TW202111046A - Method for producing antistatic surface- protective film, and antistatic surface- protective film - Google Patents

Method for producing antistatic surface- protective film, and antistatic surface- protective film Download PDF

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TW202111046A
TW202111046A TW109119165A TW109119165A TW202111046A TW 202111046 A TW202111046 A TW 202111046A TW 109119165 A TW109119165 A TW 109119165A TW 109119165 A TW109119165 A TW 109119165A TW 202111046 A TW202111046 A TW 202111046A
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antistatic
weight
meth
parts
protective film
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TW109119165A
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Chinese (zh)
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長倉毅
塚田高士
鈴木史恵
大津賀健太郎
吉田弘幸
廣神萌美
宍戸啓太
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日商藤森工業股份有限公司
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Abstract

The present disclosure provides an antistatic surface-protective film which has a balanced adhesive force under a low-speed peeling and a high-speed peeling, and also may achieve both antistatic properties and anti-pollution properties. As a solution, a peeling film (5) laminated with a peeling agent layer (4) containing an antistatic agent is adhered to a surface of a adhersive agent layer (2) formed by crosslinking an adhersive agent composition through the peeling agent layer (4); the antistatic agent in the peeling agent layer (4) is transferred to the surface of the adhersive agent layer (2). The adhersive agent composition includes (A) acrylic polymer, (C) isocyanate compounds with more than trifunctionality, (D) cross-linking retarder, and (E) cross-linking accelerator other than tin compounds. The (A) acrylic polymer contains 2-ethylhexyl acrylate in a proportion of 50 parts by weight or more and at least one type of the monofunctional methacrylate monomers with a homopolymer having Tg being 0°C or more in a proportion of 5-40 parts by weight or more with respect to 100 parts by weight of at least two types of alkyl (meth)acrylates with C1-C10 carbon atoms in the alkyl group.

Description

抗靜電表面保護膜的製造方法、抗靜電表面保護膜Method for manufacturing antistatic surface protective film, and antistatic surface protective film

本發明涉及能夠適宜地使用於偏振片用表面保護膜等的表面保護膜的抗靜電表面保護膜的製造方法、抗靜電表面保護膜。進一步詳細而言，涉及提供在低速的剝離速度及高速的剝離速度下具有得到了平衡的黏著力，且可謀求兼顧抗靜電性能與抗污染性能的抗靜電表面保護膜的製造方法、抗靜電表面保護膜。The present invention relates to a method for producing an antistatic surface protective film and an antistatic surface protective film that can be suitably used for surface protective films such as surface protective films for polarizing plates. In more detail, it relates to a method for manufacturing an antistatic surface protective film that has a balanced adhesive force at a low peeling speed and a high peeling speed, and can achieve both antistatic performance and anti-fouling performance, and an antistatic surface Protective film.

一直以來，在作為構成液晶顯示器的構件的偏振片等光學構件的製造步驟中，為了暫時保護光學構件的表面而貼合表面保護膜。這種表面保護膜僅在製造光學構件的步驟中使用，將光學構件安裝於液晶顯示器時，將其從光學構件上剝離而去除。由於這種用於保護光學構件的表面之表面保護膜僅在光學構件的製造步驟中使用，因此通常也被稱作步驟膜。Conventionally, in the manufacturing process of the optical member, such as a polarizing plate which is a member which comprises a liquid crystal display, in order to temporarily protect the surface of an optical member, a surface protection film was bonded. Such a surface protection film is used only in the process of manufacturing an optical member, and when the optical member is mounted on a liquid crystal display, it is peeled and removed from the optical member. Since such a surface protection film for protecting the surface of an optical member is only used in the manufacturing step of the optical member, it is usually also called a step film.

在製造這種光學構件的步驟中使用的表面保護膜，在具有光學透明性的聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)樹脂膜的單面上形成黏著劑層。此外，為了在貼合於光學構件之前保護表面保護膜的黏著劑層，在表面保護膜的黏著劑層的表面上貼合有經脫模處理的脫模膜。 並且，偏振片等的光學構件以貼合有表面保護膜的狀態，接受伴隨液晶顯示板的顯示能力、色調、對比度、雜質混入等的光學評價的產品檢驗。因此，作為對表面保護膜的性能要求，要求黏著劑層中未混入氣泡、雜質等，且能夠減少黏著劑組合物的低分子量成分附著於被黏物的表面，即要求具有抗污染性能。 此外，從偏振片等的光學構件上剝離表面保護膜時，伴隨著從被黏物上剝離黏著劑層時所產生的靜電而產生剝離靜電，而該剝離靜電可能會對液晶顯示器的電氣控制電路的故障造成影響。因此，要求表面保護膜的黏著劑層具有優異的抗靜電性能。 進一步，近年來，作為偏振片的起偏鏡的保護層(有時也被稱作保護膜)，除了以往所使用的三醋酸纖維素(triacetate cellulose，TAC)以外，正在擴大對聚甲基丙烯酸甲酯(polymethyl methacrylate，PMMA)等丙烯酸類樹脂、聚對苯二甲酸乙二酯(PET)等聚酯類樹脂、環狀烯烴類聚合物、聚碳酸酯等的、剝離偏振片的表面保護膜時容易產生剝離靜電的材料的應用。因此，對用於偏振片的表面保護膜的黏著劑層所要求的抗靜電性能需要比以往優異。 此外，最終從偏振片等的光學構件上剝離表面保護膜時，要求能夠快速地剝離。即，要求黏著力因剝離速度造成的變化小，以便即使在高速剝離的情況下也能夠快速地剝離。In the surface protection film used in the step of manufacturing such an optical member, an adhesive layer is formed on one side of a polyethylene terephthalate (PET) resin film having optical transparency. In addition, in order to protect the adhesive layer of the surface protection film before bonding to the optical member, a release film subjected to mold release treatment is bonded to the surface of the adhesive layer of the surface protection film. In addition, optical members such as a polarizing plate are in a state where a surface protection film is bonded, and are subject to product inspection accompanied by optical evaluation of the display ability, color tone, contrast, and mixing of impurities of the liquid crystal display panel. Therefore, as the performance requirements for the surface protective film, it is required that no bubbles, impurities, etc. are mixed in the adhesive layer, and that the low molecular weight components of the adhesive composition can be reduced from adhering to the surface of the adherend, that is, it is required to have anti-pollution performance. In addition, when the surface protective film is peeled from the optical member such as the polarizer, peeling static electricity is generated when the adhesive layer is peeled from the adherend, and the peeling static electricity may affect the electrical control circuit of the liquid crystal display. The failure caused the impact. Therefore, the adhesive layer of the surface protection film is required to have excellent antistatic properties. Furthermore, in recent years, as a protective layer (sometimes referred to as a protective film) of the polarizer of a polarizer, in addition to the triacetate cellulose (TAC) used in the past, the use of polymethacrylic acid is being expanded. Acrylic resins such as polymethyl methacrylate (PMMA), polyester resins such as polyethylene terephthalate (PET), cyclic olefin polymers, polycarbonate, etc., peel-off polarizer surface protective film The application of materials that are prone to peeling static electricity. Therefore, the antistatic performance required for the adhesive layer of the surface protective film used for the polarizing plate needs to be superior to the past. In addition, when the surface protective film is finally peeled off from an optical member such as a polarizing plate, it is required to be able to peel off quickly. That is, it is required that the change in the adhesive force due to the peeling speed is small in order to be able to peel quickly even in the case of high-speed peeling.

如上所述，近年來，從使用表面保護膜時的使用難易度出發，要求構成表面保護膜的黏著劑層具有如下性能：(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡；(2)具有抗污染性能；(3)具有優異的抗靜電性能等。 然而，關於對構成表面保護膜的黏著劑層的性能要求，即使能夠分別滿足上述(1)~(3)的個別的性能要求，同時滿足對表面保護膜的黏著劑層所要求的(1)~(3)的所有性能要求也是非常困難的技術問題。As mentioned above, in recent years, starting from the ease of use when using a surface protective film, the adhesive layer constituting the surface protective film is required to have the following properties: (1) Adhesive strength can be obtained at a low peeling speed and a high peeling speed. Balance; (2) Has anti-pollution performance; (3) Has excellent antistatic performance. However, with regard to the performance requirements for the adhesive layer constituting the surface protective film, even if the individual performance requirements (1) to (3) above can be met respectively, while meeting the requirements for the adhesive layer of the surface protective film (1) All the performance requirements of ~(3) are also very difficult technical problems.

為了解決這樣的技術問題，例如，針對(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡、(2)具有抗污染性能以及(3)具有優異的抗靜電性能，分別已知有如下方案。In order to solve such technical problems, for example, (1) achieving a balance of adhesion at low and high peeling speeds, (2) having anti-pollution performance, and (3) having excellent antistatic performance, respectively. The following solutions are known.

關於(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡，在將具有碳原子數為7以下的烷基的(甲基)丙烯酸烷基酯與含羧基的共聚性化合物的共聚物作為主要成分，並使用交聯劑對其進行交聯處理而成的丙烯酸類的黏著劑層中，在進行長時間黏合的情況下，存在黏著劑向被黏物一側移動而附著於被黏物，或者對被黏物的黏合力的經時上升性較大的問題。為了避免該問題，已知一種黏著劑層及設置有該黏著劑層的表面保護構件，所述黏著劑層為使用具有碳原子數為8~10的烷基的(甲基)丙烯酸烷基酯與具有醇羥基的共聚性化合物的共聚物，並使用交聯劑對其進行交聯處理而成的凝膠分率為60%以上的黏著劑層(專利文獻1)。 然而，專利文獻1中記載的黏著劑層存在無法完全解決對被黏物的黏合力隨時間變化而增大的問題。 此外，已知一種設置有下述黏著劑層的技術方案，所述黏著劑層為向與上述相同的共聚物中，摻合少量的(甲基)丙烯酸烷基酯與含羧基的共聚性化合物的共聚物，並使用交聯劑對其進行交聯處理而成的黏著劑層。然而，若將這些黏著劑層用於表面張力低且表面光滑的塑膠板等的表面保護，則還存在因加工時、保存等時的加熱而產生浮起等剝離現象的問題、在手工操作領域的高速的剝離速度下的黏著力大且再剝離性差的問題。Regarding (1) A balance of adhesion between a low-speed peeling speed and a high-speed peeling speed is achieved by combining an alkyl (meth)acrylate having an alkyl group with 7 or less carbon atoms and a copolymerizable compound containing a carboxyl group. In the acrylic adhesive layer formed by using a copolymer as the main component and cross-linking it with a cross-linking agent, in the case of long-term bonding, the adhesive moves to the side of the adherend and adheres to it. It is a problem that the adherend or the adhesion to the adherend has a large rise over time. In order to avoid this problem, there is known an adhesive layer and a surface protection member provided with the adhesive layer. The adhesive layer is an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms. A copolymer with a copolymerizable compound having an alcoholic hydroxyl group, and an adhesive layer having a gel fraction of 60% or more obtained by cross-linking with a cross-linking agent (Patent Document 1). However, the adhesive layer described in Patent Document 1 cannot completely solve the problem that the adhesive force to the adherend increases with time. In addition, there is known a technical solution provided with the following adhesive layer, the adhesive layer is blended with a small amount of alkyl (meth)acrylate and a carboxyl-containing copolymerizable compound into the same copolymer as described above The adhesive layer is formed by cross-linking with a cross-linking agent. However, if these adhesive layers are used to protect the surface of plastic plates with low surface tension and smooth surfaces, there is also a problem of peeling phenomenon such as floating due to heating during processing and storage, etc., in the manual operation field The high-speed peeling speed has high adhesion and poor repeelability.

為了解決這些技術問題，提出了一種黏著劑組合物，其在100重量份的a)以具有碳原子數為8~10的烷基的(甲基)丙烯酸烷基酯為主要成分的(甲基)丙烯酸烷基酯中，加入b)1~15重量份的含羧基的共聚性化合物以及c)3~100重量份的碳原子數為1~5的脂肪族羧酸的乙烯基酯而形成單體混合物的共聚物，並在該共聚物中摻合了相對於上述b)成分的羧基為當量以上的交聯劑(專利文獻2)。 對於使專利文獻2中記載的黏著劑組合物交聯而成的黏著劑層，在加工時、保存時等不會產生浮起等剝離現象，並且黏合力的經時上升性小，再剝離性優異，即使長期保存、特別是在高溫氛圍下長期保存，也能夠以較小的力進行再剝離，此時不會在被黏物上產生殘膠，且即使在進行高速剝離時也能夠以較小的力進行再剝離。 然而，對於使專利文獻2中記載的黏著劑組合物交聯而成的黏著劑層，實施例1~3中的黏著劑層的凝膠分率均為90%，在低速的剝離速度下的黏著力易於變得過大，未聚合單體或低聚物(oligomer)易於從黏著劑層中溶出。此外，專利文獻2中沒有關於抗靜電性能及抗污染性能的記載，在將易於產生剝離靜電的材料作為被黏物的情況下，存在難以改良成具備優異的抗靜電性能及抗污染性能的黏著劑層的問題。In order to solve these technical problems, an adhesive composition has been proposed, which has a (meth)acrylic acid alkyl ester having an alkyl group with 8 to 10 carbon atoms as the main component in 100 parts by weight of a) (methyl) ) In the alkyl acrylate, b) 1 to 15 parts by weight of a carboxyl group-containing copolymerizable compound and c) 3 to 100 parts by weight of a vinyl ester of aliphatic carboxylic acid having 1 to 5 carbon atoms are added to form a monomer A copolymer of a bulk mixture, and a crosslinking agent equivalent to or greater than the carboxyl group of component b) is blended in the copolymer (Patent Document 2). The adhesive layer formed by cross-linking the adhesive composition described in Patent Document 2 does not cause peeling phenomena such as floating during processing and storage, and the increase in adhesive force over time is small, and the peelability is small. Excellent. Even if stored for a long time, especially in a high temperature atmosphere, it can be peeled again with a small force. At this time, there will be no glue residue on the adherend, and it can be peeled at a higher speed even when peeling at a high speed. Peel again with a small force. However, with regard to the adhesive layer formed by crosslinking the adhesive composition described in Patent Document 2, the gel fraction of the adhesive layer in Examples 1 to 3 is all 90%, which is effective at a low peeling speed. The adhesive force tends to become too large, and unpolymerized monomers or oligomers are easily eluted from the adhesive layer. In addition, Patent Document 2 does not describe antistatic performance and anti-pollution performance. When a material that easily generates peeling static electricity is used as an adherend, it is difficult to improve an adhesive with excellent antistatic performance and anti-pollution performance. The problem of the agent layer.

此外，關於(2)具有抗污染性能，公開了一種黏著劑組合物，其含有：100質量份的重均分子量(也稱為種量平均分子量)為10萬以上且小於100萬的(甲基)丙烯酸類共聚物，該共聚物由0質量份以上且小於0.5質量份的含羧基單體、0.6~9質量份的含羥基的(甲基)丙烯酸類單體及99.4~90.5質量份的(甲基)丙烯酸酯單體形成；及0.1~5質量份的碳二亞胺(carbodiimide)類交聯劑(專利文獻3)。 專利文獻3中記載的黏著劑組合物的特徵在於，使用碳二亞胺類交聯劑作為特定組成的(甲基)丙烯酸類共聚物的交聯劑。由此，能夠提供具有交聯結構的黏著劑層，該交聯結構可追隨由壓熱處理時的壓力及溫度引起的收縮。因此，使用專利文獻3中記載的黏著劑組合物而形成的黏著劑層即使在高溫高壓條件下(壓熱處理時)也能夠抑制並防止起泡，抗污染性能優異，此外，透明性也優異。 然而，對於使專利文獻3中記載的黏著劑組合物交聯而成的黏著劑層，其抗污染性能雖然得到了改良，但未能實現在低速的剝離速度與高速的剝離速度下取得黏著力的平衡所帶來的優異的黏著性能同時兼顧抗靜電性能，還殘留有需要進一步解決的技術問題。In addition, regarding (2) having anti-pollution properties, an adhesive composition is disclosed, which contains: 100 parts by mass of (methyl group) having a weight average molecular weight (also called species average molecular weight) of 100,000 or more and less than 1 million ) An acrylic copolymer consisting of 0 parts by mass or more and less than 0.5 parts by mass of a carboxyl group-containing monomer, 0.6-9 parts by mass of a hydroxyl group-containing (meth)acrylic monomer and 99.4-90.5 parts by mass ( Formation of meth)acrylate monomer; and 0.1 to 5 parts by mass of a carbodiimide-based crosslinking agent (Patent Document 3). The adhesive composition described in Patent Document 3 is characterized by using a carbodiimide-based crosslinking agent as a crosslinking agent for a (meth)acrylic copolymer of a specific composition. Thereby, it is possible to provide an adhesive layer having a cross-linked structure that can follow the shrinkage caused by the pressure and temperature during autoclaving. Therefore, the adhesive layer formed using the adhesive composition described in Patent Document 3 can suppress and prevent foaming even under high temperature and high pressure conditions (during autoclave heat treatment), has excellent anti-fouling performance, and also has excellent transparency. However, although the anti-fouling performance of the adhesive layer formed by crosslinking the adhesive composition described in Patent Document 3 has been improved, it has not been possible to achieve adhesion at low and high peeling speeds. The excellent adhesion performance brought about by the balance of the film also takes into account the antistatic performance, and there are still technical problems that need to be further solved.

此外，關於(3)具有優異的抗靜電性能，作為用於對表面保護膜賦予抗靜電性的方法，已知有向基材膜中捏合(kneading)抗靜電劑的方法等。劑作為抗静电劑，例如公開了：(a)鹽具有四級銨鹽、吡啶鹽鹽(pyridinium salt)、一級~三級胺基等陽離子基團團的各種陽離子抗静劑電劑；(b)具有磺酸鹽鹽基(sulfonic acid salt group)、硫酸酯鹽基、磷酸酯鹽基、膦酸鹽基等陰離子基團的陰離子抗静电劑；(c)胺基酸類、胺基硫酸酯類等兩性抗静电劑；(d)胺基醇類、甘油類、聚乙二醇類等非離子抗静电劑；(e)將如上所述的各種抗静电劑高分子量化而成的高分子型抗静电劑等(專利文獻4)。 然而，對於專利文獻4中記載的表面保護膜，雖然有涉及垃圾附著於被黏物的有關賦予抗靜電性能的記載，但並未記載同時兼顧優異的黏著性能與抗污染性能的解決手段，還殘留有需要進一步解決的技術問題。In addition, regarding (3) having excellent antistatic performance, as a method for imparting antistatic properties to a surface protective film, a method of kneading an antistatic agent into a base film, and the like are known. As an antistatic agent, for example: (a) various cationic antistatic agents with cationic groups such as quaternary ammonium salt, pyridinium salt, and primary to tertiary amine groups are disclosed; (b) Anionic antistatic agents with anionic groups such as sulfonic acid salt group, sulfate ester salt group, phosphate ester salt group, phosphonate group, etc.; (c) amino acids, amino sulfate esters, etc. Amphoteric antistatic agents; (d) nonionic antistatic agents such as amino alcohols, glycerols, polyethylene glycols, etc.; (e) high molecular weight antistatic agents made of various antistatic agents as described above. Electrostatic agent, etc. (Patent Document 4). However, for the surface protective film described in Patent Document 4, although there is a description of imparting antistatic properties related to the adhesion of garbage to the adherend, it does not describe a solution that combines excellent adhesion performance and anti-fouling performance. There are still technical problems that need to be further resolved.

此外，近年來，提出了一種直接使黏著劑層含有抗靜電劑，而不是使基材膜含有抗靜電劑或者在基材膜的表面上塗佈抗靜電劑的方案。例如公開了一種抗靜電性黏著劑組合物，其特徵在於，具備含有氟基及磺醯基的陰離子的鹽以溶解於主鏈中包含聚醚基的聚醚酯類可塑劑的狀態進行分散(專利文獻5)。 關於專利文獻5中記載的黏著劑組合物，公開了使用由下述酯構成的可塑劑作為可塑劑：由具有飽和或不飽和的非環式烴基的一元羧酸或二元羧酸與具有碳原子數為1~20的非環式烴基的醇形成的酯；或者所述不飽和的非環式烴基中的不飽和基團被環氧化而成的酯。認為：通過使這種具有飽和或不飽和的非環式烴基的一元羧酸或二元羧酸具有與構成用於黏著劑層的丙烯酸共聚物的丙烯酸單體的碳原子數相近的碳原子數，與抗靜電性黏著劑組合物的相容性變得良好，可塑劑在丙烯酸類抗靜電性黏著劑組合物中得到適當保持，因此滲出(bleed out)得以抑制。 然而，對於使專利文獻5中記載的抗靜電性黏著劑組合物交聯而成的黏著劑層，雖然有公開抗靜電性能及滲出的改良技術，但沒有記載可獲得在低速的剝離速度與高速的剝離速度下取得黏著力的平衡所帶來的優異的黏著性能，還殘留有得到具有優異的黏著性能的黏著劑層這樣的技術問題。 現有技術文獻 專利文獻In addition, in recent years, a proposal has been proposed to directly make the adhesive layer contain an antistatic agent instead of making the base film contain an antistatic agent or coating the surface of the base film with an antistatic agent. For example, an antistatic adhesive composition is disclosed, which is characterized in that a salt having an anion containing a fluorine group and a sulfonyl group is dispersed in a state of being dissolved in a polyether ester plasticizer containing a polyether group in the main chain ( Patent Document 5). Regarding the adhesive composition described in Patent Document 5, it is disclosed to use a plasticizer composed of the following ester as a plasticizer: a monocarboxylic acid or a dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group and a carbon An ester formed by an alcohol of an acyclic hydrocarbon group with 1 to 20 atoms; or an ester formed by epoxidation of an unsaturated group in the unsaturated acyclic hydrocarbon group. It is considered that by making the monocarboxylic acid or dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group have a carbon number close to the carbon number of the acrylic monomer constituting the acrylic copolymer used for the adhesive layer , The compatibility with the antistatic adhesive composition becomes good, and the plasticizer is properly maintained in the acrylic antistatic adhesive composition, so bleed out is suppressed. However, for the adhesive layer formed by cross-linking the antistatic adhesive composition described in Patent Document 5, although there are disclosed antistatic performance and bleeding improvement technology, there is no description that a low-speed peeling speed and a high-speed peeling speed can be obtained. The excellent adhesion performance brought about by the balance of the adhesion force at the peeling speed of, there is still a technical problem of obtaining an adhesive layer with excellent adhesion performance. Prior art literature Patent literature

專利文獻1：日本特開昭63-225677號公報 專利文獻2：日本特開平11-256111號公報 專利文獻3：日本特開2011-122054號公報 專利文獻4：日本特開平11-070629號公報 專利文獻5：日本特開2014-118469號公報Patent Document 1: Japanese Patent Laid-Open No. 63-225677 Patent Document 2: Japanese Patent Laid-Open No. 11-256111 Patent Document 3: Japanese Patent Application Publication No. 2011-122054 Patent Document 4: Japanese Patent Laid-Open No. 11-070629 Patent Document 5: Japanese Patent Application Laid-Open No. 2014-118469

本發明要解決的技術問題Technical problem to be solved by the present invention

如上所述，尚沒有現有技術解決同時實現作為對構成表面保護膜的黏著劑層的性能要求的以下這樣的技術問題：(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡；(2)具有抗污染性能；(3)具有優異的抗靜電性能。 此外，一直以來，使用具備抗靜電性能的黏著劑組合物而形成的黏著劑層以及使用了該黏著劑層的表面保護膜的、抗靜電性能與對被黏物的抗污染性能的關係處於權衡(trade-off)的關係，難以在維持抗靜電性能的同時改善抗污染性能。 進一步，由於近年來表面保護膜所貼合的被黏物的材質的種類增加，且被黏物的表面處理後的狀態也多種多樣，因此，構成表面保護膜的黏著劑層，對所有被黏物，特別是滿足上述的(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡、以及(2)具有抗污染性變得更加困難。As described above, there is no prior art to solve the following technical problems as the performance requirements of the adhesive layer constituting the surface protective film at the same time: (1) A balance of adhesive force is achieved at a low-speed peeling speed and a high-speed peeling speed. ; (2) Has anti-pollution performance; (3) Has excellent antistatic performance. In addition, there has been a trade-off between the antistatic properties of the adhesive layer formed using an adhesive composition with antistatic properties and the surface protective film using the adhesive layer and the anti-fouling properties of the adherend. (trade-off) relationship, it is difficult to improve the anti-pollution performance while maintaining the antistatic performance. Furthermore, in recent years, the types of adherends to which the surface protective film is attached have increased, and the state of the adherend after surface treatment is also diverse. Therefore, the adhesive layer that constitutes the surface protective film is effective for all adherends. In particular, it becomes more difficult to satisfy the above-mentioned (1) balance of adhesion at low and high peeling speeds, and (2) anti-staining properties.

本發明是鑒於上述情況而進行的，其技術問題在於提供在低速的剝離速度與高速的剝離速度下具有取得了平衡的黏著力、且可謀求兼顧抗靜電性能與抗污染性能的抗靜電表面保護膜的製造方法、抗靜電表面保護膜。 解決技術問題的技術手段The present invention was made in view of the above situation, and its technical problem is to provide an antistatic surface protection that has a balance of adhesion at low and high peel speeds, and can achieve both antistatic performance and anti-pollution performance. Film manufacturing method, antistatic surface protective film. Technical means to solve technical problems

為了解決上述技術問題，本發明的抗靜電表面保護膜將(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的丙烯酸2-乙基己酯與均聚物(homopolymer)的玻璃化轉變溫度(Tg)為0℃以上的單官能的甲基丙烯酸酯單體的含有比例規定為特定範圍。進一步，本發明的技術構思在於，塗佈黏著劑組合物並使其乾燥從而積層黏著劑層後，對該黏著劑層的表面賦予適量的在20℃下為液體的矽酮類化合物及抗靜電劑，由此將對被黏物的污染性抑制得較低(具有抗污染性能)，並且將從作為被黏物的光學用膜上剝離時的剝離靜電壓抑制得較低。In order to solve the above technical problems, the antistatic surface protective film of the present invention combines (A) 2-ethylhexyl acrylate in alkyl (meth)acrylates with C1-C10 alkyl carbon atoms and homopolymer The content rate of the monofunctional methacrylate monomer whose glass transition temperature (Tg) of (homopolymer) is 0 degreeC or more is prescribed|regulated to a specific range. Furthermore, the technical idea of the present invention is to apply an adhesive composition and dry it to laminate an adhesive layer, and then apply an appropriate amount of silicone compound and antistatic which is liquid at 20°C to the surface of the adhesive layer As a result, the stain to the adherend is suppressed low (has anti-fouling performance), and the peeling static voltage when peeling from the optical film as the adherend is suppressed to be low.

為了解決上述技術問題，本發明提供一種抗靜電表面保護膜的製造方法，其為製造抗靜電表面保護膜的方法，所述製造方法的特徵在於，以步驟(1)~(3)的順序經過以下的步驟(1)~(3)而製作抗靜電表面保護膜： 步驟(1)：製備黏著劑組合物的步驟，所述黏著劑組合物含有丙烯酸類聚合物與交聯劑，所述丙烯酸類聚合物為使(A)合計為100重量份的烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上、(B)合計為1.0~6.0重量份的含有羥基的可共聚單體中的至少1種以上、及(F)合計為1.0~50重量份的構成聚伸烷基二醇(又稱聚烯烴基二醇)(polyalkylene glycol)鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少1種以上，以不含有具有羧基的可共聚單體的方式共聚而成的、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物，在所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上的合計100重量份中，以50重量份以上的比例含有丙烯酸2-乙基己酯、以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上，所述黏著劑組合物含有作為所述交聯劑的(C)三官能以上的異氰酸酯化合物、以及(D)交聯延遲劑與作為(E)交聯促進劑的除錫化物以外的交聯促進劑而成； 步驟(2)：在由具有透明性的樹脂形成的基材膜的單面上製作使所述黏著劑組合物交聯的黏著劑層的步驟；及 步驟(3)：將在樹脂膜的單面積層有含有抗靜電劑的剝離劑層的剝離膜，經由所述剝離劑層而貼合於所述黏著劑層的表面，使所述剝離劑層的所述抗靜電劑轉印至所述黏著劑層的表面的步驟， 所述剝離劑層由樹脂組合物形成，所述樹脂組合物包含以二甲基聚矽氧烷為主要成分的剝離劑、在20℃下為液體的矽酮類化合物及抗靜電劑。In order to solve the above technical problems, the present invention provides a method of manufacturing an antistatic surface protective film, which is a method of manufacturing an antistatic surface protective film, the manufacturing method is characterized in that steps (1) to (3) are passed through in order The following steps (1)~(3) are used to make an antistatic surface protective film: Step (1): a step of preparing an adhesive composition, the adhesive composition contains an acrylic polymer and a crosslinking agent, the acrylic polymer is carbon whose total amount of (A) is 100 parts by weight of the alkyl group At least 2 or more of the alkyl (meth)acrylates having C1 to C10 atoms, (B) at least 1 or more of the hydroxyl group-containing copolymerizable monomers totaling 1.0 to 6.0 parts by weight, and (F ) A total of 1.0 to 50 parts by weight of the polyalkylene glycol chain-containing mono(meth)acrylate monomer that constitutes the polyalkylene glycol (also known as polyalkylene glycol) chain At least one or more of the acrylic polymers formed by copolymers with a weight average molecular weight of more than 300,000 and less than 1 million, which are copolymerized without containing a copolymerizable monomer having a carboxyl group, are described in (A ) A total of 100 parts by weight of at least two (meth)acrylic acid alkyl esters having C1 to C10 carbon atoms in the alkyl group contains 2-ethylhexyl acrylate in a proportion of 50 parts by weight or more. A total of 5 to 40 parts by weight contains one or more of monofunctional methacrylate monomers having a homopolymer Tg of 0°C or higher, and the adhesive composition contains as the crosslinking agent ( C) A trifunctional or higher isocyanate compound, (D) a cross-linking retarder, and (E) a cross-linking accelerator, a cross-linking accelerator other than tin compounds; Step (2): a step of fabricating an adhesive layer for crosslinking the adhesive composition on one side of a base film formed of a resin having transparency; and Step (3): A release film with a release agent layer containing an antistatic agent layered on a single area of the resin film is bonded to the surface of the adhesive layer via the release agent layer to make the release agent layer The step of transferring the antistatic agent to the surface of the adhesive layer, The release agent layer is formed of a resin composition containing a release agent containing dimethylpolysiloxane as a main component, a silicone compound that is liquid at 20° C., and an antistatic agent.

此外，優選：所述均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體為選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯組成的化合物群組中的1種以上。In addition, it is preferable that the monofunctional methacrylate monomer with a Tg of 0°C or higher for the homopolymer is selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, One or more of the compound group consisting of t-butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, ethyl methacrylate, and methyl methacrylate.

此外，所述剝離劑層中的抗靜電劑優選為鹼金屬鹽。In addition, the antistatic agent in the release agent layer is preferably an alkali metal salt.

此外，本發明提供一種抗靜電表面保護膜，其在由具有透明性的樹脂形成的基材膜的單面上形成有黏著劑層，所述黏著劑層由含有丙烯酸類聚合物與交聯劑的黏著劑組合物交聯而成，所述抗靜電表面保護膜的特徵在於，所述丙烯酸類聚合物為使(A)合計為100重量份的烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上、(B)合計為1.0~6.0重量份的含有羥基的可共聚單體中的至少1種以上、及(F)合計為1.0~50重量份的構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少1種以上，以不含有具有羧基的可共聚單體的方式共聚而成的、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物，在所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上的合計100重量份中，以50重量份以上的比例含有丙烯酸2-乙基己酯、以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上，所述黏著劑組合物含有作為所述交聯劑的(C)三官能以上的異氰酸酯化合物、以及(D)交聯延遲劑與作為(E)交聯促進劑的除錫化物以外的交聯促進劑，將在樹脂膜的單面積層有含有抗靜電劑的剝離劑層的剝離膜，經由所述剝離劑層而貼合於所述黏著劑層的表面，使所述剝離劑層的所述抗靜電劑轉印至所述黏著劑層的表面，所述剝離劑層由樹脂組合物形成，所述樹脂組合物包含以二甲基聚矽氧烷為主要成分的剝離劑、在20℃下為液體的矽酮類化合物及抗靜電劑。In addition, the present invention provides an antistatic surface protective film, which has an adhesive layer formed on one side of a base film formed of a resin having transparency, and the adhesive layer is composed of an acrylic polymer and a crosslinking agent. The adhesive composition is cross-linked, and the antistatic surface protective film is characterized in that the acrylic polymer is (A) with a total of 100 parts by weight of the alkyl group having carbon atoms of C1 to C10 ( At least 2 or more of alkyl meth)acrylates, (B) at least 1 or more of the hydroxyl-containing copolymerizable monomers totaling 1.0 to 6.0 parts by weight, and (F) totaling 1.0 to 50 parts by weight At least one of the polyalkylene glycol chain-containing mono(meth)acrylate monomers constituting the polyalkylene glycol chain is copolymerized in a manner that does not contain a copolymerizable monomer having a carboxyl group An acrylic polymer formed by a copolymer having a weight average molecular weight of more than 300,000 and less than 1 million, in the (A) alkyl (meth)acrylic acid alkyl ester with C1-C10 carbon atoms In 100 parts by weight in total of at least two or more of the at least two kinds, containing 2-ethylhexyl acrylate in a proportion of 50 parts by weight or more, and a homopolymer with a Tg of 0°C or higher in a proportion of 5 to 40 parts by weight in total. One or more functional methacrylate monomers, and the adhesive composition contains (C) a trifunctional or higher isocyanate compound as the crosslinking agent, and (D) a crosslinking retarder and as (E ) Cross-linking accelerators other than tin compounds of the cross-linking accelerator, a release film having a release agent layer containing an antistatic agent layered on a single area of the resin film is bonded to the adhesive via the release agent layer The surface of the agent layer, the antistatic agent of the release agent layer is transferred to the surface of the adhesive layer, the release agent layer is formed of a resin composition, and the resin composition contains a dimethyl poly A release agent with silicone as the main component, a silicone compound that is liquid at 20°C, and an antistatic agent.

此外，優選：所述均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體為選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯組成的化合物群組中的1種以上。In addition, it is preferable that the monofunctional methacrylate monomer with a Tg of 0°C or higher for the homopolymer is selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, One or more of the compound group consisting of t-butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, ethyl methacrylate, and methyl methacrylate.

此外，所述剝離劑層中的抗靜電劑優選為鹼金屬鹽。In addition, the antistatic agent in the release agent layer is preferably an alkali metal salt.

此外，優選：所述(F)構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中，構成聚伸烷基二醇鏈的環氧烷(亦稱伸烷基氧)(alkylene oxide)的平均重複數為3~14，所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的二酯組分為0.2%以下，所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體為選自由聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯組成的群組中的至少1種以上。In addition, it is preferable that the (F) polyalkylene glycol chain-containing mono(meth)acrylate monomer constituting the polyalkylene glycol chain is an alkylene oxide constituting the polyalkylene glycol chain The average repeating number of (also known as alkylene oxide) is 3~14, and the diester component in the polyalkylene glycol chain-containing mono(meth)acrylate monomer is 0.2% Hereinafter, the polyalkylene glycol chain-containing mono(meth)acrylate monomer is selected from polyalkylene glycol mono(meth)acrylate, methoxy polyalkylene glycol (meth) At least one of the group consisting of oxy)acrylate and ethoxy polyalkylene glycol (meth)acrylate.

此外，優選：將抗靜電表面保護膜用作偏振片用表面保護膜，在所述偏振片用表面保護膜的用途中，作為被黏物的偏振片的起偏鏡的保護層為選自由TAC類膜、PMMA類膜、PET類膜組成的群組中的至少1種，且對所述偏振片的起偏鏡的保護層的表面實施的表面處理為選自由未處理、AG處理、LR處理、AR處理、AG-LR處理、AG-AR處理組成的群組中的至少1種。In addition, it is preferable that an antistatic surface protective film is used as a surface protective film for a polarizer, and in the use of the surface protective film for a polarizer, the protective layer of the polarizer of the polarizer as an adherend is selected from TAC At least one of the group consisting of a type film, a PMMA type film, and a PET type film, and the surface treatment performed on the surface of the protective layer of the polarizer of the polarizer is selected from untreated, AG treatment, and LR treatment At least one of the group consisting of AR processing, AG-LR processing, and AG-AR processing.

此外，優選：所述(B)含有羥基的可共聚單體為選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺組成的化合物群組中的至少1種以上。In addition, preferably: the (B) hydroxyl-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Ester, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide At least one or more of the group of compounds.

此外，優選：所述(D)交聯延遲劑為酮-烯醇互變異構體(keto-enol tautomerism)的化合物，相對於100重量份的所述丙烯酸類聚合物，以0.1~300重量份的比例含有所述(D)交聯延遲劑，所述(E)交聯促進劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少1種以上的金屬螯合化合物，相對於100重量份的所述丙烯酸類聚合物，以0.001~0.5重量份的比例含有所述(E)交聯促進劑，所述(D)/所述(E)的重量份比為80~1000。In addition, it is preferred that the (D) crosslinking retarder is a keto-enol tautomerism (keto-enol tautomerism) compound, relative to 100 parts by weight of the acrylic polymer, in an amount of 0.1 to 300 parts by weight Contains the (D) crosslinking retarder, and the (E) crosslinking accelerator is at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds The metal chelate compound contains the (E) crosslinking accelerator in a ratio of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer, and the weight of the (D)/the (E) The serving ratio is 80~1000.

此外，優選：相對於100重量份的所述丙烯酸類聚合物，所述黏著劑組合物以0.01~0.5重量份的比例含有HLB值為6~12且重均分子量為10000以下的聚醚改質矽氧烷化合物。In addition, it is preferable that: relative to 100 parts by weight of the acrylic polymer, the adhesive composition contains a modified polyether having an HLB value of 6 to 12 and a weight average molecular weight of 10,000 or less in a ratio of 0.01 to 0.5 parts by weight. Siloxane compounds.

此外，所述剝離劑層中的矽酮類化合物優選為聚醚改質矽酮。In addition, the silicone compound in the release agent layer is preferably a polyether modified silicone.

此外，優選：所述剝離劑層中的抗靜電劑為Li鹽，為選自由LiTFSI、LiFSI、LiTF組成的化合物群組中的至少1種以上。 發明效果In addition, it is preferable that the antistatic agent in the release agent layer is a Li salt, which is at least one compound selected from the group consisting of LiTFSI, LiFSI, and LiTF. Invention effect

本發明的抗靜電表面保護膜對被黏物的污染少，對被黏物的抗污染性能不會隨時間變化。此外，根據本發明，即使為使用矽酮化合物、氟化物等對LR偏振片、AG-LR偏振片等被黏物的表面進行了抗污染處理的光學用膜，也能夠將從被黏物上剝離抗靜電表面保護膜時所產生的剝離靜電壓抑制得較低，能夠提供一種不發生經時劣化且具有優異的抗剝離靜電性能的抗靜電表面保護膜。The antistatic surface protective film of the present invention has less pollution to the adherend, and the anti-pollution performance of the adherend does not change with time. In addition, according to the present invention, even if it is an optical film in which the surface of adherends such as LR polarizers, AG-LR polarizers, etc., is treated with anti-fouling using silicone compounds, fluorides, etc., it can be removed from the adherend The peeling static voltage generated when the antistatic surface protection film is peeled off is suppressed to a low level, and it is possible to provide an antistatic surface protection film that does not undergo deterioration over time and has excellent peeling static resistance performance.

根據本發明的抗靜電表面保護膜，即使在以PMMA為基材的偏振片用表面保護膜中，也能夠兼顧(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡及(2)具有抗污染性能。 此外，通過將(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的丙烯酸2-乙基己酯與均聚物的玻璃化轉變溫度(Tg)為0℃以上的單官能的甲基丙烯酸酯單體的含有比例規定為特定範圍，從而特別是在以PMMA為基材的偏振片用表面保護膜中，也能夠兼顧(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡及(2)具有抗污染性能。According to the antistatic surface protective film of the present invention, even in the surface protective film for polarizing plates using PMMA as the base material, it is possible to achieve both (1) achieving a balance of adhesive force at a low-speed peeling speed and a high-speed peeling speed and ( 2) It has anti-pollution performance. In addition, by setting the glass transition temperature (Tg) of the homopolymer of 2-ethylhexyl acrylate and the homopolymer in the alkyl (meth)acrylate having C1 to C10 carbon atoms of the alkyl group to 0°C The content ratio of the above monofunctional methacrylate monomer is specified in a specific range, so that, especially in the surface protective film for polarizers using PMMA as the base material, it is possible to achieve both (1) low-speed peeling speed and high-speed peeling speed. Achieving a balance of adhesion and (2) anti-pollution performance at the peeling speed.

另外，含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上有助於兼顧(1)在低速的剝離速度與高速的剝離速度下取得黏著力的平衡及(2)具有抗污染性能的理由尚未解明。作為可考慮到的理由，推測其理由如下：即使這些甲基丙烯酸酯單體不具有羧基、醯胺基之類的極性官能團或超過C10的長鏈烷基，也可獲得Tg較高的聚合物，因此能夠大幅改善交聯狀態下的黏著性能，此外，在偏振片用表面保護膜的用途中，當作為被黏物的偏振片的起偏鏡的保護層為PMMA類膜時，與作為該PMMA類膜的主要成分的甲基丙烯酸甲酯的親和性得以提高等。In addition, one or more of the monofunctional methacrylate monomers containing homopolymers with a Tg of 0°C or higher help to balance (1) balance the adhesion between low-speed peeling speed and high-speed peeling speed And (2) The reason for having anti-pollution properties has not yet been explained. As a possible reason, it is assumed that the reason is as follows: even if these methacrylate monomers do not have polar functional groups such as carboxyl groups and amide groups or long-chain alkyl groups exceeding C10, polymers with higher Tg can be obtained. , It can greatly improve the adhesion performance in the cross-linked state. In addition, in the use of the surface protective film for polarizers, when the protective layer of the polarizer of the polarizer as the adherend is a PMMA-based film, the The affinity of methyl methacrylate, which is the main component of the PMMA-based film, is improved.

以下，基於實施方式，對本發明進行詳細說明。 圖1為示出本實施方式的抗靜電表面保護膜的概念的剖面圖。該抗靜電表面保護膜10在透明的基材膜1的單面的表面上形成有黏著劑層2。該黏著劑層2的表面上貼合有在樹脂膜3的表面上形成有剝離劑層4的剝離膜5。Hereinafter, the present invention will be described in detail based on embodiments. FIG. 1 is a cross-sectional view showing the concept of the antistatic surface protection film of this embodiment. The antistatic surface protection film 10 has an adhesive layer 2 formed on one surface of a transparent base film 1. The release film 5 in which the release agent layer 4 is formed on the surface of the resin film 3 is bonded to the surface of the adhesive layer 2.

作為用於本實施方式的抗靜電表面保護膜10的基材膜1，可使用由具有透明性及可撓性的樹脂形成的基材膜。由此，能夠以將抗靜電表面保護膜貼合於作為被黏物的光學部件的狀態進行光學部件的外觀檢測。用作基材膜1的由具有透明性的樹脂形成的膜可適當地使用聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚間苯二甲酸乙二酯、聚對苯二甲酸丁二酯等的聚酯膜。除了聚酯膜以外，只要具有所需的強度且具有光學適性，則也可使用由其他樹脂形成的膜。基材膜1可以為無拉伸膜，也可以為經單軸或雙軸拉伸的膜。此外，還可以將拉伸膜的拉伸倍率、或伴隨拉伸膜的結晶化而形成的軸方向的取向角度控制為特定的值。As the base film 1 used for the antistatic surface protection film 10 of the present embodiment, a base film formed of a resin having transparency and flexibility can be used. Thereby, it is possible to perform the appearance inspection of the optical component in a state where the antistatic surface protection film is bonded to the optical component as an adherend. The film formed of a transparent resin used as the base film 1 can suitably use polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polyethylene terephthalate. Polyester film such as butylene formate. In addition to polyester films, as long as they have required strength and optical compatibility, films made of other resins may also be used. The base film 1 may be an unstretched film, or may be a uniaxially or biaxially stretched film. In addition, the stretching magnification of the stretched film or the orientation angle in the axial direction formed with the crystallization of the stretched film may be controlled to a specific value.

用於本實施方式的抗靜電表面保護膜10的基材膜1的厚度沒有特別限定，例如優選為12~100μm左右的厚度，若為20~50μm左右的厚度則容易操作，更加優選。 此外，可根據需要在基材膜1的與形成有黏著劑層2的面為相反側的面上設置防止表面污染的防汙層、抗靜電層、防止傷痕的硬塗層等。此外，可對基材膜1的表面實施基於電暈放電(corona discharge)的表面改質、錨固劑(anchor coat agent)的塗覆等的易黏合處理。The thickness of the base film 1 used for the antistatic surface protection film 10 of this embodiment is not specifically limited, For example, the thickness of about 12-100 micrometers is preferable, and the thickness of about 20-50 micrometers is easy to handle, and it is more preferable. In addition, an antifouling layer to prevent surface contamination, an antistatic layer, a hard coat layer to prevent scratches, etc. may be provided on the surface of the base film 1 opposite to the surface on which the adhesive layer 2 is formed as needed. In addition, the surface of the base film 1 may be subjected to easy adhesion treatments such as surface modification by corona discharge and coating of an anchor coat agent.

此外，用於本實施方式的抗靜電表面保護膜10的黏著劑層2黏合於被黏物的表面，並能夠在完成使用後簡單地剝離，且只要為不易污染被黏物的黏著劑，則沒有特別限定，若考慮到貼合於光學用膜後的耐久性等，則通常使用使丙烯酸類聚合物交聯而成的丙烯酸類的黏著劑層。In addition, the adhesive layer 2 used in the antistatic surface protection film 10 of this embodiment is adhered to the surface of the adherend, and can be easily peeled off after use, and as long as it is an adhesive that does not easily contaminate the adherend, It is not particularly limited, and in consideration of durability after bonding to an optical film, etc., an acrylic adhesive layer formed by crosslinking an acrylic polymer is generally used.

作為構成所述黏著劑層2的黏著劑組合物，可列舉出下述黏著劑組合物：丙烯酸類聚合物為使(A)合計為100重量份的烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上、(B)合計為1.0~6.0重量份的含有羥基的可共聚單體中的至少1種以上、及(F)合計為1.0~50重量份的構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少1種以上，以不含有具有羧基的可共聚單體的方式共聚而成的、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物，在所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上的合計100重量份中，以50重量份以上的比例含有丙烯酸2-乙基己酯，以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上，且含有作為所述交聯劑的(C)三官能以上的異氰酸酯化合物、以及(D)交聯延遲劑與作為(E)交聯促進劑的除錫化物以外的交聯促進劑的黏著劑組合物。Examples of the adhesive composition constituting the adhesive layer 2 include the following adhesive composition: an acrylic polymer having a carbon number of C1 to C10 in which the alkyl group (A) is 100 parts by weight in total At least 2 or more of the alkyl (meth)acrylates, (B) at least 1 or more of the hydroxyl-containing copolymerizable monomers totaling 1.0 to 6.0 parts by weight, and (F) totaling 1.0 to 50 weights Part of at least one of the polyalkylene glycol chain-containing mono(meth)acrylate monomers constituting the polyalkylene glycol chain is copolymerized so as not to contain a copolymerizable monomer having a carboxyl group Acrylic polymer formed by copolymers with a weight average molecular weight of more than 300,000 and less than 1 million, and the (A) alkyl (meth)acrylate having C1-C10 carbon atoms In 100 parts by weight of at least two or more in total, it contains 2-ethylhexyl acrylate in a proportion of 50 parts by weight or more, and it contains a homopolymer with a Tg of 0°C or higher in a proportion of 5 to 40 parts by weight in total. One or more of monofunctional methacrylate monomers, and contains (C) a trifunctional or higher isocyanate compound as the crosslinking agent, and (D) a crosslinking retarder and (E) a crosslinking accelerator Adhesive composition of crosslinking accelerator other than tin compound.

作為所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯，可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸環戊基酯、(甲基)丙烯酸環己基酯等。這些(甲基)丙烯酸烷基酯的烷基可以為非環狀(直鏈、支鏈狀)、環狀(單環、多環)中的任意一種。Examples of (A) alkyl (meth)acrylates having C1 to C10 carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. N-propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate , Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyl (meth)acrylate Cyclohexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. The alkyl group of these alkyl (meth)acrylates may be any of acyclic (linear, branched) and cyclic (monocyclic, polycyclic).

所述丙烯酸類聚合物優選在合計為100重量份的所述(A)中，以50重量份以上的比例含有丙烯酸2-乙基己酯、以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上。 此外，在合計為100重量份的所述(A)中，優選以50重量份以上的比例、更優選以60重量份以上的比例、特別優選以70重量份以上的比例含有丙烯酸2-乙基己酯。 此外，作為所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的Tg為0℃以上的單官能的甲基丙烯酸酯單體，可列舉出選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸正戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯酸異己酯、甲基丙烯酸環己基酯、甲基丙烯酸異莰酯、甲基丙烯酸二環戊基酯組成的化合物群組中的1種以上。這些Tg為0℃以上的單官能的甲基丙烯酸酯單體中，優選烷基的碳原子數為C1~C6的甲基丙烯酸酯單體，更優選烷基的碳原子數為C1~C4的甲基丙烯酸酯單體，特別優選選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯組成的化合物群組中的1種以上。 此外，在合計為100重量份的所述(A)中，優選以合計為5~40重量份的比例、更優選以合計為8~40重量份的比例、特別優選以合計為10~35重量份的比例含有Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上。另外，在以下的說明中，對於單體，簡稱為Tg時有時指的是均聚物的Tg。The acrylic polymer preferably contains 2-ethylhexyl acrylate in a proportion of 50 parts by weight or more in a total of 100 parts by weight of the (A), and a homopolymer in a proportion of 5 to 40 parts by weight in total. The Tg of the product is at least one of the monofunctional methacrylate monomers at 0°C or higher. In addition, in the total of 100 parts by weight of (A), it is preferable to contain 2-ethyl acrylate in a ratio of 50 parts by weight or more, more preferably in a ratio of 60 parts by weight or more, and particularly preferably in a ratio of 70 parts by weight or more. Hexyl ester. In addition, as the monofunctional methacrylate monomer having a Tg of 0°C or higher in the alkyl (meth)acrylate having C1 to C10 carbon atoms of the alkyl group (A), selected from N-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, ethyl methacrylate, Methyl methacrylate, n-pentyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dimethacrylate One or more of the compound group consisting of cyclopentyl ester. Among these monofunctional methacrylate monomers with a Tg of 0°C or higher, methacrylate monomers with C1 to C6 carbon atoms in the alkyl group are preferred, and those with C1 to C4 carbon atoms in the alkyl group are more preferred. Methacrylate monomers, particularly preferably selected from n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, n-propyl methacrylate, methyl One or more of the compound group consisting of isopropyl acrylate, ethyl methacrylate, and methyl methacrylate. In addition, in the total of 100 parts by weight of (A), it is preferable to have a total of 5 to 40 parts by weight, more preferably a total of 8 to 40 parts by weight, and particularly preferably a total of 10 to 35 parts by weight. The ratio of parts contains 1 or more types of monofunctional methacrylate monomers whose Tg is 0 degreeC or more. In addition, in the following description, when a monomer is simply referred to as Tg, it may refer to the Tg of a homopolymer.

作為用於所述丙烯酸類聚合物的(B)含有羥基的可共聚單體，優選選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等組成的化合物群組中的至少1種以上。 相對於合計為100重量份的所述(A)，所述丙烯酸類聚合物優選以合計為1.0~6.0重量份的比例、更優選以合計為2.0~6.0重量份的比例、特別優選以合計為2.5~5.5重量份的比例含有所述(B)含有羥基的可共聚單體中的至少1種以上。The (B) hydroxyl-containing copolymerizable monomer used in the acrylic polymer is preferably selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and (meth) 4-hydroxybutyl acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(methyl) ) At least one or more of the compound group consisting of acrylamide and the like. With respect to the total of 100 parts by weight of the (A), the acrylic polymer is preferably in a ratio of 1.0 to 6.0 parts by weight in total, more preferably in a ratio of 2.0 to 6.0 parts by weight in total, and particularly preferably in total. At least one of the above-mentioned (B) hydroxyl-containing copolymerizable monomers is contained in a ratio of 2.5 to 5.5 parts by weight.

優選所述丙烯酸類聚合物共聚有(F)構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體。進一步，也可將所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，作為與所述丙烯酸類聚合物不同的成分而添加至黏著劑組合物中。在任意情況下，所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體均可作為抗靜電助劑而發揮功能。Preferably, the acrylic polymer is copolymerized with (F) a polyalkylene glycol chain-containing mono(meth)acrylate monomer constituting a polyalkylene glycol chain. Further, the polyalkylene glycol chain-containing mono(meth)acrylate monomer may be added to the adhesive composition as a component different from the acrylic polymer. In any case, the polyalkylene glycol chain-containing mono(meth)acrylate monomer can function as an antistatic auxiliary agent.

作為所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，只要為聚伸烷基二醇所具有的多個羥基中的一個羥基被酯化成作為(甲基)丙烯酸酯的化合物即可。由於(甲基)丙烯酸酯基為聚合性基團，因此能夠與所述丙烯酸類聚合物共聚。可以是其他羥基仍為OH的聚伸烷基二醇單(甲基)丙烯酸酯，也可以是其他羥基被轉化為烷基醚的烷氧基聚伸烷基二醇單(甲基)丙烯酸酯等。另外，由於聚伸烷基二醇單(甲基)丙烯酸酯對應於所述(F)，因此即使含有羥基，也不會被歸類為所述(B)。As the polyalkylene glycol chain-containing mono(meth)acrylate monomer, as long as one of the multiple hydroxyl groups possessed by the polyalkylene glycol is esterified as a (meth)acrylate The compound can be. Since the (meth)acrylate group is a polymerizable group, it can be copolymerized with the acrylic polymer. It can be other polyalkylene glycol mono(meth)acrylates whose hydroxyl groups are still OH, or alkoxy polyalkylene glycol mono(meth)acrylates whose other hydroxyl groups are converted to alkyl ethers Wait. In addition, since polyalkylene glycol mono(meth)acrylate corresponds to (F), even if it contains a hydroxyl group, it will not be classified as (B).

作為構成所述聚伸烷基二醇鏈的聚伸烷基二醇，只要為具有1種或2種以上的伸烷基(alkylene)的二醇化合物即可，例如可列舉出聚乙二醇、聚丙二醇、聚丁二醇、聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇、聚乙二醇-聚丙二醇-聚丁二醇等。As the polyalkylene glycol constituting the polyalkylene glycol chain, any diol compound having one or more kinds of alkylene (alkylene) may be used, for example, polyethylene glycol , Polypropylene glycol, polybutylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-polybutylene glycol, etc.

優選所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的構成聚伸烷基二醇鏈的環氧烷的平均重複數為3~14。“環氧烷的平均重複數”是指，在所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體的分子結構所包含的“聚伸烷基二醇鏈”的部分中，環氧烷單元重複的平均數。 此外，所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的二酯組分優選為0.2%以下。“單體中的二酯組分”是指，所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中包含的聚伸烷基二醇二(甲基)丙烯酸酯的含有率(重量%)。It is preferable that the average repeating number of the alkylene oxide constituting the polyalkylene glycol chain in the polyalkylene glycol chain-containing mono(meth)acrylate monomer is 3-14. The "average repeating number of alkylene oxide" refers to the part of the "polyalkylene glycol chain" contained in the molecular structure of the polyalkylene glycol chain-containing mono(meth)acrylate monomer In, the average number of repeating alkylene oxide units. In addition, the diester component in the polyalkylene glycol chain-containing mono(meth)acrylate monomer is preferably 0.2% or less. "The diester component in the monomer" refers to the polyalkylene glycol di(meth)acrylate contained in the polyalkylene glycol chain-containing mono(meth)acrylate monomer Content rate (weight%).

作為所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，優選選自由聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯組成的群組中的至少1種以上。As the polyalkylene glycol chain-containing mono(meth)acrylate monomer, it is preferably selected from polyalkylene glycol mono(meth)acrylate, methoxy polyalkylene glycol (meth) At least one of the group consisting of oxy)acrylate and ethoxy polyalkylene glycol (meth)acrylate.

相對於合計為100重量份的所述(A)，所述丙烯酸類聚合物優選以1~50重量份的比例、更優選以1~35重量份的比例、特別優選以1~25重量份的比例共聚有作為所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體的、選自由聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯組成的群組中的至少1種以上。With respect to the total of 100 parts by weight of (A), the acrylic polymer is preferably in a ratio of 1 to 50 parts by weight, more preferably in a ratio of 1 to 35 parts by weight, and particularly preferably in a ratio of 1 to 25 parts by weight. The ratio copolymer has as the polyalkylene glycol chain-containing mono(meth)acrylate monomer, selected from polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene two At least one of the group consisting of alcohol (meth)acrylate and ethoxy polyalkylene glycol (meth)acrylate.

所述丙烯酸類聚合物的製備方法沒有特別限定，可使用溶液聚合法、乳液聚合法等適宜且公知的聚合方法。優選所述丙烯酸類聚合物的重均分子量超過30萬且為100萬以下。此外，所述丙烯酸類聚合物為以不含有具有羧基的可共聚單體的方式共聚而成的丙烯酸類聚合物。所述丙烯酸類聚合物的酸值優選為0.1~1.0。由此，能夠改善抗污染性能。此處，“酸值”是表示酸含量的指標之一，以中和1g含有羧基的聚合物所需要的氫氧化鉀的mg數來表示。The preparation method of the acrylic polymer is not particularly limited, and suitable and well-known polymerization methods such as a solution polymerization method and an emulsion polymerization method can be used. Preferably, the weight average molecular weight of the acrylic polymer exceeds 300,000 and is 1 million or less. In addition, the acrylic polymer is an acrylic polymer copolymerized so as not to contain a copolymerizable monomer having a carboxyl group. The acid value of the acrylic polymer is preferably 0.1 to 1.0. Thus, the anti-pollution performance can be improved. Here, the "acid value" is one of the indexes indicating the acid content, and is expressed in mg of potassium hydroxide required to neutralize 1 g of the carboxyl group-containing polymer.

本實施方式的黏著劑組合物進一步含有(C)三官能以上的異氰酸酯化合物作為交聯劑。作為(C)三官能以上的異氰酸酯化合物，例如可列舉出六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯基(xylyene)二異氰酸酯等二異氰酸酯類的縮二脲改質體、異氰脲酸酯改質體等、與三羥甲基丙烷、甘油等3價以上的多元醇的加成物等。作為(C)三官能以上的異氰酸酯化合物的比例，例如相對於100重量份的所述丙烯酸類聚合物，優選以0.1~10重量份的比例、更優選以0.1~6重量份的比例含有(C)三官能以上的異氰酸酯化合物。The adhesive composition of this embodiment further contains (C) a trifunctional or higher isocyanate compound as a crosslinking agent. (C) Trifunctional or higher isocyanate compounds include, for example, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, etc. Biuret-modified isocyanate, isocyanurate-modified, etc., adducts with trimethylolpropane, glycerin, and the like with trivalent or higher polyols, etc. As the ratio of (C) trifunctional or higher isocyanate compound, for example, relative to 100 parts by weight of the acrylic polymer, it is preferably contained in a ratio of 0.1 to 10 parts by weight, more preferably in a ratio of 0.1 to 6 parts by weight (C ) An isocyanate compound having three or more functions.

本實施方式的黏著劑組合物含有(D)交聯延遲劑。作為(D)交聯延遲劑，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯(oleyl acetoacetate)、乙醯乙酸月桂酯、乙醯乙酸十八烷基酯等的β-酮酯，或者乙醯丙酮、2,4-己二酮、苯甲醯丙酮等的β-二酮。這些(D)交聯延遲劑為酮-烯醇互變異構體的化合物，通過對(C)三官能以上的異氰酸酯化合物所具有的異氰酸酯基進行嵌段(block)，能夠抑制摻合交聯劑後的黏著劑組合物的過度的黏度上升及凝膠化，能夠延長黏著劑組合物的貯存期(pot-life)。(D)交聯延遲劑特別優選為選自由乙醯丙酮、乙醯乙酸乙酯組成的化合物群組中的至少1種以上。相對於100重量份的所述丙烯酸類聚合物，優選以0.1~300重量份的比例含有(D)交聯延遲劑。The adhesive composition of this embodiment contains (D) a crosslinking retarder. (D) The crosslinking retarder includes methyl acetylacetate, ethyl acetylacetate, octyl acetylacetate, oleyl acetoacetate, lauryl acetoacetate, and acetylacetate. Β-keto esters such as octadecyl ester, or β-diketones such as acetone, 2,4-hexanedione, and benzacetone. These (D) crosslinking retarders are compounds of keto-enol tautomers, and by blocking the isocyanate group of the (C) trifunctional or higher isocyanate compound, the blending of the crosslinking agent can be suppressed The excessive viscosity rise and gelation of the adhesive composition after that can prolong the pot-life of the adhesive composition. (D) The crosslinking retarder is particularly preferably at least one compound selected from the group consisting of acetone and ethyl acetone. The (D) crosslinking retarder is preferably contained in a ratio of 0.1 to 300 parts by weight with respect to 100 parts by weight of the acrylic polymer.

本實施方式的黏著劑組合物含有除錫化物以外的交聯促進劑作為(E)交聯促進劑。當將(C)三官能以上的異氰酸酯化合物作為交聯劑時，(E)交聯促進劑只要為對丙烯酸類聚合物與交聯劑的反應(交聯反應)作為催化劑而發揮功能的物質即可。作為(E)交聯促進劑，優選金屬螯合化合物。金屬螯合化合物為在中心金屬原子M上鍵合有1個以上的多齒配體(multidentate ligand)L的化合物。金屬螯合化合物可以具有鍵合於金屬原子M上的1個以上的單齒配體X，也可以不具有鍵合於金屬原子M上的單齒配體X。作為金屬螯合化合物的具體實例，可列舉出參(2,4-戊二酮)鐵(III)、參乙醯丙酮鐵、參乙醯丙酮鈦、參乙醯丙酮釕、雙乙醯丙酮鋅、參乙醯丙酮鋁、肆乙醯丙酮鋯、參(2,4-己二酮)鐵(III)、雙(2,4-己二酮)鋅、參(2,4-己二酮)鈦、參(2,4-己二酮)鋁、肆(2,4-己二酮)鋯等。The adhesive composition of the present embodiment contains a crosslinking accelerator other than the tin compound as the (E) crosslinking accelerator. When (C) a trifunctional or higher isocyanate compound is used as a cross-linking agent, the (E) cross-linking accelerator is a substance that functions as a catalyst for the reaction between the acrylic polymer and the cross-linking agent (cross-linking reaction). can. (E) The crosslinking accelerator is preferably a metal chelate compound. The metal chelate compound is a compound in which more than one multidentate ligand L is bonded to the central metal atom M. The metal chelate compound may have one or more monodentate ligands X bonded to the metal atom M, or may not have the monodentate ligand X bonded to the metal atom M. As specific examples of the metal chelate compound, ginseng (2,4-pentanedione) iron (III), iron ginseng acetone, titanium ginseng acetone, ruthenium ginseng acetone, zinc diacetone , Ginseng aluminum acetone, zirconium acetone, ginseng (2,4-hexanedione) iron (III), bis(2,4-hexanedione) zinc, ginseng (2,4-hexanedione) Titanium, ginseng (2,4-hexanedione) aluminum, Si (2,4-hexanedione) zirconium, etc.

作為(E)交聯促進劑，優選選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少1種以上的金屬螯合化合物。相對於100重量份的所述丙烯酸類聚合物，優選以0.001~0.5重量份的比例含有(E)交聯促進劑。(E) The crosslinking accelerator is preferably at least one metal chelate compound selected from the group consisting of an aluminum chelate compound, a titanium chelate compound, and an iron chelate compound. The (E) crosslinking accelerator is preferably contained in a ratio of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer.

(D)交聯延遲劑與(E)交聯促進劑相反，其具有抑制交聯的效果，因此優選適當地設定(D)交聯延遲劑與(E)交聯促進劑的比例。為了延長黏著劑組合物的貯存期、提高貯藏穩定性，(D)/(E)的重量份比優選為80~1000，更優選為80~700，特別優選為80~300。此處，(D)/(E)的重量份比是指(D)的重量份除以(E)的重量份而得到的商的值。The (D) cross-linking retarder is opposite to the (E) cross-linking accelerator, and has an effect of suppressing cross-linking. Therefore, it is preferable to appropriately set the ratio of the (D) cross-linking retarder to the (E) cross-linking accelerator. In order to extend the shelf life of the adhesive composition and improve the storage stability, the weight ratio of (D)/(E) is preferably 80 to 1,000, more preferably 80 to 700, and particularly preferably 80 to 300. Here, the weight part ratio of (D)/(E) means the value of the quotient obtained by dividing the weight part of (D) by the weight part of (E).

本實施方式的黏著劑組合物還可以含有(G)聚醚改質矽氧烷化合物作為任意成分。所述聚醚改質矽氧烷化合物為具有聚醚基的矽氧烷化合物，除了具有通常的矽氧烷單元[-SiR1 2 -O-]以外，還具有聚醚基的矽氧烷單元[-SiR1 (R2 O(R3 O)n R4 )-O-]。此處，R1 表示1種或2種以上的烷基或芳基、R2 及R3 表示1種或2種以上的伸烷基、R4 表示1種或2種以上的烷基、醯基等(末端基團)。作為聚醚基，可列舉出聚氧伸乙基[(C2 H4 O)n ]或聚氧伸丙基[(C3 H6 O)n ]等聚氧伸烷基。在具有聚醚基的矽氧烷單元中，聚醚基的末端可以為OH基(上述通式中R4 =H)。The adhesive composition of the present embodiment may further contain (G) a polyether-modified silicone compound as an optional component. The polyether-modified siloxane compound is a siloxane compound with a polyether group, in addition to the usual siloxane unit [-SiR 1 2 -O-], it also has a polyether group siloxane unit [-SiR 1 (R 2 O(R 3 O) n R 4 )-O-]. Here, R 1 represents one or more types of alkyl or aryl groups, R 2 and R 3 represent one or more types of alkylene groups, and R 4 represents one or more types of alkyl groups or aryl groups. Group etc. (terminal group). Examples of the polyether group include polyoxyalkylene groups such as polyoxyethylene groups [(C 2 H 4 O) n ] or polyoxypropylene groups [(C 3 H 6 O) n ]. In the silicone unit having a polyether group, the end of the polyether group may be an OH group (R 4 =H in the above general formula).

優選所述聚醚改質矽氧烷化合物為HLB值為6~12的聚醚改質矽氧烷化合物。此外，相對於100重量份的所述丙烯酸類聚合物，優選以0.01~0.5重量份的比例、更優選以0.02~0.35重量份的比例、特別優選以0.02~0.25重量份的比例含有所述聚醚改質矽氧烷化合物。HLB值是指例如JIS K3211(界面活性劑用語)等中規定的親水親油平衡值(親水親油比)。Preferably, the polyether-modified siloxane compound is a polyether-modified siloxane compound with an HLB value of 6-12. In addition, relative to 100 parts by weight of the acrylic polymer, the polymer is preferably contained in a ratio of 0.01 to 0.5 parts by weight, more preferably in a ratio of 0.02 to 0.35 parts by weight, and particularly preferably in a ratio of 0.02 to 0.25 parts by weight. Ether upgrades siloxane compounds. The HLB value refers to, for example, the hydrophilic-lipophilic balance value (hydrophilic-lipophilic ratio) specified in JIS K3211 (terms of surfactants).

所述聚醚改質矽氧烷化合物例如能夠通過以下方式得到：利用氫化矽烷化反應，使具有不飽和鍵及聚氧伸烷基的有機化合物接枝(grafting)於具有氫化矽基的聚有機矽氧烷主鏈。具體而言，可列舉出二甲基矽氧烷-甲基(聚氧亞乙基)矽氧烷共聚物、二甲基矽氧烷-甲基(聚氧亞乙基)矽氧烷-甲基(聚氧亞丙基)矽氧烷共聚物、二甲基矽氧烷-甲基(聚氧亞丙基)矽氧烷聚合物等。The polyether-modified siloxane compound can be obtained, for example, by using a hydrosilylation reaction to graft an organic compound having an unsaturated bond and a polyoxyalkylene group onto a polyorganohydride group. The siloxane backbone. Specifically, dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane-methyl(polyoxyethylene)siloxane-methanone Base (polyoxypropylene) silicone copolymer, dimethylsiloxane-methyl (polyoxypropylene) silicone polymer, etc.

通過將所述聚醚改質矽氧烷化合物摻合於黏著劑組合物，能夠改善黏著劑層的黏著力及再操作性能。所述聚醚改質矽氧烷化合物的重均分子量優選為10000以下。從與所述丙烯酸類聚合物的相容性的角度出發，雖然HLB值低且分子量低時相容性更良好，但為分子量低的聚醚改質矽氧烷化合物時，即使HLB值比較高且與所述丙烯酸類聚合物的相容性略低，也可獲得優異的抗靜電性。By blending the polyether-modified silicone compound into the adhesive composition, the adhesive force and re-operability of the adhesive layer can be improved. The weight average molecular weight of the polyether-modified siloxane compound is preferably 10,000 or less. From the perspective of compatibility with the acrylic polymer, although the HLB value is low and the molecular weight is low, the compatibility is better, but when the siloxane compound is modified with a low molecular weight polyether, even if the HLB value is relatively high And the compatibility with the acrylic polymer is slightly low, and excellent antistatic properties can also be obtained.

本實施方式的黏著劑組成物並不限於摻合上述添加劑，也可適當摻合界面活性劑、固化促進劑、可塑劑、填充劑、固化延遲劑、加工助劑、抗老化劑、抗氧化劑等公知的添加劑。這些添加劑可單獨使用，或者也可同時使用2種以上。The adhesive composition of this embodiment is not limited to blending the above-mentioned additives, and surfactants, curing accelerators, plasticizers, fillers, curing retarders, processing aids, anti-aging agents, antioxidants, etc. may also be appropriately blended. Well-known additives. These additives may be used alone, or two or more of them may be used at the same time.

用於本實施方式的抗靜電表面保護膜10的黏著劑層2的厚度雖然沒有特別限定，例如優選為5~40μm左右的厚度，更優選為10~30μm左右的厚度。當黏著劑層2具有抗靜電表面保護膜對被黏物的表面的剝離強度(黏著力)為0.03~0.3N/25mm左右的微黏著力時，將抗靜電表面保護膜從被黏物上剝離時的操作性優異，故而優選。此外，由於從抗靜電表面保護膜10上剝離剝離膜5時的操作性優異，因此將剝離膜5從黏著劑層2上剝離的剝離力優選為0.2N/50mm以下。Although the thickness of the adhesive layer 2 used for the antistatic surface protection film 10 of this embodiment is not specifically limited, For example, the thickness of about 5-40 micrometers is preferable, and the thickness of about 10-30 micrometers is more preferable. When the adhesive layer 2 has a micro-adhesion strength (adhesion) of the antistatic surface protective film to the surface of the adherend of about 0.03~0.3N/25mm, peel the antistatic surface protective film from the adherend The operability at this time is excellent, so it is preferable. In addition, since the workability when peeling the peeling film 5 from the antistatic surface protective film 10 is excellent, the peeling force for peeling the peeling film 5 from the adhesive layer 2 is preferably 0.2 N/50 mm or less.

此外，對於用於本實施方式的抗靜電表面保護膜10的剝離膜5，其利用樹脂組合物在樹脂膜3的單面上形成有剝離劑層4，所述樹脂組合物包含以二甲基聚矽氧烷為主要成分的剝離劑、在20℃下為液體的矽酮類化合物及抗靜電劑。In addition, with regard to the release film 5 used in the antistatic surface protection film 10 of this embodiment, the release agent layer 4 is formed on one side of the resin film 3 using a resin composition containing a dimethyl Polysiloxane as the main component of the release agent, the silicone compound and antistatic agent that are liquid at 20°C.

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，但由於透明性優異及價格比較便宜，因此特別優選聚酯膜。樹脂膜可以為無拉伸膜，也可以為經單軸或雙軸拉伸的膜。此外，還可以將拉伸膜的拉伸倍率、或伴隨拉伸膜的結晶化而形成的軸方向的取向角度控制為特定的值。 樹脂膜3的厚度沒有特別限定，例如優選為12~100μm左右的厚度，若為20~50μm左右的厚度，則容易操作，更加優選。 此外，可根據需要，對樹脂膜3的表面實施基於電暈放電的表面改質、錨固劑的塗覆等易黏合處理。As the resin film 3, a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a polyimide film, etc. can be mentioned. However, since it is excellent in transparency and relatively inexpensive, a polyester film is particularly preferred. The resin film may be a non-stretched film, or a uniaxially or biaxially stretched film. In addition, the stretching magnification of the stretched film or the orientation angle in the axial direction formed with the crystallization of the stretched film may be controlled to a specific value. The thickness of the resin film 3 is not particularly limited. For example, it is preferably a thickness of about 12 to 100 μm, and if it is a thickness of about 20 to 50 μm, handling is easy, which is more preferable. In addition, the surface of the resin film 3 may be subjected to an easy adhesion treatment such as surface modification by corona discharge and coating of an anchoring agent as needed.

對於構成剝離劑層4的以二甲基聚矽氧烷為主要成分的剝離劑，可列舉出加成反應型、縮合反應型、陽離子聚合型、自由基聚合型等公知的矽酮類剝離劑。作為加成反應型矽酮類剝離劑而市售的產品，例如可列舉出KS-776A、KS-847T、KS-779H、KS-837、KS-778、KS-830(Shin-Etsu Chemical Co.,Ltd.製造)、SRX-211、SRX-345、SRX-357、SD7333、SD7220、SD7223、LTC-300B、LTC-350G、LTC-310(Dow Corning Toray Co.,Ltd.製造)等。作為縮合反應型而市售的產品，例如可列舉出SRX-290、SYLOFF-23(Dow Corning Toray Co.,Ltd.製造)等。作為陽離子聚合型而市售的產品，例如可列舉出TPR-6501、TPR-6500、UV9300、VU9315、UV9430(Momentive Performance Materials Inc.製造)、X62-7622(Shin-Etsu Chemical Co.,Ltd.製造)等。作為自由基聚合型而市售的產品，例如可列舉出X62-7205(Shin-Etsu Chemical Co.,Ltd.製造)等。For the release agent comprising dimethylpolysiloxane as the main component of the release agent layer 4, known silicone-based release agents such as addition reaction type, condensation reaction type, cationic polymerization type, and radical polymerization type can be cited. . Commercially available products as addition reaction type silicone release agents include, for example, KS-776A, KS-847T, KS-779H, KS-837, KS-778, and KS-830 (Shin-Etsu Chemical Co. , Ltd.), SRX-211, SRX-345, SRX-357, SD7333, SD7220, SD7223, LTC-300B, LTC-350G, LTC-310 (manufactured by Dow Corning Toray Co., Ltd.), etc. As a product that is commercially available as a condensation reaction type, for example, SRX-290, SYLOFF-23 (manufactured by Dow Corning Toray Co., Ltd.) and the like can be cited. Commercially available products of the cationic polymerization type include, for example, TPR-6501, TPR-6500, UV9300, VU9315, UV9430 (manufactured by Momentive Performance Materials Inc.), and X62-7622 (manufactured by Shin-Etsu Chemical Co., Ltd.) )Wait. As a radical polymerization type commercially available product, for example, X62-7205 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be cited.

作為構成剝離劑層4的在20℃下為液體的矽酮類化合物，可列舉出聚醚改質矽酮、烷基改質矽酮、甲醇(carbinol)高級脂肪酸酯改質矽酮等。本實施方式中，為了提高黏著劑層的表面的抗靜電性，可使用處於相容於以二甲基聚矽氧烷為主要成分的剝離劑層中的狀態，且在20℃下為液體的矽酮類化合物。就本實施方式的用途而言，在改質矽酮化合物中，優選聚醚改質矽酮。聚醚改質矽酮中的聚醚鏈由環氧乙烷、環氧丙烷等構成，例如通過選擇用於側鏈的聚環氧乙烷的分子量，可調節與矽酮剝離劑的相容性、或抗靜電效果等的物性。 此外，作為聚醚改質矽酮而市售的產品，例如可列舉出KF-351A、KF-352A、KF-353、KF-354L、KF-355A、KF-642(Shin-Etsu Chemical Co.,Ltd.製造)、SH8400、SH8700、SF8410(Dow Corning Toray Co.,Ltd.製造)、TSF-4440、TSF-4441、TSF-4445、TSF-4446、TSF-4450(Momentive Performance Materials Inc.製造)、BYK-300、BYK-306、BYK-307、BYK-320、BYK-325、BYK-330(BYK Japan KK.製造)等。 在20℃下為液體的矽酮類化合物相對於以二甲基聚矽氧烷為主要成分的剝離劑的添加量，因矽酮化合物的種類、或與剝離劑的相容性的程度等而不同，考慮將抗靜電表面保護膜從被黏物上剝離時所期望的剝離靜電壓、對被黏物的抗污染性能、黏著特性等而設定即可。Examples of the silicone compound constituting the release agent layer 4 that are liquid at 20° C. include polyether-modified silicone, alkyl-modified silicone, carbinol higher fatty acid ester-modified silicone, and the like. In this embodiment, in order to improve the antistatic property of the surface of the adhesive layer, it is possible to use a release agent layer that is compatible with a release agent layer containing dimethylpolysiloxane as the main component and is liquid at 20°C. Silicone compounds. Regarding the use of the present embodiment, among the modified silicone compounds, polyether modified silicone is preferred. The polyether chain in polyether modified silicone is composed of ethylene oxide, propylene oxide, etc. For example, by selecting the molecular weight of the polyethylene oxide used for the side chain, the compatibility with the silicone release agent can be adjusted , Or antistatic effect and other physical properties. In addition, products that are commercially available as polyether modified silicones include, for example, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, and KF-642 (Shin-Etsu Chemical Co., Ltd.), SH8400, SH8700, SF8410 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4441, TSF-4445, TSF-4446, TSF-4450 (manufactured by Momentive Performance Materials Inc.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330 (manufactured by BYK Japan KK.), etc. The amount of silicone compound that is liquid at 20°C relative to the release agent mainly composed of dimethylpolysiloxane depends on the type of silicone compound or the degree of compatibility with the release agent. It is different, considering the expected peeling static voltage when peeling the antistatic surface protective film from the adherend, the anti-fouling performance to the adherend, the adhesion characteristics, etc., and it can be set.

作為構成剝離劑層4的抗靜電劑，優選在以二甲基聚矽氧烷為主要成分的剝離劑溶液中的分散性良好、且不阻礙以二甲基聚矽氧烷為主要成分的剝離劑的固化的抗靜電劑。作為這樣的抗靜電劑，鹼金屬鹽較為適宜。作為所述鹼金屬鹽，可列舉出由鋰、鈉、鉀組成的金屬鹽。具體而言，例如可適宜地使用由Li+ 、Na+ 、K+ 組成的陽離子與由Cl- 、Br- 、I- 、BF4 - 、PF6 - 、SCN- 、ClO4 - 、CF3 SO3 - 、(FSO2 )2 N- 、(CF3 SO2 )2 N- 、(C2 F5 SO2 )2 N- 、(CF3 SO2 )3 C- 組成的陰離子構成的金屬鹽。特別優選：剝離劑層4中的抗靜電劑為Li鹽，為選自由LiTFSI、LiFSI、LiTF組成的化合物群組中的至少1種以上。此處，LiTFSI表示Li(CF3 SO2 )2 N。此外，LiFSI表示Li(FSO2 )2 N。此外，LiTF表示LiCF3 SO3 。這些鹼金屬鹽可以單獨使用，也可以混合使用2種以上。為了離子性物質的穩定化，可添加含有聚氧伸烷基結構的化合物。 抗靜電劑相對於以二甲基聚矽氧烷為主要成分的剝離劑的添加量，因抗靜電劑的種類、或與剝離劑的親和性的程度等而不同，考慮將抗靜電表面保護膜從被黏物上剝離時所期望的剝離靜電壓、對被黏物的抗污染性能、黏著特性等而設定即可。As the antistatic agent constituting the release agent layer 4, it is preferable that the dispersibility in a release agent solution containing dimethylpolysiloxane as the main component is good and does not hinder the release of dimethylpolysiloxane as the main component. Antistatic agent for curing agent. As such an antistatic agent, alkali metal salts are suitable. Examples of the alkali metal salt include metal salts composed of lithium, sodium, and potassium. Specifically, for example, can be suitably used by the Li +, Na +, K + cation and a Cl -, Br -, I - , BF 4 -, PF 6 -, SCN -, ClO 4 -, CF 3 SO 3 -, (FSO 2) 2 N -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) 3 C - anion of the metal salt thereof. It is particularly preferable that the antistatic agent in the release agent layer 4 is a Li salt, which is at least one compound selected from the group consisting of LiTFSI, LiFSI, and LiTF. Here, LiTFSI means Li(CF 3 SO 2 ) 2 N. In addition, LiFSI means Li(FSO 2 ) 2 N. In addition, LiTF means LiCF 3 SO 3 . These alkali metal salts may be used alone or in combination of two or more kinds. In order to stabilize the ionic substance, a compound containing a polyoxyalkylene structure can be added. The amount of antistatic agent added to the release agent with dimethylpolysiloxane as the main component is different depending on the type of antistatic agent, or the degree of affinity with the release agent, etc., consider using the antistatic surface protective film The desired peeling static voltage when peeling from the adherend, the anti-pollution performance to the adherend, the adhesion characteristics, etc. can be set.

以二甲基聚矽氧烷為主要成分的剝離劑與聚醚改質矽酮及抗靜電劑的混合方法沒有特別限定。可以為下述方法中的任意一種方法：向以二甲基聚矽氧烷為主要成分的剝離劑中添加聚醚改質矽酮及抗靜電劑並進行混合後，添加並混合剝離劑固化用的催化劑的方法；預先用有機溶劑稀釋以二甲基聚矽氧烷為主要成分的剝離劑，然後添加、混合聚醚改質矽酮及抗靜電劑與剝離劑固化用的催化劑的方法；預先將以矽氧烷為主要成分的剝離劑稀釋於有機溶劑後，添加並混合催化劑，然後添加、混合聚醚改質矽酮與抗靜電劑的方法等。此外，可根據需要添加矽烷偶聯劑等密合改進劑、或輔助含有聚氧伸烷基的化合物等的抗靜電效果的材料等。The mixing method of the release agent containing dimethylpolysiloxane as the main component, the polyether modified silicone, and the antistatic agent is not particularly limited. It can be any of the following methods: add polyether modified silicone and antistatic agent to the release agent with dimethylpolysiloxane as the main component and mix them, then add and mix the release agent for curing The method of the catalyst; the method of pre-diluting the release agent with dimethylpolysiloxane as the main component with an organic solvent, and then adding and mixing the polyether modified silicone and the antistatic agent and the catalyst for curing of the release agent; After diluting the release agent with silicone as the main component in an organic solvent, adding and mixing the catalyst, then adding and mixing the polyether modified silicone and antistatic agent. In addition, if necessary, an adhesion improver such as a silane coupling agent, or a material that assists the antistatic effect of a polyoxyalkylene group-containing compound or the like can be added.

以二甲基聚矽氧烷為主要成分的剝離劑與聚醚改質矽酮及抗靜電劑的混合比沒有特別限定，相對於100重量份的以二甲基聚矽氧烷為主要成分的剝離劑的固體成分，優選聚醚改質矽酮及抗靜電劑以固體成分計為5~100重量份左右的重量比。相對於100重量份的以二甲基聚矽氧烷為主要成分的剝離劑的固體成分，若聚醚改質矽酮及抗靜電劑的固體成分換算的添加量為少於5重量份的比例，則抗靜電劑在黏著劑層的表面的轉印量也變少，難以在黏著劑中發揮抗靜電的功能。此外，相對於100重量份的以二甲基聚矽氧烷為主要成分的剝離劑的固體成分，若聚醚改質矽酮及抗靜電劑的固體成分換算的添加量為超過100重量份的比例，則以二甲基聚矽氧烷為主要成分的剝離劑也會與聚醚改質矽酮及抗靜電劑一同轉印至黏著劑層的表面，因此存在使黏著劑的黏著特性降低的可能性。The mixing ratio of the release agent with dimethylpolysiloxane as the main component, polyether modified silicone and antistatic agent is not particularly limited, relative to 100 parts by weight of dimethylpolysiloxane as the main component The solid content of the release agent preferably has a weight ratio of about 5 to 100 parts by weight in terms of the solid content of the polyether modified silicone and the antistatic agent. Relative to 100 parts by weight of the solid content of the release agent with dimethylpolysiloxane as the main component, if the added amount of the solid content of the polyether modified silicone and antistatic agent is less than 5 parts by weight , The transfer amount of the antistatic agent on the surface of the adhesive layer is also reduced, and it is difficult to exert the antistatic function in the adhesive. In addition, relative to 100 parts by weight of the solid content of the release agent with dimethylpolysiloxane as the main component, if the addition amount of the solid content of the polyether modified silicone and antistatic agent is more than 100 parts by weight Ratio, the release agent with dimethylpolysiloxane as the main component will also be transferred to the surface of the adhesive layer together with polyether modified silicone and antistatic agent, so there is the possibility of reducing the adhesive properties of the adhesive. possibility.

利用公知的方法進行在本實施方式的抗靜電表面保護膜10的基材膜1上形成黏著劑層2的方法及貼合剝離膜5的方法即可，沒有特別限定。具體而言，可列舉出：(1)在基材膜1的單面上塗佈用於形成黏著劑層2的樹脂組合物並進行乾燥而形成黏著劑層，然後貼合剝離膜5的方法；(2)在剝離膜5的表面上塗佈用於形成黏著劑層2的樹脂組合物並進行乾燥而形成黏著劑層，然後貼合基材膜1的方法等，可使用任意一種方法。The method of forming the adhesive layer 2 on the base film 1 of the antistatic surface protection film 10 of this embodiment, and the method of bonding the release film 5 should just be performed by a well-known method, and it does not specifically limit. Specifically, examples include: (1) A method of coating a resin composition for forming the adhesive layer 2 on one side of the base film 1 and drying to form an adhesive layer, and then bonding the release film 5 (2) A method of coating the resin composition for forming the adhesive layer 2 on the surface of the release film 5 and drying to form an adhesive layer, and then bonding the base film 1, etc., any method can be used.

此外，利用公知的方法在基材膜1的表面上形成黏著劑層2即可。具體而言，能夠使用反向塗佈(reverse coating)、逗號塗佈(comma coating)、凹版塗佈(gravure coating)、狹縫式擠壓型塗佈(slot-die coating)、邁耶棒塗佈、氣刀塗佈等公知的塗佈方法。 此外，同樣地，利用公知的方法在樹脂膜3上形成剝離劑層4即可。具體而言，能夠使用凹版塗佈、邁耶棒塗佈、氣刀塗佈等公知的塗佈方法。In addition, what is necessary is just to form the adhesive layer 2 on the surface of the base film 1 by a well-known method. Specifically, reverse coating, comma coating, gravure coating, slot-die coating, and Meyer rod coating can be used. Known coating methods such as cloth and air knife coating. In addition, in the same manner, the release agent layer 4 may be formed on the resin film 3 by a known method. Specifically, well-known coating methods such as gravure coating, Meyer bar coating, and air knife coating can be used.

圖2為示出從抗靜電表面保護膜10中剝離了剝離膜5的狀態的剖面圖。通過從圖1所示的抗靜電表面保護膜10中剝離剝離膜5，由此剝離膜5的剝離劑層4中包含的抗靜電劑7的一部分轉印(附著)至抗靜電表面保護膜10的黏著劑層2的表面。因此，圖2中，用符號7的斑點示意性表示已轉印至抗靜電表面保護膜的黏著劑層2的表面的抗靜電劑。 對於本實施方式的抗靜電表面保護膜，將圖2所示的剝離了剝離膜的狀態的抗靜電表面保護膜11貼合於被黏物時，已轉印至該黏著劑層2的表面的抗靜電劑7與被黏物的表面接觸。由此，能夠再次將從被黏物上剝離抗靜電表面保護膜時的剝離靜電壓抑制得較低。另外，除了抗靜電劑7以外，在20℃下為液體的矽酮類化合物也可以從剝離劑層4轉印至黏著劑層2的表面。FIG. 2 is a cross-sectional view showing a state where the release film 5 is peeled from the antistatic surface protection film 10. By peeling the release film 5 from the antistatic surface protection film 10 shown in FIG. 1, a part of the antistatic agent 7 contained in the release agent layer 4 of the release film 5 is transferred (attached) to the antistatic surface protection film 10 The surface of the adhesive layer 2. Therefore, in FIG. 2, the spot with symbol 7 schematically represents the antistatic agent that has been transferred to the surface of the adhesive layer 2 of the antistatic surface protective film. For the antistatic surface protection film of this embodiment, when the antistatic surface protection film 11 in the state where the release film is peeled off as shown in FIG. 2 is attached to the adherend, it has been transferred to the surface of the adhesive layer 2 The antistatic agent 7 is in contact with the surface of the adherend. Thereby, the peeling static voltage when peeling the antistatic surface protective film from the adherend can be suppressed to be low again. In addition to the antistatic agent 7, a silicone compound that is liquid at 20° C. may also be transferred from the release agent layer 4 to the surface of the adhesive layer 2.

圖3為示出本實施方式的光學部件的實施例的剖面圖。 從本實施方式的抗靜電表面保護膜10中剝離剝離膜5而使黏著劑層2露出，以此狀態，經由該黏著劑層2而貼合於作為被黏物的光學部件8。 即，圖3中示出了貼合有本實施方式的抗靜電表面保護膜10的光學部件20。作為光學部件，可列舉出偏振片、相位差板、透鏡膜、相位差板兼用的偏振片、透鏡膜兼用的偏振片等光學用膜。這樣的光學部件可用作液晶顯示面板等液晶顯示裝置、各種計量儀器類的光學系統裝置等的構成構件。此外，作為光學部件，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。特別是能夠適宜地用作，貼合於使用矽酮化合物、或氟化物等對表面進行了防污染處理的低反射處理偏振片(LR偏振片) 、或防眩低反射處理偏振片(AG-LR偏振片)等光學用膜的進行了防污染處理的面的抗靜電表面保護膜。 根據本實施方式的光學部件，將抗靜電表面保護膜10從作為被黏物的光學部件(光學用膜)上剝離去除時，由於能夠將剝離靜電壓抑制得充分地低，因此不會破壞驅動器IC、TFT元件、閘線驅動電路等電路部件，能夠提高製造液晶顯示面板等的步驟的生產效率，確保生產步驟的可靠性。Fig. 3 is a cross-sectional view showing an example of the optical component of the present embodiment. The peeling film 5 is peeled from the antistatic surface protection film 10 of this embodiment, and the adhesive layer 2 is exposed, and in this state, the optical component 8 which is an adherend is bonded via this adhesive layer 2. That is, FIG. 3 shows the optical component 20 to which the antistatic surface protective film 10 of this embodiment is bonded. Examples of optical components include optical films such as a polarizing plate, a retardation plate, a lens film, a polarizing plate that also serves as a retardation plate, and a polarizing plate that also serves as a lens film. Such optical components can be used as constituent members of liquid crystal display devices such as liquid crystal display panels, optical system devices of various measuring instruments, and the like. Moreover, as an optical component, the optical film, such as an antireflection film, a hard coat film, and a transparent conductive film for touch panels, can also be mentioned. In particular, it can be suitably used as a low-reflection treatment polarizer (LR polarizer) or anti-glare and low-reflection treatment polarizer (AG- LR polarizer) and other optical films such as antistatic surface protective film on the anti-fouling surface. According to the optical component of this embodiment, when the antistatic surface protective film 10 is peeled off from the optical component (optical film) as the adherend, since the peeling static voltage can be suppressed sufficiently low, the drive will not be damaged. Circuit components such as ICs, TFT elements, and gate wire drive circuits can improve the production efficiency of the steps of manufacturing liquid crystal display panels and the like, and ensure the reliability of the production steps.

本實施方式的抗靜電表面保護膜10適合作為偏振片用表面保護膜。抗靜電表面保護膜10的黏著劑層2也可貼合於偏振片的起偏鏡的保護層。此處，在偏振片用表面保護膜的用途中，作為被黏物的偏振片的起偏鏡的保護層可列舉出選自由TAC類膜、PMMA類膜、PET類膜組成的群組中的至少1種以上。此處，TAC為三醋酸纖維素的縮寫，PMMA為聚甲基丙烯酸甲酯的縮寫，PET為聚對苯二甲酸乙二酯的縮寫。 此外，在偏振片用表面保護膜的用途中，對作為被黏物的偏振片的起偏鏡的保護層的表面實施的表面處理可以為選自由未處理、AG處理、LR處理、AR處理、AG-LR處理、AG-AR處理組成的群組中的至少1種以上。此處，AG是指防眩(Anti Glare)，LR是指低反射(Low Reflection)，AR是指抗反射(Anti Reflection)。The antistatic surface protection film 10 of this embodiment is suitable as a surface protection film for polarizing plates. The adhesive layer 2 of the antistatic surface protective film 10 may be bonded to the protective layer of the polarizer of the polarizer. Here, in the use of the surface protective film for polarizers, the protective layer of the polarizer of the polarizer as the adherend can be selected from the group consisting of TAC-based films, PMMA-based films, and PET-based films. At least one or more. Here, TAC is an abbreviation for cellulose triacetate, PMMA is an abbreviation for polymethyl methacrylate, and PET is an abbreviation for polyethylene terephthalate. In addition, in the use of the surface protective film for polarizers, the surface treatment applied to the surface of the protective layer of the polarizer of the polarizer as the adherend can be selected from untreated, AG treatment, LR treatment, AR treatment, At least one of the group consisting of AG-LR processing and AG-AR processing. Here, AG means Anti Glare, LR means Low Reflection, and AR means Anti Reflection.

在本實施方式的抗靜電表面保護膜10中，轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2的表面電阻率優選為1.0×10+12 Ω/□以下，更優選為5.0×10+11 Ω/□以下，特別優選為1.0×10+11 Ω/□以下。若黏著劑層2的表面電阻率大，則釋放從被黏物上剝離黏著劑層2時所產生的靜電的性能差。因此，通過使黏著劑層2的表面電阻率充分地小，可降低伴隨從被黏物上剝離黏著劑層2時所產生的靜電而產生的剝離靜電壓，抑制對被黏物造成影響。In the antistatic surface protective film 10 of the present embodiment, the surface resistivity of the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred is preferably 1.0×10 +12 Ω/□ or less, more preferably 5.0×10 +11 Ω/□ or less, particularly preferably 1.0×10 +11 Ω/□ or less. If the surface resistivity of the adhesive layer 2 is large, the performance of discharging static electricity generated when the adhesive layer 2 is peeled from the adherend is poor. Therefore, by making the surface resistivity of the adhesive layer 2 sufficiently small, it is possible to reduce the peeling static voltage caused by static electricity generated when the adhesive layer 2 is peeled from the adherend, and suppress the influence on the adherend.

在本實施方式的抗靜電表面保護膜10中，對於轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2，對使用含有氟化物的低折射率層形成用組合物而形成的低折射率層，黏著劑層2的剝離靜電壓優選在+0.3~-0.3kV的範圍內。作為用於低折射率層形成用組合物的氟化物，可列舉出為氟化烯烴類、氟化乙烯基醚類、氟化(甲基)丙烯酸烷基酯等中的1種或2種以上的聚合物的含氟共聚物、含氟化烷基的矽烷化合物等的縮合物。除了經氟化的單體以外，含氟共聚物中也可共聚有烯烴類、乙烯基醚類、(甲基)丙烯酸酯等未經氟化的單體。低折射率層也可與高折射率層等進行組合而構成防反射層。In the antistatic surface protection film 10 of the present embodiment, for the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred, the use of a fluoride-containing low In the low refractive index layer formed of the composition for forming a refractive index layer, the peeling static voltage of the adhesive layer 2 is preferably in the range of +0.3 to -0.3 kV. Examples of the fluoride used in the composition for forming the low refractive index layer include one or more of fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth)acrylates. Condensates of fluorine-containing copolymers and fluorinated alkyl-containing silane compounds. In addition to fluorinated monomers, non-fluorinated monomers such as olefins, vinyl ethers, and (meth)acrylates can also be copolymerized in the fluorinated copolymer. The low refractive index layer may be combined with a high refractive index layer or the like to form an anti-reflection layer.

測定對低折射率層的剝離靜電壓時，作為用於在表面形成低折射率層的基材，可列舉出PMMA基材及TAC基材。此外，在本實施方式的抗靜電表面保護膜10中，轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2對在PMMA基材及TAC基材的表面未做任何處理的平面(plain)層的剝離靜電壓優選在+0.3~-0.3kV的範圍內。When measuring the peeling static voltage with respect to the low refractive index layer, examples of the substrate for forming the low refractive index layer on the surface include PMMA substrates and TAC substrates. In addition, in the antistatic surface protection film 10 of this embodiment, the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred is applied to the PMMA substrate and the TAC. The peeling static voltage of the plain layer on the surface of the substrate without any treatment is preferably in the range of +0.3 to -0.3 kV.

優選：將黏著劑層2貼合於偏振片等被黏物後，在溫度為60℃、濕度為90%RH的氛圍下放置2天(48hr)，從所述氛圍下取出，然後經過1天後剝離時沒有污染。作為被黏物，可列舉出在起偏鏡上積層保護層並使用含有氟化物的組合物對保護層的表面進行了低反射表面處理的偏振片。用於低反射表面處理的含有氟化物的組合物可以與上述含有氟化物的低折射率層形成用的樹脂組合物相同，也可以不同。作為保護層及表面處理，可列舉出上述起偏鏡的保護層及對其表面實施的表面處理。具體而言，可列舉出下述偏振片：表面基材為選自由TAC類膜、PMMA類膜、PET類膜組成的組中的1種，且對所述表面基材的表面實施的表面處理為選自由未處理、AG處理、LR處理、AR處理、AG-LR處理、AG-AR處理組成的組中的1種的偏振片。Preferably: after bonding the adhesive layer 2 to an adherend such as a polarizer, leave it for 2 days (48hr) in an atmosphere with a temperature of 60°C and a humidity of 90%RH, take it out from the atmosphere, and then pass for 1 day There is no contamination during post-peeling. Examples of the adherend include a polarizer in which a protective layer is laminated on a polarizer and the surface of the protective layer is treated with a low-reflection surface treatment using a fluoride-containing composition. The fluoride-containing composition used for the low-reflection surface treatment may be the same as or different from the above-mentioned resin composition for forming the fluoride-containing low refractive index layer. Examples of the protective layer and surface treatment include the protective layer of the above-mentioned polarizer and the surface treatment performed on the surface thereof. Specifically, the following polarizers can be cited: the surface substrate is one selected from the group consisting of TAC-based films, PMMA-based films, and PET-based films, and the surface of the surface substrate is subjected to surface treatment It is a polarizing plate selected from the group consisting of untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment.

在本實施方式的抗靜電表面保護膜10中，將轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2以15μm的厚度積層於厚度為38μm的聚酯膜的單面而形成抗靜電表面保護膜10，將該抗靜電表面保護膜10貼合於偏振片的表面後，從所述偏振片上剝離抗靜電表面保護膜10時，優選在低速的剝離速度0.3m/分鐘下的黏著力為0.01~0.1N/25mm、在高速的剝離速度30m/分鐘下的黏著力為1.0N/25mm以下，更優選在高速的剝離速度30m/分鐘下的黏著力為0.2~0.8N/25mm。由此，可獲得黏著力因剝離速度造成的變化小的性能，即使通過高速剝離，也可快速地剝離。此外，即使在為了重新貼合而暫時剝離抗靜電表面保護膜10時，也不需要過大的力，可容易地從被黏物上剝離。In the antistatic surface protection film 10 of this embodiment, the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred is laminated in a thickness of 15 μm. When the antistatic surface protection film 10 is formed on one side of a 38 μm polyester film, and the antistatic surface protection film 10 is attached to the surface of the polarizer, when the antistatic surface protection film 10 is peeled off from the polarizer, it is preferable to The adhesive force at a low-speed peeling speed of 0.3m/min is 0.01~0.1N/25mm, and the adhesive force at a high-speed peeling speed of 30m/min is 1.0N/25mm or less, more preferably at a high-speed peeling speed of 30m/min. The adhesive force is 0.2~0.8N/25mm. As a result, it is possible to obtain a performance with little change in adhesive force due to the peeling speed, and it can be peeled off quickly even by high-speed peeling. In addition, even when the antistatic surface protective film 10 is temporarily peeled off for reattachment, excessive force is not required, and it can be easily peeled off from the adherend.

在本實施方式的抗靜電表面保護膜10中，轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2的凝膠分率優選為95~100%，更優選為97~100%。由於黏著劑層2的凝膠分率如此地高，因此在低速的剝離速度下的黏著力不會變得過大，未聚合單體或低聚物從黏著劑層2中的溶出得以降低，能夠改善再操作性及高溫高濕度下的耐久性，並抑制被黏物的污染。In the antistatic surface protection film 10 of this embodiment, the gel fraction of the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred is preferably 95~ 100%, more preferably 97 to 100%. Since the gel fraction of the adhesive layer 2 is so high, the adhesive force at a low peeling speed will not become too large, and the elution of unpolymerized monomers or oligomers from the adhesive layer 2 can be reduced. Improve reworkability and durability under high temperature and high humidity, and suppress contamination of adherends.

本實施方式的黏著膜在樹脂膜的單面或兩面上形成有使本實施方式的黏著劑組合物交聯而成的黏著劑層。此外，本實施方式的表面保護膜為在樹脂膜的單面上形成有使本實施方式的黏著劑組合物交聯而成的黏著劑層的表面保護膜。本實施方式的表面保護膜通過在黏著劑層2的表面轉印剝離劑層4的抗靜電劑，從而成為抗靜電表面保護膜，並具備優異的抗靜電性能。進一步，在低速的剝離速度與高速的剝離速度下，本實施方式的抗靜電表面保護膜的黏著力的平衡優異，進一步具有抗污染性能。因此，能夠適宜地用於偏振片的表面保護膜的用途。The adhesive film of this embodiment is formed with the adhesive layer which crosslinked the adhesive composition of this embodiment on one side or both surfaces of a resin film. In addition, the surface protection film of this embodiment is a surface protection film in which the adhesive layer which crosslinked the adhesive composition of this embodiment was formed in the single side|surface of a resin film. The surface protection film of the present embodiment becomes an antistatic surface protection film by transferring the antistatic agent of the release agent layer 4 on the surface of the adhesive layer 2 and has excellent antistatic performance. Furthermore, at the low-speed peeling speed and the high-speed peeling speed, the antistatic surface protection film of this embodiment has an excellent balance of adhesive force, and further has anti-fouling performance. Therefore, it can be suitably used for the use of the surface protection film of a polarizing plate.

此外，通過將轉印有剝離劑層4的抗靜電劑的使所述黏著劑組合物交聯而成的黏著劑層2積層於光學膜的至少一個面，能夠得到帶有黏著劑層的光學膜。作為光學膜，可列舉出偏振膜、相位差膜、防反射膜、防眩(Anti Glare)膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜等。作為光學構件所適用的設備，可列舉出液晶面板、有機EL面板、觸控面板等。 在為偏振片用的表面保護膜等的光學用的表面保護膜及黏著膜的情況下，優選基材膜及黏著劑層具有充分的透明性。 實施例In addition, by laminating the adhesive layer 2 formed by crosslinking the adhesive composition to which the antistatic agent of the release agent layer 4 is transferred on at least one surface of the optical film, an optical film with an adhesive layer can be obtained. membrane. As an optical film, a polarizing film, a retardation film, an anti-reflection film, an anti-glare (Anti Glare) film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, a brightness improvement film, etc. are mentioned. Examples of equipment to which the optical member is applied include liquid crystal panels, organic EL panels, touch panels, and the like. In the case of an optical surface protective film and an adhesive film such as a surface protective film for a polarizer, it is preferable that the base film and the adhesive layer have sufficient transparency. Example

以下，通過實施例對本發明進行具體的說明。Hereinafter, the present invention will be specifically explained through examples.

＜黏著劑組合物的製備＞ [實施例1] 向具備攪拌機、溫度計、回流冷凝器及氮導入管的反應裝置中導入氮氣，從而用氮氣置換反應裝置內的空氣。然後，向反應裝置中同時添加80重量份的丙烯酸2-乙基己酯、20重量份的甲基丙烯酸正丁酯、4.5重量份的丙烯酸8-羥基辛酯、10重量份的聚丙二醇單丙烯酸酯(n=12)以及溶劑(乙酸乙酯)。然後，經2小時滴加0.1重量份的作為聚合引發劑的偶氮二異丁腈，於65℃反應6小時，得到實施例1的丙烯酸類聚合物溶液。向該丙烯酸類聚合物溶液中添加8.5重量份的乙醯丙酮並攪拌後，添加2.0重量份的CORONATE HX(六亞甲基二異氰酸酯化合物的異氰脲酸酯(isocyanurate)體)、0.1重量份的參乙醯丙酮鈦、0.05重量份的聚醚改質矽氧烷化合物(HLB=7)並攪拌混合，得到實施例1的黏著劑組合物。<Preparation of adhesive composition> [Example 1] Nitrogen gas is introduced into a reaction device equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe, and the air in the reaction device is replaced with nitrogen. Then, 80 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of n-butyl methacrylate, 4.5 parts by weight of 8-hydroxyoctyl acrylate, and 10 parts by weight of polypropylene glycol monoacrylic acid were simultaneously added to the reaction device. Ester (n=12) and solvent (ethyl acetate). Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65°C for 6 hours to obtain the acrylic polymer solution of Example 1. After adding 8.5 parts by weight of acetone to the acrylic polymer solution and stirring, 2.0 parts by weight of CORONATE HX (isocyanurate body of hexamethylene diisocyanate compound) and 0.1 parts by weight were added Titanium acetone acetone, 0.05 parts by weight of polyether modified silicone compound (HLB=7) and stirred and mixed to obtain the adhesive composition of Example 1.

[實施例2~6及比較例1~4] 除了將實施例1的黏著劑組合物的組成分別調整為表1中的記載以外，以與實施例1相同的方式得到實施例2~6及比較例1~4的黏著劑組合物。比較例1、2的黏著劑組合物的情況下，進一步向黏著劑組合物中添加表2的“抗靜電劑”所示的化合物。另外，實施例1~6及比較例1~3的丙烯酸類聚合物為重均分子量超過30萬且為100萬以下的共聚物。比較例4的丙烯酸類聚合物為重均分子量為10萬的共聚物。[Examples 2 to 6 and Comparative Examples 1 to 4] Except that the composition of the adhesive composition of Example 1 was adjusted to the description in Table 1, the adhesive compositions of Examples 2 to 6 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1. In the case of the adhesive composition of Comparative Examples 1 and 2, the compound shown in the "antistatic agent" of Table 2 was further added to the adhesive composition. In addition, the acrylic polymers of Examples 1 to 6 and Comparative Examples 1 to 3 are copolymers having a weight average molecular weight of more than 300,000 and 1 million or less. The acrylic polymer of Comparative Example 4 is a copolymer having a weight average molecular weight of 100,000.

在表1的各欄及表2的“抗靜電劑”中，將(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯的合計設為100重量份來求出各成分的重量份。表2的“(D)/(E)”為重量份比。此外，表1的(B)~(G)的各欄中，將作為(A)、(B)、(F)的重量份的合計而計算的丙烯酸類聚合物的重量份設為100重量份，以括弧( )內的數值表示此時各成分的含有比例(重量份)。此外，在表2的“抗靜電劑”中，LiTFSI表示Li(CF3 SO2 )2 N，LiTF表示LiCF3 SO3 。In each column of Table 1 and "Antistatic Agent" of Table 2, the total of (A) alkyl (meth)acrylic acid alkyl esters with C1 to C10 carbon atoms is calculated as 100 parts by weight Parts by weight of each ingredient. "(D)/(E)" in Table 2 is a weight part ratio. In addition, in each column of (B) to (G) in Table 1, the weight part of the acrylic polymer calculated as the total weight part of (A), (B), and (F) is set to 100 parts by weight , The numerical value in parentheses () indicates the content ratio (parts by weight) of each component at this time. In addition, in the "antistatic agent" in Table 2, LiTFSI means Li(CF 3 SO 2 ) 2 N, and LiTF means LiCF 3 SO 3 .

[表1]   (A) (B) (F) (C) (D) (E) (G) 實施例1 2EHA 80 BMA 20 8HOA 4.5 (3.93) F-1 10 (8.73) HX 2.0 (1.75) AA 8.5 (7.42) TI 0.1 (0.09) G-1 0.05 (0.04) 實施例2 2EHA 80 EMA 20 6HHA 3.5 (2.83) F-1 20 (16.19) HL 2.0 (1.62) 140N 0.5 (0.40) AA 7 (5.67) FE 0.05 (0.04) G-2 0.1 (0.08) 實施例3 2EHA 85 MMA 15 4HBA 1.0 (0.83) HEA 4.0 (3.33) F-2 15 (12.50) 140N 1.0 (0.83) L 0.2 (0.17) AA 5.5 (4.58) TI 0.04 (0.03) G-3 0.08 (0.07) 實施例4 2EHA 90 IBMA 10 4HBA 0.5 (0.46) HEMA 3.5 (3.21) F-3 5 (4.59) HX 2.0 (1.83) 110N 0.5 (0.46) AA 5 (4.59) TI 0.04 (0.04) G-4 0.06 (0.06) 實施例5 2EHA 80 MA 10 MMA 10 6HHA 2.5 (2.13) F-3 15 (12.76) HL 1.5 (1.28) 110N 0.5 (0.43) AA 5.5 (4.68) FE 0.05 (0.04) G-2 0.1 (0.09) 實施例6 2EHA 80 MMA 20 4HBA 1.5 (1.33) HEAA 1.0 (0.89) F-2 10 (8.89) HX 2.0 (1.78) ETAC 6 (5.33) FE 0.04 (0.04) G-2 0.07 (0.06) 比較例1 2EHA 90 LMA 10 8HOA 4.5 (3.61) F-4 20 (16.06) HX 2.0 (1.61) AA 8.5 (6.83) TI 0.1 (0.08) G-1 0.05 (0.04) 比較例2 2EHA 40 MMA 60 6HHA 15 (13.0) - HX 4.5 (3.91) AA 5.0 (4.35) FE 0.05 (0.04) G-5 0.1 (0.09) 比較例3 2EHA 100 4HBA 5 (4.72) AAc 1 (0.94) - L 0.3 (0.28) AA 1.0 (0.94) DOTL 0.01 (0.01) G-6 0.05 (0.05) 比較例4 2EHA 80 BMA 20 8HOA 4.5 (3.93) F-1 10 (8.73) HX 2.0 (1.74) AA 8.5 (7.42) TI 0.1 (0.09) G-1 0.05 (0.04) [Table 1] (A) (B) (F) (C) (D) (E) (G) Example 1 2EHA 80 BMA 20 8HOA 4.5 (3.93) F-1 10 (8.73) HX 2.0 (1.75) AA 8.5 (7.42) TI 0.1 (0.09) G-1 0.05 (0.04) Example 2 2EHA 80 EMA 20 6HHA 3.5 (2.83) F-1 20 (16.19) HL 2.0 (1.62) 140N 0.5 (0.40) AA 7 (5.67) FE 0.05 (0.04) G-2 0.1 (0.08) Example 3 2EHA 85 MMA 15 4HBA 1.0 (0.83) HEA 4.0 (3.33) F-2 15 (12.50) 140N 1.0 (0.83) L 0.2 (0.17) AA 5.5 (4.58) TI 0.04 (0.03) G-3 0.08 (0.07) Example 4 2EHA 90 IBMA 10 4HBA 0.5 (0.46) HEMA 3.5 (3.21) F-3 5 (4.59) HX 2.0 (1.83) 110N 0.5 (0.46) AA 5 (4.59) TI 0.04 (0.04) G-4 0.06 (0.06) Example 5 2EHA 80 MA 10 MMA 10 6HHA 2.5 (2.13) F-3 15 (12.76) HL 1.5 (1.28) 110N 0.5 (0.43) AA 5.5 (4.68) FE 0.05 (0.04) G-2 0.1 (0.09) Example 6 2EHA 80 MMA 20 4HBA 1.5 (1.33) HEAA 1.0 (0.89) F-2 10 (8.89) HX 2.0 (1.78) ETAC 6 (5.33) FE 0.04 (0.04) G-2 0.07 (0.06) Comparative example 1 2EHA 90 LMA 10 8HOA 4.5 (3.61) F-4 20 (16.06) HX 2.0 (1.61) AA 8.5 (6.83) TI 0.1 (0.08) G-1 0.05 (0.04) Comparative example 2 2EHA 40 MMA 60 6HHA 15 (13.0) - HX 4.5 (3.91) AA 5.0 (4.35) FE 0.05 (0.04) G-5 0.1 (0.09) Comparative example 3 2EHA 100 4HBA 5 (4.72) AAc 1 (0.94) - L 0.3 (0.28) AA 1.0 (0.94) DOTL 0.01 (0.01) G-6 0.05 (0.05) Comparative example 4 2EHA 80 BMA 20 8HOA 4.5 (3.93) F-1 10 (8.73) HX 2.0 (1.74) AA 8.5 (7.42) TI 0.1 (0.09) G-1 0.05 (0.04)

[表2]   (D)/(E) 抗靜電劑 實施例1 85 - 實施例2 140 - 實施例3 138 - 實施例4 125 - 實施例5 110 - 實施例6 150 - 比較例1 85 LiTFSI 0.3 比較例2 100 LiTF 0.1 比較例3 100 - 比較例4 85 - [Table 2] (D)/(E) Antistatic agent Example 1 85 - Example 2 140 - Example 3 138 - Example 4 125 - Example 5 110 - Example 6 150 - Comparative example 1 85 LiTFSI 0.3 Comparative example 2 100 LiTF 0.1 Comparative example 3 100 - Comparative example 4 85 -

此外，將表1中使用的(A)~(G)的各成分的縮寫符號的化合物名稱示於表3。另外，CORONATE(注冊商標)HX、CORONATE HL及CORONATE L為TOSOH CORPORATION的商品名稱，TAKENATE(注冊商標)D-140N、D-110N為Mitsui Chemicals, Inc.的商品名稱。 此外，(F)構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中，F-1~F-3是二酯組分為0.2wt%以下的單體，F-4是二酯組分為0.8wt%的單體。n的值表示環氧烷的平均重複數。 此外，(G)聚醚改質矽氧烷化合物中，G-1~G-6的重均分子量為10000以下。Moreover, the compound name of the abbreviation of each component of (A)-(G) used in Table 1 is shown in Table 3. In addition, CORONATE (registered trademark) HX, CORONATE HL, and CORONATE L are trade names of TOSOH CORPORATION, and TAKENATE (registered trademark) D-140N and D-110N are trade names of Mitsui Chemicals, Inc. In addition, (F) among the polyalkylene glycol chain-containing mono(meth)acrylate monomers constituting the polyalkylene glycol chain, F-1~F-3 are the diester components, and the content is 0.2wt% For the following monomers, F-4 is a monomer with a diester component of 0.8% by weight. The value of n represents the average repeating number of alkylene oxide. In addition, in the (G) polyether modified silicone compound, the weight average molecular weight of G-1 to G-6 is 10,000 or less.

[表3] 組 縮寫符號 化合物名稱 (A)組 2EHA 丙烯酸2-乙基己酯   MA 丙烯酸甲酯   BMA 甲基丙烯酸正丁酯   EMA 甲基丙烯酸乙酯   MMA 甲基丙烯酸甲酯   IBMA 甲基丙烯酸異丁酯   LMA 甲基丙烯酸月桂酯 (B)組 8HOA 丙烯酸8-羥基辛酯   6HHA 丙烯酸6-羥基己酯   4HBA 丙烯酸4-羥基丁酯   HEA 丙烯酸2-羥基乙酯   HEMA 甲基丙烯酸2-羥基乙酯   HEAA N-羥乙基丙烯醯胺   AAc 丙烯酸 (C)組 HX CORONATE HX(HDI異氰脲酸酯體)   HL CORONATE HL(HDI加成物)   L CORONATE L(TDI加成物)   140N TAKENATE D-140N(IPDI加成物)   110N D-110N(XDI加成物) (D)組 AA 乙醯丙酮   ETAC 乙醯乙酸乙酯 (E)組 TI 參乙醯丙酮鈦   FE 參(2,4-戊二酮)鐵(III)   DOTL 二月桂酸二辛基錫 (F)組 F-1 聚丙二醇單丙烯酸酯(n=12)   F-2 甲氧基聚乙二醇丙烯酸酯(n=8)   F-3 甲氧基聚乙二醇甲基丙烯酸酯(n=9)   F-4 甲氧基聚乙二醇甲基丙烯酸酯(n=23) (G)組 G-1 聚醚改質矽氧烷化合物(HLB=7)   G-2 聚醚改質矽氧烷化合物(HLB=9)   G-3 聚醚改質矽氧烷化合物(HLB=12)   G-4 聚醚改質矽氧烷化合物(HLB=8)   G-5 聚醚改質矽氧烷化合物(HLB=16)   G-6 聚醚改質矽氧烷化合物(HLB=5) [table 3] group Abbreviation Compound name (A) Group 2EHA 2-ethylhexyl acrylate MA Methyl acrylate BMA N-Butyl methacrylate EMA Ethyl methacrylate MMA Methyl methacrylate IBMA Isobutyl methacrylate LMA Lauryl Methacrylate (B) Group 8HOA 8-hydroxyoctyl acrylate 6HHA 6-hydroxyhexyl acrylate 4HBA 4-hydroxybutyl acrylate HEA 2-hydroxyethyl acrylate HEMA 2-hydroxyethyl methacrylate HEAA N-Hydroxyethyl allylamide AAc acrylic acid (C) Group HX CORONATE HX (HDI isocyanurate body) HL CORONATE HL (HDI adduct) L CORONATE L (TDI adduct) 140N TAKENATE D-140N (IPDI adduct) 110N D-110N (XDI adduct) (D) Group AA Acetone ETAC Ethyl Acetate (E) Group TI Titanium acetone acetone FE Ginseng (2,4-pentanedione) iron (III) DOTL Dioctyltin dilaurate (F) Group F-1 Polypropylene glycol monoacrylate (n=12) F-2 Methoxy polyethylene glycol acrylate (n=8) F-3 Methoxy polyethylene glycol methacrylate (n=9) F-4 Methoxy polyethylene glycol methacrylate (n=23) (G) Group G-1 Polyether modified silicone compound (HLB=7) G-2 Polyether modified silicone compound (HLB=9) G-3 Polyether modified silicone compound (HLB=12) G-4 Polyether modified silicone compound (HLB=8) G-5 Polyether modified silicone compound (HLB=16) G-6 Polyether modified silicone compound (HLB=5)

＜抗靜電表面保護膜的製作＞ [實施例1] 將5重量份的加成反應型的矽酮(Dow Corning Toray Co.,Ltd.製造，產品名稱：SRX-345)、0.15重量份的聚醚改質矽酮(Dow Corning Toray Co.,Ltd.製造，產品名稱：SH8400)、0.5重量份的作為抗靜電劑的雙(三氟甲基磺醯基)醯亞胺鋰(LiTFSI)、95重量份的甲苯與乙酸乙酯的1:1的混合溶劑、及0.05重量份的鉑催化劑(Dow Corning Toray Co.,Ltd.製造，產品名稱：SRX-212 CATALYST)進行摻混，並進行攪拌及混合，製備形成實施例1的剝離劑層的塗料。使用邁耶棒，以使乾燥後的厚度為0.2μm的方式，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酯膜的表面上，並用120℃的熱風迴圈式烘箱乾燥1分鐘，得到實施例1的剝離膜。 以使乾燥後的厚度為15μm的方式，將實施例1的黏著劑組合物塗佈在厚度為38μm的聚對苯二甲酸乙二酯膜的表面上後，用100℃的熱風迴圈式烘箱乾燥2分鐘，形成黏著劑層。然後，在該黏著劑層的表面上貼合上述製作的實施例1的剝離膜的剝離劑層(矽酮處理面)。將所得到的黏著膜在40℃的環境下保溫5天，使黏著劑固化，得到實施例1的抗靜電表面保護膜。＜Production of antistatic surface protective film＞ [Example 1] 5 parts by weight of addition reaction type silicone (manufactured by Dow Corning Toray Co., Ltd., product name: SRX-345), and 0.15 parts by weight of polyether modified silicone (Dow Corning Toray Co., Ltd. Manufacture, product name: SH8400), 0.5 parts by weight of lithium bis(trifluoromethylsulfonyl) imide (LiTFSI) as an antistatic agent, and a 1:1 mixture of 95 parts by weight of toluene and ethyl acetate A solvent and 0.05 parts by weight of a platinum catalyst (manufactured by Dow Corning Toray Co., Ltd., product name: SRX-212 CATALYST) were blended, stirred and mixed, and a paint forming the release agent layer of Example 1 was prepared. Using a Meyer rod, the paint forming the release agent layer of Example 1 was coated on the surface of a polyethylene terephthalate film with a thickness of 38 μm so that the thickness after drying was 0.2 μm, and 120 It was dried in a hot-air circulating oven at ℃ for 1 minute to obtain a peeling film of Example 1. The adhesive composition of Example 1 was coated on the surface of a polyethylene terephthalate film with a thickness of 38 μm so that the thickness after drying was 15 μm, and then a hot-air circulating oven at 100°C was used. Dry for 2 minutes to form an adhesive layer. Then, the release agent layer (silicone-treated surface) of the release film of Example 1 produced above was bonded to the surface of the adhesive layer. The obtained adhesive film was kept at a temperature of 40° C. for 5 days to cure the adhesive, and the antistatic surface protective film of Example 1 was obtained.

[實施例2~6] 除了將形成實施例1的剝離劑層的塗料的組成分別調整為表4中的記載以外，以與實施例1相同的方式，得到形成實施例2~6的剝離劑層的塗料。 此外，除了將實施例1的黏著劑組合物及形成剝離劑層的塗料分別調整為實施例2~6的黏著劑組合物及形成剝離劑層的塗料以外，以與實施例1相同的方式，得到實施例2~6的抗靜電表面保護膜。[Examples 2~6] Except that the composition of the paint forming the release agent layer of Example 1 was adjusted to the description in Table 4, in the same manner as in Example 1, paints forming the release agent layer of Examples 2 to 6 were obtained. In addition, in the same manner as in Example 1, except that the adhesive composition of Example 1 and the paint forming the release agent layer were adjusted to the adhesive compositions of Examples 2 to 6 and the paint forming the release agent layer, respectively, The antistatic surface protective films of Examples 2 to 6 were obtained.

[比較例1] 將5重量份的加成反應型的矽酮(Dow Corning Toray Co.,Ltd.製造，產品名稱：SRX-345)、95重量份的甲苯與乙酸乙酯的1:1的混合溶劑及0.05重量份的鉑催化劑(Dow Corning Toray Co.,Ltd.製造，產品名稱：SRX-212 CATALYST)進行摻混，並進行攪拌及混合，製備形成比較例1的剝離劑層的塗料。使用邁耶棒，以使乾燥後的厚度為0.2μm的方式，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上，並用120℃的熱風迴圈式烘箱乾燥1分鐘，得到比較例1的剝離膜。 以使乾燥後的厚度為15μm的方式，將比較例1的黏著劑組合物塗佈在厚度為38μm的聚對苯二甲酸乙二醇酯膜的表面上後，用100℃的熱風迴圈式烘箱乾燥2分鐘，形成黏著劑層。然後，在該黏著劑層的表面上貼合上述製作的比較例1的剝離膜的剝離劑層(矽酮處理面)。將所得到的黏著膜在40℃的環境下保溫5天，使黏著劑固化，得到比較例1的抗靜電表面保護膜。[Comparative Example 1] 5 parts by weight of addition reaction type silicone (manufactured by Dow Corning Toray Co., Ltd., product name: SRX-345), 95 parts by weight of a 1:1 mixed solvent of toluene and ethyl acetate, and 0.05 parts by weight Part of the platinum catalyst (manufactured by Dow Corning Toray Co., Ltd., product name: SRX-212 CATALYST) was blended, stirred and mixed to prepare a paint forming the release agent layer of Comparative Example 1. Using a Meyer rod, the paint that forms the release agent layer of Comparative Example 1 was coated on the surface of a polyethylene terephthalate film with a thickness of 38 μm so that the thickness after drying was 0.2 μm, and used It was dried in a hot-air circulation oven at 120°C for 1 minute to obtain a release film of Comparative Example 1. The adhesive composition of Comparative Example 1 was coated on the surface of a polyethylene terephthalate film with a thickness of 38 μm so that the thickness after drying was 15 μm, and then it was looped with hot air at 100°C. Dry in an oven for 2 minutes to form an adhesive layer. Then, the release agent layer (silicone-treated surface) of the release film of Comparative Example 1 produced above was bonded to the surface of the adhesive layer. The obtained adhesive film was kept at a temperature of 40° C. for 5 days, the adhesive was cured, and the antistatic surface protective film of Comparative Example 1 was obtained.

[比較例2] 除了將比較例1的黏著劑組合物調整為比較例2的黏著劑組合物以外，以與比較例1相同的方式，得到比較例2的抗靜電表面保護膜。 [比較例3~4] 除了將形成實施例1的剝離劑層的塗料的組成分別調整為表4中的記載以外，以與實施例1相同的方式，得到形成比較例3~4的剝離劑層的塗料。此外，除了將實施例1的黏著劑組合物及形成剝離劑層的塗料分別調整為比較例3~4的黏著劑組合物及形成剝離劑層的塗料以外，以與實施例1相同的方式，得到比較例3~4的抗靜電表面保護膜。 另外，在表4的“抗靜電劑”中，LiTFSI表示Li(CF3 SO2 )2 N，LiFSI表示Li(FSO2 )2 N，LiTF表示LiCF3 SO3 。[Comparative Example 2] The antistatic surface protective film of Comparative Example 2 was obtained in the same manner as in Comparative Example 1, except that the adhesive composition of Comparative Example 1 was adjusted to the adhesive composition of Comparative Example 2. [Comparative Examples 3 to 4] In the same manner as in Example 1, except that the composition of the coating material forming the release agent layer of Example 1 was adjusted to the description in Table 4, the release agents forming Comparative Examples 3 to 4 were obtained. Layer of paint. In addition, in the same manner as in Example 1, except that the adhesive composition of Example 1 and the paint forming the release agent layer were adjusted to the adhesive compositions of Comparative Examples 3 to 4 and the paint forming the release agent layer, respectively, The antistatic surface protective films of Comparative Examples 3 to 4 were obtained. In addition, in the "antistatic agent" in Table 4, LiTFSI means Li(CF 3 SO 2 ) 2 N, LiFSI means Li(FSO 2 ) 2 N, and LiTF means LiCF 3 SO 3 .

[表4]   加成反應型 矽酮 聚醚 改質矽酮 抗靜電劑 鉑催化劑 實施例1 SRX-345 5 SH8400 0.15 LiTFSI 0.5 SRX-212 0.05 實施例2 SRX-345 5 SH8400 0.15 LiTF 0.5 SRX-212 0.05 實施例3~6 SRX-345 5 SH8400 0.15 LiFSI 0.5 SRX-212 0.05 比較例1~2 SRX-345 5 - - SRX-212 0.05 比較例3~4 SRX-345 5 SH8400 0.15 LiFSI 0.5 SRX-212 0.05 [Table 4] Addition reaction type silicone Polyether modified silicone Antistatic agent Platinum catalyst Example 1 SRX-345 5 SH8400 0.15 LiTFSI 0.5 SRX-212 0.05 Example 2 SRX-345 5 SH8400 0.15 LiTF 0.5 SRX-212 0.05 Examples 3~6 SRX-345 5 SH8400 0.15 LiFSI 0.5 SRX-212 0.05 Comparative example 1~2 SRX-345 5 - - SRX-212 0.05 Comparative example 3~4 SRX-345 5 SH8400 0.15 LiFSI 0.5 SRX-212 0.05

＜試驗方法及評價＞ 分別將實施例1~6及比較例1~4中的抗靜電表面保護膜在溫度為23℃、濕度為50%RH的氛圍下熟化7天后，通過以下的試驗方法進行評價。另外，實施例1~6及比較例3~4的抗靜電表面保護膜中，通過剝離脫模膜，能夠使剝離劑層的抗靜電劑轉印至黏著劑層的表面。比較例1~2中，黏著劑層整體含有抗靜電劑。＜Test method and evaluation＞ The antistatic surface protective films in Examples 1 to 6 and Comparative Examples 1 to 4 were cured for 7 days in an atmosphere at a temperature of 23° C. and a humidity of 50% RH, and then evaluated by the following test method. In addition, in the antistatic surface protection films of Examples 1 to 6 and Comparative Examples 3 to 4, by peeling the release film, the antistatic agent of the release agent layer can be transferred to the surface of the adhesive layer. In Comparative Examples 1 and 2, the entire adhesive layer contained an antistatic agent.

＜黏著力的試驗方法＞ 剝離脫模膜，將露出厚度為15μm的黏著劑層的抗靜電表面保護膜經由黏著劑層貼合於偏振片的表面，並放置1天後，於50℃、5個大氣壓下，進行20分鐘壓熱處理，進一步於室溫下放置12小時後，將其作為黏著力的測定樣品。使用拉伸試驗機、沿180°方向在低速度(0.3m/分鐘)或高速度(30m/分鐘)下剝離所得到的測定樣品，將測定的剝離強度作為黏著力。 此處，所述偏振片的起偏鏡的保護層為具有AG-LR處理層的聚甲基丙烯酸甲酯(PMMA)。＜Test method of adhesion＞ The release film was peeled off, and the antistatic surface protective film exposing the adhesive layer with a thickness of 15μm was pasted on the surface of the polarizer via the adhesive layer, and after leaving it for 1 day, it was carried out at 50°C and 5 atmospheres for 20 minutes After autoclaving and further standing at room temperature for 12 hours, it was used as a sample for measuring adhesion. A tensile tester was used to peel the obtained measurement sample in a 180° direction at a low speed (0.3 m/min) or a high speed (30 m/min), and the measured peel strength was used as the adhesive force. Here, the protective layer of the polarizer of the polarizer is polymethyl methacrylate (PMMA) with an AG-LR treatment layer.

＜表面電阻率的試驗方法＞ 在熟化抗靜電表面保護膜後、並在將其貼合於偏振片之前，剝離脫模膜而露出黏著劑層，使用電阻率儀Hiresta(注冊商標)UP-HT450(Mitsubishi Chemical Analytech, Co., Ltd.製造)測定黏著劑層的表面電阻率。＜Test method of surface resistivity＞ After curing the antistatic surface protection film and before attaching it to the polarizer, peel off the release film to expose the adhesive layer, and use the resistivity meter Hiresta (registered trademark) UP-HT450 (Mitsubishi Chemical Analytech, Co., Ltd.) The surface resistivity of the adhesive layer was measured.

＜剝離靜電壓的試驗方法＞ 剝離脫模膜，將露出黏著劑層的抗靜電表面保護膜貼合在具有低折射率層的偏振片上，所述低折射率層通過在被黏面上使用含有氟化物的低折射率層形成用組合物而形成。使用高精度靜電感測器SK-035、SK-200(KEYENCE CORPORATION製造)，測定以30m/分鐘的拉伸速度對抗靜電表面保護膜進行180°剝離時，被黏物帶電而產生的電壓(靜電壓)，將測定值的最大值作為剝離靜電壓。＜Test method of peeling static voltage＞ The release film is peeled off, and the antistatic surface protection film exposing the adhesive layer is attached to a polarizer with a low refractive index layer formed by using a low refractive index layer containing fluoride on the adhered surface It is formed with the composition. Using high-precision electrostatic sensors SK-035 and SK-200 (manufactured by KEYENCE CORPORATION), the voltage (static Voltage), and the maximum value of the measured value is taken as the peeling static voltage.

＜抗污染性能的試驗方法＞ 使用貼合機，將具有表6所示的表面基材及表面處理(平坦(Plain)時為未處理)的偏振片經由黏著劑層(雙面黏著膠帶)貼合在玻璃板的單面上。然後，使用貼合機，將抗靜電表面保護膜貼合於所述偏振片的表面。貼合於被黏物後，在溫度為60℃、濕度為90%RH的氛圍下放置2天(48hr)，從所述氛圍下取出，然後經過1天後，剝離抗靜電表面保護膜，通過目視觀察偏振片的表面的污染狀態。關於抗污染性能的判斷基準，將對所述偏振片的表面無污染的情況評價為“○”、有輕微污染的情況評價為“△”、有污染的情況評價為“×”。＜Test method of anti-pollution performance＞ Using a laminator, the polarizer with the surface substrate shown in Table 6 and the surface treatment (untreated in the case of plain) was pasted on one side of the glass plate via the adhesive layer (double-sided adhesive tape) . Then, using a laminating machine, the antistatic surface protection film was bonded to the surface of the polarizing plate. After bonding to the adherend, place it for 2 days (48hr) in an atmosphere with a temperature of 60°C and a humidity of 90%RH, take it out of the atmosphere, and then after 1 day, peel off the antistatic surface protective film, and pass The contamination state of the surface of the polarizing plate was visually observed. Regarding the judgment criteria of the anti-contamination performance, the surface of the polarizer was evaluated as "○" when there was no pollution on the surface of the polarizer, when there was slight pollution as "△", and when there was pollution as "×".

表5~6中示出了關於實施例1~6及比較例1~4的抗靜電表面保護膜的評價結果。表5的“表面電阻率”通過將“m×10+n ”記作“mE+n”的方式(其中，m為任意的實數值，n為正整數)表示。Tables 5 to 6 show the evaluation results of the antistatic surface protective films of Examples 1 to 6 and Comparative Examples 1 to 4. "Surface resistivity" in Table 5 is represented by writing "m×10 +n " as "mE+n" (where m is an arbitrary real value, and n is a positive integer).

[表5]   0.3m/分鐘 黏著力 (N/25mm) 30m/分鐘 黏著力 (N/25mm) 表面 電阻率 (Ω/□) 剝離 靜電壓 (kV) 實施例1 0.04 0.5 3.24E+10 0.2 實施例2 0.04 0.5 4.26E+10 0.2 實施例3 0.05 0.5 3.35E+10 0.1 實施例4 0.03 0.4 4.33E+10 0.1 實施例5 0.03 0.4 5.24E+10 0.1 實施例6 0.05 0.6 4.52E+10 0.1 比較例1 0.04 0.5 4.57E+10 0.2 比較例2 0.18 1.1 2.45E+11 0.4 比較例3 0.24 3.5 2.34E+12 0.6 比較例4 0.05 0.6 4.69E+10 0.3 [table 5] 0.3m/min adhesion force (N/25mm) 30m/min adhesion force (N/25mm) Surface resistivity (Ω/□) Stripping static voltage (kV) Example 1 0.04 0.5 3.24E+10 0.2 Example 2 0.04 0.5 4.26E+10 0.2 Example 3 0.05 0.5 3.35E+10 0.1 Example 4 0.03 0.4 4.33E+10 0.1 Example 5 0.03 0.4 5.24E+10 0.1 Example 6 0.05 0.6 4.52E+10 0.1 Comparative example 1 0.04 0.5 4.57E+10 0.2 Comparative example 2 0.18 1.1 2.45E+11 0.4 Comparative example 3 0.24 3.5 2.34E+12 0.6 Comparative example 4 0.05 0.6 4.69E+10 0.3

[表6]   抗污染性能 表面基材 PMMA PET PMMA TAC TAC 表面處理 LR AG-LR AG-LR Plain AG 實施例1 ○ ○ ○ ○ ○ 實施例2 ○ ○ ○ ○ ○ 實施例3 ○ ○ ○ ○ ○ 實施例4 ○ ○ ○ ○ ○ 實施例5 ○ ○ ○ ○ ○ 實施例6 ○ ○ ○ ○ ○ 比較例1 ○ △ △ ○ △ 比較例2 ○ △ × ○ △ 比較例3 × × × △ △ 比較例4 △ △ × △ △ [Table 6] Anti-pollution performance Surface substrate PMMA PET PMMA TAC TAC Surface treatment LR AG-LR AG-LR Plain AG Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Comparative example 1 ○ △ △ ○ △ Comparative example 2 ○ △ X ○ △ Comparative example 3 X X X △ △ Comparative example 4 △ △ X △ △

實施例1~6的抗靜電表面保護膜對作為被黏物的偏振片的、在低速的剝離速度0.3m/分鐘下的黏著力為0.01~0.1N/25mm，在高速的剝離速度30m/分鐘下的黏著力為1.0N/25mm以下，因此在低速的剝離速度與高速的剝離速度下，取得黏著力的平衡所帶來的黏著性能優異。 此外，對於實施例1~6的抗靜電表面保護膜，由於將剝離劑層的抗靜電劑轉印至黏著劑層的表面，因此黏著劑層的表面電阻率為1.0×10+12 Ω/□以下，黏著劑層對使用含有氟化物的低折射率層形成用組合物而形成的低折射率層的剝離靜電壓在+0.3~-0.3kV的範圍內，抗靜電性能優異。 進一步，將實施例1~6的抗靜電表面保護膜貼合於被黏物後，在溫度為60℃、濕度為90%RH的氛圍下放置48hr，從所述氛圍下取出並經過1天後，對作為被黏物的各種偏振片也沒有污染，抗污染性能也優異。 即，根據表5~6所示的評價結果，證實了實施例1~6的抗靜電表面保護膜能夠解決本發明的技術問題。The adhesive force of the antistatic surface protective film of Examples 1 to 6 to the polarizer as the adherend is 0.01~0.1N/25mm at a low-speed peeling speed of 0.3m/min, and at a high-speed peeling speed of 30m/min The adhesive force is 1.0N/25mm or less, so at low-speed peeling speed and high-speed peeling speed, the balance of adhesive force brings excellent adhesive performance. In addition, for the antistatic surface protection films of Examples 1 to 6, since the antistatic agent of the release agent layer was transferred to the surface of the adhesive layer, the surface resistivity of the adhesive layer was 1.0×10 +12 Ω/□ Hereinafter, the peeling static voltage of the adhesive layer to the low refractive index layer formed using the fluoride-containing composition for forming a low refractive index layer is in the range of +0.3 to -0.3 kV, and the antistatic performance is excellent. Furthermore, after attaching the antistatic surface protection films of Examples 1 to 6 to the adherend, they were placed in an atmosphere with a temperature of 60° C. and a humidity of 90% RH for 48 hours, and were taken out of the atmosphere after 1 day. , It does not pollute various polarizers as adherends, and has excellent anti-pollution performance. That is, according to the evaluation results shown in Tables 5 to 6, it was confirmed that the antistatic surface protective films of Examples 1 to 6 can solve the technical problems of the present invention.

比較例1的抗靜電表面保護膜(共聚在丙烯酸類聚合物中的單官能的甲基丙烯酸酯單體的Tg小於0℃，黏著劑層整體含有抗靜電劑，剝離劑層不含有在20℃下為液體的矽酮類化合物與抗靜電劑)的抗污染性能稍差。 此外，比較例2的抗靜電表面保護膜(共聚在丙烯酸類聚合物中的單官能度的甲基丙烯酸酯單體及含羥基單體過多，丙烯酸類聚合物不含有構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，黏著劑層整體含有抗靜電劑，剝離劑層不含有在20℃下為液體的矽酮類化合物與抗靜電劑)的黏著力大，剝離靜電壓高，抗污染性能差。 此外，比較例3的抗靜電表面保護膜(丙烯酸類聚合物不含有Tg為0℃以上的甲基丙烯酸酯單體及構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，含有含羧基單體)的黏著力大，表面電阻值大，剝離靜電壓高，抗污染性能差。 此外，比較例4的抗靜電表面保護膜(丙烯酸類聚合物的重均分子量小)的抗污染性能差。 如上所述，比較例1~4的抗靜電表面保護膜未能解決本發明的技術問題。The antistatic surface protection film of Comparative Example 1 (the Tg of the monofunctional methacrylate monomer copolymerized in the acrylic polymer is less than 0°C, the adhesive layer contains the antistatic agent as a whole, and the release agent layer does not contain it at 20°C. The anti-pollution properties of liquid silicone compounds and antistatic agents are slightly worse. In addition, the antistatic surface protection film of Comparative Example 2 (monofunctional methacrylate monomers and hydroxyl-containing monomers copolymerized in the acrylic polymer are too much, and the acrylic polymer does not contain polyalkylene glycol Mono(meth)acrylate monomer containing polyalkylene glycol chain, the adhesive layer contains antistatic agent as a whole, and the release agent layer does not contain silicone compounds and antistatic agents that are liquid at 20°C ) Has high adhesion, high peeling static voltage, and poor anti-pollution performance. In addition, the antistatic surface protection film of Comparative Example 3 (the acrylic polymer does not contain a methacrylate monomer with a Tg of 0°C or higher and a polyalkylene glycol chain-containing monomer that constitutes the polyalkylene glycol chain. (Meth) acrylate monomers, containing carboxyl group-containing monomers) have high adhesion, large surface resistance, high peeling static voltage, and poor anti-pollution performance. In addition, the antistatic surface protective film of Comparative Example 4 (the weight average molecular weight of the acrylic polymer is small) has poor anti-fouling performance. As described above, the antistatic surface protection films of Comparative Examples 1 to 4 failed to solve the technical problems of the present invention.

1:基材膜 2:黏著劑層 3:樹脂膜 4:剝離劑層 5:剝離膜 7:抗靜電劑 8:被黏物(光學部件) 10:抗靜電表面保護膜 11:剝離了剝離膜的抗靜電表面保護膜 20:貼合有抗靜電表面保護膜的光學部件1: Base film 2: Adhesive layer 3: Resin film 4: Release agent layer 5: Peel off the film 7: Antistatic agent 8: Adhesive (optical parts) 10: Antistatic surface protective film 11: The antistatic surface protective film of the peeling film is peeled off 20: Laminated optical parts with antistatic surface protective film

圖1為示出本發明的抗靜電表面保護膜的概念的剖面圖。 圖2為示出從本發明的抗靜電表面保護膜中剝離了剝離膜的狀態的剖面圖。 圖3為示出本發明的光學部件的1個實施例的剖面圖。Fig. 1 is a cross-sectional view showing the concept of the antistatic surface protective film of the present invention. Fig. 2 is a cross-sectional view showing a state where the release film is peeled off from the antistatic surface protection film of the present invention. Fig. 3 is a cross-sectional view showing an embodiment of the optical component of the present invention.

1:基材膜 1: Base film

2:黏著劑層 2: Adhesive layer

3:樹脂膜 3: Resin film

4:剝離劑層 4: Release agent layer

5:剝離膜 5: Peel off the film

7:抗靜電劑 7: Antistatic agent

10:抗靜電表面保護膜 10: Antistatic surface protective film

Claims (13)

一種抗靜電表面保護膜的製造方法，其為製造抗靜電表面保護膜的方法，所述抗靜電表面保護膜的製造方法的特徵在於，以步驟(1)~(3)的順序經過以下的步驟(1)~(3)而製作抗靜電表面保護膜： 步驟(1)：製備黏著劑組合物的步驟，所述黏著劑組合物含有丙烯酸類聚合物與交聯劑，所述丙烯酸類聚合物為使(A)合計為100重量份的烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上、(B)合計為1.0~6.0重量份的含有羥基的可共聚單體中的至少1種以上、及(F)合計為1.0~50重量份的構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少1種以上，以不含有具有羧基的可共聚單體的方式共聚而成的、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物， 在所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上的合計100重量份中，以50重量份以上的比例含有丙烯酸2-乙基己酯、以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上， 所述黏著劑組合物含有作為所述交聯劑的(C)三官能以上的異氰酸酯化合物、以及(D)交聯延遲劑與作為(E)交聯促進劑的除錫化物以外的交聯促進劑； 步驟(2)：在由具有透明性的樹脂形成的基材膜的單面上製作使所述黏著劑組合物交聯而成的黏著劑層的步驟；及 步驟(3)：將在樹脂膜的單面積層有含有抗靜電劑的剝離劑層的剝離膜，經由所述剝離劑層而貼合於所述黏著劑層的表面，使所述剝離劑層的所述抗靜電劑轉印至所述黏著劑層的表面的步驟， 所述剝離劑層由樹脂組合物形成，所述樹脂組合物包含以二甲基聚矽氧烷為主要成分的剝離劑、在20℃下為液體的矽酮類化合物及抗靜電劑。A method for manufacturing an antistatic surface protective film is a method for manufacturing an antistatic surface protective film. The method for manufacturing an antistatic surface protective film is characterized in that the following steps are carried out in the order of steps (1) to (3) (1)~(3) To make antistatic surface protective film: Step (1): a step of preparing an adhesive composition, the adhesive composition contains an acrylic polymer and a crosslinking agent, the acrylic polymer is carbon whose total amount of (A) is 100 parts by weight of the alkyl group At least 2 or more of the alkyl (meth)acrylates having atoms of C1 to C10, (B) at least 1 or more of the hydroxyl-containing copolymerizable monomers totaling 1.0 to 6.0 parts by weight, and (F ) A total of 1.0 to 50 parts by weight of at least one of the polyalkylene glycol chain-containing mono(meth)acrylate monomers constituting the polyalkylene glycol chain may not contain carboxyl group-containing mono(meth)acrylate monomers. Acrylic polymers formed by copolymers with a weight average molecular weight of more than 300,000 and less than 1 million, which are copolymerized by means of comonomers, The (A) alkyl group contains at least two types of alkyl (meth)acrylates having C1 to C10 carbon atoms in a total of 100 parts by weight, and contains 2-ethyl acrylate in a proportion of 50 parts by weight or more. One or more of monofunctional methacrylate monomers having a Tg of 0°C or higher containing homopolymers in a ratio of 5 to 40 parts by weight in total, The adhesive composition contains (C) a trifunctional or higher isocyanate compound as the cross-linking agent, and (D) a cross-linking retarder, and (E) a cross-linking accelerator for cross-linking promotion other than tin compounds Agent Step (2): a step of fabricating an adhesive layer formed by crosslinking the adhesive composition on one side of a base film formed of a resin having transparency; and Step (3): A release film with a release agent layer containing an antistatic agent layered on a single area of the resin film is bonded to the surface of the adhesive layer via the release agent layer to make the release agent layer The step of transferring the antistatic agent to the surface of the adhesive layer, The release agent layer is formed of a resin composition containing a release agent containing dimethylpolysiloxane as a main component, a silicone compound that is liquid at 20° C., and an antistatic agent. 如請求項1之抗靜電表面保護膜的製造方法，其特徵在於，所述均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體為選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯組成的化合物群組中的1種以上。The method for manufacturing an antistatic surface protective film according to claim 1, wherein the monofunctional methacrylate monomer having a Tg of 0° C. or more of the homopolymer is selected from the group consisting of n-butyl methacrylate and methyl methacrylate. Compound composed of isobutyl acrylate, second butyl methacrylate, tertiary butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, ethyl methacrylate, and methyl methacrylate One or more types in the group. 如請求項1或2之抗靜電表面保護膜的製造方法，其特徵在於，所述剝離劑層中的抗靜電劑為鹼金屬鹽。The method for manufacturing an antistatic surface protective film according to claim 1 or 2, wherein the antistatic agent in the release agent layer is an alkali metal salt. 一種抗靜電表面保護膜，其在由具有透明性的樹脂形成的基材膜的單面上形成有黏著劑層，所述黏著劑層由含有丙烯酸類聚合物與交聯劑的黏著劑組合物交聯而成，所述抗靜電表面保護膜的特徵在於， 所述丙烯酸類聚合物為使(A)合計為100重量份的烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上、(B)合計為1.0~6.0重量份的含有羥基的可共聚單體中的至少1種以上、及(F)合計為1.0~50重量份的構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少1種以上，以不含有具有羧基的可共聚單體的方式共聚而成的、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物， 在所述(A)烷基的碳原子數為C1~C10的(甲基)丙烯酸烷基酯中的至少2種以上的合計100重量份中，以50重量份以上的比例含有丙烯酸2-乙基己酯，以合計為5~40重量份的比例含有均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體中的1種以上， 所述黏著劑組合物含有作為所述交聯劑的(C)三官能以上的異氰酸酯化合物、以及(D)交聯延遲劑與作為(E)交聯促進劑的除錫化物以外的交聯促進劑， 將在樹脂膜的單面積層有含有抗靜電劑的剝離劑層的剝離膜，經由所述剝離劑層而貼合於所述黏著劑層的表面，使所述剝離劑層的所述抗靜電劑轉印至所述黏著劑層的表面， 所述剝離劑層由樹脂組合物形成，所述樹脂組合物包含以二甲基聚矽氧烷為主要成分的剝離劑、在20℃下為液體的矽酮類化合物及抗靜電劑。An antistatic surface protective film, which has an adhesive layer formed on one side of a substrate film formed of a transparent resin, the adhesive layer being composed of an adhesive composition containing an acrylic polymer and a crosslinking agent Cross-linked, the antistatic surface protective film is characterized by: The acrylic polymer is at least two kinds of alkyl (meth)acrylates with C1-C10 carbon atoms of the alkyl group (A) totaling 100 parts by weight, and (B) totaling 1.0- 6.0 parts by weight of at least one of the hydroxyl-containing copolymerizable monomers, and (F) a total of 1.0 to 50 parts by weight of the polyalkylene glycol chain-containing monomer ( At least one of the meth)acrylate monomers is copolymerized so that it does not contain a copolymerizable monomer having a carboxyl group, and has a weight average molecular weight of more than 300,000 and an acrylic that is less than 1 million. polymer, The (A) alkyl group contains at least two types of alkyl (meth)acrylates having C1 to C10 carbon atoms in a total of 100 parts by weight, and contains 2-ethyl acrylate in a proportion of 50 parts by weight or more. The hexyl hexyl ester contains at least one type of monofunctional methacrylate monomers having a Tg of 0° C. or more of a homopolymer in a ratio of 5 to 40 parts by weight in total, The adhesive composition contains (C) a trifunctional or higher isocyanate compound as the cross-linking agent, and (D) a cross-linking retarder, and (E) a cross-linking accelerator for cross-linking promotion other than tin compounds Agent, A release film having a release agent layer containing an antistatic agent layered on a single area of a resin film is bonded to the surface of the adhesive layer via the release agent layer to make the antistatic effect of the release agent layer Transfer to the surface of the adhesive layer, The release agent layer is formed of a resin composition containing a release agent containing dimethylpolysiloxane as a main component, a silicone compound that is liquid at 20° C., and an antistatic agent. 如請求項4之抗靜電表面保護膜，其特徵在於，所述均聚物的Tg為0℃以上的單官能的甲基丙烯酸酯單體為選自由甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯組成的化合物群組中的1種以上。The antistatic surface protective film of claim 4, wherein the monofunctional methacrylate monomer with a Tg of 0° C. or more of the homopolymer is selected from the group consisting of n-butyl methacrylate and isomethacrylate. Butyl ester, second butyl methacrylate, third butyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, ethyl methacrylate, methyl methacrylate More than one kind of. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述剝離劑層中的抗靜電劑為鹼金屬鹽。The antistatic surface protective film of claim 4 or 5, wherein the antistatic agent in the release agent layer is an alkali metal salt. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述(F)構成聚伸烷基二醇鏈的含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中，構成聚伸烷基二醇鏈的環氧烷的平均重複數為3~14， 所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中的二酯組分為0.2%以下， 所述含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體為選自由聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯組成的群組中的至少1種以上。The antistatic surface protective film of claim 4 or 5, wherein the (F) polyalkylene glycol chain-containing mono(meth)acrylate monomer constituting the polyalkylene glycol chain , The average repeating number of the alkylene oxide constituting the polyalkylene glycol chain is 3-14, The diester component in the polyalkylene glycol chain-containing mono(meth)acrylate monomer is 0.2% or less, The polyalkylene glycol chain-containing mono(meth)acrylate monomer is selected from polyalkylene glycol mono(meth)acrylate, methoxy polyalkylene glycol (meth) At least one or more of the group consisting of acrylate and ethoxy polyalkylene glycol (meth)acrylate. 如請求項4或5之抗靜電表面保護膜，其特徵在於，其為被用作偏振片用表面保護膜的抗靜電表面保護膜， 在所述偏振片用表面保護膜的用途中，作為被黏物的偏振片的起偏鏡的保護層為選自由TAC類膜、PMMA類膜、PET類膜組成的群組中的至少1種，且對所述偏振片的起偏鏡的保護層的表面實施的表面處理為選自由未處理、AG處理、LR處理、AR處理、AG-LR處理、AG-AR處理組成的群組中的至少1種。The antistatic surface protective film of claim 4 or 5, which is an antistatic surface protective film used as a surface protective film for polarizers, In the use of the surface protective film for polarizers, the protective layer of the polarizer of the polarizer as an adherend is at least one selected from the group consisting of TAC-based films, PMMA-based films, and PET-based films , And the surface treatment performed on the surface of the protective layer of the polarizer of the polarizer is selected from the group consisting of untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment At least one. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述(B)含有羥基的可共聚單體為選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺組成的化合物群組中的至少1種以上。The antistatic surface protective film of claim 4 or 5, wherein the (B) hydroxyl-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate and 6-hydroxyoctyl (meth)acrylate. Hydroxyhexyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, At least one or more of the compound group consisting of N-hydroxyethyl (meth)acrylamide. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述(D)交聯延遲劑為酮-烯醇互變異構體的化合物， 相對於100重量份的所述丙烯酸類聚合物，以0.1~300重量份的比例含有所述(D)交聯延遲劑， 所述(E)交聯促進劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少1種以上的金屬螯合化合物， 相對於100重量份的所述丙烯酸類聚合物，以0.001~0.5重量份的比例含有所述(E)交聯促進劑， 所述(D)/所述(E)的重量份比為80~1000。The antistatic surface protective film of claim 4 or 5, wherein the (D) crosslinking retarder is a compound of keto-enol tautomer, The (D) crosslinking retarder is contained in a ratio of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer, The (E) crosslinking accelerator is at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds, The (E) crosslinking accelerator is contained in a ratio of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer, The weight ratio of the (D)/the (E) is 80-1000. 如請求項4或5之抗靜電表面保護膜，其特徵在於，相對於100重量份的所述丙烯酸類聚合物，所述黏著劑組合物以0.01~0.5重量份的比例含有HLB值為6~12且重均分子量為10000以下的聚醚改質矽氧烷化合物。According to claim 4 or 5, the antistatic surface protective film is characterized in that, relative to 100 parts by weight of the acrylic polymer, the adhesive composition contains an HLB value of 6 to 0.5 parts by weight in a ratio of 0.01 to 0.5 parts by weight. 12 and a polyether modified silicone compound with a weight average molecular weight of 10,000 or less. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述剝離劑層中的矽酮類化合物為聚醚改質矽酮。According to claim 4 or 5, the antistatic surface protective film is characterized in that the silicone compound in the release agent layer is polyether modified silicone. 如請求項4或5之抗靜電表面保護膜，其特徵在於，所述剝離劑層中的抗靜電劑為Li鹽，為選自由LiTFSI、LiFSI、LiTF組成的化合物群組中的至少1種以上。The antistatic surface protective film of claim 4 or 5, wherein the antistatic agent in the release agent layer is a Li salt, which is at least one compound selected from the group consisting of LiTFSI, LiFSI, and LiTF .
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