TW201335310A - Adhesive composition, adhesive film and surface protection film - Google Patents
Adhesive composition, adhesive film and surface protection film Download PDFInfo
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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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
本發明係提供一種具有抗靜電性能的黏著劑組成物，以及使用該黏著劑組成物，在樹脂膜的至少一個面上形成具有抗靜電性能的黏著劑層的黏著薄膜，以及表面保護膜。本發明的黏著薄膜和表面保護膜具有特別優異的抗靜電性能。因此，本發明的表面保護膜能夠用於保護以容易產生靜電的塑膠膜作為組成部件使用的偏光板、相位差板、防反射膜等的光學膜表面的目的。 The present invention provides an adhesive composition having antistatic properties, and an adhesive film using the adhesive composition to form an adhesive layer having antistatic properties on at least one side of a resin film, and a surface protective film. The adhesive film and surface protective film of the present invention have particularly excellent antistatic properties. Therefore, the surface protective film of the present invention can be used for the purpose of protecting the surface of an optical film such as a polarizing plate, a phase difference plate, an antireflection film or the like which is used as a constituent member of a plastic film which is easy to generate static electricity.
一直以來，在構成液晶顯示器的偏光板、相位差板、防反射膜等的光學膜的製造步驟中，在光學膜的表面暫時貼合表面保護膜。在將光學膜組裝入液晶顯示器時，將表面保護膜從光學膜剝離而除去。為了保護光學膜表面的表面保護膜僅在製造步驟中使用，因此，也被稱為步驟膜。 In the manufacturing process of an optical film which comprises a polarizing plate, a retardation board, and an anti-reflection film of a liquid crystal display, the surface protection film is temporarily bonded to the surface of an optical film. When the optical film group is incorporated in the liquid crystal display, the surface protective film is removed from the optical film and removed. The surface protective film for protecting the surface of the optical film is used only in the manufacturing step, and is therefore also referred to as a step film.
在製造光學膜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醇酯(PET)樹脂膜的一面上形成黏著劑層。此外，直至貼合於光學膜之前，將為了保護該黏著劑層的被剝離處理的剝離膜貼合於黏著劑層的上面。 The surface protective film used in the step of producing an optical film forms an adhesive layer on one surface of a polyethylene terephthalate (PET) resin film having optical transparency. Further, the release film for protecting the adhesive layer from being peeled off is attached to the upper surface of the adhesive layer until it is bonded to the optical film.
而且，由於偏光板、相位差板、防反射膜等的光學膜，在貼合有表面保護膜的狀態下，進行伴有液晶顯示板的顯示能力、色度、對比度、雜質混入等的光學評價的產品檢驗，因此，對於表面保護膜必要的性能是，在黏著劑層中不附著氣泡或雜質。 In addition, an optical film such as a polarizing plate, a retardation film, or an antireflection film is optically evaluated in accordance with the display capability, chromaticity, contrast, and impurity incorporation of the liquid crystal display panel in a state in which the surface protective film is bonded. The product inspection, therefore, the necessary performance for the surface protective film is that no bubbles or impurities are attached to the adhesive layer.
而且，近年來，需要在將表面保護膜從偏光板、相位差板、防反射膜等的光學膜剝離時防止產生靜電的優異的抗靜電性能。這是因為從被黏物剝離黏著劑層時，伴隨著所產生的靜電產生的剝離時的帶電有可能使液晶顯示器的電氣控制電路發生故障。 Further, in recent years, it is necessary to prevent the static antistatic property from being generated when the surface protective film is peeled off from an optical film such as a polarizing plate, a retardation film, or an antireflection film. This is because when the adhesive layer is peeled off from the adherend, charging at the time of peeling accompanying the generated static electricity may cause malfunction of the electrical control circuit of the liquid crystal display.
而且，要求即使將偏光板、相位差板、防反射膜等的光学膜貼合於金屬性的被黏物例如聚光圈等上也不發生腐蝕的、具有耐腐蝕性的黏著劑組成物。 In addition, an adhesive composition having corrosion resistance which does not corrode even if an optical film such as a polarizing plate, a retardation film, or an antireflection film is bonded to a metallic adherend such as a bead or the like is required.
而且，要求在從作為被黏物的偏光板、相位差板、防反射膜等的光學膜剝離表面保護膜時，不污染被黏物，即不產生黏著劑殘留。 Further, when the surface protective film is peeled off from the optical film such as a polarizing plate, a phase difference plate, or an antireflection film which is an adherend, it is required to not contaminate the adherend, that is, no adhesive remains.
這樣，近年來，從適合於使用表面保護膜的容易使用的觀點出發，作為對於構成表面保護膜的黏著劑層的要求性能，要求：(1)具有優異的抗靜電性能；(2)具有耐腐蝕性；(3)防止黏著劑殘留的發生等。 Thus, in recent years, from the viewpoint of easiness of use suitable for the use of the surface protective film, as a required performance for the adhesive layer constituting the surface protective film, it is required to have: (1) excellent antistatic property; and (2) resistance to Corrosive; (3) Prevent the occurrence of adhesive residue.
然而，雖然能夠滿足作為對於構成表面保護膜的黏著劑層的要求性能的這些(1)~(3)的分別單獨的要求性能，但是非常難以同時滿足在表面保護膜的黏著劑層中所要求的(1)~(3)的所有要求性能。 However, although it is possible to satisfy the respective required performances of these (1) to (3) as required properties for the adhesive layer constituting the surface protective film, it is extremely difficult to simultaneously satisfy the requirements in the adhesive layer of the surface protective film. All required performance of (1) ~ (3).
例如，關於具有優異的抗靜電性能，作為賦予表面保護膜抗靜電性能的方法，顯示有向基材膜捏合入抗靜電劑的方法等。作為抗靜電劑，例如公開了(a)具有4級銨鹽、吡啶嗡鹽、1~3級胺基等的陽離子 基的各種陽離子抗靜電劑；(b)具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基、膦酸鹽基等的陰離子基的陰離子抗靜電劑；(c)胺基酸類、胺基硫酸酯類等的兩性抗靜電劑、(d)胺基醇類、甘油類、聚乙二醇類等的非離子抗靜電劑；(e)將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1)。 For example, as a method of imparting antistatic properties to a surface protective film, there is a method of kneading an antistatic agent into a base film, and the like. As the antistatic agent, for example, (a) a cation having a quaternary ammonium salt, a pyridinium salt, a 1-3 amino group or the like is disclosed. a variety of cationic antistatic agents; (b) anionic antistatic agents having an anionic group such as a sulfonate group, a sulfate group, a phosphate group, a phosphonate group, etc.; (c) an amino acid, an amine group An amphoteric antistatic agent such as a sulfate or a nonionic antistatic agent such as (d) an amino alcohol, a glycerin or a polyethylene glycol; (e) a polymer obtained by polymerizing the antistatic agent as described above A polymer type antistatic agent or the like (Patent Document 1).
並且，近年來，不只提出將這樣的抗靜電劑包含在基材膜裡、或塗佈於基材膜表面，還提出直接地使黏著劑層含有這樣的抗靜電劑。 Further, in recent years, it has been proposed not only to include such an antistatic agent in a base film or to apply it to the surface of a base film, but also to directly include such an antistatic agent in the adhesive layer.
並且，作為以往的抗靜電劑使用鹼金屬鹽，例如，專利文獻2中公開有作為(甲基)丙烯酸類聚合物中的離子物質，使用選自高氯酸的鹼金屬鹽、高氯酸的鹼土金屬鹽、有機硼絡合物的鹼金屬鹽和有機硼絡合物的鹼土金屬鹽中的1種。但是，含有由鹼金屬鹽形成的抗靜電劑的黏著劑組成物，由於具有金屬腐蝕性，因此，在被黏物為金屬的情況下，發生腐蝕。因此，需要在具有優異的抗靜電性能的同時具有耐腐蝕性的黏著劑組成物。 In addition, an alkali metal salt is used as a conventional antistatic agent. For example, Patent Document 2 discloses that an ionic substance in a (meth)acrylic polymer is used, and an alkali metal salt selected from perchloric acid or perchloric acid is used. One of an alkaline earth metal salt, an alkali metal salt of an organic boron complex, and an alkaline earth metal salt of an organic boron complex. However, since the adhesive composition containing an antistatic agent formed of an alkali metal salt has metal corrosive properties, corrosion occurs when the adherend is a metal. Therefore, there is a need for an adhesive composition having corrosion resistance while having excellent antistatic properties.
並且，關於防止黏著劑殘留的產生，例如提出了對於丙烯酸類樹脂100重量份以0.0001~10重量份向丙烯酸類樹脂中混合異氰酸酯類化合物的硬化劑和特定的矽酸鹽低聚物而得到的黏著劑組成物(專利文獻3)。 In addition, for the prevention of the generation of the adhesive residue, for example, a curing agent for mixing an isocyanate compound and a specific phthalate oligomer in an acrylic resin in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the acrylic resin has been proposed. Adhesive composition (Patent Document 3).
專利文獻3中，以烷基的碳原子數為約2~12的丙烯酸烷基酯、烷基的碳原子數為約4~12的甲基丙烯酸烷基酯等為主要單體成分，例如，能夠包含含有羧基的單體等的、含有其它官能基的單體成分。一般地，較佳為含有50重量%以上的上述主要單體，並且，希望含有官 能基的單體成分的含量為0.001~50重量%，較佳為0.001~25重量%，更佳為0.01~25重量%。由於專利文獻3中記載的黏著劑組成物即使在高溫下或者高溫高濕下，凝聚力和黏著力的經時變化也是小的，並且，對曲面的黏著力中也顯示出色的效果，此外，不發生黏著劑的起泡或剝離。 In Patent Document 3, an alkyl acrylate having an alkyl group having a carbon number of about 2 to 12, an alkyl methacrylate having an alkyl group having a carbon number of about 4 to 12, or the like is a main monomer component, for example, A monomer component containing another functional group such as a carboxyl group-containing monomer can be contained. In general, it is preferred to contain 50% by weight or more of the above-mentioned main monomer, and it is desirable to have an official The content of the monomer component of the energy group is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, more preferably 0.01 to 25% by weight. The adhesive composition described in Patent Document 3 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 to the curved surface, and Foaming or peeling of the adhesive occurs.
一般地，如果將黏著劑層製成柔性性狀，則黏著劑殘留變得容易發生。即，容易變得錯誤地貼合時剝離困難、重新貼合困難。因此，需要將具有羧基等的官能基的單體交聯於主劑上，將黏著劑層製成一定的硬度，防止黏著劑殘留的發生。 In general, if the adhesive layer is made into a flexible property, the adhesive residue tends to occur. In other words, it is easy to cause detachment and detachment is difficult, and it is difficult to reattach. Therefore, it is necessary to crosslink the monomer having a functional group such as a carboxyl group to the main component, and to form the adhesive layer to a certain hardness to prevent the occurrence of the adhesive residue.
此外，關於防止黏著劑殘留的發生，已知有以下提案。以具有碳原子數為7以下的烷基的(甲基)丙烯酸烷基酯與含有羧基的共聚化合物的共聚物作為主要成分，用交聯劑對其進行交聯處理得到丙烯酸類黏著劑層，用該黏著劑層貼合後經過長時間，則黏著劑向被黏物一側的轉移以及對於被黏物的黏著力經時上升。為了解決該問題，已知如下黏著劑(感壓黏著劑)：上述黏著劑通過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性羥基的共聚性化合物的共聚物、用交聯劑對其交聯處理而得到(專利文獻4)。 Further, regarding the prevention of the occurrence of adhesive residue, the following proposals 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 copolymer compound as a main component is crosslinked by a crosslinking agent to obtain an acrylic pressure-sensitive adhesive layer. After a long period of time after bonding with the adhesive layer, the transfer of the adhesive to the adherend side and the adhesion to the adherend increase with time. In order to solve this problem, an adhesive (pressure-sensitive adhesive) is known in which the above-mentioned adhesive is copolymerized with an alcoholic hydroxyl group by using an alkyl (meth)acrylate having an alkyl group having 8 to 10 carbon atoms. The copolymer of the compound is obtained by crosslinking treatment with a crosslinking agent (Patent Document 4).
還提出如下黏著劑等：上述黏著劑通過在上述同樣的共聚物中少量混合(甲基)丙烯酸烷基酯與含有羧基的共聚性化合物的共聚物、用交聯劑對其交聯處理而得到。但是，當將這些黏著劑用於表面張力低、表面光滑的塑膠板等的表面保護中時，有由於加工時或保存時的加熱產生浮起等的剝離現象。 Further, an adhesive or the like is proposed in which the above-mentioned adhesive is obtained by mixing a small amount of a copolymer of an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound in the same copolymer as described above, and crosslinking the mixture with a crosslinking agent. . However, when these adhesives are used for surface protection of a plastic sheet having a low surface tension and a smooth surface, there is a peeling phenomenon such as floating due to heating during processing or storage.
[專利文獻1]日本專利特開平11-070629號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-070629
[專利文獻2]日本專利特開2006-199873號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-199873
[專利文獻3]日本專利特開平8-199130號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 8-199130
[專利文獻4]日本專利特開昭63-225677號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. SHO 63-225677
以往的具有抗靜電性能的黏著劑組成物，在要求優異的抗靜電性能的用途中，作為使其含有的抗靜電劑使用鹼金屬鹽。但是，如果使用鹼金屬鹽，則在被黏物是金屬的情況下發生腐蝕。此外，以往的表面保護膜由於具有對於被黏物的污染性，因此不能夠滿足在表面保護膜中使用的黏著劑層所要求的要求性能。 In the conventional adhesive composition having antistatic properties, an alkali metal salt is used as an antistatic agent to be used in applications requiring excellent antistatic properties. However, if an alkali metal salt is used, corrosion occurs in the case where the adherend is a metal. Further, since the conventional surface protective film has contamination property to the adherend, it cannot satisfy the required performance required for the adhesive layer used in the surface protective film.
本發明借鑒了上述情況。本發明的課題是提供一種黏著劑組成物、使用其的黏著薄膜和表面保護膜，上述黏著劑組成物具有優異的抗靜電性能，並且具有耐腐蝕性，污染性低。 The present invention draws on the above. An object of the present invention is to provide an adhesive composition, an adhesive film and a surface protective film using the same, which have excellent antistatic properties, corrosion resistance, and low contamination.
本發明黏著劑組成物將含有熔點在30℃以上的離子性化合物，具有耐腐蝕性，得到優異的抗靜電性能作為技術思想。此外，由於含有具有羥基的(甲基)丙烯酸類單體，能夠得到黏著劑殘留少，污染性低的黏著劑組成物。通過使用這樣的黏著劑組成物，能夠提供具有優異的 抗靜電性能，並且具有耐腐蝕性，污染性低的黏著劑組成物，使用其的黏著薄膜和表面保護膜。 The adhesive composition of the present invention contains an ionic compound having a melting point of 30 ° C or more, has corrosion resistance, and has excellent antistatic properties as a technical idea. Further, since a (meth)acrylic monomer having a hydroxyl group is contained, an adhesive composition having less adhesive residue and low contamination can be obtained. By using such an adhesive composition, it is possible to provide excellent An antistatic property, and an adhesive composition having corrosion resistance and low contamination, using an adhesive film and a surface protective film.
為了解決上述課題，本發明提供了一種黏著劑組成物，係含有以烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體為主要成分的(甲基)丙烯酸類聚合物的黏著劑組成物，其中含有聚醚化合物和熔點30℃以上的離子性化合物。 In order to solve the above problems, the present invention provides an adhesive composition comprising a (meth)acrylic polymer containing a (meth) acrylate monomer having an alkyl group having C1 to C14 as a main component. An adhesive composition containing a polyether compound and an ionic compound having a melting point of 30 ° C or more.
較佳的是上述熔點30℃以上的離子性化合物非為鹼金屬鹽。 It is preferred that the ionic compound having a melting point of 30 ° C or higher is not an alkali metal salt.
較佳的是上述聚醚化合物為含有氧化乙烯基的化合物。 It is preferred that the above polyether compound is a compound containing an oxyethylene group.
較佳的是上述聚醚化合物係與上述(甲基)丙烯酸類聚合物共聚。 It is preferred that the above polyether compound is copolymerized with the above (meth)acrylic polymer.
較佳的是上述(甲基)丙烯酸類聚合物的酸價為1.0以下。 It is preferred that the (meth)acrylic polymer has an acid value of 1.0 or less.
較佳的是上述(甲基)丙烯酸類聚合物含有具有羥基的(甲基)丙烯酸類單體。 It is preferred that the (meth)acrylic polymer contains a (meth)acrylic monomer having a hydroxyl group.
此外，本發明提供黏著薄膜，係在樹脂膜的一面或兩面上形成使上述黏著劑組成物交聯而成的黏著劑層。 Further, the present invention provides an adhesive film in which an adhesive layer obtained by crosslinking the above-mentioned adhesive composition is formed on one surface or both surfaces of a resin film.
此外，本發明提供表面保護膜，係在樹脂膜的一面上形成使上述黏著劑組成物交聯而成的黏著劑層，其中，上述表面保護膜從被黏物剝離時，沒有向被黏物的污染轉移。 Further, the present invention provides a surface protective film in which an adhesive layer obtained by crosslinking the above-mentioned adhesive composition is formed on one surface of a resin film, wherein when the surface protective film is peeled off from the adherend, there is no adhesion to the adherend The transfer of pollution.
上述表面保護膜，較佳的係作為偏光板的表面保護膜的用途使用。此外，較佳的係在上述樹脂膜的與上述黏著劑層形成側相反的面上進行抗靜電和防污染處理。 The above surface protective film is preferably used as a surface protective film for a polarizing plate. Further, it is preferable to carry out antistatic and antifouling treatment on the surface of the above-mentioned resin film opposite to the side on which the above-mentioned adhesive layer is formed.
依據本發明，能夠提供具有優異的抗靜電性能、並且具有對於被黏物的耐腐蝕性、污染性低的黏著劑組成物以及使用其而形成的黏著薄膜和表面保護膜。 According to the present invention, it is possible to provide an adhesive composition having excellent antistatic properties and having corrosion resistance and contamination property to an adherend, and an adhesive film and a surface protective film formed using the same.
下面，基於較佳實施形態說明本發明。 Hereinafter, the present invention will be described based on preferred embodiments.
本發明的黏著劑組成物為含有以烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體為主要成分的(甲基)丙烯酸類聚合物的黏著劑組成物，上述黏著劑組成物含有聚醚化合物和熔點在30℃以上的離子性化合物。 The adhesive composition of the present invention is an adhesive composition containing a (meth)acrylic polymer containing a (meth) acrylate monomer having a C1 to C14 carbon atom as an essential component, and the above-mentioned adhesive The composition contains a polyether compound and an ionic compound having a melting point of 30 ° C or higher.
作為烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體，可以舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯等。(甲基)丙烯酸烷基酯單體的烷基可以為直鏈、支鏈、環狀的任何一種。烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體相對於(甲基)丙烯酸類聚合物的重量比較佳為50~100%。 Examples of the (meth) acrylate monomer having a C1 to C14 carbon atom in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Isopropyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( Octyl methacrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Anthracene ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, and the like. The alkyl group of the alkyl (meth) acrylate monomer may be any of a straight chain, a branched chain, and a cyclic group. The (meth) acrylate monomer having an alkyl group having a C1 to C14 carbon number is preferably from 50 to 100% by weight based on the (meth)acrylic polymer.
(甲基)丙烯酸類聚合物較佳為含有具有羥基的(甲基)丙烯酸類單體。作為具有羥基的(甲基)丙烯酸類單體，可以舉出：(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-羥基乙酯等的(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)丙烯醯胺等的含有羥基的(甲基)丙烯醯胺類等。 The (meth)acrylic polymer preferably contains a (meth)acrylic monomer having a hydroxyl group. Examples of the (meth)acrylic monomer having a hydroxyl group include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate; N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl A hydroxyl group-containing (meth) acrylamide such as ethyl (meth) acrylamide.
(甲基)丙烯酸類聚合物可以含有具有羧基的可共聚單體。作為含有羧基的可共聚單體，可以舉出：(甲基)丙烯酸、衣康酸、巴豆酸、馬來酸、富馬酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯等。 The (meth)acrylic polymer may contain a copolymerizable monomer having a carboxyl group. Examples of the carboxyl group-containing copolymerizable monomer include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyethyl (meth)acrylate, and carboxypenta(meth)acrylate. Ester and the like.
此外，(甲基)丙烯酸類聚合物也可以含有上述以外的共聚乙烯基單體。作為其它的共聚乙烯基單體，可以舉出：(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯等含有芳香基的(甲基)丙烯酸酯類，以及苯乙烯、丙烯醯胺、丙烯腈、甲基乙烯基醚、乙基乙烯基醚、醋酸乙烯酯、氯化乙烯等各種乙烯基單體。 Further, the (meth)acrylic polymer may contain a copolymerized vinyl monomer other than the above. Examples of the other copolymerized vinyl monomer include (meth)acrylates containing an aryl group such as benzyl (meth)acrylate or phenoxyethyl (meth)acrylate, and styrene and propylene oxide. Various vinyl monomers such as amine, acrylonitrile, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, and vinyl chloride.
但是，如果過分添加含有羧基的單體等的顯示酸性的單體(以下稱為酸性單體)，則由於這些酸，恐怕腐蝕性會變大。因此，(甲基)丙烯酸類聚合物的酸價較佳為1.0以下。 However, when a monomer exhibiting acidity (hereinafter referred to as an acidic monomer) such as a carboxyl group-containing monomer is excessively added, corrosion properties may increase due to these acids. Therefore, the acid value of the (meth)acrylic polymer is preferably 1.0 or less.
本文，“酸價”為表示酸含量的指標之一，其用中和1g具有酸性成分的聚合物所需要的氫氧化鉀的mg數表示。 Herein, "acid value" is one of the indexes indicating the acid content, which is expressed by the number of mg of potassium hydroxide required to neutralize 1 g of the polymer having an acidic component.
本發明的黏著劑組成物含有聚醚化合物。作為聚醚化合物可舉出，為具有聚氧化伸烷基的化合物的聚伸烷基二醇等的聚醚型多元醇 以及其衍生物。作為聚伸烷基二醇以及聚氧化伸烷基所具有的伸烷基，可舉出伸乙基、伸丙基、伸丁基等，這是非限定的。聚伸烷基二醇也可為聚乙二醇、聚丙二醇、聚丁二醇等的2種以上的聚伸烷基二醇的共聚物。作為聚伸烷基二醇的共聚物，可舉出聚乙二醇-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，該共聚物可為嵌段共聚物、無規共聚物。 The adhesive composition of the present invention contains a polyether compound. The polyether compound is a polyether polyol such as a polyalkylene glycol which is a compound having a polyoxyalkylene group. And its derivatives. Examples of the alkylene group which the polyalkylene glycol and the polyoxyalkylene group have include an exoethyl group, a propyl group, a butyl group, and the like, which are not limited. The polyalkylene glycol may be a copolymer of two or more kinds of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the copolymer of the polyalkylene glycol include polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene. The diol or the like may be a block copolymer or a random copolymer.
作為聚伸烷基二醇的衍生物可舉出，聚氧化烯單烷基醚、聚氧化烯二烷基醚等的聚氧化烯烷基醚，聚氧化烯單鏈烯基醚、聚氧化烯二鏈烯基醚等的聚氧化烯鏈烯基醚，聚氧化烯單芳基醚、聚氧化烯二芳基醚等的聚氧化烯芳基醚，聚氧化烯烷基苯基醚、聚氧化烯二醇單脂肪酸酯、聚氧化烯二醇二脂肪酸酯等的聚氧化烯二醇脂肪酸酯，聚氧化烯脫水山梨糖醇脂肪酸酯、聚氧化烯烷基胺、聚氧化烯二胺、聚醚改性的矽氧烷化合物等。 Examples of the derivative of the polyalkylene glycol include polyoxyalkylene alkyl ethers such as polyoxyalkylene monoalkyl ethers and polyoxyalkylene dialkyl ethers, polyoxyalkylene monoalkenyl ethers, and polyoxyalkylenes. Polyoxyalkylene alkenyl ethers such as dialkenyl ethers, polyoxyalkylene aryl ethers such as polyoxyalkylene monoaryl ethers and polyoxyalkylene diaryl ethers, polyoxyalkylene alkylphenyl ethers, polyoxidation Polyoxyalkylene glycol fatty acid esters such as olefinic diol mono-fatty acid esters, polyoxyalkylene diol di-fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkylamines, polyoxyalkylenes An amine, a polyether modified siloxane compound, or the like.
在此處，作為聚伸烷基二醇衍生物中的烷基醚，可舉出甲基醚、乙基醚等的低級烷基醚，十二烷基醚、十八烷基醚等的高級烷基醚。作為聚伸烷基二醇衍生物中的鏈烯基醚，可舉出乙烯基醚、烯丙基醚、油基醚等。此外，作為聚伸烷基二醇衍生物中的脂肪酸酯，可舉出醋酸酯、硬脂酸酯等的飽和脂肪酸酯、(甲基)丙烯酸酯、油酸酯等的不飽和脂肪酸酯。 Here, examples of the alkyl ether in the polyalkylene glycol derivative include a lower alkyl ether such as methyl ether or ethyl ether, and a higher alkyl group such as lauryl ether or octadecyl ether. Alkyl ether. Examples of the alkenyl ether in the polyalkylene glycol derivative include a vinyl ether, an allyl ether, and an 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 acids such as (meth) acrylate and oleic acid ester. ester.
作為聚醚改性的矽氧烷化合物，可舉出二甲基矽氧烷‧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。 Examples of the polyether-modified oxoxane compound include dimethyl methoxy ane ‧ methyl (polyoxyethylene) phthalate copolymer, dimethyl oxa oxide ‧ methyl (polyethylene oxide) oxime An alkane ‧ (polyoxypropylene) alkane copolymer, a dimethyl methoxy ane ‧ methyl (poly propylene oxide) siloxane copolymer, and the like.
聚醚化合物較佳為含有氧化乙烯基的化合物，更佳為含有聚氧化 乙烯基的化合物。 The polyether compound is preferably a compound containing an oxyethylene group, more preferably containing a polyoxygen a vinyl compound.
聚醚化合物具有聚合性官能基的情況下，可以和(甲基)丙烯酸類聚合物共聚。作為聚合性官能基，較佳的是(甲基)丙烯醯基、乙烯基、烯丙基等的乙烯基性官能基。作為具有聚合性官能基的聚醚化合物，可舉出聚伸烷基二醇單(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、烷氧基聚伸烷基二醇(甲基)丙烯酸酯、聚伸烷基二醇單烯丙基醚、聚伸烷基二醇二烯丙基醚、烷氧基聚伸烷基二醇烯丙基醚、聚伸烷基二醇單乙烯基醚、聚伸烷基二醇二乙烯基醚、烷氧基聚伸烷基二醇乙烯基醚等。 When the polyether compound has a polymerizable functional group, it can be copolymerized with a (meth)acrylic polymer. The polymerizable functional group is preferably a vinyl 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 a polyalkylene glycol mono(meth)acrylate, a polyalkylene glycol di(meth)acrylate, and an alkoxy polyalkylene group. Alcohol (meth) acrylate, polyalkylene glycol monoallyl ether, polyalkylene glycol diallyl ether, alkoxy polyalkylene glycol allyl ether, polyalkylene A diol monovinyl ether, a polyalkylene glycol divinyl ether, an alkoxy polyalkylene glycol vinyl ether or the like.
為了賦予本發明的黏著劑組成物抗靜電性能，較佳的是其含有抗靜電劑。抗靜電劑較佳為在常溫(例如30℃)下是固體，更具體地，是熔點在30℃以上的離子性化合物。這樣的抗靜電劑，由於比鹼金屬鹽熔點低，而且，由於具有長鏈的烷基，推定其與丙烯酸類共聚物具有高的親和性。 In order to impart antistatic properties to the adhesive composition of the present invention, it is preferred to contain an antistatic agent. The antistatic agent is preferably a solid at normal temperature (for example, 30 ° C), and more specifically, an ionic compound having a melting point of 30 ° C or higher. Such an antistatic agent is estimated to have a high affinity with an acrylic copolymer because it has a lower melting point than an alkali metal salt and, because of having a long-chain alkyl group.
作為熔點在30℃以上的離子性化合物，為具有陽離子和陰離子的離子性化合物，可以舉出以下化合物：陽離子為吡啶嗡陽離子、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(BF4 -)等的無機或有機陰離子的化合物。通過選擇烷基的鏈長或取代基的位置、個數等，能夠得到熔點在30℃以上 的物質。陽離子較佳的是4級含氮鎓陽離子，可以舉出：1-烷基吡啶嗡(2~6位的碳原子有取代基也可以，無取代也可以)等的4級吡啶嗡陽離子、1,3-二烷基咪唑鎓(2、4、5位的碳原子有取代基也可以，無取代也可以)等的4級咪唑鎓陽離子、四烷基銨基等的4級銨陽離子等。離子性化合物的熔點較佳為30~80℃。作為陽離子可以有的取代基，可以舉出烷基、芳基等。上述離子性化合物由於不是鹼金屬鹽，因此可以解決現有技術的鹼金屬鹽具有金屬腐蝕性的問題。 The ionic compound having a melting point of 30 ° C or higher is an ionic compound having a cation and an anion, and examples thereof include a pyridinium cation, an imidazolium cation, a pyrimidine cation, a pyrazolium cation, and a pyrrole cation. a nitrogen-containing phosphonium cation such as an ammonium cation, or a phosphonium cation, a sulfonium cation or the like, and the anion is a hexafluorophosphate (PF 6 - ), a thiocyanate (SCN - ), an alkylbenzenesulfonate (RC 6 H A compound of an inorganic or organic anion such as 4 SO 3 - ), perchlorate (ClO 4 - ) or tetrafluoroborate (BF 4 - ). By selecting the chain length of the alkyl group, the position and number of the substituents, and the like, a substance having a melting point of 30 ° C or higher can be obtained. The cation is preferably a 4-stage ruthenium-containing cation, and a 4-stage pyridinium cation such as 1-alkylpyridinium (a carbon atom having 2 to 6 carbon atoms may be substituted or unsubstituted) may be mentioned. Further, a 4-dialkylimidazolium (a carbon atom having a substituent at the 2, 4, or 5 positions may be substituted, or a substituent may be used), a 4-stage imidazolium cation such as a tetraalkylammonium group, or the like. The melting point of the ionic compound is preferably from 30 to 80 °C. Examples of the substituent which the cation may have include an alkyl group, an aryl group and the like. Since the above ionic compound is not an alkali metal salt, it can solve the problem that the alkali metal salt of the prior art has metal corrosivity.
本發明的黏著劑組成物中使用的主劑(甲基)丙烯酸類聚合物可以通過以1種或2種以上的烷基的碳原子數為C1~C14的(甲基)丙烯酸酯單體作為主要成分，根據需要添加其它單體，使其聚合而合成。(甲基)丙烯酸類聚合物的聚合方法沒有特別地限定，可以使用溶液聚合、乳液聚合等合適的聚合方法。 The main component (meth)acrylic polymer used in the adhesive composition of the present invention can be used as a (meth) acrylate monomer having one or two or more kinds of alkyl groups having C1 to C14 carbon atoms. The main component is added to other monomers as needed to be polymerized and synthesized. The polymerization method of the (meth)acrylic polymer is not particularly limited, and a suitable polymerization method such as solution polymerization or emulsion polymerization can be used.
本發明的黏著劑組成物較佳的是在形成黏著劑層時交聯黏著劑聚合物。作為使其進行交聯反應的方法，黏著劑組成物可以含有已知的交聯劑，也可以通過紫外線(UV)等的光交聯使其交聯。作為交聯劑，可以舉出：2官能基或3官能基以上的異氰酸酯化合物，2官能基或3官能基以上的環氧化合物，2官能基或3官能基以上的丙烯酸酯化合物，金屬螯合物化合物等。 The adhesive composition of the present invention preferably crosslinks the adhesive polymer when the adhesive layer is formed. As a method of causing a crosslinking reaction, the adhesive composition may contain a known crosslinking agent, or may be crosslinked by photocrosslinking by ultraviolet rays (UV) or the like. Examples of the crosslinking agent include a bifunctional or trifunctional or higher isocyanate compound, a bifunctional or trifunctional or higher epoxy compound, a bifunctional or trifunctional or higher acrylate compound, and a metal chelate compound. Compounds and the like.
此外，作為其它成分，可以適當地混合矽烷偶聯劑、抗氧化劑、表面活性劑、交聯促進劑、增塑劑、填充劑、硬化促進劑、硬化抑制劑、加工助劑、抗老化劑等的公知添加劑。可以單獨或2種以上組合使用這些添加劑。 Further, as other components, a decane coupling agent, an antioxidant, a surfactant, a crosslinking accelerator, a plasticizer, a filler, a hardening accelerator, a hardening inhibitor, a processing aid, an anti-aging agent, etc. may be appropriately mixed. Known additives. These additives may be used singly or in combination of two or more.
使上述黏著劑組成物交聯得到的黏著劑層的表面電阻率較佳為5.0×10+10Ω/□以下。此外，該黏著劑層的剝離帶電壓較佳為±0~1kV。此外，在本發明中，上述“±0~1kV”意思是0~-1kV和0~+1kV，即，-1~+1kV。由於表面電阻率大時放掉剝離時由於帶電產生的靜電的性能差，因此，通過使得表面電阻率足夠小，能夠降低伴隨從被黏物剝離黏著劑層時產生的靜電生成的剝離帶電壓，抑制對被黏物的電氣控制電路等的影響。 The surface resistivity of the adhesive layer obtained by crosslinking the above adhesive composition is preferably 5.0 × 10 + 10 Ω / □ or less. Further, the peeling tape voltage of the adhesive layer is preferably ±0 to 1 kV. Further, in the present invention, the above "±0 to 1 kV" means 0 to -1 kV and 0 to +1 kV, that is, -1 to +1 kV. When the surface resistivity is large, the performance of static electricity generated by charging is poor when the peeling is released. Therefore, by making the surface resistivity sufficiently small, the peeling band voltage generated by the static electricity generated when the adhesive layer is peeled off from the adherend can be reduced. The influence on the electrical control circuit of the adherend or the like is suppressed.
使本發明的黏著劑組成物交聯得到的黏著劑層(交聯後的黏著劑)的凝膠分率較佳為95~100%。這樣，由於凝膠分率高，能夠使低速剝離時的黏著力沒有變得過大，降低從共聚物的未聚合單體或寡聚物的溶出，改善防污染性、高溫．高濕中的耐久性，抑制被黏物的污染。 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%. Thus, since the gel fraction is high, the adhesive force at the time of low-speed peeling can be prevented from becoming excessively large, and the elution of the unpolymerized monomer or oligomer from the copolymer can be reduced, and the antifouling property and high temperature can be improved. Durability in high humidity, inhibiting contamination of adherends.
本發明的黏著薄膜是使本發明的黏著劑組成物交聯得到的黏著劑層在樹脂膜的一面或兩面上形成的黏著薄膜。此外，本發明的表面保護膜是使本發明的黏著劑組成物交聯得到的黏著劑層在樹脂膜的一面上形成的表面保護膜。本發明的黏著劑組成物由於具有優異的抗靜電性能，並且具有對於被黏物的耐腐蝕性，污染性低，因此，將本發明的表面保護膜貼合於被黏物上，即使用原子筆經由黏著劑層在表面保護膜上描繪後，從被黏物上剝離，也沒有向被黏物的轉移污染。因此，本發明的表面保護膜能夠作為偏光板的表面保護膜的用途適當地使用。 The adhesive film of the present invention is an adhesive film in which an adhesive layer obtained by crosslinking the adhesive composition of the present invention is formed on one surface or both surfaces of a resin film. Further, the surface protective film of the present invention is a surface protective film formed by laminating an adhesive layer obtained by crosslinking the adhesive composition of the present invention on one surface of a resin film. Since the adhesive composition of the present invention has excellent antistatic properties and has corrosion resistance to an adherend, the contamination is low, and therefore, the surface protective film of the present invention is attached to an adherend, that is, an atom is used. After the pen is drawn on the surface protective film via the adhesive layer, it is peeled off from the adherend and is not contaminated by the transfer of the adherend. Therefore, the surface protective film of the present invention can be suitably used as a surface protective film of a polarizing plate.
作為黏著劑層的基材膜、保護黏著面的剝離膜(隔片)可以使用聚酯 膜等的樹脂膜等。 As the base film of the adhesive layer and the release film (separator) for protecting the adhesive surface, polyester can be used. A resin film or the like such as a film.
在基材膜中，在樹脂膜的與黏著劑層形成側相反的面上，能夠實施通過矽酮類、氟類的脫模劑或塗層劑、二氧化矽微粒等的防污染處理；通過抗靜電劑的塗佈或捏合等的抗靜電處理。 In the base film, on the surface of the resin film opposite to the side on which the adhesive layer is formed, it is possible to carry out an antifouling treatment by an anthrone or a fluorine-based release agent, a coating agent, or cerium oxide fine particles; Antistatic treatment such as coating or kneading of an antistatic agent.
在剝離膜中，在黏著劑層的與黏著面黏著側的面上，實施通過矽酮類、氟類的脫模劑等的脫模處理。 In the release film, a release treatment by an anthrone or a fluorine-based release agent is applied to the surface of the pressure-sensitive adhesive layer on the side to which the adhesive surface is adhered.
在偏光板用表面保護膜等的光學用表面保護膜的情況中，基材膜和黏著劑層較佳的是具有足夠的透明性。 In the case of an optical surface protective film such as a surface protective film for a polarizing plate, the base film and the adhesive layer preferably have sufficient transparency.
下面，通過實施例具體說明本發明。 Hereinafter, the present invention will be specifically described by way of examples.
向配備有攪拌器、溫度計、回流冷凝器和氮導入管的反應裝置中導入氮氣，將反應裝置內的空氣用氮氣置換。然後，向反應裝置中加入丙烯酸2-乙基己酯100重量份、丙烯酸2-羥基乙酯3.5重量份和溶劑(乙酸乙酯)100重量份。然後，經過2小時滴入作為聚合引發劑的偶氮二異丁腈0.1重量份，於65℃使其反應8小時，得到丙烯酸類共聚物溶液。採用丙烯酸類共聚物的一部分作為下述酸價的測定樣品使用。 Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen. Then, 100 parts by weight of 2-ethylhexyl acrylate, 3.5 parts by weight of 2-hydroxyethyl acrylate, and 100 parts by weight of a solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise thereto over 2 hours, and the mixture was reacted at 65 ° C for 8 hours to obtain an acrylic copolymer solution. A part of the acrylic copolymer was used as a measurement sample of the following acid value.
對於該丙烯酸類共聚物溶液，添加1-辛基吡啶嗡六氟化磷酸鹽1.5重量份、CORONATEHX(六亞甲基二異氰酸酯化合物的異氰脲酸酯體)1.5重量份、二月桂酸二辛基锡0.1重量份、聚乙二醇(分子量400)1.0重量份，攪拌混合，得到實施例1的黏著劑組成物。 To the acrylic copolymer solution, 1.5 parts by weight of 1-octylpyridinium hexafluorophosphate, 1.5 parts by weight of CORONATEHX (isocyanurate body of hexamethylene diisocyanate compound), and dioctyltin dilaurate were added. 0.1 parts by weight of polyethylene glycol (molecular weight: 400) of 1.0 part by weight, and the mixture was stirred and mixed to obtain an adhesive composition of Example 1.
單體和添加劑的組成每一個按照表1所記載的那樣設定，除此以外，按照與上述實施例1的黏著劑組成物同樣地，得到實施例2~4和比較例1~3的黏著劑組成物。 The adhesives of Examples 2 to 4 and Comparative Examples 1 to 3 were obtained in the same manner as in the adhesive composition of Example 1 except that the composition of the monomer and the additive was set as described in Table 1. Composition.
此處，(A)丙烯酸類單體、(B)羥基單體、(B’)酸性單體、(C)聚醚化合物之中共聚性的物質(實施例4)，作為單體，在丙烯酸類共聚物溶液的聚合前加入反應裝置中，(C)聚醚化合物之中非聚合性的物質(實施例1~3)、(D)異氰酸酯(NCO)交聯劑、(E)交聯促進劑、(F)抗靜電劑，作為添加劑加入到聚合後的丙烯酸類共聚物溶液中。 Here, (A) an acrylic monomer, (B) a hydroxyl monomer, (B') acidic monomer, and (C) a copolymerizable substance (Example 4) among the polyether compounds, as a monomer, in acrylic acid The copolymer-like solution is added to the reaction apparatus before polymerization, (C) non-polymerizable substance among the polyether compounds (Examples 1-3), (D) isocyanate (NCO) crosslinking agent, (E) crosslinking promotion The agent (F) antistatic agent is added as an additive to the polymerized acrylic copolymer solution.
表1中，各成分的混合比例用括弧圈起，表示以(A)組的總和為100重量份所要求的重量份的數值。並且，表2中顯示表1中使用的各成分的縮寫對應的化合物名稱。此外，CORONATE(註冊商標)HX和同樣的HL和同樣的L-45是日本聚胺基甲酸酯(股)的商品名，TAMENATE(註冊商標)D-140N是三井化学(股)的商品名。關於表2的異氰酸酯(NCO)交聯劑的化合物名稱，HDI、IPDI、TMP的意思分別是六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、三羥甲基丙烷。 In Table 1, the mixing ratio of each component is represented by a circle, and represents a numerical value of the required part by weight of 100 parts by weight of the total of the group (A). Further, Table 2 shows the compound names corresponding to the abbreviations of the respective components used in Table 1. In addition, CORONATE (registered trademark) HX and the same HL and the same L-45 are trade names of Japanese polyurethanes, and TAMENATE (registered trademark) D-140N is the trade name of Mitsui Chemicals Co., Ltd. . Regarding the compound names of the isocyanate (NCO) crosslinking agents in Table 2, HDI, IPDI, and TMP mean hexamethylene diisocyanate, isophorone diisocyanate, and trimethylolpropane, respectively.
將實施例1的黏著劑組成物塗佈於由矽酮樹脂塗層的聚對苯二甲酸乙二醇酯(PET)膜形成的剝離膜上後，通過於90℃的乾燥除去溶劑，得到黏著劑層的厚度為25μm的黏著片。然後，將黏著片轉移至一面上經抗靜電和防污染處理的聚對苯二甲酸乙二醇酯(PET)膜的經抗靜電和防污染處理面的反面，得到具有“經抗靜電和防污染處理的PET膜/黏著劑層/剝離膜(矽酮樹脂塗層的PET膜)”的層壓結構的實施例1的表面保護膜。 After the adhesive composition of Example 1 was applied onto a release film formed of a terpene ketone resin coated polyethylene terephthalate (PET) film, the solvent was removed by drying at 90 ° C to obtain adhesion. The thickness of the agent layer was 25 μm. Then, the adhesive sheet is transferred to the opposite side of the antistatic and anti-pollution treatment surface of the antistatic and anti-pollution polyethylene terephthalate (PET) film on one side to obtain "antistatic and antistatic" The surface protective film of Example 1 of the laminated structure of the contaminated PET film/adhesive layer/release film (anthracene resin-coated PET film).
分別使用實施例2~4和比較例1~3的黏著劑組成物代替實施例1 的黏著劑組成物，除此之外，與上述實施例1的表面保護膜同樣，得到實施例2~4和比較例1~3的表面保護膜。 The adhesive compositions of Examples 2 to 4 and Comparative Examples 1 to 3 were used instead of Example 1 A surface protective film of Examples 2 to 4 and Comparative Examples 1 to 3 was obtained in the same manner as the surface protective film of Example 1 except the adhesive composition of the above.
將實施例1~4和比較例1~3中的表面保護膜於23℃、50%RH的氣氛下老化7天後，剝離剝離膜(矽酮樹脂塗層的PET膜)，將暴露出黏著劑層的物質貼合於鋁箔上後，於60℃、90%RH的高溫高濕氣氛下放置48小時，然後將其作為腐蝕性的測定樣品。 The surface protective films of Examples 1 to 4 and Comparative Examples 1 to 3 were aged for 7 days in an atmosphere of 23 ° C and 50% RH, and then the release film (PET film coated with an anthrone resin) was peeled off to expose the adhesive. After the substance of the agent layer was applied to an aluminum foil, it was allowed to stand under a high-temperature and high-humidity atmosphere of 60 ° C and 90% RH for 48 hours, and then it was used as a corrosive measurement sample.
進而，經由黏著劑層將該暴露出黏著劑層的表面保護膜貼合於黏貼在液晶盒上的偏光板的表面，放置1天後，經50℃、5個大氣壓、20分鐘的高壓釜處理，於室溫進一步放置12小時，將經以上得到的物質作為黏著力、剝離帶電壓的測試樣品。 Further, the surface protective film exposing the adhesive layer was attached to the surface of the polarizing plate adhered to the liquid crystal cell via the adhesive layer, and left for 1 day, and then subjected to autoclaving at 50 ° C, 5 atm, and 20 minutes. After further standing at room temperature for 12 hours, the material obtained above was used as a test sample for adhesion and peeling tape voltage.
丙烯酸類共聚物的酸價，將樣品溶解於溶劑(二乙醚和乙醇以體積比2：1混合的物質)中，使用電位差自動滴定裝置(京都電子工業製，AT-610)，使用0.1上述電位差滴定裝置，用濃度為約0.1mol/l的氫氧化鉀乙醇溶液進行電位差滴定，測定為了中和樣品所需的氫氧化鉀乙醇溶液的量。然後，通過下式求得酸價。 The acid value of the acrylic copolymer was dissolved in a solvent (a mixture of diethyl ether and ethanol in a volume ratio of 2:1), and a potential difference automatic titrator (AT-610, manufactured by Kyoto Electronics Industrial Co., Ltd.) was used, and the above potential difference was used. The titration apparatus was subjected to potentiometric titration 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 is obtained by the following formula.
酸價=(B×f×5.611)/S Acid value = (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) B = amount of 0.1 mol/l potassium hydroxide ethanol solution used in the titration (ml)
f=0.1mol/l氫氧化鉀乙醇溶液的因數 f=0.1mol/l factor of potassium hydroxide ethanol solution
S=樣品的固體成分的品質(g) S = quality of the solid component of the sample (g)
以下述剝離強度作為黏著力：使用拉力試驗機以拉伸速度為30m/min向180°方向剝離通過上述得到的測試樣品(在偏光板表面貼合25mm寬的表面保護膜的物質)測定的剝離強度(N/25mm)。 The following peeling strength was used as the adhesive force: peeling measured by the above-mentioned test sample (substance which bonded the surface protective film of 25 mm width on the surface of a polarizing plate) to the 180-degree direction by the tensile-stretching-speed of 30 m/min. Strength (N/25mm).
以30m/min的拉伸速度180°剝離如上上述得到的測試樣品時，使用高精度靜電傳感器SK-035、SK-200((股)KEYENCE製造)測定偏光板帶電產生的電壓(帶電壓)，以測定值的最大值作為剝離帶電壓(kV)。 When the test sample obtained as described above was peeled off at a tensile speed of 180° at a tensile rate of 30 m/min, the voltage (band voltage) generated by the polarization of the polarizing plate was measured using a high-precision electrostatic sensor SK-035, SK-200 (manufactured by KEYENCE). The maximum value of the measured value was taken as the peeling strip voltage (kV).
將樣品貼合於鋁箔上後，在60℃×90%RH的高溫高濕條件下放置48小時。然後，從鋁箔剝離樣品，目視確認鋁箔表面，以下述基準評價。 After the sample was attached to an aluminum foil, it was allowed to stand under high temperature and high humidity conditions of 60 ° C × 90% RH for 48 hours. Then, the sample was peeled off from the aluminum foil, and the surface of the aluminum foil was visually confirmed and evaluated based on the following criteria.
○：未確認鋁箔表面變色。 ○: The surface of the aluminum foil was not confirmed to be discolored.
△：確認鋁箔表面的一部分變色。 △: A part of the surface of the aluminum foil was confirmed to be discolored.
×：確認鋁箔表面變色。 ×: The surface of the aluminum foil was confirmed to be discolored.
用原子筆(負荷500g，往復3次)在通過上述得到的測試樣品的表面保護膜上描繪後，70℃×24小時放置。從偏光板剝離表面保護膜，觀察偏光板表面，確認沒有向偏光板轉移污染，用下述基準評價。 After drawing on the surface protective film of the test sample obtained above by a ball pen (loading 500 g, reciprocating three times), it was left at 70 ° C for 24 hours. The surface protective film was peeled off from the polarizing plate, and the surface of the polarizing plate was observed. It was confirmed that no contamination was transferred to the polarizing plate, and it was evaluated by the following criteria.
○：沒有向偏光板轉移污染。 ○: No contamination was transferred to the polarizing plate.
△：沿著原子筆描繪的軌跡確認向至少一部分轉移污染。 △: It is confirmed that the contamination is transferred to at least a part along the trajectory drawn by the atomic pen.
×：沿著原子筆描繪的軌跡確認轉移污染，從黏著劑表面也有黏著 劑脫離。 ×: The transfer contamination is confirmed along the trajectory drawn by the ball pen, and there is adhesion from the surface of the adhesive. The agent is detached.
表3中顯示試驗和評價的結果。 The results of the tests and evaluations are shown in Table 3.
以熔點在30℃以上的離子性化合物作為抗靜電劑的實施例1~4中，形成了抗靜電性能優異，並且具有對於被黏物的耐腐蝕性、污染性也低的物質。 In Examples 1 to 4 in which an ionic compound having a melting point of 30 ° C or more was used as an antistatic agent, it was excellent in antistatic property and had low corrosion resistance and contamination property to an adherend.
在抗靜電劑中使用高氯酸鋰的比較例1中，形成了腐蝕性大、污染性也稍高的物質。 In Comparative Example 1 in which lithium perchlorate was used as the antistatic agent, a substance having high corrosivity and a slightly high degree of contamination was formed.
在抗靜電劑中使用雙(三氟甲磺醯)亞胺鋰、黏著劑的丙烯酸類聚合物的酸價高的比較例2中，形成了剝離帶電壓高、抗靜電性能差、污染性高、腐蝕性也稍大的物質。 In Comparative Example 2 in which the acid value of the acrylic polymer using lithium bis(trifluoromethanesulfonate)imide or an adhesive was high in the antistatic agent, the peeling strip voltage was high, the antistatic property was poor, and the contamination was high. A substance that is slightly corrosive.
在抗靜電劑中使用三氟甲磺酸鋰的比較例3中，形成了腐蝕性稍大、污染性也稍高的物質。 In Comparative Example 3 in which lithium trifluoromethanesulfonate was used as the antistatic agent, a substance having a slightly corrosive property and a slightly high degree of contamination was formed.
因此，比較例1~3的表面保護膜不能夠同時滿足(1)優異的抗靜電性能，(2)耐腐蝕性，(3)防止黏著劑殘留的發生。 Therefore, the surface protective films of Comparative Examples 1 to 3 could not simultaneously satisfy (1) excellent antistatic properties, (2) corrosion resistance, and (3) prevention of occurrence of adhesive residue.
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