TWI772483B - Adhesive composition for protective film, and protective film - Google Patents
Adhesive composition for protective film, and protective film Download PDFInfo
- Publication number
- TWI772483B TWI772483B TW107127194A TW107127194A TWI772483B TW I772483 B TWI772483 B TW I772483B TW 107127194 A TW107127194 A TW 107127194A TW 107127194 A TW107127194 A TW 107127194A TW I772483 B TWI772483 B TW I772483B
- Authority
- TW
- Taiwan
- Prior art keywords
- meth
- mass
- isocyanate compound
- polysiloxane
- group
- Prior art date
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明關於保護薄膜用黏著劑組成物及保護薄膜。The present invention relates to an adhesive composition for a protective film and a protective film.
保護薄膜用以保護例如液晶型顯示裝置、有機EL(electroluminescence)型顯示裝置等顯示裝置所使用的光學構件等，而受到廣泛的利用。 保護薄膜疊層於光學構件的表面，保護該光學構件的表面免受污染或損傷，並於不需要表面保護的時候從光學構件剝離去除。因此，保護薄膜要求在剝離後不會污染光學構件(被黏著體)的表面(耐污染性)。Protective films are widely used for protecting optical members and the like used in display devices such as liquid crystal display devices and organic EL (electroluminescence) display devices, for example. The protective film is laminated on the surface of the optical member, protects the surface of the optical member from contamination or damage, and is peeled off from the optical member when surface protection is not required. Therefore, the protective film is required not to contaminate the surface of the optical member (adhered body) after peeling (contamination resistance).
又，從光學構件剝離保護薄膜時，若產生靜電的話，會造成灰塵等附著於光學構件、破壞液晶顯示裝置電路等困擾，故保護薄膜要求可防止在剝離時產生的靜電之性質(抗靜電性)。In addition, when the protective film is peeled off from the optical member, if static electricity is generated, dust and the like may adhere to the optical member, and the circuit of the liquid crystal display device will be damaged. ).
例如，日本特開2015-160907號公報揭示：含有例如具有酸性基及羥基之(甲基)丙烯酸系共聚物、具有反應性基之二甲基聚矽氧烷化合物、及交聯劑之黏著劑組成物，作為能形成可輕易剝離且被黏著體之污染少的黏著薄膜之黏著劑組成物。 例如，日本特開2005-314579號公報揭示：含有鹼金屬鹽，且使用15重量%~100重量%之(甲基)丙烯酸環氧烷(alkylene oxide)加成物作為單體成分之黏著劑組成物，作為抗靜電性優良，對被保護體之污染性降低之黏著劑組成物。For example, Japanese Patent Laid-Open No. 2015-160907 discloses an adhesive containing, for example, a (meth)acrylic copolymer having an acidic group and a hydroxyl group, a dimethylpolysiloxane compound having a reactive group, and a crosslinking agent The composition is used as an adhesive composition that can form an adhesive film that can be easily peeled off and has less contamination by the adhesive. For example, Japanese Patent Laid-Open No. 2005-314579 discloses that an adhesive composition containing an alkali metal salt and using 15% by weight to 100% by weight of an alkylene oxide (meth)acrylic acid adduct as a monomer component As an adhesive composition with excellent antistatic properties and reduced contamination to the protected body.
[發明所欲解決之課題][The problem to be solved by the invention]
近年，針對保護薄膜，對於被黏著體之抗污染的要求提高。發明人們探討後，例如針對日本特開2015-160907號公報及日本特開2005-314579號公報所記載之黏著劑組成物，要求更進一步的耐污染性之改良。 為了更進一步改善耐污染性，考慮例如將二甲基聚矽氧烷化合物等抗靜電助劑及抗靜電劑的添加量減少。但是，僅將抗靜電助劑或抗靜電劑的添加量減少時，抗靜電性會有降低的傾向，故將保護薄膜剝離去除時，會變得容易產生靜電，有可能致生液晶顯示裝置等之瑕疵。因此，習知的黏著劑組成物難以於高水平維持耐污染性與抗靜電性的兼備。In recent years, for protective films, the requirements for anti-contamination of the adherend have increased. After examination by the inventors, for example, the adhesive compositions described in Japanese Patent Laid-Open No. 2015-160907 and Japanese Patent Laid-Open No. 2005-314579 have demanded further improvement in stain resistance. In order to further improve the stain resistance, for example, it is considered to reduce the addition amount of antistatic aids such as dimethylpolysiloxane compounds and antistatic agents. However, when the antistatic auxiliary agent or the amount of antistatic agent added is only reduced, the antistatic property tends to decrease. Therefore, when the protective film is peeled off and removed, static electricity is likely to be generated, which may cause liquid crystal display devices, etc. flaws. Therefore, it is difficult for the conventional adhesive composition to maintain both contamination resistance and antistatic properties at a high level.
本發明係鑑於上述而成，旨在提供耐污染性及抗靜電性優良的保護薄膜用黏著劑組成物以及保護薄膜。 [解決課題之手段]The present invention is made in view of the above, and aims to provide an adhesive composition for protective films and a protective film which are excellent in contamination resistance and antistatic properties. [Means of Solving Problems]
本發明包含下列態樣。 ＜1＞ 一種保護薄膜用黏著劑組成物，含有： 至少具有交聯性官能基之(甲基)丙烯酸系樹脂(A)； 異氰酸酯化合物(B)； 前述異氰酸酯化合物(B)以外之具有聚矽氧烷結構及環氧烷(alkylene oxide)結構之異氰酸酯化合物(C)；及 抗靜電劑(D)， 相對於前述(甲基)丙烯酸系樹脂(A)100質量份，前述異氰酸酯化合物(C)之含量為0.10質量份以上。 ＜2＞ 如＜1＞所記載之保護薄膜用黏著劑組成物，其中，前述異氰酸酯化合物(C)相對於前述異氰酸酯化合物(B)之質量比[(C)/(B)]為1/1~1/20。 ＜3＞ 如＜1＞或＜2＞所記載之保護薄膜用黏著劑組成物，其中，前述異氰酸酯化合物(C)包含下述結構式(1)表示之結構。The present invention includes the following aspects. <1> An adhesive composition for a protective film, comprising: (meth)acrylic resin (A) having at least a crosslinkable functional group; an isocyanate compound (B); a polysilicon other than the aforementioned isocyanate compound (B) Isocyanate compound (C) of oxane structure and alkylene oxide structure; and antistatic agent (D), with respect to 100 parts by mass of the (meth)acrylic resin (A), the isocyanate compound (C) The content is 0.10 parts by mass or more. <2> The adhesive composition for protective films according to <1>, wherein the mass ratio [(C)/(B)] of the isocyanate compound (C) to the isocyanate compound (B) is 1/1 ~1/20. <3> The adhesive composition for protective films according to <1> or <2>, wherein the isocyanate compound (C) has a structure represented by the following structural formula (1).
[化1]
結構式(1)中，r表示1~100之整數，b表示1~100之整數，X表示含有異氰酸酯基之1價有機基。In structural formula (1), r represents an integer of 1 to 100, b represents an integer of 1 to 100, and X represents a monovalent organic group containing an isocyanate group.
＜4＞ 如＜1＞~＜3＞中任一項所記載之保護薄膜用黏著劑組成物，其中，前述異氰酸酯化合物(C)係以下述通式(1-1)表示。<4> The adhesive composition for protective films according to any one of <1> to <3>, wherein the isocyanate compound (C) is represented by the following general formula (1-1).
[化2]
通式(1-1)中，p或q各別獨立地表示0~100之整數，r表示1~100之整數，a表示0~100之整數，b表示1~100之整數，X表示含有異氰酸酯基之1價有機基。In general formula (1-1), p or q independently represent an integer from 0 to 100, r represents an integer from 1 to 100, a represents an integer from 0 to 100, b represents an integer from 1 to 100, and X represents an integer containing Monovalent organic group of isocyanate group.
＜5＞ 如＜1＞~＜4＞中任一項所記載之保護薄膜用黏著劑組成物，其中，前述抗靜電劑(D)為鹼金屬鹽或有機鹽。 ＜6＞ 如＜1＞~＜5＞中任一項所記載之保護薄膜用黏著劑組成物，其係使用於光學構件。 ＜7＞ 一種保護薄膜，具有： 係如＜1＞~＜6＞中任一項所記載之保護薄膜用黏著劑組成物之交聯物之黏著劑層；及 基材。 [發明之效果]<5> The adhesive composition for protective films according to any one of <1> to <4>, wherein the antistatic agent (D) is an alkali metal salt or an organic salt. <6> The adhesive composition for protective films according to any one of <1> to <5>, which is used for an optical member. <7> A protective film comprising: an adhesive layer which is a cross-linked product of the adhesive composition for protective films according to any one of <1> to <6>; and a base material. [Effect of invention]
根據本發明可提供耐污染性及抗靜電性優良的保護薄膜用黏著劑組成物以及保護薄膜。According to the present invention, an adhesive composition for a protective film and a protective film having excellent contamination resistance and antistatic properties can be provided.
以下，針對本發明之黏著劑組成物進行詳細地說明。 另外，在本發明，數值範圍中的「~」意指包含「~」之前後所記載的數值各別作為最小值及最大值。本說明書中階段地記載之數值範圍中，以某數值範圍記載之上限值或下限值也可置換為另一階段性記載的數值範圍之上限值或下限值。又，本說明書所記載的數值範圍中，以某數值範圍記載之上限值或下限值也可置換為實施例所例示之值。 在本說明書，組成物中之各成分的量，在組成物中隸屬各成分之物質存在多種時，除非特別限定，否則意指組成物中所存在的該多種物質之合計量。 本說明書中，理想態樣之組合為更理想之態樣。Hereinafter, the adhesive composition of the present invention will be described in detail. In addition, in this invention, "~" in a numerical range means that the numerical value described before and after "~" is included as a minimum value and a maximum value, respectively. In the numerical range described in steps in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value described in another stepwise description. In addition, in the numerical range described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value illustrated in an Example. In this specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when there are two or more substances belonging to each component in the composition. In this specification, a combination of ideal aspects is a more ideal aspect.
本說明書中，(甲基)丙烯酸系樹脂或(甲基)丙烯酸系寡聚物意指：構成它們的單體之中至少係為主成分之具有(甲基)丙烯醯基之單體聚合而形成的樹脂或寡聚物。 (甲基)丙烯酸系樹脂或(甲基)丙烯酸系寡聚物中的主成分意指：形成樹脂或寡聚物之單體成分之中含有率(質量%)最多者。例如(甲基)丙烯酸系樹脂的情況，係指成為主成分之來自具有(甲基)丙烯醯基之單體之構成單元的含有率為全部構成單元的50質量%以上。 本說明書中，「(甲基)丙烯酸系」意指「丙烯酸系」及「甲基丙烯酸系」中之至少一者，「(甲基)丙烯酸酯」意指「丙烯酸酯」及「甲基丙烯酸酯」中之至少一者，「(甲基)丙烯醯基」意指「丙烯醯基」及「甲基丙烯醯基」中之至少一者。In this specification, (meth)acrylic resin or (meth)acrylic oligomer means that among the monomers constituting them, at least a monomer having a (meth)acryloyl group as the main component is polymerized and obtained resins or oligomers formed. The main component in the (meth)acrylic resin or the (meth)acrylic oligomer means the one with the highest content rate (mass %) among the monomer components forming the resin or the oligomer. For example, in the case of a (meth)acrylic resin, it means that the content rate of the structural unit derived from a monomer having a (meth)acryloyl group serving as the main component is 50 mass % or more of all the structural units. In this specification, "(meth)acrylic" means at least one of "acrylic" and "methacrylic", and "(meth)acrylate" means "acrylate" and "methacrylic" At least one of "ester" and "(meth)acryloyl" means at least one of "acryloyl" and "methacryloyl".
≪保護薄膜用黏著劑組成物≫ 本發明之保護薄膜用黏著劑組成物(以下，亦簡稱「黏著劑組成物」)含有：至少具有交聯性官能基之(甲基)丙烯酸系樹脂(A)、異氰酸酯化合物(B)、前述異氰酸酯化合物(B)以外之具有聚矽氧烷結構及環氧烷結構之異氰酸酯化合物(C)、及抗靜電劑(D)，且相對於前述(甲基)丙烯酸系樹脂(A)100質量份，前述異氰酸酯化合物(C)之含有率為0.10質量份以上。≪Adhesive composition for protective films≫ The adhesive composition for protective films of the present invention (hereinafter, also referred to as “adhesive composition”) contains: a (meth)acrylic resin (A) having at least a crosslinkable functional group. ), an isocyanate compound (B), an isocyanate compound (C) having a polysiloxane structure and an alkylene oxide structure other than the aforementioned isocyanate compound (B), and an antistatic agent (D), and relative to the aforementioned (methyl) The content rate of the said isocyanate compound (C) is 0.10 mass part or more with respect to 100 mass parts of acrylic resins (A).
藉由使黏著劑組成物具有上述構成，能形成耐污染性及抗靜電性優良的黏著劑層。該理由尚未明確，但推測如下。By making the adhesive composition have the above-mentioned structure, an adhesive layer excellent in contamination resistance and antistatic property can be formed. The reason for this has not been clarified, but is presumed as follows.
已知具有環氧烷結構之聚矽氧化合物通常係作為抗靜電助劑而發揮作用。含有抗靜電劑與具有環氧烷結構之聚矽氧化合物之黏著劑組成物，在剛塗佈於基材上時，聚矽氧化合物中之環氧烷結構會以配位於抗靜電劑之狀態而局部存在於黏著劑層的表面附近，故即使黏著劑組成物所含的抗靜電劑為少量，本發明之黏著劑組成物所形成的黏著劑層之抗靜電性仍會輕易展現。 另一方面，已知上述聚矽氧化合物容易局部存在於黏著劑層的表面附近，故容易因轉移而成為污染被黏著體的表面之要因之一。It is known that polysiloxanes having an alkylene oxide structure generally function as antistatic additives. An adhesive composition containing an antistatic agent and a polysiloxane with an alkylene oxide structure. When it is just coated on a substrate, the alkylene oxide structure in the polysiloxane will be in the state of being coordinated with the antistatic agent. Since it is locally present near the surface of the adhesive layer, even if the antistatic agent contained in the adhesive composition is small, the antistatic property of the adhesive layer formed by the adhesive composition of the present invention can be easily exhibited. On the other hand, it is known that the above-mentioned polysiloxane compound is easily localized in the vicinity of the surface of the adhesive layer, and thus easily becomes one of the factors that contaminate the surface of the adherend due to transfer.
利用含有至少具有交聯性官能基之(甲基)丙烯酸系樹脂(A)與一定量以上之異氰酸酯化合物(B)以外之具有聚矽氧烷結構及環氧烷結構之異氰酸酯化合物(C)(以下，亦簡稱「聚矽氧系異氰酸酯化合物(C)」)之黏著劑組成物而形成的黏著劑層，聚矽氧系異氰酸酯化合物(C)會局部存在於表面附近，然後，聚矽氧系異氰酸酯化合物(C)中的異氰酸酯(NCO)基與(甲基)丙烯酸系樹脂(A)中的交聯性官能基會反應而形成交聯結構。據推測因交聯結構的形成，聚矽氧系異氰酸酯化合物(C)會保持在錨定於黏著劑層中之狀態。因此，將保護薄膜從被黏著體剝離時，可抑制黏著劑組成物中所含的例如抗靜電劑及抗靜電助劑(以下，亦稱為「污染成分」)轉移到被黏著體表面，由本發明之黏著劑組成物形成的黏著劑層會展現優良的耐污染性。 又，據推測聚矽氧系異氰酸酯化合物(C)由於在分子中具有聚矽氧烷結構，故表面自由能量變低，不易和(甲基)丙烯酸系樹脂(A)相容，而聚矽氧系異氰酸酯化合物(C)則會局部存在於黏著劑層的表面附近。此外，聚矽氧系異氰酸酯化合物(C)由於在分子中具有環氧烷結構，故作為抗靜電助劑與一般而言所使用的具有環氧烷結構之聚矽氧化合物同樣，會和抗靜電劑進行配位。因此，能使抗靜電劑局部存在到黏著劑層表面，而由本發明之黏著劑組成物形成的黏著劑層即使少量的抗靜電劑仍會展現優良的抗靜電性能。Using the isocyanate compound (C) having a polysiloxane structure and an alkylene oxide structure other than the (meth)acrylic resin (A) having at least a crosslinkable functional group and a certain amount or more of the isocyanate compound (B) ( Hereinafter, also referred to as the "polysiloxane-based isocyanate compound (C)"), the adhesive layer is formed from the adhesive composition. The polysiloxane-based isocyanate compound (C) is locally present near the surface, and then the polysiloxane-based isocyanate compound (C) The isocyanate (NCO) group in the isocyanate compound (C) and the crosslinkable functional group in the (meth)acrylic resin (A) react to form a crosslinked structure. It is presumed that the polysiloxane-based isocyanate compound (C) is kept in a state of being anchored in the adhesive layer due to the formation of the cross-linked structure. Therefore, when the protective film is peeled off from the adherend, for example, the antistatic agent and antistatic auxiliary (hereinafter, also referred to as "contamination component") contained in the adhesive composition can be inhibited from transferring to the surface of the adherend. The adhesive layer formed by the adhesive composition of the invention exhibits excellent stain resistance. In addition, it is presumed that the polysiloxane-based isocyanate compound (C) has a polysiloxane structure in the molecule, so the surface free energy becomes low, and it is difficult to be compatible with the (meth)acrylic resin (A). The isocyanate-based compound (C) is locally present in the vicinity of the surface of the adhesive layer. In addition, since the polysiloxane-based isocyanate compound (C) has an alkylene oxide structure in the molecule, as an antistatic auxiliary agent, like the polysiloxane compound having an alkylene oxide structure that is generally used, it has the same effect as an antistatic agent. agent for coordination. Therefore, the antistatic agent can be locally present on the surface of the adhesive layer, and the adhesive layer formed by the adhesive composition of the present invention can still exhibit excellent antistatic performance even with a small amount of the antistatic agent.
綜上，本發明之黏著劑組成物適於耐污染性及抗靜電性優良的黏著劑層之形成。 以下，針對本發明之黏著劑組成物所使用的各成分的詳細內容進行說明。In conclusion, the adhesive composition of the present invention is suitable for the formation of an adhesive layer with excellent contamination resistance and antistatic properties. Hereinafter, the details of each component used in the adhesive composition of the present invention will be described.
＜(甲基)丙烯酸系樹脂(A)＞ 黏著劑組成物含有至少具有交聯性官能基之(甲基)丙烯酸系樹脂(A)(以下，亦稱為「特定(甲基)丙烯酸系樹脂」)。特定(甲基)丙烯酸系樹脂中的交聯性官能基，與後述異氰酸酯化合物(B)及聚矽氧系異氰酸酯化合物(C)反應，而形成交聯結構。聚矽氧系異氰酸酯化合物(C)由於會和特定(甲基)丙烯酸系樹脂反應而形成交聯結構，故聚矽氧系異氰酸酯化合物(C)容易保持在錨定於黏著劑層中之狀態。藉此，在剝離保護薄膜時，會抑制污染成分轉移到被黏著體，由黏著劑組成物形成的黏著劑層之耐污染性優良。<(Meth)acrylic resin (A)> The adhesive composition contains at least a (meth)acrylic resin (A) having a crosslinkable functional group (hereinafter, also referred to as "specific (meth)acrylic resin) ”). The crosslinkable functional group in the specific (meth)acrylic resin reacts with the later-described isocyanate compound (B) and polysiloxane-based isocyanate compound (C) to form a crosslinked structure. Since the polysiloxane-based isocyanate compound (C) reacts with the specific (meth)acrylic resin to form a cross-linked structure, the polysiloxane-based isocyanate compound (C) is easily maintained in a state anchored in the adhesive layer. Thereby, when the protective film is peeled off, the transfer of contamination components to the adherend is suppressed, and the adhesive layer formed of the adhesive composition is excellent in contamination resistance.
特定(甲基)丙烯酸系樹脂至少具有交聯性官能基。特定(甲基)丙烯酸系樹脂可為具有交聯性官能基之(甲基)丙烯酸系單體進行均聚合而形成的樹脂，也可為不具交聯性官能基之具有(甲基)丙烯醯基之單體與具有交聯性官能基之單體利用加成聚合反應而形成的樹脂。The specific (meth)acrylic resin has at least a crosslinkable functional group. The specific (meth)acrylic resin may be a resin formed by homopolymerizing a (meth)acrylic monomer having a crosslinkable functional group, or may be a (meth)acryloyl group having no crosslinkable functional group. It is a resin formed by addition polymerization of a monomer having a crosslinkable functional group and a monomer having a crosslinkable functional group.
就具有交聯性官能基之單體而言，若能和後述異氰酸酯化合物(B)及聚矽氧系異氰酸酯化合物(C)形成交聯結構，則無特別限制。 就具有交聯性官能基之單體而言，可列舉具有羧基、羥甲基、羥基、環氧丙基、醯胺基、胺基等之單體。 它們之中，考慮和聚矽氧系異氰酸酯化合物(C)之反應性的觀點，就交聯性官能基而言，宜選自於由羧基、羥基、胺基及環氧丙基構成之群組中之至少1種，選自於由羧基及羥基構成之群組中之至少一者更佳。 具有交聯性官能基之單體可單獨使用1種，或也可將2種以上合併使用。The monomer having a crosslinkable functional group is not particularly limited as long as it can form a crosslinked structure with the isocyanate compound (B) and the polysiloxane-based isocyanate compound (C) described later. As a monomer which has a crosslinkable functional group, the monomer which has a carboxyl group, a methylol group, a hydroxyl group, a glycidyl group, an amide group, an amine group, etc. is mentioned. Among them, from the viewpoint of reactivity with the polysiloxane-based isocyanate compound (C), the crosslinkable functional group is preferably selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and a glycidyl group At least one of them is more preferably at least one selected from the group consisting of a carboxyl group and a hydroxyl group. The monomer which has a crosslinkable functional group may be used individually by 1 type, or may be used in combination of 2 or more types.
又，特定(甲基)丙烯酸系樹脂宜含有2種以上之來自具有交聯性官能基之單體之構成單元，含有來自具有羧基之單體之構成單元與來自具有羥基之單體之構成單元更佳。Furthermore, the specific (meth)acrylic resin preferably contains two or more structural units derived from a monomer having a crosslinkable functional group, a structural unit derived from a monomer having a carboxyl group, and a structural unit derived from a monomer having a hydroxyl group better.
就具有羧基之單體而言，並無特別限制，例如可列舉：丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、富馬酸、巴豆酸、伊康酸、檸康酸、桂皮酸、2-(甲基)丙烯醯氧乙基琥珀酸、馬來酸(甲基)丙烯酸單羥乙酯、富馬酸(甲基)丙烯酸單羥乙酯、苯二甲酸(甲基)丙烯酸單羥乙酯、1,2-二羧基環己烷(甲基)丙烯酸單羥乙酯、(甲基)丙烯酸二聚物及ω-羧基-聚己內酯單(甲基)丙烯酸酯。 具有羧基之單體可單獨使用1種，或也可將2種以上合併使用。The monomer having a carboxyl group is not particularly limited, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, 2-(meth)acryloyloxyethylsuccinic acid, monohydroxyethyl maleic acid (meth)acrylate, monohydroxyethyl fumaric acid (meth)acrylate, monohydroxyphthalic acid (meth)acrylate Ethyl ester, 1,2-dicarboxycyclohexane (meth)acrylate monohydroxyethyl, (meth)acrylic acid dimer and ω-carboxy-polycaprolactone mono(meth)acrylate. The monomer which has a carboxyl group may be used individually by 1 type, or may be used in combination of 2 or more types.
考慮和後述聚矽氧系異氰酸酯化合物(C)之反應性的觀點，就具有羧基之單體而言，宜含有選自於由丙烯酸、甲基丙烯酸、伊康酸及ω-羧基-聚己內酯單(甲基)丙烯酸酯構成之群組中之至少1種，含有選自於由丙烯酸、甲基丙烯酸及ω-羧基-聚己內酯單(甲基)丙烯酸酯構成之群組中之至少1種更佳，含有丙烯酸又更佳。From the viewpoint of reactivity with the polysiloxane-based isocyanate compound (C) described later, the monomer having a carboxyl group preferably contains a monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and ω-carboxyl-polycaprolactone. At least one kind selected from the group consisting of acrylic acid, methacrylic acid and ω-carboxy-polycaprolactone mono(meth)acrylate At least 1 type is more preferable, and it is more preferable to contain acrylic acid.
就具有羥基之單體而言，例如可列舉：(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-4-羥丁酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-6-羥己酯、(甲基)丙烯酸-10-羥癸酯、(甲基)丙烯酸-12-羥月桂酯及(甲基)丙烯酸-3-甲基-3-羥丁酯。Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( 3-Hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and (meth)acrylate )-3-methyl-3-hydroxybutyl acrylate.
考慮和後述聚矽氧系異氰酸酯化合物(C)之反應性的觀點，就具有羥基之單體而言，宜含有選自於由(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-4-羥丁酯及(甲基)丙烯酸-6-羥己酯構成之群組中之至少1種，含有選自於由(甲基)丙烯酸-2-羥乙酯及(甲基)丙烯酸-4-羥丁酯構成之群組中之至少一者更佳。From the viewpoint of reactivity with the polysiloxane-based isocyanate compound (C) described later, the monomer having a hydroxyl group preferably contains a monomer selected from the group consisting of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid -At least one kind selected from the group consisting of -4-hydroxybutyl ester and -6-hydroxyhexyl (meth)acrylate, containing selected from the group consisting of -2-hydroxyethyl (meth)acrylate and (meth)acrylic acid More preferably, at least one of the group consisting of -4-hydroxybutyl ester.
來自具有交聯性官能基之單體之構成單元之含有率，相對於特定(甲基)丙烯酸系樹脂之全部構成單元，宜為0.1質量%~10質量%。 來自具有交聯性官能基之單體之構成單元之含有率為0.1質量%~10質量%的話，可和後述異氰酸酯化合物(B)及聚矽氧系異氰酸酯化合物(C)中之至少一者反應並充分形成交聯結構，能更抑制污染成分轉移到被黏著體。 考慮上述觀點，就來自具有交聯性官能基之單體之構成單元之含有率而言，宜為0.5質量%~8質量%，為1質量%~5質量%更佳。It is preferable that the content rate of the structural unit derived from the monomer which has a crosslinkable functional group is 0.1 mass % - 10 mass % with respect to all the structural units of a specific (meth)acrylic-type resin. When the content rate of the constituent unit derived from the monomer having a crosslinkable functional group is 0.1% by mass to 10% by mass, it can react with at least one of the isocyanate compound (B) and the polysiloxane-based isocyanate compound (C) described later. And fully form a cross-linked structure, which can further inhibit the transfer of contaminant components to the adherend. Considering the above-mentioned viewpoint, the content rate of the structural unit derived from the monomer having a crosslinkable functional group is preferably 0.5% by mass to 8% by mass, and more preferably 1% by mass to 5% by mass.
特定(甲基)丙烯酸系樹脂含有具有羧基之單體作為來自具有交聯性官能基之單體之構成單元時，來自具有羧基之單體之構成單元之含有率，相對於特定(甲基)丙烯酸系樹脂之全部構成單元，宜為0.1質量%~5質量%。 來自具有羧基之單體之構成單元之含有率為0.1質量%~5質量%的話，可和後述異氰酸酯化合物(B)及聚矽氧系異氰酸酯化合物(C)中之至少一者反應並充分形成交聯結構，能更抑制污染成分轉移到被黏著體。 考慮上述觀點，來自具有羧基之單體之構成單元之含有率為0.2質量%~5質量%更佳，為0.3質量%~3質量%又更佳。When a specific (meth)acrylic resin contains a monomer having a carboxyl group as a structural unit derived from a monomer having a crosslinkable functional group, the content rate of the structural unit derived from a monomer having a carboxyl group relative to the specific (methyl) All the structural units of the acrylic resin are preferably 0.1% by mass to 5% by mass. When the content rate of the structural unit derived from the monomer having a carboxyl group is 0.1% by mass to 5% by mass, it can react with at least one of the isocyanate compound (B) and the polysiloxane-based isocyanate compound (C) described later to sufficiently form a cross-linked compound. The combined structure can further inhibit the transfer of contaminant components to the adherend. Considering the above-mentioned viewpoint, the content rate of the structural unit derived from the monomer having a carboxyl group is more preferably 0.2 to 5 mass %, and still more preferably 0.3 to 3 mass %.
特定(甲基)丙烯酸系樹脂含有具有羥基之單體作為來自具有交聯性官能基之單體之構成單元時，來自具有羥基之單體之構成單元之含有率，相對於特定(甲基)丙烯酸系樹脂之全部構成單元，宜為0.5質量%~10質量%。 來自具有羥基之單體之構成單元之含有率為0.5質量%~10質量%的話，可和後述異氰酸酯化合物(B)反應並充分形成交聯結構，能更抑制污染成分轉移到被黏著體。 考慮上述觀點，來自具有羥基之單體之構成單元之含有率為1質量%~9質量%更佳，為2質量%~8質量%又更佳。When a specific (meth)acrylic resin contains a monomer having a hydroxyl group as a structural unit derived from a monomer having a crosslinkable functional group, the content rate of the structural unit derived from a monomer having a hydroxyl group relative to the specific (methyl) It is preferable that all the structural units of an acrylic resin are 0.5 mass % - 10 mass %. When the content rate of the structural unit derived from the monomer having a hydroxyl group is 0.5% by mass to 10% by mass, it can react with the isocyanate compound (B) described later to sufficiently form a cross-linked structure, thereby further suppressing the transfer of contaminant components to the adherend. Considering the above-mentioned viewpoint, the content rate of the structural unit derived from the monomer having a hydroxyl group is more preferably 1 to 9 mass %, and even more preferably 2 to 8 mass %.
特定(甲基)丙烯酸系樹脂含有上述來自具有交聯性官能基之單體之構成單元，此外也可更含有來自不具交聯性官能基之(甲基)丙烯酸烷基酯之構成單元。 特定(甲基)丙烯酸系樹脂含有來自不具交聯性官能基之(甲基)丙烯酸烷基酯之構成單元時，就不具交聯性官能基之(甲基)丙烯酸烷基酯而言，宜為無取代之(甲基)丙烯酸烷基酯，其種類並無特別限制。 (甲基)丙烯酸烷基酯之烷基為直鏈狀或支鏈狀中之任一均可。(甲基)丙烯酸烷基酯之烷基的碳數宜為1~18之範圍，為1~12之範圍更佳。烷基的碳數在上述範圍內的話，適於保護薄膜之黏接性有更優良的傾向。A specific (meth)acrylic-type resin may contain the structural unit derived from the monomer which has the above-mentioned crosslinkable functional group, and may further contain the structural unit derived from the (meth)acrylic acid alkyl ester which does not have a crosslinkable functional group. When the specific (meth)acrylic resin contains a structural unit derived from an alkyl (meth)acrylate without a crosslinkable functional group, the alkyl (meth)acrylate without a crosslinkable functional group is suitable. It is an unsubstituted alkyl (meth)acrylate, and the kind is not particularly limited. The alkyl group of the alkyl (meth)acrylate may be linear or branched. The carbon number of the alkyl group of the alkyl (meth)acrylate is preferably in the range of 1 to 18, more preferably in the range of 1 to 12. When the carbon number of the alkyl group is within the above range, the adhesiveness suitable for the protective film tends to be more excellent.
就(甲基)丙烯酸烷基酯而言，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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸正十二烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯及(甲基)丙烯酸異莰酯。 (甲基)丙烯酸烷基酯可單獨使用1種，或也可將2種以上合併使用。Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, Secondary butyl (meth)acrylate, tertiary 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, stearyl (meth)acrylate, ( Cyclohexyl meth)acrylate and isobornyl (meth)acrylate. Alkyl (meth)acrylate may be used individually by 1 type, or may be used in combination of 2 or more types.
考慮可獲得適於保護薄膜之黏接性的觀點，就(甲基)丙烯酸烷基酯而言，宜包含選自於由(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯及(甲基)丙烯酸-2-乙基己酯構成之群組中之至少1種。From the viewpoint of obtaining the adhesiveness suitable for the protective film, the alkyl (meth)acrylate preferably contains a compound selected from the group consisting of ethyl (meth)acrylate, n-butyl (meth)acrylate and (meth)acrylate At least one of the group consisting of meth)acrylate-2-ethylhexyl.
考慮改善對被黏著體之黏接性的觀點，就來自(甲基)丙烯酸烷基酯之構成單元之含有率而言，將對於特定(甲基)丙烯酸系樹脂之全部構成單元，宜為70.0質量%~99.99質量%，為80.0質量%~99.9質量%更佳，為85.0質量%~99.9質量%又更佳，為85.0質量%~99.0質量%特佳。From the viewpoint of improving the adhesiveness to the adherend, the content of the structural unit derived from the alkyl (meth)acrylate is preferably 70.0 for all the structural units of the specific (meth)acrylic resin. Mass % to 99.99 mass %, more preferably 80.0 mass % to 99.9 mass %, still more preferably 85.0 mass % to 99.9 mass %, and particularly preferably 85.0 mass % to 99.0 mass %.
特定(甲基)丙烯酸系樹脂中，在會發揮本發明之效果的範圍內，也可含有來自於來自具有交聯性官能基之單體之構成單元及來自(甲基)丙烯酸烷基酯之構成單元以外之其他單體之構成單元(以下也稱為「其他構成單元」)。構成其他構成單元之單體，若為可和具有交聯性官能基之單體共聚者，則無特別限制，可因應目的而適當選擇。The specific (meth)acrylic resin may contain a structural unit derived from a monomer having a crosslinkable functional group and a unit derived from an alkyl (meth)acrylate within the range in which the effect of the present invention is exhibited. Structural units of other monomers other than the structural units (hereinafter also referred to as "other structural units"). The monomer constituting the other structural unit is not particularly limited as long as it is copolymerizable with the monomer having a crosslinkable functional group, and can be appropriately selected according to the purpose.
就構成其他構成單元之單體而言，例如可列舉：多官能丙烯酸系單體、芳香族單乙烯系單體。As a monomer which comprises another structural unit, a polyfunctional acrylic monomer and an aromatic monovinyl type monomer are mentioned, for example.
就多官能丙烯酸系單體而言，例如可列舉：二(甲基)丙烯酸-1,4-丁二醇酯、二(甲基)丙烯酸-1,6-己二醇酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸聚乙二醇酯、己內酯改性二(甲基)丙烯酸二環戊烯酯、環氧乙烷改性二(甲基)丙烯酸酯、異氰尿酸二(甲基)丙烯醯氧基乙酯、二(甲基)丙烯酸三環癸烷二甲醇酯、二(甲基)丙烯酸二羥甲基二環戊烷酯、環氧乙烷改性六氫苯二甲酸二(甲基)丙烯酸酯、新戊二醇改性二(甲基)丙烯酸三甲基丙烷酯、三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸二新戊四醇酯、四(甲基)丙烯酸二甘油酯、四(甲基)丙烯酸新戊四醇酯、六(甲基)丙烯酸二新戊四醇酯。The polyfunctional acrylic monomers include, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and bis(meth)acrylate. ) Neopentyl glycol acrylate, polyethylene glycol di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate , Di(meth)acryloyloxyethyl isocyanurate, tricyclodecane dimethanol di(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, ethylene oxide Modified hexahydrophthalate di(meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(methyl)propane ) Dipivalerythritol acrylate, Diglycerol tetra(meth)acrylate, Neotaerythritol tetra(meth)acrylate, Dipivalerythritol hexa(meth)acrylate.
就芳香族單乙烯系單體而言，例如可列舉：苯乙烯、α-甲基苯乙烯、三級丁基苯乙烯、對氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯。As an aromatic monovinyl-type monomer, styrene, (alpha)-methylstyrene, tertiary butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyltoluene are mentioned, for example.
就特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)而言，宜為10萬~190萬。特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)在上述範圍的話，本發明之保護薄膜用黏著劑組成物所形成的黏著劑層會有更容易顯現適於保護薄膜之黏接性的傾向。 考慮上述觀點，就特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)而言，為30萬~180萬更佳，為40萬~150萬再更佳，為40萬~130萬特佳，為40萬~100萬最佳。The weight average molecular weight (Mw) of the specific (meth)acrylic resin is preferably 100,000 to 1,900,000. When the weight-average molecular weight (Mw) of the specific (meth)acrylic resin is within the above range, the adhesive layer formed by the adhesive composition for protective films of the present invention can more easily exhibit adhesiveness suitable for protective films. tendency. Considering the above viewpoints, the weight average molecular weight (Mw) of the specific (meth)acrylic resin is preferably 300,000 to 1.8 million, more preferably 400,000 to 1.5 million, and particularly preferably 400,000 to 1.3 million , 400,000 to 1,000,000 is the best.
特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)係利用下述方法測得的值。 (重量平均分子量(Mw)之測定方法) 依循下述(1)~(3)進行測定。 (1)將特定(甲基)丙烯酸系樹脂之溶液塗佈於剝離紙，於100℃乾燥1分鐘，獲得薄膜狀之特定(甲基)丙烯酸系樹脂。 (2)使用上述(1)所得到的薄膜狀之特定(甲基)丙烯酸系樹脂與四氫呋喃，獲得固體成分濃度為0.2質量%之樣本溶液。 (3)以下述條件，使用凝膠滲透層析(GPC)，以標準聚苯乙烯換算值的形式，測定特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)。 (條件) GPC：HLC-8220 GPC[東曹(股)製] 管柱：使用TSK-GEL GMHXL 移動相溶劑：四氫呋喃 流速：0.6mL/分鐘 管柱溫度：40℃The weight average molecular weight (Mw) of a specific (meth)acrylic-type resin is the value measured by the following method. (Measurement method of weight average molecular weight (Mw)) The measurement was carried out in accordance with the following (1) to (3). (1) The solution of a specific (meth)acrylic-type resin was apply|coated to a release paper, and it dried at 100 degreeC for 1 minute, and obtained the specific (meth)acrylic-type resin in a film form. (2) A sample solution having a solid content concentration of 0.2 mass % was obtained using the film-like specific (meth)acrylic resin and tetrahydrofuran obtained in the above (1). (3) The weight average molecular weight (Mw) of a specific (meth)acrylic-type resin was measured as a standard polystyrene conversion value using gel permeation chromatography (GPC) under the following conditions. (Conditions) GPC: HLC-8220 GPC [manufactured by Tosoh Corporation] Column: TSK-GEL GMHXL Mobile Phase Solvent: Tetrahydrofuran Flow Rate: 0.6 mL/min Column Temperature: 40°C
考慮剝離性的觀點，特定(甲基)丙烯酸系樹脂之玻璃轉移溫度宜為-40℃以下，為-50℃以下更佳。From the viewpoint of releasability, the glass transition temperature of the specific (meth)acrylic resin is preferably -40°C or lower, more preferably -50°C or lower.
特定(甲基)丙烯酸系樹脂之玻璃轉移溫度(Tg)係利用下式之計算而求得的莫耳平均玻璃轉移溫度。 1/Tg=m1 /Tg1 ＋m2 /Tg2 ＋･･･＋m(k-1) /Tg(k-1) ＋mk /Tgk ･･･(式1) 式1中，Tg1 、Tg2 、･･･、Tg(k-1) 、Tgk 係以將構成特定(甲基)丙烯酸系樹脂之各單體製成均聚物時之絕對溫度(K)來表示之玻璃轉移溫度。m1 、m2 、･･･、m(k-1) 、mk 各別表示構成特定(甲基)丙烯酸系樹脂之各單體的莫耳分率，且m1 ＋m2 ＋･･･＋m(k-1) ＋mk =1。The glass transition temperature (Tg) of a specific (meth)acrylic resin is the molar average glass transition temperature calculated|required by the following formula. 1/Tg=m 1 /Tg 1 ＋m 2 /Tg 2 ＋･･･＋m (k-1) /Tg (k-1) ＋m k /Tg k ･･･(Formula 1) In Formula 1, Tg 1 , Tg 2 ,･･･, Tg (k-1) , Tg k are glass transition temperatures represented by the absolute temperature (K) at which each monomer constituting the specific (meth)acrylic resin is made into a homopolymer . m 1 , m 2 , ･･･, m (k-1) , and m k each represent the molar fraction of each monomer constituting the specific (meth)acrylic resin, and m 1 +m 2 +･･･ +m (k-1) +m k =1.
另外，「以製成均聚物時之絕對溫度(K)來表示之玻璃轉移溫度」係指：以將該單體進行均聚合而製得的均聚物之絕對溫度(K)來表示之玻璃轉移溫度。均聚物之玻璃轉移溫度係將該均聚物使用差示掃描熱量測定裝置(DSC)(Seiko Instruments(股)製，EXSTAR6000)，以在氮氣流中、測定樣本10mg、昇溫速度10℃/分鐘之條件實施測定，並令得到的DSC曲線之反曲點為均聚物之玻璃轉移溫度。In addition, "glass transition temperature expressed by the absolute temperature (K) of the homopolymer" means: expressed by the absolute temperature (K) of the homopolymer obtained by homopolymerizing the monomer glass transition temperature. The glass transition temperature of the homopolymer was measured using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Co., Ltd., EXSTAR6000) for the homopolymer to measure 10 mg of a sample in a nitrogen stream, and a heating rate of 10°C/min. The measurement was carried out under the same conditions, and the inflection point of the obtained DSC curve was the glass transition temperature of the homopolymer.
具代表性的單體之「均聚物以攝氏溫度(℃)來表示之玻璃轉移溫度」如下：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℃；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℃。 例如，藉由使用這些具代表性的單體，可適當調整上述玻璃轉移溫度。The "glass transition temperature of homopolymer expressed in degrees Celsius (°C)" of representative monomers is as follows: methyl acrylate is 5°C; ethyl acrylate is -27°C; methyl methacrylate is 103°C; -57°C for n-butyl acrylate; -76°C for -2-ethylhexyl acrylate; -65°C for n-octyl acrylate; -58°C for isooctyl acrylate; -58°C for isononyl acrylate; is 163°C; ω-carboxy-polycaprolactone (n≒2) monoacrylate is -30°C; 2-propenyloxyethyl-succinic acid is -40°C. For example, by using these representative monomers, the above-mentioned glass transition temperature can be appropriately adjusted.
黏著劑組成物中的特定(甲基)丙烯酸系樹脂之含有率可因應目的而適當選擇。就特定(甲基)丙烯酸系樹脂之含有率而言，在黏著劑組成物之固體成分總質量中，宜為80質量%~99質量%，為85質量%~99質量%更佳，90質量%~98質量%再更佳。 另外，固體成分總質量意指從黏著劑組成物去除溶劑等揮發性成分後之殘渣的總質量。The content rate of the specific (meth)acrylic resin in the adhesive composition can be appropriately selected according to the purpose. Regarding the content rate of the specific (meth)acrylic resin, in the total mass of the solid content of the adhesive composition, it is preferably 80% by mass to 99% by mass, more preferably 85% by mass to 99% by mass, and 90% by mass. % to 98% by mass is even better. In addition, the total mass of solid content means the total mass of the residue after removing volatile components, such as a solvent, from an adhesive composition.
＜異氰酸酯化合物(B)＞ 本發明之黏著劑組成物含有異氰酸酯化合物(B)。異氰酸酯化合物(B)係和特定(甲基)丙烯酸系樹脂中之交聯性官能基反應並形成交聯結構。藉此，能對本發明之黏著劑組成物所形成的黏著劑層賦予適當的硬度。又，能對黏著劑層賦予作為保護薄膜所必要的黏著力，同時可保有適於保護薄膜之用途的剝離性。<Isocyanate Compound (B)> The adhesive composition of the present invention contains an isocyanate compound (B). The isocyanate compound (B) reacts with the crosslinkable functional group in the specific (meth)acrylic resin to form a crosslinked structure. Thereby, appropriate hardness can be imparted to the adhesive layer formed of the adhesive composition of the present invention. Moreover, the adhesive force required as a protective film can be given to an adhesive bond layer, and the peelability suitable for the use of a protective film can be maintained.
就異氰酸酯化合物(B)而言，若能和特定(甲基)丙烯酸系樹脂中的交聯性官能基反應，則無特別限制，例如可列舉：以二異氰酸伸二甲苯酯、二異氰酸二苯基甲烷酯、三異氰酸三苯基甲烷酯、二異氰酸甲苯酯為代表之芳香族多異氰酸酯化合物；二異氰酸六亞甲酯、異佛爾酮二異氰酸酯、芳香族多異氰酸酯化合物之氫化物為代表之鏈狀或環狀之脂肪族多異氰酸酯化合物等雙官能以上之多異氰酸酯化合物；以及這些多異氰酸酯化合物之縮二脲、二聚物(例如脲二酮(uretdione)改性物)、三聚物(例如異氰尿酸酯改性物、亞胺基
它們之中，考慮和交聯性官能基之反應性的觀點，就異氰酸酯化合物(B)而言，宜為鏈狀或環狀之脂肪族多異氰酸酯化合物、鏈狀或環狀之脂肪族多異氰酸酯化合物之二聚物、鏈狀或環狀之脂肪族多異氰酸酯化合物與多元醇化合物之加成物、包含鏈狀或環狀之脂肪族多異氰酸酯化合物之異氰尿酸酯改性物之三聚物或五聚物、或來自鏈狀或環狀之脂肪族多異氰酸酯化合物之縮二脲等之多異氰酸酯化合物。 此外，考慮反應性優良可提高交聯密度且和特定(甲基)丙烯酸系樹脂之相容性優良的觀點，就異氰酸酯化合物(B)而言，宜為選自於由二異氰酸六亞甲酯之異氰尿酸酯改性物及異佛爾酮二異氰酸酯構成之群組中之至少一者，為二異氰酸六亞甲酯之異氰尿酸酯改性物更佳。Among them, from the viewpoint of reactivity with the crosslinkable functional group, the isocyanate compound (B) is preferably a chain or cyclic aliphatic polyisocyanate compound, a chain or cyclic aliphatic polyisocyanate Dimers of compounds, adducts of chain or cyclic aliphatic polyisocyanate compounds and polyol compounds, trimerization of isocyanurate modified products containing chain or cyclic aliphatic polyisocyanate compounds Polyisocyanate compounds such as biuret compounds or pentamers, or biurets derived from linear or cyclic aliphatic polyisocyanate compounds. In addition, considering the excellent reactivity, the crosslinking density can be increased, and the compatibility with the specific (meth)acrylic resin is excellent, the isocyanate compound (B) is preferably selected from the group consisting of hexamethylene diisocyanate At least one of the group consisting of the isocyanurate modified product of methyl ester and isophorone diisocyanate is more preferably the modified isocyanurate of hexamethylene diisocyanate.
異氰酸酯化合物(B)也可使用市售品。就市售品而言，例如可適當使用以如下商品名而市售者：「CORONATE HX」、「CORONATE HL-S」、「CORONATE L」、「CORONATE 2031」、「CORONATE 2030」、「CORONATE 2037」、「CORONATE 2234」、「CORONATE 2785」、「CORONATE T-80」、「AQUANATE 200」、及「AQUANATE 210」及「HDI」[以上為東曹(股)製]；「SUMIDUR N-3300」、「DESMODUR N-3400」、「SUMIDUR N-75」及「DESMODUR I」[以上為Sumika Covestro Urethane公司製]；「DURANATE E-405-80T」、「DURANATE 24A-100」及「DURANATE TSE-100」[以上為旭化成(股)製]、以及「TAKENATE 500」、「TAKENATE 600」、「TAKENATE D-110N」、「TAKENATE D-120N」、「TAKENATE M-631N」及「MT-OLESTER NP1200」[以上為三井化學(股)製]。A commercial item can also be used for the isocyanate compound (B). As a commercially available product, for example, those marketed under the following trade names can be appropriately used: "CORONATE HX", "CORONATE HL-S", "CORONATE L", "CORONATE 2031", "CORONATE 2030", "CORONATE 2037" ", "CORONATE 2234", "CORONATE 2785", "CORONATE T-80", "AQUANATE 200", and "AQUANATE 210" and "HDI" [the above are Tosoh Corporation]; "SUMIDUR N-3300" , "DESMODUR N-3400", "SUMIDUR N-75" and "DESMODUR I" (the above are manufactured by Sumika Covestro Urethane); "DURANATE E-405-80T", "DURANATE 24A-100" and "DURANATE TSE-100" ” [The above are manufactured by Asahi Kasei Corporation], and “TAKENATE 500”, “TAKENATE 600”, “TAKENATE D-110N”, “TAKENATE D-120N”, “TAKENATE M-631N” and “MT-OLESTER NP1200” [ The above is made by Mitsui Chemicals Co., Ltd.].
就異氰酸酯化合物(B)(使用2種以上時為總含量)之含量而言，相對於特定(甲基)丙烯酸系樹脂100質量份，宜為0.5質量份~8.0質量份，為1.0質量份~7.0質量份更佳，為3.0質量份~6.0質量份再更佳。 異氰酸酯化合物(B)之含量在上述範圍內的話，會有更抑制從被黏著體之剝離，且保有更適於保護薄膜之用途的黏著力之傾向。The content of the isocyanate compound (B) (total content when two or more types are used) is preferably 0.5 parts by mass to 8.0 parts by mass, and 1.0 parts by mass to 100 parts by mass of the specific (meth)acrylic resin. 7.0 parts by mass is more preferable, and 3.0 parts by mass to 6.0 parts by mass is even more preferable. When the content of the isocyanate compound (B) is within the above range, the peeling from the adherend is more suppressed, and the adhesive force more suitable for the use of the protective film tends to be maintained.
＜聚矽氧系異氰酸酯化合物(C)＞ 黏著劑組成物含有異氰酸酯化合物(B)以外之具有聚矽氧烷結構及環氧烷結構之異氰酸酯化合物(C)(亦即聚矽氧系異氰酸酯化合物(C))。 聚矽氧系異氰酸酯化合物(C)含有異氰酸酯基，故會和特定(甲基)丙烯酸系樹脂中的交聯性官能基反應並形成交聯結構，而變得容易維持錨定於黏著劑層中之狀態。因此，將保護薄膜剝離時，會抑制污染成分轉移到被黏著體表面，故本發明之黏著劑組成物所形成的黏著劑層會發揮優良的耐污染性。 又，聚矽氧系異氰酸酯化合物(C)在分子中具有聚矽氧烷結構，故不易和特定(甲基)丙烯酸系樹脂相容，有局部存在黏著劑層的表面附近之傾向。此外，聚矽氧系異氰酸酯化合物(C)在分子中具有環氧烷結構，故會有和作為抗靜電助劑來使用之具有環氧烷結構之聚矽氧化合物同樣，以配位於抗靜電劑的狀態而局部存在黏著劑層的表面附近之傾向。因此，黏著劑組成物所形成的黏著劑層即使少量的抗靜電劑仍可發揮優良的抗靜電性能。 本說明書中，聚矽氧烷結構係指矽氧烷基(-Si-O-)連結而成的結構。本發明使用的聚矽氧系異氰酸酯化合物(C)中之聚矽氧烷結構所含的矽原子的數目宜為1~100之範圍。<Polysilicone-based isocyanate compound (C)> The adhesive composition contains an isocyanate compound (C) having a polysiloxane structure and an alkylene oxide structure other than the isocyanate compound (B) (that is, a polysiloxane-based isocyanate compound ( C)). Since the polysiloxane-based isocyanate compound (C) contains an isocyanate group, it reacts with the cross-linkable functional group in the specific (meth)acrylic resin to form a cross-linked structure, and it becomes easy to maintain the anchoring in the adhesive layer. state. Therefore, when the protective film is peeled off, the transfer of contamination components to the surface of the adherend is suppressed, so that the adhesive layer formed by the adhesive composition of the present invention exhibits excellent contamination resistance. Moreover, since the polysiloxane-based isocyanate compound (C) has a polysiloxane structure in the molecule, it is difficult to be compatible with the specific (meth)acrylic-based resin, and there is a tendency that the adhesive layer is locally present near the surface. In addition, since the polysiloxane-based isocyanate compound (C) has an alkylene oxide structure in the molecule, it is possible to coordinate with the antistatic agent in the same way as the polysiloxane compound having an alkylene oxide structure used as an antistatic auxiliary. The state tends to exist locally near the surface of the adhesive layer. Therefore, the adhesive layer formed by the adhesive composition can still exhibit excellent antistatic performance even with a small amount of antistatic agent. In this specification, the polysiloxane structure refers to a structure in which siloxane groups (-Si-O-) are linked. The number of silicon atoms contained in the polysiloxane structure in the polysiloxane-based isocyanate compound (C) used in the present invention is preferably in the range of 1 to 100.
聚矽氧系異氰酸酯化合物(C)，可利用具有反應性基且具有環氧烷結構之聚矽氧化合物和異氰酸酯化合物之反應(以下也稱為「預反應」)而獲得。The polysiloxane-based isocyanate compound (C) can be obtained by the reaction (hereinafter also referred to as "pre-reaction") of a polysiloxane compound having a reactive group and an alkylene oxide structure with an isocyanate compound.
就具有反應性基且具有環氧烷結構之聚矽氧化合物中的反應性基而言，可列舉：羥基、羧基、取代或無取代之醯胺基、取代或無取代之胺基、環氧基、巰基、含矽之基等反應性基。 它們之中，考慮有效地促進反應性基與異氰酸酯化合物中的NCO基之反應，且可有效地抑制對被黏著體之污染的發生之觀點，就反應性基而言，宜為羥基。 反應性基可導入到具有環氧烷結構之聚矽氧化合物的兩末端、一末端、側鏈中之任意位置。 在此，一末端意指：例如具有具矽氧烷基重複單元之聚矽氧烷鏈(主鏈)之聚矽氧化合物之前述主鏈之其中一個末端。兩末端意指：例如具有具矽氧烷基重複單元之分子鏈(主鏈)之聚矽氧化合物之前述主鏈之兩個末端。The reactive groups in the polysiloxane compound having a reactive group and having an alkylene oxide structure include: a hydroxyl group, a carboxyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted amino group, an epoxy group. reactive groups such as radicals, mercapto radicals, and silicon-containing radicals. Among them, from the viewpoint of effectively promoting the reaction between the reactive group and the NCO group in the isocyanate compound and effectively suppressing the occurrence of contamination of the adherend, the reactive group is preferably a hydroxyl group. The reactive group can be introduced into any position of both ends, one end and side chain of the polysiloxane having an alkylene oxide structure. Here, one terminal means, for example, one terminal of the aforementioned main chain of a polysiloxane compound having a polysiloxane chain (main chain) having a siloxane group repeating unit. Both ends mean: for example, both ends of the aforementioned main chain of a polysiloxane compound having a molecular chain (main chain) having a siloxane group repeating unit.
就具有反應性基且具有環氧烷結構之聚矽氧化合物而言，例如可列舉：環氧烷結構以接枝形態鍵結在聚矽氧鏈(亦即聚矽氧烷主鏈)而成的化合物、或以嵌段形態鍵結在聚矽氧鏈而成的化合物。 就上述具有環氧烷結構之化合物而言，例如可列舉：具有反應性基之聚環氧乙烷、聚環氧丙烷等，也可為環氧乙烷與環氧丙烷以嵌段形態或無規地加成而得的聚環氧烷。For polysiloxane compounds having reactive groups and an alkylene oxide structure, for example, the alkylene oxide structure is bonded to a polysiloxane chain (that is, a polysiloxane main chain) in a grafted form. compound, or a compound bonded to a polysiloxane chain in a block form. The compound having the above-mentioned alkylene oxide structure includes, for example, polyethylene oxide and polypropylene oxide having a reactive group, and ethylene oxide and propylene oxide may be in a block form or without Polyalkylene oxide obtained by regular addition.
考慮展現優良的抗靜電性，且有效地抑制對被黏著體之污染的觀點，具有反應性基且具有環氧烷結構之聚矽氧化合物宜為含有環氧烷結構、及羥基鍵結在環氧烷結構之末端而成的結構之聚矽氧化合物(以下也稱為「含有特定環氧烷結構之聚矽氧化合物」)。 含有特定環氧烷結構之聚矽氧化合物具有羥基鍵結在環氧烷結構之末端而成的結構的話，能發揮更優良的耐污染性。 具有環氧烷鏈之聚矽氧化合物會和後述抗靜電劑(D)交互作用，並有局部存在黏著劑層的表面附近之傾向。據推測其結果會使黏著劑層的表面之表面電阻值降低。亦即，藉由使用聚矽氧系異氰酸酯化合物(C)，可降低本發明之黏著劑組成物中抗靜電劑的量。From the viewpoint of exhibiting excellent antistatic properties and effectively suppressing the contamination of the adherend, the polysiloxane compound having a reactive group and an alkylene oxide structure is preferably an alkylene oxide structure and a hydroxyl group bonded to a ring. A polysiloxane compound having a structure formed at the end of an oxane structure (hereinafter also referred to as "polysiloxane compound containing a specific alkylene oxide structure"). If the polysiloxane compound containing a specific alkylene oxide structure has a structure in which a hydroxyl group is bonded to the end of the alkylene oxide structure, it can exhibit more excellent contamination resistance. The polysiloxane compound having an alkylene oxide chain interacts with the antistatic agent (D) described later, and tends to locally exist near the surface of the adhesive layer. As a result, it is presumed that the surface resistance value of the surface of the adhesive layer decreases. That is, by using the polysiloxane-based isocyanate compound (C), the amount of the antistatic agent in the adhesive composition of the present invention can be reduced.
考慮賦予抗靜電性且降低對被黏著體之污染性的觀點，就含有特定環氧烷結構之聚矽氧化合物而言，宜為包含來自二烷基矽氧烷之構成單元、與來自烷基(羥基聚伸烷基氧基烷基)矽氧烷之構成單元的聚矽氧烷化合物。 二烷基矽氧烷中的烷基之碳數宜為1~4，為1更佳。 又，烷基(羥基聚伸烷基氧基烷基)矽氧烷中的環氧烷鏈之碳數宜為2~4，為2~3更佳。 烷基(羥基聚伸烷基氧基烷基)矽氧烷中的環氧烷鏈之含有數量宜為1~100，為10~100更佳。烷基(羥基聚伸烷基氧基烷基)矽氧烷中的烷基之碳數宜為1~4。From the viewpoint of imparting antistatic properties and reducing contamination to the adherend, the polysiloxane compound containing a specific alkylene oxide structure is preferably composed of a constituent unit derived from a dialkylsiloxane and a unit derived from an alkyl group. A polysiloxane compound that is a constituent unit of (hydroxypolyalkyleneoxyalkyl)siloxane. The carbon number of the alkyl group in the dialkylsiloxane is preferably 1 to 4, more preferably 1. In addition, the number of carbon atoms in the alkylene oxide chain in the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane is preferably 2 to 4, 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 number of carbon atoms in the alkyl group in the alkyl (hydroxypolyalkyleneoxyalkyl) siloxane is preferably 1 to 4.
含有特定環氧烷結構之聚矽氧化合物含有來自二烷基矽氧烷之構成單元與來自烷基(羥基聚伸烷基氧基烷基)矽氧烷之構成單元時，來自二烷基矽氧烷之構成單元之含有數量宜為100以下，為1~80更佳。又，來自烷基(羥基聚伸烷基氧基烷基)矽氧烷之構成單元之含有數量宜為2~100，為2~80更佳。When the polysiloxane compound containing a specific alkylene oxide structure contains a structural unit derived from dialkylsiloxane and a structural unit derived from an alkyl (hydroxypolyalkyleneoxyalkyl)siloxane, it is derived from dialkylsiloxane. The content of the constituent units of oxane is preferably 100 or less, more preferably 1 to 80. In addition, the content of the constituent units derived from the alkyl (hydroxypolyalkyleneoxyalkyl)siloxane is preferably 2 to 100, more preferably 2 to 80.
考慮黏著性、抗靜電性及降低對被黏著體之污染性的觀點，含有特定環氧烷結構之聚矽氧化合物宜為下述通式(3)或通式(4)表示之化合物。From the viewpoints of adhesiveness, antistatic property and reduction of contamination to the adherend, the polysiloxane compound containing a specific alkylene oxide structure is preferably a compound represented by the following general formula (3) or general formula (4).
[化3]
通式(3)中，p表示二甲基矽氧烷結構單元之重複數，為0~100之數。q表示具有聚環氧乙烷鏈之甲基伸丙基矽氧烷結構單元之重複數，為2~100之數。又，a表示環氧乙烷結構單元之重複數，為1~100之數。在此，通式(3)表示之化合物為多種化合物之集合體時，p、q及a為化合物就集合體而言之平均值，為有理數。In the general formula (3), p represents the repetition number of the dimethylsiloxane structural unit, and is a number from 0 to 100. q represents the repeating number of the methylidene siloxane structural unit having a polyethylene oxide chain, and is a number from 2 to 100. Moreover, a represents the repetition number of an ethylene oxide structural unit, and is a number 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 the average values of the aggregates of the compounds and are rational numbers.
環氧乙烷結構單元之重複數a為1~100之數，宜為10~100之數。a為1以上的話，可獲得充分的導電性，且有進一步改善抗靜電效果之傾向。又，a為100以下的話，會變得容易局部存在黏著劑層的表面附近。The repeating number a of the ethylene oxide structural unit is a number from 1 to 100, preferably a number from 10 to 100. When a is 1 or more, sufficient electrical conductivity can be obtained, and the antistatic effect tends to be further improved. In addition, when a is 100 or less, it becomes easy to locally exist in the vicinity of the surface of an adhesive bond layer.
又，二甲基矽氧烷結構單元之重複數p為0~100之數，宜為1~80之數。p為0以上時，會有改善抗靜電效果之傾向。又，p為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並改善黏著劑層的透明性之傾向。 此外，甲基伸丙基矽氧烷結構單元之重複數q為2~100之數，宜為2~80之數。q為2以上的話，會有容易獲得充分的導電性，並使抗靜電效果改善之傾向。又，q為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並改善黏著劑層的透明性之傾向。In addition, the repeating number p of the dimethylsiloxane structural unit is a number of 0 to 100, preferably a number of 1 to 80. When p is 0 or more, the antistatic effect tends to be improved. Moreover, when p is 100 or less, the compatibility with other components which comprise an adhesive composition tends to improve, and the transparency of an adhesive layer tends to improve. In addition, the repeating number q of the methylidene siloxane structural unit is a number of 2 to 100, preferably a number of 2 to 80. When q is 2 or more, sufficient conductivity tends to be easily obtained, and the antistatic effect tends to be improved. In addition, when q 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.
就通式(3)表示之化合物之具體例而言，可列舉：「SF-8428」、「FZ-2162」、「SH-3773M」、「FZ-77」、「FZ-2104」、「FZ-2110」、「L-7001」、「L-7002」、「SH-3749」[以上為東麗･道康寧(股)製]。Specific examples of the compound represented by the general formula (3) include "SF-8428", "FZ-2162", "SH-3773M", "FZ-77", "FZ-2104", "FZ" -2110", "L-7001", "L-7002", "SH-3749" [The above are manufactured by Toray and Dow Corning].
[化4]
通式(4)中，R1 及R2 各別獨立地表示碳數1~6之伸烷基，c表示10~80之整數，d表示環氧乙烷(EO)構成單元之重複數，為1以上之整數，e表示環氧丙烷(PO)構成單元之重複數，為0以上之整數，且d＋e表示1~30之整數。環氧乙烷及環氧丙烷的順序也可為無規(random)。In the general formula (4), R 1 and R 2 each independently represent an alkylene group having 1 to 6 carbon atoms, c represents an integer of 10 to 80, and d represents the repeating number of ethylene oxide (EO) constituent units, It is an integer of 1 or more, e represents the repeating number of a propylene oxide (PO) structural unit, it is an integer of 0 or more, and d+e represents an integer of 1 to 30. The order of ethylene oxide and propylene oxide may also be random.
就通式(4)表示之化合物之具體例而言，可列舉：「BY-16-201」、「SF-8427」[以上為東麗･道康寧(股)製]。Specific examples of the compound represented by the general formula (4) include "BY-16-201" and "SF-8427" [the above are manufactured by Toray Dow Corning].
就含有特定環氧烷結構之聚矽氧化合物之重量平均分子量(Mw)而言，並無特別限制，例如宜為1,000~20,000，為3,000~15,000更佳。 含有特定環氧烷結構之聚矽氧化合物之重量平均分子量(Mw)可和上述特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)的測定方法同樣地進行測定。The weight average molecular weight (Mw) of the polysiloxane containing a specific alkylene oxide structure is not particularly limited, for example, it is preferably 1,000-20,000, more preferably 3,000-15,000. The weight average molecular weight (Mw) of the polysiloxane compound containing a specific alkylene oxide structure can be measured similarly to the measuring method of the weight average molecular weight (Mw) of the above-mentioned specific (meth)acrylic resin.
又，針對含有特定環氧烷結構之聚矽氧化合物的HLB值，並無特別限制。考慮和特定(甲基)丙烯酸系樹脂之相容性、局部存在的容易性、及適於保護薄膜之黏接性的觀點，HLB值宜為5以上未達16，為7~15更佳。In addition, there is no particular limitation on the HLB value of the polysiloxane containing a specific alkylene oxide structure. Considering the compatibility with the specific (meth)acrylic resin, the easiness of local presence, and the adhesiveness suitable for the protective film, the HLB value is preferably 5 or more but less than 16, and more preferably 7 to 15.
HLB值為表示具有環氧烷結構之聚矽氧化合物之親水性與疏水性的平衡之尺度。本說明書中係依循以下式計算而得的格里芬(Griffin)法之定義，當具有環氧烷結構之聚矽氧存在市售品時，則優先採用市售品的型錄資料。 HLB=[(親水性基部分的化學式量之總和)/(具有環氧烷結構之聚矽氧化合物的分子量)]×20The HLB value is a scale representing the balance of hydrophilicity and hydrophobicity of a polysiloxane having an alkylene oxide structure. In this specification, the definition of Griffin method is calculated according to the following formula. When there is a commercial product of polysiloxane with an alkylene oxide structure, the catalog data of the commercial product is preferentially used. HLB=[(the sum of the chemical formula amounts of the hydrophilic group moieties)/(the molecular weight of the polysiloxane compound having an alkylene oxide structure)]×20
含有特定環氧烷結構之聚矽氧化合物可為選自如上述之市售品，又，含有特定環氧烷結構之聚矽氧化合物，也可藉由對具有氫化矽之二甲基聚矽氧烷主鏈利用矽氫化反應使具有不飽和鍵及聚環氧乙烷鏈之有機化合物進行接枝而得。The polysiloxane compound containing a specific alkylene oxide structure can be selected from the above-mentioned commercial products, and the polysiloxane compound containing a specific alkylene oxide structure can also be obtained by treating the dimethyl polysiloxane with silicon hydride. The alkane main chain is obtained by grafting organic compounds with unsaturated bonds and polyethylene oxide chains through hydrosilation reaction.
就聚矽氧系異氰酸酯化合物(C)之預反應所使用的異氰酸酯化合物而言，若為可和上述具有反應性基且具有環氧烷結構之聚矽氧化合物反應，則無特別限制。 就如此的異氰酸酯化合物而言，例如可例舉上述異氰酸酯化合物(B)，和異氰酸酯化合物(B)之具體例同樣。The isocyanate compound used for the pre-reaction of the polysiloxane-based isocyanate compound (C) is not particularly limited as long as it can react with the above-mentioned polysiloxane compound having a reactive group and having an alkylene oxide structure. As such an isocyanate compound, the said isocyanate compound (B) is mentioned, for example, It is the same as the specific example of an isocyanate compound (B).
考慮預反應中的反應性之觀點，就預反應所使用的異氰酸酯化合物而言，宜為選自於異佛爾酮二異氰酸酯或二異氰酸二甲苯酯、及二異氰酸六亞甲酯與多元醇之異氰尿酸酯改性物中之至少1種，考慮尤會抑制後述預反應時之凝膠化的觀點，為異佛爾酮二異氰酸酯及二異氰酸二甲苯酯中之至少一者更佳。From the viewpoint of reactivity in the pre-reaction, the isocyanate compound used in the pre-reaction is preferably selected from isophorone diisocyanate, dimethyl isocyanate, and hexamethylene diisocyanate. At least one of isocyanurate-modified products with polyols is one of isophorone diisocyanate and xylyl diisocyanate from the viewpoint of particularly suppressing gelation during the pre-reaction described later. At least one is better.
此外，考慮抗靜電性的觀點，就預反應所使用的異氰酸酯化合物而言，宜為和前述異氰酸酯化合物(B)不同的異氰酸酯化合物。 異氰酸酯化合物(B)若和在聚矽氧系異氰酸酯化合物(C)之預反應所使用的異氰酸酯化合物為不同的話，在黏著劑層中，異氰酸酯化合物(B)不易和聚矽氧系異氰酸酯化合物(C)相容。因此，聚矽氧系異氰酸酯化合物(C)容易局部存在黏著劑層表面，故會有可獲得更優良的抗靜電性之傾向。In addition, from the viewpoint of antistatic properties, the isocyanate compound used for the pre-reaction is preferably an isocyanate compound different from the aforementioned isocyanate compound (B). If the isocyanate compound (B) is different from the isocyanate compound used in the pre-reaction of the polysiloxane-based isocyanate compound (C), in the adhesive layer, the isocyanate compound (B) cannot easily interact with the polysiloxane-based isocyanate compound (C). ) compatible. Therefore, the polysiloxane-based isocyanate compound (C) tends to locally exist on the surface of the adhesive layer, so that there is a tendency to obtain better antistatic properties.
預反應使用的異氰酸酯化合物可單獨使用1種，或也可將2種以上合併使用。例如合併使用二異氰酸六亞甲酯與異佛爾酮二異氰酸酯時，會有可更抑制預反應時之凝膠化的傾向。The isocyanate compound used for the preliminary reaction may be used alone or in combination of two or more. For example, when hexamethylene diisocyanate and isophorone diisocyanate are used in combination, there is a tendency that gelation during the pre-reaction can be further suppressed.
聚矽氧系異氰酸酯化合物(C)宜包含下述結構式(1)表示之結構。The polysiloxane-based isocyanate compound (C) preferably contains a structure represented by the following structural formula (1).
[化5]
結構式(1)中，r表示1~100之整數，b表示1~100之整數，X表示含有異氰酸酯基之1價有機基。In structural formula (1), r represents an integer of 1 to 100, b represents an integer of 1 to 100, and X represents a monovalent organic group containing an isocyanate group.
甲基伸丙基矽氧烷結構單元之重複數r宜為2~80之整數。r為1以上的話，會有可獲得充分的導電性，並更改善抗靜電性之傾向。又，r為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並更改善黏著劑層的透明性之傾向。The repeating number r of the methylidene siloxane structural unit is preferably an integer ranging from 2 to 80. When r is 1 or more, sufficient electrical conductivity can be obtained, and the antistatic property tends to be further improved. In addition, when r 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 further improved.
環氧乙烷結構單元之重複數b為1~100之整數，宜為10~100之整數。b為1以上的話，會有可獲得充分的導電性，並改善抗靜電性之傾向。又，b為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並進一步改善黏著劑層的透明性之傾向。The repetition number b of the ethylene oxide structural unit is an integer of 1 to 100, preferably an integer of 10 to 100. When b is 1 or more, sufficient electrical conductivity can be obtained and antistatic properties tend to be improved. Moreover, when b is 100 or less, the compatibility with other components which comprise an adhesive composition tends to improve, and there exists a tendency for the transparency of an adhesive layer to be improved further.
就X表示之1價有機基而言，可列舉從上述雙官能以上之異氰酸酯化合物(B)去除1個異氰酸酯基(亦即NCO基)而得的1價基。 它們之中，考慮和特定(甲基)丙烯酸系樹脂之反應性的觀點，就X表示之1價有機基而言，宜為從選自於由鏈狀或環狀之脂肪族多異氰酸酯化合物、鏈狀或環狀之脂肪族多異氰酸酯化合物之二聚物、及包含鏈狀或環狀之脂肪族多異氰酸酯化合物之異氰尿酸酯改性物之三聚物或五聚物構成之群組中之至少1種多異氰酸酯化合物去除1個異氰酸酯基而得的1價基，為從選自於由異佛爾酮二異氰酸酯、二異氰酸二甲苯酯或二異氰酸六亞甲酯、二異氰酸六亞甲酯之二聚物、及包含二異氰酸六亞甲酯之異氰尿酸酯改性物之三聚物或五聚物構成之群組中之至少1種多異氰酸酯化合物去除1個異氰酸酯基而得的1價基更佳，為從選自於由異佛爾酮二異氰酸酯、二異氰酸二甲苯酯及包含二異氰酸六亞甲酯之異氰尿酸酯改性物之三聚物構成之群組中之至少一者去除1個異氰酸酯基而得的1價基更佳，為從選自於由異佛爾酮二異氰酸酯及二異氰酸二甲苯酯構成之群組中之至少一者去除1個異氰酸酯基而得的1價基特佳。 又，考慮抗靜電性的觀點，就X表示之1價有機基而言，宜為從和本發明之黏著劑組成物所含的異氰酸酯化合物(B)不同的其他雙官能以上之異氰酸酯化合物去除1個異氰酸酯基(NCO基)而得的1價基。The monovalent organic group represented by X includes a monovalent group obtained by removing one isocyanate group (that is, an NCO group) from the above-mentioned bifunctional or higher isocyanate compound (B). Among them, from the viewpoint of reactivity with a specific (meth)acrylic resin, the monovalent organic group represented by X is preferably selected from the group consisting of chain or cyclic aliphatic polyisocyanate compounds, The group consisting of dimers of chain-like or cyclic aliphatic polyisocyanate compounds and trimers or pentamers of isocyanurate-modified products comprising chain-like or cyclic aliphatic polyisocyanate compounds At least one of the polyisocyanate compounds is a monovalent group obtained by removing one isocyanate group, and is a monovalent group selected from isophorone diisocyanate, diisocyanate, or hexamethylene diisocyanate, At least one kind selected from the group consisting of dimers of hexamethylene diisocyanate and trimers or pentamers of hexamethylene diisocyanate modified isocyanurates More preferably, the monovalent group obtained by removing one isocyanate group from the isocyanate compound is selected from the group consisting of isophorone diisocyanate, ditolyl diisocyanate and isocyanuric acid containing hexamethylene diisocyanate. More preferably, at least one of the group consisting of trimers of the ester modified product has a monovalent group obtained by removing one isocyanate group, and is selected from isophorone diisocyanate and diisocyanate diisocyanate. A monovalent group obtained by removing one isocyanate group from at least one of the group consisting of tolyl is particularly preferred. Furthermore, from the viewpoint of antistatic properties, the monovalent organic group represented by X is preferably one that is removed from other bifunctional or higher isocyanate compounds different from the isocyanate compound (B) contained in the adhesive composition of the present invention. A monovalent group derived from an isocyanate group (NCO group).
上述結構式(1)表示之結構之具體例如下所示。另外，結構式(1)表示之結構並不限於如下之例示結構，若為結構式(1)表示之結構所包含的結構，則無特別限制。A specific example of the structure represented by the above-mentioned structural formula (1) is shown below. In addition, the structure represented by the structural formula (1) is not limited to the following exemplary structures, and is not particularly limited as long as it is a structure included in the structure represented by the structural formula (1).
[化6]
[化7]
[化8]
[化9]
[化10]
考慮耐污染性的觀點，就聚矽氧系異氰酸酯化合物(C)而言，宜為通式(1-1)或通式(2)表示之化合物，為通式(1-1)表示之化合物更佳。From the viewpoint of contamination resistance, the polysiloxane-based isocyanate compound (C) is preferably a compound represented by general formula (1-1) or general formula (2), and a compound represented by general formula (1-1) better.
[化11]
通式(1-1)中，p或q各別獨立地表示0~100之整數，q及r各別獨立地表示1~100之整數，a表示0~100之整數，b表示1~100之整數。又，X表示含有異氰酸酯基之1價有機基。 在此，通式(1-1)表示之化合物為多種化合物之集合體時，p、q、r、a及b為化合物就集合體而言之平均值，為有理數。In the general formula (1-1), p or q each independently represent an integer from 0 to 100, q and r each independently represent an integer from 1 to 100, a represents an integer from 0 to 100, and b represents an integer from 1 to 100 the integer. Moreover, X represents the monovalent organic group containing an isocyanate group. Here, when the compound represented by the general formula (1-1) is an aggregate of a plurality of compounds, p, q, r, a and b are the average values of the aggregates of the compounds and are rational numbers.
環氧乙烷結構單元之重複數a為1~100之整數，宜為10~100之數量。a為1以上的話，會有可獲得充分的導電性，並改善抗靜電性之傾向。又，a為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並進一步改善黏著劑層的透明性之傾向。The repeating number a of the ethylene oxide structural unit is an integer from 1 to 100, preferably 10 to 100. When a is 1 or more, there is a tendency that sufficient conductivity is obtained and antistatic properties are 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 further improved.
又，二甲基矽氧烷結構單元之重複數p為0~100之整數，宜為1~80之整數。p為0以上時，會有改善抗靜電性之傾向。 又，p為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並改善黏著劑層的透明性之傾向。 此外，甲基伸丙基矽氧烷結構單元之重複數q宜為2~80之數量。q為2以上的話，會有可獲得充分的導電性，並進一步改善抗靜電性之傾向。又，q為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並更改善黏著劑層的透明性之傾向。In addition, the repeating number p of the dimethylsiloxane structural unit is an integer of 0 to 100, preferably an integer of 1 to 80. When p is 0 or more, the antistatic property tends to be improved. Moreover, when p is 100 or less, the compatibility with other components which comprise an adhesive composition tends to improve, and the transparency of an adhesive layer tends to improve. In addition, the repeating number q of the methylidene siloxane structural unit is preferably the number of 2-80. When q is 2 or more, sufficient electrical conductivity can be obtained, and the antistatic property tends to be further improved. In addition, when q 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 further improved.
通式(1-1)中，r及b和結構式(1)中之r及b同義，理想範圍也同樣。In general formula (1-1), r and b are synonymous with r and b in structural formula (1), and the ideal range is also the same.
[化12]
通式(2)中，R1 及R2 各別獨立地表示碳數1~6之伸烷基，c表示10~80之整數，d表示環氧乙烷(EO)結構單元之重複數，為1以上之整數，e表示環氧丙烷(PO)結構單元之重複數，為0以上之整數，且d＋e表示1~30之整數。環氧乙烷結構單元及環氧丙烷結構單元的順序也可為無規。In the general formula (2), R 1 and R 2 each independently represent an alkylene group having 1 to 6 carbon atoms, c represents an integer of 10 to 80, and d represents the repeating number of ethylene oxide (EO) structural units, It is an integer of 1 or more, e represents the repetition number of a propylene oxide (PO) structural unit, it is an integer of 0 or more, and d+e represents an integer of 1 to 30. The order of the ethylene oxide structural units and the propylene oxide structural units may also be random.
通式(2)，就R1 或R2 表示之碳數1~6之伸烷基而言，並無特別限制，例如可列舉：亞甲基、伸乙基、伸丙基、伸丁基等。The general formula (2) is not particularly limited in terms of the alkylene group having 1 to 6 carbon atoms represented by R 1 or R 2 , for example, methylene group, ethylidene group, propylidene group, and butylene group are exemplified. Wait.
環氧乙烷結構單元之重複數d宜為1~100之整數，為10~100之整數更佳。 d為1以上的話，會有可獲得充分的導電性，並改善抗靜電性之傾向。又，d為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並進一步改善黏著劑層的透明性之傾向。The repeating number d of the ethylene oxide structural unit is preferably an integer of 1-100, more preferably an integer of 10-100. When d is 1 or more, sufficient electrical conductivity can be obtained and antistatic properties tend to be improved. In addition, when d 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 further improved.
環氧丙烷結構單元之重複數e宜為1~100之整數，為10~100之整數更佳。 e為1以上的話，會有可獲得充分的導電性，並改善抗靜電性之傾向。又，e為100以下的話，會有改善和構成黏著劑組成物之其他成分之相容性，並進一步改善黏著劑層的透明性之傾向。The repeating number e of the propylene oxide structural unit is preferably an integer of 1-100, more preferably an integer of 10-100. When e is 1 or more, sufficient electrical conductivity can be obtained and antistatic properties tend to be improved. In addition, when e 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 further improved.
環氧乙烷結構單元之重複數d與環氧丙烷結構單元之重複數量e之和為1~50之整數更佳。More preferably, the sum of the repeating number d of the ethylene oxide structural unit and the repeating number e of the propylene oxide structural unit is an integer from 1 to 50.
聚矽氧系異氰酸酯化合物(C)之具體例如下所示。另外，聚矽氧系異氰酸酯化合物(C)並不限於如下之例示化合物，若為包含上述結構式(1)表示之結構之化合物所包含的化合物，則無特別限制。Specific examples of the polysiloxane-based isocyanate compound (C) are shown below. In addition, the polysiloxane-based isocyanate compound (C) is not limited to the following exemplified compounds, and is not particularly limited as long as it is a compound included in the compound having the structure represented by the above-mentioned structural formula (1).
[化13]
[化14]
[化15]
[化16]
[化17]
[化18]
[化19]
[化20]
[化21]
[化22]
[化23]
[化24]
[化25]
[化26]
[化27]
[化28]
聚矽氧系異氰酸酯化合物(C)之製造方法並無特別限制，可使用公知的製造方法。 例如藉由分別將預定量之具有反應性基且具有環氧烷結構之聚矽氧化合物、異氰酸酯化合物投入反應容器中，均勻地攪拌使其反應(預反應)，可獲得聚矽氧系異氰酸酯化合物(C)。There is no restriction|limiting in particular as the manufacturing method of a polysiloxane-type isocyanate compound (C), A well-known manufacturing method can be used. For example, a polysiloxane-based isocyanate compound can be obtained by putting a predetermined amount of a polysiloxane compound and an isocyanate compound having a reactive group and an alkylene oxide structure into a reaction vessel, and uniformly stirring them to react (pre-reaction). (C).
就預反應之溫度而言，宜為40℃~100℃，為45℃~95℃更佳，為50℃~95℃再更佳。As far as the pre-reaction temperature is concerned, it is preferably 40°C to 100°C, more preferably 45°C to 95°C, and even more preferably 50°C to 95°C.
聚矽氧系異氰酸酯化合物(C)之含量相對於(甲基)丙烯酸系樹脂(A)100質量份，為0.10質量份以上。 聚矽氧系異氰酸酯化合物(C)之含量為0.10質量份以上的話，由於聚矽氧系異氰酸酯化合物(C)含有異氰酸酯基，故會和特定(甲基)丙烯酸系樹脂中之交聯性官能基反應而形成交聯結構，變得容易維持錨定於黏著劑層中之狀態。因此，從被黏著體剝離保護薄膜時，會抑制污染成分轉移到被黏著體，由黏著劑組成物形成的黏著劑層會發揮優良的耐污染性。 又，聚矽氧系異氰酸酯化合物(C)在分子中具有聚矽氧烷結構，故不易和特定(甲基)丙烯酸系樹脂相容，容易局部存在黏著劑層的表面附近。此外，聚矽氧系異氰酸酯化合物(C)在分子中具有環氧烷結構，故會和通常使用作為抗靜電助劑之具有環氧烷結構之聚矽氧化合物同樣，以配位於抗靜電劑的狀態容易局部存在黏著劑層的表面附近。因此，黏著劑組成物所形成的黏著劑層，即使少量的抗靜電劑仍會發揮優良的抗靜電性能。 考慮上述觀點，就聚矽氧系異氰酸酯化合物(C)之含量而言，相對於(甲基)丙烯酸系樹脂(A)100質量份，宜為0.2質量份~3質量份，為0.25質量份~2.5質量份更佳，為0.3質量份~2質量份再更佳。The content of the polysiloxane-based isocyanate compound (C) is 0.10 parts by mass or more with respect to 100 parts by mass of the (meth)acrylic resin (A). If the content of the polysiloxane-based isocyanate compound (C) is 0.10 parts by mass or more, since the polysiloxane-based isocyanate compound (C) contains an isocyanate group, it will interact with the crosslinkable functional group in the specific (meth)acrylic resin. It reacts to form a cross-linked structure, and it becomes easy to maintain the state of being anchored in the adhesive layer. Therefore, when the protective film is peeled off from the adherend, the transfer of contamination components to the adherend is suppressed, and the adhesive layer formed of the adhesive composition exhibits excellent contamination resistance. Moreover, since the polysiloxane-based isocyanate compound (C) has a polysiloxane structure in the molecule, it is not easy to be compatible with the specific (meth)acrylic resin, and it is easy to locally exist in the vicinity of the surface of the adhesive layer. In addition, the polysiloxane-based isocyanate compound (C) has an alkylene oxide structure in the molecule, so it will be coordinated to the The state is likely to be localized near the surface of the adhesive layer. Therefore, the adhesive layer formed by the adhesive composition can still exert excellent antistatic performance even with a small amount of antistatic agent. Considering the above point of view, the content of the polysiloxane-based isocyanate compound (C) is preferably 0.2 parts by mass to 3 parts by mass, and preferably 0.25 parts by mass to 100 parts by mass of the (meth)acrylic resin (A). 2.5 parts by mass is more preferable, and 0.3 parts by mass to 2 parts by mass is even more preferable.
聚矽氧系異氰酸酯化合物(C)相對於異氰酸酯化合物(B)之質量比[(C)/(B)]宜為1/1~1/20。 質量比[(C)/(B)]為1/20以下的話，黏著劑組成物中所含的異氰酸酯化合物(B)不會變得過多，且聚矽氧系異氰酸酯化合物(C)適度地存在，故會有耐污染性更受控的傾向。又，質量比[(C)/(B)]為1/1以上的話，會有特定(甲基)丙烯酸系樹脂(A)與異氰酸酯化合物(B)可充分地反應而形成交聯結構，並賦予黏著劑層更適合的黏著力之傾向。 考慮上述觀點，就質量比[(C)/(B)]而言，為1/2~1/15更佳，為1/3~1/10再更佳。The mass ratio [(C)/(B)] of the polysiloxane-based isocyanate compound (C) to the isocyanate compound (B) is preferably 1/1 to 1/20. When the mass ratio [(C)/(B)] is 1/20 or less, the isocyanate compound (B) contained in the adhesive composition does not become excessively large, and the polysiloxane-based isocyanate compound (C) is present in a moderate amount , so there will be a tendency for contamination resistance to be more controlled. In addition, when the mass ratio [(C)/(B)] is 1/1 or more, the specific (meth)acrylic resin (A) and the isocyanate compound (B) can sufficiently react to form a crosslinked structure, and The tendency to impart more suitable adhesion to the adhesive layer. Considering the above point of view, the mass ratio [(C)/(B)] is more preferably 1/2 to 1/15, and more preferably 1/3 to 1/10.
＜抗靜電劑(D)＞ 黏著劑組成物含有抗靜電劑(D)。黏著劑組成物所形成的黏著劑層會發揮優良的抗靜電性能。 就抗靜電劑而言，可例舉離子性化合物。就離子性化合物而言，並無特別限制，可列舉：鹼金屬鹽、有機鹽等。 考慮離子解離性高，且即使少量仍易於顯現優良的抗靜電性之觀點，就抗靜電劑而言，宜為鹼金屬鹽或有機鹽。<Antistatic agent (D)> The adhesive composition contains an antistatic agent (D). The adhesive layer formed by the adhesive composition exhibits excellent antistatic properties. As an antistatic agent, an ionic compound is mentioned. The ionic compound is not particularly limited, and examples thereof include alkali metal salts, organic salts, and the like. The antistatic agent is preferably an alkali metal salt or an organic salt from the viewpoint of having high ion dissociation property and apt to exhibit excellent antistatic property even in a small amount.
就鹼金屬鹽而言，若為以鋰離子(Li＋ )、鈉離子(Na＋ )、鉀離子(K＋ )、銣離子(Rb＋ )等作為陽離子之金屬鹽，則無特別限制。 例如可適當地使用由選自於由Li＋ 、Na＋ 及K＋ 構成之群組中之至少1種陽離子與選自於由Cl- 、Br- 、I- 、BF4 - 、PF6 - 、SCN- 、ClO4 - 、CF3 SO3 - 、(FSO2 )2 N- 、(CF3 SO2 )2 N- 、(C2 F5 SO2 )2 N- 及(CF3 SO2 )3 C- 構成之群組中之至少1種陰離子構成的金屬鹽。The alkali metal salt is not particularly limited as long as it is a metal salt having a cation such as lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), or the like. For example, at least one cation selected from the group consisting of Li + , Na + and K + and a cation selected from 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 - and (CF 3 SO 2 ) 3 A metal salt composed of at least one anion in the group consisting of C-.
其中，就鹼金屬鹽而言，考慮抗靜電性的觀點，宜為LiBr、LiI、LiBF4 、LiPF6 、LiSCN、LiClO4 、LiCF3 SO3 (LiTFS)、Li(FSO2 )2 N、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(CF3 SO2 )3 C等鋰鹽，為LiClO4 、LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(CF3 SO2 )3 C更佳。 鹼金屬鹽可單獨使用1種，或也可將2種以上合併使用。Among them, the alkali metal salts are preferably LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 (LiTFS), Li(FSO 2 ) 2 N, Li from the viewpoint of antistatic properties. Lithium salts such as (CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, and Li(CF 3 SO 2 ) 3 C are LiClO 4 , LiCF 3 SO 3 , and Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, and Li(CF 3 SO 2 ) 3 C are more preferred. The alkali metal salts may be used alone or in combination of two or more.
有機鹽含有有機陽離子及其相對離子。有機鹽包含例如熔點為30℃以上之離子性固體與熔點未達30℃之離子性液體。 就有機鹽而言，熔點宜為30℃以上。有機鹽之熔點為30℃以上的話，不易遷移到被黏著體，污染性低，較理想。 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。它們之中，考慮抗靜電性的觀點，就有機陽離子而言，宜為吡啶鎓陽離子、咪唑鎓陽離子。Organic salts contain organic cations and their opposite ions. Organic salts include, for example, ionic solids with a melting point of 30°C or higher and ionic liquids with a melting point of less than 30°C. In the case of organic salts, the melting point is preferably 30°C or higher. If the melting point of the organic salt is above 30°C, it is not easy to migrate to the adherend, and the pollution is low, which is ideal. Examples of organic cations include imidazolium cations, pyridinium cations, alkylpyrrolidinium cations, ammonium cations having an organic group as a substituent, perium cations having an organic group as a substituent, and an organic group as a substituent base phosphonium cation. Among them, from the viewpoint of antistatic properties, the organic cations are preferably pyridinium cations and imidazolium cations.
成為有機陽離子的對離子之陰離子部並無特別限制，為無機陰離子或有機陰離子均可。其中，就陰離子而言，含有氟原子之含氟之陰離子由於抗靜電性優良，故特佳，為六氟磷酸根離子(PF6 - )又更佳。The anion part of the counter ion to be an organic cation is not particularly limited, and may be either an inorganic anion or an organic anion. Among them, in terms of anions, fluorine-containing anions containing fluorine atoms are particularly preferred because of their excellent antistatic properties, and hexafluorophosphate ions (PF 6 − ) are even more preferred.
就有機鹽之例而言，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，就有機鹽而言，宜為吡啶鎓鹽、咪唑鎓鹽，為吡啶鎓陽離子、咪唑鎓陽離子，與含氟之陰離子之鹽更佳。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, the organic salts are preferably pyridinium salts and imidazolium salts, more preferably pyridinium cations, imidazolium cations, and salts of fluorine-containing anions.
就抗靜電劑(D)之含量而言，相對於特定(甲基)丙烯酸系樹脂100質量份，宜為0.05質量份~0.50質量份，為0.10質量份~0.30質量份更佳。 相對於特定(甲基)丙烯酸系樹脂100質量份，抗靜電劑(D)之含量為0.05質量份以上的話，會有抗靜電性更優良的傾向。抗靜電劑(D)之含量為0.50質量份以下的話，會有抗靜電效果相對於抗靜電劑(D)的含量之效率變得更高的傾向。The content of the antistatic agent (D) is preferably 0.05 parts by mass to 0.50 parts by mass, more preferably 0.10 parts by mass to 0.30 parts by mass, with respect to 100 parts by mass of the specific (meth)acrylic resin. When content of an antistatic agent (D) is 0.05 mass part or more with respect to 100 mass parts of specific (meth)acrylic resins, there exists a tendency for an antistatic property to be more excellent. When the content of the antistatic agent (D) is 0.50 parts by mass or less, the efficiency of the antistatic effect with respect to the content of the antistatic agent (D) tends to be higher.
(其他聚矽氧化合物) 本發明之黏著劑組成物中，在不損及本發明的效果之範圍內也可含有聚矽氧系異氰酸酯化合物(C)以外之聚矽氧化合物(以下也稱為「其他聚矽氧化合物」)。(Other polysiloxane compounds) The adhesive composition of the present invention may contain polysiloxane compounds other than the polysiloxane-based isocyanate compound (C) (hereinafter also referred to as the "Other Polysiloxanes").
就其他聚矽氧化合物而言，例如可例舉使用於聚矽氧系異氰酸酯化合物(C)之預反應中之具有反應性基且具有環氧烷結構之聚矽氧化合物，和上述具有反應性基且具有環氧烷結構之聚矽氧化合物的具體例同樣，理想範圍也同樣。 含有其他聚矽氧化合物時，能使抗靜電性進一步改善。 其他聚矽氧化合物可單獨使用1種，或也可將2種以上合併使用。As for other polysiloxane compounds, for example, polysiloxane compounds having a reactive group and having an alkylene oxide structure used in the pre-reaction of the polysiloxane-based isocyanate compound (C), and the above-mentioned reactive The specific example of the polysiloxane compound having an alkylene oxide structure is the same, and the ideal range is also the same. When other polysiloxanes are contained, the antistatic property can be further improved. Other polysiloxane compounds may be used alone or in combination of two or more.
黏著劑組成物含有其他聚矽氧化合物時，就其他聚矽氧化合物之含量而言，相對於特定(甲基)丙烯酸系樹脂100質量份，宜為0.05質量份~1質量份，為0.05質量份~0.7質量份更佳，為0.05質量份~0.3質量份再更佳。 其他聚矽氧化合物之含量為0.05質量份以上的話，會有抗靜電性更優良的傾向。又，藉由使其他聚矽氧化合物之含量為1質量份以下，能抑制對被黏著體之污染(起霧，fogging)的發生，且更能抑制與特定(甲基)丙烯酸系樹脂之相容性降低而發生的白濁。When the adhesive composition contains other polysiloxane compounds, the content of the other polysiloxane compounds is preferably 0.05 mass part to 1 mass part, 0.05 mass part relative to 100 mass parts of the specific (meth)acrylic resin part to 0.7 part by mass is more preferably 0.05 part by mass to 0.3 part by mass. When the content of other polysiloxanes is 0.05 parts by mass or more, the antistatic properties tend to be more excellent. In addition, by making the content of other polysiloxane compounds to be 1 part by mass or less, the occurrence of contamination (fogging) to the adherend can be suppressed, and the phase with the specific (meth)acrylic resin can be further suppressed. White turbidity due to reduced capacitance.
((甲基)丙烯酸系寡聚物) 本發明之黏著劑組成物也可含有(甲基)丙烯酸系寡聚物。 考慮更優良的抗靜電性及發揮對被黏著體之耐污染性的觀點，就(甲基)丙烯酸系寡聚物而言，宜為含有環氧烷結構單元之(甲基)丙烯酸系寡聚物。((Meth)acrylic oligomer) The adhesive composition of the present invention may contain a (meth)acrylic oligomer. From the viewpoints of better antistatic properties and exhibiting contamination resistance to the adherend, the (meth)acrylic oligomer is preferably a (meth)acrylic oligomer containing an alkylene oxide structural unit. thing.
據推測藉由(甲基)丙烯酸系寡聚物含有環氧烷結構單元且分子量比起特定(甲基)丙烯酸系樹脂更小，可在黏著劑組成物中較容易地移動。藉此，能更有效地降低黏著劑組成物的表面電阻值，並賦予更優良的抗靜電性。It is presumed that the (meth)acrylic oligomer contains an alkylene oxide structural unit and has a smaller molecular weight than a specific (meth)acrylic resin, so that it can move easily in the adhesive composition. Thereby, the surface resistance value of the adhesive composition can be more effectively reduced, and more excellent antistatic properties can be imparted.
就環氧烷結構單元所含的伸烷基氧基而言，宜為碳數2~4之伸烷基氧基，為碳數2~3之伸烷基氧基更佳。The alkyleneoxy group contained in the alkylene oxide structural unit is preferably an alkyleneoxy group having 2 to 4 carbon atoms, and more preferably an alkyleneoxy group having 2 to 3 carbon atoms.
伸烷基氧基之含有數可因應目的等而適當選擇。考慮抗靜電性的觀點，伸烷基氧基之含有數宜為20以上，為20~100更佳，為20~50再更佳。藉由伸烷基氧基之含有數為20以上，會有因和上述抗靜電劑(D)之組合而發揮更顯著的抗靜電性之傾向。 另外，(甲基)丙烯酸系寡聚物所含之具有伸烷基氧基之構成單元為2種以上時，伸烷基氧基之含有數為含有數之平均值，係為有理數。The content of the alkyleneoxy group can be appropriately selected according to the purpose and the like. From the viewpoint of antistatic properties, the number of alkyleneoxy groups contained is preferably 20 or more, more preferably 20 to 100, and even more preferably 20 to 50. When the number of content of alkyleneoxy groups is 20 or more, there is a tendency that more remarkable antistatic properties are exhibited in combination with the above-mentioned antistatic agent (D). Moreover, when the structural unit which has an alkyleneoxy group contained in a (meth)acrylic-type oligomer is 2 or more types, the content number of an alkyleneoxy group is an average value of a content number, and it is a rational number.
伸烷基氧基之末端部可為羥基，也可為烷氧基，考慮抗靜電性的觀點，宜為烷氧基。聚環氧烷基之末端部為烷氧基時，烷氧基之碳數宜為1~10，為1~5更佳。The terminal part of the alkyleneoxy group may be a hydroxyl group or an alkoxy group, and from the viewpoint of antistatic properties, an alkoxy group is preferable. When the terminal part of the polyoxyalkyl group is an alkoxy group, the carbon number of the alkoxy group is preferably 1-10, more preferably 1-5.
來自伸烷基氧基之構成單元可為來自具有伸烷基氧基及乙烯基之單體者，也可為利用高分子反應將伸烷基氧基導入到不具伸烷基氧基之構成單元而成者。 考慮生產性的觀點，來自伸烷基氧基之構成單元宜為來自具有伸烷基氧基及乙烯基之單體者。The structural unit derived from an alkyleneoxy group may be derived from a monomer having an alkyleneoxy group and a vinyl group, or may be a structural unit that does not have an alkyleneoxy group by introducing an alkyleneoxy group through a polymer reaction become. From the viewpoint of productivity, the constituent unit derived from an alkyleneoxy group is preferably one derived from a monomer having an alkyleneoxy group and a vinyl group.
就具有伸烷基氧基及乙烯基之單體而言，具體可列舉：(甲基)丙烯酸聚乙二醇酯、甲氧基聚伸乙基氧(甲基)丙烯酸酯、乙氧基聚伸乙基氧(甲基)丙烯酸酯、(甲基)丙烯酸聚丙二醇酯、甲氧基聚伸丙基氧(甲基)丙烯酸酯、乙氧基聚伸丙基氧(甲基)丙烯酸酯等。 其中，宜為選自於由甲氧基聚伸乙基氧(甲基)丙烯酸酯及甲氧基聚伸丙基氧(甲基)丙烯酸酯構成之群組中之至少1種，為選自於由伸乙基氧基之含有數為20以上之甲氧基聚伸乙基氧(甲基)丙烯酸酯及伸丙基氧基之含有數為20以上之甲氧基聚伸丙基氧(甲基)丙烯酸酯構成之群組中之至少1種更佳。Specific examples of monomers having an alkyleneoxy group and a vinyl group include polyethylene glycol (meth)acrylate, methoxypolyethoxylate (meth)acrylate, and ethoxypolyethylene glycol. Ethoxylate (meth)acrylate, (meth)acrylate polypropylene glycol, methoxypolypropyleneoxy (meth)acrylate, ethoxypolypropyleneoxy (meth)acrylate, etc. . Among them, at least one selected from the group consisting of methoxypolyethyleneoxy (meth)acrylate and methoxypolypropyleneoxy (meth)acrylate is preferably selected from From the methoxypolyethyleneoxy (meth)acrylate containing 20 or more methoxypolyethyleneoxy groups and the methoxypolypropyleneoxy (methyl) containing 20 or more propylideneoxy groups At least one of the group consisting of acrylates is more preferable.
(甲基)丙烯酸系寡聚物可單獨含有1種來自伸烷基氧基之構成單元，或也可合併含有2種以上。The (meth)acrylic oligomer may contain one type of structural unit derived from an alkyleneoxy group alone, or may contain two or more types in combination.
就(甲基)丙烯酸系寡聚物中的來自伸烷基氧基之構成單元之含有率而言，考慮抗靜電性的觀點，相對於(甲基)丙烯酸系寡聚物之總質量，宜為1質量%~50質量%，為1質量%~30質量%更佳，為5質量%~20質量%再更佳。Regarding the content rate of the structural unit derived from the alkyleneoxy group in the (meth)acrylic oligomer, from the viewpoint of antistatic property, it is suitable to be It is 1 to 50 mass %, more preferably 1 to 30 mass %, and even more preferably 5 to 20 mass %.
(甲基)丙烯酸系寡聚物含有來自伸烷基氧基之構成單元，除此之外宜更含有至少1種之來自具有羧基之單體之構成單元。 (甲基)丙烯酸系寡聚物含有來自具有羧基之單體之構成單元的話，會有對剝離性之改善具有貢獻之傾向。 就具有羧基之單體之種類而言，並無特別限制，可例舉上述(甲基)丙烯酸系樹脂中的具有羧基之單體。考慮剝離性的觀點，就具有羧基之單體而言，宜為(甲基)丙烯酸。The (meth)acrylic oligomer preferably contains at least one structural unit derived from a monomer having a carboxyl group in addition to a structural unit derived from an alkyleneoxy group. When the (meth)acrylic oligomer contains a structural unit derived from a monomer having a carboxyl group, it tends to contribute to the improvement of peelability. There is no restriction|limiting in particular about the kind of the monomer which has a carboxyl group, The monomer which has a carboxyl group in the said (meth)acrylic-type resin is mentioned. From the viewpoint of releasability, the monomer having a carboxyl group is preferably (meth)acrylic acid.
就來自具有羧基之單體之構成單元之含有率而言，考慮進一步降低污染性的觀點，相對於(甲基)丙烯酸系寡聚物之全部構成單元，宜為0.1質量%~10質量%，為0.5質量%~7質量%更佳，為1質量%~5質量%再更佳。From the viewpoint of further reducing contamination, the content rate of the structural unit derived from the monomer having a carboxyl group is preferably 0.1% by mass to 10% by mass relative to the total structural unit of the (meth)acrylic oligomer, 0.5 mass % - 7 mass % are more preferable, and 1 mass % - 5 mass % are still more preferable.
(甲基)丙烯酸系寡聚物也可更含有來自(甲基)丙烯酸烷基酯之構成單元。來自(甲基)丙烯酸烷基酯之構成單元具有對黏著力的調整有貢獻之傾向。 就(甲基)丙烯酸烷基酯而言，和上述特定(甲基)丙烯酸系樹脂中的(甲基)丙烯酸烷基酯同義，具體例也同樣。 將黏著劑層暴露在高溫高濕環境下時，考慮發揮高耐久性之觀點，就(甲基)丙烯酸烷基酯而言，宜為碳數4~12之(甲基)丙烯酸烷基酯，為具有支鏈之碳數4~12之(甲基)丙烯酸烷基酯更佳，為甲基丙烯酸-2-乙基己酯再更佳。The (meth)acrylic oligomer may further contain a structural unit derived from an alkyl (meth)acrylate. The structural unit derived from the alkyl (meth)acrylate tends to contribute to the adjustment of the adhesive force. The alkyl (meth)acrylate has the same meaning as the alkyl (meth)acrylate in the above-mentioned specific (meth)acrylic resin, and the specific examples are also the same. When exposing the adhesive layer to a high temperature and high humidity environment, from the viewpoint of exerting high durability, the alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having 4 to 12 carbon atoms. More preferably, it is an alkyl (meth)acrylate having a branched carbon number of 4 to 12, and more preferably, it is 2-ethylhexyl methacrylate.
考慮耐久性的觀點，就來自(甲基)丙烯酸烷基酯之構成單元之含有率而言，相對於(甲基)丙烯酸系寡聚物之全部構成單元，宜為65質量%以上，為75質量%以上更佳，為80質量%以上再更佳。 又，就來自(甲基)丙烯酸烷基酯之構成單元之含有率而言，考慮耐久性的觀點，相對於(甲基)丙烯酸系寡聚物之全部構成單元，宜為99質量%以下，為95質量%以下更佳，為90質量%以下再更佳。From the viewpoint of durability, the content of the structural unit derived from the alkyl (meth)acrylate is preferably 65% by mass or more and 75% by mass relative to all the structural units of the (meth)acrylic oligomer. More preferably, it is at least 80% by mass, and even more preferably at least 80% by mass. In addition, the content rate of the structural unit derived from the alkyl (meth)acrylate is preferably 99% by mass or less with respect to all the structural units of the (meth)acrylic oligomer from the viewpoint of durability. 95 mass % or less is more preferable, and 90 mass % or less is even more preferable.
(甲基)丙烯酸系寡聚物中，在本發明之效果可發揮的範圍內，也可含有來自具有羧基之單體之構成單元、來自(甲基)丙烯酸烷基酯之構成單元及來自具有伸烷基氧基之單體之構成單元以外的構成單元(其他構成單元)。 (甲基)丙烯酸系寡聚物含有其他構成單元時，就(甲基)丙烯酸系寡聚物之全部構成單元中所佔之來自具有羧基之單體之構成單元、來自(甲基)丙烯酸烷基酯之構成單元及來自具有伸烷基氧基之單體之構成單元之合計含量而言，相對於(甲基)丙烯酸系寡聚物之全部構成單元，宜為80質量%以上，為90質量%以上更佳，為95質量%以上再更佳。In the (meth)acrylic oligomer, a structural unit derived from a monomer having a carboxyl group, a structural unit derived from an alkyl (meth)acrylate, and a structural unit derived from a A structural unit (other structural unit) other than the structural unit of the monomer of an alkyleneoxy group. When the (meth)acrylic oligomer contains other constituent units, the constituent units derived from the monomer having a carboxyl group in the total constituent units of the (meth)acrylic oligomer, the constituent units derived from the alkyl (meth)acrylate The total content of the constituent units of the base ester and the constituent units derived from the monomer having an alkyleneoxy group is preferably 80% by mass or more and 90% by mass relative to the total constituent units of the (meth)acrylic oligomer. More preferably, it is at least 95% by mass, and even more preferably at least 95% by mass.
就構成其他構成單元之單體而言，可列舉上述具有羥基之單體、具有環狀基之單體，具體例及理想範圍也同樣。As a monomer which comprises another structural unit, the monomer which has the above-mentioned hydroxyl group, and the monomer which has a cyclic group can be mentioned, and the concrete example and the ideal range are also the same.
(甲基)丙烯酸系寡聚物之重量平均分子量(Mw)若比特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)小，則無特別限制。特定(甲基)丙烯酸系寡聚物之重量平均分子量(Mw)宜為3,000~60,000，為3,000~20,000更佳。重量平均分子量(Mw)為3,000以上的話，會有可更有效地抑制對被黏著體之污染的發生之傾向。又，重量平均分子量(Mw)為60,000以下的話，會有進一步改善抗靜電性之傾向。The weight average molecular weight (Mw) of the (meth)acrylic oligomer is not particularly limited as long as it is smaller than the weight average molecular weight (Mw) of the specific (meth)acrylic resin. The weight average molecular weight (Mw) of the specific (meth)acrylic oligomer is preferably 3,000 to 60,000, more preferably 3,000 to 20,000. When the weight average molecular weight (Mw) is 3,000 or more, the occurrence of contamination to the adherend tends to be more effectively suppressed. Moreover, when the weight average molecular weight (Mw) is 60,000 or less, the antistatic property tends to be further improved.
(甲基)丙烯酸系寡聚物之重量平均分子量(Mw)可和上述特定(甲基)丙烯酸系樹脂之重量平均分子量(Mw)的測定方法同樣地進行測定。The weight average molecular weight (Mw) of the (meth)acrylic oligomer can be measured in the same manner as the method for measuring the weight average molecular weight (Mw) of the above-mentioned specific (meth)acrylic resin.
(甲基)丙烯酸系寡聚物之玻璃轉移溫度(Tg)宜為50℃以下。(甲基)丙烯酸系寡聚物之Tg為50℃以下的話，可抑制加熱處理所致之黏著力的上昇，故會有剝離性更優良的傾向。The glass transition temperature (Tg) of the (meth)acrylic oligomer is preferably 50°C or lower. When the Tg of the (meth)acrylic oligomer is 50° C. or lower, the increase in the adhesive force due to the heat treatment can be suppressed, so that the peelability tends to be more excellent.
(甲基)丙烯酸系寡聚物之玻璃轉移溫度可和上述特定(甲基)丙烯酸系樹脂之玻璃轉移溫度的計算方法同樣地進行計算。The glass transition temperature of the (meth)acrylic oligomer can be calculated in the same manner as the calculation method of the glass transition temperature of the above-mentioned specific (meth)acrylic resin.
就(甲基)丙烯酸系寡聚物之含有率而言，考慮賦予黏著劑層作為保護薄膜所必需的黏著力，同時保有適於保護薄膜的用途之剝離性的觀點，相對於(甲基)丙烯酸系樹脂100質量份，宜為0.05質量份~2質量份，為0.1質量份~1.5質量份更佳，為0.1質量份~1.2質量份再更佳。 (甲基)丙烯酸系寡聚物之含有率為0.05質量份~2質量份的話，能賦予黏著劑層保護薄膜所必需的黏著力，同時更保有適於保護薄膜的用途之剝離性。The content of the (meth)acrylic oligomer is considered from the viewpoint of imparting the adhesive force necessary for the adhesive layer as a protective film while maintaining the peelability suitable for the application of the protective film. 100 parts by mass of the acrylic resin is preferably 0.05 parts by mass to 2 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass, and even more preferably 0.1 parts by mass to 1.2 parts by mass. When the content rate of the (meth)acrylic oligomer is 0.05 parts by mass to 2 parts by mass, the adhesive force necessary for the protective film of the adhesive layer can be imparted, and the peelability suitable for the use of the protective film can be maintained.
＜其他成分＞ 黏著劑組成物含有特定(甲基)丙烯酸系樹脂、異氰酸酯化合物(B)、聚矽氧系異氰酸酯化合物(C)、抗靜電劑(D)及(甲基)丙烯酸系寡聚物，除此之外，可因應需要適當地含有特定(甲基)丙烯酸系樹脂以外的樹脂、異氰酸酯化合物以外的交聯劑、交聯觸媒、耐候性安定劑、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。<Other components> The adhesive composition contains specific (meth)acrylic resin, isocyanate compound (B), polysiloxane isocyanate compound (C), antistatic agent (D), and (meth)acrylic oligomer , In addition, resins other than specific (meth)acrylic resins, crosslinking agents other than isocyanate compounds, crosslinking catalysts, weather resistance stabilizers, tackifiers, plasticizers, Softeners, peeling aids, dyes, pigments, inorganic fillers, surfactants, etc.
就交聯觸媒而言，可列舉：促進封端化異氰酸酯化合物之封端化劑的解離之觸媒、促進因解離而再生的異氰酸酯基與其他官能基的反應之觸媒等。As a crosslinking catalyst, a catalyst which accelerates the dissociation of the blocking agent of a blocked isocyanate compound, a catalyst which promotes the reaction of the isocyanate group regenerated by dissociation, and other functional groups, etc. are mentioned.
就交聯觸媒而言，並無特別限制，可使用公知的觸媒。例如可列舉：有機金屬化合物、三級胺化合物、金屬鹽等。 就有機金屬化合物之具體例而言，可列舉：二月桂酸二辛基錫、1,3-二乙醯氧基四丁基錫氧烷(1,3-diacetoxy tetrabutyl stannoxane)等。 就三級胺化合物之具體例而言，可列舉：三乙二胺、N-甲基
[用途] 本發明之黏著劑組成物宜使用於光學構件。本發明之黏著劑組成物所形成的黏著劑層由於耐污染性及抗靜電性優良，故可理想地使用於光學構件之保護薄膜。[Use] The adhesive composition of the present invention is suitable for use in optical members. Since the adhesive layer formed by the adhesive composition of the present invention is excellent in contamination resistance and antistatic property, it can be ideally used as a protective film for optical members.
[保護薄膜] 本發明之保護薄膜，至少具有保護薄膜用黏著劑組成物之交聯物即黏著劑層與基材。 保護薄膜具有的黏著劑層，會對光學構件發揮優良的耐污染性及抗靜電性。[Protective Film] The protective film of the present invention has at least an adhesive layer and a substrate, which is a cross-linked product of the adhesive composition for a protective film. The protective film has an adhesive layer that exhibits excellent contamination resistance and antistatic properties to optical members.
就保護薄膜所使用的基材而言，若可在基材上形成黏著劑層，則無特別限制。 考慮利用透視所為之光學構件的檢查及管理之觀點，就基材而言，可列舉使用了選自於聚酯系樹脂、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薄膜。 其中，就基材而言，考慮表面保護性能的觀點，宜為使用了聚酯系樹脂之薄膜，考慮實用性的話，為使用了聚對苯二甲酸乙二酯(PET)樹脂之薄膜更佳。The base material used for the protective film is not particularly limited as long as an adhesive layer can be formed on the base material. From the viewpoint of inspection and management of optical members by fluoroscopy, as the base material, those selected from polyester-based resins, acetate-based resins, polyether-based resins, polycarbonate-based resins, Films of polyimide resins, polyimide resins, polyolefin resins, and acrylic resins. Among them, as the base material, from the viewpoint of surface protection performance, a film using a polyester resin is preferable, and considering practicality, a film using a polyethylene terephthalate (PET) resin is more preferable. .
就基材之厚度而言，通常可設定為500μm以下，宜為5μm~300μm，為10μm~200μm更佳。As for the thickness of the base material, it can usually be set to 500 μm or less, preferably 5 μm to 300 μm, and more preferably 10 μm to 200 μm.
基材的單面或雙面也可設置抗靜電層。又，基材設有黏著劑層之側的表面也可為了使黏著劑層與基材之密接性改善而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, the surface on the side where the base material is provided with the adhesive layer may be subjected to corona discharge treatment or the like in order to improve the adhesion between the adhesive layer and the base material.
基材上設置有黏著劑組成物之交聯物即黏著劑層。 就黏著劑層之形成方法而言，例如可採用將黏著劑組成物直接塗佈於基材或因應需要以適當的溶劑稀釋再將其塗佈於基材，然後進行乾燥將溶劑去除之方法。 又，也可採用先將黏著劑組成物塗佈於利用聚矽氧樹脂等施予脫模處理而成的紙、聚酯薄膜等適當的薄膜構成的剝離片材上，再加熱乾燥形成黏著劑層，然後將剝離片材之黏著劑層側壓接於基材，使黏著劑層轉印於基材之方法。A cross-linked product of the adhesive composition, that is, an adhesive layer, is arranged on the substrate. For the method of forming the adhesive layer, for example, a method of directly coating the adhesive composition on the substrate or diluting it with an appropriate solvent as needed, coating the substrate on the substrate, and then drying to remove the solvent can be adopted. In addition, the adhesive composition can also be applied to a release sheet composed of a suitable film such as paper, polyester film, etc., which has been subjected to mold release treatment with polysiloxane resin, and then heated and dried to form an adhesive. Layer, and then press the adhesive layer side of the peeling sheet to the substrate, so that the adhesive layer is transferred to the substrate.
基材上所形成的黏著劑層之厚度可因應保護薄膜所要求的黏著力、光學構件之表面粗糙度等而適當地設定。就黏著劑層之厚度而言，通常可例示為1μm~100μm，宜為5μm~50μm，為約15μm~30μm之厚度更佳。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, and the like. The thickness of the adhesive layer is usually 1 μm to 100 μm, preferably 5 μm to 50 μm, and more preferably about 15 μm to 30 μm.
亦即，對於光學構件之黏著劑層之180°剝離(剝離速度0.3m/分鐘)(低速剝離)的黏著力(剝離力)宜為0.05N/25mm以上，為0.06N/25mm以上更佳。藉由使低速剝離時的黏著力為0.05N/25mm以上，會有進一步抑制翻捲或錯位的發生之傾向。That is, the adhesive force (peeling force) for 180° peeling (peeling speed 0.3 m/min) (low-speed peeling) of the adhesive layer of the optical member is preferably 0.05 N/25 mm or more, more preferably 0.06 N/25 mm or more. When the adhesive force at the time of low-speed peeling is made 0.05N/25mm or more, it exists in the tendency to suppress the generation|occurence|production of rolling and misalignment more.
又，黏著力變高的話，高速剝離時之作業性會降低，故剝離速度30m/分鐘(高速剝離)的黏著力(剝離力)宜未達1.5N/25mm，未達1.2N/25mm更佳，未達0.9N/25mm再更佳。In addition, if the adhesive force increases, the workability during high-speed peeling will decrease. Therefore, the adhesive force (peeling force) at a peeling speed of 30m/min (high-speed peeling) should preferably be less than 1.5N/25mm, preferably less than 1.2N/25mm. , less than 0.9N/25mm is better.
考慮抑制剝離時之帶電所致對光學構件之影響的觀點，黏著劑組成物對偏光板(商品名：SRDB31E，住友化學(股)製)以30m/分鐘剝離時之剝離帶電壓的絕對值宜為0.9kV以下，為0.7kV以下更佳，為0.5kV以下再更佳。From the viewpoint of suppressing the influence on the optical member due to the electrification during peeling, the absolute value of the peeling electrification voltage when peeling off the polarizing plate (trade name: SRDB31E, manufactured by Sumitomo Chemical Co., Ltd.) at 30 m/min of the adhesive composition is suitable. It is 0.9kV or less, more preferably 0.7kV or less, and even more preferably 0.5kV or less.
又，考慮防止剝離時之薄膜側的帶電之觀點，黏著劑層之表面電阻值宜為4.9E＋11(Ω/□)(亦即，4.9×1011 Ω/□)以下。Furthermore, from the viewpoint of preventing electrification on the film side during peeling, the surface resistance value of the adhesive layer is preferably 4.9E+11(Ω/□) (that is, 4.9×10 11 Ω/□) or less.
基材上所形成的黏著劑層之厚度可因應光學構件表面保護薄膜所要求的黏著力、光學構件表面粗糙度等而適當地設定，通常可例示設定為1μm~100μm，宜為5μm~50μm，為約15μm~30μm之厚度更佳。The thickness of the adhesive layer formed on the substrate can be appropriately set according to the adhesive force required by the surface protection film of the optical member, the surface roughness of the optical member, etc. It can be exemplified as 1 μm~100 μm, preferably 5 μm~50 μm, A thickness of about 15 μm to 30 μm is more preferable.
就光學構件而言，可列舉構成圖像顯示裝置、輸入裝置等設備(光學設備)之構件或這些設備所使用的構件。就光學構件之具體例而言，例如可列舉：偏光板、AG偏光板、波長板、包含1/2、1/4等波長板之相位差板、視角補償薄膜、光學補償薄膜、增亮薄膜、導光板、反射薄膜、抗反射薄膜、ITO薄膜等透明導電薄膜、稜鏡片、透鏡片、散射板等使用於顯示裝置者。 [實施例]As an optical member, the member which comprises the apparatus (optical apparatus), such as an image display apparatus and an input apparatus, or the member used for these apparatuses is mentioned. Specific examples of optical members include polarizing plates, AG polarizing plates, wave plates, retardation plates including wavelength plates such as 1/2 and 1/4, viewing angle compensation films, optical compensation films, and brightness enhancement films. , Light guide plate, reflective film, anti-reflection film, ITO film and other transparent conductive films, crystal sheets, lens sheets, diffuser plates, etc. are used in display devices. [Example]
以下，利用實施例更具體地說明本發明，但本發明並不限於這些實施例。Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
(聚矽氧交聯劑1(聚矽氧系異氰酸酯化合物(C)) -聚矽氧交聯劑1之製造- 將異佛爾酮二異氰酸酯(IPDI)(商品名：DESMODUR I，Sumika Covestro Urethane(股)製)118質量份、SH-3773M(化學名：聚醚改性聚矽氧化合物，東麗･道康寧(股)製)82質量份進料於具備攪拌葉片、溫度計、氮氣導入管及回流冷卻器、滴液漏斗之四口燒瓶中，將反應容器的空氣以氮氣取代30分鐘後，邊將內溫維持於50℃邊攪拌4小時，獲得聚矽氧交聯劑1。得到的聚矽氧交聯劑1之組成如表1所示。(Polysilicone crosslinking agent 1 (polysiloxane-based isocyanate compound (C)) - Production of polysiloxane crosslinking agent 1 - Isophorone diisocyanate (IPDI) (trade name: DESMODUR I, Sumika Covestro Urethane) (stock) 118 parts by mass, SH-3773M (chemical name: polyether modified polysiloxane, manufactured by Toray Dow Corning Co., Ltd.) 82 parts by mass were fed into a device equipped with a stirring blade, a thermometer, a nitrogen introduction pipe and In a four-necked flask of a reflux cooler and a dropping funnel, the air in the reaction vessel was replaced with nitrogen for 30 minutes, and the internal temperature was maintained at 50° C. while stirring for 4 hours to obtain polysiloxane crosslinking agent 1. The obtained polysiloxane crosslinking agent 1 was obtained. The composition of the silicon-oxygen crosslinking agent 1 is shown in Table 1.
(聚矽氧交聯劑2~聚矽氧交聯劑8) 於聚矽氧交聯劑1中，將組成如表1所示進行變更，除此之外利用和聚矽氧交聯劑1之製造同樣的方法，製得聚矽氧交聯劑2~聚矽氧交聯劑8。(polysiloxane crosslinking agent 2 ~ polysiloxane crosslinking agent 8) In polysiloxane crosslinking agent 1, the composition was changed as shown in Table 1, and in addition to polysiloxane crosslinking agent 1 In the same manner as in the manufacturing process, polysiloxane crosslinking agent 2 to polysiloxane crosslinking agent 8 were prepared.
[表1]
表1中的縮寫如下所示。 ･SH-3773M：含有特定環氧烷結構之聚矽氧化合物(聚醚改性聚矽氧化合物，東麗･道康寧(股)製)(通式(3)表示之聚矽氧烷化合物) ･SF-8427：含有特定環氧烷結構之聚矽氧化合物(甲醇(carbinol)改性聚矽氧化合物(兩末端改性)，東麗･道康寧(股)製)(通式(4)表示之聚矽氧烷化合物) ･DESMODUR I：異氰酸酯化合物(化學名：異佛爾酮二異氰酸酯(IPDI)，Sumika Covestro Urethane(股)製) ･N-3300：異氰酸酯化合物(化學名：異氰尿酸酯改性二異氰酸六亞甲酯，商品名：SUMIDUR N-3300，Sumika Covestro Urethane(股)製，固體成分100質量%) ･TAKENATE 500：異氰酸酯化合物(化學名：二異氰酸二甲苯酯(XDI)，三井化學(股)製)Abbreviations in Table 1 are as follows. ･SH-3773M: Polysiloxane compound containing specific alkylene oxide structure (polyether-modified polysiloxane compound, manufactured by Toray & Dow Corning Co., Ltd.) (polysiloxane compound represented by general formula (3)) ･ SF-8427: Polysiloxane containing a specific alkylene oxide structure (carbinol modified polysiloxane (modified at both ends), manufactured by Toray Dow Corning Co., Ltd.) (represented by the general formula (4) Polysiloxane compound) ･DESMODUR I: Isocyanate compound (chemical name: isophorone diisocyanate (IPDI), manufactured by Sumika Covestro Urethane Co., Ltd.) ･N-3300: Isocyanate compound (chemical name: isocyanurate) Modified hexamethylene diisocyanate, trade name: SUMIDUR N-3300, manufactured by Sumika Covestro Urethane Co., Ltd., solid content 100% by mass) ･TAKENATE 500: Isocyanate compound (chemical name: dimethyldiisocyanate) (XDI), Mitsui Chemicals Co., Ltd.)
(製造例1) -(甲基)丙烯酸系樹脂(A)之製造- 將乙酸乙酯171.0質量份、三級丁醇249質量份放入具備溫度計、攪拌機、氮氣導入管及回流冷卻器之反應容器內。又，將作為單體之丙烯酸正丁酯(nBA)217.8質量份、丙烯酸-2-乙基己酯(2EHA)360.0質量份、丙烯酸-4-羥丁酯(4HBA)18.0質量份、及丙烯酸(AA)4.2質量份放入另一個反應容器內，進行混合製成單體混合物。取該單體混合物之中的20.0質量%加入反應容器中，然後將反應容器的空氣以氮氣取代後，添加作為聚合起始劑之偶氮雙異丁腈(AIBN)0.08質量份，於攪拌下在氮氣環境中使反應容器內之混合物溫度昇溫至85℃，以使初始反應開始。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%、以及乙酸乙酯88.0質量份及AIBN0.80質量份之混合物，邊使其反應約2小時，然後，再使其反應2小時。其後，將已將過氧三甲基乙酸三級丁酯0.60質量份溶解於乙酸乙酯132.0質量份而成的溶液，歷時1小時滴加於上述混合物中，再使其反應1.5小時。反應結束後，獲得(甲基)丙烯酸系樹脂(A)溶液。得到的(甲基)丙烯酸系樹脂(A)溶液之重量平均分子量(Mw)如表2所示。 另外，重量平均分子量(Mw)係以上述方法進行測定而得。(Production Example 1) - Production of (meth)acrylic resin (A) - 171.0 parts by mass of ethyl acetate and 249 parts by mass of tertiary butanol were put into a reaction equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, and a reflux cooler inside the container. In addition, 217.8 parts by mass of n-butyl acrylate (nBA), 360.0 parts by mass of 2-ethylhexyl acrylate (2EHA), 18.0 parts by mass of 4-hydroxybutyl acrylate (4HBA), and acrylic acid ( AA) 4.2 parts by mass was put into another reaction vessel, and mixed to prepare a monomer mixture. 20.0 mass % of the monomer mixture was taken into the reaction vessel, and then the air in the reaction vessel was replaced with nitrogen, 0.08 mass part of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was stirred. The temperature of the mixture in the reaction vessel was raised to 85°C under nitrogen to start the initial reaction. After the initial reaction was substantially completed, 80.0 mass % of the remaining monomer mixture, 88.0 mass parts of ethyl acetate and 0.80 mass parts of AIBN were added successively, and the reaction was carried out for about 2 hours, and then the reaction was carried out again. 2 hours. Then, the solution which melt|dissolved 0.60 mass parts of tertiary butyl peroxytrimethyl acetate in 132.0 mass parts of ethyl acetates was dripped at the said mixture over 1 hour, and it was made to react for 1.5 hours. After completion of the reaction, a (meth)acrylic resin (A) solution was obtained. Table 2 shows the weight average molecular weight (Mw) of the obtained (meth)acrylic resin (A) solution. In addition, the weight average molecular weight (Mw) is measured by the above-mentioned method.
(製造例2~製造例4) 於製造例1中，將單體如表2所示進行變更，適當變更起始劑的量、聚合條件等來調整重量平均分子量，除此之外利用和製造例1同樣的方法，製得(甲基)丙烯酸系樹脂(A)溶液。得到的(甲基)丙烯酸系樹脂(A)溶液之固體成分的組成(質量%)及重量平均分子量(Mw)如表2所示。 另外，重量平均分子量(Mw)係以上述方法進行測定而得。(Production Example 2 to Production Example 4) In Production Example 1, the monomers were changed as shown in Table 2, and the amount of the initiator, polymerization conditions, etc. were appropriately changed to adjust the weight average molecular weight, and other than that, the use and production were carried out. In the same manner as in Example 1, a (meth)acrylic resin (A) solution was obtained. Table 2 shows the composition (mass %) and the weight average molecular weight (Mw) of the solid content of the obtained (meth)acrylic resin (A) solution. In addition, the weight average molecular weight (Mw) is measured by the above-mentioned method.
[表2]
另外，表2中的「-」表示不含該相應成分。In addition, "-" in Table 2 means that the corresponding component is not contained.
-(甲基)丙烯酸系寡聚物之製造- 將甲乙酮100.0份放入具備溫度計、攪拌葉片、氮氣導入管、冷卻器、滴液漏斗之反應容器內，於氮氣環境下邊攪拌邊加熱到回流溫度。將已預先混合而得的甲基丙烯酸正丁酯(nBMA)68.0質量份、甲基丙烯酸-2-羥乙酯(2HEMA)20.0質量份、甲基丙烯酸甲氧基聚乙二醇酯(環氧烷基之含有數：23)10份、丙烯酸(AA)2.0質量份、甲乙酮100.0質量份及偶氮雙異丁腈5.0質量份之混合溶液放入滴液漏斗，歷時120分鐘逐次添加到回流溫度之反應容器中。其後，以維持回流溫度240分鐘之狀態使其反應，並結束反應。以此方式，獲得(甲基)丙烯酸系寡聚物溶液。 得到的(甲基)丙烯酸系寡聚物之溶液的固體成分為33.0質量%，重量平均分子量(Mw)為7,000。另外，重量平均分子量(Mw)係以上述方法進行測定而得。-Manufacture of (meth)acrylic oligomer- 100.0 parts of methyl ethyl ketone was put into a reaction vessel equipped with a thermometer, a stirring blade, a nitrogen introduction tube, a cooler, and a dropping funnel, and heated to reflux temperature with stirring under a nitrogen atmosphere . 68.0 parts by mass of n-butyl methacrylate (nBMA), 20.0 parts by mass of 2-hydroxyethyl methacrylate (2HEMA), methoxy polyethylene glycol methacrylate (epoxy The number of alkyl groups contained: 23) A mixed solution of 10 parts by mass, 2.0 parts by mass of acrylic acid (AA), 100.0 parts by mass of methyl ethyl ketone, and 5.0 parts by mass of azobisisobutyronitrile was put into a dropping funnel and added to the reflux temperature for 120 minutes. in the reaction vessel. Then, it was made to react while maintaining the reflux temperature for 240 minutes, and the reaction was completed. In this way, a (meth)acrylic oligomer solution was obtained. The solid content of the solution of the obtained (meth)acrylic oligomer was 33.0 mass %, and the weight average molecular weight (Mw) was 7,000. In addition, the weight average molecular weight (Mw) is measured by the above-mentioned method.
(實施例1) 將製造例1所製得的(甲基)丙烯酸系樹脂(A)溶液(固體成分45%)222.2質量份(就固體成分而言為100質量份)、上述所製得的(甲基)丙烯酸系寡聚物溶液(固體成分33%)0.9質量份(就固體成分而言為0.80質量份)、作為抗靜電劑(D)之LiTFS(化學名：LiCF3 SO3 ，森田化學工業(股)製)0.25質量份進料於具備攪拌葉片、溫度計、冷卻器、滴液漏斗之四口燒瓶中，將燒瓶內的液溫維持在25℃附近實施4.0小時混合攪拌。添加作為異氰酸酯化合物(B)之SUMIDUR N-3300稀釋物(化學名：二異氰酸六亞甲酯(HMDI)，Sumika Covestro Urethane公司製)12.0質量份(就固體成分而言為3.00質量份)、上述所製得的聚矽氧交聯劑1相當於0.38質量份量，充分地攪拌，獲得黏著劑組成物溶液。(Example 1) 222.2 parts by mass (100 parts by mass in terms of solid content) of the (meth)acrylic resin (A) solution (solid content 45%) obtained in Production Example 1, the (Meth)acrylic oligomer solution (solid content 33%) 0.9 parts by mass (0.80 parts by mass in terms of solid content), LiTFS (chemical name: LiCF 3 SO 3 , Morita) as antistatic agent (D) Chemical Industry Co., Ltd.) 0.25 parts by mass was charged into a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel, and the liquid temperature in the flask was maintained at around 25° C. to perform mixing and stirring for 4.0 hours. As the isocyanate compound (B), 12.0 parts by mass (3.00 parts by mass in terms of solid content) of SUMIDUR N-3300 dilution (chemical name: hexamethylene diisocyanate (HMDI), manufactured by Sumika Covestro Urethane) was added , The polysiloxane cross-linking agent 1 prepared above is equivalent to 0.38 parts by mass, and is fully stirred to obtain an adhesive composition solution.
[評價] -耐污染性- ＜保護薄膜之製作＞ 將上述得到的黏著劑組成物溶液以乾燥後之塗佈量成為15g/m2 的方式塗佈於經以聚矽氧系脫模劑表面處理而得的脫模薄膜(商品名：FILMBYNA 25E0010BD，厚度100μm，藤森工業(股)製)上，於100℃以熱風循環式乾燥機乾燥60秒鐘。其後，將塗佈有黏著劑組成物溶液之脫模薄膜塗佈面重疊於另外準備的經以聚矽氧系脫模劑表面處理而得的脫模薄膜(商品名：FILMBYNA 100E-0010NO23，厚度25μm，藤森工業(股)製)之表面處理面，製成疊層體。將該疊層體通過加壓夾輥對進行壓接貼合後，於23℃、50%RH之條件下熟成96小時，製得無基材型之黏著片材。[Evaluation] -Contamination resistance- <Preparation of protective film> The adhesive composition solution obtained above was applied on the surface of the polysiloxane-based mold release agent so that the coating amount after drying was 15 g/m 2 . The processed release film (trade name: FILMBYNA 25E0010BD, thickness 100 μm, manufactured by Fujimori Kogyo Co., Ltd.) was dried at 100° C. for 60 seconds with a hot air circulation dryer. After that, the coating surface of the release film coated with the adhesive composition solution was superimposed on the release film (trade name: FILMBYNA 100E-0010NO23, The thickness of 25 μm, the surface treatment surface of Fujimori Industry Co., Ltd.), was made into a laminated body. After the laminated body was pressed and bonded by a pair of pressure nip rolls, it was aged for 96 hours under the conditions of 23° C. and 50% RH to obtain a base material-free adhesive sheet.
＜聚矽氧反應率＞ 從已裁切成75mm×75mm大小之無基材型的黏著片材，將其中一側之脫模薄膜剝離，將露出黏著劑層之面貼合於已裁切成100mm×100mm之250網目之金屬網(真鍋工業(股)製)。然後，將剩下的脫模薄膜剝離，並以溶劑浸漬時黏著劑不會洩漏的方式包入250網目之金屬網，準備好裝有黏著劑之金屬網。重複此操作，準備好6個裝有黏著劑之金屬網，並測定黏著劑之總質量。 黏著劑之總質量=裝有黏著劑之金屬網的質量(g)-金屬網的質量(g)<Reaction rate of polysiloxane> From a substrateless adhesive sheet that has been cut into a size of 75mm × 75mm, peel off the release film on one side, and stick the exposed surface of the adhesive layer to the cut sheet. 100mm×100mm 250-mesh metal mesh (manufactured by Manabe Industry Co., Ltd.). Then, peel off the remaining release film and wrap it in a 250-mesh metal mesh in such a way that the adhesive will not leak during solvent dipping, and prepare the metal mesh with the adhesive. Repeat this operation, prepare 6 metal meshes with adhesive, and measure the total mass of the adhesive. The total mass of the adhesive = the mass of the metal mesh with the adhesive (g) - the mass of the metal mesh (g)
將6個裝有黏著劑之金屬網浸漬於裝有乙酸乙酯80g之容器中，於23℃環境下靜置3天。經過3天後，從容器將6個裝有黏著劑之金屬網全部取出，將浸漬後之乙酸乙酯以250網目之金屬網過濾，製成樣本樣品。The 6 metal meshes containing the adhesive were immersed in a container containing 80 g of ethyl acetate, and allowed to stand at 23° C. for 3 days. After 3 days, all the 6 metal meshes containing the adhesive were taken out from the container, and the impregnated ethyl acetate was filtered through a metal mesh of 250 meshes to prepare a sample.
首先量取樣本樣品10g~11g，收集於50ml之鐵氟龍(註冊商標)製皿後，於約80℃之加熱板上充分地蒸發乾固後暫時放冷。放冷後將殘留物移至聚丙烯(PP)製之錶玻璃，添加1.5ml之鹽酸(特級試藥，和光純藥工業(股)製)，於約80℃之加熱板上進行約5分鐘之加熱溶解後，再度放冷。 再度放冷後，將殘留溶液倒入聚乙烯或聚丙烯容器中，並將全氟烷氧基樹脂(PFA)製之蒸發皿以蒸餾水10ml清洗後，將清洗液倒入聚乙烯或聚丙烯容器中，將殘留物作為測定用樣品。 以下列測定條件並使用感應耦合電漿發光分光分析(ICP-AES)裝置(型號：ICPS-7510型，島津製作所(股)製)來定量測定用樣品中所含的矽(Si)原子之量。First, measure 10g~11g of the sample, collect it in a 50ml Teflon (registered trademark) dish, fully evaporate to dryness on a heating plate at about 80°C, and let it cool temporarily. After cooling, the residue was transferred to a polypropylene (PP) watch glass, 1.5 ml of hydrochloric acid (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated on a heating plate at about 80°C for about 5 minutes. After heating and dissolving, let it cool again. After letting it cool again, pour the residual solution into a polyethylene or polypropylene container, wash the evaporating dish made of perfluoroalkoxy resin (PFA) with 10ml of distilled water, and pour the cleaning solution into a polyethylene or polypropylene container , the residue was used as a sample for measurement. The amount of silicon (Si) atoms contained in the sample for quantitative measurement was measured under the following measurement conditions using an inductively coupled plasma emission spectrometer (ICP-AES) apparatus (model: ICPS-7510, manufactured by Shimadzu Corporation). .
＜測定條件＞ 分析設備：感應耦合電漿發光分光分析裝置(ICP-AES)(型號：ICPS-7510型，島津製作所(股)製) 噴霧室：旋風噴霧室 測定位置：橫方向觀測 霧化器：同軸霧化器 高頻功率：1.2kW 冷卻劑氣體：14.0L/分鐘 載氣：氬氣，0.7L/分鐘 定量方法：利用檢量線法實施 檢量線用樣品濃度：0.2ppm、1.0ppm、5.0ppm(和光純藥工業(股)製原子吸光用標準液(Si 1000ppm))<Measurement conditions> Analysis equipment: Inductively Coupled Plasma Emission Spectroscopy (ICP-AES) (Model: ICPS-7510, manufactured by Shimadzu Corporation) Spray chamber: Cyclone spray chamber Measurement position: Horizontal observation atomizer : Coaxial nebulizer High frequency power: 1.2kW Coolant gas: 14.0L/min Carrier gas: Argon, 0.7L/min Quantitative method: Using the calibration curve method Sample concentrations for calibration: 0.2ppm, 1.0ppm , 5.0ppm (Standard solution for atomic absorption (Si 1000ppm) manufactured by Wako Pure Chemical Industries, Ltd.)
根據檢測到的矽(Si)原子之量，以下述計算式算出聚矽氧反應率。Based on the amount of detected silicon (Si) atoms, the polysiloxane reaction rate was calculated by the following formula.
聚矽氧反應率(%)=(1-(A/B))×100 A：溶出到乙酸乙酯之聚矽氧化合物量(ppm)=檢測到的矽(Si)原子之量的值(ppm)-0.04(ppm) 另外，檢測到的矽(Si)原子之量，係已扣除作為脫模薄膜所含的聚矽氧化合物之影響程度0.04ppm而得的數值。 B：黏著劑層中含有的聚矽氧化合物量(ppm)=(w×s)/e×t×1000000 w：黏著劑之總質量(g) s：黏著劑中含有的聚矽氧化合物之比例(質量%) e：乙酸乙酯質量；80(g) t：聚矽氧化合物中的Si原子量(為ICP-AES實測值，SH-3773M(側鏈聚醚改性聚矽氧化合物(東麗･道康寧(股)製))之Si原子量為0.20，SF-8427(兩末端聚醚改性聚矽氧化合物(東麗･道康寧(股)製))之Si原子量為0.45。)Polysiloxane reaction rate (%)=(1-(A/B))×100 A: The amount of polysiloxane eluted into ethyl acetate (ppm)=the value of the amount of detected silicon (Si) atoms ( ppm)-0.04 (ppm) In addition, the amount of detected silicon (Si) atoms is a value obtained by deducting 0.04 ppm, which is the degree of influence of the polysiloxane contained in the release film. B: The amount of polysiloxane contained in the adhesive layer (ppm)=(w×s)/e×t×1000000 w: The total mass of the adhesive (g) s: The amount of polysiloxane contained in the adhesive Ratio (mass %) e: mass of ethyl acetate; 80(g) t: Si atomic weight in polysiloxane (measured value by ICP-AES, SH-3773M (side chain polyether modified polysiloxane (East) The atomic weight of Si is 0.20, and the atomic weight of Si in SF-8427 (two-terminal polyether-modified polysiloxane (manufactured by Toray Dow Corning)) is 0.45.)
實施例1中的聚矽氧反應率為94.5%，係使用下述數值而求得的值。 A：0.24-0.04=0.20 B：(w×s)/e×t×1000000=3.67 w：0.51(g) s：0.30/(100＋0.80＋0.25＋0.38＋0.13＋3.0)=0.002869 e：80(g) t：0.20The polysiloxane reaction rate in Example 1 was 94.5%, which was obtained using the following numerical values. A: 0.24-0.04=0.20 B: (w×s)/e×t×1000000=3.67 w: 0.51(g) s: 0.30/(100＋0.80＋0.25＋0.38＋0.13＋3.0)=0.002869 e: 80 (g) t: 0.20
實施例1中的s(黏著劑所含的聚矽氧化合物之比例(質量%))，係聚矽氧化合物之含量0.30除以有效成分之總質量104.25而得的值。 另外，有效成分之總質量，為(甲基)丙烯酸系樹脂之含量100、(甲基)丙烯酸系寡聚物之含量0.80、抗靜電劑之含量0.25、聚矽氧系異氰酸酯化合物(C)之含量0.38、預反應中的未反應之異氰酸酯化合物之含量0.13及異氰酸酯化合物(B)之含量3.0的和。In Example 1, s (the ratio (mass %) of the polysiloxane contained in the adhesive) is the value obtained by dividing the content of the polysiloxane by 0.30 of the total mass of the active ingredients, 104.25. In addition, the total mass of the active ingredients is the content of (meth)acrylic resin 100, the content of (meth)acrylic oligomer 0.80, the content of antistatic agent 0.25, the content of polysiloxane isocyanate compound (C) The sum of the content of 0.38, the content of 0.13 of the unreacted isocyanate compound in the pre-reaction, and the content of 3.0 of the isocyanate compound (B).
計算而得的聚矽氧反應率依循下述評價基準評價耐污染性。結果如表3所示。 聚矽氧反應率若較高，則黏著劑組成物之耐污染性優良。評價若為「A」以上，則判斷為耐污染性優良。The calculated polysiloxane reaction rate was used to evaluate contamination resistance according to the following evaluation criteria. The results are shown in Table 3. If the polysiloxane reaction rate is high, the stain resistance of the adhesive composition is excellent. When the evaluation was "A" or higher, it was judged that the stain resistance was excellent.
(評價基準) AA：90%以上。 A：60%~未達90%。 B：40%~未達60%。 C：未達40%。(Evaluation Criteria) AA: 90% or more. A: 60% to less than 90%. B: 40% to less than 60%. C: Less than 40%.
-抗靜電性- ＜保護薄膜之製作＞ 將黏著劑組成物溶液以乾燥後之塗佈量成為15g/m2 的方式塗佈於聚對苯二甲酸乙二酯(PET)薄膜(商品名：TEIJIN TETORON FILM G2，厚度38μm，帝人杜邦薄膜(股)製)上，於100℃以熱風循環式乾燥機乾燥60秒鐘。其後，將塗佈有黏著劑組成物溶液之塗佈面重疊於經以聚矽氧系脫模劑表面處理而得的脫模薄膜(商品名：FILMBYNA 25E0010BD，厚度100μm，藤森工業(股)製)之表面處理面，製成疊層體。將該疊層體通過加壓夾輥對進行壓接貼合後，於23℃、50%RH之條件下熟成96小時，製得黏著片材。 使用表面電阻測定裝置(ADVANTEST(股)製：R12704 RESISTIVITY CHAMBER)，於23℃、50%RH、施加電壓100V之條件下測定於上述製得之黏著片材之表面電阻值，並依循下述評價基準進行評價。結果如表3所示。 表面電阻值愈小則抗靜電性愈優良。另外，評價若為「C」以上，則評價為具有抗靜電性。 -Antistatic property- <Preparation of protective film> The adhesive composition solution was applied on a polyethylene terephthalate (PET) film (trade name: TEIJIN TETORON FILM G2, thickness 38 μm, manufactured by Teijin DuPont Film Co., Ltd.), was dried at 100° C. for 60 seconds with a hot air circulation dryer. After that, the coating surface coated with the adhesive composition solution was superimposed on a release film (trade name: FILMBYNA 25E0010BD, thickness 100 μm, Fujimori Industry Co., Ltd.) which was surface-treated with a polysiloxane-based release agent. The surface-treated surface of the system) was made into a laminated body. After the laminated body was pressure-bonded and bonded by a pair of pressure nip rolls, it was aged for 96 hours under the conditions of 23° C. and 50% RH to obtain an adhesive sheet. Using a surface resistance measuring device (manufactured by ADVANTEST Co., Ltd.: R12704 RESISTIVITY CHAMBER), the surface resistance value of the adhesive sheet obtained above was measured under the conditions of 23° C., 50% RH, and an applied voltage of 100 V, and the following evaluation was performed. benchmark for evaluation. The results are shown in Table 3. The smaller the surface resistance value, the better the antistatic property. In addition, when the evaluation was "C" or higher, it was evaluated as having antistatic properties.
(評價基準) A：表面電阻值未達1.0×1011 Ω/□，抗靜電性非常優秀。 B：表面電阻值為1.0×1011 Ω/□~4.9×1011 Ω/□，抗靜電性優良。 C：表面電阻值超過4.9×1011 Ω/□但為9.9×1011 Ω/□以下，具有抗靜電性。 D：表面電阻值超過9.9×1011 Ω/□，抗靜電性不良。(Evaluation Criteria) A: The surface resistance value is less than 1.0×10 11 Ω/□, and the antistatic property is very excellent. B: The surface resistance value is 1.0×10 11 Ω/□ to 4.9×10 11 Ω/□, and the antistatic property is excellent. C: The surface resistance value exceeds 4.9×10 11 Ω/□ but is 9.9×10 11 Ω/□ or less, and has antistatic properties. D: The surface resistance value exceeds 9.9×10 11 Ω/□, and the antistatic property is poor.
(實施例2~實施例18以及比較例1~3及比較例5) 於製造例1中，變更為如表1所示之單體組成，並適當地調整起始劑量等，除此之外和製造例1同樣地進行，製得黏著劑組成物。使用製得的黏著劑組成物，和實施例1同樣地進行製得保護薄膜，並和實施例1同樣地實施各種評價。結果如表3所示。(Examples 2 to 18 and Comparative Examples 1 to 3 and Comparative Example 5) In Production Example 1, except that the monomer composition shown in Table 1 was changed, and the starting dose was appropriately adjusted. In the same manner as in Production Example 1, an adhesive composition was obtained. Using the obtained adhesive composition, a protective film was produced in the same manner as in Example 1, and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.
(比較例4) 將DESMODUR I(化學名：異佛爾酮二異氰酸酯，Sumika Covestro Urethane(股)製)118質量份、SH-8400(側鏈聚醚改性非反應性聚矽氧化合物，東麗･道康寧(股)製)82質量份進料於具備攪拌葉片、溫度計、氮氣導入管及回流冷卻器、滴液漏斗之四口燒瓶中，將反應容器的空氣以氮氣取代30分鐘後，邊保持內溫50℃邊攪拌4小時，製得非反應性聚矽氧化合物及異氰酸酯化合物之混合液。 比較例4係以表3所記載之摻合比率混合於上述製得的非反應性聚矽氧化合物及異氰酸酯化合物之混合液、於製造例1製得的(甲基)丙烯酸系樹脂(A)、異氰酸酯化合物(B)及抗靜電劑(D)，製得黏著劑組成物溶液。使用製得的黏著劑組成物，和實施例1同樣地進行製得保護薄膜，並和實施例1同樣地實施各種評價。結果如表3所示。(Comparative Example 4) 118 parts by mass of DESMODUR I (chemical name: isophorone diisocyanate, manufactured by Sumika Covestro Urethane Co., Ltd.), SH-8400 (side chain polyether-modified non-reactive polysiloxane, East 82 parts by mass of Dow Corning Co., Ltd. was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a reflux cooler, and a dropping funnel, and the air in the reaction vessel was replaced with nitrogen for 30 minutes. The mixture was stirred for 4 hours while maintaining the internal temperature at 50° C. to obtain a mixed solution of the non-reactive polysiloxane compound and the isocyanate compound. Comparative Example 4 is the (meth)acrylic resin (A) obtained in Production Example 1, which was mixed with the mixed solution of the non-reactive polysiloxane compound and isocyanate compound obtained above at the mixing ratio described in Table 3. , an isocyanate compound (B) and an antistatic agent (D) to obtain an adhesive composition solution. Using the obtained adhesive composition, a protective film was produced in the same manner as in Example 1, and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.
[表3]
表3中的縮寫如下所示。另外，表3中的「-」表示不含該相應成分或無法測定，「N.D」表示未檢出。Abbreviations in Table 3 are shown below. In addition, "-" in Table 3 means that the corresponding component is not contained or cannot be measured, and "N.D" means that it is not detected.
･N-3300：異氰酸酯化合物(化學名：異氰尿酸酯改性二異氰酸六亞甲酯，商品名：SUMIDUR N-3300，Sumika Covestro Urethane(股)製，固體成分100質量%) ･IPDI：異氰酸酯化合物(化學名：異佛爾酮二異氰酸酯，商品名：DESMODUR I，Sumika Covestro Urethane(股)製) ･XDI：異氰酸酯化合物(化學名：二異氰酸二甲苯酯(XDI)，商品名：TAKENATE 500，三井化學(股)製) ･LiTS：抗靜電劑(化學名：Li(CF3 SO2 )O，森田化學工業(股)製) ･MP-402：抗靜電劑(化學名：三甲基十二烷基銨雙(氟磺醯基)醯亞胺，第一工業製藥(股)製) ･SH-3773M：含有特定環氧烷結構之聚矽氧化合物(側鏈聚醚改性聚矽氧化合物，東麗･道康寧(股)製) ･SH-8400：聚矽氧化合物(側鏈聚醚改性非反應性聚矽氧化合物，東麗･道康寧(股)製) ･DOBDL：交聯觸媒(化學名：二月桂酸二辛基錫，商品名：OT-1，ADEKA(股)製，利用乙醯基丙酮適當稀釋後使用)･N-3300: Isocyanate compound (chemical name: isocyanurate-modified hexamethylene diisocyanate, trade name: SUMIDUR N-3300, manufactured by Sumika Covestro Urethane Co., Ltd., solid content 100% by mass) ･ IPDI: Isocyanate compound (chemical name: isophorone diisocyanate, trade name: DESMODUR I, manufactured by Sumika Covestro Urethane Co., Ltd.) ･XDI: Isocyanate compound (chemical name: xylene diisocyanate (XDI), trade name Name: TAKENATE 500, manufactured by Mitsui Chemicals Co., Ltd.) ･LiTS: Antistatic agent (chemical name: Li(CF 3 SO 2 )O, manufactured by Morita Chemical Co., Ltd.) ･MP-402: Antistatic agent (chemical name) : Trimethyldodecylammonium bis(fluorosulfonyl)imide, manufactured by Daiichi Kogyo Co., Ltd.) ･SH-3773M: Polysiloxane containing a specific alkylene oxide structure (side-chain polyether) Modified polysiloxane, Toray Dow Corning Co., Ltd.) ･SH-8400: Polysiloxane (side-chain polyether-modified non-reactive polysiloxane, Toray Dow Corning Co., Ltd.) ･ DOBDL: Cross-linking catalyst (chemical name: dioctyltin dilaurate, trade name: OT-1, manufactured by ADEKA Co., Ltd., used after appropriate dilution with acetylacetone)
表3中，未反應異氰酸酯化合物，意指在具有反應性基且具有環氧烷結構之聚矽氧化合物與異氰酸酯化合物之預反應中，不和具有反應性基且具有環氧烷結構之聚矽氧化合物反應之異氰酸酯化合物。 表3中，SH-3773M(※)，意指在製備聚矽氧系異氰酸酯化合物(C)中，不和異氰酸酯化合物反應之具有反應性基且具有環氧烷結構之聚矽氧化合物。In Table 3, the unreacted isocyanate compound means that in the pre-reaction of the polysiloxane compound having a reactive group and having an alkylene oxide structure with an isocyanate compound, it does not mix with the polysilicon having a reactive group and having an alkylene oxide structure. Oxygen compound-reacted isocyanate compound. In Table 3, SH-3773M (*) means a polysiloxane compound having a reactive group and having an alkylene oxide structure that does not react with the isocyanate compound in the preparation of the polysiloxane-based isocyanate compound (C).
含有至少具有交聯性官能基之(甲基)丙烯酸系樹脂(A)、異氰酸酯化合物(B)、前述異氰酸酯化合物(B)以外之具有聚矽氧烷結構及環氧烷結構之異氰酸酯化合物(C)(聚矽氧系異氰酸酯化合物(C))、及抗靜電劑(D)，且前述異氰酸酯化合物(C)之含量相對於前述(甲基)丙烯酸系樹脂(A)100質量份，為0.10質量份以上之實施例1~實施例18之黏著劑組成物的交聯物即黏著劑層，其耐污染性及抗靜電性優良。 尤其是實施例1之黏著劑組成物的交聯物即黏著劑層，其耐污染性及抗靜電性特別優良。實施例1係使用和異氰酸酯化合物(B)不同的其他異氰酸酯化合物來製備聚矽氧交聯劑1(聚矽氧系異氰酸酯化合物(C))者。Contains (meth)acrylic resin (A) having at least a crosslinkable functional group, isocyanate compound (B), and isocyanate compound (C) other than the aforementioned isocyanate compound (B) having a polysiloxane structure and an alkylene oxide structure ) (polysiloxane-based isocyanate compound (C)), and antistatic agent (D), and the content of the aforementioned isocyanate compound (C) is 0.10 mass parts relative to 100 mass parts of the aforementioned (meth)acrylic resin (A) The cross-linked products of the adhesive compositions of Examples 1 to 18 above, namely the adhesive layer, are excellent in contamination resistance and antistatic properties. In particular, the cross-linked product of the adhesive composition of Example 1, that is, the adhesive layer, is particularly excellent in contamination resistance and antistatic property. In Example 1, the polysiloxane crosslinking agent 1 (polysiloxane-based isocyanate compound (C)) was prepared by using another isocyanate compound different from the isocyanate compound (B).
相對於此，聚矽氧系異氰酸酯化合物(C)之含量相對於(甲基)丙烯酸系樹脂(A)100質量份，未達0.10質量份之比較例1之黏著劑組成物的交聯物即黏著劑層，在聚矽氧系異氰酸酯化合物(C)之製備中，由於異氰酸酯化合物相對於具有反應性基且具有環氧烷結構之聚矽氧化合物之量少，故聚矽氧反應率低，未反應之聚矽氧化合物大量生成，因此耐污染性不良。 又，不含抗靜電劑(D)之比較例2之黏著劑組成物的交聯物即黏著劑層，其抗靜電性不良。On the other hand, the content of the polysiloxane-based isocyanate compound (C) relative to 100 parts by mass of the (meth)acrylic resin (A) was less than 0.10 parts by mass of the adhesive composition of Comparative Example 1. The crosslinked product is For the adhesive layer, in the preparation of the polysiloxane-based isocyanate compound (C), since the amount of the isocyanate compound relative to the polysiloxane compound having a reactive group and having an alkylene oxide structure is small, the polysiloxane reaction rate is low, A large amount of unreacted polysiloxane is generated, and thus the contamination resistance is poor. Moreover, the crosslinked product of the adhesive composition of Comparative Example 2 which does not contain the antistatic agent (D), that is, the adhesive layer, has poor antistatic properties.
在聚矽氧系異氰酸酯化合物(C)之製備中，不使具有反應性基且具有環氧烷結構之聚矽氧化合物與異氰酸酯化合物進行預反應之比較例3、及使不含反應性基且具有環氧烷結構之聚矽氧化合物與異氰酸酯化合物進行預反應之比較例4之黏著劑組成物的交聯物即黏著劑層，由於並未生成聚矽氧系異氰酸酯化合物(C)，故耐污染性不良。 不含聚矽氧系異氰酸酯化合物(C)之比較例5之黏著劑組成物的交聯物即黏著劑層，由於抗靜電劑(D)並未局部存在黏著劑層的表面附近，故抗靜電性不良。In the preparation of the polysiloxane-based isocyanate compound (C), Comparative Example 3 in which the polysiloxane compound having a reactive group and having an alkylene oxide structure was not pre-reacted with the isocyanate compound, and the The cross-linked product of the adhesive composition of Comparative Example 4 in which the polysiloxane compound having an alkylene oxide structure and the isocyanate compound are pre-reacted is the adhesive layer, since the polysiloxane-based isocyanate compound (C) is not formed, it is resistant to Poor contamination. The cross-linked product of the adhesive composition of Comparative Example 5 without the polysiloxane-based isocyanate compound (C), namely the adhesive layer, is antistatic since the antistatic agent (D) does not locally exist near the surface of the adhesive layer. Bad sex.
綜上，本發明之黏著劑組成物的交聯物即黏著劑層，其耐污染性及抗靜電性優良，故可理想地使用作為光學構件之保護薄膜。In conclusion, the cross-linked product of the adhesive composition of the present invention, that is, the adhesive layer, has excellent contamination resistance and antistatic properties, so it can be ideally used as a protective film for optical members.
無none
Claims (6)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-156120 | 2017-08-10 | ||
| JP2017156120 | 2017-08-10 | ||
| JP2018-017312 | 2018-02-02 | ||
| JP2018017312A JP7020606B2 (en) | 2017-08-10 | 2018-02-02 | Adhesive composition for protective film and protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201910469A TW201910469A (en) | 2019-03-16 |
| TWI772483B true TWI772483B (en) | 2022-08-01 |
Family
ID=65637000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW107127194A TWI772483B (en) | 2017-08-10 | 2018-08-06 | Adhesive composition for protective film, and protective film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7020606B2 (en) |
| TW (1) | TWI772483B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6927866B2 (en) * | 2017-11-30 | 2021-09-01 | 日本カーバイド工業株式会社 | Adhesive composition for protective film and protective film |
| JP2020183461A (en) * | 2019-04-26 | 2020-11-12 | 日立化成株式会社 | Composition for pressure-sensitive adhesives, pressure-sensitive adhesive film, and surface-protective film |
| JP7456822B2 (en) * | 2020-03-23 | 2024-03-27 | 日本カーバイド工業株式会社 | Adhesive composition for optical member protective film and optical member protective film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010018813A (en) * | 1999-07-30 | 2010-01-28 | Ppg Ind Ohio Inc | Coating composition having improved scratch resistance, coated substrate and method related to the same |
| JP2013185007A (en) * | 2012-03-06 | 2013-09-19 | Fujimori Kogyo Co Ltd | Adhesive composition and surface protecting film |
| CN104903417A (en) * | 2012-12-27 | 2015-09-09 | 日本电石工业株式会社 | Adhesive composition and optical member surface protective film |
| JP2017128636A (en) * | 2016-01-19 | 2017-07-27 | 日本カーバイド工業株式会社 | Adhesive composition and optical member surface protective film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100922684B1 (en) | 2007-08-31 | 2009-10-19 | 제일모직주식회사 | Photocuring Composition for Adhesive Layer and Dicing Die Bonding Film Comprising the Same |
| KR101666479B1 (en) * | 2013-08-27 | 2016-10-14 | 서울대학교산학협력단 | Benzotriazole based (meth)acrylate copolymer and adhesive composition comprising same |
-
2018
- 2018-02-02 JP JP2018017312A patent/JP7020606B2/en active Active
- 2018-08-06 TW TW107127194A patent/TWI772483B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010018813A (en) * | 1999-07-30 | 2010-01-28 | Ppg Ind Ohio Inc | Coating composition having improved scratch resistance, coated substrate and method related to the same |
| JP2013185007A (en) * | 2012-03-06 | 2013-09-19 | Fujimori Kogyo Co Ltd | Adhesive composition and surface protecting film |
| CN104903417A (en) * | 2012-12-27 | 2015-09-09 | 日本电石工业株式会社 | Adhesive composition and optical member surface protective film |
| JP2017128636A (en) * | 2016-01-19 | 2017-07-27 | 日本カーバイド工業株式会社 | Adhesive composition and optical member surface protective film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019035066A (en) | 2019-03-07 |
| JP7020606B2 (en) | 2022-02-16 |
| TW201910469A (en) | 2019-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI772483B (en) | Adhesive composition for protective film, and protective film | |
| TWI720114B (en) | Adhesive composition for protective film, and protective film | |
| TWI493001B (en) | Adhesive composition | |
| TWI529228B (en) | Adhesive composition and film for optical member | |
| KR101718558B1 (en) | Adhesive composition | |
| TWI618768B (en) | Pressure-sensitive adhesive composition and optical element surface protection film | |
| TW200932856A (en) | Pressure sensitive adhesive, pressure sensitive adhesive for optical member, optical member and pressure sensitive adhesive for impermanently protecting surface | |
| TWI557199B (en) | Adhesive composition, adhesive film, and surface-protective adhesive film | |
| JP2017128636A (en) | Adhesive composition and optical member surface protective film | |
| KR102158871B1 (en) | Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same | |
| KR102464960B1 (en) | Adhesive composition for protective film, and protective film | |
| TWI826590B (en) | Adhesive composition for protective film of optical member and protective film of optical member | |
| CN106133098A (en) | Adhesion agent composition and the Polarizer comprising this adhesion agent composition | |
| JP6927866B2 (en) | Adhesive composition for protective film and protective film | |
| TWI813805B (en) | Adhesive composition, optical film comprising same, organic electronic device comprising same and display device | |
| JP6827670B2 (en) | Adhesive composition for optical member protective film and optical member protective film | |
| JP7496451B2 (en) | Pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and surface protection film for polarizing plate | |
| TW201823412A (en) | Pressure sensitive adhesive, pressure sensitive adhesive film, and optical laminate | |
| JP6999735B2 (en) | Surface protective film | |
| JP7350922B2 (en) | Adhesive layer, adhesive film, surface protection film | |
| JP7454719B2 (en) | surface protection film | |
| JP2016030830A (en) | Antistatic agent and adhesive composition | |
| CN106255734A (en) | Antistatic behaviour adhesion agent composition and utilize its Polarizer manufactured | |
| CN106103624B (en) | Adhesion agent composition and polarizer comprising adhesion agent composition | |
| TW201542759A (en) | Adhesive composition including ionic antistatic agent |