TW201404846A - Adhesive composition and surface-protective adhesive film - Google Patents

Adhesive composition and surface-protective adhesive film Download PDF

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TW201404846A
TW201404846A TW102123410A TW102123410A TW201404846A TW 201404846 A TW201404846 A TW 201404846A TW 102123410 A TW102123410 A TW 102123410A TW 102123410 A TW102123410 A TW 102123410A TW 201404846 A TW201404846 A TW 201404846A
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meth
adhesive composition
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acrylate
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TWI550048B (en
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Takeshi Nagakura
Ryuusuke Shimaguchi
Ryo Hasegawa
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Fujimori Kogyo Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The present invention provides an adhesive composition that has excellent antistatic performance, that has excellent adhesive strength balance at a slow peel rate and at a fast peel rate, and that further also has excellent durability performance and reworking performance. In accordance with the present invention, an adhesive composition comprising an acrylic-based polymer of a copolymer including: (A) a (meth)acrylic acid ester monomer having a C4 to C10 alkyl group; (B) a hydroxyl group-containing copolymerizable monomer; and (C) a carboxyl group-containing copolymerizable monomer, wherein the adhesive composition further contains (D) an antistatic agent that is an ionic compound having a melting point of 30 to 80 DEG C, is provided.

Description

黏著劑組成物及表面保護膜Adhesive composition and surface protective film

於本發明關於一種用於液晶顯示器的製造過程中的表面保護膜。更詳細來說，本發明關於一種表面保護膜用黏著劑組合物及使用該黏著劑組合物的表面保護膜，藉由貼附在構成液晶顯示器的偏光板、相位差板等光學部件的表面，為了保護偏光板、相位差板等光學部件表面所使用。
The present invention relates to a surface protective film for use in a manufacturing process of a liquid crystal display. More specifically, the present invention relates to an adhesive composition for a surface protective film and a surface protective film using the same, which are attached to a surface of an optical member such as a polarizing plate or a phase difference plate constituting a liquid crystal display. In order to protect the surface of optical components such as polarizers and phase difference plates.

一直以來，在做為構成液晶顯示器的部件的偏光板、相位差板等光學部件的製造過程中，為了暫時保護光學部件的表面而黏貼表面保護膜。這種表面保護膜僅在製造光學部件的過程中使用，當將光學部件組裝於液晶顯示器時，將其從光學部件剝離而去除。由於這種用於保護光學部件表面的表面保護膜僅在製造過程中使用，因此，通常也被稱作“程序膜”。In the manufacturing process of an optical member such as a polarizing plate or a phase difference plate which is a member constituting a liquid crystal display, the surface protective film is adhered to temporarily protect the surface of the optical member. Such a surface protective film is used only in the process of manufacturing an optical component, and when the optical component is assembled to a liquid crystal display, it is peeled off from the optical component and removed. Since such a surface protective film for protecting the surface of an optical component is used only in a manufacturing process, it is also generally called a "program film."

對如此的製造光學部件的過程中使用的表面保護膜而言，在具有光學透明性的聚對苯二甲酸乙二醇酯（PET）樹脂膜的單面上形成有黏著劑層，但在黏著劑層上貼合有經過剝離處理的剝離膜，以保護該黏著劑層直至貼合於光學部件。
另外，對偏光板、相位差板等光學部件而言，由於在貼合了表面保護膜的狀態下進行伴隨液晶顯示板的顯示能力、色調、對比度、雜質混入等光學評價的產品檢驗，所以，做為對表面保護膜的性能要求，要求黏著劑層中不帶有氣泡、雜質。
另外，近年來，從偏光板、相位差板等光學部件上剝離表面保護膜時，伴隨著從被黏附體剝離黏著劑層時發生的靜電所產生的剝離靜電，有可能會影響到液晶顯示器的電控制電路的故障，因此，要求黏著劑層具有優良的抗靜電性能。
另外，在偏光板、相位差板等光學部件上貼合表面保護膜時，由於各種原因，會存在暫時剝離表面保護膜後再次重新黏貼表面保護膜的情況，此時要求容易從做為被黏附體的光學部件上剝離（再加工性）。
另外，從最終的偏光板、相位差板等光學部件剝離表面保護膜時，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。
如此地，近年來，從使用表面保護膜時容易操作的觀點出發，要求構成表面保護膜的黏著劑層具有如下性能：（1）在低剝離速度和高剝離速度下，取得黏著力的平衡；（2）防止黏著劑殘留的發生；（3）優良的抗靜電性能；以及（4）再加工（ReWork）性能等。
但是，雖然能夠分別滿足對構成表面保護膜的黏著劑層的性能要求，即，雖然能夠分別滿足上述（1）～（4）中的個別性能要求，但同時滿足要求表面保護膜的黏著劑層具有的（1）～（4）的全部性能要求，是非常困難的。
例如，關於（1）在低剝離速度和高剝離速度下取得黏著力的平衡、以及（2）防止黏著劑殘留的發生，已知有如下所述的建議。
在以具有碳原子數7以下的烷基的（甲基）丙烯酸烷基酯與含有羧基的共聚性化合物的共聚物做為主要成分，並且用交聯劑對它進行交聯處理而製成的丙烯酸類黏著劑層中，在經過長時間黏接的情況下，存在黏著劑向被黏附體一側移動而附著在被黏附體，並且對被黏附體的黏接力的經時上升性大的問題。為了避免該問題，已知有一種設置黏著劑層的技術方案，該黏著劑層是使用具有碳原子數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，並且用交聯劑對它進行交聯處理而成的黏著劑層（專利文獻1）。
另外，還提出了一種設置黏著劑層的技術方案，該黏著劑層是通過在與上述相同的共聚物中，配合少量的（甲基）丙烯酸烷基酯和含有羧基的共聚性化合物的共聚物，併用交聯劑對它進行交聯處理而成的黏著劑層。但是，當將其用於表面張力低且表面光滑的塑膠板等的表面保護中時，因加工時或保存時的加熱而產生分離等剝離現象、在手工操作領域中的高速剝離時再剝離性差。
為了解決這些問題，提出了一種黏著劑組合物，該黏著劑組合物是：在a）以具有碳原子數 8～10的烷基的（甲基）丙烯酸烷基酯做為主要成分的（甲基）丙烯酸烷基酯100重量份中，加入b）1～15重量份的含有羧基的共聚性化合物、以及c）3～100重量份的碳原子數1～5的脂肪族羧酸的乙烯基酯而得到單體混合物的共聚物，並且向該共聚物中配合上述b）成分的羧基的當量以上的交聯劑而成的黏著劑組合物（專利文獻2）。
在專利文獻2記載的黏著劑組合物中，在加工時或保存時不會產生分離等的剝離現象，並且，黏接力的經時上升性小，從而再剝離性優良，即使是長期保存、特別是在高溫環境下長期保存，也能夠以小的力量進行再剝離，此時在被黏附體上不殘留黏著劑，並且即使在進行高速剝離的情況下也能夠以小的力量進行再剝離。
另外，對（3）優良的抗靜電性能而言，做為用於對表面保護膜賦予抗靜電性能的方法，提出了在基材膜中混入抗靜電劑的方法等。做為抗靜電劑，例如公開了（a）具有季銨鹽、吡啶鎓、伯～叔氨基等陽離子基的各種陽離子抗靜電劑；（b）具有磺酸堿基、硫酸酯堿基、磷酸酯堿基、膦酸堿基等的陰離子基的陰離子抗靜電劑；（c）氨基酸類、氨基硫酸酯類等的兩性抗靜電劑、（d）氨基醇類、甘油類、聚乙二醇類等的非離子抗靜電劑；（e）使如上所述的抗靜電劑高分子量化得到的高分子型抗靜電劑等（專利文獻 3）。
另外，近年來提出了將如此的抗靜電劑直接包含於黏著劑層中，而不包含於基材膜或者塗佈於基材膜表面的方案。
另外，關於（4）再加工性，例如，提出了一種黏著劑組合物，該黏著劑組合物是：相對於100重量份丙烯酸類樹脂，配合0.0001～10重量份的異氰酸酯類化合物的固化劑和特定的矽酸鹽低聚物而獲得（專利文獻4）。
在專利文獻4中，記載有：以烷基的碳原子數為2～12左右的丙烯酸烷基酯、烷基的碳原子數為4～12左右的甲基丙烯酸烷基酯等做為主要單體成分，可含有例如含羧基的單體等含其他官能團的單體成分。通常而言，優選含有50重量％以上的上述主要單體，並希望含官能團的單體成分的含量為0.001～50重量％，優選為0.001～25重量％，更優選為0.01～25重量％。這種專利文獻4記載的黏著劑組合物，即使在高溫下或者高溫高濕下，其凝聚力和黏接力的經時變化也小，並對曲面的黏接力也顯示出優良的效果，因此具有再加工性。
通常，若黏著劑層為柔軟性狀，則容易產生黏著劑殘留、再加工性也容易降低。即，在錯誤貼合後剝離困難，並且難以重新黏貼。從該觀點出發，為了使其具有再加工性，需要將具有羧基等官能團的單體交聯於主劑上以使黏著劑層具有一定的硬度。For such a surface protective film used in the process of manufacturing an optical component, an adhesive layer is formed on one surface of an optically transparent polyethylene terephthalate (PET) resin film, but adhesively A release film that has been subjected to release treatment is attached to the agent layer to protect the adhesive layer until it is bonded to the optical member.
In addition, in an optical member such as a polarizing plate or a phase difference plate, product inspection with optical evaluation such as display performance, color tone, contrast, and impurity incorporation of the liquid crystal display panel is performed in a state in which the surface protective film is bonded, As a performance requirement for the surface protective film, it is required that the adhesive layer does not contain bubbles or impurities.
In addition, when the surface protective film is peeled off from an optical member such as a polarizing plate or a retardation plate, the static electricity generated by the static electricity generated when the adhesive layer is peeled off from the adherend is likely to affect the liquid crystal display. The failure of the electrical control circuit, therefore, requires the adhesive layer to have excellent antistatic properties.
In addition, when a surface protective film is bonded to an optical member such as a polarizing plate or a phase difference plate, there is a case where the surface protective film is temporarily peeled off after temporarily peeling off the surface protective film for various reasons, and at this time, it is required to be easily adhered. Peeling (reworkability) on the optical component of the body.
Further, when the surface protective film is peeled off from an optical member such as a final polarizing plate or a phase difference plate, it is required to be able to be quickly peeled off. That is, it is required that the adhesion force is small due to the change in the peeling speed, so that the peeling can be quickly performed even in the case of high-speed peeling.
As described above, in recent years, from the viewpoint of easy handling when using a surface protective film, it is required that the adhesive layer constituting the surface protective film has the following properties: (1) at a low peeling speed and a high peeling speed, a balance of adhesive force is obtained; (2) Prevention of the occurrence of adhesive residue; (3) Excellent antistatic properties; and (4) Rework performance.
However, the performance requirements for the adhesive layer constituting the surface protective film can be satisfied, that is, the adhesive properties of the surface protective film can be satisfied while satisfying the individual performance requirements of the above (1) to (4), respectively. It is very difficult to have all the performance requirements of (1) to (4).
For example, regarding (1) obtaining a balance of adhesive force at a low peeling speed and a high peeling speed, and (2) preventing occurrence of adhesive residue, the following suggestions are known.
a copolymer of a (meth)acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component, and which is crosslinked by a crosslinking agent. In the acrylic adhesive layer, when the adhesive is applied for a long period of time, there is a problem that the adhesive moves to the adherend to adhere to the adherend, and the adhesion to the adherend is increased with time. . In order to avoid this problem, a technical solution is provided in which an adhesive layer is used, which is an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group. The copolymer is a pressure-sensitive adhesive layer obtained by crosslinking the copolymer with a crosslinking agent (Patent Document 1).
In addition, a technical solution for providing an adhesive layer by copolymerizing a small amount of a (meth)acrylic acid alkyl ester and a carboxyl group-containing copolymerizable compound in the same copolymer as above is also proposed. And an adhesive layer formed by crosslinking the cross-linking agent with a crosslinking agent. However, when it is used for the surface protection of a plastic plate or the like having a low surface tension and a smooth surface, peeling phenomenon such as separation due to heating during processing or storage, and high peeling property in the field of manual operation are poor. .
In order to solve these problems, an adhesive composition is proposed which is based on a) an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms as a main component (A) To 100 parts by weight of 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 group having 1 to 5 carbon atoms of an aliphatic carboxylic acid; An adhesive composition obtained by mixing a copolymer of a monomer mixture and a crosslinking agent having a carboxyl group equivalent or more of the above b) component to the copolymer (Patent Document 2).
In the adhesive composition described in Patent Document 2, peeling phenomenon such as separation does not occur during processing or storage, and the adhesion strength is small with time, and the removability is excellent, even for long-term storage and special use. It is stored in a high-temperature environment for a long period of time, and it can be peeled off with a small force. In this case, the adhesive does not remain on the adherend, and the peeling can be performed with a small force even when high-speed peeling is performed.
Further, (3) excellent antistatic performance, as a method for imparting antistatic properties to the surface protective film, a method of mixing an antistatic agent into the base film has been proposed. As the antistatic agent, for example, (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium group, a primary to a tertiary amino group, and the like; (b) having a sulfonic acid sulfhydryl group, a sulfate sulfhydryl group, a phosphate ester An anionic antistatic agent such as an anion group such as a mercapto group or a phosphonium thiol group; (c) an amphoteric antistatic agent such as an amino acid or an aminosulfate; (d) an amino alcohol, a glycerin or a polyethylene glycol; (e) a polymer type antistatic agent obtained by polymerizing an antistatic agent as described above (Patent Document 3).
Further, in recent years, it has been proposed to incorporate such an antistatic agent directly into the adhesive layer without being contained in the substrate film or applied to the surface of the substrate film.
Further, regarding (4) reworkability, for example, an adhesive composition is proposed which is a curing agent containing 0.0001 to 10 parts by weight of an isocyanate compound per 100 parts by weight of the acrylic resin. It is obtained by a specific citrate oligomer (Patent Document 4).
Patent Document 4 describes that an alkyl acrylate having an alkyl group having a carbon number of from 2 to 12 or an alkyl methacrylate having an alkyl group having a carbon number of from 4 to 12 is used as a main single. The body component may contain, for example, a monomer component containing another functional group such as a carboxyl group-containing monomer. In general, it is preferable to contain 50% by weight or more of the above-mentioned main monomer, and it is desirable that the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, and more preferably 0.01 to 25% by weight. The adhesive composition described in Patent Document 4 has a small change in the cohesive force and the adhesive force over time even under high temperature or high temperature and high humidity, and exhibits an excellent effect on the adhesion of the curved surface. Processability.
In general, when the adhesive layer is soft, the adhesive remains easily and the reworkability is easily lowered. That is, it is difficult to peel off after the wrong bonding, and it is difficult to re-stick. From this point of view, in order to impart reworkability, it is necessary to crosslink a monomer having a functional group such as a carboxyl group to the main component so that the adhesive layer has a certain hardness.

現有技術文獻
專利文獻
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：日本特開平11-070629號公報
專利文獻4：日本特開平8-199130號公報
CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. -199130

發明要解決的課題
在現有技術中，做為對構成表面保護膜的黏著劑層的性能要求，一直以來要求其具有在低剝離速度和高剝離速度下取得黏著力的平衡、優良的抗靜電性能以及再加工性能等。但是，即使能夠分別滿足各項性能要求，也無法滿足做為表面保護膜的黏著劑層所要求的全部性能要求。

本發明是鑑於上述情況而完成的，其課題在於，提供一種黏著劑組合物和表面保護膜，具有優良的抗靜電性能、在低剝離速度和高剝離速度下的黏著力的平衡性優良、並且耐久性能和再加工性能也優良。
解決課題的方法
為了解決上述課題，本發明提供一種黏著劑組合物，其由共聚物的丙烯酸類聚合物構成，該共聚物的丙烯酸類聚合物含有（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體以及（C）含有羧基的可共聚的單體，更含有（D）熔點為30～80℃的做為離子化合物的抗靜電劑。
另外，相對於100重量份的前述（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，含有0.1～8.0重量份的前述（B）含有羥基的可共聚的單體；並且，在前述（B）含有羥基的可共聚的單體中，優選（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯以及（甲基）丙烯酸4-羥基丁酯的合計量為0～0.9重量份。
另外，相對於100重量份的前述（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選含有0.35～1.0重量份的前述（C）含有羧基的可共聚的單體，並且前述共聚物的酸值是0.01～9.0。
另外，優選前述（D）的做為離子化合物的抗靜電劑的熔點為30～49℃。
並且，優選含有（E）三官能以上的異氰酸酯化合物。
另外，前述（E）三官能以上的異氰酸酯化合物包括選自（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（E-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，並且相對於100重量份的前述共聚物，前述（E）三官能以上的異氰酸酯化合物的合計含量優選為0.5～5.0重量份。
另外，在前述黏著劑組合物中，相對於100重量份的前述共聚物，優選含有1.0～5.0重量份做為交聯抑制劑的酮烯醇互變異構化合物；相對於100重量份的前述共聚物，優選含有0.01～0.5重量份做為交聯催化劑的有機錫化合物。
另外，優選使前述黏著劑組合物交聯而成的黏著劑層在低剝離速度0.3m/min下的黏著力為0.05～0.1N/25mm，在高剝離速度30m/min下的黏著力為1.0N/25mm以下。
另外，優選使前述黏著劑組合物交聯而成的黏著劑層的表面電阻率為5.0×10+11Ω/□以下，剝離靜電壓為±0～0.3kV。
另外，本發明提供一種黏著膜，其是在樹脂膜的單面或雙面上形成黏著劑層而成，該黏著劑層是使前述黏著劑組合物交聯而成。
另外，本發明提供一種表面保護膜，其是在樹脂膜的單面上形成黏著劑層而成，該黏著劑層是使前述黏著劑組合物交聯而成。
另外，本發明的表面保護膜可做為偏光板的表面保護膜的用途加以使用。
另外，本發明的表面保護膜中，優選在樹脂膜的與形成有黏著劑層的一側相反的面上實施有抗靜電和防污處理。
發明效果
基於本發明，能夠滿足在現有技術中無法解決的對表面保護膜的黏著劑層所要求的全部性能，而且還能夠改善在低剝離速度和高剝離速度下黏著力的平衡性。

SUMMARY OF THE INVENTION Problems to be Solved by the Invention In the prior art, as a performance requirement for an adhesive layer constituting a surface protective film, it has been required to have a balance of adhesion at a low peeling speed and a high peeling speed, and excellent antistatic properties. And reworkability and so on. However, even if the performance requirements can be individually satisfied, it is impossible to satisfy all the performance requirements required for the adhesive layer as the surface protective film.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition and a surface protective film which have excellent antistatic properties, excellent balance of adhesion at a low peeling speed and a high peeling speed, and Durability and reworkability are also excellent.
Solution to Problem In order to solve the above problems, the present invention provides an adhesive composition comprising an acrylic polymer of a copolymer, wherein the acrylic polymer of the copolymer contains (A) an alkyl group having a carbon number of C4 to a (meth) acrylate monomer of C10, (B) a copolymerizable monomer having a hydroxyl group, and (C) a copolymerizable monomer having a carboxyl group, further containing (D) a melting point of 30 to 80 ° C as an ion An antistatic agent for the compound.
Further, the (B) hydroxyl group-containing (meth) acrylate monomer having a C4 to C10 carbon number is contained in an amount of 0.1 to 8.0 parts by weight based on 100 parts by weight of the (A) alkyl group-containing (C) hydroxyl group-containing copolymerizable monomer. Further, among the above (B) hydroxyl group-containing copolymerizable monomers, 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxy(meth)acrylate are preferable. The total amount of the butyl ester is from 0 to 0.9 parts by weight.
Further, it is preferable to contain 0.35 to 1.0 part by weight of the (C) carboxyl group-containing copolymerizable monomer with respect to 100 parts by weight of the (A) alkyl group having a C4 to C10 carbon atom (C). The monomer, and the aforementioned copolymer has an acid value of 0.01 to 9.0.
Further, it is preferable that the antistatic agent as the ionic compound of the above (D) has a melting point of 30 to 49 °C.
Further, it is preferred to contain (E) a trifunctional or higher isocyanate compound.
Further, the above (E) trifunctional or higher isocyanate compound includes at least one selected from the group consisting of (E-1) first aliphatic isocyanate compounds and selected from the group consisting of (E-2) second aromatic isocyanate compounds. The total content of the above-mentioned (E) trifunctional or higher isocyanate compound is preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer.
Further, in the above adhesive composition, it is preferred to contain 1.0 to 5.0 parts by weight of a ketoenol tautomer compound as a crosslinking inhibitor with respect to 100 parts by weight of the copolymer; and 100 parts by weight of the aforementioned copolymerization The material preferably contains 0.01 to 0.5 part by weight of an organotin compound as a crosslinking catalyst.
Further, it is preferable that the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has an adhesive force of 0.05 to 0.1 N/25 mm at a low peeling speed of 0.3 m/min, and an adhesive force of 1.0 at a high peeling speed of 30 m/min. N/25mm or less.
Further, it is preferable that the adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition has a surface resistivity of 5.0 × 10 + 11 Ω / □ or less and a peeling static voltage of ± 0 to 0.3 kV.
Further, the present invention provides an adhesive film obtained by forming an adhesive layer on one surface or both surfaces of a resin film, which is obtained by crosslinking the above-mentioned adhesive composition.
Further, the present invention provides a surface protective film obtained by forming an adhesive layer on one surface of a resin film, which is obtained by crosslinking the above-mentioned adhesive composition.
Further, the surface protective film of the present invention can be used as a surface protective film for a polarizing plate.
Further, in the surface protective film of the present invention, it is preferred to carry out an antistatic and antifouling treatment on the surface of the resin film opposite to the side on which the adhesive layer is formed.
Advantageous Effects of Invention According to the present invention, it is possible to satisfy all the properties required for the adhesive layer of the surface protective film which cannot be solved in the prior art, and it is also possible to improve the balance of the adhesive force at a low peeling speed and a high peeling speed.

下面，基於優選的實施方式說明本發明。
本發明的黏著劑組合物，其特徵在於，該黏著劑組合物由共聚物的丙烯酸類聚合物構成，該共聚物的丙烯酸類聚合物含有（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體以及（C）含有羧基的可共聚的單體，更含有（D）熔點為30～80℃的做為離子化合物的抗靜電劑。
做為（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，可列舉：（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（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）丙烯酸癸酯等。
做為（B）含有羥基的可共聚的單體，可以列舉：（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-羥基乙酯等（甲基）丙烯酸羥基烷基酯類；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）丙烯醯胺等含有羥基的（甲基）丙烯醯胺類等。
優選上述（B）含有羥基的可共聚的單體是選自於由（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）丙烯醯胺所組成的化合物組中的至少一種以上。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選含有0.1～8.0重量份的前述（B）含有羥基的可共聚的單體。
並且，在（B）含有羥基的可共聚的單體中，（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯和（甲基）丙烯酸4-羥基丁酯的合計量優選為低於1重量份（也允許不含有的情況），更優選為0～0.9重量份。
優選（C）含有羧基的可共聚的單體是選自於由（甲基）丙烯酸、（甲基）丙烯酸羧乙酯、（甲基）丙烯酸羧戊酯、2-（甲基）丙烯醯氧基乙基六氫鄰苯二甲酸、2-（甲基）丙烯醯氧基丙基六氫鄰苯二甲酸、2-（甲基）丙烯醯氧基乙基鄰苯二甲酸、2-（甲基）丙烯醯氧基乙基琥珀酸、2-（甲基）丙烯醯氧基乙基馬來酸、羧基聚己內酯單（甲基）丙烯酸酯、2-（甲基）丙烯醯氧基乙基四氫鄰苯二甲酸所組成的化合物組中的至少一種以上。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，（C）含有羧基的可共聚的單體的含量優選為0.35～1.0重量份，更優選為0.35～0.6重量份。
本發明中所用的丙烯酸類聚合物，還可以包括聚亞烷基二醇單（甲基）丙烯酸酯單體。做為聚亞烷基二醇單（甲基）丙烯酸酯單體，只要是聚亞烷基二醇所具有的多個羥基中的一個羥基被酯化為（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，因此能夠與主劑聚合物進行共聚。其他羥基，既可以保持OH的狀態，也可以成為甲醚、乙醚等的烷基醚，或者醋酸酯等飽和羧酸酯等。
做為聚亞烷基二醇所具有的亞烷基，可以列舉乙烯基、丙烯基、丁烯基等，但並不限定於這些。聚亞烷基二醇也可以是聚乙二醇、聚丙二醇、聚丁二醇等中的兩種以上聚亞烷基二醇的共聚物。做為聚亞烷基二醇的共聚物，可以列舉聚乙二醇-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，該共聚物可以是嵌段共聚物、無規共聚物。
做為前述聚亞烷基二醇單（甲基）丙烯酸酯單體，優選為選自聚亞烷基二醇單（甲基）丙烯酸酯、甲氧基聚亞烷基二醇（甲基）丙烯酸酯、乙氧基聚亞烷基二醇（甲基）丙烯酸酯中的至少一種以上。
更具體而言，可以列舉：聚乙二醇-單（甲基）丙烯酸酯、聚丙二醇-單（甲基）丙烯酸酯、聚丁二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丙二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丁二醇-單（甲基）丙烯酸酯、聚丙二醇-聚丁二醇-單（甲基）丙烯酸酯、聚乙二醇-聚丙二醇-聚丁二醇-單（甲基）丙烯酸酯；甲氧基聚乙二醇-（甲基）丙烯酸酯、甲氧基聚丙二醇-（甲基）丙烯酸酯、甲氧基聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯、甲氧基-聚乙二醇-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯；乙氧基聚乙二醇-（甲基）丙烯酸酯、乙氧基聚丙二醇-（甲基）丙烯酸酯、乙氧基聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丙二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯、乙氧基-聚乙二醇-聚丙二醇-聚丁二醇-（甲基）丙烯酸酯等。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，優選含有1～20重量份的前述聚亞烷基二醇單（甲基）丙烯酸酯單體。
本發明中使用的丙烯酸類聚合物，還可以包括含氮的乙烯基單體。做為含氮的乙烯基單體，可以列舉：含有醯胺鍵的乙烯基單體、含有氨基的乙烯基單體、具有含氮的雜環結構的乙烯基單體等。更具體而言，可以列舉：N-乙烯基-2-吡咯烷酮、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基呱啶酮、N-乙烯基嘧啶、N-乙烯基呱嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-乙烯基嗎啉、N-乙烯基己內醯胺、N-乙烯基十二內醯胺等的具有N-乙烯基取代的雜環結構的環狀氮乙烯基化合物；N-（甲基）丙烯醯基嗎啉、N-（甲基）丙烯醯基呱嗪、N-（甲基）丙稀醯基氮丙啶、N-（甲基）丙烯醯基吖丁啶、N-（甲基）丙烯醯基吡咯烷、N-（甲基）丙烯醯基呱啶、N-（甲基）丙烯醯基氮雜環庚烷、N-（甲基）丙烯醯基氮雜環辛烷等的具有N-（甲基）丙烯醯基取代的雜環結構的環狀氮乙烯基化合物；N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等具有在環內含有氮原子和乙烯基類不飽和鍵的雜環結構的環狀氮乙烯基化合物；（甲基）丙烯醯胺、N-甲基（甲基）丙烯醯胺、N-異丙基（甲基）丙烯醯胺、N-叔丁基（甲基）丙烯醯胺等未取代或者單烷基取代的（甲基）丙烯醯胺；N,N-二甲基（甲基）丙烯醯胺、N,N-二乙基（甲基）丙烯醯胺、N,N-二丙基丙烯醯胺、N,N-二異丙基（甲基）丙烯醯胺、N,N-二丁基（甲基）丙烯醯胺、N-乙基-N-甲基（甲基）丙烯醯胺、N-甲基-N-丙基（甲基）丙烯醯胺、N-甲基-N-異丙基（甲基）丙烯醯胺等二烷基取代（甲基）丙烯醯胺；N,N-二甲基氨基甲基（甲基）丙烯酸酯、N,N-二甲基氨基乙基（甲基）丙烯酸酯、N,N-二甲基氨基丙基（甲基）丙烯酸酯、N,N-二甲基氨基異丙基（甲基）丙烯酸酯、N,N-二甲基氨基丁基（甲基）丙烯酸酯、N,N-二乙基氨基甲基（甲基）丙烯酸酯、N,N-二乙基氨基乙基（甲基）丙烯酸酯、N-乙基-N-甲基氨基乙基（甲基）丙烯酸酯、N-甲基-N-丙基氨基乙基（甲基）丙烯酸酯、N-甲基-N-異丙基氨基乙基（甲基）丙烯酸酯、N,N-二丁基氨基乙基（甲基）丙烯酸酯、叔丁基氨基乙基（甲基）丙烯酸酯等二烷基氨基（甲基）丙烯酸酯；N,N-二甲基氨基丙基（甲基）丙烯醯胺、N,N-二乙基氨基丙基（甲基）丙烯醯胺、N,N-二丙基氨基丙基（甲基）丙烯醯胺、N,N-二異丙基氨基丙基（甲基）丙烯醯胺、N-乙基-N-甲基氨基丙基（甲基）丙烯醯胺、N-甲基-N-丙基氨基丙基（甲基）丙烯醯胺、N-甲基-N-異丙基氨基丙基（甲基）丙烯醯胺等的N,N-二烷基取代氨基丙基（甲基）丙烯醯胺；N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基-N-甲基乙醯胺等N-乙烯基羧酸醯胺類；N-甲氧基甲基（甲基）丙烯醯胺、N-乙氧基乙基（甲基）丙烯醯胺、N-丁氧基甲基（甲基）丙烯醯胺、二丙酮丙烯醯胺、N,N-亞甲基雙（甲基）丙烯醯胺等（甲基）丙烯醯胺類；（甲基）丙烯腈等不飽和羧酸腈類；等。
做為前述含氮的乙烯基單體，優選不含羥基，更優選不含羥基和羧基。做為這種單體，優選為上面例示的單體，例如：含有N,N-二烷基取代氨基、N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基-2-吡咯烷酮、N-乙烯基己內醯胺、N-乙烯基-2-呱啶酮等N-乙烯基取代內醯胺；N-（甲基）丙烯醯基嗎啉、N-（甲基）丙烯醯基吡咯烷等N-（甲基）丙烯醯基取代環狀胺類。
本發明中使用的丙烯酸類聚合物，還可以包括含有烷氧基的（甲基）丙烯酸烷基酯單體。做為含有烷氧基的（甲基）丙烯酸烷基酯單體，可以列舉：（甲基）丙烯酸2-甲氧基乙酯、（甲基）丙烯酸2-乙氧基乙酯、（甲基）丙烯酸2-丙氧基乙酯、（甲基）丙烯酸2-異丙氧基乙酯、（甲基）丙烯酸2-丁氧基乙酯、（甲基）丙烯酸2-甲氧基丙酯、（甲基）丙烯酸2-乙氧基丙酯、（甲基）丙烯酸2-丙氧基丙酯、（甲基）丙烯酸2-異丙氧基丙酯、（甲基）丙烯酸2-丁氧基丙酯、（甲基）丙烯酸3-甲氧基丙酯、（甲基）丙烯酸3-乙氧基丙酯、（甲基）丙烯酸3-丙氧基丙酯、（甲基）丙烯酸3-異丙氧基丙酯、（甲基）丙烯酸3-丁氧基丙酯、（甲基）丙烯酸4-甲氧基丁酯、（甲基）丙烯酸4-乙氧基丁酯、（甲基）丙烯酸4-丙氧基丁酯、（甲基）丙烯酸4-異丙氧基丁酯、（甲基）丙烯酸4-丁氧基丁酯等。
這些含有烷氧基的（甲基）丙烯酸烷基酯單體，具有（甲基）丙烯酸烷基酯中的烷基的原子被烷氧基取代的結構。
相對於100重量份的（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，前述不含羥基而含氮的乙烯基單體或者前述含有烷氧基的（甲基）丙烯酸烷基酯單體的含量優選為1～20重量份。對前述不含羥基而含氮的乙烯基單體和前述含有烷氧基的（甲基）丙烯酸烷基酯單體而言，可以分別使用一種，或者也可以併用兩種以上。
本發明的黏著劑組合物，含有（D）熔點為30～80℃的做為離子化合物的抗靜電劑。抗靜電劑可以是含有丙烯醯基的季銨鹽型離子化合物。
在本發明中，做為抗靜電劑，包括（D）熔點為30～80℃的做為離子化合物的抗靜電劑。由於這些抗靜電劑的熔點低且具有長鏈烷基，因此，推測與丙烯酸共聚物的親和性高。
（D）熔點為30～80℃的做為離子化合物的抗靜電劑，是具有陽離子和陰離子的離子化合物，可以列舉：陽離子為吡啶鎓陽離子、咪唑鎓陽離子、嘧啶鎓陽離子、吡唑鎓陽離子、吡咯鎓陽離子、銨基陽離子等的含氮鎓陽離子、或者磷鎓陽離子、硫鎓陽離子等，陰離子為六氟化磷酸根（PF6 -）、硫氰酸根（SCN-）、烷基苯磺酸根（RC6H4SO3 -）、高氯酸根（ClO4 -）、四氟化硼酸根()等的無機或有機陰離子的化合物。優選在常溫（例如30℃）下是固體，並通過選擇烷基的鏈長、取代基的位置、個數等，能夠得到熔點為30～80℃的化合物。優選陽離子為季氮鎓陽離子，可以列舉：1-烷基吡啶鎓（2～6位的碳原子既可以具有取代基也可以不具有取代基）等的季吡啶鎓陽離子、1,3-二烷基咪唑鎓（2、4、5位的碳原子既可以具有取代基也可以不具有取代基）等的季咪唑鎓陽離子、四烷基銨等的季銨陽離子等。
相對於100重量份的共聚物，優選含有0.1～5.0重量份的（D）熔點為30～80℃的做為離子化合物的抗靜電劑。
另外，優選（D）的做為離子化合物的抗靜電劑的熔點為30～49℃。
做為前述含有丙烯醯基的季銨鹽型離子化合物，是具有陽離子和陰離子的離子化合物，可以列舉：陽離子為（甲基）丙烯醯氧基烷基三烷基銨（R3N+-CnH2n-OCOCQ＝CH2，其中，Q＝H或CH3，R＝烷基）等的含有（甲基）丙烯醯基的季銨，陰離子為六氟化磷酸根（PF6 -）、硫氰酸根（SCN-）、有機磺酸根（RSO3 -）、高氯酸根（ClO4 -）、四氟化硼酸根（BF4 -）、含有F的醯亞胺根（RF 2N-）等的無機或有機陰離子的化合物。做為含F醯亞胺根（RF 2N-）的RF，可以列舉三氟甲磺醯基、五氟乙磺醯基等的全氟烷基磺醯基、氟磺醯基。做為含F醯亞胺根，可以列舉雙(氟磺醯基)醯亞胺根〔(FSO2)2N-〕、雙(三氟甲磺醯基)醯亞胺根〔(CF3SO2)2N-〕、雙(五氟乙磺醯基)醯亞胺根〔(C2F5SO2)2N-〕等的雙磺醯基醯亞胺根。
前述含有丙烯醯基的季銨鹽型離子化合物，優選在共聚物中共聚有0.1～5.0重量%。
做為前述抗靜電劑的具體例子，沒有特別限定，但做為前述熔點為30～80℃的離子化合物的具體例子，可以列舉1-辛基吡啶鎓六氟磷酸鹽、1-壬基吡啶鎓六氟磷酸鹽、2-甲基-1-十二烷基吡啶鎓六氟磷酸鹽、1-辛基吡啶鎓十二烷基苯磺酸鹽、1-十二烷基吡啶鎓硫氰酸鹽、1-十二烷基吡啶鎓十二烷基苯磺酸鹽、4-甲基-1-辛基吡啶鎓六氟磷酸鹽等。另外，做為前述含有丙烯醯基的季銨鹽型離子化合物的具體例子，可以列舉二甲基氨基甲基（甲基）丙烯酸酯六氟磷酸甲基鹽〔(CH3)3N＋CH2OCOCQ＝CH2‧PF6 -、其中，Q＝H或CH3〕、二甲基氨基乙基（甲基）丙烯酸酯雙(三氟甲磺醯基)醯亞胺甲基鹽〔(CH3)3N＋(CH2)2OCOCQ＝CH2‧(CF3SO2)2N-，其中，Q＝H或CH3〕、甲基丙烯酸二甲基氨基甲酯雙(氟磺醯基)醯亞胺甲基鹽〔(CH3)3N＋CH2OCOCQ＝CH2‧，其中，Q＝H或CH3〕等。
本發明的黏著劑組合物，優選在形成黏著劑層時使黏著劑聚合物進行交聯。做為使交聯反應發生的方法，既可以使黏著劑組合物含有已知的交聯劑，也可以通過紫外線（UV）等光交聯來進行交聯。做為交聯劑，可以列舉：二官能或三官能以上的異氰酸酯化合物、二官能或三官能以上的環氧化物、二官能或者三官能以上的丙烯酸酯化合物、金屬螯合物等。其中，優選為聚異氰酸酯化合物（二官能或三官能以上的異氰酸酯化合物），更優選為（E）三官能以上的異氰酸酯化合物。
做為（E）三官能以上的異氰酸酯化合物，只要是在一分子中至少具有三個以上的異氰酸酯（NCO）基的聚異氰酸酯化合物即可。聚異氰酸酯化合物包括脂肪族類異氰酸酯、芳香族類異氰酸酯、非環式類異氰酸酯、脂環式類異氰酸酯等分類，本發明可以是其中的任意種類。做為聚異氰酸酯化合物的具體例子，可以列舉：六亞甲基二異氰酸酯（HDI）、異佛爾酮二異氰酸酯（IPDI）、三甲基六亞甲基二異氰酸酯（TMDI）等脂肪族類異氰酸酯化合物；二苯基甲烷二異氰酸酯（MDI）、苯二甲基二異氰酸酯（XDI）、氫化苯二甲基二異氰酸酯（H6XDI）、二甲基二亞苯基二異氰酸酯（TOID）、甲苯二異氰酸酯（TDI）等芳香族類異氰酸酯化合物。
做為三官能以上的異氰酸酯化合物，可以列舉：二異氰酸酯類（在一分子中具有兩個NCO基的化合物）的縮二脲改質體或異氰脲酸酯改質體，與三羥甲基丙烷（TMP）或甘油等三價以上的多元醇（在一分子中至少具有三個以上OH基的化合物）的加成物（多元醇改質體）等。
並且，做為本發明中使用的（E）三官能以上的異氰酸酯化合物，優選包括選自（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（E-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，其中，該（E-1）第一脂肪族類異氰酸酯化合物組是由六亞甲基二異氰酸酯化合物的異氰脲酸酯、異佛爾酮二異氰酸酯化合物的異氰脲酸酯、六亞甲基二異氰酸酯化合物的加成物、異佛爾酮二異氰酸酯化合物的加成物、六亞甲基二異氰酸酯化合物的縮二脲、異佛爾酮二異氰酸酯化合物的縮二脲所組成；該（E-2）第二芳香族類異氰酸酯化合物組是由甲苯二異氰酸酯化合物的異氰脲酸酯、苯二甲基二異氰酸酯化合物的異氰脲酸酯、氫化苯二甲基二異氰酸酯化合物的異氰脲酸酯、甲苯二異氰酸酯化合物的加成物、苯二甲基二異氰酸酯化合物的加成物、氫化苯二甲基二異氰酸酯化合物的加成物所組成。優選併用（E-1）第一脂肪族類異氰酸酯化合物組和（E-2）第二芳香族類異氰酸酯化合物組。在本發明中，做為（E）三官能以上的異氰酸酯化合物，通過併用選自（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（E-2）第二芳香族類異氰酸酯化合物組中的至少一種以上，能夠進一步改善低速剝離區域和高速剝離區域中的黏著力的平衡性。
另外，優選（E）三官能以上的異氰酸酯化合物包括選自前述（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自前述（E-2）選自第二芳香族類異氰酸酯化合物組中的至少一種以上，並且相對於100重量份的前述共聚物，該（E）三官能以上的異氰酸酯化合物的合計含量為0.5～5.0重量份。另外，做為選自（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上與選自（E-2）第二芳香族類異氰酸酯化合物組中的至少一種以上的混合比率，以重量比計算優選為（E-1）:（E-2）在10% : 90%～90% : 10%的範圍內。
本發明的黏著劑組合物可以含有交聯抑制劑。做為交聯抑制劑，可以列舉：乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油酯、乙醯乙酸月桂酯、乙醯乙酸硬脂醯酯等的β-酮酯；乙醯丙酮、2,4-己二酮、苯甲醯丙酮等的β-二酮。這些是酮烯醇互變異構化合物，在以聚異氰酸酯化合物做為交聯劑的黏著劑組合物中，通過將交聯劑所具有的異氰酸酯基進行封閉，能夠抑制配合交聯劑後黏著劑組合物的粘度過度上升或凝膠化的現象，能夠延長黏著劑組合物的儲存期。
優選前述交聯抑制劑為酮烯醇互變異構化合物，特別優選為選自乙醯丙酮、乙醯乙酸乙酯所組成的化合物組中的至少一種以上。
相對於100重量份的共聚物，優選前述交聯抑制劑的含量為1.0～5.0重量份。
本發明的黏著劑組合物可以含有交聯催化劑。在以聚異氰酸酯化合物做為交聯劑的情況下，交聯催化劑只要是做為催化劑對前述共聚物和交聯劑的反應（交聯反應）發揮功能的物質即可，可以列舉：叔胺等的胺類化合物、有機錫化合物、有機鉛化合物、有機鋅化合物等有機金屬化合物等。
做為叔胺可以列舉：三烷基胺、N,N,N',N'-四烷基二胺、N,N-二烷基氨基醇、三乙烯基二胺、嗎啉衍生物、呱嗪衍生物等。
做為有機錫化合物，可以列舉：二烷基錫氧化物、二烷基錫的脂肪酸鹽、亞錫的脂肪酸鹽等。
優選前述交聯催化劑為有機錫化合物，特別優選為選自於由氧化二辛基錫、二月桂酸二辛基錫所組成的化合物組中的至少一種以上。
相對於100重量份的共聚物，優選前述交聯催化劑的含量為0.01～0.5重量份。
本發明的黏著劑組合物可以含有聚醚改質矽氧烷化合物。聚醚改質矽氧烷化合物是具有聚醚基的矽氧烷化合物，除了通常的矽氧烷單元（-SiR1 2-O-）之外，還具有包含聚醚基的矽氧烷單元（-SiR1(R2O(R3O)nR4)-O-）。在此，R1表示一種或兩種以上的烷基或芳基，R2和R3表示一種或兩種以上的亞烷基、R4表示一種或兩種以上的烷基、醯基等（末端基）。做為聚醚基可以列舉：聚氧化乙烯基（(C2H4O)n）或聚氧化丙烯基（(C3H6O)n）等聚氧化亞烷基。
優選前述聚醚改質矽氧烷化合物是HLB值為7～12的聚醚改質矽氧烷化合物。另外，相對於100重量份的共聚物，前述聚醚改質矽氧烷化合物的含量優選為0.01～0.5重量份。更優選為0.1～0.5重量份。
HLB是指例如JIS K3211（表面活性劑用語）等規定的親水親油平衡（親水性與親油性的比值）。
聚醚改質矽氧烷化合物，例如，可通過如下方法獲得：通過氫化矽烷化反應，使具有不飽和鍵和聚氧化亞烷基的有機化合物接枝在具有矽烷基的聚有機矽氧烷的主鏈而獲得。具體而言，可以列舉：二甲基矽氧烷-甲基（聚氧化乙烯）矽氧烷共聚物，二甲基矽氧烷-甲基（聚氧化乙烯）矽氧烷-甲基（聚氧化丙烯）矽氧烷共聚物，二甲基矽氧烷-甲基（聚氧化丙烯）矽氧烷共聚物等。
通過將上述聚醚改質矽氧烷化合物配合於黏著劑組合物，能夠改善黏著劑的黏著力和再加工性能。
本發明的黏著劑組合物還可以含有聚醚化合物。做為聚醚化合物，是具有聚烯化氧基(聚亞烷氧基，polyalkylene oxide group)的化合物，可以列舉聚亞烷基二醇等聚醚多元醇以及它們的衍生物。做為聚亞烷基二醇和聚烯化氧基中具有的亞烷基，可以列舉乙烯基、丙烯基、丁烯基等，但並不限定於這些。聚亞烷基二醇也可以是聚乙二醇、聚丙二醇、聚丁二醇等中的兩種以上聚亞烷基二醇的共聚物。做為聚亞烷基二醇的共聚物，可以列舉聚乙二醇-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，該共聚物可以是嵌段共聚物、無規共聚物。
做為聚亞烷基二醇的衍生物，可以列舉：聚氧化亞烷基單烷基醚、聚氧化亞烷基二烷基醚等聚氧化亞烷基烷基醚；聚氧化亞烷基單烯基醚、聚氧化亞烷基二烯基醚等聚氧化亞烷基烯基醚；聚氧化亞烷基單芳基醚、聚氧化亞烷基二芳基醚等聚氧化亞烷基芳基醚；聚氧化亞烷基烷基苯基醚、聚氧化亞烷基二醇單脂肪酸酯、聚氧化亞烷基二醇二脂肪酸酯等聚氧化亞烷基二醇脂肪酸酯；聚氧化亞烷基山梨糖醇酐脂肪酸酯，聚氧化亞烷基烷基胺，聚氧化亞烷基二胺等。
在此，做為聚亞烷基二醇衍生物中的烷基醚，可以列舉：甲醚、乙醚等低級烷基醚；十二烷基醚、十八烷基醚等高級烷基醚。做為聚亞烷基二醇衍生物中的烯基醚，可以列舉乙烯醚、烯丙醚、油醚（oleyl ether）等。另外，做為聚亞烷基二醇衍生物中的脂肪酸酯，可以列舉：醋酸酯、硬脂酸酯等飽和脂肪酸酯；（甲基）丙烯酸酯、油酸酯等不飽和脂肪酸酯。
優選聚醚化合物是含有氧化乙烯基（ethyleneoxide group）的化合物，更優選是含有聚氧化乙烯基（polyethyleneoxide group）的化合物。
當聚醚化合物具有聚合性官能團時，也可以使其與（甲基）丙烯酸類聚合物發生共聚。做為聚合性官能團，優選為（甲基）丙烯醯基、乙烯基、烯丙基等乙烯性官能團。做為具有聚合性官能團的聚醚化合物，可以列舉：聚亞烷基二醇單（甲基）丙烯酸酯、聚亞烷基二醇二（甲基）丙烯酸酯、烷氧基聚亞烷基二醇（甲基）丙烯酸酯、聚亞烷基二醇單烯丙醚、聚亞烷基二醇二烯丙醚、烷氧基聚亞烷基二醇烯丙醚、聚亞烷基二醇單乙烯醚、聚亞烷基二醇二乙烯醚、烷氧基聚亞烷基二醇乙烯醚等。
並且，做為其他成分，還可適當地配合含有烯化氧（alkylene oxide）的可共聚的（甲基）丙烯酸單體、（甲基）丙烯醯胺單體、二烷基取代丙烯醯胺單體、表面活性劑、固化促進劑、增塑劑、填充劑、固化抑制劑、加工助劑、抗老化劑、抗氧化劑等公知的添加劑。這些既可以單獨使用，也可以組合兩種以上使用。
做為用於本發明黏著劑組合物的主劑的共聚物，可通過使（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體以及（C）含有羧基的可共聚的單體進行聚合而合成。對共聚物的聚合方法沒有特別的限定，可以使用溶液聚合、乳液聚合等適當的聚合方法。在前述共聚物中，也可以使聚亞烷基二醇單（甲基）丙烯酸酯單體、不含羥基而含氮的乙烯基單體、含有烷氧基的（甲基）丙烯酸烷基酯單體、含有丙烯醯基的季銨鹽型離子化合物等其他單體進行共聚。
本發明的黏著劑組合物可通過在上述共聚物中配合（D）熔點為30～80℃的做為離子化合物的抗靜電劑、以及適當的任意添加劑來進行配製。
優選前述共聚物為丙烯酸類聚合物，優選含有50～100重量%的（甲基）丙烯酸酯單體或者（甲基）丙烯酸、（甲基）丙烯醯胺類等丙烯酸類單體。
另外，優選前述共聚物的酸值（丙烯酸類聚合物的酸值）為0.01～9.0。由此，能夠改善污染性並且提高防止黏著劑殘留現象發生的性能。
在此，“酸值”是表示酸含量的指標之一，是以中和1g含有羧基的聚合物所需要的氫氧化鉀的mg數來表示。
優選使前述黏著劑組合物交聯而成的黏著劑層在低剝離速度0.3m/min下的黏著力為0.05～0.1N/25mm，在高剝離速度30m/min下的黏著力為1.0N/25mm以下。由此，能夠獲得黏著力隨剝離速度的變化小的性能，即使是在高速剝離的情況下也可以迅速剝離。並且，即使為了重新黏貼而暫時剝離表面保護膜時，也無需過大的力量，易於從被黏附體剝離。
優選使前述黏著劑組合物進行交聯而成的黏著劑層的表面電阻率在5.0×10+11Ω/□以下，剝離靜電壓為±0～0.3kV。此外，在本發明中，所謂“±0～0.3kV”的意思是指“0～－0.3kV”和“0～＋0.3kV”、即“－0.3～＋0.3kV”。若表面電阻率大，則對剝離時因帶電而產生的靜電進行釋放的性能差，因此，通過使表面電阻率足夠小，能夠降低伴隨從被黏附體剝離黏著劑層時發生的靜電所產生的剝離靜電壓，能夠抑制對被黏附體的電控制電路等的影響。
優選使本發明的黏著劑組合物交聯而成的黏著劑層（交聯後的黏著劑）的凝膠分數為95～100％。由於凝膠分數如此高，在低剝離速度的情況下黏著力不會變得過大，降低了從共聚物中溶出未聚合單體或寡聚物的現象，從而能夠改善再加工性、高溫/高濕下的耐久性，並抑制被黏附體的污染。
本發明的黏著膜是在樹脂膜的單面或雙面形成黏著劑層而成，該黏著劑層是使本發明的黏著劑組合物交聯而成。另外，本發明的表面保護膜是在樹脂膜的單面形成黏著劑層而成，該黏著劑層是使本發明的黏著劑組合物交聯而成。在本發明的黏著劑組合物中，由於以良好的平衡性配合有上述（A）～（D）的各成分，所以具有優良的抗靜電性能，在低剝離速度和高剝離速度下的黏著力的平衡性優良，並且耐久性能以及再加工性能（用原子筆隔著黏著劑層在表面保護膜上進行描繪後，沒有向被黏附體轉移污染）也優良。因此，本發明的黏著膜能夠優選用作偏光板的表面保護膜。
做為黏著劑層的基材膜、保護黏著面的剝離膜（隔膜），可以使用聚酯膜等樹脂膜等。
對基材膜而言，可在樹脂膜的與形成有黏著劑層一側相反的面上，實施通過矽酮類、氟類的脫模劑或塗層劑、二氧化矽微粒等進行的防污處理，可實施通過抗靜電劑的塗佈或混入等進行的抗靜電處理。
對剝離膜而言，在與黏著劑層的黏著面進行貼合一側的面上，實施通過矽酮類、氟類的脫模劑等進行的脫模處理。

實施例
下面，基於實施例具體說明本發明。
<丙烯酸共聚物的製造>
[實施例1]
向配有攪拌器、溫度計、回流冷凝器和氮導入管的反應裝置中導入氮氣，從而用氮氣置換了反應裝置內的空氣。然後，向反應裝置中加入了100重量份的丙烯酸2-乙基己酯、0.9重量份的丙烯酸6-羥基己酯、0.4重量份的丙烯酸，並同時加入60重量份的溶劑（乙酸乙酯）。然後，經過2小時滴入0.1重量份的做為聚合反應起始劑的偶氮二異丁腈，在65℃下使其反應6小時，獲得了重均分子量為50萬的、用於實施例1的丙烯酸共聚物溶液1。取丙烯酸共聚物的一部分，做為後述的酸值測定試樣使用。

[實施例2～9和比較例1～4]
除了如表1中的（A）～（C）所述地分別調整了各單體的組成以外，與上述用於實施例1的丙烯酸共聚物溶液1同樣地進行操作，獲得了用於實施例2～9和比較例1～4中的丙烯酸共聚物溶液。

<黏著劑組合物和表面保護膜的製造>
[實施例1]
對按照如上所述製造的實施例1的丙烯酸共聚物溶液1，加入1.5重量份1-辛基吡啶鎓六氟磷酸鹽並進行攪拌後，加入0.5重量份Coronate HX（コロネートHX，六亞甲基二異氰酸酯化合物的異氰脲酸酯）、0.5重量份Coronate L（コロネートL，甲苯二異氰酸酯化合物與三羥甲基丙烷的加成物）後攪拌混合，獲得了實施例1的黏著劑組合物。將該黏著劑組合物塗佈於由塗有矽酮樹脂的聚對苯二甲酸乙二醇酯（PET）膜構成的剝離膜上，然後在90℃下進行乾燥而去除溶劑，獲得了黏著劑層厚度為25μm的黏著片。
然後，準備一個面上實施有抗靜電處理和防污處理的聚對苯二甲酸乙二醇酯（PET）膜，並將黏著片轉移至該聚對苯二甲酸乙二醇酯（PET）膜的與實施有抗靜電處理和防污處理的面的相反面上，獲得了具有“實施有抗靜電處理和防污處理的PET膜/黏著劑層/剝離膜（塗有矽酮樹脂的PET膜）”的層疊構成的實施例1的表面保護膜。
[實施例2～9和比較例1～4]
除了如表1的（D）～（E）所述地分別調整了各添加劑的組成以外，與上述實施例1的表面保護膜同樣地進行操作而獲得實施例2～9和比較1～4的表面保護膜。

表1中，括弧內的數值均表示以（A）組的合計重量設為100重量份而求出的各成分重量份的數值。另外，將表1中使用的各成分的縮寫對應的化合物名稱示於表2中。此外，Coronate（コロネート、註冊商標）HX、Coronate HL和Coronate L是日本聚氨酯工業股份有限公司（Nippon Polyurethane Industry Co., Ltd.）的商品名稱，Takenate（タケネート、註冊商標）D-140N、D-127N、D-110N、D-120N是三井化學股份有限公司的商品名稱。

<試驗方法和評價>
在23℃、50％RH的環境下，將實施例1～9和比較例1～4的表面保護膜老化7天後，剝掉剝離膜（塗有矽酮樹脂的PET膜），從而使黏著劑層外露，並做為測定表面電阻率的試樣。
進而，將該黏著劑層外露的表面保護膜，通過黏著劑層貼合於已黏貼在液晶單元上的偏光板表面，放置1天後在50℃、5個大氣壓下進行高壓鍋處理20分鐘，進一步在室溫下放置12小時，將由此得到的表面保護膜做為測定黏著力、剝離靜電壓、再加工性和耐久性的試樣。
<酸值>
丙烯酸類聚合物的酸值：將試樣溶解於溶劑（將二乙醚和乙醇以體積比2:1進行混合的溶劑）中，採用電位差自動滴定裝置（AT-610，京都電子工業股份有限公司製造），用濃度約0.1mol/L的氫氧化鉀乙醇溶液進行電位差滴定，測定了用於中和試樣所需的氫氧化鉀乙醇溶液的量。然後，根據下式來求出酸值。
酸值＝（B×f×5.611）/S
B＝滴定中使用的0.1mol/L氫氧化鉀乙醇溶液的量（mL）
f＝0.1mol/L氫氧化鉀乙醇溶液的係數
S＝試樣的固體成分的品質（g）
<黏著力>
採用拉伸試驗機，以低剝離速度（0.3m/min）和高剝離速度（30m/min），向180°方向剝離上述所得到的測定試樣（將25mm寬的表面保護膜貼合於偏光板表面而成的試樣），測定了剝離強度，並將該剝離強度做為黏著力。
<表面電阻率>
在老化後、貼合偏光板之前，剝掉剝離膜（塗有矽酮樹脂的PET膜）而使黏著劑層外露，採用電阻率儀HirestaUP-HT450（ハイレスタUP-HT450、股份有限公司三菱化學分析技術（Mitsubishi Chemical Analytech Co., Ltd.）製造），測定了黏著劑層的表面電阻率。
<剝離靜電壓>
採用高精度靜電感測器SK-035、SK-200（股份有限公司基恩士（Keyence Corporation）製造），測定當對上述所得到的測定試樣以30m/min的拉伸速度進行180°剝離時，偏光板帶電而產生的電壓（靜電壓），將測定值的最大值做為剝離靜電壓。
<再加工性>
用原子筆在上述得到的測定試樣的表面保護膜上進行描繪（載荷為500g、來回3次）後，從偏光板剝離表面保護膜，觀察偏光板的表面，確認沒有向偏光板轉移污染。評價目標基準：當沒有向偏光板轉移污染時評價為“○”；當確認沿著原子筆描繪的軌跡至少向局部轉移了污染時評價為“△”；當確認沿著原子筆描繪的軌跡有污染轉移並且從黏著劑表面也確認有黏著劑的脫離時評價為“×”。
<耐久性>
在60℃、90％RH環境下放置上述所得到的測定試樣250小時後，將其取出置於室溫下進一步地放置12小時，然後測定黏著力，確認與初期黏著力相比較沒有明顯的增加。評價目標基準：當試驗後的黏著力是初期黏著力的1.5倍以下的情況評價為“○”、超過1.5倍的情況評價為“×”。
將評價結果示於表3中。另外，在表面電阻率中，通過“mE+n”來表示“m×10+n”（其中，m為任意的實數，n為正整數）。

對實施例1～9的表面保護膜而言，在低剝離速度0.3m/min下的黏著力是0.05～0.1N/25mm，在高剝離速度30m/min下的黏著力是1.0N/25mm以下；表面電阻率在5.0×10+11Ω/□以下，剝離靜電壓為±0～0.3kV；並且，在使用原子筆隔著黏著劑層在表面保護膜進行描繪後，沒有向被黏附體轉移污染，而且在60℃、90％RH的環境下放置250小時後的耐久性也是優良的。
即，同時滿足了如下全部的性能要求：（1）取得低剝離速度和高剝離速度下黏著力的平衡性；（2）防止黏著劑殘留的發生；（3）優異的抗靜電性能；以及（4）再加工性能。
另外，通過併用選自（E-1）第一脂肪族類異氰酸酯化合物組中的一種以上和選自（E-2）第二芳香族類異氰酸酯化合物組中的一種以上，能夠改善低速剝離區域和高速剝離區域的黏著力的平衡性。
對比較例1的表面保護膜而言，由於不包含（C）含有羧基的可共聚的單體，其酸值為0；另外，可能是由於不包含（E）異氰酸酯化合物的緣故，其低剝離速度0.3m/min和高剝離速度30m/min下的黏著力過大，再加工性和耐久性差。
對比較例2的表面保護膜而言，可能是由於（B）含有羥基的單體過少、（E）異氰酸酯化合物中未併用（E-1）和（E-2）的緣故，其在低剝離速度0.3m/min下的黏著力和高剝離速度30m/min下的黏著力過大、表面電阻率和剝離靜電壓高、再加工性和耐久性差。
對比較例3的表面保護膜而言，其儲存期過短，由於在塗佈前已進行了交聯，因此，無法進行塗佈，這可能是因（E）異氰酸酯化合物過多的緣故。
對比較例4的表面保護膜而言，其儲存期過短，由於在塗佈前已進行了交聯，因此，無法進行塗佈，這可能是因（E）異氰酸酯化合物過多的緣故。
如上所述，在比較例1～4的表面保護膜中，無法同時滿足如下全部的性能要求：（1）取得低剝離速度和高剝離速度下的黏著力的平衡性；（2）防止黏著劑殘留的發生；（3）優異的抗靜電性能；以及（4）再加工性能。Hereinafter, the present invention will be described based on preferred embodiments.
The adhesive composition of the present invention is characterized in that the adhesive composition is composed of an acrylic polymer of a copolymer, and the acrylic polymer of the copolymer contains (A) an alkyl group having a carbon number of C4 to C10. a (meth) acrylate monomer, (B) a hydroxyl group-containing copolymerizable monomer, and (C) a carboxyl group-containing copolymerizable monomer, further containing (D) a melting point of 30 to 80 ° C as an ionic compound Antistatic agent.
Examples of the (meth) acrylate monomer having a CA to C10 carbon atom as the (A) alkyl group include butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. Amyl ester, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (A) Base) decyl acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, and the like.
Examples of the (B) hydroxyl group-containing copolymerizable monomer include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl A (meth) acrylamide containing hydroxyl group, such as a (meth) acrylamide.
Preferably, the (B) hydroxyl group-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Composition of 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide At least one or more of the compound groups.
The (B) hydroxyl group-containing copolymerizable monomer is preferably contained in an amount of 0.1 to 8.0 parts by weight based on 100 parts by weight of the (A) alkyl group-containing (meth) acrylate monomer having a C4 to C10 carbon number.
Further, in (B) a hydroxyl group-containing copolymerizable monomer, a total of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate The amount is preferably less than 1 part by weight (may not be contained), and more preferably 0 to 0.9 part by weight.
Preferably, the (C) carboxyl group-containing copolymerizable monomer is selected from the group consisting of (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(methyl)acrylonitrile. Ethyl hexahydrophthalic acid, 2-(methyl) propylene methoxypropyl hexahydrophthalic acid, 2-(methyl) propylene methoxyethyl phthalate, 2-(A Acryloxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2-(methyl) propylene decyloxy At least one or more of the compound groups consisting of ethyltetrahydrophthalic acid.
The content of the (C) carboxyl group-containing copolymerizable monomer is preferably 0.35 to 1.0 part by weight based on 100 parts by weight of the (A) alkyl group having a C4 to C10 (meth) acrylate monomer. More preferably, it is 0.35-0.6 weight part.
The acrylic polymer used in the present invention may further comprise a polyalkylene glycol mono(meth)acrylate monomer. The polyalkylene glycol mono(meth)acrylate monomer is a compound in which one of a plurality of hydroxyl groups of the polyalkylene glycol is esterified to a (meth)acrylate. . Since the (meth) acrylate group is a polymerizable group, it can be copolymerized with the main agent polymer. The other hydroxyl group may be in the state of OH, or may be an alkyl ether such as methyl ether or diethyl ether or a saturated carboxylic acid ester such as acetate.
The alkylene group which the polyalkylene glycol has may be, for example, a vinyl group, a propenyl group or a butenyl group, but is not limited thereto. The polyalkylene glycol may be a copolymer of two or more polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the copolymer of polyalkylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-polybutylene The diol or the like may be a block copolymer or a random copolymer.
As the polyalkylene glycol mono (meth) acrylate monomer, preferably selected from polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (methyl) At least one of acrylate and ethoxypolyalkylene glycol (meth) acrylate.
More specifically, polyethylene glycol mono- (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol - Polypropylene glycol-mono(meth)acrylate, polyethylene glycol-polybutylene glycol-mono(meth)acrylate, polypropylene glycol-polybutylene glycol-mono(meth)acrylate, polyethylene glycol- Polypropylene glycol-polybutylene glycol-mono(meth)acrylate; methoxypolyethylene glycol-(meth)acrylate, methoxypolypropylene glycol-(meth)acrylate, methoxy polybutylene Alcohol-(meth) acrylate, methoxy-polyethylene glycol-polypropylene glycol-(meth) acrylate, methoxy-polyethylene glycol-polybutylene glycol-(meth) acrylate, A Oxy-polypropylene glycol-polybutylene glycol-(meth)acrylate, methoxy-polyethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate; ethoxylated polyethylene glycol- (Meth) acrylate, ethoxypolypropylene glycol-(meth) acrylate, ethoxylated polybutylene glycol-(meth) acrylate, ethoxy-polyethylene glycol-polypropylene glycol-(A Acrylate, ethoxy-polyethylene glycol-polybutylene glycol-(meth) acrylate, ethoxy-polypropylene glycol-polybutylene glycol-(meth) acrylate, ethoxy-poly Ethylene glycol-polypropylene glycol-polybutylene glycol-(meth)acrylate or the like.
The polyalkylene glycol mono(meth)acrylic acid is preferably contained in an amount of from 1 to 20 parts by weight per 100 parts by weight of the (A) alkyl group having a C4 to C10 carbon atom (meth) acrylate monomer. Ester monomer.
The acrylic polymer used in the present invention may further include a nitrogen-containing vinyl monomer. Examples of the nitrogen-containing vinyl monomer include a vinyl monomer containing a guanamine bond, a vinyl monomer containing an amino group, a vinyl monomer having a nitrogen-containing heterocyclic structure, and the like. More specifically, it may, for example, be N-vinyl-2-pyrrolidone, N-vinylpyrrolidone, methylvinylpyrrolidone, N-vinylpyridine, N-vinylacridone, N-vinylpyrimidine, N -vinylpyridazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- a cyclic nitrogen-vinyl compound having an N-vinyl substituted heterocyclic structure such as vinyl dodecanoin; N-(methyl)propenylmorpholine, N-(methyl)propenylpyridazine , N-(methyl) acrylonitrile aziridine, N-(methyl) propylene decyl pyridine, N-(methyl) propylene decyl pyrrolidine, N-(methyl) propylene fluorenyl hydrazine Ring having a N-(meth)acrylinyl group-substituted heterocyclic ring structure such as pyridine, N-(methyl)propenylfluorenyl azepine or N-(methyl)propenyl azepine Nitro-vinyl compound; N-cyclohexylmaleimide, N-phenylmaleimide, etc. cyclic nitrogen-vinyl group having a heterocyclic structure containing a nitrogen atom and a vinyl-based unsaturated bond in the ring Compound; (methyl) Unsubstituted or monoalkyl substituted such as anilide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide (Meth) acrylamide; N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) acrylamide, N,N-dipropyl acrylamide, N , N-diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, N-A Dialkyl substituted (meth) acrylamide such as N-propyl-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide; N, N-dimethyl Aminomethyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, N,N-dimethylaminopropyl (meth) acrylate, N, N-di Methylaminoisopropyl (meth) acrylate, N,N-dimethylaminobutyl (meth) acrylate, N,N-diethylaminomethyl (meth) acrylate, N, N -Diethylaminoethyl (meth) acrylate, N-ethyl-N-methylaminoethyl (meth) acrylate, N-methyl-N-propylamino (meth) acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, tert-butylamino Dialkylamino (meth) acrylate such as methacrylic acid ester; N,N-dimethylaminopropyl (meth) acrylamide, N,N-diethylaminopropyl (methyl) Acrylamide, N,N-dipropylaminopropyl(meth)acrylamide, N,N-diisopropylaminopropyl(meth)acrylamide, N-ethyl-N-A Aminopropyl propyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) propylene N,N-dialkyl substituted aminopropyl (meth) acrylamide of guanamine or the like; N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamidine N-vinyl carboxylic acid amides such as amines; N-methoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, N-butoxymethyl ( Methyl) acrylamide, diacetone acrylamide, N,N-methylenebis(meth) acrylamide, etc. (meth) propylene Amine; (meth) acrylonitrile, unsaturated carboxylic acid nitriles and the like; and the like.
As the aforementioned nitrogen-containing vinyl monomer, it is preferably free of a hydroxyl group, and more preferably does not contain a hydroxyl group and a carboxyl group. As such a monomer, preferred are the monomers exemplified above, for example, an acrylic monomer containing an N,N-dialkyl substituted amino group, an N,N-dialkyl substituted guanamine group; N-vinyl- N-vinyl substituted indoleamine such as 2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-acridone; N-(methyl)propenylmorpholine, N-(methyl N-(meth)acrylinyl substituted cyclic amines such as acrylamidopyrrolidine.
The acrylic polymer used in the present invention may further include an alkyloxyalkyl (meth)acrylate monomer. Examples of the alkyl (meth)acrylate monomer containing an alkoxy group include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and (methyl). ) 2-propoxyethyl acrylate, 2-isopropoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 2-Ethoxypropyl (meth)acrylate, 2-propoxypropyl (meth)acrylate, 2-isopropoxypropyl (meth)acrylate, 2-butoxy (meth)acrylate Propyl ester, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 3-propoxypropyl (meth)acrylate, 3-iso(meth)acrylate Propyl propyl ester, 3-butoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, (meth)acrylic acid 4-propoxybutyl ester, 4-isopropoxybutyl (meth)acrylate, 4-butoxybutyl (meth)acrylate, and the like.
These alkoxy group-containing alkyl (meth)acrylate monomers have a structure in which an atom of an alkyl group in an alkyl (meth)acrylate is substituted with an alkoxy group.
a (meth) acrylate monomer having a C4 to C10 carbon number in terms of 100 parts by weight of the (A) alkyl group, a vinyl group containing no hydroxyl group and containing nitrogen, or the aforementioned alkoxy group-containing (A) The content of the alkyl acrylate monomer is preferably from 1 to 20 parts by weight. The above-mentioned hydroxyl group-free nitrogen-containing vinyl monomer and the alkoxy group-containing alkyl (meth)acrylate monomer may be used alone or in combination of two or more.
The adhesive composition of the present invention contains (D) an antistatic agent as an ionic compound having a melting point of 30 to 80 °C. The antistatic agent may be a quaternary ammonium salt type ionic compound containing an acrylonitrile group.
In the present invention, as the antistatic agent, (D) an antistatic agent as an ionic compound having a melting point of 30 to 80 ° C is included. Since these antistatic agents have a low melting point and a long-chain alkyl group, it is presumed that the affinity with the acrylic copolymer is high.
(D) an antistatic agent which is an ionic compound having a melting point of 30 to 80 ° C, and is an ionic compound having a cation and an anion, and examples thereof include a cation as a pyridinium cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, and a nitrogen-containing phosphonium cation such as a pyrrolidine cation or an ammonium cation, or a phosphonium cation or a sulfonium cation, and the anion is a hexafluorophosphate (PF)6 -), thiocyanate (SCN-), alkyl benzene sulfonate (RC6H4SO3 -), perchlorate (ClO4 -), tetrafluoroborate (Or a compound of an inorganic or organic anion. It is preferably a solid at normal temperature (for example, 30 ° C), and a compound having a melting point of 30 to 80 ° C can be obtained by selecting the chain length of the alkyl group, the position of the substituent, the number, and the like. Preferably, the cation is a quaternary nitrogen sulfonium cation, and a quaternary pyridinium cation or a 1,3-dioxane such as 1-alkylpyridinium (having a substituent or a substituent at a carbon atom of 2 to 6) may be mentioned. A quaternary immonium cation such as a quaternary imidazolium cation (a carbon atom at the 2, 4 or 5 position or a carbon atom at the 2, 4 or 5 position may have a substituent or a substituent), or a quaternary ammonium cation such as a tetraalkylammonium.
It is preferable to contain 0.1 to 5.0 parts by weight of (D) an antistatic agent as an ionic compound having a melting point of 30 to 80 ° C with respect to 100 parts by weight of the copolymer.
Further, it is preferred that the antistatic agent as the ionic compound of (D) has a melting point of 30 to 49 °C.
The quaternary ammonium salt type ionic compound containing the acryl fluorenyl group is an ionic compound having a cation and an anion, and examples thereof include a (meth) propylene decyloxyalkyltrialkylammonium (R).3N+-CnH2n-OCOCQ=CH2, where Q=H or CH3a quaternary ammonium salt containing (meth)acryl fluorenyl group such as R=alkyl group, and an anion of hexafluorophosphate (PF)6 -), thiocyanate (SCN-), organic sulfonate (RSO)3 -), perchlorate (ClO4 -), boron tetrafluoride (BF)4 -), yttrium ion containing F (RF 2N-Or a compound of an inorganic or organic anion. As a F-containing imine root (RF 2N-R)FExamples thereof include a perfluoroalkylsulfonyl group such as a trifluoromethanesulfonyl group or a pentafluoroethanesulfonyl group, and a fluorosulfonyl group. As F-containing imine roots, bis(fluorosulfonyl) ruthenium roots (FSO)2)2N-], bis(trifluoromethanesulfonyl) sulfhydryl root [(CF3SO2)2N-〕, bis(pentafluoroethanesulfonyl) ruthenium root [(C2F5SO2)2N-[] bis-sulfonyl ruthenium iodide.
The quaternary ammonium salt type ionic compound containing an acrylonitrile group is preferably copolymerized in the copolymer in an amount of 0.1 to 5.0% by weight.
Specific examples of the antistatic agent are not particularly limited, but specific examples of the ionic compound having a melting point of 30 to 80 ° C include 1-octylpyridinium hexafluorophosphate and 1-decylpyridinium. Hexafluorophosphate, 2-methyl-1-dodecylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzenesulfonate, 1-dodecylpyridinium thiocyanate , 1-dodecylpyridinium dodecylbenzenesulfonate, 4-methyl-1-octylpyridinium hexafluorophosphate, and the like. In addition, as a specific example of the quaternary ammonium salt type ionic compound containing an acrylonitrile group, dimethylaminomethyl (meth) acrylate hexafluorophosphate methyl salt [(CH)3)3N+CH2OCOCQ=CH2‧PF6 -Where Q=H or CH3], dimethylaminoethyl (meth) acrylate bis(trifluoromethanesulfonyl) quinone imine methyl salt [(CH3)3N+(CH2)2OCOCQ=CH2‧(CF3SO2)2N-, where Q=H or CH3], dimethyl methacrylate bis(fluorosulfonyl) quinone imine methyl salt [(CH3)3N+CH2OCOCQ=CH2‧, where Q=H or CH3〕Wait.
The adhesive composition of the present invention preferably crosslinks the adhesive polymer when the adhesive layer is formed. As a method of causing the crosslinking reaction to occur, the adhesive composition may contain a known crosslinking agent or may be crosslinked by photocrosslinking such as ultraviolet rays (UV). Examples of the crosslinking agent include a difunctional or trifunctional or higher isocyanate compound, a difunctional or trifunctional or higher epoxide, a difunctional or trifunctional or higher acrylate compound, a metal chelate compound, and the like. Among them, a polyisocyanate compound (difunctional or trifunctional or higher isocyanate compound) is preferable, and (E) a trifunctional or higher isocyanate compound is more preferable.
The (E) trifunctional or higher isocyanate compound may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule. The polyisocyanate compound includes a classification of an aliphatic isocyanate, an aromatic isocyanate, an acyclic isocyanate, an alicyclic isocyanate, and the like, and the present invention may be any of them. Specific examples of the polyisocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMDI). Diphenylmethane diisocyanate (MDI), benzodimethyl diisocyanate (XDI), hydrogenated dimethyl diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), toluene diisocyanate (TDI An aromatic isocyanate compound.
Examples of the trifunctional or higher isocyanate compound include a biuret modified or an isocyanurate modified product of a diisocyanate (a compound having two NCO groups in one molecule), and a trimethylol group. An adduct (polyol modified body) of a trivalent or higher polyvalent alcohol (a compound having at least three or more OH groups in one molecule) such as propane (TMP) or glycerin.
Further, the (E) trifunctional or higher isocyanate compound used in the present invention preferably includes at least one selected from the group consisting of (E-1) first aliphatic isocyanate compounds and selected from (E-2) At least one or more of the group of diaromatic isocyanate compounds, wherein the (E-1) first aliphatic isocyanate compound group is an isocyanurate or isophorone II from a hexamethylene diisocyanate compound An isocyanurate of an isocyanate compound, an adduct of a hexamethylene diisocyanate compound, an adduct of an isophorone diisocyanate compound, a biuret of a hexamethylene diisocyanate compound, and an isophorone II a biuret of an isocyanate compound; the (E-2) second aromatic isocyanate compound group is an isocyanurate of a toluene diisocyanate compound, an isocyanurate of a benzene dimethyl diisocyanate compound, An isocyanurate of a hydrogenated dimethylated diisocyanate compound, an adduct of a toluene diisocyanate compound, an adduct of a benzene diisocyanate compound, and a hydrogenated benzene An adduct of a methyl diisocyanate compound. Preferably, (E-1) a first aliphatic isocyanate compound group and (E-2) a second aromatic isocyanate compound group are used in combination. In the present invention, the (E) trifunctional or higher isocyanate compound is used in combination with at least one selected from the group consisting of (E-1) a first aliphatic isocyanate compound and a second aromatic selected from (E-2). At least one or more of the group of isocyanate compounds can further improve the balance of adhesion in the low-speed peeling region and the high-speed peeling region.
Further, it is preferable that the (E) trifunctional or higher isocyanate compound includes at least one selected from the group consisting of the above (E-1) first aliphatic isocyanate compound group and selected from the above (E-2) selected from the second aromatic group. At least one or more of the isocyanate compound groups, and the total content of the (E) trifunctional or higher isocyanate compound is 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer. Further, as a mixing ratio of at least one or more selected from the group consisting of (E-1) the first aliphatic isocyanate compound group and at least one selected from the group consisting of (E-2) second aromatic isocyanate compound, The weight ratio calculation is preferably (E-1): (E-2) is in the range of 10%: 90% to 90%: 10%.
The adhesive composition of the present invention may contain a crosslinking inhibitor. As the crosslinking inhibitor, there may be mentioned, for example, methyl acetate, ethyl acetate, octyl acetate, ethyl acetate, ethyl lauryl acetate, stearyl acetate, etc. a ketoester; a β-diketone such as acetamidineacetone, 2,4-hexanedione or benzamidineacetone. These are ketoenol tautomer compounds, and in the adhesive composition using a polyisocyanate compound as a crosslinking agent, by blocking the isocyanate group of the crosslinking agent, it is possible to suppress the adhesive composition after the crosslinking agent is blended. The phenomenon that the viscosity of the substance excessively rises or gels can prolong the storage period of the adhesive composition.
The crosslinking inhibitor is preferably a ketoenol tautomer compound, and particularly preferably at least one selected from the group consisting of ethyl acetonide and ethyl acetate.
The content of the crosslinking inhibitor is preferably 1.0 to 5.0 parts by weight based on 100 parts by weight of the copolymer.
The adhesive composition of the present invention may contain a crosslinking catalyst. In the case where the polyisocyanate compound is used as a crosslinking agent, the crosslinking catalyst may be a compound which functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent, and examples thereof include a tertiary amine. An amine compound, an organotin compound, an organic lead compound, an organometallic compound such as an organic zinc compound, or the like.
As the tertiary amine, there may be mentioned: trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylamino alcohol, trivinyldiamine, morpholine derivative, hydrazine Pyrazine derivatives and the like.
Examples of the organotin compound include a dialkyl tin oxide, a fatty acid salt of a dialkyl tin, a fatty acid salt of stannous, and the like.
The crosslinking catalyst is preferably an organotin compound, and particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.
The content of the crosslinking catalyst is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the copolymer.
The adhesive composition of the present invention may contain a polyether modified oxirane compound. The polyether modified siloxane compound is a siloxane compound having a polyether group, in addition to the usual siloxane unit (-SiR)1 2In addition to -O-), it also has a siloxane unit containing a polyether group (-SiR)1(R2O(R3O)nR4)-O-). Here, R1Represents one or two or more alkyl or aryl groups, R2And R3Represents one or two or more alkylene groups, R4One or two or more alkyl groups, mercapto groups and the like (end group) are indicated. As a polyether group, a polyoxyethylene group (C)2H4O)n) or polyoxypropylene base ((C3H6O)na polyalkylene oxide.
Preferably, the polyether modified oxirane compound is a polyether modified siloxane compound having an HLB value of 7 to 12. Further, the content of the polyether modified siloxane compound is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the copolymer. More preferably, it is 0.1 to 0.5 part by weight.
HLB is a predetermined hydrophilic-lipophilic balance (ratio of hydrophilicity to lipophilicity) such as JIS K3211 (surfactant term).
The polyether modified oxoxane compound can be obtained, for example, by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group to a polyorganosiloxane having a decyl group by a hydrogenation oximation reaction. Obtained from the main chain. Specifically, a dimethyl methoxy oxane-methyl (polyoxyethylene) phthalate copolymer, dimethyl methoxy oxane-methyl (polyethylene oxide) decane-methyl (polyoxidation) Propylene) a decane copolymer, a dimethyl methoxy alkane-methyl (polyoxypropylene) siloxane copolymer, and the like.
By blending the above polyether modified siloxane compound with the adhesive composition, the adhesion and reworkability of the adhesive can be improved.
The adhesive composition of the present invention may further contain a polyether compound. The polyether compound is a compound having a polyalkylene oxide group, and examples thereof include polyether polyols such as polyalkylene glycols and derivatives thereof. The alkylene group contained in the polyalkylene glycol and the polyalkylene oxide may, for example, be a vinyl group, a propenyl group or a butenyl group, but is not limited thereto. The polyalkylene glycol may be a copolymer of two or more polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the copolymer of polyalkylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-polybutylene The diol or the like may be a block copolymer or a random copolymer.
Examples of the derivative of the polyalkylene glycol include a polyoxyalkylene alkyl ether such as a polyoxyalkylene monoalkyl ether or a polyoxyalkylene dialkyl ether; and a polyoxyalkylene group. a polyoxyalkylene alkenyl ether such as an alkenyl ether or a polyoxyalkylene dialkyl ether; a polyoxyalkylene aryl group such as a polyoxyalkylene monoaryl ether or a polyoxyalkylene diaryl ether; Polyoxyalkylene alkyl phenyl ether, polyoxyalkylene glycol mono fatty acid ester, polyoxyalkylene glycol di fatty acid ester and other polyoxyalkylene glycol fatty acid ester; polyoxidation An alkylene sorbitan fatty acid ester, a polyoxyalkylene alkylamine, a polyoxyalkylene diamine or the like.
Here, examples of the alkyl ether in the polyalkylene glycol derivative include lower alkyl ethers such as methyl ether and diethyl ether; and higher alkyl ethers such as lauryl ether and octadecyl ether. Examples of the alkenyl ether in the polyalkylene glycol derivative include vinyl ether, allyl ether, and oleyl ether. Further, examples of the fatty acid ester in the polyalkylene glycol derivative include saturated fatty acid esters such as acetate and stearate; and unsaturated fatty acid esters such as (meth) acrylate and oleic acid ester. .
Preferably, the polyether compound is a compound containing an ethylene oxide group, and more preferably a compound containing a polyoxyethylene group.
When the polyether compound has a polymerizable functional group, it can also be copolymerized with a (meth)acrylic polymer. The polymerizable functional group is preferably an ethylenic functional group such as a (meth)acryl fluorenyl group, a vinyl group or an allyl group. Examples of the polyether compound having a polymerizable functional group include polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and alkoxypolyalkylene II. Alcohol (meth) acrylate, polyalkylene glycol monoallyl ether, polyalkylene glycol diallyl ether, alkoxy polyalkylene glycol allyl ether, polyalkylene glycol single Vinyl ether, polyalkylene glycol divinyl ether, alkoxy polyalkylene glycol vinyl ether, and the like.
Further, as other components, a copolymerizable (meth)acrylic monomer, a (meth)acrylamide monomer, a dialkyl-substituted acrylamide monoamine containing an alkylene oxide may be appropriately blended. A well-known additive such as a body, a surfactant, a curing accelerator, a plasticizer, a filler, a curing inhibitor, a processing aid, an anti-aging agent, and an antioxidant. These may be used alone or in combination of two or more.
The copolymer used as the main component of the adhesive composition of the present invention may be a (meth) acrylate monomer having (C) an alkyl group having a C4 to C10 carbon number, and (B) a hydroxyl group-containing copolymer. The copolymerized monomer and (C) a carboxyl group-containing copolymerizable monomer are polymerized and synthesized. The polymerization method of the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used. In the above copolymer, a polyalkylene glycol mono(meth)acrylate monomer, a hydroxyl group-free nitrogen-containing vinyl monomer, and an alkoxy group-containing (meth)acrylic acid alkyl ester may also be used. Other monomers such as a monomer or a quaternary ammonium salt type ionic compound containing an acrylonitrile group are copolymerized.
The adhesive composition of the present invention can be prepared by blending (D) an antistatic agent as an ionic compound having a melting point of 30 to 80 ° C in the above copolymer, and an appropriate optional additive.
The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100% by weight of a (meth) acrylate monomer or an acrylic monomer such as (meth)acrylic acid or (meth)acrylamide.
Further, the acid value (acid value of the acrylic polymer) of the copolymer is preferably 0.01 to 9.0. Thereby, it is possible to improve the staining property and improve the performance of preventing the occurrence of the adhesive residue.
Here, the "acid value" is one of the indexes indicating the acid content, and is expressed by the number of mg of potassium hydroxide required to neutralize 1 g of the carboxyl group-containing polymer.
Preferably, the adhesive layer obtained by crosslinking the above-mentioned adhesive composition has an adhesive force of 0.05 to 0.1 N/25 mm at a low peeling speed of 0.3 m/min, and an adhesive force of 1.0 N/at a high peeling speed of 30 m/min. 25mm or less. Thereby, it is possible to obtain a performance in which the change in the adhesive force with the peeling speed is small, and it is possible to quickly peel off even in the case of high-speed peeling. Further, even if the surface protective film is temporarily peeled off for re-adhesion, it does not require excessive force and is easily peeled off from the adherend.
Preferably, the adhesive layer obtained by crosslinking the above adhesive composition has a surface resistivity of 5.0 × 10+11Below Ω/□, the peeling static voltage is ±0 to 0.3 kV. Further, in the present invention, "±0 to 0.3 kV" means "0 to -0.3 kV" and "0 to +0.3 kV", that is, "-0.3 to +0.3 kV". When the surface resistivity is large, the performance of releasing static electricity due to charging at the time of peeling is inferior. Therefore, by making the surface resistivity sufficiently small, it is possible to reduce the static electricity generated when the adhesive layer is peeled off from the adherend. By peeling off the static voltage, it is possible to suppress the influence on the electric control circuit or the like of the adherend.
The adhesive layer (adhesive after crosslinking) obtained by crosslinking the adhesive composition of the present invention preferably has a gel fraction of 95 to 100%. Since the gel fraction is so high, the adhesion does not become excessive at a low peeling speed, and the phenomenon of eluting unpolymerized monomers or oligomers from the copolymer is lowered, thereby improving reworkability, high temperature/high Durability under wet and inhibit contamination by adherends.
The adhesive film of the present invention is formed by forming an adhesive layer on one or both sides of a resin film which is obtained by crosslinking the adhesive composition of the present invention. Further, the surface protective film of the present invention is obtained by forming an adhesive layer on one surface of a resin film, and the adhesive layer is obtained by crosslinking the adhesive composition of the present invention. In the adhesive composition of the present invention, since the components (A) to (D) are blended with good balance, they have excellent antistatic properties and adhesion at a low peeling speed and a high peeling speed. It is also excellent in balance, durability, and reworkability (the ink is not transferred to the adherend after being drawn on the surface protective film with the pen atom through the adhesive layer). Therefore, the adhesive film of the present invention can be preferably used as a surface protective film of a polarizing plate.
As the base film of the adhesive layer and the release film (separator) which protects the adhesive surface, a resin film such as a polyester film or the like can be used.
In the base film, the surface of the resin film opposite to the side on which the adhesive layer is formed can be prevented by a release agent, a coating agent, cerium oxide particles or the like of an anthrone or a fluorine-based release agent. For the stain treatment, an antistatic treatment by coating or mixing of an antistatic agent or the like can be performed.
In the release film, a release treatment by an anthrone or a fluorine release agent is performed on the surface on the side where the adhesive surface of the adhesive layer is bonded.

Example
Hereinafter, the present invention will be specifically described based on examples.
<Manufacture of Acrylic Copolymer>
[Example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, thereby replacing the air in the reaction apparatus with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 parts by weight of 6-hydroxyhexyl acrylate, 0.4 parts by weight of acrylic acid, and 60 parts by weight of a solvent (ethyl acetate) were simultaneously added to the reaction apparatus. . Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain a weight average molecular weight of 500,000, which was used in the examples. 1 acrylic copolymer solution 1. A part of the acrylic copolymer was used as an acid value measurement sample to be described later.

[Examples 2 to 9 and Comparative Examples 1 to 4]
Except that the composition of each monomer was adjusted as described in (A) to (C) in Table 1, the operation was carried out in the same manner as in the above-described acrylic copolymer solution 1 used in Example 1, and the obtained examples were used. The acrylic copolymer solution of 2 to 9 and Comparative Examples 1 to 4.

<Manufacture of Adhesive Composition and Surface Protective Film>
[Example 1]
To the acrylic copolymer solution 1 of Example 1 produced as described above, 1.5 parts by weight of 1-octylpyridinium hexafluorophosphate was added and stirred, and then 0.5 part by weight of Coronate HX (コロネート HX, hexamethylene group) was added. The isocyanurate of the diisocyanate compound and 0.5 part by weight of Coronate L (an adduct of a toluene diisocyanate compound and trimethylolpropane) were stirred and mixed to obtain an adhesive composition of Example 1. The adhesive composition was applied onto a release film composed of a polyethylene terephthalate (PET) film coated with an anthrone resin, and then dried at 90 ° C to remove the solvent to obtain an adhesive. An adhesive sheet having a layer thickness of 25 μm.
Then, a polyethylene terephthalate (PET) film having an antistatic treatment and an antifouling treatment on one surface is prepared, and the adhesive sheet is transferred to the polyethylene terephthalate (PET) film. On the opposite side of the surface on which antistatic treatment and antifouling treatment was carried out, a PET film/adhesive layer/release film (PET film coated with an anthrone resin) having antistatic treatment and antifouling treatment was obtained. The surface protective film of Example 1 which is laminated.
[Examples 2 to 9 and Comparative Examples 1 to 4]
The compositions of Examples 2 to 9 and Comparative Examples 1 to 4 were obtained in the same manner as in the surface protective film of Example 1 except that the composition of each additive was adjusted as described in (D) to (E) of Table 1 . Surface protection film.

In Table 1, the numerical values in the parentheses indicate the numerical values of the respective component parts by weight obtained by setting the total weight of the group (A) to 100 parts by weight. In addition, the compound name corresponding to the abbreviation of each component used in Table 1 is shown in Table 2. In addition, Coronate (registered trademark) HX, Coronate HL and Coronate L are trade names of Nippon Polyurethane Industry Co., Ltd., Takenate (registered trademark) D-140N, D- 127N, D-110N, and D-120N are trade names of Mitsui Chemicals Co., Ltd.

<Test method and evaluation>
After the surface protective films of Examples 1 to 9 and Comparative Examples 1 to 4 were aged for 7 days in an environment of 23 ° C and 50% RH, the release film (PET film coated with an anthrone resin) was peeled off to adhere the film. The agent layer was exposed and used as a sample for measuring the surface resistivity.
Further, the surface protective film exposed to the adhesive layer was bonded to the surface of the polarizing plate adhered to the liquid crystal cell through an adhesive layer, and left for 1 day, and then subjected to autoclave treatment at 50 ° C and 5 atm for 20 minutes, further. The surface protective film thus obtained was used as a sample for measuring adhesion, peeling static voltage, reworkability, and durability by allowing to stand at room temperature for 12 hours.
<acid value>
Acid value of acrylic polymer: The sample is dissolved in a solvent (a solvent in which diethyl ether and ethanol are mixed at a volume ratio of 2:1), and an electric potential difference automatic titrator (AT-610, manufactured by Kyoto Electronics Industry Co., Ltd.) is used. The potentiometric titration was carried out with a potassium hydroxide ethanol solution having a concentration of about 0.1 mol/L, and the amount of the potassium hydroxide ethanol solution required for neutralizing the sample was measured. Then, the acid value was determined according to the following formula.
Acid value = (B × f × 5.611) / S
B = amount of 0.1 mol/L potassium hydroxide ethanol solution used in the titration (mL)
f=0.1mol/L coefficient of potassium hydroxide ethanol solution
S = quality of the solid component of the sample (g)
<adhesion>
Using a tensile tester, the above-obtained measurement sample was peeled off at a low peeling speed (0.3 m/min) and a high peeling speed (30 m/min) in a 180° direction (a 25 mm wide surface protective film was attached to the polarized light). The sample formed on the surface of the plate was measured for peel strength, and the peel strength was used as the adhesion.
<surface resistivity>
After aging, before peeling off the polarizing plate, peeling off the peeling film (PET film coated with fluorenone resin) to expose the adhesive layer, using a resistivity meter HirestaUP-HT450 (ハイレスタUP-HT450, Ltd. Mitsubishi Chemical Analysis The surface resistivity of the adhesive layer was measured by a technique (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
<peeling static voltage>
Using a high-precision electrostatic sensor SK-035, SK-200 (manufactured by Keyence Corporation), the 180 ° peeling was performed on the measurement sample obtained above at a tensile speed of 30 m/min. At the time, the voltage (static voltage) generated when the polarizing plate is charged is used, and the maximum value of the measured value is taken as the peeling static voltage.
<Reworkability>
The surface protective film of the measurement sample obtained above was drawn with a ball pen (loading was 500 g, three times back and forth), and the surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed, and it was confirmed that no contamination was transferred to the polarizing plate. Evaluation target criterion: when the contamination is not transferred to the polarizing plate, it is evaluated as "○"; when it is confirmed that the trajectory drawn along the atomic pen is at least partially transferred to the pollution, it is evaluated as "△"; when it is confirmed that the trajectory drawn along the atomic pen has The contamination was transferred and evaluated as "X" when the adhesion of the adhesive was confirmed from the surface of the adhesive.
<Durability>
After the measurement sample obtained above was placed in an environment of 60 ° C and 90% RH for 250 hours, it was taken out and left at room temperature for further 12 hours, and then the adhesion was measured, and it was confirmed that there was no significant difference compared with the initial adhesion. increase. Evaluation target standard: When the adhesion after the test was 1.5 times or less of the initial adhesive force, it was evaluated as "○", and when it was more than 1.5 times, it was evaluated as "X".
The evaluation results are shown in Table 3. In addition, in the surface resistivity, "m × 10" means "m × 10"+n"(where m is an arbitrary real number and n is a positive integer).

The surface protective films of Examples 1 to 9 had an adhesive force at a low peeling speed of 0.3 m/min of 0.05 to 0.1 N/25 mm, and an adhesive force at a high peeling speed of 30 m/min of 1.0 N/25 mm or less. ; surface resistivity is 5.0×10+11Ω/□ or less, the peeling static voltage is ±0 to 0.3 kV; and, after being drawn on the surface protective film with the pen holder through the adhesive layer, no contamination is transferred to the adherend, and at 60 ° C, 90% RH The durability after leaving for 250 hours is also excellent.
That is, all of the following performance requirements are satisfied: (1) achieving balance of adhesion at low peeling speed and high peeling speed; (2) preventing occurrence of adhesive residue; (3) excellent antistatic property; 4) Reworkability.
In addition, by using one or more selected from the group consisting of (E-1) the first aliphatic isocyanate compound and one or more selected from the group consisting of the (E-2) second aromatic isocyanate compound, the low-speed peeling region and the low-speed peeling region can be improved. The balance of adhesion in the high speed peeling zone.
The surface protective film of Comparative Example 1 has an acid value of 0 because it does not contain (C) a carboxyl group-containing copolymerizable monomer; and may have a low peeling because it does not contain the (E) isocyanate compound. The adhesion at a speed of 0.3 m/min and a high peeling speed of 30 m/min is too large, and the workability and durability are poor.
In the surface protective film of Comparative Example 2, the (B) hydroxyl group-containing monomer was too small, and (E) the isocyanate compound was not used in combination (E-1) and (E-2), which was low in peeling. The adhesion at a speed of 0.3 m/min and the high peeling speed at 30 m/min are too large, the surface resistivity and the peeling static voltage are high, and the workability and durability are poor.
The surface protective film of Comparative Example 3 had a short storage period, and since it was crosslinked before coating, coating could not be performed, which may be due to excessive (E) isocyanate compound.
The surface protective film of Comparative Example 4 had a too short storage period, and since it was crosslinked before coating, coating could not be performed, which may be due to excessive (E) isocyanate compound.
As described above, in the surface protective films of Comparative Examples 1 to 4, it was not possible to simultaneously satisfy all of the following performance requirements: (1) achieving a balance of adhesion at a low peeling speed and a high peeling speed; (2) preventing an adhesive Residual occurrence; (3) excellent antistatic properties; and (4) reworkability.

 

Claims (1)

1．一種黏著劑組合物，由共聚物的丙烯酸類聚合物構成，該共聚物的丙烯酸類聚合物含有（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體、（B）含有羥基的可共聚的單體以及（C）含有羧基的可共聚的單體，更含有（D）熔點為30～80℃的做為離子化合物的抗靜電劑。
2．如申請專利範圍第1項所述的黏著劑組合物，其中相對於100重量份的該（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，含有0.1～8.0重量份的該（B）含有羥基的可共聚的單體，在該（B）含有羥基的可共聚的單體中，（甲基）丙烯酸8-羥基辛酯、（甲基）丙烯酸6-羥基己酯以及（甲基）丙烯酸4-羥基丁酯的合計量為0～0.9重量份。
3．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中相對於100重量份的該（A）烷基的碳原子數為C4～C10的（甲基）丙烯酸酯單體，含有0.35～1.0重量份的該（C）含有羧基的可共聚的單體，該共聚物的酸值是0.01～9.0。
4．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中該（D）的做為離子化合物的抗靜電劑的熔點為30～49℃。
5．如申請專利範圍第3項所述的黏著劑組合物，其中該（D）的做為離子化合物的抗靜電劑的熔點為30～49℃。
6．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中更含有（E）三官能以上的異氰酸酯化合物。
7．如申請專利範圍第3項所述的黏著劑組合物，其中更含有（E）三官能以上的異氰酸酯化合物。
8．如申請專利範圍第4項所述的黏著劑組合物，其中更含有（E）三官能以上的異氰酸酯化合物。
9．如申請專利範圍第5項所述的黏著劑組合物，其中更含有（E）三官能以上的異氰酸酯化合物。
10．如申請專利範圍第6項所述的黏著劑組合物，其中該（E）三官能以上的異氰酸酯化合物包括選自（E-1）第一脂肪族類異氰酸酯化合物組中的至少一種以上和選自（E-2）第二芳香族類異氰酸酯化合物組中的至少一種以上；相對於100重量份的該共聚物，該（E）三官能以上的異氰酸酯化合物的合計含量為0.5～5.0重量份。
11．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中在該黏著劑組合物中，相對於100重量份的該共聚物，含有1.0～5.0重量份做為交聯抑制劑的酮烯醇互變異構化合物；相對於100重量份的該共聚物，含有0.01～0.5重量份做為交聯催化劑的有機錫化合物。
12．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中使該黏著劑組合物交聯而成的黏著劑層在低剝離速度0.3m/min下的黏著力為0.05～0.1N/25mm，在高剝離速度30m/min下的黏著力為1.0N/25mm以下。
13．如申請專利範圍第1項或第2項所述的黏著劑組合物，其中使該黏著劑組合物交聯而成的黏著劑層的表面電阻率為以下，剝離靜電壓為±0～0.3kV。
14．一種黏著膜，其在樹脂膜的單面或雙面形成黏著劑層而成，該黏著劑層是使申請專利範圍第1項至第13項中任一項所述的黏著劑組合物交聯而成。
15．一種表面保護膜，其在樹脂膜的單面形成黏著劑層而成，該黏著劑層是使申請專利範圍第1項至第13項中任一項所述的黏著劑組合物交聯而成。
16．如申請專利範圍第15項所述的表面保護膜，其做為偏光板的表面保護膜用途加以使用。
17．如申請專利範圍第15項所述的表面保護膜，其中在該樹脂膜的與形成有該黏著劑層的一側相反的面上，實施有抗靜電和防污處理。
1. An adhesive composition comprising an acrylic polymer of a copolymer comprising (A) a (meth) acrylate monomer having an alkyl group having a C4 to C10 carbon number, (B) The hydroxyl group-containing copolymerizable monomer and (C) the carboxyl group-containing copolymerizable monomer further contain (D) an antistatic agent as an ionic compound having a melting point of 30 to 80 °C.
2. The adhesive composition according to claim 1, wherein the (A) alkyl group has a C4 to C10 (meth) acrylate monomer in an amount of from 0.1 to 8.0 per 100 parts by weight. The (B) hydroxyl group-containing copolymerizable monomer in the (B) hydroxyl group-containing copolymerizable monomer, 8-hydroxyoctyl (meth)acrylate, 6-hydroxyl (meth)acrylate The total amount of hexyl ester and 4-hydroxybutyl (meth)acrylate is 0 to 0.9 parts by weight.
3. The adhesive composition according to claim 1 or 2, wherein the (A) alkyl group has a C4 to C10 (meth) acrylate monomer with respect to 100 parts by weight of the (A) alkyl group, The (C) carboxyl group-containing copolymerizable monomer is contained in an amount of from 0.35 to 1.0 part by weight, and the acid value of the copolymer is from 0.01 to 9.0.
4. The adhesive composition according to claim 1 or 2, wherein the antistatic agent of the (D) as an ionic compound has a melting point of 30 to 49 °C.
5. The adhesive composition according to claim 3, wherein the antistatic agent of the (D) as an ionic compound has a melting point of 30 to 49 °C.
6. The adhesive composition according to claim 1 or 2, further comprising (E) a trifunctional or higher isocyanate compound.
7. The adhesive composition according to claim 3, further comprising (E) a trifunctional or higher isocyanate compound.
8. The adhesive composition according to claim 4, further comprising (E) a trifunctional or higher isocyanate compound.
9. The adhesive composition according to claim 5, further comprising (E) a trifunctional or higher isocyanate compound.
10. The adhesive composition according to claim 6, wherein the (E) trifunctional or higher isocyanate compound comprises at least one selected from the group consisting of (E-1) a first aliphatic isocyanate compound and selected from the group consisting of (E-2) At least one or more of the second aromatic isocyanate compound group; and the total content of the (E) trifunctional or higher isocyanate compound is 0.5 to 5.0 parts by weight based on 100 parts by weight of the copolymer.
11. The adhesive composition according to claim 1 or 2, wherein the adhesive composition contains 1.0 to 5.0 parts by weight as a crosslinking inhibitor with respect to 100 parts by weight of the copolymer. A ketoenol tautomer compound; containing 0.01 to 0.5 part by weight of an organotin compound as a crosslinking catalyst with respect to 100 parts by weight of the copolymer.
12. The adhesive composition according to claim 1 or 2, wherein the adhesive layer obtained by crosslinking the adhesive composition has an adhesive force of 0.05 to 0.1 at a low peeling speed of 0.3 m/min. N/25mm, the adhesion at a high peeling speed of 30m/min is 1.0N/25mm or less.
13. The adhesive composition according to claim 1 or 2, wherein the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is Hereinafter, the peeling static voltage is ±0 to 0.3 kV.
14. An adhesive film formed by forming an adhesive layer on one or both sides of a resin film, the adhesive layer being crosslinked by the adhesive composition according to any one of claims 1 to 13. Made.
15. A surface protective film which is formed by forming an adhesive layer on one side of a resin film, and the adhesive layer is obtained by crosslinking the adhesive composition according to any one of claims 1 to 13. .
16. The surface protective film according to claim 15, which is used as a surface protective film for a polarizing plate.
17. The surface protective film according to claim 15, wherein an antistatic and antifouling treatment is performed on a surface of the resin film opposite to a side on which the adhesive layer is formed.
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