoxyalkylene group-containing compounds with the (meth) acrylate copolymer, a binder to which a polyoxyalkylene group-containing compound is added can be obtained.
作為添加於黏結劑層2的固化劑,作為使(甲基)丙烯酸酯共聚物交聯的交聯劑,可列舉出異氰酸酯化合物、環氧化合物、三聚氰胺化合物、金屬螯合物等。此外,作為增黏劑,可列舉出松香類、香豆酮茚類(coumarone indene)、萜烯類(terpene)、石油類、酚類等。 Examples of the curing agent added to the adhesive layer 2 include a isocyanate compound, an epoxy compound, a melamine compound, and a metal chelate as a crosslinking agent that crosslinks the (meth) acrylate copolymer. Examples of the thickener include rosin, coumarone indene, terpene, petroleum, and phenol.
黏結劑層2含有防靜電劑。作為黏結劑層2中含有的防靜電劑,可列舉出表面活性劑類、離子液體、鹼金屬鹽、 金屬氧化物、金屬微粒、導電性聚合物、碳、碳納米管等,從透明性、對(甲基)丙烯酸類聚合物的親和性、被黏附體污染性等來看,優選鹼金屬鹽以外的離子化合物等,特別優選在溫度25℃下為固體的離子化合物。 The adhesive layer 2 contains an antistatic agent. Examples of the antistatic agent contained in the adhesive layer 2 include surfactants, ionic liquids, alkali metal salts, Metal oxides, metal fine particles, conductive polymers, carbon, carbon nanotubes, etc. are preferably other than alkali metal salts in terms of transparency, affinity for (meth) acrylic polymers, and contamination by adherends, etc. The ionic compound and the like are particularly preferably an ionic compound which is solid at a temperature of 25 ° C.
此外,可在黏結劑層2的防靜電劑中添加各種樹脂。作為向防靜電劑中添加的樹脂,可列舉出聚酯類樹脂、聚醯胺類樹脂、聚氨酯類樹脂、聚烯烴樹脂、聚乙烯醇縮丁醛樹脂、聚乙烯醇樹脂、聚醋酸乙烯酯樹脂、纖維素樹脂、矽氧樹脂樹脂、氟樹脂等。 In addition, various resins can be added to the antistatic agent of the adhesive layer 2. Examples of the resin added to the antistatic agent include polyester resins, polyamide resins, polyurethane resins, polyolefin resins, polyvinyl butyral resins, polyvinyl alcohol resins, and polyvinyl acetate resins. , Cellulose resin, silicone resin, fluororesin, etc.
黏結劑層2中包含的防靜電劑不需要集中於黏結劑層2的表面,可在黏結劑層2中均勻溶解或分散。 The antistatic agent contained in the adhesive layer 2 need not be concentrated on the surface of the adhesive layer 2, and can be uniformly dissolved or dispersed in the adhesive layer 2.
離子化合物是指由陰離子與陽離子構成,具有在常溫下為液體的離子液體與在常溫下為固體的離子固體。作為陽離子部分,可列舉出咪唑鎓離子等環狀脒離子、吡啶鎓離子、銨離子、鋶離子、鏻離子等的有機陽離子或無機陽離子。此外,作為陰離子部分,可列舉出CnH2n+1COO-、CnF2n+1COO-、NO3 -、CnF2n+1SO3 -、(CnF2n+1SO2)2N-、(CnF2n+1SO2)3C-、PO4 3-、AlCl4 -、Al2Cl7 -、ClO4 -、BF4 -、PF6 -、AsF6 -、SbF6 -等的有機陰離子或無機陰離子。 An ionic compound refers to an ionic liquid composed of an anion and a cation, and has an ionic liquid that is liquid at normal temperature and an ionic solid that is solid at normal temperature. Examples of the cationic moiety include organic cations and inorganic cations such as cyclic sulfonium ions such as imidazolium ions, pyridinium ions, ammonium ions, sulfonium ions, and sulfonium ions. Further, as the anionic moiety include C n H 2n + 1 COO - , C n F 2n + 1 COO -, NO 3 -, C n F 2n + 1 SO 3 -, (C n F 2n + 1 SO 2 ) 2 N -, (C n F 2n + 1 SO 2) 3 C -, PO 4 3-, AlCl 4 -, Al 2 Cl 7 -, ClO 4 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 - and other organic or inorganic anions.
用於本發明的表面保護膜10的、含有防靜電劑的黏結劑層2的厚度沒有特別的限定,但例如優選5~40μm左右的厚度,更優選10~30μm左右的厚度。由於從被黏附體上剝下表面保護膜時的操作性優異,故而優選表面保護膜對於被黏附體表面的剝離強度(黏結力)為0.03~0.3N/25mm左右的、 具有弱黏結力的黏結劑層2。此外,從將剝離膜5從表面保護膜10上剝下時的操作性優異的方面來看,剝離膜5的來自於黏結劑層2的剝離力優選為0.005~0.3N/50mm。 The thickness of the antistatic agent-containing adhesive layer 2 used in the surface protective film 10 of the present invention is not particularly limited, but for example, a thickness of about 5 to 40 μm is preferred, and a thickness of about 10 to 30 μm is more preferred. Since the workability when peeling the surface protection film from the adherend is excellent, it is preferable that the peel strength (adhesive force) of the surface protection film to the surface of the adherend is about 0.03 to 0.3N / 25mm, Adhesive layer 2 with weak adhesion. In addition, from the viewpoint of excellent operability when peeling the peeling film 5 from the surface protective film 10, the peeling force of the peeling film 5 from the adhesive layer 2 is preferably 0.005 to 0.3 N / 50 mm.
此外,用於本發明的表面保護膜10的剝離膜5在樹脂膜3的一個面上層疊有含有矽氧樹脂剝離劑及不與該剝離劑反應的防靜電劑7的剝離劑層4。 In addition, the release film 5 used in the surface protection film 10 of the present invention has a release agent layer 4 containing a silicone resin release agent and an antistatic agent 7 which does not react with the release agent, laminated on one surface of the resin film 3.
作為樹脂膜3,可列舉出聚酯膜、聚醯胺膜、聚乙烯膜、聚丙烯膜、聚醯亞胺膜等,從透明性優異、較廉價的方面來看,優選聚酯膜。樹脂膜可以是無拉伸膜,也可以是經單軸或雙軸拉伸的膜。此外,也可以將拉伸膜的拉伸倍率、隨拉伸膜的結晶化而形成的軸方向的配向角度控製為特定的值。 Examples of the resin film 3 include a polyester film, a polyimide film, a polyethylene film, a polypropylene film, and a polyimide film. A polyester film is preferred in terms of excellent transparency and low cost. The resin film may be a non-stretched film or a film which is uniaxially or biaxially stretched. The stretching ratio of the stretched film and the alignment angle in the axial direction formed by the crystallization of the stretched film may be controlled to specific values.
樹脂膜3的厚度沒有特別的限定,例如優選12~100μm左右的厚度,若為20~50μm左右的厚度則容易操作,因而更優選。 The thickness of the resin film 3 is not particularly limited. For example, a thickness of about 12 to 100 μm is preferable, and a thickness of about 20 to 50 μm is easy to handle, and thus it is more preferable.
此外,也可根據需要,在樹脂膜3的表面上施加經由電暈放電導致的表面改質、塗佈增黏塗劑等易黏合處理。 In addition, if necessary, the surface of the resin film 3 may be subjected to an easy-adhesion treatment such as surface modification by corona discharge and application of a tackifier.
作為構成剝離劑層4的矽氧樹脂類剝離劑,其為以聚二甲基矽氧烷為主成分的剝離劑,可列舉出加成反應型、縮合反應型、陽離子聚合型、自由基聚合型(radical polymerization type)等已知的矽氧樹脂類剝離劑。作為加成反應型矽氧樹脂類剝離劑而在市面販售的產品,例如可列舉出KS-776A、KS-847T、KS-779H、KS-837、KS-778、KS-830(信越化學工業(股)製)、SRX-211、SRX-345、SRX-357、SD7333、SD7220、SD7223、LTC-300B、LTC-350G、LTC-310(Dow Corning Toray(股)製)等。作為縮合反應型而在市面販售的產品,例如可列舉出SRX-290、SYLOFF-23(Dow Corning Toray(股)製)等。作為陽離子聚合型而在市面販售的產品,例如可列舉出TPR-6501、TPR-6500、UV9300、VU9315、UV9430(Momentive Performance Materials公司製)、X62-7622(信越化學工業(股)製)等。作為自由基聚合型而在市面販售的產品,例如可列舉出X62-7205(信越化學工業(股)製)等。 The silicone resin-based release agent constituting the release agent layer 4 is a release agent mainly composed of polydimethylsiloxane, and examples thereof include addition reaction type, condensation reaction type, cation polymerization type, and radical polymerization. Type (radical polymerization type) and other known silicone-based release agents. Examples of products that are commercially available as addition reaction type silicone resin strippers include KS-776A, KS-847T, KS-779H, KS-837, KS-778, and KS-830 (Shin-Etsu Chemical Industry Co., Ltd. (Stock) system), SRX-211, SRX-345, SRX-357, SD7333, SD7220, SD7223, LTC-300B, LTC-350G, LTC-310 (Dow Corning Toray (shares) system) and so on. Examples of products that are commercially available as condensation reaction types include SRX-290 and SYLOFF-23 (manufactured by Dow Corning Toray). Examples of products sold on the market as a cationic polymerization type include TPR-66501, TPR-6500, UV9300, VU9315, UV9430 (manufactured by Momentive Performance Materials), X62-7622 (manufactured by Shin-Etsu Chemical Industry (Stock)) . As a product which is marketed as a radical polymerization type, X62-7205 (made by Shin-Etsu Chemical Industry Co., Ltd.) etc. are mentioned, for example.
作為構成剝離劑層4的防靜電劑,優選對於以二甲基聚矽氧烷作為主成分的剝離劑溶液的分散性良好,且不阻礙以二甲基聚矽氧烷作為主成分的剝離劑固化。此外,為了從剝離劑層4轉移到黏結劑層2的表面並賦予黏結劑層防靜電效果,優選不與以二甲基聚矽氧烷為主成分的剝離劑反應的防靜電劑。作為這樣的防靜電劑,鹼金屬鹽較為合適。 As the antistatic agent constituting the release agent layer 4, it is preferable that the dispersant has a dimethylpolysiloxane as a main component, has good dispersibility, and does not hinder a release agent containing a dimethylpolysiloxane as a main component. Curing. Further, in order to transfer from the release agent layer 4 to the surface of the adhesive layer 2 and impart an antistatic effect to the adhesive layer, an antistatic agent that does not react with a release agent containing dimethylpolysiloxane as a main component is preferred. As such an antistatic agent, an alkali metal salt is suitable.
作為鹼金屬鹽,可列舉出由鋰、鈉、鉀形成的金屬鹽。具體而言,例如,可適宜地使用選自Li+、Na+、K+的陽離子與選自Cl-、Br-、I-、BF4-、PF6-、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-的陰離子所構成的金屬鹽。其中,特別優選使用LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C等鋰鹽。這些鹼金屬鹽可以單獨使用,或者可以2種以上混合使用。為了離子物質的穩定化,可以添加含有聚氧化烯基結構的化合物。 Examples of the alkali metal salt include metal salts formed of lithium, sodium, and potassium. Specifically, for example, may be suitably selected from Li +, Na +, K + is a cation selected from Cl -, Br -, I - , BF4 -, PF6 -, SCN -, ClO 4 -, CF 3 SO 3 -, (CF 3 SO 2 ) 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) 3 C - anions consisting of a metal salt. Among them, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C and other lithium salts. These alkali metal salts may be used singly or in combination of two or more kinds. In order to stabilize the ionic substance, a compound containing a polyoxyalkylene structure may be added.
對於以二甲基聚矽氧烷作為主成分的剝離劑的防靜電劑的添加量,因防靜電劑的種類或與剝離劑的親和性程度而異, 只要考慮將表面保護膜從被黏附體上剝離時所期望的剝離靜電壓、對被黏附體的污染性、黏結特性等而設定即可。 The addition amount of the antistatic agent of the release agent containing dimethyl polysiloxane as a main component varies depending on the type of the antistatic agent or the degree of affinity with the release agent. It may be set in consideration of a desired peeling static voltage when peeling the surface protective film from the adherend, contamination to the adherend, adhesion characteristics, and the like.
剝離劑層4可為由以二甲基聚矽氧烷為主成分的剝離劑與和該剝離劑不反應的防靜電劑的混合物構成的剝離劑層4。以二甲基聚矽氧烷為主成分的剝離劑與防靜電劑的混合方法沒有特別的限定。以下任一方法均可:向以二甲基聚矽氧烷為主成分的剝離劑中添加防靜電劑,在混合後添加、混合剝離劑固化用催化劑的方法;以二甲基聚矽氧烷為主成分的剝離劑預先用有機溶劑稀釋之後,添加、混合防靜電劑及剝離劑固化用催化劑的方法;將以二甲基聚矽氧烷作為主成分的剝離劑預先在有機溶劑中稀釋後,添加、混合催化劑,然後添加、混合防靜電劑的方法等。此外,也可以根據需要,添加矽烷偶聯劑等貼附促進劑、含聚氧化烯基的化合物等輔助防靜電效果的材料。 The release agent layer 4 may be a release agent layer 4 composed of a mixture of a release agent containing dimethylpolysiloxane as a main component and an antistatic agent which does not react with the release agent. The mixing method of the peeling agent which has dimethyl polysiloxane as a main component and an antistatic agent is not specifically limited. Either of the following methods: a method of adding an antistatic agent to a release agent containing dimethylpolysiloxane as a main component, and adding and mixing the catalyst for curing the release agent after mixing; using dimethylpolysiloxane A method in which a stripping agent having a main component is diluted with an organic solvent in advance, and an antistatic agent and a curing agent for curing the stripping agent are added and mixed. , The method of adding and mixing catalyst, and then adding and mixing antistatic agent. In addition, if necessary, materials such as an adhesion promoter such as a silane coupling agent, or a polyoxyalkylene group-containing compound may be added to assist the antistatic effect.
以二甲基聚矽氧烷作為主成分的剝離劑與防靜電劑的混合比率沒有特別的限定,相對於100重量份的以二甲基聚矽氧烷作為主成分的剝離劑的固體成分,以固體成分計防靜電劑優選為5~100重量份左右的比例。相對於100重量份的以二甲基聚矽氧烷作為主成分的剝離劑的固體成分,若防靜電劑的固體成分換算的添加量小於5重量份的比例,防靜電劑向黏結劑層表面的轉印量變少,難以在黏結劑中發揮防靜電的功能。此外,相對於100重量份的以二甲基聚矽氧烷作為主成分的剝離劑的固體成分,若防靜電劑的固體成分換算的添加量超過100重量份的比例,則防靜電劑與以二甲基聚矽氧烷作為主 成分的剝離劑被同時轉印到黏結劑層的表面,因此存在黏結劑的黏結特性降低的可能性。 The mixing ratio of the release agent containing dimethyl polysiloxane as the main component and the antistatic agent is not particularly limited. With respect to 100 parts by weight of the solid content of the release agent containing dimethyl polysiloxane as the main component, The proportion of the antistatic agent in terms of solid content is preferably about 5 to 100 parts by weight. The antistatic agent is added to the surface of the adhesive layer when the solid content of the antistatic agent is less than 5 parts by weight relative to 100 parts by weight of the solid content of the release agent containing dimethylpolysiloxane as a main component. The transfer amount becomes smaller, making it difficult to exert an antistatic function in the adhesive. In addition, with respect to 100 parts by weight of the solid content of the release agent containing dimethylpolysiloxane as a main component, if the solid content of the antistatic agent is added in an amount exceeding 100 parts by weight, the antistatic agent and the Dimethyl polysiloxane as main The component release agent is simultaneously transferred to the surface of the adhesive layer, so there is a possibility that the adhesive properties of the adhesive are reduced.
在本發明的表面保護膜10的基材膜1上形成含有防靜電劑的黏結劑層2的方法、及貼合剝離膜5的方法,可透過已知的方法進行,沒有特別的限定。具體而言,可列舉出下列方法:(1)在基材膜1的一個面上,塗佈、乾燥用於形成含有防靜電劑的黏結劑層2的樹脂組合物,形成黏結劑層後,貼合剝離膜5的方法;(2)在剝離膜5的表面,塗佈、乾燥用於形成含有防靜電劑的黏結劑層2的樹脂組合物,形成黏結劑層後,貼合基材膜1的方法等;使用上述任一方法均可。 The method of forming the adhesive layer 2 containing an antistatic agent on the base film 1 of the surface protection film 10 of the present invention, and the method of bonding the release film 5 can be performed by known methods, and are not particularly limited. Specifically, the following methods can be enumerated: (1) coating and drying a resin composition for forming an adhesive layer 2 containing an antistatic agent on one surface of the base film 1 to form an adhesive layer; A method for bonding a release film 5; (2) coating and drying a resin composition for forming an adhesive layer 2 containing an antistatic agent on the surface of the release film 5 to form a bonding agent layer, and then bonding a base film 1 method, etc .; any one of the above methods can be used.
此外,在基材膜1的表面形成含有防靜電劑的黏結劑層2可透過已知的方法進行。具體而言,可使用反向塗佈法、逗號塗佈法(Comma Coating)、凹版塗佈法(gravure coating)、狹縫式塗佈法(slot die coating)、線棒塗佈法(Meyer bar coating)、氣刀塗佈法等已知的塗佈方法。 The formation of the adhesive layer 2 containing an antistatic agent on the surface of the base film 1 can be performed by a known method. Specifically, a reverse coating method, a comma coating method, a gravure coating method, a slot die coating method, and a wire bar coating method (Meyer bar) can be used. coating), air knife coating, and other known coating methods.
此外,在樹脂膜3上形成剝離劑層4同樣可透過已知的方法進行。具體而言,可使用凹版塗佈法、線棒塗佈法、氣刀塗佈法等已知的塗佈方法。 In addition, the formation of the release agent layer 4 on the resin film 3 can also be performed by a known method. Specifically, known coating methods such as a gravure coating method, a bar coating method, and an air knife coating method can be used.
具有上述構成的本發明的表面保護膜10從作為被黏附體的光學用膜上剝離時的表面電勢優選為+0.7kV~-0.7kV。更進一步,表面電勢更優選為+0.5kV~-0.5kV,特別優選為+0.1kV~-0.1kV。該表面電勢可透過對黏結劑層2中含有的防靜電劑及剝離劑層4中含有的防靜電劑7的種類、添加量等進行增減來調整。對將表面保護膜10從作為被黏附體的光 學用膜剝離後的、作為被黏附體的光學用膜的表面污染性進行考慮,來調整黏結劑層2的防靜電劑及剝離劑層4的防靜電劑7的種類、添加量即可。 The surface potential of the surface protective film 10 of the present invention having the above-mentioned structure when peeled from the optical film as an adherend is preferably +0.7 kV to -0.7 kV. Furthermore, the surface potential is more preferably +0.5 kV to -0.5 kV, and particularly preferably +0.1 kV to -0.1 kV. This surface potential can be adjusted by increasing or decreasing the type, addition amount, and the like of the antistatic agent 7 contained in the adhesive layer 2 and the antistatic agent 7 contained in the release agent layer 4. To the surface protection film 10 from light as an adherend After considering the surface contamination of the optical film as an adherend after the academic film is peeled off, the type and amount of the antistatic agent 7 of the adhesive layer 2 and the antistatic agent 7 of the release agent layer 4 may be adjusted.
第2圖為表示將剝離膜從本發明的表面保護膜上剝下的狀態的剖面圖。 Fig. 2 is a cross-sectional view showing a state where the release film is peeled from the surface protective film of the present invention.
透過將剝離膜5從第1圖所示的表面保護膜10上剝下,剝離膜5的剝離劑層4中含有的防靜電劑(符號7)的一部分轉印到(附著於)表面保護膜10的黏結劑層2的表面。因此,在第2圖中,示意性地以符號7的斑點(圓形)表示在表面保護膜的黏結劑層2的表面附著的防靜電劑。防靜電劑7的成分從剝離膜5被轉印至黏結劑層2的表面,由此,與轉印前的黏結劑層2相比,從被黏附體上剝離黏結劑層2時的剝離靜電壓降低。此外,從被黏附體上剝離黏結劑層時的剝離靜電壓可透過已知的方法測定。例如,在將表面保護膜貼合至偏光板等被黏附體後,使用高速剝離試驗機(Tester產業製),以每分鐘40m的剝離速度將表面保護膜剝離,同時使用表面電勢計(Keyence(股)製)每10ms測定一次被黏附體表面的表面電勢,將此時的表面電勢的絕對值的最大值設為剝離靜電壓(kV)。 By peeling the release film 5 from the surface protection film 10 shown in FIG. 1, a part of the antistatic agent (symbol 7) contained in the release agent layer 4 of the release film 5 is transferred to (attached to) the surface protection film. 10 of the surface of the adhesive layer 2. Therefore, in FIG. 2, the antistatic agent adhered to the surface of the adhesive layer 2 of the surface protective film is indicated schematically by a spot (circle) of symbol 7. The components of the antistatic agent 7 are transferred from the release film 5 to the surface of the adhesive layer 2. Therefore, compared with the adhesive layer 2 before the transfer, the peeling time when the adhesive layer 2 is peeled from the adherend is smaller. The voltage drops. The peeling static voltage when the adhesive layer is peeled from the adherend can be measured by a known method. For example, after the surface protective film is attached to an adherend such as a polarizing plate, the surface protective film is peeled at a peeling speed of 40 m per minute using a high-speed peel tester (manufactured by Tester Industries), and a surface potential meter (Keyence ( Co., Ltd.) The surface potential of the surface of the adherend was measured every 10 ms, and the maximum value of the absolute value of the surface potential at this time was taken as the peeling static voltage (kV).
在本發明的表面保護膜中,將第2圖所示的剝下了剝離膜的狀態的表面保護膜11貼合於被黏附體時,轉印至該黏結劑層2的表面的防靜電劑與被黏附體的表面接觸。由此,能夠再次將從被黏附體上剝下表面保護膜時的剝離靜電壓抑制為較低。 In the surface protective film of the present invention, when the surface protective film 11 in a state where the release film is peeled off as shown in FIG. 2 is bonded to an adherend, the antistatic agent transferred to the surface of the adhesive layer 2 Make contact with the surface of the adherend. Accordingly, the peeling static voltage when the surface protective film is peeled from the adherend can be suppressed to be low again.
第3圖為表示將本發明的表面保護膜貼合於光學元件的實施例的剖面圖。 FIG. 3 is a cross-sectional view showing an example in which the surface protective film of the present invention is bonded to an optical element.
本發明的表面保護膜10以剝下了剝離膜5、露出黏結劑層2的狀態(第2圖的表面保護膜11),經由該黏結劑層2貼合於作為被黏附體的光學元件8上。 The surface protective film 10 of the present invention is in a state in which the release film 5 is peeled off and the adhesive layer 2 is exposed (surface protective film 11 in FIG. 2), and the optical element 8 as an adherend is bonded via the adhesive layer 2. on.
即,第3圖表示貼合有表面保護膜11的光學元件20,該表面保護膜11為從本發明的表面保護膜10上剝下了剝離膜5的狀態。作為光學元件,可列舉出偏光板、相位差板、透鏡膜、兼用為相位差板的偏振片、兼用為透鏡膜的偏振片等光學用膜。這樣的光學元件可作為液晶顯示面板等液晶顯示裝置、各種計量儀器類的光學類裝置等的構成元件使用。此外,作為光學元件,還可列舉出防反射膜、硬塗膜、觸控面板用透明導電性膜等光學用膜。 That is, FIG. 3 shows the optical element 20 to which the surface protective film 11 is bonded, and the surface protective film 11 is in a state where the release film 5 is peeled from the surface protective film 10 of the present invention. Examples of the optical element include optical films such as a polarizing plate, a retardation plate, a lens film, a polarizing plate also serving as a retardation plate, and a polarizing plate also serving as a lens film. Such an optical element can be used as a structural element such as a liquid crystal display device such as a liquid crystal display panel, and various optical devices such as measuring instruments. Examples of the optical element include optical films such as antireflection films, hard coat films, and transparent conductive films for touch panels.
將從本發明的防靜電表面保護膜10剝下剝離膜5的狀態的表面保護膜11從作為被黏附體的光學元件(光學用膜)上剝離去除時,能夠充分地將剝離靜電壓抑制為較低。因此,沒有破壞驅動IC、TFT元件、柵線驅動電路等電路元件的可能性,能夠提高在製造液晶顯示面板的步驟中的生產效率,確保生產步驟的可靠性。 When the surface protection film 11 in a state where the release film 5 is peeled from the antistatic surface protection film 10 of the present invention is peeled off from the optical element (optical film) as an adherend, the peeling static voltage can be sufficiently suppressed to Lower. Therefore, there is no possibility of destroying circuit elements such as a driving IC, a TFT element, and a gate line driving circuit, and it is possible to improve the production efficiency in the step of manufacturing the liquid crystal display panel and ensure the reliability of the production step.
實施例 Examples
接著,透過實施例對本發明進一步說明。 Next, the present invention will be further described through examples.
(實施例1) (Example 1)
(表面保護膜的製作) (Production of surface protective film)
將5重量份加成反應型的矽氧樹脂(Dow Corning Toray (股)製、商品名:SRX-345)、0.75重量份雙氟磺醯亞胺鋰(Lithium bis(fluorosulfonyl)imide)、95重量份甲苯與醋酸乙酯的1:1的混合溶劑、0.05重量份鉑催化劑(Dow Corning Toray(股)製、商品名:SRX-212)摻混,攪拌混合,配製形成實施例1的剝離劑層的塗料。以乾燥後的厚度為0.2μm的方式,用線棒將形成實施例1的剝離劑層的塗料塗佈在厚度為38μm的聚對苯二甲酸乙二醇酯膜的表面上,使用120℃的熱風循環式烘箱進行1分鐘乾燥,得到實施例1的剝離膜。 5 parts by weight of addition reaction type silicone resin (Dow Corning Toray (Stock), trade name: SRX-345), 0.75 parts by weight of lithium bis (fluorosulfonyl) imide, 95 parts by weight of a 1: 1 mixed solvent of toluene and ethyl acetate, 0.05 weight A part of a platinum catalyst (produced by Dow Corning Toray Co., Ltd., trade name: SRX-212) was blended, stirred and mixed to prepare a coating material for forming the release agent layer of Example 1. The coating material forming the release agent layer of Example 1 was coated on a surface of a polyethylene terephthalate film having a thickness of 38 μm with a wire rod so that the thickness after drying was 0.2 μm. The hot air circulation type oven was dried for 1 minute, and the peeling film of Example 1 was obtained.
另一方面,由80重量份2-乙基己基丙烯酸酯、17重量份甲氧基聚乙二醇(400)甲基丙烯酸酯、3重量份2-羥基乙基丙烯酸酯的共聚物構成黏結劑,相對於100重量份該黏接劑的40%醋酸乙酯溶液,攪拌混合0.2重量份1-壬基吡啶鎓六氟化磷酸鹽(1-nonyl pyridinium hexafluoride phosphate)、2重量份異氰酸酯類固化劑(東曹公司製CORONATE(註冊商標)HX),製備實施例1的黏結劑。 On the other hand, a binder is composed of a copolymer of 80 parts by weight of 2-ethylhexyl acrylate, 17 parts by weight of methoxypolyethylene glycol (400) methacrylate, and 3 parts by weight of 2-hydroxyethyl acrylate. Based on 100 parts by weight of a 40% ethyl acetate solution of the adhesive, stir and mix 0.2 parts by weight of 1-nonyl pyridinium hexafluoride phosphate and 2 parts by weight of an isocyanate curing agent (CORONATE (registered trademark) HX manufactured by Tosoh Corporation), and the adhesive of Example 1 was prepared.
在厚度為38μm的聚對苯二甲酸乙二醇酯膜的表面上,以使乾燥後的厚度為20μm的方式塗佈製備好的黏結劑後,使用100℃的熱風循環式烘箱乾燥2分鐘,形成黏結劑層。然後,在該黏結劑層的表面,貼合上述製作的實施例1的剝離膜的剝離劑層(矽氧樹脂處理面)。將所得的黏結膜在40℃的環境下保溫5天,使黏結劑固化,得到實施例1的表面保護膜。 The prepared adhesive was coated on the surface of a polyethylene terephthalate film having a thickness of 38 μm so that the thickness after drying was 20 μm, and then dried in a hot air circulation oven at 100 ° C. for 2 minutes. Form an adhesive layer. Then, on the surface of this adhesive layer, the release agent layer (silicone resin treated surface) of the release film of Example 1 produced as described above was bonded. The obtained adhesive film was held in an environment at 40 ° C. for 5 days to cure the adhesive to obtain a surface protection film of Example 1.
(實施例2) (Example 2)
除了將形成實施例1的剝離劑層的塗料之乾燥後厚度設為0.1μm以外,以與實施例1相同的方式,得到實施例2的表面 保護膜。 The surface of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the coating material forming the release agent layer in Example 1 was 0.1 μm after drying. Protective film.
(實施例3) (Example 3)
除了將實施例1的加成反應型的矽氧樹脂設為Dow Corning Toray(股)製、商品名:SRX-211,用雙三氟甲烷磺醯亞胺鋰代替雙氟磺醯亞胺鋰以外,以與實施例1相同的方式,得到實施例3的表面保護膜。 Except that the addition reaction type silicone resin of Example 1 was made by Dow Corning Toray Co., Ltd., trade name: SRX-211, and lithium bistrifluoromethanesulfonimide was used instead of lithium bissulfonimide. In the same manner as in Example 1, a surface protection film of Example 3 was obtained.
(比較例1) (Comparative example 1)
將5重量份加成反應型的矽氧樹脂(Dow Corning Toray(股)製、商品名:SRX-345)、95重量份甲苯與醋酸乙酯的1:1的混合溶劑、0.05重量份鉑催化劑(Dow Corning Toray(股)製、商品名:SRX-212)摻混,攪拌混合,配製形成比較例1的剝離劑層的塗料。以乾燥後的厚度為0.2μm的方式,用線棒將形成比較例1的剝離劑層的塗料塗佈在厚度為38μm的聚對苯二甲酸乙二醇酯膜的表面,使用120℃的熱風迴圈式烘箱乾燥1分鐘,得到比較例1的剝離膜。 5 parts by weight of an addition reaction type silicone resin (manufactured by Dow Corning Toray Co., Ltd., trade name: SRX-345), 95 parts by weight of a 1: 1 mixed solvent of toluene and ethyl acetate, and 0.05 parts by weight of a platinum catalyst (Dow Corning Toray Co., Ltd., trade name: SRX-212) was blended, stirred and mixed to prepare a coating material for forming the release agent layer of Comparative Example 1. The coating material forming the release agent layer of Comparative Example 1 was coated on the surface of a polyethylene terephthalate film having a thickness of 38 μm with a wire rod so that the thickness after drying was 0.2 μm, and hot air at 120 ° C. was used. Dry in a loop oven for 1 minute to obtain a release film of Comparative Example 1.
另一方面,以乾燥後的厚度為20μm的方式,將實施例1的黏結劑塗佈在厚度為38μm的聚對苯二甲酸乙二醇酯膜的表面,然後使用100℃的熱風迴圈式烘箱乾燥2分鐘,形成黏結劑層。然後,在該黏結劑層的表面貼合上述製作的比較例1的剝離膜的剝離劑層(矽氧樹脂處理面)。將得到的黏結膜在40℃的環境下保溫5天,使黏結劑固化,得到比較例1的表面保護膜。 On the other hand, the adhesive of Example 1 was coated on the surface of a polyethylene terephthalate film having a thickness of 38 μm so that the thickness after drying was 20 μm, and then a 100 ° C. hot air loop type was used. Dry in an oven for 2 minutes to form an adhesive layer. Then, the release agent layer (silicone resin-treated surface) of the release film of Comparative Example 1 produced as described above was bonded to the surface of the adhesive layer. The obtained adhesive film was held in an environment at 40 ° C. for 5 days to cure the adhesive to obtain a surface protection film of Comparative Example 1.
(比較例2) (Comparative example 2)
除了不在黏結劑中添加1-壬基吡啶鎓六氟化磷酸鹽以 外,以與實施例1相同的方式,得到比較例2的表面保護膜。 In addition to not adding 1-nonylpyridinium hexafluoride phosphate to the binder, In addition, in the same manner as in Example 1, a surface protection film of Comparative Example 2 was obtained.
(比較例3) (Comparative example 3)
除了用雙氟磺醯亞胺鋰代替實施例1的1-壬基吡啶鎓六氟化磷酸鹽以外,以與實施例1相同的方式,得到比較例3的表面保護膜。 A surface protection film of Comparative Example 3 was obtained in the same manner as in Example 1 except that lithium bisfluorosulfimide was used instead of the 1-nonylpyridinium hexafluorophosphate of Example 1.
以下,顯示出評價試驗的方法及結果。 The methods and results of the evaluation tests are shown below.
〈剝離膜的剝離力的測定方法〉 <Method for measuring peeling force of release film>
將表面保護膜的樣本剪裁成寬度50mm、長度150mm。在23℃×50%RH的試驗環境下,用拉伸試驗機以300mm/分鐘的剝離速度在180°的方向上,測定將剝離膜剝離時的強度,將其作為剝離膜的剝離力(N/50mm)。 A sample of the surface protective film was cut into a width of 50 mm and a length of 150 mm. In a test environment of 23 ° C. × 50% RH, a tensile tester was used at a peeling speed of 300 mm / min in a direction of 180 ° to measure the strength when peeling the peeling film, and this was taken as the peeling force of the peeling film (N / 50mm).
(防靜電劑層的表面電阻率) (Surface resistivity of antistatic agent layer)
將剝離膜從防靜電表面保護膜的樣本上剝離後,使用高性能高電阻率計(三菱化學Analytech公司製Hiresta(註冊商標)-UP),在施加電壓100V、測定時間30秒的條件下測定防靜電劑層的表面電阻率(Ω/□)。 After the release film was peeled from the sample of the antistatic surface protection film, it was measured using a high-performance high-resistance meter (Hiresta (registered trademark) -UP manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under a voltage of 100 V and a measurement time of 30 seconds. Surface resistivity of the antistatic agent layer (Ω / □).
〈表面保護膜的黏結力的測定方法〉 <Method for measuring adhesive force of surface protective film>
將在偏光鏡(含碘的聚乙烯醇膜)上使用紫外線固化型黏合劑貼合有丙烯酸膜的、經過防眩低反射處理的偏光板(AG-LR偏光板)作為被黏附體。在玻璃板的表面用貼合機貼合該偏光板。然後,在偏光板的表面的丙烯酸膜上,貼合剪裁成寬度25mm的表面保護膜後,在23℃×50%RH的試驗環境下保存1天。然後,使用拉伸試驗機,以300mm/分鐘的剝離速度在180°的方向上,測定剝離表面保護膜時的強度,將其作為 黏結力(N/25mm)。 An anti-glare and low-reflection polarizer (AG-LR polarizer) with an acrylic film bonded to a polarizer (an iodine-containing polyvinyl alcohol film) using a UV-curable adhesive was used as an adherend. This polarizing plate was bonded to the surface of the glass plate with a bonding machine. Then, a surface protective film having a width of 25 mm was bonded to the acrylic film on the surface of the polarizing plate, and then stored in a test environment at 23 ° C. × 50% RH for 1 day. Then, using a tensile tester, the strength at the time of peeling the surface protective film was measured at a peeling speed of 300 mm / min in a direction of 180 °, and this was defined as Adhesion (N / 25mm).
〈表面保護膜的剝離靜電壓的測定方法〉 <Method for measuring peeling static voltage of surface protective film>
將在偏光鏡(含碘的聚乙烯醇膜)上使用紫外線固化型黏合劑貼合有丙烯酸膜的、經過防眩低反射處理的偏光板(AG-LR偏光板)作為被黏附體。在玻璃板的表面用貼合機貼合該偏光板。之後,在偏光板的表面的丙烯酸膜上,貼合剪裁成寬度25mm的表面保護膜後,在23℃×50%RH的試驗環境下保存1天。然後,使用高速剝離試驗機(Tester產業製)以每分鐘40m的剝離速度剝離表面保護膜,同時使用表面電勢計(Keyence(股)製)每10ms測定一次所述偏光板表面的表面電勢,將此時的表面電勢的絕對值的最大值作為剝離靜電壓(kV)。 An anti-glare and low-reflection polarizer (AG-LR polarizer) with an acrylic film bonded to a polarizer (an iodine-containing polyvinyl alcohol film) using a UV-curable adhesive was used as an adherend. This polarizing plate was bonded to the surface of the glass plate with a bonding machine. Then, a 25 mm-wide surface protective film was bonded to the acrylic film on the surface of the polarizing plate, and stored in a test environment at 23 ° C. × 50% RH for 1 day. Then, the surface protective film was peeled at a peeling speed of 40 m per minute using a high-speed peel tester (manufactured by Tester Industries), and the surface potential of the surface of the polarizing plate was measured every 10 ms using a surface potential meter (manufactured by Keyence). The maximum value of the absolute value of the surface potential at this time was taken as the peeling static voltage (kV).
〈表面保護膜的表面污染性的確認方法〉 <A method for confirming the surface contamination of a surface protective film>
將在偏光鏡(含碘的聚乙烯醇膜)上使用紫外線固化型黏合劑貼合有丙烯酸膜的、經過防眩光低反射處理的偏光板(AG-LR偏光板)作為被黏附體。在玻璃板的表面用貼合機貼合該偏光板。然後,在偏光板的表面的丙烯酸膜上貼合剪裁成寬度25mm的表面保護膜後,在23℃×50%RH的試驗環境下保存3天及30天。然後,剝下表面保護膜,以目視觀察偏光板的表面有無污染,確認表面污染性。作為表面污染性的判定標準,以偏光板上無污染轉移的情況為(○),在偏光板上確認到污染轉移的情況為(×)。 An anti-glare low-reflection polarizing plate (AG-LR polarizing plate) with an acrylic film bonded to a polarizer (polyvinyl alcohol film containing iodine) using a UV-curable adhesive was used as an adherend. This polarizing plate was bonded to the surface of a glass plate with a bonding machine. Then, an acrylic film on the surface of the polarizing plate was bonded and cut into a surface protective film having a width of 25 mm, and then stored in a test environment at 23 ° C. × 50% RH for 3 days and 30 days. Then, the surface protective film was peeled off, and the surface of the polarizing plate was visually observed for contamination to confirm the surface contamination. As a criterion for determining the surface contamination property, a case where no pollution transfer occurred on the polarizing plate was (○), and a case where pollution transfer was confirmed on the polarizing plate was (×).
對所得到的實施例1~3及比較例1~3的表面保護膜進行測定的測定結果如表1所示。“2EHA”表示2-乙基己基 丙烯酸酯,“HEA”表示2-羥基乙基丙烯酸酯,“# 400G”表示甲氧基聚乙二醇(400)甲基丙烯酸酯,“AS劑(1)”表示雙氟磺醯亞胺鋰,“AS劑(2)”表示雙三氟甲烷磺醯亞胺鋰,“AS劑(3)”表示1-壬基吡啶鎓六氟化磷酸鹽,“SRX-345”表示SRX-345,“SRX-211”表示SRX-211,“SRX212”表示鉑催化劑SRX-212。此外,表面電阻率的“1.5E10”表示1.5×1010。 The measurement results of the obtained surface protective films of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1. "2EHA" means 2-ethylhexyl acrylate, "HEA" means 2-hydroxyethyl acrylate, "# 400G" means methoxypolyethylene glycol (400) methacrylate, and "AS agent (1) "Means lithium bisfluorosulfimide," AS agent (2) "means lithium bistrifluoromethanesulfonylimide," AS agent (3) "means 1-nonylpyridinium hexafluorophosphate," SRX "-345" means SRX-345, "SRX-211" means SRX-211, and "SRX212" means platinum catalyst SRX-212. In addition, "1.5E10" of the surface resistivity means 1.5 × 10 10 .
由表1所示的測定結果可知以下內容:本發明的實施例1~3的表面保護膜具有適度的黏結力,對被黏附體的表面無污染。此外,即使被黏附體為使用了丙烯酸膜的偏光板,將表面保護膜從被黏附體上剝離時的剝離靜電壓也低。 From the measurement results shown in Table 1, it can be known that the surface protective films of Examples 1 to 3 of the present invention have a moderate adhesive force and have no pollution to the surface of the adherend. In addition, even if the adherend is a polarizing plate using an acrylic film, the peeling static voltage when peeling the surface protective film from the adherend is low.
另一方面,對於在剝離劑層中未添加防靜電劑的比較例1 的表面保護膜、及在黏結劑層中未添加防靜電劑的比較例2的表面保護膜,將表面保護膜從被黏附體上剝離時的剝離靜電壓變高。此外,對於在黏結劑層與剝離劑層中使用了相同種類防靜電劑的比較例3的表面保護膜,將表面保護膜從被黏附體上剝離時的剝離靜電壓低,是良好的,但在剝離後,對被黏附體的污染增多。 On the other hand, Comparative Example 1 in which no antistatic agent was added to the release agent layer The surface protection film of Comparative Example 2 and the surface protection film of Comparative Example 2 in which no antistatic agent was added to the adhesive layer had a high peeling static voltage when the surface protection film was peeled from the adherend. In addition, for the surface protection film of Comparative Example 3 using the same type of antistatic agent in the adhesive layer and the release agent layer, the peeling static voltage when the surface protection film was peeled from the adherend was low, which was good, but After peeling, contamination of the adherend increases.
即,比較例1~3的表面保護膜難以兼顧剝離靜電壓的降低及對被黏附體的低污染性。另一方面,對於在黏結劑層與剝離劑層中添加了不同種類防靜電劑的實施例1~3的表面保護膜,剝離靜電壓的降低效果高,且沒有對被黏附體的污染,能獲得良好的表面保護膜。 That is, it is difficult for the surface protective films of Comparative Examples 1 to 3 to achieve both a reduction in peeling static voltage and a low contamination property to an adherend. On the other hand, for the surface protection films of Examples 1 to 3 in which different types of antistatic agents were added to the adhesive layer and the release agent layer, the effect of reducing the peeling static voltage was high, and there was no contamination of the adherend. Obtain a good surface protective film.
工業實用性 Industrial applicability
本發明的表面保護膜能夠用於在例如偏光板、相位差板、透鏡膜、防反射膜、硬塗膜、透明導電性膜等光學用膜、其他各種光學元件等生產步驟等中,貼合於該光學元件等而保護其表面。此外,本發明的表面保護膜從被黏附體上剝離時產生的靜電量低,且剝離防靜電性能的經時變化及對被黏附體的污染少,能夠提高生產步驟的成品率,在工業上的利用價值大。 The surface protective film of the present invention can be used in the production steps of optical films such as polarizing plates, retardation plates, lens films, anti-reflection films, hard coating films, and transparent conductive films, and various other optical elements. The surface of the optical element is protected. In addition, the surface protection film of the present invention has a low amount of static electricity when it is peeled from the adherend, and the time-dependent change of the peeling antistatic performance and less pollution to the adherend can improve the yield of the production step. The use value is great.
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