TWI720114B - Adhesive composition for protective film, and protective film - Google Patents
Adhesive composition for protective film, and protective 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- 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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
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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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- Chemical Kinetics & Catalysis (AREA)
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
本發明關於保護膜用黏接劑組成物及保護膜。 The present invention relates to an adhesive composition for a protective film and a protective film.
液晶顯示裝置所使用之偏光板等光學構件,在經由衝壓加工、檢查、輸送、液晶顯示面板之組裝等各步驟的期間,為了使其表面不受到污染或損傷而利用保護膜進行保護,該保護膜在不需光學構件之表面保護的階段係從光學構件剝離去除。 Optical components such as polarizing plates used in liquid crystal display devices are protected by a protective film in order to prevent contamination or damage on the surface during various steps such as press processing, inspection, transportation, and assembly of the liquid crystal display panel. The film is peeled and removed from the optical member at a stage where the surface protection of the optical member is not required.
將保護膜從光學構件剝離時,若產生靜電的話,會有灰塵等附著於光學構件、或液晶顯示裝置的電路受到破壞的不良情況產生。因此,對於保護膜要求能防止剝離時產生之靜電的性質(抗靜電性)。 When the protective film is peeled from the optical member, if static electricity is generated, there may be a problem that dust or the like adheres to the optical member, or the circuit of the liquid crystal display device is damaged. Therefore, the protective film is required to prevent static electricity (antistatic property) from being generated during peeling.
又,對於保護膜要求直到不需保護為止不會發生突然剝離之程度的黏接力。進一步近年來,為了提高作業效率,保護膜從被黏體的剝離有於高速(例如30m/分)進行的傾向,要求即使於高速剝離時仍能輕易地從被黏體剝離。亦即, 對於保護膜要求不會發生突然剝離、且保護膜之高速剝離時的黏接力低、高速剝離性優異。 In addition, the protective film is required to have adhesive strength to the extent that it does not suddenly peel off until it is no longer needed. Furthermore, in recent years, in order to improve work efficiency, the peeling of the protective film from the adherend tends to proceed at a high speed (for example, 30 m/min), and it is required that it can be easily peeled from the adherend even during high-speed peeling. that is, For the protective film, it is required that no sudden peeling occurs, and the adhesive force of the protective film during high-speed peeling is low, and the high-speed peeling performance is excellent.
又,就保護膜所使用之黏接劑層而言,為了確保光學構件的可見性,大多以高透明性的丙烯酸系黏接劑組成物形成。如此之具有丙烯酸系黏接劑層之保護膜的製造時,將黏接劑組成物塗覆於基材膜,進行乾燥並去除溶劑後,直到交聯反應結束為止需進行7天左右的熟化。因此,在直到熟化完成為止的期間,需確保將保護膜予以保存的空間。考量生產效率的方面,也希望縮短直到熟化完成所需的時間(以下,亦稱為「熟化完成時間」)。 In addition, the adhesive layer used in the protective film is often formed with a highly transparent acrylic adhesive composition in order to ensure the visibility of the optical member. When manufacturing such a protective film with an acrylic adhesive layer, the adhesive composition is applied to the base film, dried and the solvent is removed, and it takes about 7 days to mature until the crosslinking reaction is completed. Therefore, it is necessary to secure a space to store the protective film until the maturation is completed. In consideration of production efficiency, it is also desired to shorten the time required until the maturation is completed (hereinafter, also referred to as "maturing completion time").
作為能形成抗靜電性優異之黏接劑層的保護膜用之黏接劑組成物,有人揭示了一種黏接劑組成物,其包含以(甲基)丙烯酸烷酯為主成分之酸價為29以下的(甲基)丙烯酸系聚合物、及含氟的醯亞胺鋰鹽(例如,參照日本特開2005-306937號公報)。 As an adhesive composition for a protective film that can form an adhesive layer with excellent antistatic properties, someone has disclosed an adhesive composition, which contains an alkyl (meth)acrylate as the main component of the acid value of (Meth)acrylic polymer of 29 or less, and fluorine-containing iminium lithium salt (for example, refer to Japanese Patent Application Laid-Open No. 2005-306937).
作為能形成抗靜電性優異、且熟化完成時間亦短之黏接劑層的保護膜用之黏接劑組成物,有人揭示了一種黏接劑組成物,其包含具有來自具羥基之(甲基)丙烯醯胺之構成單元的(甲基)丙烯酸系聚合物、及抗靜電劑(例如,參照日本特開2009-126929號公報)。 As an adhesive composition that can form a protective film for an adhesive layer with excellent antistatic properties and a short curing completion time, some people have disclosed an adhesive composition that contains a (methyl group) derived from a hydroxyl group. ) The (meth)acrylic polymer of the structural unit of acrylamide, and an antistatic agent (for example, refer to Japanese Patent Application Laid-Open No. 2009-126929).
作為能形成熟化完成時間短、高速剝離時之黏接力低之黏接劑層的黏接劑組成物,有人揭示了一種包含黏接劑層的保護片,該黏接劑層含有丙烯酸系樹脂、胺甲酸乙酯(甲基)丙烯酸酯、及離子性化合物,且係利用活性能量射線進行交聯而得(例如,參照日本特開2010-31255號公報)。 As an adhesive composition for an adhesive layer with a short time to complete the maturation and low adhesive force during high-speed peeling, some people have disclosed a protective sheet including an adhesive layer containing acrylic resin, Urethane (meth)acrylate and an ionic compound are obtained by crosslinking with active energy rays (for example, refer to JP 2010-31255 A).
但,日本特開2005-306937號公報所記載之保護膜,雖具有優異的抗靜電性,但熟化完成時間長,生產性差。 However, although the protective film described in JP 2005-306937 A has excellent antistatic properties, it takes a long time to complete the curing and is poor in productivity.
作為確保抗靜電性同時縮短熟化完成時間的技術,如上述般揭示有日本特開2009-126929號公報所記載之技術。日本特開2009-126929號公報所記載之黏接劑組成物,直至熟化完成需3天左右的時間,就熟化完成時間而言並非令人滿意,要求進一步的縮短。且,未針對高速剝離時之黏接力進行研究,會有高速剝離時之黏接力高、高速剝離性差的情況。 As a technique for ensuring antistatic properties while shortening the maturation completion time, the technique described in Japanese Patent Application Laid-Open No. 2009-126929 is disclosed as described above. The adhesive composition described in Japanese Patent Laid-Open No. 2009-126929 takes about 3 days until the maturation is completed, which is not satisfactory in terms of the maturation completion time, and further shortening is required. Moreover, the adhesion force during high-speed peeling has not been studied, and there may be cases where the adhesive force during high-speed peeling is high and the high-speed peeling performance is poor.
又,日本特開2010-31255號公報所記載之包含利用活性能量射線進行交聯而得之黏接劑層的保護片,熟化完成時間雖短,但就保護片之製造設備而言,需活性能量射線照射機。 In addition, the protective sheet including an adhesive layer crosslinked by active energy rays described in Japanese Patent Application Laid-Open No. 2010-31255 has a short curing completion time, but the protective sheet manufacturing equipment requires active Energy ray irradiation machine.
本發明係鑒於上述情況而進行,其課題在於提供熟化完成時間短、抗靜電性優異、具有不會突然剝離之程度之黏接力、高速剝離時之黏接力低、高速剝離性優異的保護膜用黏接劑組成物、及使用該保護膜用黏接劑組成物而成的保護膜。 The present invention has been made in view of the above circumstances, and its subject is to provide a protective film with a short curing completion time, excellent antistatic properties, an adhesive force that does not peel off suddenly, low adhesive force during high-speed peeling, and excellent high-speed peelability. Adhesive composition, and a protective film formed by using the adhesive composition for protective film.
用於解決前述課題之具體手段包括以下態樣。 The specific methods used to solve the aforementioned problems include the following aspects.
<1>一種保護膜用黏接劑組成物,包含:酸價為9mgKOH/g以上70mgKOH/g以下之(甲基)丙烯酸系聚合物、相對於該(甲基)丙烯酸系聚合物之酸性基1當量為0.3當量以上2.0當量以下之金屬螯合物系交聯劑、以及抗靜電劑。 <1> An adhesive composition for a protective film, comprising: a (meth)acrylic polymer having an acid value of 9 mgKOH/g or more and 70 mgKOH/g or less, and an acidic group relative to the (meth)acrylic polymer One equivalent of a metal chelate crosslinking agent and an antistatic agent of 0.3 to 2.0 equivalents.
<2>如前述<1>之保護膜用黏接劑組成物,其中,該(甲基)丙烯酸系聚合物包含下列通式(1)表示之構成單元。 <2> The adhesive composition for a protective film according to the above <1>, wherein the (meth)acrylic polymer includes a structural unit represented by the following general formula (1).
通式(1)中,R1表示氫原子或甲基。L表示選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成的2價連結基。 In the general formula (1), R 1 represents a hydrogen atom or a methyl group. L represents a divalent linking group consisting of at least one selected from the group consisting of an alkylene group, an arylene group, a carbonyl group, and an oxygen atom.
<3>如前述<1>或<2>之保護膜用黏接劑組成物,其中,該(甲基)丙烯酸系聚合物之酸價與該金屬螯合物系交聯劑之當量的乘積為3~40之範圍內。 <3> The adhesive composition for protective film of the aforementioned <1> or <2>, wherein the product of the acid value of the (meth)acrylic polymer and the equivalent of the metal chelate crosslinking agent It is in the range of 3~40.
<4>如前述<1>~<3>中任一項之保護膜用黏接劑組成物,更包含聚醚改性聚矽氧,該聚醚改性聚矽氧之含量,相對於該(甲基)丙烯酸系聚合物100質量份為0.05質量份以上1.00質量份以下。 <4> The adhesive composition for a protective film as described in any one of <1> to <3>, further comprising polyether-modified polysiloxane. The content of the polyether-modified polysiloxane is relative to the 100 parts by mass of the (meth)acrylic polymer is 0.05 parts by mass or more and 1.00 parts by mass or less.
<5>如前述<1>~<4>中任一項之保護膜用黏接劑組成物,更包含來自具有羧基之單體的構成單元,且包含重量平均分子量為3,000以上30,000以下之(甲基)丙烯酸系低聚物,該(甲基)丙烯酸系低聚物之含量,相對於該(甲基)丙烯酸系聚合物100質量份為0.05質量份以上2.00質量份以下。 <5> The adhesive composition for a protective film as described in any one of the aforementioned <1> to <4>, further comprising a structural unit derived from a monomer having a carboxyl group, and containing a weight average molecular weight of 3,000 to 30,000 ( The meth)acrylic oligomer, and the content of the (meth)acrylic oligomer is 0.05 parts by mass or more and 2.00 parts by mass or less with respect to 100 parts by mass of the (meth)acrylic polymer.
<6>如前述<5>之保護膜用黏接劑組成物,其中,該(甲基)丙烯酸系低聚物中,以相對於全部構成單元為5質量%以上30質量%以下之範圍含有來自含環氧烷(alkylene oxide)鏈之單體的構成單元。 <6> The adhesive composition for a protective film according to the aforementioned <5>, wherein the (meth)acrylic oligomer contains 5% by mass to 30% by mass relative to all structural units A structural unit derived from a monomer containing an alkylene oxide chain.
<7>一種保護膜,包含:使用如前述<1>~<6>中任一項之保護膜用黏接劑組成物而配置成的黏接劑層、以及基材。 <7> A protective film, comprising: an adhesive layer configured using the adhesive composition for a protective film as described in any one of the aforementioned <1> to <6>, and a substrate.
根據本揭示,可提供熟化完成時間短、抗靜電性優異、具有不會突然剝離之程度之黏接力、高速剝離時之黏接力低、高速剝離性優異的保護膜用黏接劑組成物、及使用該保護膜用黏接劑組成物而成的保護膜。 According to the present disclosure, it is possible to provide an adhesive composition for a protective film that has a short curing completion time, excellent antistatic properties, adhesive strength that does not peel off suddenly, low adhesive strength during high-speed peeling, and excellent high-speed peelability, and A protective film formed using this adhesive composition for protective film.
[圖1]係說明黏接力及高速剝離時之剝離性之評價方法的說明圖。 [Fig. 1] An explanatory diagram explaining the evaluation method of adhesive strength and peelability during high-speed peeling.
以下,針對本揭示之保護膜用黏接劑組劑成物及保護膜進行詳細說明。此外,本揭示中,數值範圍中之「~」意指包括「~」前後之數值分別作為該數值範圍之下限及上限。 Hereinafter, a detailed description will be given of the adhesive composition product for the protective film of the present disclosure and the protective film. In addition, in the present disclosure, the "~" in the numerical range means to include the numerical values before and after the "~" as the lower limit and the upper limit of the numerical range, respectively.
本說明書中,組成物中之各成分的量,在組成物中存在多數相當於各成分之物質時,除非另有說明,意指存在於組成物中之該多數物質的合計量。 In this specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when there are many substances equivalent to each component in the composition, unless otherwise specified.
本說明書中,(甲基)丙烯酸系聚合物或(甲基)丙烯酸系低聚物,意指構成其之單體中至少係主成分之單體為具有(甲基)丙烯醯基之單體的聚合物或低聚物。係主成分之單體,意指構成聚合物或低聚物之單體中含有率(質量%)最大的單體。本揭示之(甲基)丙烯酸系聚合物或(甲基)丙烯酸系低聚物的較佳實施態樣為:來自係主成分之(甲基)丙烯酸酯單體之構成單元的含有率為全部構成單元的50質量%以上。 In this specification, (meth)acrylic polymer or (meth)acrylic oligomer means that at least the main component of the monomers constituting it is a monomer having a (meth)acrylic group The polymer or oligomer. The monomer of the main component means the monomer with the largest content (% by mass) among the monomers constituting the polymer or oligomer. The preferred embodiment of the (meth)acrylic polymer or (meth)acrylic oligomer of the present disclosure is that the content of the constituent units of the (meth)acrylate monomer derived from the main component of the system is all More than 50% by mass of the constituent unit.
本說明書中,「(甲基)丙烯酸基」意指「丙烯酸基」及「甲基丙烯酸基」之兩者。「(甲基)丙烯酸酯」意指「丙烯酸酯」及「甲基丙烯酸酯」之兩者。「(甲基)丙烯醯基」意指「丙烯醯基」及「甲基丙烯醯基」之兩者。 In this specification, "(meth)acryl group" means both of "acryl group" and "methacryl group". "(Meth)acrylate" means both of "acrylate" and "methacrylate". "(Meth)acryloyl" means both of "acryloyl" and "methacryloyl".
<<保護膜用黏接劑組成物>> <<Adhesive composition for protective film>>
本揭示之保護膜用黏接劑組成物(以下,亦簡稱為「本揭示之黏接劑組成物」)包含:酸價為9mgKOH/g以上70mgKOH/g以下之(甲基)丙烯酸系聚合物(以下,有時稱為「特定(甲基)丙烯酸系聚合物」)、相對於該(甲基)丙烯酸系聚合物之酸性基1當量為0.3當量以上2.0當量以下之金屬螯合物系交聯劑、及抗靜電劑。 The adhesive composition for protective film of the present disclosure (hereinafter, also referred to as "the adhesive composition of the present disclosure") includes: (meth)acrylic polymer with an acid value of 9 mgKOH/g or more and 70 mgKOH/g or less (Hereinafter, sometimes referred to as "specific (meth)acrylic polymer"), a metal chelate compound with an acidic group equivalent of 0.3 to 2.0 equivalents relative to the (meth)acrylic polymer Coupling agent, and antistatic agent.
藉由保護膜用黏接劑組成物具有上述構成,能縮短製作保護膜時的熟化完成時間,可獲得抗靜電性優異、具有不會突然剝離之程度的黏接力、高速剝離時之黏接力低、高速剝離性優異的保護膜。原因考慮如下。 The adhesive composition for protective film having the above-mentioned structure can shorten the maturation completion time when making the protective film, obtain excellent antistatic properties, have an adhesive force that does not peel off suddenly, and has low adhesive force during high-speed peeling. , A protective film with excellent high-speed peeling. The reason is considered as follows.
為了縮短熟化完成時間,一般認為增加(甲基)丙烯酸系聚合物所具有之交聯點的數目、使用高反應性的交聯劑即可。例如,併用具有係酸性基之羧基之(甲基)丙烯酸系聚合物與金屬螯合物系交聯劑時,交聯反應速度快,此點廣為人知。 In order to shorten the maturation completion time, it is generally considered that the number of crosslinking points possessed by the (meth)acrylic polymer should be increased and a highly reactive crosslinking agent should be used. For example, when a (meth)acrylic polymer having a carboxyl group with an acidic group is used in combination with a metal chelate-based crosslinking agent, it is widely known that the crosslinking reaction speed is fast.
但,使用具有酸性基之(甲基)丙烯酸系聚合物與金屬螯合物系交聯劑而得之保護膜用黏接劑,有彈性變低、黏接力變高的傾向,故會有高速剝離時難以將保護膜從被黏體剝離的情況。且,酸性基會使抗靜電性惡化。因此,在原本要求抗靜電性之保護膜用黏接劑中,該等的併用視為不適合。 However, adhesives for protective films obtained by using (meth)acrylic polymers with acidic groups and metal chelate crosslinking agents tend to have lower elasticity and higher adhesive strength, so there is a high speed When peeling off, it is difficult to peel the protective film from the adherend. In addition, acidic groups deteriorate the antistatic properties. Therefore, the combined use of these adhesives for protective films that originally required antistatic properties was deemed unsuitable.
本揭示中,藉由使酸性基之當量與金屬螯合物系交聯劑之當量的比率成為預定範圍,可將因酸性基所致之抗靜電性的降低抑制到最小限。又,據考慮藉由使(甲基)丙烯酸系聚合物之酸價成為預定之範圍,可賦予交聯體適度的硬度,並可降低高速剝離時之黏接力。亦即,本揭示中,係根據酸價與金屬螯合物系交聯劑的量,實現抗靜電性與黏接力的平衡。 In the present disclosure, by setting the ratio of the equivalent of the acidic group to the equivalent of the metal chelate-based crosslinking agent in a predetermined range, the decrease in antistatic property due to the acidic group can be suppressed to the minimum. In addition, it is considered that by setting the acid value of the (meth)acrylic polymer to a predetermined range, appropriate hardness can be imparted to the cross-linked body, and the adhesive force during high-speed peeling can be reduced. That is, in the present disclosure, the balance of antistatic property and adhesive force is achieved based on the acid value and the amount of the metal chelate-based crosslinking agent.
進一步,根據本揭示,將具有係酸性基之羧基之(甲基)丙烯酸系聚合物、與金屬螯合物系交聯劑予以併用,故相較於以往將異氰酸酯化合物作為交聯劑使用的情況,可大幅縮短熟化完成時間,能獲得高生產效率的保護膜用黏接劑組成物。 Furthermore, according to the present disclosure, a (meth)acrylic polymer having a carboxyl group with an acidic group is used in combination with a metal chelate-based crosslinking agent. Therefore, compared with the conventional case where an isocyanate compound is used as a crosslinking agent , Can greatly shorten the maturation completion time, and can obtain the adhesive composition for protective film with high production efficiency.
[(甲基)丙烯酸系聚合物] [(Meth) acrylic polymer]
本揭示中之保護膜用黏接劑組成物,包含至少1種之酸價為9mgKOH/g以上70mgKOH/g以下之(甲基)丙烯酸系聚合物。本揭示之黏接劑組成物,視需要亦可進一步包含和前述(甲基)丙烯酸系聚合物不同的(甲基)丙烯酸系聚合物。 The adhesive composition for a protective film in the present disclosure includes at least one (meth)acrylic polymer having an acid value of 9 mgKOH/g or more and 70 mgKOH/g or less. The adhesive composition of the present disclosure may further include a (meth)acrylic polymer different from the aforementioned (meth)acrylic polymer if necessary.
本揭示之黏接劑組成物所含之(甲基)丙烯酸系聚合物的酸價,考量將高速剝離時之黏接力壓抑為低的觀點,亦即考量進一步改善高速剝離性的觀點,酸價宜為9mgKOH/g以上70mgKOH/g以下,考量同樣的觀點,酸價宜為11mgKOH/g以上40mgKOH/g以下較佳,酸價為13mgKOH/g以上30mgKOH/g以下更佳。 The acid value of the (meth)acrylic polymer contained in the adhesive composition of the present disclosure takes into consideration the viewpoint of suppressing the adhesive force during high-speed peeling to be low, that is, the viewpoint of further improving the high-speed peelability. It is preferably 9 mgKOH/g or more and 70 mgKOH/g or less. Considering the same point of view, the acid value is preferably 11 mgKOH/g or more and 40 mgKOH/g or less, and the acid value is more preferably 13 mgKOH/g or more and 30 mgKOH/g or less.
(甲基)丙烯酸系聚合物之酸價超過70mgKOH/g的話,包含本揭示之黏接劑組成物而製得之黏接劑層變硬,黏接劑層之黏接力變得過低,保護膜容易從被黏體突然剝離。又,抗靜電性亦降低。又,(甲基)丙烯酸系聚合物之酸價未達9mgKOH/g的話,使用本揭示之黏接劑組成物形成黏接劑層時,形成之黏接劑層過於柔軟,黏接力變得過高,故會有高速剝離時難以剝離的情況。 If the acid value of the (meth)acrylic polymer exceeds 70 mgKOH/g, the adhesive layer prepared by including the adhesive composition of the present disclosure becomes hard, and the adhesive force of the adhesive layer becomes too low, which protects The film is easy to peel off suddenly from the adherend. In addition, the antistatic property is also reduced. In addition, if the acid value of the (meth)acrylic polymer is less than 9 mgKOH/g, when the adhesive composition of the present disclosure is used to form the adhesive layer, the formed adhesive layer is too soft and the adhesive force becomes excessive High, so it may be difficult to peel during high-speed peeling.
(甲基)丙烯酸系聚合物或後述(甲基)丙烯酸系低聚物之酸價,分別根據以下計算式求出。 The acid value of the (meth)acrylic polymer or the (meth)acrylic oligomer described later is calculated according to the following calculation formula, respectively.
酸價(mgKOH/g)={(A/100)÷B}×56.1×1000×C Acid value (mgKOH/g)={(A/100)÷B}×56.1×1000×C
A=(甲基)丙烯酸系聚合物或(甲基)丙烯酸系低聚物所使用之全部單體中的具有羧基之單體的含有率(質量%) A=(meth)acrylic polymer or (meth)acrylic oligomer content rate (mass%) of monomers having carboxyl group in all monomers used in (meth)acrylic oligomer
B=(甲基)丙烯酸系聚合物或(甲基)丙烯酸系低聚物所使用之具有羧基之單體的分子量 B=(meth)acrylic polymer or (meth)acrylic oligomer used in the molecular weight of the monomer with carboxyl group
C=具有羧基之單體1分子中所含之羧基的數目 C=The number of carboxyl groups contained in 1 molecule of the monomer with carboxyl groups
此外,56.1為KOH之分子量。 In addition, 56.1 is the molecular weight of KOH.
又,具有羧基之單體有多數種時,可將針對各個單體利用上式求得的值相加而求出酸價。 In addition, when there are multiple types of monomers having a carboxyl group, the acid value can be obtained by adding the values obtained by the above formula for each monomer.
本揭示之黏接劑組成物中之特定(甲基)丙烯酸系聚合物具有酸性基。特定(甲基)丙烯酸系聚合物宜包含具有酸性基之構成單元較佳。具有酸性基之構成單元宜為來自具有羧基之單體的構成單元較佳。其中,來自具有羧基之單體的構成單元,可列舉來自(甲基)丙烯酸的構成單元、來自具有羧基之(甲基)丙烯酸酯的構成單元等。來自具有羧基之(甲基)丙烯酸酯的構成單元,可列舉下列通式(1)表示之構成單元。 The specific (meth)acrylic polymer in the adhesive composition of the present disclosure has an acidic group. The specific (meth)acrylic polymer preferably contains a structural unit having an acidic group. The structural unit having an acidic group is preferably a structural unit derived from a monomer having a carboxyl group. Among them, the structural unit derived from a monomer having a carboxyl group includes a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate having a carboxyl group, and the like. The structural unit derived from the (meth)acrylate having a carboxyl group includes the structural unit represented by the following general formula (1).
具有通式(1)表示之構成單元的話,羧基介由L鍵結,藉此可將高速剝離時之黏接力壓抑為低。 If it has a structural unit represented by the general formula (1), the carboxyl group is bonded via L, thereby suppressing the adhesive force during high-speed peeling to be low.
上述通式(1)表示之構成單元中,L表示選自於由伸烷基、伸芳基、羰基及氧原子構成之群組中之至少1種構成的2價連結基,R1表示氫原子或甲基。但,L含有氧原子時,氧原子形成和選自於由伸烷基、伸芳基及羰基構成之群組中之至少1種鍵結而成的基,並與-COO-及-CO-鍵結。 In the structural unit represented by the above general formula (1), L represents a divalent linking group composed of at least one selected from the group consisting of an alkylene group, an aryl group, a carbonyl group and an oxygen atom, and R 1 represents a hydrogen atom Or methyl. However, when L contains an oxygen atom, the oxygen atom forms a group formed by bonding at least one selected from the group consisting of an alkylene group, an aryl group, and a carbonyl group, and is bonded to -COO- and -CO- Knot.
L中之伸烷基可為直鏈狀、分支鏈狀及環狀中之任一者。L中之伸烷基為直鏈狀或分支鏈狀時,伸烷基之碳數宜為1~12較佳,2~10更佳,2~6尤佳。 The alkylene group in L may be any of linear, branched and cyclic. When the alkylene group in L is linear or branched, the carbon number of the alkylene group is preferably 1-12, more preferably 2-10, and particularly preferably 2-6.
又,L中之伸烷基為環狀時,例如可為伸烷基之碳數為3~5之環狀基。 In addition, when the alkylene group in L is cyclic, for example, it may be a cyclic group having 3 to 5 carbon atoms in the alkylene group.
就L中之伸芳基而言,碳數宜為6~10較佳,伸苯基更佳。伸芳基中之鍵結位置並無特別限制。例如伸芳基為伸苯基時,鍵結位置可為1位與4位、1位與2位、及1位與3位中之任一者,宜為1位與2位較佳。 For the aryl group in L, the carbon number is preferably 6-10, and the phenyl group is more preferable. The bonding position in the aryl group is not particularly limited. For example, when the aryl group is a phenyl group, the bonding position can be any of the 1-position and the 4-position, the 1-position and the 2-position, and the 1-position and the 3-position, and the 1-position and the 2-position are preferred.
L中之伸烷基及伸芳基,也可具有取代基。就取代基而言,可列舉碳數1~12之烷基、鹵素原子、羥基、胺基、硝基、苯基等。 The alkylene and arylene groups in L may also have substituents. The substituent includes an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a nitro group, and a phenyl group.
通式(1)中之L表示之2價連結基,考量抗靜電性及高速剝離性的觀點,宜為下列通式(2a)或通式(2b)表示之2價連結基較佳。 The divalent linking group represented by L in the general formula (1) is preferably the divalent linking group represented by the following general formula (2a) or general formula (2b) in consideration of antistatic properties and high-speed peelability.
通式(2a)及(2b)中,R21~R24各自獨立地表示碳數1~12之伸烷基或碳數6~10之伸芳基。n表示0~10之數值,m表示1~10之數值。 In the general formulas (2a) and (2b), R 21 to R 24 each independently represent an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms. n represents the value from 0 to 10, and m represents the value from 1 to 10.
R21~R24中之伸烷基可為直鏈狀、分支鏈狀及環狀中之任一者,宜為直鏈狀或分支鏈狀較佳,直鏈狀更佳。 The alkylene group in R 21 to R 24 may be any of linear, branched and cyclic, preferably linear or branched, and more preferably linear.
R21~R24中之伸芳基中之鍵結位置並無特別限制。例如伸芳基為伸苯基或環伸己基時,鍵結位置可為1位與4位、1位與2位、及1位與3位中之任一者,宜為1位與2位較佳。 The bonding position of the aryl extension in R 21 to R 24 is not particularly limited. For example, when the aryl group is a phenyl group or a cyclohexene group, the bonding position can be any one of the 1-position and the 4-position, the 1-position and the 2-position, and the 1-position and the 3-position, preferably the 1-position and the 2-position. Better.
R21及R22中之伸烷基,宜各自獨立地為碳數2~10較佳,碳數2~6更佳。R21及R22中之伸烷基可相同也可不同。 Preferably, the alkylene groups in R 21 and R 22 each independently have a carbon number of 2-10, more preferably a carbon number of 2-6. The alkylene groups in R 21 and R 22 may be the same or different.
R21及R22中之伸芳基,宜各自獨立地為伸苯基或伸萘基較佳,伸苯基更佳。 The arylene groups in R 21 and R 22 are preferably phenylene or naphthylene each independently, and phenylene is more preferred.
通式(2a)中之R21及R22,考量抗靜電性及高速剝離性的觀點,宜各自獨立地地為碳數1~12之伸烷基較佳,碳數2~6之伸烷基更佳,碳數2~6且為直鏈狀或分支鏈狀之伸烷基尤佳。 R 21 and R 22 in the general formula (2a), considering the antistatic properties and high-speed peeling properties, should each independently be an alkylene having 1 to 12 carbon atoms, preferably an alkylene having 2 to 6 carbon atoms The group is more preferable, and the alkylene group having a carbon number of 2-6 and being linear or branched is particularly preferable.
通式(2a)中,n表示0~10之數值。特定(甲基)丙烯酸系聚合物僅包含1種通式(1)表示之構成單元時,n為整數,包含2種以上時,n為係平均值之有理數。n宜為0~4較佳,0~2更佳。 In the general formula (2a), n represents a value from 0 to 10. When the specific (meth)acrylic polymer contains only one type of structural unit represented by the general formula (1), n is an integer, and when two or more types are included, n is a rational number based on an average value. n is preferably 0~4, more preferably 0~2.
R23宜為碳數1~12之伸烷基較佳,碳數2~6之伸烷基更佳,碳數2~4之伸烷基尤佳。 R 23 is preferably an alkylene having 1 to 12 carbon atoms, more preferably an alkylene having 2 to 6 carbon atoms, and particularly preferably an alkylene having 2 to 4 carbon atoms.
R24宜為碳數2~6之直鏈狀或分支鏈狀之伸烷基、碳數4~8之環狀伸烷基(2價之環狀基)、或碳數6~10之伸芳基較佳,碳數2~4之直鏈狀或分支鏈狀之伸烷基、碳數5~6之環狀伸烷基、或伸苯基更佳,碳數2~4之直鏈狀或分支鏈狀之伸烷基、環伸己基、或伸苯基尤佳。 R 24 is preferably a straight or branched chain alkylene group with carbon number 2-6, cyclic alkylene group with carbon number 4-8 (divalent cyclic group), or carbon number 6-10. Aryl is preferred, linear or branched alkylene having 2 to 4 carbons, cyclic alkylene having 5 to 6 carbons, or phenylene is more preferred, straight chain having 2 to 4 carbons Shaped or branched alkylene, cyclohexylene, or phenylene is particularly preferred.
通式(2b)中,m表示1~10之數值。特定(甲基)丙烯酸系聚合物僅包含1種通式(1)表示之構成單元時,m為整數,包含2種以上時,m為係平均值之有理數。m宜為1~4較佳,1~2更佳。 In the general formula (2b), m represents a value from 1 to 10. When the specific (meth)acrylic polymer contains only one type of structural unit represented by the general formula (1), m is an integer, and when two or more types are contained, m is a rational number based on an average value. m is preferably 1~4, more preferably 1~2.
通式(1)表示之構成單元,例如,可藉由使下列通式(1a)表示之單體、與構成特定(甲基)丙烯酸系聚合物之其他單體一同進行共聚而導入到特定(甲基)丙烯酸系聚合物中。 The structural unit represented by the general formula (1), for example, can be introduced into the specific ( Meth)acrylic polymer.
通式(1a)中,R1及L和通式(1)中之R1及L分別為同義。 In the general formula (1a), R 1 and L general formula (1) in the R 1 and L are synonymous.
通式(1a)表示之單體,可為利用常法製得者,亦可為從市售之單體中適當選擇者。作為通式(1a)表示之單體中L為通式(2a)表示的單體,例如,可列舉(甲基)丙烯酸二聚物(較佳為通式(2a)中之n之平均值為約0.4者)、ω-羧基-聚己內酯單(甲基)丙烯酸酯(較佳為通式(2a)中之n之平均值為約1.0者)。就該等單體而言,例如可使用「ARONIX M-5600」、「ARONIX M-5300」(以上,東亞合成(股)公司製,商品名)市售品。 The monomer represented by the general formula (1a) may be obtained by a conventional method, or may be appropriately selected from commercially available monomers. As the monomer represented by the general formula (1a), L is a monomer represented by the general formula (2a), for example, (meth)acrylic acid dimer (preferably the average value of n in the general formula (2a) Is about 0.4), ω-carboxy-polycaprolactone mono(meth)acrylate (preferably those whose average value of n in general formula (2a) is about 1.0). For these monomers, for example, "ARONIX M-5600" and "ARONIX M-5300" (above, manufactured by Toagosei Co., Ltd., trade name) commercially available products can be used.
又,作為通式(1a)表示之單體中L為通式(2b)表示的單體,例如,可列舉2-(甲基)丙烯醯氧乙基琥珀酸、2-(甲基)丙烯醯氧乙基富馬酸、2-(甲基)丙烯醯氧乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧乙基鄰苯二甲酸。就該等單體而言,例如可使用「LIGHT ESTER HO-MS」、「LIGHT ACRYLATE HOA-MS(N)」、「LIGHT ACRYLATE HOA-HH(N)」、「LIGHT ACRYLATE HOA-MPL(N)」(以上,共榮社化學(股)公司製,商品名)市售品。 In addition, as the monomer represented by the general formula (1a), L is a monomer represented by the general formula (2b), for example, 2-(meth)acryloxyethyl succinic acid, 2-(meth)propylene Glyoxyethyl fumaric acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid. For these monomers, for example, "LIGHT ESTER HO-MS", "LIGHT ACRYLATE HOA-MS(N)", "LIGHT ACRYLATE HOA-HH(N)", "LIGHT ACRYLATE HOA-MPL(N)" can be used "(The above, manufactured by Kyoeisha Chemical Co., Ltd., trade name) is a commercially available product.
特定(甲基)丙烯酸系聚合物中之通式(1)表示之構成單元的含有率,宜相對於全部構成單元為3質量%以上較佳,6質量%以上更佳,8質量%以上尤佳。 The content of the structural unit represented by the general formula (1) in the specific (meth)acrylic polymer is preferably 3% by mass or more relative to all the structural units, preferably 6% by mass or more, and especially 8% by mass or more good.
特定(甲基)丙烯酸系聚合物中之通式(1)表示之構成單元的含有率為3質量%以上的話,高速剝離時之黏接力可壓抑為更低。 If the content of the structural unit represented by the general formula (1) in the specific (meth)acrylic polymer is 3% by mass or more, the adhesive force during high-speed peeling can be suppressed to be lower.
又,特定(甲基)丙烯酸系聚合物中之通式(1)表示之構成單元的含有率,考量高速剝離性與抗靜電性的觀點,宜為40質量%以下較佳,20質量%以下更佳,10質量%以下尤佳。 In addition, the content of the structural unit represented by the general formula (1) in the specific (meth)acrylic polymer is preferably 40% by mass or less, and 20% by mass or less in consideration of high-speed peelability and antistatic properties. More preferably, 10% by mass or less is particularly preferable.
特定(甲基)丙烯酸系聚合物,除通式(1)表示之構成單元外,宜進一步含有至少1種之來自(甲基)丙烯酸烷酯之構成單元較佳。 The specific (meth)acrylic polymer preferably contains at least one structural unit derived from alkyl (meth)acrylate in addition to the structural unit represented by the general formula (1).
就(甲基)丙烯酸烷酯而言,例如,可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸異十四酯、(甲基)丙烯酸硬脂酯、(甲基) 丙烯酸環己酯、(甲基)丙烯酸異莰酯。(甲基)丙烯酸烷酯之烷基可為直鏈、分支或環狀中之任一者。 As for the alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( Second butyl meth)acrylate, third butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( N-nonyl meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, isotetradecyl (meth)acrylate, (meth) Stearyl acrylate, (meth) Cyclohexyl acrylate, isobornyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate may be any one of linear, branched, or cyclic.
其中,形成均聚物時之玻璃轉移溫度為-30℃以下之(甲基)丙烯酸烷酯為較佳。 Among them, alkyl (meth)acrylates having a glass transition temperature of -30°C or less when forming a homopolymer are preferred.
特定(甲基)丙烯酸系聚合物可單獨含有1種來自(甲基)丙烯酸烷酯之構成單元,亦可含有2種以上,宜含有2種以上較佳。 The specific (meth)acrylic polymer may contain one type of structural unit derived from alkyl (meth)acrylate alone, or two or more types, preferably two or more types.
其中,來自(甲基)丙烯酸烷酯之構成單元宜包含丙烯酸正丁酯及丙烯酸2-乙基己酯中之至少一者較佳,包含兩者更佳。 Among them, the structural unit derived from alkyl (meth)acrylate preferably contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate, and more preferably contains both.
特定(甲基)丙烯酸系聚合物包含來自(甲基)丙烯酸烷酯之構成單元(較佳為來自形成均聚物時之玻璃轉移溫度為-30℃以下之(甲基)丙烯酸烷酯的構成單元)時,來自(甲基)丙烯酸烷酯之構成單元(較佳為來自形成均聚物時之玻璃轉移溫度為-30℃以下之(甲基)丙烯酸烷酯的構成單元)的總含有率,宜相對於全部構成單元為65質量%以上99質量%以下較佳,75質量%以上97質量%以下更佳,80質量%以上95質量%以下尤佳。來自(甲基)丙烯酸烷酯之構成單元的總含有率為65質量%以上的話,有順應性(潤濕性)更加優異的傾向。又,來自(甲基)丙烯酸烷酯之構成單元的總含有率為99質量%以下的話,高速剝離時之黏接力不會變得過高,有高速剝離性優異的傾向。 The specific (meth)acrylic polymer contains structural units derived from alkyl (meth)acrylate (preferably from the structure of alkyl (meth)acrylate whose glass transition temperature when forming a homopolymer is below -30°C) Unit), the total content of structural units derived from alkyl (meth)acrylate (preferably derived from structural units derived from alkyl (meth)acrylate whose glass transition temperature when forming a homopolymer is -30°C or less) , Relative to all constituent units, it is preferably 65% by mass or more and 99% by mass or less, more preferably 75% by mass or more and 97% by mass or less, and more preferably 80% by mass or more and 95% by mass or less. When the total content of the structural units derived from the alkyl (meth)acrylate is 65% by mass or more, the compliance (wettability) tends to be more excellent. In addition, when the total content of the structural units derived from the alkyl (meth)acrylate is 99% by mass or less, the adhesive force during high-speed peeling does not become too high, and there is a tendency that the high-speed peelability is excellent.
特定(甲基)丙烯酸系聚合物,亦可進一步含有除通式(1)表示之構成單元及來自(甲基)丙烯酸烷酯之構成單元以外的其他構成單元。其他構成單元只要能與通 式(1)表示之構成單元一同構成聚合物即可,並無特別限制,可因應目的適當選擇。 The specific (meth)acrylic polymer may further contain other structural units other than the structural unit represented by the general formula (1) and the structural unit derived from alkyl (meth)acrylate. As long as other components can communicate with The structural units represented by the formula (1) only need to constitute a polymer together, and are not particularly limited, and can be appropriately selected according to the purpose.
能形成其他構成單元之單體,例如,可列舉具有羥基之單體、具有環氧烷鏈之單體、具有環狀基之單體。 Examples of monomers capable of forming other structural units include monomers having hydroxyl groups, monomers having alkylene oxide chains, and monomers having cyclic groups.
具有羥基之單體,例如,可列舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸3-甲基-3-羥基丁酯。 Monomers having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl ester, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 3-methyl-3-hydroxy (meth)acrylate Butyl ester.
具有環氧烷鏈之單體,例如,可列舉(甲基)丙烯酸甲氧基乙酯、丙烯酸2-(乙氧基乙氧基)乙酯、聚乙二醇(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、聚丙二醇(甲基)丙烯酸酯。 Monomers having alkylene oxide chains, for example, methoxyethyl (meth)acrylate, 2-(ethoxyethoxy)ethyl acrylate, polyethylene glycol (meth)acrylate, methyl acrylate Oxypolyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate.
具有環狀基之單體,例如,可列舉(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苯氧基乙酯。 The monomer having a cyclic group includes, for example, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
特定(甲基)丙烯酸系聚合物之玻璃轉移溫度,考量高速剝離性的觀點,宜為-40℃以下較佳,-50℃以下更佳。 The glass transition temperature of the specific (meth)acrylic polymer is preferably -40°C or less from the viewpoint of high-speed peelability, and more preferably -50°C or less.
特定(甲基)丙烯酸系聚合物之玻璃轉移溫度(Tg),係將根據下式計算而求出之絕對溫度(K)換算成攝氏溫度(℃)的莫耳平均玻璃轉移溫度。 The glass transition temperature (Tg) of the specific (meth)acrylic polymer is the molar average glass transition temperature obtained by converting the absolute temperature (K) calculated according to the following formula to the Celsius temperature (°C).
1/Tg=m1/Tg1+m2/Tg2+‧‧‧+m(k-1)/Tg(k-1)+mk/Tgk 1/Tg=m1/Tg1+m2/Tg2+‧‧‧+m(k-1)/Tg(k-1)+mk/Tgk
式中,Tg1、Tg2、‧‧‧、Tg(k-1)、Tgk分別表示構成(甲基)丙烯酸系聚合物之各單體形成均聚物時的以絕對溫度(K)表示之玻璃轉移溫度。m1、m2、‧‧‧、m(k-1)、mk分別表示構成(甲基)丙烯酸系聚合物之各單體的莫耳分率,m1+m2+‧‧‧+m(k-1)+mk=1。 In the formula, Tg1, Tg2, ‧‧‧, Tg(k-1), Tgk respectively represent the glass transition expressed in absolute temperature (K) when the monomers constituting the (meth)acrylic polymer form a homopolymer temperature. m1, m2, ‧‧‧, m(k-1), mk respectively represent the molar fraction of each monomer constituting the (meth)acrylic polymer, m1+m2+‧‧‧+m(k-1) +mk=1.
此外,「形成均聚物時的以絕對溫度(K)表示之玻璃轉移溫度」,係指將該單體單獨聚合而製得之均聚物的以絕對溫度(K)表示之玻璃轉移溫度。 In addition, "the glass transition temperature expressed in absolute temperature (K) when forming a homopolymer" refers to the glass transition temperature expressed in absolute temperature (K) of a homopolymer prepared by polymerizing the monomer alone.
就均聚物之玻璃轉移溫度而言,係利用差示掃描熱量測定裝置(DSC)(SEIKO INSTRUMENTS公司製,EXSTAR6000),於氮氣氣流中以測定試樣10mg、升溫速度10℃/分之條件,對其均聚物實施測定,並將獲得之DSC曲線的反曲點作為均聚物之玻璃轉移溫度。 Regarding the glass transition temperature of the homopolymer, a differential scanning calorimetry device (DSC) (manufactured by SEIKO INSTRUMENTS, EXSTAR6000) was used to measure the sample under the conditions of 10 mg and a temperature increase rate of 10°C/min in a nitrogen stream. The homopolymer was measured, and the inflection point of the obtained DSC curve was taken as the glass transition temperature of the homopolymer.
關於代表性的單體的「均聚物之以攝氏溫度(℃)表示之玻璃轉移溫度」,丙烯酸甲酯為5℃,丙烯酸乙酯為-27℃,甲基丙烯酸甲酯為103℃,丙烯酸正丁酯為-57℃,丙烯酸2-乙基己酯為-76℃,甲基丙烯酸正十二酯為-65℃,丙烯酸正辛酯為-65℃,丙烯酸異辛酯為-58℃,丙烯酸異壬酯為-58℃,丙烯酸異十四酯為-56℃,丙烯酸為163℃,ω-羧基-聚己內酯(n≒2)單丙烯酸酯為-30℃,2-丙烯醯氧乙基-琥珀酸為-40℃。 Regarding the "Glass Transition Temperature in Celsius (°C) of Homopolymers" of representative monomers, methyl acrylate is 5°C, ethyl acrylate is -27°C, methyl methacrylate is 103°C, and acrylic acid N-butyl ester is -57°C, 2-ethylhexyl acrylate is -76°C, n-lauryl methacrylate is -65°C, n-octyl acrylate is -65°C, isooctyl acrylate is -58°C, Isononyl acrylate is -58°C, isotetradecyl acrylate is -56°C, acrylic acid is 163°C, ω-carboxy-polycaprolactone (n≒2) monoacrylate is -30°C, 2-propenyloxy Ethyl-succinic acid is -40°C.
藉由使用例如該等代表性的單體,可適當調整已述之玻璃轉移溫度。 By using, for example, these representative monomers, the aforementioned glass transition temperature can be adjusted appropriately.
特定(甲基)丙烯酸系聚合物之重量平均分子量並無特別限制,特定(甲基)丙烯酸系聚合物之重量平均分子量(Mw)宜為20萬以上100萬以下較佳,30萬以上80萬以下更佳。特定(甲基)丙烯酸系聚合物之重量平均分子量(Mw)若為20萬以上的話,有能更加有效地抑制高速剝離時特定(甲基)丙烯酸系聚合物殘留於被黏 體、污染性更為降低的傾向。又,若為100萬以下的話,有順應性(潤濕性)更加優異的傾向。 The weight average molecular weight of the specific (meth)acrylic polymer is not particularly limited. The weight average molecular weight (Mw) of the specific (meth)acrylic polymer is preferably 200,000 or more and 1 million or less, and 300,000 or more and 800,000. The following is better. If the weight average molecular weight (Mw) of the specific (meth)acrylic polymer is 200,000 or more, it can more effectively prevent the specific (meth)acrylic polymer from remaining on the adhesive during high-speed peeling. The body and pollution tend to decrease. In addition, if it is 1 million or less, the compliance (wettability) tends to be more excellent.
又,係特定(甲基)丙烯酸系聚合物之重量平均分子量(Mw)與數量平均分子量(Mn)之比的分散度(Mw/Mn),宜為20以下較佳,3~15之範圍更佳。分散度(Mw/Mn)的值若為20以下的話,有能更加有效地抑制高速剝離時特定(甲基)丙烯酸系聚合物殘留於被黏體、污染性更為降低的傾向。 In addition, the dispersion degree (Mw/Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the specific (meth)acrylic polymer is preferably 20 or less, and more preferably in the range of 3-15 good. If the value of the degree of dispersion (Mw/Mn) is 20 or less, there is a tendency that the specific (meth)acrylic polymer remains on the adherend during high-speed peeling and the staining properties tend to be further reduced.
此外,(甲基)丙烯酸系聚合物之重量平均分子量(Mw)及數量平均分子量(Mn)係依照下列(1)~(3)測得的值。 In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the (meth)acrylic polymer are values measured in accordance with the following (1) to (3).
(1)將(甲基)丙烯酸系聚合物的溶液塗布於剝離紙,在100℃乾燥2分鐘,獲得膜狀的(甲基)丙烯酸系聚合物。 (1) A solution of (meth)acrylic polymer was applied to release paper, and dried at 100°C for 2 minutes to obtain a film-like (meth)acrylic polymer.
(2)使用上述(1)獲得之膜狀的(甲基)丙烯酸系聚合物與四氫呋喃,獲得固體成分濃度為0.2質量%的試樣溶液。 (2) Using the film-like (meth)acrylic polymer obtained in (1) above and tetrahydrofuran, a sample solution having a solid content concentration of 0.2% by mass is obtained.
(3)依下列條件,利用凝膠滲透層析法(GPC),以標準聚苯乙烯換算值的方式測定(甲基)丙烯酸系聚合物之重量平均分子量(Mw)及數量平均分子量(Mn)。 (3) Measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of (meth)acrylic polymers using gel permeation chromatography (GPC) under the following conditions with standard polystyrene conversion values .
(條件) (condition)
GPC:HLC-8220 GPC[東曹(股)公司製] GPC: HLC-8220 GPC [Tosoh Corporation System]
管柱:TSK-GEL GMHXL使用4根 Column: 4 for TSK-GEL GMHXL
移動相溶劑:四氫呋喃 Mobile phase solvent: tetrahydrofuran
流速:0.6mL/分 Flow rate: 0.6mL/min
管柱溫度:40℃ Column temperature: 40℃
黏接劑組成物中之特定(甲基)丙烯酸系聚合物的含有率,可因應目的等適當選擇。特定(甲基)丙烯酸系聚合物的含有率,宜為黏接劑組成物之固體成分總質量中之80質量%以上99質量%以下較佳,85質量%以上99質量%以下更佳,90質量%以上98質量%以下尤佳。此外,固體成分總質量意指從黏接劑組成物除去溶劑等揮發性成分後之殘渣的總質量。 The content of the specific (meth)acrylic polymer in the adhesive composition can be appropriately selected according to the purpose and the like. The content of the specific (meth)acrylic polymer is preferably 80% by mass or more and 99% by mass or less of the total solid content of the adhesive composition, more preferably 85% by mass or more and 99% by mass or less, 90 The mass% or more and 98 mass% or less is particularly preferred. In addition, the total mass of solid content means the total mass of the residue after removing the solvent and other volatile components from the adhesive composition.
[(甲基)丙烯酸系低聚物] [(Meth) acrylic oligomer]
本揭示之黏接劑組成物可具有來自具羧基之單體的構成單元,並可包含重量平均分子量為3,000以上30,000以下之(甲基)丙烯酸系低聚物。 The adhesive composition of the present disclosure may have structural units derived from a monomer having a carboxyl group, and may include (meth)acrylic oligomers with a weight average molecular weight of 3,000 or more and 30,000 or less.
藉由本揭示之黏接劑組成物進一步包含上述(甲基)丙烯酸系低聚物,可抑制抗靜電劑的量、及包含後述聚醚改性聚矽氧時的聚醚改性聚矽氧的量。藉此,將保護膜從被黏體剝離時黏接劑層的一部分變得不易殘留於被黏體,故有對於被黏體之污染(污點)的發生受到抑制、污染性變低的傾向。此外,由於(甲基)丙烯酸系聚合物之相容性降低,可抑制白濁發生。 When the adhesive composition of the present disclosure further includes the above-mentioned (meth)acrylic oligomer, the amount of the antistatic agent can be suppressed, and the content of the polyether-modified polysiloxane when the polyether-modified polysiloxane described later is contained the amount. Thereby, when the protective film is peeled from the adherend, a part of the adhesive layer becomes less likely to remain on the adherend, so the occurrence of contamination (stain) on the adherend is suppressed, and the contamination tends to decrease. In addition, since the compatibility of the (meth)acrylic polymer is reduced, the occurrence of white turbidity can be suppressed.
本揭示之黏接劑組成物包含(甲基)丙烯酸系低聚物時,可僅為1種(甲基)丙烯酸系低聚物,亦可為單體之組成、重量平均分子量等不同的2種以上。 When the adhesive composition of the present disclosure contains (meth)acrylic oligomer, it may be only one (meth)acrylic oligomer, or may be different in monomer composition, weight average molecular weight, etc. More than species.
(甲基)丙烯酸系低聚物所含之來自具有羧基之單體的構成單元有助於高速剝離性的改善。具有羧基之單體的種類並無特別限制。 The structural unit derived from the monomer having a carboxyl group contained in the (meth)acrylic oligomer contributes to the improvement of high-speed peelability. The type of the monomer having a carboxyl group is not particularly limited.
具有羧基之單體,可列舉已述之(甲基)丙烯酸系聚合物中之具有羧基之單體,該等中,(甲基)丙烯酸為較佳。 The monomer having a carboxyl group includes the monomer having a carboxyl group in the aforementioned (meth)acrylic polymer, and among these, (meth)acrylic acid is preferred.
(甲基)丙烯酸系低聚物中之來自具有羧基之單體之構成單元的含有率,考量降低污染性的觀點,宜相對於全部構成單元為0.1質量%以上10質量%以下較佳,0.5質量%以上7.0質量%以下更佳,1.0質量%以上5.0質量%以下尤佳。 The content of the structural unit derived from the monomer having a carboxyl group in the (meth)acrylic oligomer is preferably 0.1% by mass or more and 10% by mass or less relative to all the structural units from the viewpoint of reducing pollution, 0.5 It is more preferable that the mass% is more than 7.0 mass%, and more preferably 1.0 mass% or more and 5.0 mass% or less.
(甲基)丙烯酸系低聚物宜包含來自(甲基)丙烯酸烷酯之構成單元較佳。來自(甲基)丙烯酸烷酯之構成單元有助於黏接力的調整。 The (meth)acrylic oligomer preferably contains a structural unit derived from alkyl (meth)acrylate. The structural unit derived from the alkyl (meth)acrylate contributes to the adjustment of the adhesive force.
就(甲基)丙烯酸烷酯而言,可列舉已述之(甲基)丙烯酸系聚合物中之(甲基)丙烯酸烷酯。 As for the alkyl (meth)acrylate, the alkyl (meth)acrylate among the above-mentioned (meth)acrylic polymers can be cited.
其中,考量即使將黏接劑層暴露在高溫高濕環境下,仍可發揮高耐久性的觀點,宜為碳數4~12之(甲基)丙烯酸烷酯較佳,具有分支鏈之碳數4~12之(甲基)丙烯酸烷酯更佳,甲基丙烯酸2-乙基己酯尤佳。 Among them, considering that the adhesive layer can still exhibit high durability even when exposed to a high temperature and high humidity environment, it is preferably alkyl (meth)acrylate with 4 to 12 carbon atoms, which has a branched chain carbon number 4~12 alkyl (meth)acrylate is more preferred, and 2-ethylhexyl methacrylate is particularly preferred.
(甲基)丙烯酸系低聚物中之來自(甲基)丙烯酸烷酯之構成單元的含有率,考量耐久性的觀點,宜相對於全部構成單元為65質量%以上較佳,75質量%以上更佳,80質量%以上尤佳。 The content of the structural unit derived from alkyl (meth)acrylate in the (meth)acrylic oligomer, considering durability, is preferably 65% by mass or more, preferably 75% by mass or more, relative to all the structural units More preferably, more than 80% by mass is particularly preferred.
又,(甲基)丙烯酸系低聚物中之來自(甲基)丙烯酸烷酯之構成單元的含有率,考量耐久性的觀點,宜為99質量%以下較佳,95質量%以下更佳,90質量%以下尤佳。 In addition, the content of the structural unit derived from the alkyl (meth)acrylate in the (meth)acrylic oligomer is preferably 99% by mass or less from the viewpoint of durability, and more preferably 95% by mass or less. 90% by mass or less is particularly preferred.
(甲基)丙烯酸系低聚物,宜包含來自具有環氧烷鏈之單體的構成單元較佳。 The (meth)acrylic oligomer preferably contains a structural unit derived from a monomer having an alkylene oxide chain.
(甲基)丙烯酸系低聚物中之來自具有環氧烷鏈之單體之構成單元的含有率,宜相對於全部構成單元為5質量%以上30質量%以下較佳,5質量%以上20質量%以下更佳,5質量%以上15質量%以下特佳。 The content of the structural unit derived from the monomer having an alkylene oxide chain in the (meth)acrylic oligomer is preferably 5 mass% or more and 30 mass% or less, preferably 5 mass% or more, relative to all the structural units. The mass% or less is more preferable, and 5 mass% or more and 15 mass% or less are particularly preferable.
來自具有環氧烷鏈之單體之構成單元的含有率為5質量%以上的話,有抗靜電更加優異的傾向。又,來自具有環氧烷鏈之單體之構成單元的含有率為30質量%以下的話,有聚合反應後未聚合而殘存之單體變少、污染性更為降低的傾向。 When the content of the structural unit derived from the monomer having an alkylene oxide chain is 5 mass% or more, there is a tendency that the antistatic property is more excellent. In addition, when the content rate of the structural unit derived from the monomer having an alkylene oxide chain is 30% by mass or less, there is a tendency that there is less unpolymerized but remaining monomer after the polymerization reaction, and the pollution is further reduced.
就(甲基)丙烯酸系低聚物而言,在發揮本揭示之效果的範圍內,亦可包含除來自具有羧基之單體之構成單元、來自(甲基)丙烯酸烷酯之構成單元及來自具有環氧烷鏈之單體之構成單元以外的構成單元(其他構成單元)。 For (meth)acrylic oligomers, within the scope of exerting the effects of the present disclosure, they may also include constituent units derived from monomers having a carboxyl group, constituent units derived from alkyl (meth)acrylate, and constituent units derived from The structural unit (other structural unit) other than the structural unit of the monomer having an alkylene oxide chain.
此時,(甲基)丙烯酸系低聚物之來自具有羧基之單體之構成單元、來自(甲基)丙烯酸烷酯之構成單元、及來自具有環氧烷鏈之單體之構成單元在全部構成單元中所佔的合計含有率,宜相對於全部構成單元為80質量%以上較佳,90質量%以上更佳,95質量%以上尤佳。 At this time, the structural units derived from the monomer having a carboxyl group of the (meth)acrylic oligomer, the structural unit derived from the alkyl (meth)acrylate, and the structural unit derived from the monomer having an alkylene oxide chain are in all The total content of the constituent units is preferably 80% by mass or more relative to all the constituent units, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
構成其他構成單元之單體,可列舉已述之具有羥基之單體、具有環狀基之單體等。 Examples of the monomers constituting other structural units include the monomers having a hydroxyl group and the monomers having a cyclic group as described above.
(甲基)丙烯酸系低聚物之含量,宜相對於(甲基)丙烯酸系聚合物100質量份為0.05質量份以上2.00質量份以下較佳,0.10質量份以上1.50質量份以下更佳,0.10質量份以上1.20質量份以下尤佳。(甲基)丙烯酸系低聚物之含量為0.05質量份以上的話,有高速剝離時之黏接力不會變得過高、高速剝離性更加優異的傾向。(甲基)丙烯酸系低聚物之含量為2.00質量份以下的話,有容易賦予黏接劑層保護膜不會從被黏體突然剝離之程度之必要的黏接力、高速剝離性更加優異的傾向。 The content of the (meth)acrylic oligomer is preferably 0.05 parts by mass to 2.00 parts by mass relative to 100 parts by mass of the (meth)acrylic polymer, more preferably 0.10 parts by mass to 1.50 parts by mass, and 0.10 Part by mass or more and 1.20 parts by mass or less is particularly preferred. When the content of the (meth)acrylic oligomer is 0.05 parts by mass or more, the adhesive force during high-speed peeling does not become too high, and the high-speed peelability tends to be more excellent. When the content of the (meth)acrylic oligomer is 2.00 parts by mass or less, it is easy to provide the adhesive layer with the necessary adhesive force to the extent that the protective film does not suddenly peel off from the adherend, and the high-speed peelability tends to be better .
(甲基)丙烯酸系低聚物之酸價,考量使其與(甲基)丙烯酸系聚合物充分交聯、進一步改善高速剝離性的觀點,宜為10mgKOH/g以上較佳,15mgKOH/g以上更佳。 The acid value of the (meth)acrylic oligomer, considering that it is fully crosslinked with the (meth)acrylic polymer to further improve the high-speed peelability, is preferably 10mgKOH/g or more, preferably 15mgKOH/g or more Better.
又,(甲基)丙烯酸系低聚物之酸價,考量保持良好的抗靜電性的觀點,宜為200mgKOH/g以下較佳,100mgKOH/g以下更佳,50mgKOH/g以下尤佳。 In addition, the acid value of the (meth)acrylic oligomer is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less, and particularly preferably 50 mgKOH/g or less from the viewpoint of maintaining good antistatic properties.
此外,(甲基)丙烯酸系低聚物之酸價的計算方法如已述。 In addition, the calculation method of the acid value of the (meth)acrylic oligomer is as already mentioned.
(甲基)丙烯酸系低聚物之重量平均分子量,考量防止高速剝離時(甲基)丙烯酸系低聚物殘留於被黏體的觀點,宜為1,000以上較佳,4,000以上更佳,7,000以上尤佳。(甲基)丙烯酸系低聚物之重量平均分子量,考量降低黏接劑層之霧度的觀點,宜為30,000以下較佳,25,000以下更佳,20,000以下尤佳。 The weight average molecular weight of the (meth)acrylic oligomer, considering the viewpoint of preventing the (meth)acrylic oligomer from remaining on the adherend during high-speed peeling, is preferably 1,000 or more, more preferably 4,000 or more, and 7,000 or more Especially good. The weight average molecular weight of the (meth)acrylic oligomer is preferably 30,000 or less from the viewpoint of reducing the haze of the adhesive layer, preferably 25,000 or less, and particularly preferably 20,000 or less.
(甲基)丙烯酸系低聚物之重量平均分子量(Mw)相對於數量平均分子量(Mn)之比表示的分散度(Mw/Mn)並無特別限制。例如,考量進一步降低污染性的觀點,(甲基)丙烯酸系低聚物之分散度(Mw/Mn)宜為1~30之範圍較佳。 The degree of dispersion (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) of the (meth)acrylic oligomer to the number average molecular weight (Mn) is not particularly limited. For example, from the viewpoint of further reducing pollution, the dispersion degree (Mw/Mn) of the (meth)acrylic oligomer is preferably in the range of 1-30.
(甲基)丙烯酸系低聚物之重量平均分子量(Mw)及數量平均分子量(Mn),和已述之(甲基)丙烯酸系聚合物之重量平均分子量(Mw)及數量平均分子量(Mn)之測定方法同樣進行測定。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the (meth)acrylic oligomer, and the weight average molecular weight (Mw) and number average molecular weight (Mn) of the (meth)acrylic polymer described above The measurement method is the same for measurement.
(甲基)丙烯酸系低聚物之玻璃轉移溫度(Tg)宜為50℃以下較佳。(甲基)丙烯酸系低聚物之Tg為50℃以下的話,可抑制由於加熱處理所致之黏接力的上升,故高速剝離性更加優異。 The glass transition temperature (Tg) of the (meth)acrylic oligomer is preferably 50°C or less. When the Tg of the (meth)acrylic oligomer is 50°C or less, the increase in adhesive force due to heat treatment can be suppressed, and the high-speed peelability is more excellent.
(甲基)丙烯酸系低聚物之玻璃轉移溫度,和已述之(甲基)丙烯酸系聚合物之玻璃轉移溫度之計算方法同樣進行計算。 The glass transition temperature of the (meth)acrylic oligomer is calculated in the same way as the calculation method of the glass transition temperature of the (meth)acrylic polymer described above.
[金屬螯合物系交聯劑] [Metal Chelate Crosslinking Agent]
本揭示之黏接劑組成物包含特定(甲基)丙烯酸系聚合物,同時還包含至少1種之相對於(甲基)丙烯酸系聚合物之酸性基為0.3當量以上2.0當量以下之金屬螯合物系交聯劑。 The adhesive composition of the present disclosure includes a specific (meth)acrylic polymer, and also includes at least one metal chelate with an acidic group of 0.3 to 2.0 equivalents relative to the (meth)acrylic polymer. The cross-linking agent.
金屬螯合物系交聯劑和(甲基)丙烯酸系聚合物所含之羧基反應而形成交聯結構。藉由使用金屬螯合物系交聯劑,相較於使用異氰酸酯系交聯劑、環氧系交聯劑等的情況,交聯反應快,可縮短熟化完成時間。 The metal chelate crosslinking agent reacts with the carboxyl group contained in the (meth)acrylic polymer to form a crosslinked structure. By using a metal chelate-based crosslinking agent, the crosslinking reaction is quicker than when an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, etc. are used, and the curing completion time can be shortened.
金屬螯合物系交聯劑,可列舉多價金屬與有機化合物配位鍵結而成者。就多價金屬原子而言,例如,可列舉Al、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti。該等中,考量低成本及容易取得的觀點,宜為Al、Zr、及Ti較佳,Al更佳。 The metal chelate-based crosslinking agent includes one formed by coordinately bonding a polyvalent metal and an organic compound. For multivalent metal atoms, for example, Al, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti. Among them, considering the viewpoints of low cost and easy acquisition, Al, Zr, and Ti are preferable, and Al is more preferable.
配位鍵結之有機化合物中之原子可列舉氧原子等,有機化合物可列舉烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。 Examples of the atoms in the coordinately bonded organic compounds include oxygen atoms, and examples of the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
本揭示中,尤其可適當使用穩定且操作容易之參乙醯丙酮鋁等。又,金屬螯合物系交聯劑亦可併用2種以上。 In this disclosure, in particular, aluminum acetone acetone, which is stable and easy to handle, can be suitably used. In addition, two or more types of metal chelate-based crosslinking agents may be used in combination.
金屬螯合物系交聯劑之當量,相對於特定(甲基)丙烯酸系聚合物之酸性基1當量為0.3當量以上2.0當量以下,較佳為0.4當量以上1.5當量以下,更佳為0.6當量以上1.2當量以下。金屬螯合物系交聯劑之含量未達0.3當量的話,高速剝離時 之黏接力變高。金屬螯合物系交聯劑之含量超過2.0當量的話,黏接劑層之黏接力變得過低,保護膜容易從被黏體突然剝離,又,抗靜電性亦降低。 The equivalent weight of the metal chelate crosslinking agent is 0.3 equivalent or more and 2.0 equivalent or less, preferably 0.4 equivalent or more and 1.5 equivalent or less, more preferably 0.6 equivalent relative to 1 equivalent of the acidic group of the specific (meth)acrylic polymer Above 1.2 equivalent. If the content of the metal chelate crosslinking agent is less than 0.3 equivalent, it will peel off at high speed The adhesive force becomes higher. If the content of the metal chelate-based crosslinking agent exceeds 2.0 equivalents, the adhesive force of the adhesive layer becomes too low, the protective film is easily peeled from the adherend, and the antistatic property is also reduced.
上述當量係根據下式算出的值。 The above equivalent is a value calculated according to the following formula.
當量=(A×B/C)/(D1×E1/F1+D2×E2/F2+‧‧‧‧+Dn×En/Fn) Equivalent=(A×B/C)/(D 1 ×E 1 /F 1 +D 2 ×E 2 /F 2 +‧‧‧‧+D n ×E n /F n )
A=金屬螯合物系交聯劑之金屬的價數 A=The valence of the metal of the metal chelate crosslinking agent
B=金屬螯合物系交聯劑之質量份數(固體成分的量) B = The mass parts of the metal chelate crosslinking agent (the amount of solid content)
C=金屬螯合物系交聯劑之分子量 C=Molecular weight of metal chelate crosslinking agent
D1、D2、‧‧‧Dn=(甲基)丙烯酸系聚合物所使用之全部單體中的具有酸性基之各單體的含有率(質量%) D 1 , D 2 , ‧‧‧D n = the content of each monomer having acidic groups in all monomers used in the (meth)acrylic polymer (mass%)
E1、E2、‧‧‧En=具有酸性基之各單體之1分子中所含酸性基的數目 E 1 , E 2 , ‧‧‧E n = the number of acidic groups contained in one molecule of each monomer with acidic groups
F1、F2、‧‧‧Fn=(甲基)丙烯酸系聚合物所使用之具有酸性基之各單體的分子量 F 1 , F 2 , ‧‧‧F n = the molecular weight of the monomers with acidic groups used in (meth)acrylic polymers
此外,n表示所使用之單體的種類數,例如,使用之(甲基)丙烯酸系單體為1種時,僅D1用於計算,D2‧‧‧Dn不用於計算。 In addition, n represents the number of types of monomers used. For example, when the (meth)acrylic monomer used is one type, only D 1 is used for calculation, and D 2 ‧‧‧D n is not used for calculation.
就金屬螯合物系交聯劑而言,宜以特定(甲基)丙烯酸系聚合物之酸價與金屬螯合物系交聯劑之當量的乘積成為3以上40以下之範圍使用較佳,以成為5以上35以下之範圍使用更佳,以成為8以上35以下之範圍使用尤佳。特定(甲基)丙烯酸系聚合物之酸價與金屬螯合物系交聯劑之當量的乘積為3以上的話,有高速剝離性更加優異的傾向。又,與金屬螯合物系交聯劑之當量的乘積為40以下的話,有容易賦予黏接劑層保護膜不會從被黏體突然剝離之程度之必要的黏接力、高速剝離性與抗靜電性更加優異的傾向。 Regarding the metal chelate crosslinking agent, it is preferable to use the product of the acid value of the specific (meth)acrylic polymer and the equivalent of the metal chelate crosslinking agent in the range of 3 or more and 40 or less. It is more preferable to use it in the range of 5 to 35, and it is particularly preferable to use it in the range of 8 to 35. If the product of the acid value of the specific (meth)acrylic polymer and the equivalent of the metal chelate crosslinking agent is 3 or more, the high-speed peelability tends to be more excellent. In addition, if the product of the equivalent with the metal chelate crosslinking agent is 40 or less, it is easy to give the adhesive layer protective film the necessary adhesive strength, high-speed peelability, and resistance to the extent that the protective film does not suddenly peel off from the adherend. Tendency to be more excellent in electrostatic properties.
[抗靜電劑] [Antistatic Agent]
本揭示之黏接劑組成物含有至少1種之抗靜電劑。 The adhesive composition of the present disclosure contains at least one antistatic agent.
抗靜電劑可列舉離子性化合物。前述離子性化合物可列舉鹼金屬鹽、有機鹽等。前述抗靜電劑,考量離子解離性高、即使為少量亦容易顯現優異的抗靜電性的觀點,宜為鹼金屬鹽及有機鹽較佳。考量若能減少抗靜電劑之含量的話,可進一步抑制污染性的觀點,有較佳傾向。 Examples of antistatic agents include ionic compounds. Examples of the aforementioned ionic compound include alkali metal salts and organic salts. The aforementioned antistatic agent has a high ion dissociation property and easily exhibits excellent antistatic properties even in a small amount, and an alkali metal salt and an organic salt are preferable. Considering that if the content of the antistatic agent can be reduced, the pollution can be further suppressed, and there is a better tendency.
就前述鹼金屬鹽而言,只要是以鋰離子(Li+)、鈉離子(Na+)、鉀離子(K+)、銣(Rb+)等作為陽離子的金屬鹽即可,並無特別限制。 Regarding the aforementioned alkali metal salt, any metal salt with lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium (Rb + ), etc. as cations is sufficient, and there is no particular limitation. .
例如,可適當使用由選自於由Li+、Na+、K+構成之群組中之至少1種之陽離子、與選自於由Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(FSO2)2N-、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-構成之群組中之至少1種之陰離子構成的金屬鹽。 For example, use may be suitably selected from consisting of Li +, Na +, K + in the group consisting of at least one kind of cation selected from the group consisting of Cl -, Br -, I - , BF 4 -, PF 6 -, SCN -, ClO 4 - , CF 3 SO 3 -, (FSO 2) 2 N -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2 ) 3 C - A metal salt composed of at least one anion in the group consisting of 3 C -.
其中,就鹼金屬鹽而言,考量抗靜電性的觀點,宜為LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(FSO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C等鋰鹽較佳,LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3C更佳。該等鹼金屬鹽可單獨使用,亦可將2種以上混合使用。 Among them, as for the alkali metal salt, considering the antistatic property, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 , Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C and other lithium salts are preferred, LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N , Li(C 2 F 5 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C is more preferable. These alkali metal salts may be used alone, or two or more of them may be mixed and used.
前述有機鹽包含有機陽離子及其抗衡離子(counter ion)。 The aforementioned organic salt contains an organic cation and its counter ion.
就有機鹽而言,熔點宜為30℃以上較佳。有機鹽的熔點為30℃以上的話,向被黏體的轉移少,污染性低,為較佳。 For organic salts, the melting point is preferably 30°C or higher. If the melting point of the organic salt is 30°C or higher, the transfer to the adherend is small and the pollution is low, which is preferable.
就有機陽離子而言,例如,可列舉咪唑鎓陽離子、吡啶鎓陽離子、烷基吡咯啶鎓陽離子、具有有機基作為取代基之銨陽離子、具有有機基作為取代基之鋶陽離子、具有有機基作為取代基之鏻陽離子。該等中,考量抗靜電性的觀點,宜為吡啶鎓陽離子、咪唑鎓陽離子較佳。 As for organic cations, for example, imidazolium cations, pyridinium cations, alkylpyrrolidinium cations, ammonium cations having organic groups as substituents, sulfonium cations having organic groups as substituents, and organic groups as substituents The phosphonium cation of the base. Among these, from the viewpoint of antistatic properties, pyridinium cations and imidazolium cations are more preferable.
成為有機陽離子之抗衡離子的陰離子部並無特別限定,可為無機陰離子或有機陰離子中之任一者。其中,由於抗靜電性優異,包含氟原子的含氟陰離子為特佳,六氟磷酸根陰離子(PF6 -)更佳。 The anion part that becomes the counter ion of the organic cation is not particularly limited, and may be either an inorganic anion or an organic anion. Wherein, due to the excellent antistatic properties, containing a fluorine atom is particularly preferred fluorine-containing anion, a hexafluorophosphate anion (PF 6 -) better.
作為有機鹽之示例,可適當列舉吡啶鎓鹽、咪唑鎓鹽、烷基銨鹽、烷基吡咯啶鎓鹽、烷基鏻鹽等。其中,吡啶鎓鹽、咪唑鎓鹽為較佳,吡啶鎓陽離子、咪唑鎓陽離子與含氟陰離子的鹽特佳。 As an example of an organic salt, a pyridinium salt, an imidazolium salt, an alkylammonium salt, an alkylpyrrolidinium salt, an alkylphosphonium salt, etc. are mentioned suitably. Among them, pyridinium salts and imidazolium salts are preferred, and salts of pyridinium cations, imidazolium cations, and fluorine-containing anions are particularly preferred.
本揭示之黏接劑組成物中的抗靜電劑之含量,宜相對於特定(甲基)丙烯酸系聚合物100質量份為0.05質量份以上0.50質量份以下較佳,0.10質量份以上0.30質量份以下更佳。抗靜電劑之含量相對於特定相對於(甲基)丙烯酸系聚合物100質量份為0.05質量份以上的話,有抗靜電性優異的傾向。另一方面,藉由抗靜電劑之含量為0.50質量份以下,有抗靜電效果相對於抗靜電劑之含量的效率變高的傾向。 The content of the antistatic agent in the adhesive composition of the present disclosure is preferably 0.05 parts by mass to 0.50 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer, preferably 0.10 parts by mass to 0.30 parts by mass The following is better. When the content of the antistatic agent is 0.05 parts by mass or more with respect to 100 parts by mass of the (meth)acrylic polymer, the antistatic properties tend to be excellent. On the other hand, when the content of the antistatic agent is 0.50 parts by mass or less, the antistatic effect tends to be higher than the efficiency of the content of the antistatic agent.
[聚醚改性聚矽氧] [Polyether modified polysiloxane]
本揭示之黏接劑組成物可含有至少1種之聚醚改性聚矽氧。藉由聚醚改性聚矽氧具有反應性基,黏接膜能輕易地從被黏體剝離,且可獲得對於被黏體之污染少的黏接膜。 The adhesive composition of the present disclosure may contain at least one polyether modified polysiloxane. With the polyether modified polysiloxane having reactive groups, the adhesive film can be easily peeled from the adherend, and an adhesive film with less pollution to the adherend can be obtained.
聚醚改性聚矽氧與具有通式(1)表示之構成單元的特定(甲基)丙烯酸系聚合物、及金屬螯合物系交聯劑一同使用時,可有效地顯現抗靜電性。 When polyether-modified polysiloxane is used together with a specific (meth)acrylic polymer having a structural unit represented by the general formula (1), and a metal chelate-based crosslinking agent, it can effectively exhibit antistatic properties.
藉由聚醚改性聚矽氧具有聚醚基,並於聚醚基之末端具有羥基,可顯示更加優異的抗靜電性,並能有效地抑制對於被黏體的污染。特別是藉由在聚醚改性聚矽氧之分子內具有末端為羥基之聚環氧烷鏈,可有效地發揮抗靜電性能。據認為其原因為:聚醚改性聚矽氧偏置在由保護膜用黏接劑組成物而得之黏接劑層的表面附近,藉此與鹼金屬鹽相互作用之聚環氧烷鏈集中在黏接劑層的表面附近,其結果可降低黏接劑層表面的表面電阻值。如此藉由併用聚醚改性聚矽氧,可抑制本揭示之黏接劑組成物中之抗靜電劑的量。 The polyether modified polysiloxane has a polyether group and a hydroxyl group at the end of the polyether group, which can show more excellent antistatic properties and can effectively inhibit the contamination of the adherend. In particular, by having a polyalkylene oxide chain with a hydroxyl terminal in the molecule of the polyether modified polysiloxane, the antistatic performance can be effectively exerted. It is believed that the reason is that the polyether-modified polysiloxane is biased near the surface of the adhesive layer obtained from the adhesive composition for the protective film, whereby the polyalkylene oxide chain interacts with the alkali metal salt Concentrated near the surface of the adhesive layer, as a result, the surface resistance value of the surface of the adhesive layer can be reduced. In this way, the combined use of polyether-modified polysiloxane can suppress the amount of antistatic agent in the adhesive composition of the present disclosure.
就聚醚改性聚矽氧而言,考量抗靜電性、降低對於被黏體之污染性的觀點,宜為包含來自二烷基矽氧烷之構成單元、與來自烷基(羥基聚伸烷氧基烷基)矽氧烷之構成單元的聚矽氧烷化合物較佳。 For polyether-modified polysiloxanes, considering the antistatic properties and reducing the pollution to the adherend, it is preferable to include constituent units derived from dialkylsiloxanes and those derived from alkyl (hydroxypolyalkylene oxide). The polysiloxane compound which is a constituent unit of oxyalkyl)siloxane is preferred.
二烷基矽氧烷中之烷基,碳數宜為1~4較佳,1更佳。 For the alkyl group in the dialkylsiloxane, the carbon number is preferably 1 to 4, and 1 is more preferable.
又,烷基(羥基聚伸烷氧基烷基)矽氧烷中之環氧烷鏈,碳數宜為2~4較佳,2~3更佳。烷基(羥基聚伸烷氧基烷基)矽氧烷中之環氧烷鏈的含有數,宜為1~100較佳,10~100更佳。烷基(羥基聚伸烷氧基烷基)矽氧烷中之烷基,碳數宜為1~4較佳。 In addition, the number of carbon atoms in the alkylene oxide chain in the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane is preferably 2 to 4, and more preferably 2 to 3. The content of the alkylene oxide chain in the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane is preferably 1-100, more preferably 10-100. The alkyl group in the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane preferably has a carbon number of 1 to 4.
聚醚改性聚矽氧包含來自二烷基矽氧烷之構成單元、與來自烷基(羥基聚伸烷氧基烷基)矽氧烷之構成單元時,來自二烷基矽氧烷之構成單元的含有數宜為 100以下較佳,1~80更佳。又,來自烷基(羥基聚伸烷氧基烷基)矽氧烷之構成單元的含有數宜為2~100較佳,2~80更佳。 When the polyether-modified polysiloxane contains a structural unit derived from a dialkylsiloxane and a structural unit derived from an alkyl (hydroxypolyalkyleneoxyalkyl)siloxane, the structure is derived from a dialkylsiloxane The number of units should be 100 or less is preferable, and 1 to 80 is more preferable. In addition, the content of the structural unit derived from the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane is preferably 2-100, and more preferably 2-80.
就聚醚改性聚矽氧而言,考量黏接性、抗靜電性及降低對於被黏體之污染性的觀點,宜為下列通式(3)表示之聚矽氧烷化合物較佳。 For polyether-modified polysiloxane, considering the adhesion, antistatic properties, and reducing the pollution to the adherend, the polysiloxane compound represented by the following general formula (3) is preferred.
通式(3)中,p為二甲基矽氧烷構成單元之重複數,表示0~100的數值。q為具有聚環氧乙烷鏈之甲基伸丙基矽氧烷構成單元之重複數,表示2~100的數值。又,a為環氧乙烷構成單元之重複數,表示1~100的數值。此處,通式(3)表示之化合物為多數化合物的集合體時,p、q及a為化合物之集合體之平均值的有理數。 In the general formula (3), p is the repeating number of the dimethylsiloxane structural unit, and represents a value of 0-100. q is the repeating number of the methacrylic acid constitutive unit having a polyethylene oxide chain, and represents a value of 2-100. In addition, a is the repeating number of the ethylene oxide structural unit, and represents a value of 1-100. Here, when the compound represented by the general formula (3) is an aggregate of a plurality of compounds, p, q, and a are rational numbers of the average value of the aggregate of compounds.
聚環氧乙烷構成單元之重複數a為1~100的數值,宜為10~100的數值較佳。a為1以上的話,有可獲得充分的導電性、抗靜電效果得到改善的傾向。又,a為100以下的話,有與構成黏接劑組成物之其他成分的相容性得到改善、黏接劑層的透明性更為提升的傾向。 The repeating number a of the polyethylene oxide constituent unit is a value of 1 to 100, preferably a value of 10 to 100. When a is 1 or more, sufficient conductivity may be obtained and the antistatic effect tends to be improved. In addition, when a is 100 or less, the compatibility with other components constituting the adhesive composition tends to be improved, and the transparency of the adhesive layer tends to be improved.
又,二甲基矽氧烷構成單元之重複數p為0~100的數值,宜為1~80的數值較佳。p為0以上時,有抗靜電效果得到改善的傾向。又,p為100以下的話,有與構成黏接劑組成物之其他成分的相容性得到改善,且黏接劑層的透明性更為提升的傾向。 In addition, the repeating number p of the dimethylsiloxane structural unit is a value of 0 to 100, preferably a value of 1 to 80. When p is 0 or more, the antistatic effect tends to be improved. In addition, when p is 100 or less, the compatibility with other components constituting the adhesive composition is improved, and the transparency of the adhesive layer tends to be improved.
進一步,甲基伸丙基矽氧烷構成單元之重複數q為2~100的數值,宜為2~80的數值較佳。q為2以上的話,有可獲得充分的導電性、抗靜電效果得到改善的傾向。又,q為100以下的話,有與構成黏接劑組成物之其他成分的相容性得到改善,且黏接劑層的透明性更為提升的傾向。 Furthermore, the repeating number q of the methacrylic siloxane structural unit is a value of 2 to 100, and a value of 2 to 80 is more preferable. If q is 2 or more, there is a tendency that sufficient conductivity can be obtained and the antistatic effect will be improved. In addition, when q is 100 or less, compatibility with other components constituting the adhesive composition is improved, and the transparency of the adhesive layer tends to be improved.
關於聚醚改性聚矽氧之重量平均分子量,並無特別限制,例如,可為5,000以上20,000以下,宜為6,000以上15,000以下較佳。 The weight average molecular weight of the polyether-modified silicone is not particularly limited. For example, it may be 5,000 or more and 20,000 or less, preferably 6,000 or more and 15,000 or less.
又,關於聚醚改性聚矽氧之HLB值,並無特別限制,考量與樹脂的相容性、表面偏置性、及黏接性的觀點,宜為5以上未達16較佳,7以上15以下更佳。 In addition, there is no particular limitation on the HLB value of the polyether-modified polysiloxane. Considering the compatibility with the resin, the surface offset, and the adhesion, it is preferably 5 or more, but not 16 or more. 7 Above 15 is more preferable.
前述HLB值係表示聚醚改性聚矽氧之親水性與疏水性之平衡的尺度。本揭示中,係依照下式算出之格力芬法(Griffin method)的定義,但聚醚改性聚矽氧為市售品時,優先採用其商品型錄資料。 The aforementioned HLB value is a measure of the balance between the hydrophilicity and hydrophobicity of the polyether-modified silicone. In this disclosure, the Griffin method is calculated according to the following formula, but when the polyether-modified polysiloxane is a commercially available product, the product catalog data is preferentially used.
HLB={(親水性基部分之式量的總和)/(聚醚改性聚矽氧之分子量)}×20 HLB={(Sum of formula weight of hydrophilic group part)/(Molecular weight of polyether modified polysiloxane)}×20
聚醚改性聚矽氧於分子內具有:二甲基矽氧烷構成單元、及具聚環氧乙烷鏈之甲基伸丙基矽氧烷構成單元。該等構成單元可分別構成嵌段共聚物,亦可構成無規共聚物。 The polyether-modified polysiloxane has in the molecule: dimethylsiloxane structural unit and methylpropylene siloxane structural unit with polyethylene oxide chain. These structural units may each constitute a block copolymer, or may constitute a random copolymer.
前述通式(3)表示之聚醚改性聚矽氧之具體例,例如,可列舉「SF-8428」、「FZ-2162」、「SH-3773M」[以上,東麗道康寧(股)公司製]。 Specific examples of the polyether-modified silicone represented by the aforementioned general formula (3), for example, include "SF-8428", "FZ-2162", "SH-3773M" [above, Toray Dow Corning Co., Ltd. system].
聚醚改性聚矽氧可為選自於如上述之市售品者。又,就聚醚改性聚矽氧而言,可將具有不飽和鍵及聚環氧乙烷鏈之有機化合物藉由矽氫化反應接枝於具有氫化矽之二甲基聚矽氧烷主鏈而獲得。 The polyether-modified polysiloxane may be selected from the above-mentioned commercial products. In addition, for polyether-modified polysiloxane, organic compounds with unsaturated bonds and polyethylene oxide chains can be grafted to the main chain of dimethyl polysiloxane with hydrogenated silicon by hydrosilation reaction. And get.
本揭示之黏接劑組成物中的聚醚改性聚矽氧之含量,宜相對於特定(甲基)丙烯酸系聚合物100質量份為0.05質量份以上1.00質量份以下較佳,0.05質量份以上0.70質量份以下更佳,0.05質量份以上0.30質量份以下尤佳。 The content of the polyether-modified polysiloxane in the adhesive composition of the present disclosure is preferably 0.05 parts by mass to 1.00 parts by mass relative to 100 parts by mass of the specific (meth)acrylic polymer, preferably 0.05 parts by mass The above is more preferably 0.70 parts by mass or less, and more preferably 0.05 parts by mass or more and 0.30 parts by mass or less.
聚醚改性聚矽氧之含量為0.05質量份以上的話,有抗靜電性更加優異的傾向。又,藉由聚醚改性聚矽氧之含量為1.00質量份以下,對於被黏體之污染(污點)的發生受到抑制,又,可抑制與特定(甲基)丙烯酸系聚合物之相容性降低而發生之白濁。 When the content of the polyether-modified silicone is 0.05 parts by mass or more, there is a tendency that the antistatic property is more excellent. In addition, when the content of polyether-modified silicone is 1.00 parts by mass or less, the occurrence of contamination (stain) on the adherend can be suppressed, and the compatibility with the specific (meth)acrylic polymer can be suppressed White turbidity occurs due to decreased sex.
本揭示之黏接劑組成物可包含:前述通式(3)表示之聚矽氧烷化合物,及具有與通式(3)不同之結構並含聚環氧乙烷基之二甲基聚矽氧烷化合物。 The adhesive composition of the present disclosure may include: a polysiloxane compound represented by the aforementioned general formula (3), and a dimethyl polysiloxane having a structure different from that of the general formula (3) and containing a polyethylene oxide group Oxyane compounds.
具有與通式(3)不同之結構並含聚環氧乙烷鏈之二甲基聚矽氧烷化合物,例如,可列舉聚環氧乙烷鏈之末端為烷氧基、醯氧基之化合物、於主鏈或末端而非於側鏈含有聚環氧乙烷鏈之化合物。 A dimethylpolysiloxane compound having a structure different from the general formula (3) and containing a polyethylene oxide chain, for example, a compound in which the end of the polyethylene oxide chain is an alkoxy group or an oxy group , Compounds containing polyethylene oxide chains in the main chain or at the end rather than in the side chain.
具體而言,例如,可列舉「BY-16-201」、「FZ-77」、「FZ-2104」、「FZ-2110」、「FZ-2203」、「FZ-2207」、「FZ-2208」、「L-7001」、「L-7002」、「SF-8427」、「SH-3749」、「SH-8400」(以上,東麗道康寧(股)公司製)。 Specifically, for example, "BY-16-201", "FZ-77", "FZ-2104", "FZ-2110", "FZ-2203", "FZ-2207", "FZ-2208" ", "L-7001", "L-7002", "SF-8427", "SH-3749", "SH-8400" (above, manufactured by Toray Dow Corning Co., Ltd.).
前述黏接劑組成物包含具有與前述通式(3)不同之結構且含聚環氧乙烷鏈之二甲基聚矽氧烷化合物時,其含有率宜為聚矽氧烷化合物之總質量中0.05質量%以下較佳,0.03質量%以下更佳。 When the aforementioned adhesive composition contains a dimethylpolysiloxane compound having a structure different from the aforementioned general formula (3) and containing a polyethylene oxide chain, its content is preferably the total mass of the polysiloxane compound Among them, 0.05% by mass or less is preferable, and 0.03% by mass or less is more preferable.
[其他成分] [Other ingredients]
本揭示之保護膜用黏接劑組成物,除特定(甲基)丙烯酸系聚合物、金屬螯合物系交聯劑、及抗靜電劑外,視需要可適當含有耐候性穩定劑、增黏劑、塑化劑、軟化劑、剝離助劑、染料、顏料、無機填充劑、界面活性劑等。 The adhesive composition for protective film of the present disclosure may contain weather resistance stabilizers and viscosity-increasing agents as needed, in addition to specific (meth)acrylic polymers, metal chelate crosslinking agents, and antistatic agents. Agents, plasticizers, softeners, peeling aids, dyes, pigments, inorganic fillers, surfactants, etc.
<保護膜> <Protective Film>
本揭示之保護膜具備:由保護膜用黏接劑組成物而得之黏接劑層、及基材。 The protective film of the present disclosure includes an adhesive layer obtained from the adhesive composition for the protective film, and a base material.
藉由前述黏接劑層係由保護膜用黏接劑組成物而得者,可構成黏接性、由於剝離帶電所致之靜電的發生抑制、及高速剝離性優異的黏接劑層。 When the aforementioned adhesive layer is obtained from the adhesive composition for a protective film, an adhesive layer with excellent adhesiveness, suppression of the generation of static electricity due to peeling and charging, and high-speed peelability can be formed.
本揭示之保護膜所使用之基材,只要是能在該基材上形成黏接劑層即可,並無特別限制。 The substrate used in the protective film of the present disclosure is not particularly limited as long as the adhesive layer can be formed on the substrate.
就基材而言,考量藉由透視進行光學構件之檢查及管理的觀點,可列舉使用選自於聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、及丙烯酸系樹脂等之樹脂而得的膜。其中,就基材而言,考量表面保護性能的觀點,使用聚酯系樹脂而得的膜為較佳,考慮實用性的話,使用聚對苯二甲酸乙二酯樹脂而得的膜特佳。 As for the base material, considering the viewpoint of inspection and management of optical components by fluoroscopy, the use of selected from polyester resins, acetate resins, polyether resins, polycarbonate resins, and polycarbonate resins can be cited. A film made of resins such as amide resins, polyimide resins, polyolefin resins, and acrylic resins. Among them, in terms of the substrate, a film obtained using a polyester resin is preferable from the viewpoint of surface protection performance, and a film obtained using a polyethylene terephthalate resin is particularly preferable in consideration of practicality.
基材之厚度一般可為500μm以下,較佳為5μm以上300μm以下,更佳為10μm以上200μm以下。 The thickness of the substrate may generally be 500 μm or less, preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.
亦可於基材之單面或兩面設置抗靜電層。又,為了改善與黏接劑層之黏合性,亦可在基材之設置有黏接劑層側的表面施以電暈放電處理等。 An antistatic layer can also be provided on one or both sides of the substrate. In addition, in order to improve the adhesion with the adhesive layer, corona discharge treatment or the like may be applied to the surface of the substrate on the side where the adhesive layer is provided.
本揭示之保護膜,係於基材上配置由本揭示之黏接劑組成物而得之黏接劑層而成。 The protective film of the present disclosure is formed by disposing an adhesive layer obtained from the adhesive composition of the present disclosure on a substrate.
黏接劑層之形成方法,例如可採用將黏接劑組成物直接或視需要以適當溶劑進行稀釋並塗布於基材後,進行乾燥以去除溶劑的方法。 The method of forming the adhesive layer can be, for example, a method of directly or as necessary diluting the adhesive composition with a suitable solvent and coating it on the substrate, and then drying to remove the solvent.
又,亦可採用以下方法:首先在由利用聚矽氧樹脂等施以脫模處理的紙、聚酯膜等適當的膜構成之剝離片上塗布黏接劑組成物,進行加熱乾燥以形成黏接劑層,然後將前述剝離片之黏接劑層側壓接於基材,而將前述黏接劑層轉印於前述基材。 In addition, the following method can also be used: first, the adhesive composition is coated on a release sheet composed of a suitable film such as paper or polyester film that has been subjected to mold release treatment with silicone resin, etc., and then heated and dried to form an adhesive bond. Then, the adhesive layer side of the release sheet is crimped to the substrate, and the adhesive layer is transferred to the substrate.
本揭示之保護膜之黏接劑層中,特定(甲基)丙烯酸系聚合物藉由金屬螯合物系交聯劑進行交聯。藉此,可將黏接劑層之高速剝離時之黏接力壓抑為低,進一步,可縮短熟化完成時間。 In the adhesive layer of the protective film of the present disclosure, the specific (meth)acrylic polymer is crosslinked by a metal chelate crosslinking agent. Thereby, the adhesive force during high-speed peeling of the adhesive layer can be suppressed to be low, and further, the curing completion time can be shortened.
使特定(甲基)丙烯酸系聚合物藉由金屬螯合物系交聯劑交聯的條件並無特別限制。 The conditions for crosslinking the specific (meth)acrylic polymer with the metal chelate-based crosslinking agent are not particularly limited.
在基材上形成之黏接劑層的厚度,可因應對於保護膜所要求之黏接力、光學構件之表面粗糙度等而適當設定,一般可例示1μm以上100μm以下,較佳為5μm以上50μm以下,尤佳為15μm以上30μm以下左右的厚度。 The thickness of the adhesive layer formed on the substrate can be appropriately set according to the adhesive force required for the protective film, the surface roughness of the optical member, etc. Generally, 1 μm or more and 100 μm or less can be exemplified, preferably 5 μm or more and 50 μm or less , Particularly preferably a thickness of about 15 μm or more and 30 μm or less.
黏接劑層之黏接力變高的話,於大面積之高速剝離時的作業性降低,故於剝離速度30m/分(高速剝離)之黏接力(剝離力)宜未達2.00N/25mm較佳,未達1.20N/25mm更佳,未達0.70N/25mm尤佳。 If the adhesive strength of the adhesive layer becomes higher, the workability during high-speed peeling of a large area will decrease. Therefore, the adhesive force (peeling force) at a peeling speed of 30m/min (high-speed peeling) should be less than 2.00N/25mm. , Less than 1.20N/25mm is better, less than 0.70N/25mm is especially better.
又,考量防止保護膜之突然剝離的觀點,於剝離速度30m/分(高速剝離)之黏接力(剝離力)宜為0.05N/25mm以上較佳,0.20N/25mm以上更佳。 In addition, considering the viewpoint of preventing sudden peeling of the protective film, the adhesive force (peeling force) at a peeling speed of 30m/min (high-speed peeling) is preferably 0.05N/25mm or more, more preferably 0.20N/25mm or more.
就保護膜而言,係疊層於光學構件之表面,並保護該光學構件之表面不受到污染或損傷,光學構件在加工成液晶顯示面板等時,可直接以保護膜疊層於光學構件的狀態提供給衝壓加工、檢查、輸送、液晶顯示面板之組裝等各步驟,視需要可施以高壓釜處理、高溫熟化處理等加熱加壓處理,於不需表面保護的階段再從光學構件剝離去除。 As far as the protective film is concerned, it is laminated on the surface of the optical component and protects the surface of the optical component from contamination or damage. When the optical component is processed into a liquid crystal display panel, the protective film can be directly laminated on the surface of the optical component. The state is provided for the various steps of press processing, inspection, transportation, LCD panel assembly, etc., if necessary, it can be subjected to heating and pressure treatment such as autoclave treatment, high temperature curing treatment, etc., and then peeling and removing from the optical member at the stage where surface protection is not required .
作為光學構件,可列舉構成影像顯示裝置、輸入裝置等設備(光學設備)的構件、或該等設備所使用之構件,例如,可列舉偏光板、波長板、相位差板、光學補償膜、亮度增強膜、導光板、反射膜、防反射膜、透明導電膜(ITO膜等)。 Examples of optical members include members that constitute devices (optical devices) such as image display devices and input devices, or members used in such devices, for example, polarizing plates, wavelength plates, retardation plates, optical compensation films, and brightness Reinforcement film, light guide plate, reflective film, anti-reflection film, transparent conductive film (ITO film, etc.).
就使用本揭示之保護膜的光學構件而言,偏光板為較佳。 As for the optical member using the protective film of this disclosure, a polarizing plate is preferable.
[實施例] [Example]
以下,藉由實施例對本揭示進行更加具體地說明,但本揭示並不限定於該等實施例。 Hereinafter, the present disclosure will be explained in more detail through examples, but the present disclosure is not limited to these examples.
(製造例A-1) (Manufacturing example A-1)
-(甲基)丙烯酸系聚合物(A-1)之製造- -Production of (meth)acrylic polymer (A-1)-
於配備有溫度計、攪拌機、氮氣導入管及回流冷卻器的反應器內,加入乙酸乙酯70.0質量份,於另外的容器中,加入丙烯酸正丁酯(BA)60.0質量份、丙烯酸2-乙基己酯(2EHA)31.0質量份、通式(1a)表示之單體(製品名:ARONIX M-5300,東亞合成(股)公司製)9.0質量份作為單體,進行混合而製成單體混合物。將該單體混合物中20.0質量%加入反應器中,然後以氮氣置換前述反應容器的空氣後,添加偶氮雙丁腈(以下,亦稱為「AIBN」。)0.01質量份作為聚合引發劑,於攪拌下在氮氣環境中將前述反應容器內的混合物溫度升溫至85℃,並開始初始反應。在初始反應大致結束後,邊分別逐次添加剩下的單體混合物80.0質量%、和乙酸乙酯15.0質量份及AIBN0.10質量份之混合物,邊使其反應約2小時,然後,進一步使其反應2小時。之後,於上述混合物中歷時1小時滴加使過氧化新戊酸第三丁酯0.10質量份溶解於乙酸乙酯25.0質量份而得的溶液,進一步使其反應1.5小時。反應結束後,獲得(甲基)丙烯酸系聚合物(A-1)的溶液。 In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux cooler, 70.0 parts by mass of ethyl acetate was added. In a separate container, 60.0 parts by mass of n-butyl acrylate (BA) and 2-ethyl acrylate were added. 31.0 parts by mass of hexyl ester (2EHA) and 9.0 parts by mass of the monomer represented by the general formula (1a) (product name: ARONIX M-5300, manufactured by Toagosei Co., Ltd.) are used as monomers and mixed to prepare a monomer mixture . 20.0% by mass of the monomer mixture was added to the reactor, and after replacing the air in the aforementioned reaction vessel with nitrogen, 0.01 parts by mass of azobisbutyronitrile (hereinafter also referred to as "AIBN") was added as a polymerization initiator, The temperature of the mixture in the aforementioned reaction vessel was increased to 85°C under stirring in a nitrogen atmosphere, and the initial reaction was started. After the initial reaction was almost completed, the remaining monomer mixture 80.0% by mass, 15.0 mass parts of ethyl acetate and 0.10 mass parts of AIBN were added successively, and reacted for about 2 hours, and then further React for 2 hours. After that, a solution obtained by dissolving 0.10 parts by mass of tert-butyl peroxypivalate in 25.0 parts by mass of ethyl acetate was added dropwise to the above mixture over 1 hour, and the reaction was further carried out for 1.5 hours. After the reaction was completed, a solution of (meth)acrylic polymer (A-1) was obtained.
(甲基)丙烯酸系聚合物(A-1)的溶液的固體成分為48.0質量%。獲得之(甲基)丙烯酸系聚合物(A-1)的溶液的酸價、玻璃轉移溫度(Tg)、重量平均分子量(Mw)、係重量平均分子量(Mw)相對於數量平均分子量(Mn)之比的分散度(Mw/Mn)顯示於表1。 The solid content of the solution of the (meth)acrylic polymer (A-1) was 48.0% by mass. The acid value, glass transition temperature (Tg), weight average molecular weight (Mw), weight average molecular weight (Mw) of the obtained (meth)acrylic polymer (A-1) solution relative to the number average molecular weight (Mn) The ratio of dispersion (Mw/Mn) is shown in Table 1.
此外,「固體成分」係從(甲基)丙烯酸系聚合物的溶液去除溶劑後的殘渣。酸價、玻璃轉移溫度(Tg)、重量平均分子量(Mw)及分散度(Mw/Mn)係利用已述之方法算出。 In addition, the "solid content" is the residue after removing the solvent from the solution of the (meth)acrylic polymer. The acid value, the glass transition temperature (Tg), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are calculated by the method described above.
酸價如下述般計算。 The acid value is calculated as follows.
酸價(mgKOH/g)={(A/100)÷B}×56.1×1000×C Acid value (mgKOH/g)={(A/100)÷B}×56.1×1000×C
A=(甲基)丙烯酸系聚合物或(甲基)丙烯酸系低聚物所使用之全部單體中的具有羧基之單體的含有率(質量%):9.0 A=(Meth)acrylic polymer or (meth)acrylic oligomer content rate (mass%) of monomers having carboxyl group in all monomers used in (meth)acrylic oligomer: 9.0
B=ARONIXM-5300之分子量:300.4 B=The molecular weight of ARONIXM-5300: 300.4
C=具有羧基之單體1分子中所含的羧基數目:1 C=Number of carboxyl groups contained in 1 molecule of monomer with carboxyl group: 1
酸價={(9.0/100)÷300.4}×56.1×1000×1=約16.8 Acid value={(9.0/100)÷300.4}×56.1×1000×1=about 16.8
(製造例A-2~A-10) (Manufacturing examples A-2~A-10)
-(甲基)丙烯酸系聚合物(A-2)~(A-10)之製造- -Manufacturing of (meth)acrylic polymers (A-2)~(A-10)-
將製造例1中之單體組成變更成表1所示之單體組成,並適當調整引發劑量等,除此以外,和製造例1同樣進行,製造(甲基)丙烯酸系聚合物(A-2)~(A-10)的溶液。獲得之丙烯酸系聚合物的酸價、玻璃轉移溫度(Tg)、重量平均分子量(Mw)及分散度(Mw/Mn)顯示於表1。 The monomer composition in Production Example 1 was changed to the monomer composition shown in Table 1, and the initiator amount and the like were appropriately adjusted, except that the same procedure as in Production Example 1 was carried out to produce a (meth)acrylic polymer (A- 2)~(A-10) solution. The acid value, glass transition temperature (Tg), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the obtained acrylic polymer are shown in Table 1.
此外,酸價、玻璃轉移溫度(Tg)、重量平均分子量(Mw)及分散度(Mw/Mn)係利用已述之方法算出。 In addition, the acid value, the glass transition temperature (Tg), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are calculated by the method already described.
(製造例B) (Manufacturing Example B)
-(甲基)丙烯酸系低聚物(B)之製造- -Production of (meth)acrylic oligomer (B)-
於配備有攪拌葉片、溫度計、氮氣導入管、冷卻器、滴加漏斗的反應容器內,加入甲乙酮100.0質量份、甲氧基聚乙二醇甲基丙烯酸酯(環氧烷單元之平均加成莫耳數23)(MePEGMA)10.0質量份,在氮氣環境下邊攪拌邊加熱至回流溫度。在滴加漏斗中加入預先混合的甲基丙烯酸2-乙基己酯(2EHMA)87.0質量份、丙烯酸(AA)3.0質量份、甲乙酮100.0質量份、偶氮雙異丁腈5.0質量份之混合溶液,歷時120分鐘逐次添加至回流溫度之反應容器中。之後,於維持回流溫度240分鐘的狀態使其反應,並結束反應。 In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a cooler, and a dropping funnel, 100.0 parts by mass of methyl ethyl ketone, methoxy polyethylene glycol methacrylate (the average addition value of the alkylene oxide unit Ears 23) (MePEGMA) 10.0 parts by mass, heated to reflux temperature while stirring in a nitrogen atmosphere. In the dropping funnel was added a pre-mixed solution of 87.0 parts by mass of 2-ethylhexyl methacrylate (2EHMA), 3.0 parts by mass of acrylic acid (AA), 100.0 parts by mass of methyl ethyl ketone, and 5.0 parts by mass of azobisisobutyronitrile. , Added to the reaction vessel at reflux temperature one by one over 120 minutes. After that, the reaction was performed while maintaining the reflux temperature for 240 minutes, and the reaction was terminated.
獲得之(甲基)丙烯酸系低聚物(B)的溶液的固體成分為33.0質量%。(甲基)丙烯酸系低聚物(B)的溶液的酸價、重量平均分子量(Mw)、分散度(Mw/Mn)顯示於表1。 The solid content of the solution of the obtained (meth)acrylic oligomer (B) was 33.0% by mass. Table 1 shows the acid value, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of the solution of the (meth)acrylic oligomer (B).
此外,酸價、玻璃轉移溫度(Tg)、重量平均分子量(Mw)及分散度(Mw/Mn)係利用已述之方法算出。 In addition, the acid value, the glass transition temperature (Tg), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are calculated by the method already described.
表1中的簡稱如下。 The abbreviations in Table 1 are as follows.
‧BA:丙烯酸正丁酯 ‧BA: n-Butyl Acrylate
‧2EHA:丙烯酸2-乙基己酯 ‧2EHA: 2-ethylhexyl acrylate
‧M-5300:ω-羧基-聚己內酯(n≒2)單丙烯酸酯(商品名:ARONIX M-5300,東亞合成(股)公司製)(通式(1a)表示之單體) ‧M-5300: ω-carboxy-polycaprolactone (n≒2) monoacrylate (trade name: ARONIX M-5300, manufactured by Toagosei Co., Ltd.) (monomer represented by general formula (1a))
‧2EHMA:甲基丙烯酸2-乙基己酯 ‧2EHMA: 2-ethylhexyl methacrylate
‧AA:丙烯酸 ‧AA: Acrylic
‧HOA-MS:2-丙烯醯氧乙基-琥珀酸(通式(1a)表示之單體,共榮社化學(股)公司製,商品名:LIGHT ACRYLATE HOA-MS(N)) ‧HOA-MS: 2-propylene oxyethyl-succinic acid (monomer represented by general formula (1a), manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE HOA-MS(N))
‧MePEGMA:甲氧基聚乙二醇甲基丙烯酸酯(環氧烷單元之平均加成莫耳數為23) ‧MePEGMA: Methoxy polyethylene glycol methacrylate (the average addition mole number of the alkylene oxide unit is 23)
<實施例1> <Example 1>
於配備有攪拌葉片、溫度計、冷卻器、滴加漏斗的四口燒瓶中,加入製造例1製備的(甲基)丙烯酸系聚合物(A-1)的溶液(固體成分48.0質量%)208.3質量份(固體成分為100質量份)、製造例3製備的(甲基)丙烯酸系低聚物(B)的溶液(固體成分33.0質量%)1.5質量份(固體成分為0.50質量份)、作為抗靜電劑之Li(CF3SO2)2N(森田化學工業(股)公司製LiTFSI)0.20質量份,將燒瓶內的液溫保持在25℃附近,並進行4.0小時的混合攪拌。於此添加作為聚醚改性聚矽氧之SH-3773M(商品名,東麗道康寧製,固體成分100.0質量%)0.10質量份、作為金屬螯合物系交聯劑之將參乙醯丙酮鋁(商品名:鋁螯合物A,川研精細化學(股)公司製)以乙醯丙酮與甲苯進行稀釋而得的鋁螯合物A稀釋物(固體成分9.72質量%)32.9質量份(固體成分為3.2質量份,1.0當量),充分攪拌,獲得保護膜用黏接劑組成物溶液。使用該黏接劑組成物溶液,根據以下試驗用黏接片之製作方法製作試驗用保護膜,並進行各種物性試驗。獲得之結果顯示於表2。 Into a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, the solution (solid content 48.0% by mass) of the (meth)acrylic polymer (A-1) prepared in Production Example 1 was added by 208.3 mass Parts (100 parts by mass of solid content), a solution (33.0% by mass of solid content) of the (meth)acrylic oligomer (B) prepared in Production Example 3, 1.5 parts by mass (0.50 parts by mass of solid content), as a resistance The electrostatic agent Li(CF 3 SO 2 ) 2 N (LiTFSI manufactured by Morita Chemical Industry Co., Ltd.) was 0.20 parts by mass, and the liquid temperature in the flask was maintained at around 25° C., and mixing and stirring were performed for 4.0 hours. 0.10 parts by mass of SH-3773M (trade name, manufactured by Toray Dow Corning, solid content 100.0% by mass) as polyether-modified polysiloxane, and aluminum acetone as a metal chelate crosslinking agent (Trade name: Aluminum chelate A, manufactured by Kawaken Fine Chemicals Co., Ltd.) 32.9 parts by mass (solid) of aluminum chelate A diluted product (solid content 9.72% by mass) obtained by diluting acetone and toluene The composition is 3.2 parts by mass, 1.0 equivalent), and fully stirred to obtain an adhesive composition solution for a protective film. Using this adhesive composition solution, a protective film for testing was made according to the following manufacturing method of the adhesive sheet for testing, and various physical property tests were performed. The results obtained are shown in Table 2.
此外,上述鋁螯合物A稀釋物所含之參乙醯丙酮鋁(鋁螯合物)的當量,相對於(甲基)丙烯酸系聚合物所含之羧基,顯示為1當量。 In addition, the equivalent of aluminum ginsenoside (aluminum chelate) contained in the above-mentioned aluminum chelate A dilution is shown to be 1 equivalent with respect to the carboxyl group contained in the (meth)acrylic polymer.
鋁螯合物之當量的計算係利用已述之方法進行計算,具體而言係如以下般計算。 The calculation of the equivalent weight of the aluminum chelate is performed using the method already described, and specifically it is calculated as follows.
當量=(A×B/C)/(D1×E1/F1+D2×E2/F2+‧‧‧‧+Dn×En/Fn) Equivalent=(A×B/C)/(D 1 ×E 1 /F 1 +D 2 ×E 2 /F 2 +‧‧‧‧+D n ×E n /F n )
A=鋁螯合物之金屬的價數:3.0 A=The valence of the metal of aluminum chelate: 3.0
B=鋁螯合物之質量份數(固體成分的量):3.2質量份 B= parts by mass of aluminum chelate (amount of solid content): 3.2 parts by mass
C=鋁螯合物之分子量:324.3 C=The molecular weight of aluminum chelate: 324.3
D1=(甲基)丙烯酸系聚合物所使用之全部單體中的具有酸性基之各單體的含有率(質量%):9.0質量% D 1 = The content rate (mass%) of each monomer having an acidic group in all monomers used in the (meth)acrylic polymer: 9.0% by mass
E1=各具有酸性基之單體之1分子中所含的酸性基數目:1 E 1 = the number of acidic groups contained in one molecule of each monomer having an acidic group: 1
F1=ARONIX M-5300之分子量:300.4 F 1 = Molecular weight of ARONIX M-5300: 300.4
n=使用之(甲基)丙烯酸系單體的種類:1 n=Type of (meth)acrylic monomer used: 1
當量=(A×B/C)/(D1×E1/F1)=(3×3.2/324.3)/(9×1/300.4)=約1.0 Equivalent=(A×B/C)/(D 1 ×E 1 /F 1 )=(3×3.2/324.3)/(9×1/300.4)=about 1.0
(1)試驗用保護膜之製作 (1) Production of protective film for testing
以使乾燥後之塗覆量成為20g/m2的方式,在聚對苯二甲酸乙二酯(PET)膜(商品名:Teijin Tetoron Film Type G2,厚度38μm,帝人-杜邦薄膜(股)公司製)上塗布黏接劑組成物溶液,並於100℃利用熱風循環式乾燥機乾燥60秒而形成黏接劑層,製作附黏接劑層之PET膜。之後,在經以聚矽氧系脫模劑進行表面處理之脫模膜(商品名:FILMBYNA 100E-0010NO23,厚度100μm,藤森工業(股)公司製)上,以該黏接劑層面接觸的方式載置附黏接劑層之PET膜而製成疊層體,通過加壓夾輥對將該疊層體予以壓接並貼合後,於23℃、50%RH之條件下熟化1小時,獲得試驗用保護膜。 In such a way that the coating amount after drying becomes 20g/m 2 , the polyethylene terephthalate (PET) film (trade name: Teijin Tetoron Film Type G2, thickness 38μm, Teijin-DuPont Film Co., Ltd.) (Preparation) Coat the adhesive composition solution on it, and dry it with a hot air circulating dryer at 100°C for 60 seconds to form an adhesive layer, and make a PET film with the adhesive layer. After that, on a release film (trade name: FILMBYNA 100E-0010NO23, thickness 100 μm, manufactured by Fujimori Kogyo Co., Ltd.) that has been surface-treated with a silicone-based release agent, the adhesive layer is brought into contact with each other. Place the PET film with the adhesive layer to form a laminate. After pressing and bonding the laminate with a pressure nip roller, the laminate is cured under the conditions of 23°C and 50%RH for 1 hour. Obtain a protective film for testing.
(2)黏接力與高速剝離時之剝離性 (2) Adhesion and peelability during high-speed peeling
將上述(1)獲得之試驗用保護膜裁切成25mm×150mm,製成保護膜片。從該保護膜片除去剝離膜,將露出的黏接劑層貼附至TAC膜(商品名:Lonza TAC100,PANAC(股)公司製),使2kg的橡膠輥來回2次進行壓接,製成試驗樣品。將該試驗樣品於23℃、50%RH之條件下放置24小時後,在剝離速度30m/分之高速條件下測定於如圖1所示之180°剝離之黏接力,並依以下之評價基準評價高速剝離時之剝離性與黏接力的平衡,其結果顯示於表2。 The protective film for the test obtained in (1) above was cut into 25mm×150mm to make a protective film. The release film was removed from the protective film, and the exposed adhesive layer was attached to the TAC film (trade name: Lonza TAC100, manufactured by PANAC Co., Ltd.), a 2 kg rubber roller was crimped back and forth twice to prepare a test sample. After placing the test sample at 23°C and 50%RH for 24 hours, the adhesive force at 180° peeling as shown in Figure 1 was measured at a high-speed peeling speed of 30m/min, and the following evaluation criteria were followed. The balance of peelability and adhesive force during high-speed peeling was evaluated, and the results are shown in Table 2.
就評價而言,係如圖1般以TAC膜表面接觸的方式將試驗樣品放置在玻璃板上,把持試驗樣品的一端,沿著玻璃板之表面於180°方向進行拉扯,將PET膜從黏接劑層剝離而進行。 In terms of evaluation, the test sample is placed on a glass plate with the surface of the TAC film in contact as shown in Figure 1, holding one end of the test sample, and pulling it along the surface of the glass plate in a direction of 180° to remove the PET film from the adhesive. The adhesive layer is peeled off.
[評價基準] [Evaluation criteria]
AA:0.20N/25mm以上未達0.70N/25mm(剝離性非常優異,且不易發生突然剝離,黏接力優異) AA: 0.20N/25mm or more and less than 0.70N/25mm (excellent peelability, and is not prone to sudden peeling, excellent adhesion)
A:0.05N/25mm以上未達0.20N/25mm、或0.70N/25mm以上未達1.20N/25mm(剝離性優異,且不太容易發生突然剝離,黏接力略為優異) A: 0.05N/25mm or more and less than 0.20N/25mm, or 0.70N/25mm or more and less than 1.20N/25mm (excellent peelability, and less prone to sudden peeling, slightly superior adhesion)
B:1.20N/25mm以上未達2.0N/25mm(剝離性稍差,但為容許範圍內) B: 1.20N/25mm or more and less than 2.0N/25mm (peelability is slightly worse, but within the allowable range)
C:2.0N/25mm以上(剝離性差,為不能容許之範圍) C: 2.0N/25mm or more (the peelability is poor, and it is an unacceptable range)
D:未達0.05N/25mm(有發生突然剝離的可能性,為不能容許之範圍) D: Less than 0.05N/25mm (there is a possibility of sudden peeling, this is an unacceptable range)
(3)抗靜電性 (3) Antistatic
將上述(1)獲得之試驗用保護膜裁切成25mm×150mm,製成試驗用保護膜片。從該試驗用保護膜片除去剝離膜,將露出的黏接劑層貼附至TAC膜(商品名:Lonza TAC100,PANAC(股)公司製),使2kg的橡膠輥來回2次進行壓接,製成試驗樣品。將該試驗樣品於23℃、50%RH之條件下放置24小時後,以和上述(2)同 樣的方法,如圖1所示般在180°方向以剝離速度30m/分(高速)進行剝離。利用固定配置於預定位置(距TAC膜表面10mm的位置)之電位測定器(商品名:KSD-0303,春日電機(股)公司製)測定此時產生的TAC膜表面之電位。將該測定值的絕對值作為剝離靜電壓,並依以下評價基準評價抗靜電性,其結果顯示於表2。 The test protective film obtained in (1) above was cut into 25 mm×150 mm to prepare a test protective film. The peeling film was removed from the protective film for the test, the exposed adhesive layer was attached to the TAC film (trade name: Lonza TAC100, manufactured by PANAC Co., Ltd.), and a 2 kg rubber roller was pressed back and forth twice. Make test samples. After placing the test sample at 23°C and 50%RH for 24 hours, it is the same as the above (2) In such a method, peeling is performed in the 180° direction at a peeling speed of 30 m/min (high speed) as shown in FIG. 1. The potential of the TAC film surface generated at this time was measured with a potential measuring device (trade name: KSD-0303, manufactured by Kasuga Electric Co., Ltd.) fixedly arranged at a predetermined position (a position 10 mm from the surface of the TAC film). The absolute value of the measured value was used as the peeling static voltage, and the antistatic property was evaluated according to the following evaluation criteria. The results are shown in Table 2.
[評價基準] [Evaluation criteria]
AA:未達0.4kv(抗靜電性非常優異) AA: less than 0.4kv (excellent antistatic property)
A:0.4kv以上未達0.6kv(抗靜電性優異) A: 0.4kv or more and less than 0.6kv (excellent antistatic property)
B:0.6kv以上未達1.0kv(抗靜電性稍差,但為可容許之範圍) B: 0.6kv or more and less than 1.0kv (the antistatic property is slightly worse, but it is an allowable range)
C:1.0kv以上(抗靜電性差) C: 1.0kv or more (poor antistatic)
(4)熟化完成時間 (4) Time of maturation completion
以使乾燥後之塗覆量成為20g/m2的方式,在聚對苯二甲酸乙二酯(PET)膜(商品名:Teijin Tetoron Film Type G2,厚度38μm,帝人-杜邦薄膜(股)公司製)上塗布保護膜用黏接劑組成物溶液,並於100℃利用熱風循環式乾燥機乾燥60秒而形成黏接劑層,製作附黏接劑層之PET膜。之後,在經以聚矽氧系脫模劑進行表面處理之脫模膜(商品名:FILMBYNA 100E-0010NO23,厚度100μm,藤森工業(股)公司製)上,以黏接劑層面接觸的方式載置附黏接劑層之PET膜而製成疊層體,通過加壓夾輥對將該疊層體予以壓接並貼合。於23℃、50%RH環境下進行熟化,獲得試驗用保護膜。此時,熟化時間設定為1小時、24小時、96小時,經過各個熟化時間後,立即以使脫模膜剝落後露出的黏接劑層接觸的方式,把將試驗用保護膜裁切成25mm×150mm而獲得之各試驗用保護膜片貼附至TAC膜(商品 名:Lonza TAC100,PANAC(股)公司製),使2kg的橡膠輥來回2次進行壓接,製成試驗樣品。 In such a way that the coating amount after drying becomes 20g/m 2 , the polyethylene terephthalate (PET) film (trade name: Teijin Tetoron Film Type G2, thickness 38μm, Teijin-DuPont Film Co., Ltd.) (Preparation) Coat the adhesive composition solution for the protective film and dry it at 100°C with a hot-air circulating dryer for 60 seconds to form an adhesive layer to produce a PET film with an adhesive layer. After that, the mold release film (trade name: FILMBYNA 100E-0010NO23, thickness 100μm, manufactured by Fujimori Kogyo Co., Ltd.) is surface-treated with a silicone-based mold release agent, and placed in contact with the adhesive layer. The PET film with the adhesive layer is placed to form a laminate, and the laminate is press-bonded and bonded by a pressure nip roller pair. Maturation was performed in an environment of 23°C and 50% RH to obtain a protective film for testing. At this time, the curing time is set to 1 hour, 24 hours, and 96 hours. Immediately after each curing time, the protective film for the test is cut into 25mm in such a way that the adhesive layer exposed after the release film is peeled off is in contact with each other. Each test protective film obtained by ×150 mm was attached to a TAC film (trade name: Lonza TAC100, manufactured by PANAC Co., Ltd.), and a 2 kg rubber roller was pressed back and forth twice to prepare a test sample.
將該試驗樣品於23℃、50%RH之條件下放置24小時後,以和上述(2)同樣的方法,如圖1所示般在180°方向以剝離速度30m/分(高速)進行剝離,並依以下之評價基準評價熟化完成時間。獲得之結果顯示於表2。 After leaving the test sample at 23°C and 50%RH for 24 hours, it was peeled off in the 180° direction at a peeling speed of 30m/min (high speed) in the same way as in (2) above as shown in Figure 1. , And evaluate the maturation completion time according to the following evaluation criteria. The results obtained are shown in Table 2.
[評價基準] [Evaluation criteria]
A:熟化1小時後之黏接力與熟化24小時後之黏接力的差的絕對值為0.05N/25mm以下(熟化在1小時以內完成,熟化完成時間短,為良好) A: The absolute value of the difference between the adhesive force after curing for 1 hour and the adhesive force after curing for 24 hours is less than 0.05N/25mm (the curing is completed within 1 hour, and the curing completion time is short, which is good)
B:不符合評價A,且熟化24小時後之黏接力與熟化96小時後之黏接力的差的絕對值為0.05N/25mm以下(熟化在1小時以上24小時以內完成,熟化完成時間稍短,略為良好) B: Does not meet the evaluation A, and the absolute value of the difference between the adhesive force after aging for 24 hours and the adhesive force after aging for 96 hours is 0.05N/25mm or less (the aging is completed within 1 hour or more within 24 hours, and the aging completion time is slightly shorter , Slightly good)
C:不符合評價A、B中之任一者(熟化未在24小時以內完成,熟化完成時間長,為不良) C: Does not meet either of the evaluations A and B (the maturation is not completed within 24 hours, and the maturation completion time is long, which is bad)
<實施例2~實施例18、比較例1~7> <Example 2~Example 18, Comparative Examples 1~7>
將實施例1之組成變更成表2所示之組成,除此以外,和實施例1同樣進行,製作如表2所示之保護膜用黏接劑組成物。使用製得之黏接劑組成物,根據以下試驗用保護膜之製作方法製作試驗用保護膜,並進行各種物性試驗。獲得之結果顯示於表2。 Except having changed the composition of Example 1 to the composition shown in Table 2, the same procedure as in Example 1 was carried out, and the adhesive composition for protective film shown in Table 2 was produced. Using the prepared adhesive composition, a protective film for testing was made according to the following manufacturing method of protective film for testing, and various physical properties were tested. The results obtained are shown in Table 2.
此外,熟化未在1小時以內完成時,亦即熟化完成時間的評價為B或C時,進行240小時的熟化,而獲得試驗用保護膜。具體而言,比較例5、6、7係進行240小時的熟化,而獲得試驗用保護膜。 In addition, when the aging was not completed within 1 hour, that is, when the evaluation of the aging completion time was B or C, the aging was performed for 240 hours to obtain a protective film for a test. Specifically, Comparative Examples 5, 6, and 7 were cured for 240 hours to obtain a protective film for a test.
此外,比較例5、6中之交聯劑的添加份數,係設定為使異氰酸酯化合物所含之異氰酸酯基相對於(甲基)丙烯酸系聚合物所含之羧基之合計成為1當量的量。又,比較例7中之交聯劑的添加份數,係設定為使環氧化合物所含之環氧基相對於(甲基)丙烯酸系聚合物所含之羧基之合計成為1當量的量。 In addition, the addition part of the crosslinking agent in Comparative Examples 5 and 6 was set so that the total amount of the isocyanate groups contained in the isocyanate compound and the carboxyl groups contained in the (meth)acrylic polymer became 1 equivalent. In addition, the addition part of the crosslinking agent in Comparative Example 7 was set so that the epoxy group contained in the epoxy compound was 1 equivalent to the total of the carboxyl group contained in the (meth)acrylic polymer.
【表2】
表2中的簡稱如下。 The abbreviations in Table 2 are as follows.
‧LiTFSI:Li(CF3SO2)2N(森田化學工業(股)公司製) ‧LiTFSI: Li(CF 3 SO 2 ) 2 N (manufactured by Morita Chemical Industry Co., Ltd.)
‧LiTFS:LiCF3SO3(森田化學工業(股)公司製) ‧LiTFS: LiCF 3 SO 3 (manufactured by Morita Chemical Industry Co., Ltd.)
‧有機鹽A:N-己基吡啶鎓‧PF6 -(具有己基吡啶鎓離子作為有機陽離子的有機鹽,熔點45℃) ‧ Organic Salt A: N- hexylpyridinium ‧PF 6 - (pyridinium ion having a hexyl group as an organic salt of an organic cation, a melting point of 45 ℃)
‧SH-3773M:於側鏈導入有聚伸烷氧基的二甲基矽氧烷化合物(東麗道康寧(股)公司製,聚伸烷氧基之末端為羥基,HLB值=8) ‧SH-3773M: Dimethylsiloxane compound with polyalkoxyl group introduced into the side chain (manufactured by Toray Dow Corning Co., Ltd., the end of the polyalkoxyl group is a hydroxyl group, HLB value = 8)
‧Al螯合物:將參乙醯丙酮鋁(商品名:鋁螯合物A,川研精細化學(股)公司製)用甲苯及乙醯丙酮稀釋成固體成分9.7質量%而得者 ‧Al chelate: obtained by diluting ginseng aluminum acetone aluminum (trade name: aluminum chelate A, manufactured by Kaiken Fine Chemical Co., Ltd.) with toluene and acetone to a solid content of 9.7% by mass
‧異氰酸酯交聯劑A:甲苯二異氰酸酯與三羥甲基丙烷之加成物(商品名:CORONATE L,東曹(股)公司製,固體成分100質量%) ‧Isocyanate crosslinking agent A: adduct of toluene diisocyanate and trimethylolpropane (trade name: CORONATE L, manufactured by Tosoh Corporation, solid content 100% by mass)
‧異氰酸酯交聯劑B:六亞甲基二異氰酸酯與三羥甲基丙烷之加成物(商品名:DESMODUR N3300,Sumika Covestro Urethane(股)公司製,固體成分100質量%) ‧Isocyanate crosslinking agent B: adduct of hexamethylene diisocyanate and trimethylolpropane (trade name: DESMODUR N3300, manufactured by Sumika Covestro Urethane Co., Ltd., solid content 100% by mass)
‧環氧交聯劑A:1,3-伸苯基雙(N,N-二環氧丙基甲胺)(商品名:TETRAD-X,三菱瓦斯化學(股)公司製,固體成分100質量%) ‧Epoxy crosslinking agent A: 1,3-phenylene bis(N,N-diepoxypropyl methylamine) (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd., solid content 100 mass %)
可知本實施例1~5中,由於使用酸價為9mgKOH/g以上70mgKOH/g以下之(甲基)丙烯酸系聚合物、相對於上述(甲基)丙烯酸系聚合物之酸性基1當量為0.3當量以上2.0當量以下之金屬螯合物系交聯劑、及抗靜電劑,熟化完成時間短,抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。可知特別是本實施例2~5中,即使是(甲基)丙烯酸系聚合物之酸價在9mgKOH/g以上 70mgKOH/g以下之範圍內有所增減的情況下,熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。 It can be seen that in Examples 1 to 5, since a (meth)acrylic polymer with an acid value of 9 mgKOH/g or more and 70 mgKOH/g or less is used, the acidic group 1 equivalent of the above-mentioned (meth)acrylic polymer is 0.3 The metal chelate crosslinking agent and antistatic agent with the equivalent of more than 2.0 equivalents have a short curing completion time, excellent antistatic properties, adhesive strength to the extent that they will not peel off suddenly, and excellent high-speed peeling. It can be seen that especially in Examples 2 to 5, even if the acid value of the (meth)acrylic polymer is above 9mgKOH/g In the case of an increase or decrease in the range of 70 mgKOH/g or less, the curing completion time is also short, and the antistatic property is excellent, and the adhesive force is not suddenly peeled off, and the high-speed peeling property is excellent.
可知本實施例6~8中,即使是金屬螯合物系交聯劑之當量在相對於(甲基)丙烯酸系聚合物之酸性基1當量為0.3當量以上2.0當量以下之範圍內有所增減的情況下,熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離時之剝離性優異。 It can be seen that in Examples 6 to 8, the equivalent weight of the metal chelate crosslinking agent is increased within the range of 0.3 to 2.0 equivalents relative to 1 equivalent of the acidic group of the (meth)acrylic polymer. In the case of reduction, the curing completion time is also short, and the antistatic property is excellent, and it has an adhesive force to the extent that it does not peel off suddenly, and it has excellent peelability during high-speed peeling.
可知本實施例9及10中,即使使用LiTFSI以外之鹼金屬鹽的LiTFS及鹼金屬鹽以外之離子性化合物的有機鹽A作為抗靜電劑時,熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。 It can be seen that in Examples 9 and 10, even when LiTFS of an alkali metal salt other than LiTFSI and an organic salt A of an ionic compound other than an alkali metal salt are used as the antistatic agent, the maturation completion time is short and the antistatic property is excellent. It has adhesive strength to the extent that it does not suddenly peel off, and it has excellent high-speed peeling properties.
可知本實施例11~13中,即使使用利用單體組成中之主成分、或酸性基之種類改變了的單體而製成的(甲基)丙烯酸系聚合物時,獲得之保護膜用黏接劑組成物,其熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。 It can be seen that in Examples 11 to 13, even when a (meth)acrylic polymer made from a monomer whose main component in the monomer composition or the type of acidic group is changed is used, the obtained protective film adhesive The adhesive composition has a short curing completion time, is excellent in antistatic properties, has an adhesive force that does not suddenly peel off, and has excellent high-speed peeling properties.
可知實施例14及15中,即使是聚醚改性聚矽氧之含量在0.05質量份以上1.0質量份以下之範圍內有所增減的情況下,熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。 It can be seen that in Examples 14 and 15, even when the content of polyether-modified silicone is increased or decreased within the range of 0.05 parts by mass to 1.0 part by mass, the maturation completion time is short and the antistatic property is excellent. , It has the adhesive force to the extent that it will not peel off suddenly, and it has excellent high-speed peeling performance.
可知實施例16~18中,即使是(甲基)丙烯酸系低聚物之含量有所增減,或即使是不含(甲基)丙烯酸系低聚物及聚醚改性聚矽氧的情況下,熟化完成時間亦短,且抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離性優異。 It can be seen that in Examples 16 to 18, even if the content of (meth)acrylic oligomer is increased or decreased, or even if it does not contain (meth)acrylic oligomer and polyether modified silicone Bottom, the curing completion time is short, and the antistatic property is excellent, it has the adhesive force to the extent that it will not peel off suddenly, and the high-speed peeling property is excellent.
可知比較例1中,使用酸價未達9mgKOH/g之(甲基)丙烯酸系聚合物,故高速剝離性差。可知比較例2中,使用酸價超過70mgKOH/g之(甲基)丙烯酸系聚合物, 故黏接力低,有從被黏體突然剝離的可能性,此外,抗靜電性能差。可知比較例3中,金屬螯合物系交聯劑之當量未達0.3當量,故高速剝離性差。可知比較例4中,金屬螯合物系交聯劑之當量超過2.0當量,故黏接力低,有從被黏體突然剝離的可能性,此外,抗靜電性能差。可知比較例5中,係使用甲苯二異氰酸酯系交聯劑而非金屬螯合物系交聯劑,故抗靜電性差,此外,熟化完成時間亦長。可知比較例6中,係使用六亞甲基二異氰酸酯系交聯劑而非金屬螯合物系交聯劑,故熟化完成時間長。可知比較例7中,係使用環氧系交聯劑,故熟化完成時間長。 It can be seen that in Comparative Example 1, a (meth)acrylic polymer having an acid value of less than 9 mgKOH/g was used, so the high-speed peelability was poor. It can be seen that in Comparative Example 2, a (meth)acrylic polymer with an acid value of more than 70 mgKOH/g was used, Therefore, the adhesive force is low, and there is a possibility of sudden peeling from the adherend. In addition, the antistatic performance is poor. It can be seen that in Comparative Example 3, the equivalent weight of the metal chelate-based crosslinking agent was less than 0.3 equivalent, so the high-speed peelability was poor. It can be seen that in Comparative Example 4, the equivalent weight of the metal chelate-based crosslinking agent exceeds 2.0 equivalents, so the adhesive force is low, and there is a possibility of sudden peeling from the adherend. In addition, the antistatic performance is poor. It can be seen that in Comparative Example 5, a toluene diisocyanate-based crosslinking agent was used instead of a metal chelate-based crosslinking agent, so the antistatic property was poor, and the maturation completion time was also long. It can be seen that in Comparative Example 6, a hexamethylene diisocyanate-based crosslinking agent was used instead of a metal chelate-based crosslinking agent, so the maturation completion time was long. It can be seen that in Comparative Example 7, an epoxy-based crosslinking agent was used, so the maturation completion time was long.
與此相對,可知由本揭示之黏接劑組成物形成的保護膜,熟化完成時間短,抗靜電性優異,具有不會突然剝離之程度的黏接力,高速剝離時之黏接力可壓抑為低。 In contrast, it can be seen that the protective film formed from the adhesive composition of the present disclosure has a short curing completion time, is excellent in antistatic properties, has an adhesive force that does not suddenly peel off, and the adhesive force during high-speed peeling can be suppressed to be low.
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KR101806803B1 (en) * | 2017-09-01 | 2017-12-08 | (주)도은 | Hard coating composition for spectacle lens not-containing organic solvent |
CN109844052B (en) * | 2017-09-25 | 2021-11-23 | 日本电石工业株式会社 | Adhesive composition for protective film and protective film |
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JP6885313B2 (en) * | 2017-11-30 | 2021-06-09 | 東洋インキScホールディングス株式会社 | Adhesives and adhesive sheets |
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KR102236532B1 (en) | 2018-04-25 | 2021-04-06 | 주식회사 엘지화학 | Crosslinkable Composition |
CN109207083B (en) * | 2018-08-29 | 2021-04-23 | 四川羽玺电子科技有限公司 | Hot bending film and preparation method thereof |
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JP6905579B1 (en) * | 2019-12-27 | 2021-07-21 | 株式会社有沢製作所 | Adhesive tape |
JP7308166B2 (en) * | 2020-03-11 | 2023-07-13 | 日本カーバイド工業株式会社 | Adhesive composition for vehicle protective film and vehicle protective film |
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