TW201516123A - Adhesive layer for chemical liquid treatment, adhesive sheet for chemical liquid treatment, surface protective sheet, and glass substrate - Google Patents
Adhesive layer for chemical liquid treatment, adhesive sheet for chemical liquid treatment, surface protective sheet, and glass substrate Download PDFInfo
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本發明係關於一種藥液處理用黏著劑層。具體而言,係關於一種具有防藥液浸入性及抗靜電性之黏著劑層,使用其製成片狀、或帶狀等形態而成之黏著片,表面保護片,以及貼附有上述表面保護片而成之玻璃基板。更詳細而言,係關於一種能夠於用藥液處理被接著體時遮罩非處理對象部分(欲排除藥液之影響之部分)的藥液處理用之表面保護片等。 The present invention relates to an adhesive layer for treating a liquid medicine. Specifically, it relates to an adhesive layer having a chemical solution immersion property and an antistatic property, and is used to form an adhesive sheet in the form of a sheet or a belt, a surface protective sheet, and the above surface. A glass substrate made of a protective sheet. More specifically, the present invention relates to a surface protective sheet for treating a chemical liquid which can cover a non-treated object portion (a portion to be excluded from the influence of the chemical liquid) when the adherend is treated with the chemical liquid.
於用藥液處理被接著體(被處理材料)時,用以遮罩上述被接著體之非處理對象部分(欲排除藥液之影響之部分)的黏著片(保護片),典型而言包括薄膜狀之黏著劑(黏著劑層)及支持上述黏著劑之基材而構成,將上述黏著劑貼附於被接著體來使用。此種藥液處理用之黏著片(保護片)例如可較佳地用於為了調整玻璃之厚度、或去除形成於玻璃之切斷端面之毛邊等而進行之用藥液(蝕刻液)溶解玻璃之蝕刻處理,用藥液(蝕刻液)部分性腐蝕金屬之表面的蝕刻處理,用藥液(電鍍液)部分電鍍電路基板(印刷基板、柔性印刷基板(FPC)等)之連接端子部等的電鍍處理等中。作為與此種技術相關之文獻,可列舉專利文獻1及2。 An adhesive sheet (protective sheet) for covering a non-treated object portion (the portion to be affected by the influence of the chemical liquid) of the above-mentioned adherend when the material to be treated (the material to be treated) is treated with the chemical liquid, and typically includes a film The adhesive (adhesive layer) and the substrate supporting the adhesive are attached, and the adhesive is applied to the adherend. The adhesive sheet (protective sheet) for treating such a chemical solution can be preferably used, for example, for dissolving glass by a chemical solution (etching liquid) for adjusting the thickness of the glass or removing the burrs formed on the cut end surface of the glass. Etching treatment, partial etching of the surface of the metal by the chemical solution (etching solution), plating treatment of the connection terminal portion of the circuit board (printed substrate, flexible printed circuit (FPC), etc.) by the chemical liquid (electroplating solution) in. Patent Documents 1 and 2 can be cited as documents related to such a technique.
保護片要求具有防止藥液自其表面(直接暴露於藥液之界面,即與貼附於被接著體之側相反側之表面)、或外緣(以下亦稱為端面或側 面)浸入之性質,即防藥液浸入性(密封性)。 The protective sheet is required to have a chemical liquid from the surface thereof (the interface directly exposed to the chemical liquid, that is, the surface opposite to the side attached to the side of the adherend), or the outer edge (hereinafter also referred to as an end surface or side) The nature of the immersion, that is, the immersion resistance (sealing property).
此處,藥液自保護片之外緣之浸入亦自保護片之黏著劑與被接著體之界面發生。為了防止此種藥液自界面之浸入,重要為構成保護片之黏著劑(黏著劑層)與被接著體之表面無間隙地密著的性質(密著性)及接著強度(黏著力)。 Here, the infiltration of the chemical liquid from the outer edge of the protective sheet also occurs from the interface between the adhesive of the protective sheet and the adherend. In order to prevent such a chemical solution from entering the interface, it is important that the adhesive (adhesive layer) constituting the protective sheet adheres to the surface of the adherend without any gap (adhesiveness) and adhesion strength (adhesion).
並且,保護片於不再需要之階段被剝離去除。一般而言,保護片、或構成被接著體之塑膠材料及玻璃之電絕緣性較高,於摩擦、或剝離時會產生靜電。因此,於自被接著體剝離保護片時亦會產生靜電。因此,除了發生空氣中之塵埃、或灰塵等之吸附,或者由電擊引起之不適感以外,存在引起因靜電引起之電路基板、或連接端子之破壞等各種靜電危害之虞。因此,為了防止此種不利情況,保護片實施各種抗靜電處理。 Also, the protective sheet is peeled off at a stage that is no longer needed. In general, the protective sheet or the plastic material constituting the adherend and the glass have high electrical insulation, and static electricity is generated during friction or peeling. Therefore, static electricity is also generated when the protective sheet is peeled off from the adherend. Therefore, in addition to the adsorption of dust or dust in the air or the discomfort caused by electric shock, there are various electrostatic hazards such as damage to the circuit board or the connection terminal due to static electricity. Therefore, in order to prevent such an unfavorable situation, the protective sheet is subjected to various antistatic treatments.
例如,揭示有於黏著劑中添加低分子之界面活性劑,將界面活性劑自黏著劑中轉印至被接著體來抗靜電之方法(例如參照專利文獻3)。然而,該方法中,界面活性劑容易滲出至黏著劑表面,於應用於保護片之情形時,存在污染被接著體之虞。因此,於將添加有低分子之界面活性劑之黏著劑應用於保護片之情形時,難以不損害被接著體之特性而表現充分之抗靜電特性。 For example, a method of adding a surfactant having a low molecular weight to an adhesive and transferring the surfactant from the adhesive to the adherend to prevent static electricity has been disclosed (for example, see Patent Document 3). However, in this method, the surfactant easily bleeds out to the surface of the adhesive, and when applied to the protective sheet, there is a problem that the adherend is contaminated. Therefore, when an adhesive to which a surfactant having a low molecular weight is added is applied to a protective sheet, it is difficult to exhibit sufficient antistatic properties without impairing the characteristics of the adherend.
另外揭示將包含聚醚多元醇及鹼金屬鹽之抗靜電劑添加至丙烯酸黏著劑中來抑制抗靜電劑滲出至黏著劑表面之方法(例如參照專利文獻4)。然而,於該方法中亦無法避免抗靜電劑之滲出,結果於實際應用於保護片之情形時,若實施高溫下之處理,則會由於滲出現象而產生對被接著體之污染。 Further, a method of adding an antistatic agent containing a polyether polyol and an alkali metal salt to an acrylic adhesive to suppress the exudation of the antistatic agent to the surface of the adhesive is disclosed (for example, refer to Patent Document 4). However, in the method, the bleed out of the antistatic agent cannot be avoided. As a result, when it is actually applied to the protective sheet, if the treatment at a high temperature is performed, contamination of the adherend due to the occurrence of bleed may occur.
另外揭示有關於含有於側鏈具有環氧烷鏈之丙烯酸系共聚物及離子化合物之抗靜電丙烯酸黏著劑的技術(專利文獻5),實現抗靜電性與低污染性之兼具。然而,於該方法中,存在產生浮起、或剝離等 與密著性相關之問題之虞。 Further, a technique of an antistatic acrylic adhesive containing an acrylic copolymer having an alkylene oxide chain and an ionic compound in a side chain (Patent Document 5) is disclosed, and both antistatic property and low pollution property are achieved. However, in this method, there are floating, peeling, etc. The problem with the issue of adhesion.
[專利文獻1]日本專利特開2010-53346號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-53346
[專利文獻2]日本專利特開2003-82299號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-82299
[專利文獻3]日本專利特開平9-165460號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 9-165460
[專利文獻4]日本專利特開平6-128539號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 6-128539
[專利文獻5]日本專利特開2005-206776號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-206776
因此,本發明之目的在於提供一種能夠兼具防藥液浸入性及自未經抗靜電處理之被接著體剝離時抑制剝離靜電壓(抗靜電性)的藥液處理用黏著劑層,具有上述黏著劑層之藥液處理用黏著片,表面保護片,以及貼附有上述表面保護片之附表面保護片之玻璃基板。 In view of the above, it is an object of the present invention to provide an adhesive layer for a chemical treatment which can prevent the peeling static voltage (antistatic property) from being detached from the adherend without the antistatic treatment. An adhesive sheet for treating a liquid medicine layer of an adhesive layer, a surface protective sheet, and a glass substrate with a surface protective sheet attached to the surface protective sheet.
本發明之藥液處理用黏著劑層之特徵在於,其係由含有玻璃轉移溫度未達0℃之聚合物(A)之黏著劑組合物形成者,且溶劑不溶成分率為50~90質量%,且表面電阻率為103~1013Ω/□。 The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 ° C, and the solvent insoluble component ratio is 50 to 90% by mass. And the surface resistivity is 10 3 ~ 10 13 Ω / □.
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物含有(甲基)丙烯酸系聚合物(B),上述(甲基)丙烯酸系聚合物(B)之重量平均分子量為1000以上且未達30000,且包含下述通式(1)所示之具有脂環式結構之(甲基)丙烯酸系單體作為單體成分。 Preferably, the adhesive composition of the present invention contains the (meth)acrylic polymer (B), and the (meth)acrylic polymer (B) has a weight average molecular weight of 1,000. The above is less than 30,000, and contains a (meth)acrylic monomer having an alicyclic structure represented by the following formula (1) as a monomer component.
CH2=C(R1)COOR2 (1) CH 2 =C(R 1 )COOR 2 (1)
[式(1)中,R1為氫原子或甲基,R2為具有脂環式結構之脂環式烴基。] [In the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alicyclic hydrocarbon group having an alicyclic structure. ]
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物含有 離子性化合物(C)。 Preferably, the adhesive layer for treating a chemical solution of the present invention contains the above adhesive composition Ionic compound (C).
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物含有具有聚氧伸烷基鏈之化合物(D)。 In the adhesive layer for treating a chemical solution of the present invention, it is preferable that the above-mentioned adhesive composition contains a compound (D) having a polyoxyalkylene chain.
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物相對於上述聚合物(A)100質量份,含有0.005~2質量份之上述(甲基)丙烯酸系聚合物(B)。 In the adhesive layer for a chemical treatment of the present invention, the pressure-sensitive adhesive composition preferably contains 0.005 to 2 parts by mass of the (meth)acrylic polymer (B) per 100 parts by mass of the polymer (A). .
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物相對於上述聚合物(A)100質量份,含有0.005~2質量份之上述離子性化合物(C)。 In the adhesive layer for a chemical liquid treatment of the present invention, the pressure-sensitive adhesive composition preferably contains 0.005 to 2 parts by mass of the ionic compound (C) per 100 parts by mass of the polymer (A).
本發明之藥液處理用黏著劑層較佳為,上述黏著劑組合物相對於上述聚合物(A)100質量份,含有0.005~1質量份之上述具有聚氧伸烷基鏈之化合物(D)。 In the adhesive layer for a chemical treatment of the present invention, the adhesive composition preferably contains 0.005 to 1 part by mass of the above compound having a polyoxyalkylene chain with respect to 100 parts by mass of the polymer (A). ).
本發明之藥液處理用黏著劑層較佳為,上述聚合物(A)為(甲基)丙烯酸系聚合物(a)。 In the adhesive layer for treating a chemical solution of the present invention, the polymer (A) is preferably a (meth)acrylic polymer (a).
本發明之藥液處理用黏著劑層較佳為,上述具有脂環式結構之(甲基)丙烯酸系單體之脂環式烴基具有橋接環結構。 In the adhesive layer for chemical liquid treatment of the present invention, it is preferable that the alicyclic hydrocarbon group of the (meth)acrylic monomer having an alicyclic structure has a bridged ring structure.
本發明之藥液處理用黏著劑層較佳為,上述(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度為0~300℃。 In the adhesive layer for chemical liquid treatment of the present invention, it is preferred that the (meth)acrylic polymer (B) has a glass transition temperature of 0 to 300 °C.
本發明之藥液處理用黏著劑層較佳為,上述離子性化合物(C)為鹼金屬鹽及/或離子液體。 In the adhesive layer for treating a chemical solution of the present invention, the ionic compound (C) is preferably an alkali metal salt and/or an ionic liquid.
本發明之藥液處理用黏著劑層較佳為,上述鹼金屬鹽為鋰鹽。 In the adhesive layer for treating a chemical liquid of the present invention, it is preferred that the alkali metal salt is a lithium salt.
本發明之藥液處理用黏著劑層較佳為,上述離子液體為含氮鎓鹽、含硫鎓鹽或含磷鎓鹽中之任1種以上。 In the adhesive layer for a chemical liquid treatment of the present invention, the ionic liquid is preferably one or more selected from the group consisting of a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt, and a phosphorus-containing phosphonium salt.
本發明之藥液處理用黏著劑層較佳為,上述離子液體含有下述通式(C1)~(C5)所示之1種以上之陽離子。 In the adhesive layer for treating a chemical solution of the present invention, the ionic liquid preferably contains one or more kinds of cations represented by the following general formulae (C1) to (C5).
[化1]
[式(C1)中之Ra表示碳數4~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Rb及Rc相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。但,於氮原子含有雙鍵之情形時,Rc不存在。] [R in the formula (C1) represents a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R b and R c are the same or different and represent hydrogen or a carbon number of 1 to 16. The hydrocarbon group, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. However, when the nitrogen atom contains a double bond, R c does not exist. ]
[式(C2)中之Rd表示碳數2~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Re、Rf及Rg相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。] In the [Formula (C2) R d represents C 1-50 hydrocarbon group having 2 to 20, the portion of the hydrocarbon groups may be substituted with the as heteroatom functional group, R e, the same or different R f and R g, represents hydrogen or a C The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]
[式(C3)中之Rh表示碳數2~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Ri、Rj及Rk相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。] [R h in the formula (C3) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom, and R i , R j and R k are the same or different and represent hydrogen or a carbon number of 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]
[式(C4)中之Z表示氮、硫或磷原子,Rl、Rm、Rn及Ro相同或不同,表示碳數1~20之烴基,上述烴基之一部分可為經雜原子取代之官能基。但,於Z為硫原子之情形時,Ro不存在。] [Z in the formula (C4) represents a nitrogen, sulfur or phosphorus atom, and R l , R m , R n and R o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, and a part of the above hydrocarbon group may be substituted by a hetero atom Functional group. However, when Z is a sulfur atom, R o does not exist. ]
[式(C5)中之RP表示碳數1~18之烴基,上述烴基之一部分可為經雜原子取代之官能基。] [R P in the formula (C5) represents a hydrocarbon group having 1 to 18 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. ]
本發明之藥液處理用黏著劑層較佳為,上述具有聚氧伸烷基鏈之化合物(D)為具有聚氧伸烷基鏈之有機聚矽氧烷。 In the adhesive layer for treating a chemical solution of the present invention, the compound (D) having a polyoxyalkylene chain is preferably an organopolyoxane having a polyoxyalkylene chain.
本發明之藥液處理用黏著劑層較佳為,上述具有聚氧伸烷基鏈之有機聚矽氧烷為下述通式(D1)~(D3)所示之有機聚矽氧烷。 In the adhesive layer for chemical treatment of the present invention, the organopolyoxyalkylene having a polyoxyalkylene chain is preferably an organopolyoxane represented by the following formulas (D1) to (D3).
[化2]
[式(D1)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m及n為0~1000之整數。但,m、n不同時為0。a及b為0~1000之整數。但,a、b不同時為0。] In the [Formula (D1) R 1 is a monovalent organic group, R 2, R 3 and R 4 is alkylene, R 5 is hydrogen or an organic group, m and n are integers of 0 to 1000. However, m and n are not 0 at the same time. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]
[式(D2)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m為1~2000之整數。a及b為0~1000之整數。但,a、b不同時為0。] In the [Formula (D2) R 1 is a monovalent organic group, R 2, R 3 and R 4 is alkylene, R 5 is hydrogen or an organic group, m is an integer of 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]
[式(D3)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m為1~2000之整數。a及b為0~1000之整數。但,a、b不同時為0。] In the [Formula (D3) R 1 is a monovalent organic group, R 2, R 3 and R 4 is alkylene, R 5 is hydrogen or an organic group, m is an integer of 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time. ]
本發明之藥液處理用黏著劑層較佳為,含有含羥基之單體,作為構成上述(甲基)丙烯酸系聚合物(a)之單體成分。 The pressure-sensitive adhesive layer for treating a chemical solution of the present invention preferably contains a hydroxyl group-containing monomer as a monomer component constituting the (meth)acrylic polymer (a).
本發明之藥液處理用黏著劑層較佳為,相對於構成上述(甲基)丙烯酸系聚合物(a)之單體成分總量,含有5.0質量%以下之氧伸烷基單元之平均加成莫耳數為3~40之含氧伸烷基之反應性單體。 The pressure-sensitive adhesive layer for treating a chemical solution of the present invention preferably contains an average of 5.0% by mass or less of an oxygen-extended alkyl unit based on the total amount of the monomer components constituting the (meth)acryl-based polymer (a). A reactive monomer having an oxygen-containing alkylene group having a molar number of 3 to 40.
本發明之藥液處理用黏著片較佳為,於支持體之至少單面形成 有上述黏著劑層。 The adhesive sheet for treating a liquid medicine of the present invention is preferably formed on at least one side of the support. There is the above adhesive layer.
本發明之藥液處理用黏著片較佳為,上述支持體為經抗靜電處理之塑膠薄膜。 Preferably, the support for treating a liquid medicine according to the present invention is that the support is an antistatic treated plastic film.
本發明之表面保護片較佳為,包含上述藥液處理用黏著片。 The surface protection sheet of the present invention preferably comprises the above-mentioned pressure-sensitive adhesive sheet for chemical liquid treatment.
本發明之附表面保護片之玻璃基板較佳為,於玻璃基板上貼附有上述表面保護片。 In the glass substrate with a surface protection sheet of the present invention, it is preferable that the surface protection sheet is attached to the glass substrate.
根據本發明,可提供一種能夠兼具防藥液浸入性及自未經抗靜電處理之被接著體剝離時抑制剝離靜電壓(抗靜電性)之藥液處理用黏著劑層,具有上述黏著劑層之藥液處理用黏著片,表面保護片,以及貼附有上述表面保護片之附表面保護片之玻璃基板,較為有用。 According to the present invention, it is possible to provide an adhesive layer for a chemical solution which can prevent the peeling static voltage (antistatic property) from being detached from the adherend without antistatic treatment, and has the above adhesive. The adhesive sheet for a chemical liquid treatment layer, a surface protective sheet, and a glass substrate with a surface protection sheet to which the surface protection sheet is attached are useful.
1‧‧‧支持體 1‧‧‧Support
2‧‧‧黏著劑層 2‧‧‧Adhesive layer
3‧‧‧剝離襯墊 3‧‧‧Release liner
4‧‧‧抗靜電層 4‧‧‧Antistatic layer
10‧‧‧黏著片(表面保護片) 10‧‧‧Adhesive sheet (surface protection sheet)
20‧‧‧玻璃 20‧‧‧ glass
30‧‧‧樣品固定台 30‧‧‧sample fixed table
40‧‧‧電位測定器 40‧‧‧potentiometer
圖1係示意性表示藥液處理用保護片之一構成例之剖面圖。 Fig. 1 is a cross-sectional view schematically showing a configuration example of a protective sheet for chemical liquid processing.
圖2係示意性表示藥液處理用保護片之另一構成例之剖面圖。 Fig. 2 is a cross-sectional view schematically showing another configuration example of a protective sheet for chemical treatment.
圖3係示意性表示藥液處理用保護片之另一構成例之剖面圖。 Fig. 3 is a cross-sectional view schematically showing another configuration example of the protective sheet for chemical treatment.
圖4係示意性表示藥液處理用保護片之另一構成例之剖面圖。 Fig. 4 is a cross-sectional view schematically showing another configuration example of the protective sheet for chemical treatment.
圖5係實施例等中於剝離靜電壓之測定中使用之電位測定部的概略構成圖。 Fig. 5 is a schematic configuration diagram of a potential measuring unit used for measurement of a peeling static voltage in the examples and the like.
本發明之藥液處理用黏著劑層之特徵在於,其係由含有玻璃轉移溫度未達0℃之聚合物(A)之黏著劑組合物形成者,且溶劑不溶成分率為50~90質量%,且表面電阻率為103~1013Ω/□。若上述溶劑不溶成分率在50~90質量%之範圍,則接著可靠性(密著性、接著性、再剝離性)良好,可防止藥液之浸入。此外,若表面電阻率在103~1013Ω/□之範圍,則可抑制剝離靜電壓之產生(賦予抗靜電性)。 The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 ° C, and the solvent insoluble component ratio is 50 to 90% by mass. And the surface resistivity is 10 3 ~ 10 13 Ω / □. When the solvent-insoluble component ratio is in the range of 50 to 90% by mass, the reliability (adhesiveness, adhesion, and re-peelability) is good, and the penetration of the chemical solution can be prevented. Further, when the surface resistivity is in the range of 10 3 to 10 13 Ω/□, the generation of the peeling static voltage (the antistatic property is imparted) can be suppressed.
以下對於在形成本發明之藥液處理用黏著劑層(有時簡稱為「黏 著劑層」)時所使用之黏著劑組合物、由上述黏著劑組合物所形成之黏著劑層、具有上述黏著劑層之藥液處理用黏著片(有時簡稱為「黏著片」)、表面保護片(有時簡稱為「保護片」)以及貼附有上述表面保護片之玻璃基板,進行詳細說明。 The following is an adhesive layer for forming a liquid chemical treatment of the present invention (sometimes referred to as "sticky" Adhesive composition used in the coating layer", an adhesive layer formed of the above adhesive composition, an adhesive sheet for chemical treatment having the above adhesive layer (sometimes referred to simply as "adhesive sheet"), A surface protective sheet (sometimes abbreviated as "protective sheet") and a glass substrate to which the surface protective sheet is attached will be described in detail.
此處所揭示之藥液處理用黏著片(表面保護片)具備支持體及設置於上述支持體之至少單面之黏著劑層。上述黏著片之形狀為片狀即可,例如可為輥狀、或附隔離體之單板狀等。 The adhesive sheet for processing a chemical solution (surface protective sheet) disclosed herein includes a support and an adhesive layer provided on at least one side of the support. The shape of the adhesive sheet may be a sheet shape, and may be, for example, a roll shape or a single plate shape with a separator.
該黏著片之典型構成例示意性示於圖1。該黏著片10具備片狀之支持體(例如樹脂製之片狀基材)1及設置於其一側面(單面)之黏著劑層2。黏著片10於用藥液處理被接著體(被處理材料)之前將該黏著劑層2側貼附於被接著體之特定部位(保護對象部分,典型而言為欲排除藥液之影響之部分。以下亦稱為「非處理對象部分」)來使用。藉此,可保護上述非處理對象部分不受藥液影響。此外,使用前(即貼附於被接著體之前)之黏著片10典型而言如圖2所示,黏著劑層2之表面(貼附於被接著體之面。以下亦稱為「黏著面」)為由至少黏著劑層2側為剝離面之剝離襯墊3所保護的形態。或者亦可為支持體1之另一面(設置有黏著劑層2之面之背面)為剝離面,藉由將黏著片10捲成輥狀而使上述另一面與黏著劑層2抵接來保護其表面(黏著面)之形態。此外,黏著片10亦可為於支持體1之各面分別設置有黏著劑層2之雙面黏著片。於該情形時,各黏著劑層之與被接著體之貼附面(黏著面)可分別為由至少黏著劑層側為剝離面之剝離襯墊3所保護的形態,亦可為經由兩面為剝離面之剝離襯墊3捲成輥狀之形態。此外,如圖3所示,亦可為於支持體1之另一面(設置有黏著劑層2之面之背面)具有抗靜電層4的形態。進而,如圖4所示,亦可為於支持體1與黏著劑層2之中間具有抗靜電層4之形態。另外,本發明中之「片」包含與片相比厚度相 對較薄之薄膜、或一般被稱為黏著帶之類的膠帶。 A typical configuration example of the adhesive sheet is schematically shown in Fig. 1. The adhesive sheet 10 includes a sheet-shaped support (for example, a sheet-like substrate made of resin) 1 and an adhesive layer 2 provided on one side (one side) thereof. The adhesive sheet 10 is attached to a specific portion of the adherend before the treatment of the adherend (the material to be treated) with the chemical solution (the portion to be protected, typically the portion to be excluded from the influence of the chemical solution). The following is also referred to as "non-processing object portion"). Thereby, the above-mentioned non-treated object portion can be protected from the chemical liquid. Further, the adhesive sheet 10 before use (i.e., before being attached to the adherend) is typically as shown in Fig. 2, the surface of the adhesive layer 2 (attached to the surface of the adherend. Hereinafter also referred to as "adhesive surface" ") is a form protected by the release liner 3 having at least the release surface of the adhesive layer 2 side. Alternatively, the other surface of the support 1 (the back surface of the surface on which the adhesive layer 2 is provided) may be a peeling surface, and the adhesive sheet 10 may be wound into a roll to protect the other surface from the adhesive layer 2. The shape of the surface (adhesive surface). Further, the adhesive sheet 10 may be a double-sided adhesive sheet in which the adhesive layer 2 is provided on each surface of the support 1 . In this case, the attachment surface (adhesive surface) of each of the adhesive layers and the adherend may be protected by the release liner 3 having at least the adhesive layer side as the release surface, or may be The release liner 3 of the peeling surface is wound into a roll shape. Further, as shown in FIG. 3, the antistatic layer 4 may be provided on the other surface of the support 1 (the back surface of the surface on which the adhesive layer 2 is provided). Further, as shown in FIG. 4, the antistatic layer 4 may be provided between the support 1 and the adhesive layer 2. In addition, the "sheet" in the present invention includes a thickness phase compared to the sheet. For thinner films, or tapes commonly referred to as adhesive tapes.
本發明之藥液處理用黏著劑層之特徵在於,其由含有玻璃轉移溫度未達0℃之聚合物(A)之黏著劑組合物形成。上述聚合物(A)只要玻璃轉移溫度未達0℃則無特別限定,可使用例如丙烯酸系聚合物、橡膠系聚合物、矽酮系聚合物、聚胺基甲酸酯系聚合物及聚酯系聚合物等通常作為黏著劑使用之各種聚合物。特別較佳使用容易與較佳用於本發明之黏著劑層之下述(甲基)丙烯酸系聚合物(B)相容且透明性較高之(甲基)丙烯酸系聚合物。 The adhesive layer for treating a chemical solution according to the present invention is characterized in that it is formed of an adhesive composition containing a polymer (A) having a glass transition temperature of less than 0 °C. The polymer (A) is not particularly limited as long as the glass transition temperature is less than 0 ° C, and for example, an acrylic polymer, a rubber-based polymer, an anthrone-based polymer, a polyurethane-based polymer, and a polyester can be used. A polymer or the like which is usually used as an adhesive. It is particularly preferable to use a (meth)acrylic polymer which is compatible with the following (meth)acrylic polymer (B) which is preferably used in the adhesive layer of the present invention and which has high transparency.
上述聚合物(A)之玻璃轉移溫度(Tg)未達0℃,較佳為未達-10℃,更佳為未達-40℃,通常為-80℃以上。若聚合物(A)之玻璃轉移溫度(Tg)為0℃以上,則存在聚合物不易流動、對被接著體(被保護體)之潤濕變得不充分、密著性降低的情況。此外,上述聚合物(A)之玻璃轉移溫度不過低,有助於防止藥液浸入(典型而言主要起因於黏著劑利用藥液而膨潤之藥液浸入)。 The glass transition temperature (Tg) of the above polymer (A) is less than 0 ° C, preferably less than -10 ° C, more preferably less than -40 ° C, and usually -80 ° C or more. When the glass transition temperature (Tg) of the polymer (A) is 0° C. or more, the polymer may not easily flow, and the wetting of the adherend (protected body) may be insufficient, and the adhesion may be lowered. Further, the glass transition temperature of the above polymer (A) is not too low, and it is advantageous in preventing the infiltration of the chemical solution (typically, the chemical solution which is mainly caused by the swelling of the adhesive by the chemical solution).
再者,於本說明書中,「形成均聚物時之玻璃轉移溫度」意指「該單體之均聚物之玻璃轉移溫度」,意指僅以某單體(有時稱為「單體X」)作為單體成分所形成之聚合物的玻璃轉移溫度(Tg)。具體而言,「於聚合物手冊(Polymer Handbook)」(第3版,John Wiley & Sons,Inc.,1989年)中列舉有數值。 In addition, in the present specification, "the glass transition temperature at the time of forming a homopolymer" means "the glass transition temperature of the homopolymer of the monomer", meaning that only a certain monomer (sometimes referred to as "monomer" X") The glass transition temperature (Tg) of the polymer formed as a monomer component. Specifically, numerical values are listed in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989).
另外,上述文獻中未記載之均聚物之玻璃轉移溫度(Tg)係指,例如由以下之測定方法獲得之值。 Further, the glass transition temperature (Tg) of the homopolymer which is not described in the above document means, for example, a value obtained by the following measurement method.
即,向具備溫度計、攪拌機、氮氣導入管以及回流冷凝管之反應器中投入單體X 100質量份、2,2'-偶氮雙異丁腈0.2質量份以及作為聚合溶劑之乙酸乙酯200質量份,一面導入氮氣一面攪拌1小時。於如上操作除去聚合體系內之氧氣之後,升溫至63℃並反應10小時。繼 而,冷卻至室溫,獲得固形物成分濃度為33質量%之均聚物溶液。繼而,於剝離襯墊上流延塗佈該均聚物溶液,進行乾燥,製作厚度約2mm之試驗樣品(片狀之均聚物)。然後,稱量約1~2mg該試驗樣品放入至鋁製之開放室(open cell)中,使用溫度調變DSC(商品名「Q-2000」TA Instruments公司製造),於50ml/min之氮氣氣氛下,以升溫速度5℃/min,獲得均聚物之可逆熱流(Reversing Heat Flow,比熱成分)行為。 In other words, 100 parts by mass of the monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and ethyl acetate 200 as a polymerization solvent are charged into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, and a reflux condenser. The mass fraction was stirred while introducing nitrogen gas for 1 hour. After removing oxygen in the polymerization system as above, the temperature was raised to 63 ° C and reacted for 10 hours. Following On the other hand, the mixture was cooled to room temperature to obtain a homopolymer solution having a solid content concentration of 33% by mass. Then, the homopolymer solution was cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of the test sample was weighed into an open cell made of aluminum, and a temperature-adjusted DSC (trade name "Q-2000" TA Instruments) was used, and nitrogen gas at 50 ml/min was used. The reversing heat flow (Reversing Heat Flow) behavior of the homopolymer was obtained at a heating rate of 5 ° C/min.
參考JIS-K-7121,將於縱軸方向上距所得之可逆熱流之低溫側之基線與高溫側之基線延長之直線等距離的直線與玻璃轉移之階段狀變化部分之曲線相交的點之溫度作為製成均聚物時之玻璃轉移溫度(Tg)。 Referring to JIS-K-7121, the temperature at the point where the straight line equidistant from the line on the low temperature side of the obtained reversible heat flow and the line extending on the high temperature side in the longitudinal direction intersects the curve of the stepwise change portion of the glass transition. The glass transition temperature (Tg) as a homopolymer.
此外,上述聚合物(A)之重量平均分子量(Mw)例如較佳為3萬~500萬,更佳為10萬~200萬,進而較佳為20萬~100萬。若重量平均分子量(Mw)未達3萬,則存在黏著劑(層)之凝聚力不足、容易發生藥液浸入之情況。另一方面,若重量平均分子量(Mw)超過500萬,則存在黏著劑之流動性降低、對被接著體之潤濕不足、密著性降低的情況。 Further, the weight average molecular weight (Mw) of the polymer (A) is, for example, preferably from 30,000 to 5,000,000, more preferably from 100,000 to 2,000,000, and still more preferably from 200,000 to 1,000,000. When the weight average molecular weight (Mw) is less than 30,000, the cohesive force of the adhesive (layer) may be insufficient, and the chemical solution may easily enter. On the other hand, when the weight average molecular weight (Mw) exceeds 5,000,000, the fluidity of the adhesive may be lowered, the wetting of the adherend may be insufficient, and the adhesion may be lowered.
以下,對於上述聚合物(A)之較佳之具體例即(甲基)丙烯酸系聚合物(a)進行詳細說明。 Hereinafter, the (meth)acrylic polymer (a) which is a preferable specific example of the above polymer (A) will be described in detail.
上述(甲基)丙烯酸系聚合物(a)例如較佳為含有50質量%以上之具有碳數1~20之直鏈或支鏈狀烷基之(甲基)丙烯酸烷基酯作為單體成分的聚合物。此外,(甲基)丙烯酸系聚合物(a)可為由單獨一種具有碳數1~20之烷基之(甲基)丙烯酸烷基酯的構成,或者為由2種以上組合之構成。 The (meth)acrylic polymer (a) is preferably a monomer component containing 50% by mass or more of a linear alkyl group or a branched alkyl group having 1 to 20 carbon atoms as a monomer component. Polymer. Further, the (meth)acrylic polymer (a) may be composed of a single alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, or a combination of two or more kinds.
對獲得上述(甲基)丙烯酸系聚合物(a)之方法並無特別限定,可應 用溶液聚合、乳化聚合、塊狀聚合、懸浮聚合、放射線硬化聚合等作為(甲基)丙烯酸系聚合物之合成方法通常使用之各種聚合方法。另外,將本發明之藥液處理用黏著劑層(黏著片)用於下述之表面保護片之情形時,較佳地使用溶液聚合、乳化聚合為較佳之態樣。 The method for obtaining the above (meth)acrylic polymer (a) is not particularly limited and may be Solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, radiation hardening polymerization, and the like are various polymerization methods generally used in the synthesis method of a (meth)acrylic polymer. Further, when the adhesive layer (adhesive sheet) for treating a chemical solution of the present invention is used in the case of the surface protective sheet described below, solution polymerization or emulsion polymerization is preferably used.
作為上述具有碳數1~20之烷基之(甲基)丙烯酸烷基酯的比例,相對於用以調製(甲基)丙烯酸系聚合物(a)之單體成分總量(100質量%),較佳為50質量%以上,更佳為50質量%~99.9質量%,進而較佳為60質量%~98質量%,特別較佳為70質量%~95質量%。若在上述範圍內,則可獲得對藥液處理用黏著劑層(黏著片、表面保護片)較佳之接著特性(密著性、接著性、再剝離性),故為較佳之態樣。 The ratio of the alkyl (meth)acrylate having the alkyl group having 1 to 20 carbon atoms to the total amount of the monomer component (100% by mass) for preparing the (meth)acrylic polymer (a) It is preferably 50% by mass or more, more preferably 50% by mass to 99.9% by mass, still more preferably 60% by mass to 98% by mass, and particularly preferably 70% by mass to 95% by mass. When it is in the above range, it is preferable to obtain a preferable adhesive property (adhesive sheet, surface protective sheet) for the chemical solution treatment (adhesiveness, adhesion, re-peelability).
作為上述具有碳數1~20之烷基之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯[較佳為(甲基)丙烯酸C2-14烷基酯,進而較佳為(甲基)丙烯酸C2-10烷基酯]等。再者,(甲基)丙烯酸烷基酯意指丙烯酸烷基酯及/或甲基丙烯酸烷基酯,「(甲基)……」均表示同樣之意思。 Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A) Isooctyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Ester, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (methyl) Cetyl acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate (meth) acrylic acid C 1-20 alkyl [Preferably (meth) acrylic acid C 2-14 alkyl ester, and further preferably (meth) acrylic acid C 2-10 alkyl esters] and the like. Further, the alkyl (meth)acrylate means an alkyl acrylate and/or an alkyl methacrylate, and "(meth)"" means the same meaning.
另外,為了改善凝聚力、耐熱性、交聯性等,上述(甲基)丙烯酸 系聚合物(a)可根據需要含有可與上述(甲基)丙烯酸烷基酯共聚之其他單體成分(共聚性單體)。因此,上述(甲基)丙烯酸系聚合物(a)可於含有作為主成分之(甲基)丙烯酸烷基酯的同時含有共聚性單體。作為共聚性單體,可較佳地使用具有極性基之單體。 In addition, in order to improve cohesive force, heat resistance, crosslinkability, etc., the above (meth)acrylic acid The polymer (a) may contain other monomer components (copolymerizable monomers) copolymerizable with the above alkyl (meth)acrylate, as needed. Therefore, the (meth)acrylic polymer (a) may contain a copolymerizable monomer while containing an alkyl (meth)acrylate as a main component. As the copolymerizable monomer, a monomer having a polar group can be preferably used.
作為上述共聚性單體之具體例,可列舉:丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸、異巴豆酸等含羧基之單體;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)甲酯等(甲基)丙烯酸羥基烷基酯等含羥基之單體;馬來酸酐、衣康酸酐等含酸酐基之單體;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體;2-羥基乙基丙烯醯基磷酸酯等含磷酸基之單體;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二丙基(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二(正丁基)(甲基)丙烯醯胺、N,N-二(第三丁基)(甲基)丙烯醯胺等N,N-二烷基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-甲氧基乙基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-丙烯醯基嗎啉等(N-取代)醯胺系單體; N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基衣康醯亞胺、N-乙基衣康醯亞胺、N-丁基衣康醯亞胺、N-辛基衣康醯亞胺、N-2-乙基己基衣康醯亞胺、N-環己基衣康醯亞胺、N-月桂基衣康醯亞胺等衣康醯亞胺系單體;乙酸乙烯酯、丙酸乙烯酯等乙烯酯類;N-乙烯基-2-吡咯烷酮、N-甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-(甲基)丙烯醯基-2-吡咯烷酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯烷、N-乙烯基嗎啉、N-乙烯基-2-哌啶酮、N-乙烯基-3-嗎啉酮、N-乙烯基-2-己內醯胺、N-乙烯基-1,3-噁嗪-2-酮、N-乙烯基-3,5-嗎啉二酮、N-乙烯基吡唑、N-乙烯基異噁唑、N-乙烯基噻唑、N-乙烯基異噻唑、N-乙烯基噠嗪等含氮之雜環系單體;N-乙烯基羧醯胺類;N-乙烯基己內醯胺等內醯胺系單體;丙烯腈、甲基丙烯腈等含氰基之單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸第三丁胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基丙酯等(甲基)丙烯酸烷氧基烷基酯系單體;苯乙烯、α-甲基苯乙烯等苯乙烯系單體; (甲基)丙烯酸縮水甘油酯等含環氧基之丙烯酸系單體;(甲基)丙烯酸四氫糠酯、含氟原子(甲基)丙烯酸酯、矽酮(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體;異戊二烯、丁二烯、異丁烯等烯烴系單體;甲基乙烯醚、乙基乙烯醚等乙烯醚系單體;乙酸乙烯酯、丙酸乙烯酯等乙烯酯類;乙烯基甲苯、苯乙烯等芳香族乙烯化合物;乙烯、丁二烯、異戊二烯、異丁烯等烯烴或二烯類;乙烯基烷基醚等乙烯醚類;氯乙烯;乙烯基磺酸鈉等含磺酸基之單體;環己基馬來醯亞胺、異丙基馬來醯亞胺等含醯亞胺基之單體;(甲基)丙烯酸2-異氰酸基乙酯等含異氰酸基之單體;丙烯醯嗎啉;(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等具有脂環式烴基之(甲基)丙烯酸酯;(甲基)丙烯酸苯酯、(甲基)丙烯酸苯氧基乙酯等具有芳香族烴基之(甲基)丙烯酸酯;由萜烯化合物衍生物醇獲得之(甲基)丙烯酸酯等。再者,該等共聚性單體可單獨使用亦可將2種以上組合使用。 Specific examples of the copolymerizable monomer include carboxyl groups such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Monomer; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (A) (8-hydroxyoctyl acrylate), 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc. (methyl) a hydroxyl group-containing monomer such as a hydroxyalkyl acrylate; an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, and 2-(methyl)propenylamine-2- a sulfonic acid group-containing monomer such as methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethyl a phosphate group-containing monomer such as a acryloyl phosphatidyl phosphate; (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) propylene oxime Amine, N,N-dipropyl (methyl) propyl Indoleamine, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl) (A) N,N-dialkyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl, etc. (Meth) acrylamide, N-n-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxy Methylpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (A a (N-substituted) guanamine monomer such as acrylamide or N-propenylmorpholine; N-(methyl) propylene oxime methylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl- Amber quinone imine monomer such as 8-oxo octamethylene succinimide; N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide , a maleimide monomer such as N-phenylmaleimide; N-methyl itaconimine, N-ethyl itaconimine, N-butyl itaconimine, N-octyl ketamine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-lauryl ketimine, etc. Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinyl Pyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(methyl)propenyl-2-pyrrolidone, N -(Meth)acryloylpiperidine, N-(methyl)propenylpyrrolidine, N-vinylmorpholine, N-vinyl-2-piperidone, N-vinyl-3- Linoleone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrrolidone a nitrogen-containing heterocyclic monomer such as azole, N-vinyl isoxazole, N-vinylthiazole, N-vinylisothiazole or N-vinylpyridazine; N-vinyl carboxamide; N- An internal amide monomer such as vinyl caprolactam; a cyano group-containing monomer such as acrylonitrile or methacrylonitrile; an aminoethyl (meth) acrylate or a N, N-dimethyl methacrylate Aminoalkyl (meth) acrylate monomer such as aminoethyl ester or tert-butylaminoethyl (meth)acrylate; methoxyethyl (meth)acrylate; ethoxylated (meth) acrylate Alkoxyalkyl (meth)acrylate such as ethyl ethyl acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate or ethoxypropyl methacrylate Body; styrene monomer such as styrene or α-methylstyrene; An epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; fluorine atom (meth)acrylate; anthrone (meth)acrylate; An acrylate monomer such as a ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; and vinyl acetate Vinyl esters such as vinyl propionate; aromatic vinyl compounds such as vinyl toluene and styrene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; and vinyl ethers such as vinyl alkyl ethers a monomer containing a sulfonic acid group such as vinyl chloride or sodium vinyl sulfonate; a monomer containing a quinone imine group such as cyclohexylmaleimide or isopropyl maleimide; (meth)acrylic acid 2 - an isocyanate group-containing monomer such as isocyanatoethyl ester; propylene morpholine; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate having an alicyclic hydrocarbon group such as dicyclopentanyl methacrylate; phenyl (meth) acrylate or (meth) acrylate Group, ethyl (methyl) acrylate of an aromatic hydrocarbon; terpene compound is obtained from the derivative of an alcohol (meth) acrylate. In addition, these copolymerizable monomers may be used alone or in combination of two or more.
上述(甲基)丙烯酸系聚合物(a)於含有作為主要成分之(甲基)丙烯酸烷基酯的同時含有共聚性單體之情形時,作為上述共聚性單體,尤其可較佳地使用上述含羥基之單體、或上述含羧基之單體。其中,作為含羥基之單體,可較佳地使用(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁酯,作為上述含羧基之單體,可較佳地使用丙烯酸。 When the (meth)acrylic polymer (a) contains a copolymerizable monomer while containing an alkyl (meth)acrylate as a main component, it is preferably used as the above copolymerizable monomer. The above hydroxyl group-containing monomer or the above carboxyl group-containing monomer. Among them, as the hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate can be preferably used, and as the carboxyl group-containing monomer, acrylic acid is preferably used. .
作為上述共聚性單體之含量,並無特別限制,通常相對於用以 調製上述丙烯酸系聚合物(a)之單體成分總量(100質量%),可較佳含有上述共聚性單體0.01質量%~40質量%、更佳為0.1質量%~30質量%、進而較佳為0.5質量%~20質量%。藉由含有0.01質量%以上之上述共聚性單體,能夠防止黏著劑(層)之凝聚力降低,並且能夠防止自被接著體剝離時之污染。此外,藉由使上述共聚性單體之含量為40質量%以下,能夠防止凝聚力過高,並且能夠提高常溫(25℃)下之黏著感。 The content of the above copolymerizable monomer is not particularly limited, and is usually relative to The total amount (100% by mass) of the monomer component of the acrylic polymer (a) is preferably 0.01% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, based on the copolymerizable monomer. It is preferably 0.5% by mass to 20% by mass. By containing 0.01% by mass or more of the above copolymerizable monomer, it is possible to prevent the cohesive force of the adhesive (layer) from being lowered, and it is possible to prevent contamination from peeling of the adherend. In addition, by setting the content of the copolymerizable monomer to 40% by mass or less, it is possible to prevent the cohesive force from being excessively high and to improve the adhesiveness at normal temperature (25 ° C).
上述(甲基)丙烯酸系聚合物(a)亦可進而含有5.0質量%以下之氧伸烷基單元之平均加成莫耳數為3~40之含氧伸烷基之反應性單體作為單體成分。 The (meth)acrylic polymer (a) may further contain 5.0% by mass or less of an oxygen-extended alkyl unit having an average addition molar amount of 3 to 40, and an oxygen-containing alkyl group as a reactive monomer. Body composition.
作為上述含氧伸烷基之反應性單體中之氧伸烷基單元之平均加成莫耳數,就與離子性化合物之相容性之觀點而言,較佳為3~40,更佳為4~35,特別較佳為5~30。於上述平均加成莫耳數為3以上之情形時,存在可高效獲得被接著體(被保護體)之污染減小效果之傾向。此外,於上述平均加成莫耳數大於40之情形時,存在與作為抗靜電劑起作用之離子性化合物的相互作用增強、黏著劑組合物形成凝膠狀而難以塗覆之傾向,故而不佳。另外,氧伸烷基鏈之末端可直接為羥基,亦可經其他官能基等所取代。 The average addition mole number of the oxygen-extended alkyl unit in the above-mentioned oxygen-containing alkyl group-reactive monomer is preferably from 3 to 40, more preferably from the viewpoint of compatibility with the ionic compound. It is 4 to 35, and particularly preferably 5 to 30. When the average addition molar number is 3 or more, there is a tendency that the contamination reducing effect of the adherend (protected body) can be efficiently obtained. Further, when the average addition molar number is more than 40, the interaction with the ionic compound acting as an antistatic agent is enhanced, and the adhesive composition is gel-like and difficult to coat, so good. Further, the terminal of the oxygen alkyl group may be directly a hydroxyl group, or may be substituted with another functional group or the like.
上述含氧伸烷基之反應性單體可單獨使用,亦可混合2種以上使用,相對於上述(甲基)丙烯酸系聚合物(a)之單體成分總量(100質量%)之含量較佳為5.0質量%以下,更佳為4.0質量%以下,進而較佳為3.0質量%以下,特別較佳為1.0質量%以下。若上述含氧伸烷基之反應性單體之含量超過5.0質量%,則與作為抗靜電劑起作用之離子性化合物之相互作用增強,妨礙離子傳導,抗靜電性降低,不佳。 The reactive monomer having an oxygen-containing alkylene group may be used singly or in combination of two or more kinds thereof, and the total amount of the monomer component (100% by mass) based on the (meth)acryl-based polymer (a). It is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.0% by mass or less, and particularly preferably 1.0% by mass or less. When the content of the above-mentioned oxygen-containing alkyl group-containing reactive monomer exceeds 5.0% by mass, the interaction with the ionic compound acting as an antistatic agent is enhanced, the ion conduction is hindered, and the antistatic property is lowered, which is not preferable.
作為上述含氧伸烷基之反應性單體之氧伸烷基單元,可列舉具有碳數1~6之伸烷基的單元,例如可列舉:氧亞甲基、氧伸乙基、氧 伸丙基、氧伸丁基等。氧伸烷基鏈之烴基可為直鏈,亦可為支鏈。 Examples of the oxygen-extended alkyl unit of the above-mentioned oxygen-containing alkyl group-reactive monomer include a unit having an alkylene group having 1 to 6 carbon atoms, and examples thereof include an oxymethylene group, an oxygen-extended ethyl group, and an oxygen group. Propylene, oxygen and butyl groups. The hydrocarbyl group of the oxygen alkyl chain may be straight or branched.
此外,進而更佳為上述含氧伸烷基之反應性單體為具有環氧乙烷基之反應性單體。藉由使用含有具有環氧乙烷基之反應性單體之(甲基)丙烯酸系聚合物作為基礎聚合物,可提高基礎聚合物與離子性化合物之相容性,較佳地抑制其滲出至被接著體,可獲得低污染性之黏著劑(層)。 Further, it is more preferred that the above-mentioned oxygen-containing alkylene group-reactive monomer is a reactive monomer having an oxiranyl group. By using a (meth)acrylic polymer containing a reactive monomer having an oxiranyl group as a base polymer, the compatibility of the base polymer with the ionic compound can be improved, and the bleed out is preferably suppressed. By the adherend, a highly polluting adhesive (layer) can be obtained.
作為上述含氧伸烷基之反應性單體,例如可列舉:(甲基)丙烯酸環氧烷加成物、分子中具有丙烯醯基、甲基丙烯醯基、烯丙基等反應性取代基之反應性界面活性劑等。 Examples of the reactive monomer of the oxygen-containing alkylene group include a (meth)acrylic acid alkylene oxide adduct and a reactive substituent having a propylene group, a methacryloyl group or an allyl group in the molecule. Reactive surfactants and the like.
作為上述(甲基)丙烯酸環氧烷加成物之具體例,例如可列舉:聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、聚乙二醇-聚丙二醇(甲基)丙烯酸酯、聚乙二醇-聚丁二醇(甲基)丙烯酸酯、聚丙二醇-聚丁二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、丁氧基聚乙二醇(甲基)丙烯酸酯、辛氧基聚乙二醇(甲基)丙烯酸酯、十二烷氧基聚乙二醇(甲基)丙烯酸酯、十八烷氧基聚乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、辛氧基聚乙二醇-聚丙二醇(甲基)丙烯酸酯等。 Specific examples of the (meth)acrylic acid alkylene oxide adduct include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (A). Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, B Oxypolyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, dodecyloxy polyethylene glycol (Meth) acrylate, octadecyloxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, xin Oxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.
此外,作為上述反應性界面活性劑之具體例,例如可列舉:具有(甲基)丙烯醯基或烯丙基之陰離子型反應性界面活性劑、非離子型反應性界面活性劑、陽離子型反應性界面活性劑等。 Further, specific examples of the reactive surfactant include an anionic reactive surfactant having a (meth)acryl fluorenyl group or an allyl group, a nonionic reactive surfactant, and a cationic reaction. Sexual surfactants, etc.
作為上述陰離子型反應性界面活性劑,例如可列舉式(A1)~(A10)所示者等。 Examples of the anionic reactive surfactant include those represented by the formulae (A1) to (A10).
[化3]
[式(A1)中之R1表示氫或甲基,R2表示碳數1至30之烴基或醯基,X表示陰離子性親水基,R3及R4相同或不同,表示碳數1至6之伸烷基,平均加成莫耳數m及n表示0~40,但(m+n)表示3~40之數。]。 [R 1 in the formula (A1) represents hydrogen or a methyl group, R 2 represents a hydrocarbon group or a fluorenyl group having 1 to 30 carbon atoms, X represents an anionic hydrophilic group, and R 3 and R 4 are the same or different and represent a carbon number of 1 to The alkyl group of 6 has an average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].
[式(A2)中之R1表示氫或甲基,R2及R7相同或不同,表示碳數1至6之伸烷基,R3及R5相同或不同,表示氫或烷基,R4及R6相同或不同,表示氫、烷基、苄基或苯乙烯基,X表示陰離子性親水基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。]。 [R 1 in the formula (A2) represents hydrogen or a methyl group, and R 2 and R 7 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R 3 and R 5 are the same or different and represent hydrogen or an alkyl group; R 4 and R 6 are the same or different and represent hydrogen, an alkyl group, a benzyl group or a styryl group, and X represents an anionic hydrophilic group. The average addition molar number m and n represent 0 to 40, but (m+n) Indicates the number from 3 to 40. ].
[式(A3)中之R1表示氫或甲基,R2表示碳數1~6之伸烷基,X表示陰離子性親水基,平均加成莫耳數n表示3~40之數。]。 [In the formula (A3), R 1 represents hydrogen or a methyl group, R 2 represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and an average addition molar number n represents a number of 3 to 40. ].
[化6]
[式(A4)中之R1表示氫或甲基,R2表示碳數1~30之烴基或醯基,R3及R4相同或不同,表示碳數1~6之伸烷基,X表示陰離子性親水基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。]。 [In the formula (A4), R 1 represents hydrogen or a methyl group, R 2 represents a hydrocarbon group having 1 to 30 carbon atoms or a fluorenyl group, and R 3 and R 4 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, X. It represents an anionic hydrophilic group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].
[式(A5)中之R1表示烴基、胺基、羧酸殘基,R2表示碳數1~6之伸烷基,X表示陰離子性親水基,平均加成莫耳數n表示3~40之整數。]。 [In the formula (A5), R 1 represents a hydrocarbon group, an amine group, a carboxylic acid residue, R 2 represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and an average addition molar number n represents 3~ An integer of 40. ].
[式(A6)中之R1表示碳數1~30之烴基,R2表示氫或碳數1~30之烴基,R3表示氫或丙烯基,R4表示碳數1~6之伸烷基,X表示陰離子性親水基,平均加成莫耳數n表示3~40之數。]。 [In the formula (A6), R 1 represents a hydrocarbon group having 1 to 30 carbon atoms, R 2 represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, R 3 represents hydrogen or a propenyl group, and R 4 represents a hydrocarbon having 1 to 6 carbon atoms; Base, X represents an anionic hydrophilic group, and the average addition molar number n represents a number from 3 to 40. ].
[式(A7)中之R1表示氫或甲基,R2及R4相同或不同,表示碳數1~6之伸烷基,R3表示碳數1~30之烴基,M表示氫、鹼金屬、銨基或烷醇銨基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。]。 [In the formula (A7), R 1 represents hydrogen or a methyl group, and R 2 and R 4 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R 3 represents a hydrocarbon group having 1 to 30 carbon atoms; and M represents hydrogen; The alkali metal, ammonium or alkanolammonium group has an average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ].
[式(A8)中之R1及R5相同或不同,表示氫或甲基,R2及R4相同或不同,表示碳數1~6之伸烷基,R3表示碳數1~30之烴基,M表示氫、鹼金屬、銨基或烷醇銨基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。] [R 1 and R 5 in the formula (A8) are the same or different and each represents hydrogen or a methyl group, and R 2 and R 4 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and R 3 represents a carbon number of 1 to 30. The hydrocarbon group, M represents hydrogen, an alkali metal, an ammonium group or an alkanolammonium group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents a number of 3 to 40. ]
[式(A9)中之R1表示碳數1~6之伸烷基,R2表示碳數1~30之烴基,M表示氫、鹼金屬、銨基或烷醇銨基,平均加成莫耳數n表示3~40之數。] [In the formula (A9), R 1 represents an alkylene group having 1 to 6 carbon atoms, R 2 represents a hydrocarbon group having 1 to 30 carbon atoms, and M represents a hydrogen, an alkali metal, an ammonium group or an alkanolammonium group, and the average addition is mo The number of ears n represents the number from 3 to 40. ]
[化12]
[式(A10)中之R1、R2及R3相同或不同,表示氫或甲基,R4表示碳數0~30之烴基(於碳數為0之情形時表示R4不存在),R5及R6相同或不同,表示碳數1~6之伸烷基,X表示陰離子性親水基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。]。 [R 1 , R 2 and R 3 in the formula (A10) are the same or different and represent hydrogen or a methyl group, and R 4 represents a hydrocarbon group having a carbon number of 0 to 30 (in the case where the carbon number is 0, R 4 does not exist) R 5 and R 6 are the same or different and represent an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition molar number m and n represents 0 to 40, but (m+n) represents 3~40 number. ].
上述式(A1)~(A6)、及(A10)中之X表示陰離子性親水基。作為陰離子性親水基,可列舉下述式(a1)~(a2)所示者。 X in the above formulae (A1) to (A6) and (A10) represents an anionic hydrophilic group. Examples of the anionic hydrophilic group include those represented by the following formulas (a1) to (a2).
[化13]-SO3M1 (a1) [Chemical 13]-SO 3 M 1 (a1)
[式(a1)中之M1表示氫、鹼金屬、銨基或烷醇銨基。] [M 1 in the formula (a1) represents a hydrogen, an alkali metal, an ammonium group or an alkanolammonium group. ]
[式(a2)中之M2及M3相同或不同,表示氫、鹼金屬、銨基、或烷醇銨基。] [M 2 and M 3 in the formula (a2) are the same or different and each represents a hydrogen, an alkali metal, an ammonium group, or an alkanolammonium group. ]
作為非離子型反應性界面活性劑,例如可列舉式(N1)~(N6)所示者等。 Examples of the nonionic reactive surfactant include those represented by the formulae (N1) to (N6).
[化15]
[式(N1)中之R1表示氫或甲基,R2表示碳數1~30之烴基或醯基,R3及R4相同或不同,表示碳數1~6之伸烷基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。] [In the formula (N1), R 1 represents hydrogen or a methyl group, R 2 represents a hydrocarbon group having 1 to 30 carbon atoms or a fluorenyl group, and R 3 and R 4 are the same or different, and represent an alkylene group having a carbon number of 1 to 6, an average The addition moiré m and n represent 0 to 40, but (m+n) represents the number of 3 to 40. ]
[式(N2)中之R1表示氫或甲基,R2、R3及R4相同或不同,表示碳數1~6之伸烷基,平均加成莫耳數n、m及l表示0~40,但(n+m+l)表示3~40之數。] [In the formula (N2), R 1 represents hydrogen or a methyl group, and R 2 , R 3 and R 4 are the same or different, and represent an alkylene group having 1 to 6 carbon atoms, and the average addition molar number n, m and l represents 0~40, but (n+m+l) means 3~40. ]
[式(N3)中之R1表示氫或甲基,R2及R3相同或不同,表示碳數1~6之伸烷基,R4表示碳數1~30之烴基或醯基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。] [In the formula (N3), R 1 represents hydrogen or a methyl group, and R 2 and R 3 are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R 4 represents a hydrocarbon group or a mercapto group having 1 to 30 carbon atoms, and an average The addition moiré m and n represent 0 to 40, but (m+n) represents the number of 3 to 40. ]
[化18]
[式(N4)中之R1及R2相同或不同,表示碳數1~30之烴基,R3表示氫或丙烯基,R4表示碳數1~6之伸烷基,平均加成莫耳數n表示3~40之數。] [In the formula (N4), R 1 and R 2 are the same or different and each represents a hydrocarbon group having 1 to 30 carbon atoms, R 3 represents hydrogen or a propenyl group, and R 4 represents an alkylene group having 1 to 6 carbon atoms, and the average addition is Mo. The number of ears n represents the number from 3 to 40. ]
[式(N5)中之R1及R3相同或不同,表示碳數1~6之伸烷基,R2及R4相同或不同,表示氫、碳數1~30之烴基或醯基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。] [wherein R 1 and R 3 in the formula (N5) are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; and R 2 and R 4 are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms or a mercapto group; The average addition mole number m and n represent 0 to 40, but (m+n) represents the number from 3 to 40. ]
[式(N6)中之R1、R2及R3相同或不同,表示氫或甲基,R4表示碳數0~30之烴基(於碳數為0之情形時表示R4不存在),R5及R6相同或不同,表示碳數1~6之伸烷基,平均加成莫耳數m及n表示0~40,但,(m+n)表示3~40之數。] [R 1 , R 2 and R 3 in the formula (N6) are the same or different and represent hydrogen or a methyl group, and R 4 represents a hydrocarbon group having a carbon number of 0 to 30 (in the case where the carbon number is 0, R 4 does not exist) R 5 and R 6 are the same or different and represent an alkylene group having 1 to 6 carbon atoms. The average addition molar number m and n represent 0 to 40. However, (m+n) represents a number of 3 to 40. ]
此外,作為上述含氧伸烷基之反應性單體之具體市售品,例如 可列舉:BLEMMER PME-400、BLEMMER PME-1000、BLEMMER 50POEP-800B(以上均為日本油脂公司製造),LATEMUL PD-420、LATEMUL PD-430(以上均為花王公司製造),ADEKA REASOAP ER-10、ADEKA REASOAP NE-10(以上均為旭電化工業公司製造)等。 Further, as a specific commercial product of the above oxygen-containing alkyl group-reactive monomer, for example, For example, BLEMMER PME-400, BLEMMER PME-1000, BLEMMER 50POEP-800B (all manufactured by Nippon Oil & Fats Co., Ltd.), LATEMUL PD-420, LATEMUL PD-430 (all of which are manufactured by Kao Corporation), ADEKA REASOAP ER-10 ADEKA REASOAP NE-10 (all of which are manufactured by Asahi Denki Kogyo Co., Ltd.).
此外,於上述(甲基)丙烯酸系聚合物(a)中,為了調整所獲得之黏著劑層之凝聚力,可根據需要而含有多官能性單體。 Further, in the above (meth)acryl-based polymer (a), in order to adjust the cohesive force of the obtained adhesive layer, a polyfunctional monomer may be contained as needed.
作為上述多官能性單體,例如可列舉:(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯基苯、環氧丙烯酸酯、聚酯丙烯酸酯、胺基甲酸酯丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯等。其中,可較佳地使用三羥甲基丙烷三(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯。上述多官能性單體可單獨使用或將2種以上組合使用。 Examples of the polyfunctional monomer include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate , allyl (meth) acrylate, vinyl (meth) acrylate, divinyl benzene, epoxy acrylate, polyester acrylate, urethane acrylate, butane diol di (meth) acrylate Ester, hexanediol di(meth)acrylate, and the like. Among them, trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate can be preferably used. These polyfunctional monomers may be used singly or in combination of two or more.
作為上述多官能性單體之含量,根據其分子量、或官能基數等而有所不同,以相對於用以調製上述(甲基)丙烯酸系聚合物(a)之單體成分總量(100質量%)較佳為0.01~3質量%、更佳為0.02~2質量%、進而較佳為0.03~1質量%之方式添加。若上述多官能性單體之含量超過3質量%,則存在例如所獲得之黏著劑層之凝聚力過高、黏著力降低的情況。另一方面,若未達0.01質量%,則存在例如所得之黏著劑層之凝聚力降低、於自被接著體(被保護體)剝離時黏著劑層之一部分殘留於被接著體而將其污染的情況。 The content of the above polyfunctional monomer varies depending on the molecular weight, the number of functional groups, and the like, relative to the total amount of the monomer component (100 mass) for preparing the above (meth)acrylic polymer (a). %) is preferably added in an amount of 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, still more preferably 0.03 to 1% by mass. When the content of the above polyfunctional monomer exceeds 3% by mass, for example, the cohesive force of the obtained adhesive layer is too high, and the adhesive strength may be lowered. On the other hand, if it is less than 0.01% by mass, for example, the cohesive force of the obtained adhesive layer is lowered, and when one part of the adhesive layer is peeled off from the adherend (protected body), it remains in the adherend and is contaminated. Happening.
於調製(聚合)上述(甲基)丙烯酸系聚合物(a)時,利用使用有熱聚 合起始劑、或光聚合起始劑(光起始劑)等聚合起始劑之因熱、或放射線引起之硬化反應,能夠容易地形成丙烯酸系聚合物。尤其,就能夠縮短聚合時間之優點等而言,可較佳地使用熱聚合。聚合起始劑可單獨使用亦可將2種以上組合使用。 When the (meth)acrylic polymer (a) is prepared (polymerized), it is used by heat polymerization. An acrylic polymer can be easily formed by heat or radiation-induced hardening reaction of a polymerization initiator such as a starter or a photopolymerization initiator (photoinitiator). In particular, thermal polymerization can be preferably used in terms of the advantage of being able to shorten the polymerization time and the like. The polymerization initiators may be used singly or in combination of two or more.
作為上述熱聚合起始劑,例如可列舉:偶氮系聚合起始劑(例如2,2'-偶氮雙異丁腈、2,2'-偶氮雙-2-甲基丁腈、2,2'-偶氮雙(2-甲基丙酸)二甲酯、4,4'-偶氮雙-4-氰基戊酸、偶氮雙異戊腈、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)二鹽酸鹽等);過氧化物系聚合起始劑(例如過氧化二苯甲醯、過氧化馬來酸第三丁酯、過氧化月桂醯等);氧化還原系聚合起始劑等。 Examples of the thermal polymerization initiator include an azo polymerization initiator (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2 , 2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisoprene, 2,2'-azo double (2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'- Azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethyleneisobutylphosphonium) dihydrochloride, etc.; peroxide polymerization An initiator (for example, benzamidine peroxide, tert-butyl peroxymaleate, laurel, etc.); a redox polymerization initiator or the like.
作為上述熱聚合起始劑之含量,並無特別限制,例如相對於用以調製上述(甲基)丙烯酸系聚合物(a)之單體成分總量100質量份,較佳為0.01~5質量份,更佳為0.05~3質量份。 The content of the thermal polymerization initiator is not particularly limited. For example, it is preferably 0.01 to 5 by mass based on 100 parts by mass of the total of the monomer components for preparing the (meth)acryl-based polymer (a). More preferably, it is 0.05 to 3 parts by mass.
作為上述光聚合起始劑,並無特別限制,例如可使用安息香醚系光聚合起始劑、苯乙酮系光聚合起始劑、α-酮醇系光聚合起始劑、芳香族磺醯氯系光聚合起始劑、光活性肟系光聚合起始劑、安息香系光聚合起始劑、苄基系光聚合起始劑、二苯甲酮系光聚合起始劑、縮酮系光聚合起始劑、噻噸酮系光聚合起始劑、醯基氧化膦系光聚合起始劑等。 The photopolymerization initiator is not particularly limited, and for example, a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-keto alcohol photopolymerization initiator, an aromatic sulfonium sulfonate can be used. Chlorine photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal light A polymerization initiator, a thioxanthone-based photopolymerization initiator, a mercaptophosphine oxide-based photopolymerization initiator, and the like.
具體而言,作為安息香醚系光聚合起始劑,例如可列舉:安息香甲醚、安息香乙醚、安息香丙醚、安息香異丙醚、安息香異丁醚、2,2-二甲氧基-1,2-二苯基乙烷-1-酮[商品名:Irgacure 651,BASF公司製造]、茴香醚甲基醚等。作為苯乙酮系光聚合起始劑,例如可列舉:1-羥基環己基苯基酮[商品名:Irgacure 184,BASF公司製造]、4- 苯氧基二氯苯乙酮、4-第三丁基-二氯苯乙酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮[商品名:Irgacure 2959,BASF公司製造]、2-羥基-2-甲基-1-苯基-丙烷-1-酮[商品名:Darocur 1173,BASF公司製造]、甲氧基苯乙酮等。作為α-酮醇系光聚合起始劑,例如可列舉:2-甲基-2-羥基苯丙酮、1-[4-(2-羥基乙基)-苯基]-2-羥基-2-甲基丙烷-1-酮等。作為芳香族磺醯氯系光聚合起始劑,例如可列舉:2-萘磺醯氯等。作為光活性肟系光聚合起始劑,例如可列舉:1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟等。 Specific examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1. 2-Diphenylethane-1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisole methyl ether or the like. Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF Corporation], 4- Phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1 -propan-1-one [trade name: Irgacure 2959, manufactured by BASF Corporation], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [trade name: Darocur 1173, manufactured by BASF Corporation], A Oxyacetophenone and the like. Examples of the α-keto alcohol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2- Methylpropan-1-one and the like. Examples of the aromatic sulfonium chloride-based photopolymerization initiator include 2-naphthalenesulfonium chloride and the like. The photoactive oxime-based photopolymerization initiator may, for example, be 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-ruthenium or the like.
此外,安息香系光聚合起始劑包括例如安息香等。苄基系光聚合起始劑包括例如苄基等。二苯甲酮系光聚合起始劑包括例如二苯甲酮、苯甲醯基苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮、聚乙烯基二苯甲酮、α-羥基環己基苯基酮等。縮酮系光聚合起始劑包括例如苄基二甲基縮酮等。噻噸酮系光聚合起始劑包括例如噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、異丙基噻噸酮、2,4-二異丙基噻噸酮、十二烷基噻噸酮等。 Further, the benzoin-based photopolymerization initiator includes, for example, benzoin or the like. The benzyl photopolymerization initiator includes, for example, a benzyl group or the like. The benzophenone photopolymerization initiator includes, for example, benzophenone, benzhydrylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone , α-hydroxycyclohexyl phenyl ketone, and the like. The ketal-based photopolymerization initiator includes, for example, benzyldimethylketal or the like. The thioxanthone photopolymerization initiator includes, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
作為醯基氧化膦系光聚合起始劑,例如可列舉:雙(2,6-二甲氧基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)(2,4,4-三甲基戊基)氧化膦、雙(2,6-二甲氧基苯甲醯基)正丁基氧化膦、雙(2,6-二甲氧基苯甲醯基)-(2-甲基丙烷-1-基)氧化膦、雙(2,6-二甲氧基苯甲醯基)-(1-甲基丙烷-1-基)氧化膦、雙(2,6-二甲氧基苯甲醯基)-第三丁基氧化膦、雙(2,6-二甲氧基苯甲醯基)環己基氧化膦、雙(2,6-二甲氧基苯甲醯基)辛基氧化膦、雙(2-甲氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2-甲氧基苯甲醯基)(1-甲基丙烷-1-基)氧化膦、雙(2,6-二乙氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2,6-二乙氧基苯甲醯基)(1-甲基丙烷-1-基)氧化膦、雙(2,6-二丁氧基苯甲醯基)(2-甲基丙烷-1-基)氧化 膦、雙(2,4-二甲氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2,4,6-三甲基苯甲醯基)(2,4-二戊氧基苯基)氧化膦、雙(2,6-二甲氧基苯甲醯基)苄基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基丙基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基乙基氧化膦、雙(2,6-二甲氧基苯甲醯基)苄基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基丙基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基乙基氧化膦、2,6-二甲氧基苯甲醯基苄基丁基氧化膦、2,6-二甲氧基苯甲醯基苄基辛基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,5-二異丙基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2-甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-4-甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,5-二乙基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,3,5,6-四甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,4-二正丁氧基苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)異丁基氧化膦、2,6-二甲氧基苯甲醯基-2,4,6-三甲基苯甲醯基正丁基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,4-二丁氧基苯基氧化膦、1,10-雙[雙(2,4,6-三甲基苯甲醯基)氧化膦]癸烷、三(2-甲基苯甲醯基)氧化膦等。 Examples of the fluorenylphosphine oxide-based photopolymerization initiator include bis(2,6-dimethoxybenzylidene)phenylphosphine oxide and bis(2,6-dimethoxybenzylidene). (2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzylidene) n-butylphosphine oxide, bis(2,6-dimethoxybenzoate) Mercapto)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzylidene)-(1-methylpropan-1-yl)phosphine oxide, double 2,6-dimethoxybenzimidyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzylidene)cyclohexylphosphine oxide, bis(2,6-dimethoxy Benzoyl fluorenylphosphine, bis(2-methoxybenzimidyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzhydryl) ( 1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzhydryl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethyl) (1-Methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzylidene) (2-methylpropan-1-yl) oxidation Phosphine, bis(2,4-dimethoxybenzylidene)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzylidene) (2, 4-dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzylidene)benzylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2- Phenylpropylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzylidene)benzyl oxidation Phosphine, bis(2,6-dimethoxybenzylidene)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2-phenylethyl oxide Phosphine, 2,6-dimethoxybenzimidylbenzyl butylphosphine oxide, 2,6-dimethoxybenzimidylbenzyloctylphosphine oxide, bis(2,4,6-trimethyl) Benzobenzhydryl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2-methylphenylphosphine oxide, bis(2, 4,6-trimethylbenzylidene)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,5-diethylphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzamide Diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide Isobutylphosphine oxide, 2,6-dimethoxybenzhydryl-2,4,6-trimethylbenzimidyl-n-butylphosphine oxide, bis(2,4,6-trimethyl) Benzobenzino)phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[double (2 , 4,6-trimethylbenzimidyl)phosphine oxide]decane, tris(2-methylbenzhydryl)phosphine oxide, and the like.
對上述光聚合起始劑之含量並無特別限制,例如相對於用以調製上述(甲基)丙烯酸系聚合物(a)之單體成分總量100質量份,較佳為0.01~5質量份,更佳為0.05~3質量份。此處,若上述光聚合起始劑之含量少於0.01質量份,則存在聚合反應不充分之情況。若上述光聚合起始劑之含量超過5質量份,則存在由於光聚合起始劑吸收紫外線而紫外線無法到達至黏著劑層內部之情況。於該情形時,會導致聚合率降低,或所生成之聚合物之分子量減小。而且,存在藉此所形成之黏著劑層之凝聚力降低、將黏著劑層自被接著體剝離時黏著劑層之一部分殘留於被接著體、被接著體無法再利用之情況。另外,光聚合起 始劑可單獨使用亦可將2種以上組合使用。 The content of the photopolymerization initiator is not particularly limited. For example, it is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total of the monomer components for preparing the (meth)acryl-based polymer (a). More preferably, it is 0.05 to 3 parts by mass. Here, when the content of the photopolymerization initiator is less than 0.01 parts by mass, the polymerization reaction may be insufficient. When the content of the photopolymerization initiator exceeds 5 parts by mass, the photopolymerization initiator absorbs ultraviolet rays and the ultraviolet rays cannot reach the inside of the pressure-sensitive adhesive layer. In this case, the polymerization rate is lowered or the molecular weight of the produced polymer is decreased. Further, there is a case where the cohesive force of the adhesive layer formed thereby is lowered, and a part of the adhesive layer remains in the adherend when the adhesive layer is peeled off from the adherend, and the adherend cannot be reused. In addition, photopolymerization The starting agents may be used singly or in combination of two or more.
於本實施形態中,上述(甲基)丙烯酸系聚合物(a)亦可調製成對調配上述單體成分及聚合起始劑而成之混合物照射放射線(紫外線等)而使單體成分部分性聚合而成之部分聚合物(丙烯酸系聚合物漿液)。亦可於丙烯酸系聚合物漿液中調配下述之(甲基)丙烯酸系聚合物(B)來調製黏著劑組合物,將該黏著劑組合物塗佈於特定之被塗佈體上之後照射放射線(紫外線等)來完成聚合。 In the present embodiment, the (meth)acrylic polymer (a) may be prepared by irradiating a mixture of the monomer component and the polymerization initiator with radiation (ultraviolet rays or the like) to partially form a monomer component. Part of the polymer (acrylic polymer slurry) polymerized. The following (meth)acrylic polymer (B) may be blended in an acrylic polymer slurry to prepare an adhesive composition, and the adhesive composition may be applied to a specific coated body to irradiate radiation. (ultraviolet rays, etc.) to complete the polymerization.
作為上述放射線,例如可列舉:紫外線(UV)、雷射線、α射線、β射線、γ射線、X射線、電子束等,就控制性及操作性之良好程度、成本之方面而言,較佳使用紫外線。更佳使用波長200~400nm之紫外線。紫外線可使用高壓水銀燈、微波激發型燈、化學燈等適當光源進行照射。 Examples of the radiation include ultraviolet rays (UV), thunder rays, α rays, β rays, γ rays, X rays, and electron beams, and are preferable in terms of controllability and workability, and cost. Use ultraviolet light. It is better to use ultraviolet rays having a wavelength of 200 to 400 nm. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp.
亦可進而與上述光聚合起始劑一起併用胺類等光聚合起始助劑。作為上述光聚合起始助劑,例如可列舉:2-二甲胺基乙基苯甲酸酯、二甲胺基苯乙酮、對二甲胺基苯甲酸乙酯、對二甲胺基苯甲酸異戊酯等。該等化合物可單獨使用,亦可混合2種以上使用。相對於上述聚合物(A)100質量份,光聚合起始助劑較佳為調配0.05~10質量份,更佳為以0.1~7質量份之範圍調配。若在上述範圍內,則就容易控制聚合反應、獲得適度之分子量之觀點而言較佳。 Further, a photopolymerization initiation aid such as an amine may be used in combination with the above photopolymerization initiator. Examples of the photopolymerization initiation aid include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, and p-dimethylaminobenzene. Isoamyl formate and the like. These compounds may be used singly or in combination of two or more. The photopolymerization initiation aid is preferably formulated in an amount of from 0.05 to 10 parts by mass, more preferably from 0.1 to 7 parts by mass, based on 100 parts by mass of the polymer (A). When it is in the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.
另外,於調配有上述光聚合起始劑之情形時,藉由將上述黏著劑組合物直接塗覆於被接著體(被保護體)上,或者塗覆於隔離體等特定之被塗佈體上之後,或者塗覆於具有抗靜電性之支持體(基材)上之單面之後,進行光照射,藉此可獲得黏著劑層。通常,藉由以光量200~4000mJ/cm2左右照射波長300~400nm下之照度為1~200mW/cm2的紫外線進行光聚合,可獲得黏著劑層。 Further, in the case where the above photopolymerization initiator is formulated, the above-mentioned adhesive composition is directly applied to the adherend (protected body) or to a specific coated body such as a separator. After the above, or after coating on one side of the support (substrate) having antistatic properties, light irradiation is performed, whereby an adhesive layer can be obtained. In general, an adhesive layer can be obtained by photopolymerizing ultraviolet rays having an illuminance of from 1 to 200 mW/cm 2 at a wavelength of from 300 to 400 nm at a light amount of about 200 to 4000 mJ/cm 2 .
上述(甲基)丙烯酸系聚合物(a)之重量平均分子量(Mw)例如較佳 為3萬~500萬,更佳為10萬~200萬,進而較佳為20萬~100萬。若重量平均分子量(Mw)過於小於上述範圍,則存在黏著劑(層)之凝聚力不足、容易發生藥液浸入的情況。另一方面,若重量平均分子量(Mw)過於大於上述範圍,則存在黏著劑之流動性降低、對被接著體之潤濕不足、密著性降低的情況。 The weight average molecular weight (Mw) of the above (meth)acrylic polymer (a) is preferably, for example, preferably It is 30,000 to 5 million, more preferably 100,000 to 2 million, and more preferably 200,000 to 1 million. When the weight average molecular weight (Mw) is too smaller than the above range, the cohesive force of the adhesive (layer) may be insufficient, and the chemical solution may be easily infiltrated. On the other hand, when the weight average molecular weight (Mw) is too larger than the above range, the fluidity of the adhesive may be lowered, the wetting of the adherend may be insufficient, and the adhesion may be lowered.
另外,上述(甲基)丙烯酸系聚合物(a)之玻璃轉移溫度(Tg)未達0℃,較佳為未達-10℃,更佳為未達-40℃,通常為-80℃以上。若上述(甲基)丙烯酸系聚合物(a)之玻璃轉移溫度(Tg)為0℃以上,則存在聚合物不易流動、對被接著體之潤濕不充分、密著性降低的情況。此外,上述(甲基)丙烯酸系聚合物(a)之玻璃轉移溫度(Tg)不過低有助於防止藥液浸入(典型而言主要起因於黏著劑因藥液而膨潤之藥液浸入)。 Further, the glass transition temperature (Tg) of the (meth)acrylic polymer (a) is less than 0 ° C, preferably less than -10 ° C, more preferably less than -40 ° C, and usually -80 ° C or more. . When the glass transition temperature (Tg) of the (meth)acrylic polymer (a) is 0° C. or higher, the polymer may not easily flow, and the wetting of the adherend may be insufficient, and the adhesion may be lowered. Further, the glass transition temperature (Tg) of the (meth)acrylic polymer (a) described above is not too low to prevent the infiltration of the chemical solution (typically, the chemical solution which is mainly caused by the swelling of the adhesive due to the chemical solution).
於本發明中,於上述(甲基)丙烯酸系聚合物(a)為共聚物之情形時,其玻璃轉移溫度(Tg)為根據以下之式(2)(Fox式)算出的值。 In the case where the (meth)acrylic polymer (a) is a copolymer, the glass transition temperature (Tg) is a value calculated according to the following formula (2) (Fox formula).
1/Tg=W1/Tg1+W2/Tg2+‧‧‧+Wn/Tgn (2) 1/Tg=W 1 /Tg 1 +W 2 /Tg 2 +‧‧‧+Wn/Tg n (2)
[式(2)中,Tg表示共聚物之玻璃轉移溫度(單位:K),Tgi(i=1、2、…n)表示單體i形成均聚物時之玻璃轉移溫度(單位:K),Wi(i=1、2、…n)表示單體i於全部單體成分中之質量分率。] [In the formula (2), Tg represents the glass transition temperature (unit: K) of the copolymer, and Tg i (i = 1, 2, ... n) represents the glass transition temperature (unit: K) when the monomer i forms a homopolymer. ), W i (i = 1, 2, ... n) represents the mass fraction of monomer i in all monomer components. ]
此外,單體i之玻璃轉移溫度Tgi為文獻(例如聚合物手冊、黏著手冊等)中記載之標稱值。 Further, the glass transition temperature Tgi of the monomer i is a nominal value described in the literature (for example, a polymer manual, an adhesive manual, etc.).
本發明之藥液處理用黏著劑層之形成中使用的黏著劑組合物較佳為含有(甲基)丙烯酸系聚合物(B),上述(甲基)丙烯酸系聚合物(B)之重量平均分子量為1000以上且未達30000,且包含下述通式(1)所示之具有脂環式結構的(甲基)丙烯酸系單體作為單體成分。 The adhesive composition used in the formation of the adhesive layer for treating a chemical solution of the present invention preferably contains a (meth)acrylic polymer (B), and the weight average of the above (meth)acrylic polymer (B) The (meth)acrylic monomer having an alicyclic structure represented by the following formula (1) is a monomer component having a molecular weight of 1,000 or more and less than 30,000.
CH2=C(R1)COOR2 (1) CH 2 =C(R 1 )COOR 2 (1)
[式(1)中,R1為氫原子或甲基,R2為具有脂環式結構之脂環式烴基。] [In the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alicyclic hydrocarbon group having an alicyclic structure. ]
上述(甲基)丙烯酸系聚合物(B)可發揮作為增黏樹脂之功能。此外,於形成本發明之藥液處理用黏著劑層時使用之黏著劑組合物為丙烯酸系黏著劑組合物之情形時,例如容易與上述(甲基)丙烯酸系聚合物(a)相容而特別較佳。 The (meth)acrylic polymer (B) functions as a tackifying resin. In the case where the adhesive composition used in forming the pressure-sensitive adhesive layer for chemical solution treatment of the present invention is an acrylic pressure-sensitive adhesive composition, for example, it is easily compatible with the above (meth)acrylic polymer (a). Particularly preferred.
作為上述通式(1)中之脂環式烴基R2,可列舉環己基、異冰片基、二環戊基等脂環式烴基等。作為具有此種脂環式烴基之(甲基)丙烯酸酯,例如可列舉:具有環己基之(甲基)丙烯酸環己酯、具有異冰片基之(甲基)丙烯酸異冰片酯、具有二環戊基之(甲基)丙烯酸二環戊酯等(甲基)丙烯酸與脂環族醇之酯。藉由如此使(甲基)丙烯酸系聚合物(B)中含有具有較大體積之結構之丙烯酸系單體作為單體成分,能夠提高接著強度(黏著力)。 The alicyclic hydrocarbon group R 2 in the above formula (1) may, for example, be an alicyclic hydrocarbon group such as a cyclohexyl group, an isobornyl group or a dicyclopentyl group. Examples of the (meth) acrylate having such an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate having a cyclohexyl group, isobornyl (meth)acrylate having an isobornyl group, and a bicyclic ring. An ester of (meth)acrylic acid such as dipentyl (meth)acrylate or an alicyclic alcohol. By using the acrylic monomer having a structure having a large volume in the (meth)acrylic polymer (B) as a monomer component, the bonding strength (adhesive strength) can be improved.
進而,構成上述(甲基)丙烯酸系聚合物(B)之脂環式烴基較佳為具有橋接環結構。橋接環結構係指三環以上之脂環式結構。藉由使(甲基)丙烯酸系聚合物(B)具有如橋接環結構般之體積較大之結構,能夠進一步提高藥液處理用黏著劑層(黏著片、表面保護片)之接著強度(黏著力)。 Further, the alicyclic hydrocarbon group constituting the (meth)acryl-based polymer (B) preferably has a bridged ring structure. The bridged ring structure refers to an alicyclic structure of three or more rings. By making the (meth)acrylic polymer (B) have a bulky structure such as a bridged ring structure, the adhesion strength (adhesive sheet, surface protective sheet) of the chemical treatment layer can be further improved (adhesion) force).
作為具有上述橋接環結構之脂環式烴基R2,例如可列舉:下述式(3a)表示之二環戊基、下述式(3b)表示之二環戊烯基、下述式(3c)表示之金剛烷基、下述式(3d)表示之三環戊基、下述式(3e)表示之三環戊烯基等。另外,於合成(甲基)丙烯酸系聚合物(B)時、或製作黏著劑組合物時採用UV聚合之情形時,就不易發生聚合抑制之方面而言,於具有含橋接環結構之三環以上之脂環式結構的(甲基)丙烯酸系單體之中,可特別較佳地使用具有下述式(3a)表示之二環戊基、或下述式(3c)表示之金剛烷基、下述式(3d)表示之三環戊基等飽和結構之(甲基) 丙烯酸系單體作為構成(甲基)丙烯酸系聚合物(B)的單體。 Examples of the alicyclic hydrocarbon group R 2 having the above-mentioned bridge ring structure include a dicyclopentanyl group represented by the following formula (3a), a dicyclopentenyl group represented by the following formula (3b), and the following formula (3c). And the adamantyl group represented by the following formula (3d), the tricyclopentenyl group represented by the following formula (3e), and the like. Further, when the (meth)acrylic polymer (B) is synthesized or when the UV-polymerization is used in the production of the adhesive composition, the polymerization is less likely to occur, and the ring has a bridge ring structure. Among the above (meth)acrylic monomers having an alicyclic structure, a dicyclopentyl group represented by the following formula (3a) or an adamantyl group represented by the following formula (3c) can be particularly preferably used. A (meth)acrylic monomer having a saturated structure such as a tricyclopentyl group represented by the following formula (3d) is a monomer constituting the (meth)acrylic polymer (B).
此外,作為此種具有含橋接環結構之三環以上之脂環式結構的(甲基)丙烯酸系單體的例,可列舉:甲基丙烯酸二環戊基酯、丙烯酸二環戊基酯、甲基丙烯酸二環戊氧基乙酯、丙烯酸二環戊氧基乙酯、甲基丙烯酸三環戊基酯、丙烯酸三環戊基酯、甲基丙烯酸1-金剛烷基酯、丙烯酸1-金剛烷基酯、甲基丙烯酸2-甲基-2-金剛烷基酯、丙烯酸2-甲基-2-金剛烷基酯、甲基丙烯酸2-乙基-2-金剛烷基酯、丙烯酸2-乙基-2-金剛烷基酯等(甲基)丙烯酸酯。該(甲基)丙烯酸系單體可單獨使用或將2種以上組合使用。 Further, examples of the (meth)acrylic monomer having an alicyclic structure having three or more rings having a bridged ring structure include dicyclopentyl methacrylate and dicyclopentyl acrylate. Dicyclopentyloxyethyl methacrylate, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 1-gold acrylate Alkyl ester, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2- (Meth) acrylate such as ethyl-2-adamantyl ester. These (meth)acrylic monomers may be used singly or in combination of two or more.
上述(甲基)丙烯酸系聚合物(B)可為具有脂環式結構之(甲基)丙烯酸系單體之均聚物,或者亦可為具有脂環式結構之(甲基)丙烯酸系單體與其他(甲基)丙烯酸酯單體或共聚性單體之共聚物。 The (meth)acrylic polymer (B) may be a homopolymer of a (meth)acrylic monomer having an alicyclic structure, or may be a (meth)acrylic monomer having an alicyclic structure. a copolymer of a body with another (meth) acrylate monomer or a copolymerizable monomer.
作為此種(甲基)丙烯酸酯單體之例,可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基) 丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯之類之(甲基)丙烯酸烷基酯;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯之類之(甲基)丙烯酸芳基酯;由萜烯化合物衍生物醇獲得之(甲基)丙烯酸酯等。此種(甲基)丙烯酸酯可單獨使用或將2種以上組合使用。 Examples of such a (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. Butyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Dibutyl acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) (meth)acrylic acid alkyl ester such as decyl acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate; (methyl) An aryl (meth)acrylate such as phenyl acrylate or benzyl (meth) acrylate; a (meth) acrylate obtained from a terpene compound derivative alcohol. Such (meth) acrylate may be used singly or in combination of two or more.
另外,(甲基)丙烯酸系聚合物(B)除上述(甲基)丙烯酸酯成分單元之外,亦可使能與(甲基)丙烯酸酯共聚之其他單體成分(共聚性單體)共聚而獲得。 Further, the (meth)acrylic polymer (B) may copolymerize other monomer components (copolymerizable monomers) copolymerizable with (meth) acrylate in addition to the above (meth) acrylate component unit. And get.
作為能與上述(甲基)丙烯酸酯共聚之其他單體,可列舉:丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸、異巴豆酸等含羧基之單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基丙酯之類之(甲基)丙烯酸烷氧基烷基酯系單體;(甲基)丙烯酸鹼金屬鹽等鹽;乙二醇之二(甲基)丙烯酸酯、二乙二醇之二(甲基)丙烯酸酯、三乙二醇之二(甲基)丙烯酸酯、聚乙二醇之二(甲基)丙烯酸酯、丙二醇之二(甲基)丙烯酸酯、二丙二醇之二(甲基)丙烯酸酯、三丙二醇之二(甲基)丙烯酸酯之類之(聚)伸烷基二醇之二(甲基)丙烯酸酯單體;三羥甲基丙烷三(甲基)丙烯酸酯之類之多元(甲基)丙烯酸酯單體; 乙酸乙烯酯、丙酸乙烯酯等乙烯酯類;偏氯乙烯、(甲基)丙烯酸-2-氯乙酯之類之鹵化乙烯化合物;2-乙烯基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-異丙烯基-2-噁唑啉之類之含噁唑啉基之聚合性化合物;(甲基)丙烯醯基氮丙啶、(甲基)丙烯酸-2-氮丙啶基乙酯之類之含氮丙啶基之聚合性化合物;烯丙基縮水甘油醚、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸乙基縮水甘油醚之類之含環氧基之乙烯單體;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、內酯類與(甲基)丙烯酸-2-羥基乙酯之加成物之類之含羥基的乙烯單體;聚丙二醇、聚乙二醇、聚四亞甲基二醇、聚丁二醇、聚乙二醇與聚丙二醇之共聚物、聚丁二醇與聚乙二醇之共聚物之類之於聚伸烷基二醇之末端鍵結有(甲基)丙烯醯基、苯乙烯基、乙烯基等不飽和基的大分子單體;氟取代(甲基)丙烯酸烷基酯之類之含氟乙烯之單體;馬來酸酐、衣康酸酐等含酸酐基之單體;苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯化合物系單體;2-氯乙基乙烯醚、單氯乙酸乙烯酯之類之含反應性鹵素之乙烯單體;(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-甲氧基乙基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-丙烯醯基嗎啉之類之含醯胺基的乙烯單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧 六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基衣康醯亞胺、N-乙基衣康醯亞胺、N-丁基衣康醯亞胺、N-辛基衣康醯亞胺、N-2-乙基己基衣康醯亞胺、N-環己基衣康醯亞胺、N-月桂基衣康醯亞胺等衣康醯亞胺系單體;N-乙烯基-2-吡咯烷酮、N-甲基乙烯基吡咯烷酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌嗪、N-乙烯基吡嗪、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基噁唑、N-(甲基)丙烯醯基-2-吡咯烷酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯烷、N-乙烯基嗎啉、N-乙烯基吡唑、N-乙烯基異噁唑、N-乙烯基噻唑、N-乙烯基異噻唑、N-乙烯基噠嗪等含氮之雜環系單體;N-乙烯基羧醯胺類;N-乙烯基己內醯胺等內醯胺系單體;(甲基)丙烯腈等含氰基之單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸第三丁胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體;環己基馬來醯亞胺、異丙基馬來醯亞胺等含醯亞胺基之單體;(甲基)丙烯酸2-異氰酸酯基乙酯等含異氰酸基之單體;乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、烯丙基三甲氧基矽烷、三甲氧基矽烷基丙基烯丙基胺、2-甲氧基乙氧基三甲氧基矽烷之類之含有機矽的乙烯單體;(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥基甲基 環己基)甲酯等(甲基)丙烯酸羥基烷基酯等含羥基之單體;(甲基)丙烯酸四氫糠酯、含氟原子(甲基)丙烯酸酯、矽酮(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體;異戊二烯、丁二烯、異丁烯等烯烴系單體;甲基乙烯醚、乙基乙烯醚等乙烯醚系單體;乙烯、丁二烯、異戊二烯、異丁烯等烯烴或二烯類;乙烯基烷基醚等乙烯醚類;氯乙烯;以及於聚合有乙烯基之單體末端具有自由基聚合性乙烯基的大分子單體類等。該等單體可單獨或者組合地與上述(甲基)丙烯酸酯共聚。 Examples of other monomers copolymerizable with the above (meth) acrylate include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, a carboxyl group-containing monomer such as isocrotonic acid; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxy (meth)acrylate (meth)acrylic acid alkoxyalkyl ester monomer such as ethyl methacrylate or ethoxypropyl methacrylate; salt of (meth)acrylic acid alkali metal salt; Acrylate, di(meth)acrylate of diethylene glycol, di(meth)acrylate of triethylene glycol, di(meth)acrylate of polyethylene glycol, di(methyl) of propylene glycol a bis(meth) acrylate monomer such as acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate or the like (poly)alkyl diol; trishydroxyl a poly (meth) acrylate monomer such as a propane tri(meth) acrylate; Vinyl esters such as vinyl acetate and vinyl propionate; halogenated vinyl compounds such as vinylidene chloride and 2-chloroethyl (meth)acrylate; 2-vinyl-2-oxazoline, 2-vinyl a oxazoline group-containing polymerizable compound such as 5-methyl-2-oxazoline or 2-isopropenyl-2-oxazoline; (meth)acryloyl aziridine, (methyl) a polymerizable compound containing aziridine group such as 2-aziridine ethyl acrylate; allyl glycidyl ether, glycidyl (meth)acrylate, ethyl glycidyl (meth)acrylate Ethylene group-containing ethylene monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactone and 2-hydroxyethyl (meth)acrylate a hydroxyl group-containing ethylene monomer such as an ester adduct; a polypropylene glycol, a polyethylene glycol, a polytetramethylene glycol, a polytetramethylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, and a polybutylene a copolymer of an alcohol and a polyethylene glycol, or a macromonomer having an unsaturated group such as a (meth) acrylonitrile group, a styryl group or a vinyl group bonded to a terminal of the polyalkylene glycol; Alkyl (meth)acrylate a fluorine-containing ethylene monomer; an anhydride group-containing monomer such as maleic anhydride or itaconic anhydride; an aromatic vinyl compound monomer such as styrene, α-methylstyrene or vinyltoluene; 2-chloroethyl A vinyl monomer containing a reactive halogen such as a vinyl ether or a monochloroacetic acid ester; (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (methyl) Acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyl Ethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (methyl) An amidino group-containing ethylene monomer such as acrylamide or N-propylene decylmorpholine; N-(methyl) propylene oxymethylene succinimide, N-(meth) acrylonitrile -6-oxygen Amber quinone imine monomer such as hexamethylene succinimide, N-(methyl) propylene decyl-8-oxy octamethylene succinimide; N-cyclohexylmaleimide, N - maleic imine monomer such as isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide; N-methyl itaconimine, N -ethyl ketimine, N-butyl ketimine, N-octyl ketimine, N-2-ethylhexyl ketimine, N-cyclohexyl ketamine Amine, N-Lauryl ketimine, etc.; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidine Ketone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(methyl)acrylonitrile -2-pyrrolidone, N-(meth)acrylopylpiperidine, N-(methyl)propenylpyrrolidine, N-vinylmorpholine, N-vinylpyrazole, N-vinylisoxazole a nitrogen-containing heterocyclic monomer such as N-vinylthiazole, N-vinylisothiazole or N-vinylpyridazine; N-vinyl carboxamide; N-vinyl group An indoleamine monomer such as indoleamine; a cyano group-containing monomer such as (meth)acrylonitrile; an aminoethyl (meth)acrylate; and N,N-dimethylaminoethyl (meth)acrylate An aminoalkylalkyl (meth) acrylate such as tributylaminoethyl (meth)acrylate; a quinone imine group such as cyclohexylmaleimide or isopropylmaleimide Monomer; isocyanate-containing monomer such as 2-isocyanatoethyl (meth)acrylate; vinyltrimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, allyl An organic monomer containing trimethyl decane, trimethoxydecyl propylallylamine, 2-methoxyethoxytrimethoxydecane, or the like; hydroxyethyl (meth) acrylate; Hydroxypropyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxyl (meth)acrylate Lauryl ester, methacrylic acid (4-hydroxymethyl) a hydroxyl group-containing monomer such as a hydroxyalkyl (meth) acrylate such as cyclohexyl) methyl ester; tetrahydrofurfuryl (meth) acrylate, fluorine atom (meth) acrylate, fluorenone (meth) acrylate An acrylate monomer having a hetero ring, a halogen atom or a ruthenium atom; an olefin monomer such as isoprene, butadiene or isobutylene; and a vinyl ether monomer such as methyl vinyl ether or ethyl vinyl ether; An olefin or a diene such as ethylene, butadiene, isoprene or isobutylene; a vinyl ether such as a vinyl alkyl ether; a vinyl chloride; and a radically polymerizable vinyl group at the terminal of the monomer having a vinyl group polymerized; Macromonomers, etc. These monomers may be copolymerized with the above (meth) acrylate either singly or in combination.
作為上述(甲基)丙烯酸系聚合物(B),例如可列舉:甲基丙烯酸環己酯(CHMA)與甲基丙烯酸異丁酯(IBMA)之共聚物、甲基丙烯酸環己酯(CHMA)與甲基丙烯酸異冰片酯(IBXMA)之共聚物、甲基丙烯酸甲酯(MMA)與甲基丙烯酸異冰片酯(IBXMA)之共聚物、甲基丙烯酸環己酯(CHMA)與丙烯醯嗎啉(ACMO)之共聚物、甲基丙烯酸環己酯(CHMA)與二乙基丙烯醯胺(DEAA)之共聚物、丙烯酸1-金剛烷基酯(ADA)與甲基丙烯酸甲酯(MMA)之共聚物、甲基丙烯酸二環戊基酯(DCPMA)與甲基丙烯酸異冰片酯(IBXMA)之共聚物、甲基丙烯酸二環戊基酯(DCPMA)與甲基丙烯酸甲酯(MMA)之共聚物、甲基丙烯酸環己酯(CHMA)與甲基丙烯酸甲酯(MMA)之共聚物、甲基丙烯酸二環戊基酯(DCPMA)與丙烯酸(AA)之共聚物、甲基丙烯酸二環戊基酯(DCPMA)、甲基丙烯酸環己酯(CHMA)、甲基丙烯酸異冰片酯(IBXMA)、丙烯酸異冰片酯(IBXA)、丙烯酸二環戊基酯(DCPA)、甲基丙烯酸1-金剛烷基酯(ADMA)、丙烯酸1-金剛烷基酯(ADA)各自的均聚物等。 Examples of the (meth)acryl-based polymer (B) include a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and cyclohexyl methacrylate (CHMA). Copolymer with isobornyl methacrylate (IBXMA), copolymer of methyl methacrylate (MMA) and isobornyl methacrylate (IBXMA), cyclohexyl methacrylate (CHMA) and propylene morpholine Copolymer of (ACMO), copolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA), 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA) Copolymer, copolymer of dicyclopentyl methacrylate (DCPMA) with isobornyl methacrylate (IBXMA), copolymerization of dicyclopentyl methacrylate (DCPMA) and methyl methacrylate (MMA) , copolymer of cyclohexyl methacrylate (CHMA) and methyl methacrylate (MMA), copolymer of dicyclopentyl methacrylate (DCPMA) and acrylic acid (AA), dicyclopentyl methacrylate Base ester (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentyl acrylate (D) CPA), a homopolymer of 1-adamantyl methacrylate (ADMA), 1-adamantyl acrylate (ADA), and the like.
進而,上述(甲基)丙烯酸系聚合物(B)可導入與環氧基或異氰酸基具有反應性之官能基。作為此種官能基之例,可列舉:羥基、羧基、胺基、醯胺基、巰基,於製造(甲基)丙烯酸系聚合物(B)時可使用(共聚)具有此種官能基之單體。 Further, the (meth)acryl-based polymer (B) may be introduced with a functional group reactive with an epoxy group or an isocyanate group. Examples of such a functional group include a hydroxyl group, a carboxyl group, an amine group, a decylamino group, and a fluorenyl group. When the (meth)acrylic polymer (B) is produced, a single copolymer having such a functional group can be used. body.
使上述(甲基)丙烯酸系聚合物(B)為具有脂環式結構之(甲基)丙烯酸系單體與其他(甲基)丙烯酸酯單體或共聚性單體之共聚物之情形時,於構成(甲基)丙烯酸系聚合物(B)之單體成分總量(100質量%)中,具有脂環式結構之(甲基)丙烯酸系單體的含有比例較佳為5質量%以上,更佳為10質量%以上,進而較佳為20質量%以上,特別較佳為30質量%以上(通常未達100質量%,較佳為90質量%以下)。只要含有5質量%以上之具有脂環式結構之(甲基)丙烯酸系單體,則能夠提高接著強度(黏著力)。此外,藉由含有上述具有脂環式結構之(甲基)丙烯酸系單體,上述(甲基)丙烯酸系聚合物(B)與具有聚氧伸烷基鏈之化合物(D)發生適度的相分離,由聚氧伸烷基鏈所搬運之離子性化合物(C)的移動性因上述(甲基)丙烯酸系聚合物(B)而提高,其結果能夠實現抗靜電性能之提高。另一方面,於未達5質量%之情形時,存在接著性較差之情況。 When the (meth)acrylic polymer (B) is a copolymer of a (meth)acrylic monomer having an alicyclic structure and another (meth) acrylate monomer or a copolymerizable monomer, In the total amount of the monomer component (100% by mass) of the (meth)acrylic polymer (B), the content of the (meth)acrylic monomer having an alicyclic structure is preferably 5% by mass or more. More preferably, it is 10 mass% or more, further preferably 20 mass% or more, and particularly preferably 30 mass% or more (usually less than 100 mass%, preferably 90 mass% or less). When the (meth)acrylic monomer having an alicyclic structure is contained in an amount of 5 mass% or more, the bonding strength (adhesion) can be improved. Further, the (meth)acrylic polymer (B) and the compound (D) having a polyoxyalkylene chain have a moderate phase by containing the above (meth)acrylic monomer having an alicyclic structure. In the separation, the mobility of the ionic compound (C) transported by the polyoxyalkylene chain is improved by the (meth)acrylic polymer (B), and as a result, the antistatic property can be improved. On the other hand, when it is less than 5% by mass, there is a case where the adhesion is poor.
上述(甲基)丙烯酸系聚合物(B)之重量平均分子量(Mw)較佳為1000以上且未達30000,更佳為1500以上且未達20000,進而較佳為2000以上且未達10000。若重量平均分子量為30000以上,則接著強度(黏著力)降低。此外,若重量平均分子量未達1000,則由於為低分子量而存在產生被接著體之污染的情況。 The weight average molecular weight (Mw) of the (meth)acrylic polymer (B) is preferably 1,000 or more and less than 30,000, more preferably 1,500 or more and less than 20,000, more preferably 2,000 or more and less than 10,000. When the weight average molecular weight is 30,000 or more, the strength (adhesion) is lowered. Further, when the weight average molecular weight is less than 1,000, it may be contaminated by the adherend due to the low molecular weight.
上述聚合物(A)((甲基)丙烯酸系聚合物(a))、或上述(甲基)丙烯酸系聚合物(B)等之重量平均分子量(Mw)之測定可利用凝膠滲透色譜(GPC)法進行聚苯乙烯換算而求得。具體而言,根據下述之實施例中記載的方法、條件進行測定。 The measurement of the weight average molecular weight (Mw) of the polymer (A) ((meth)acrylic polymer (a)) or the (meth)acrylic polymer (B) or the like can be carried out by gel permeation chromatography ( The GPC method was obtained by converting polystyrene. Specifically, the measurement was carried out according to the methods and conditions described in the following examples.
上述(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度(Tg)較佳為0~300℃,更佳為50℃~280℃,進而較佳為90℃~280℃,特別較佳為110℃~250℃。若上述(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度(Tg)未達0℃,則存在無法獲得充分之接著強度(黏著力)的情況。若為300℃以上,則由於黏著劑層之凝聚力過高而存在對被接著體之潤濕性不足的情況,不佳。於本實施形態中,能作為上述(甲基)丙烯酸系聚合物(B)使用之代表性材料的玻璃轉移溫度(Tg)示於以下之表1。表1所示之玻璃轉移溫度(Tg)為文獻、產品名錄等記載之標稱值,或者基於下述式(3)(Fox式)算出之值。 The glass transition temperature (Tg) of the (meth)acrylic polymer (B) is preferably from 0 to 300 ° C, more preferably from 50 ° C to 280 ° C, still more preferably from 90 ° C to 280 ° C, particularly preferably 110 ° C ~ 250 ° C. When the glass transition temperature (Tg) of the (meth)acryl-based polymer (B) is less than 0 ° C, sufficient adhesion strength (adhesion) may not be obtained. When it is 300 ° C or more, since the cohesive force of the adhesive layer is too high, the wettability to the adherend is insufficient, which is not preferable. In the present embodiment, the glass transition temperature (Tg) of a representative material which can be used as the (meth)acryl-based polymer (B) is shown in Table 1 below. The glass transition temperature (Tg) shown in Table 1 is a nominal value described in the literature, the product list, or the like, or a value calculated based on the following formula (3) (Fox formula).
1/Tg=W1/Tg1+W2/Tg2+‧‧‧+Wn/Tgn (3) 1/Tg=W 1 /Tg 1 +W 2 /Tg 2 +‧‧‧+Wn/Tg n (3)
[式(3)中,Tg表示(甲基)丙烯酸系聚合物(B)之玻璃轉移溫度(單位:K),Tgi(i=1、2、…n)表示單體i形成均聚物時之玻璃轉移溫度(單位:K),Wi(i=1、2、…n)表示單體i於全部單體成分中之質量分率。] [In the formula (3), Tg represents a glass transition temperature (unit: K) of the (meth)acrylic polymer (B), and Tg i (i = 1, 2, ..., n) represents a monomer i to form a homopolymer The glass transition temperature (unit: K), W i (i = 1, 2, ... n) represents the mass fraction of monomer i in all monomer components. ]
上述式(3)為(甲基)丙烯酸系聚合物(B)由單體1、單體2、…、單體n之n種單體成分構成時之計算式。 The above formula (3) is a calculation formula when the (meth)acrylic polymer (B) is composed of n kinds of monomer components of the monomer 1, the monomer 2, ..., and the monomer n.
表1中之縮寫表示以下之化合物。 The abbreviations in Table 1 indicate the following compounds.
DCPMA:甲基丙烯酸二環戊基酯 DCPMA: Dicyclopentyl methacrylate
DCPA:丙烯酸二環戊基酯 DCPA: Dicyclopentyl acrylate
IBXMA:甲基丙烯酸異冰片酯 IBXMA: Isobornyl Methacrylate
IBXA:丙烯酸異冰片酯 IBXA: Isobornyl acrylate
CHMA:甲基丙烯酸環己酯 CHMA: cyclohexyl methacrylate
CHA:丙烯酸環己酯 CHA: cyclohexyl acrylate
IBMA:甲基丙烯酸異丁酯 IBMA: isobutyl methacrylate
MMA:甲基丙烯酸甲酯 MMA: Methyl methacrylate
ADMA:甲基丙烯酸1-金剛烷基酯 ADMA: 1-adamantyl methacrylate
ADA:丙烯酸1-金剛烷基酯 ADA: 1-adamantyl acrylate
對上述(甲基)丙烯酸系聚合物(B)之含量並無特別限制,例如相 對於上述聚合物(A)100質量份,較佳為0.005~2質量份,更佳為0.01~1.5質量份,進而較佳為0.05~0.5質量份。若上述(甲基)丙烯酸系聚合物(B)超過2.0質量份,則存在黏著劑層之抗靜電性降低的情況,於少於0.005質量份之情形,存在無法獲得接著強度(黏著力)之提高效果的情況,不佳。 The content of the above (meth)acrylic polymer (B) is not particularly limited, for example, phase The amount of the polymer (A) is preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, even more preferably 0.05 to 0.5 parts by mass. When the amount of the (meth)acrylic polymer (B) exceeds 2.0 parts by mass, the antistatic property of the adhesive layer may be lowered. When the amount of the (meth)acrylic polymer (B) is less than 0.005 parts by mass, the adhesive strength (adhesive strength) may not be obtained. The situation of improving the effect is not good.
上述(甲基)丙烯酸系聚合物(B)可將具有上述結構之上述(甲基)丙烯酸系單體與上述(甲基)丙烯酸系聚合物(a)同樣,以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合、放射線硬化聚合等作為合成方法,應用通常使用之各種聚合方法。 In the (meth)acrylic polymer (B), the (meth)acrylic monomer having the above-described structure can be solution-polymerized, emulsion-polymerized, and block-formed in the same manner as the above (meth)acryl-based polymer (a). Polymerization, suspension polymerization, radiation hardening polymerization, and the like are used as a synthesis method, and various polymerization methods generally used are applied.
為了調整上述(甲基)丙烯酸系聚合物(B)之重量平均分子量(Mw),可於其聚合中使用鏈轉移劑。作為所使用之鏈轉移劑之例,可列舉:辛基硫醇、月桂基硫醇、第三(十二烷基)硫醇、巰基乙醇、α-硫代甘油等具有巰基之化合物;巰基乙酸、巰基乙酸甲酯、巰基乙酸乙酯、巰基乙酸丙酯、巰基乙酸丁酯、巰基乙酸第三丁酯、巰基乙酸2-乙基己酯、巰基乙酸辛酯、巰基乙酸癸酯、巰基乙酸十二烷基酯、乙二醇之巰基乙酸酯、新戊二醇之巰基乙酸酯、季戊四醇之巰基乙酸酯等巰基乙酸酯類;α-甲基苯乙烯二聚物等。 In order to adjust the weight average molecular weight (Mw) of the above (meth)acryl-based polymer (B), a chain transfer agent may be used in the polymerization. Examples of the chain transfer agent to be used include octyl mercaptan, lauryl mercaptan, third (dodecyl) mercaptan, mercaptoethanol, α-thioglycerol and the like having a mercapto group; mercaptoacetic acid Methyl thioglycolate, ethyl decyl acetate, propyl thioglycolate, butyl thioglycolate, tert-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, thioglycolic acid A mercaptoacetate such as a dialkyl ester, a mercaptoacetate of ethylene glycol, a mercaptoacetate of neopentyl glycol, a mercaptoacetate of pentaerythritol, or the like, an α-methylstyrene dimer or the like.
作為上述鏈轉移劑之含量,並無特別限制,通常,相對於構成上述(甲基)丙烯酸系聚合物(B)之上述(甲基)丙烯酸系單體總量100質量份,較佳為含有鏈轉移劑0.1~20質量份、更佳為0.2~15質量份、進而較佳為0.3~10質量份。藉由如此調整鏈轉移劑之添加量,可獲得較佳分子量之(甲基)丙烯酸系聚合物(B)。另外,鏈轉移劑可單獨使用亦可將2種以上組合使用。 The content of the chain transfer agent is not particularly limited, and it is preferably contained in an amount of 100 parts by mass based on 100 parts by mass of the total of the (meth)acrylic monomers constituting the (meth)acrylic polymer (B). The chain transfer agent is 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass. By adjusting the amount of the chain transfer agent added in this manner, a (meth)acrylic polymer (B) having a preferred molecular weight can be obtained. Further, the chain transfer agents may be used singly or in combination of two or more.
本發明之藥液處理用黏著劑層較佳為上述黏著劑組合物含有離子性化合物(C),更佳為上述離子性化合物(C)為鹼金屬鹽及/或離子液 體。上述離子性化合物為於常溫下顯示離子解離性之化合物,藉由含有上述離子性化合物,能夠賦予優異之抗靜電性。其中,上述鹼金屬鹽即便為微量之含量(調配量),離子解離性亦較高,因此能夠一面抑制對被接著體之污染一面表現優異之抗靜電能,較為有用。此外,上述離子液體自身顯示優異之導電性,因此僅使黏著劑層含有微量離子液體則能夠賦予充分之抗靜電能,較為有用。 In the adhesive layer for treating a chemical solution of the present invention, it is preferred that the adhesive composition contains an ionic compound (C), and more preferably the ionic compound (C) is an alkali metal salt and/or an ionic liquid. body. The ionic compound is a compound which exhibits ionic dissociation at normal temperature, and can provide excellent antistatic properties by containing the ionic compound. In addition, even if the amount of the alkali metal salt is a small amount (adjusted amount), the ionic dissociation property is high, and therefore it is useful to suppress the antistatic property which is excellent in the contamination of the adherend. Further, since the ionic liquid itself exhibits excellent electrical conductivity, it is useful to provide sufficient antistatic energy only by allowing the adhesive layer to contain a trace amount of ionic liquid.
作為上述鹼金屬鹽,例如可較佳地使用由包含Li+、Na+、K+之陽離子與包含Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、C9H19COO-、CF3COO-、C3F7COO-、CH3SO3 -、CF3SO3 -、C4F9SO3 -、C2H5OSO3 -、C6H13OSO3 -、C8H17OSO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、(CF3SO2)(CF3CO)N-、(CH3)2PO4 -、(C2H5)2PO4 -、CH3(OC2H4)2OSO3 -、C6H4(CH3)SO3 -、(C2F5)3PF3 -、CH3CH(OH)COO-及(FSO2)2N-之陰離子構成的金屬鹽。更佳為LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(FSO2)2N、Li(CF3SO2)3C等鋰鹽,進而較佳使用LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C3F7SO2)2N、Li(C4F9SO2)2N、Li(FSO2)2N、Li(CF3SO2)3C。該等鹼金屬鹽可單獨使用,亦可混合2種以上使用。 As the above alkali metal salt, for example, a cation containing Li + , Na + , K + and containing Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF can be preferably used. 6 - , SCN - , ClO 4 - , NO 3 - , CH 3 COO - , C 9 H 19 COO - , CF 3 COO - , C 3 F 7 COO - , CH 3 SO 3 - , CF 3 SO 3 - , C 4 F 9 SO 3 - , C 2 H 5 OSO 3 - , C 6 H 13 OSO 3 - , C 8 H 17 OSO 3 - , (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , (C 3 F 7 SO 2 ) 2 N - , (C 4 F 9 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , F(HF) n - , (CN) 2 N - , (CF 3 SO 2 )(CF 3 CO)N - , (CH 3 ) 2 PO 4 - , (C 2 H 5 ) 2 PO 4 - , CH 3 (OC 2 H 4 ) 2 OSO 3 - , C 6 H 4 (CH 3 )SO 3 - , (C 2 F 5 ) 3 PF 3 - , CH 3 CH(OH)COO - and (FSO 2 a metal salt composed of an anion of 2 N - . More preferably, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(FSO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C and other lithium salts, and further preferably LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 3 F 7 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C. These alkali metal salts may be used singly or in combination of two or more.
上述離子液體係指於0~150℃之範圍內之任一溫度下為液體(液態)且不揮發性之熔融鹽。由於上述離子液體在上述範圍內之任一溫度下為液態,因此與固體之鹽相比更容易進行於黏著劑中之添加及分散或溶解。進而,由於離子液體不具有蒸氣壓(不揮發性),因此亦不 會經時消失,可持續獲得抗靜電特性。 The above ionic liquid system refers to a liquid (liquid) non-volatile molten salt at any temperature in the range of 0 to 150 °C. Since the ionic liquid is liquid at any temperature within the above range, it is easier to add, disperse or dissolve in the adhesive than the solid salt. Furthermore, since the ionic liquid does not have a vapor pressure (non-volatile), it is not It will disappear in time and will continue to obtain antistatic properties.
此外,藉由使用上述離子液體作為抗靜電劑,可獲得抗靜電效果較高之黏著劑層而無損接著(黏著)特性。雖不明確藉由使用離子液體可獲得優異之抗靜電特性之理由的詳細情況,但認為由於離子液體與通常之離子性化合物相比為低熔點(熔點150℃以下),因此分子運動容易,可獲得優異之抗靜電能。並且認為特別是於實現對被接著體之抗靜電時,藉由將極微量之離子液體轉印至被接著體,可實現被接著體之優異之剝離抗靜電性。尤其,由於熔點為室溫(25℃)以下之離子液體可更高效地進行向被接著體之轉印,因此可獲得優異之抗靜電性。 Further, by using the above ionic liquid as an antistatic agent, an adhesive layer having a high antistatic effect can be obtained without impairing the adhesion property. Although the details of the reason why excellent antistatic properties can be obtained by using an ionic liquid are not clear, it is considered that since the ionic liquid has a low melting point (melting point of 150 ° C or less) as compared with a usual ionic compound, molecular motion is easy. Get excellent antistatic energy. Further, it is considered that particularly when the antistatic property to the adherend is achieved, by transferring a very small amount of the ionic liquid to the adherend, excellent peeling antistatic property of the adherend can be achieved. In particular, since the ionic liquid having a melting point of room temperature (25 ° C) or less can be more efficiently transferred to the adherend, excellent antistatic properties can be obtained.
作為上述離子液體,較佳為含氮鎓鹽、含硫鎓鹽或含磷鎓鹽中之任一種,更佳使用包含下述通式(C1)~(C5)表示之有機陽離子成分與陰離子成分者。利用此種具有陽離子之離子液體,可獲得抗靜電能進而優異者。 The ionic liquid is preferably any one of a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt or a phosphorus-containing phosphonium salt, and more preferably an organic cationic component and an anionic component represented by the following general formulae (C1) to (C5). By. By using such a cation-containing ionic liquid, antistatic energy can be obtained and thus excellent.
上述式(C1)中之Ra表示碳數4~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Rb及Rc相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。但,於氮原子含有雙鍵之情形時,Rc不存在。 R a in the above formula (C1) represents a hydrocarbon group having 4 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R b and R c are the same or different and represent hydrogen or a carbon number of 1 to 16. The hydrocarbon group, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom. However, when the nitrogen atom contains a double bond, R c does not exist.
上述式(C2)中之Rd表示碳數2~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Re、Rf及Rg相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。 R d in the above formula (C2) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R e , R f and R g are the same or different and represent hydrogen or carbon number 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.
上述式(C3)中之Rh表示碳數2~20之烴基,上述烴基之一部分可為經雜原子取代之官能基,Ri、Rj及Rk相同或不同,表示氫或碳數1~16之烴基,上述烴基之一部分可為經雜原子取代之官能基。 R h in the above formula (C3) represents a hydrocarbon group having 2 to 20 carbon atoms, and a part of the above hydrocarbon group may be a hetero atom-substituted functional group, and R i , R j and R k are the same or different and represent hydrogen or carbon number 1 The hydrocarbon group of ~16, a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.
上述式(C4)中之Z表示氮、硫或磷原子,Rl、Rm、Rn及Ro相同或不同,表示碳數1~20之烴基,上述烴基之一部分可為經雜原子取代之官能基。但,於Z為硫原子之情形時,Ro不存在。 Z in the above formula (C4) represents a nitrogen, sulfur or phosphorus atom, and R l , R m , R n and R o are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms, and a part of the above hydrocarbon group may be substituted by a hetero atom. Functional group. However, when Z is a sulfur atom, R o does not exist.
上述式(C5)中之RP表示碳數1~18之烴基,上述烴基之一部分可為經雜原子取代之官能基。 R P in the above formula (C5) represents a hydrocarbon group having 1 to 18 carbon atoms, and a part of the above hydrocarbon group may be a functional group substituted with a hetero atom.
作為式(C1)所示之陽離子,例如可列舉:吡啶鎓陽離子、哌啶鎓陽離子、吡咯烷鎓陽離子、具有吡咯啉骨架之陽離子、具有吡咯骨架之陽離子、嗎啉鎓陽離子等。 Examples of the cation represented by the formula (C1) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, a morpholinium cation, and the like.
作為具體例,例如可列舉:1-乙基吡啶鎓陽離子、1-丁基吡啶鎓陽離子、1-己基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-丁基-4-甲基吡啶鎓陽離子、1-己基-3-甲基吡啶鎓陽離子、1-丁基-3,4-二甲基吡啶鎓陽離子、1,1-二甲基吡咯烷鎓陽離子、1-乙基-1-甲基吡咯烷鎓陽離子、1-甲基-1-丙基吡咯烷鎓陽離子、1-甲基-1-丁基吡咯烷鎓陽離子、1-甲基-1-戊基吡咯烷鎓陽離子、1-甲基-1-己基吡咯烷鎓陽離子、1-甲基-1-庚基吡咯烷鎓陽離子、1-乙基-1-丙基吡咯烷鎓陽離子、1-乙基-1-丁基吡咯烷鎓陽離子、1-乙基-1-戊基吡咯烷鎓陽離子、1-乙基-1-己基吡咯烷鎓陽離子、1-乙基-1-庚基吡咯烷鎓陽離子、1,1-二丙基吡咯烷鎓陽離子、1-丙基-1-丁基吡咯烷鎓陽離子、1,1-二丁基吡咯烷鎓陽離子、吡咯烷鎓-2-酮陽離子、1-丙基哌啶鎓陽離子、1-戊基哌啶鎓陽離子、1,1-二甲基哌啶鎓陽離子、1-甲基-1-乙 基哌啶鎓陽離子、1-甲基-1-丙基哌啶鎓陽離子、1-甲基-1-丁基哌啶鎓陽離子、1-甲基-1-戊基哌啶鎓陽離子、1-甲基-1-己基哌啶鎓陽離子、1-甲基-1-庚基哌啶鎓陽離子、1-乙基-1-丙基哌啶鎓陽離子、1-乙基-1-丁基哌啶鎓陽離子、1-乙基-1-戊基哌啶鎓陽離子、1-乙基-1-己基哌啶鎓陽離子、1-乙基-1-庚基哌啶鎓陽離子、1,1-二丙基哌啶鎓陽離子、1-丙基-1-丁基哌啶鎓陽離子、1,1-二丁基哌啶鎓陽離子、2-甲基-1-吡咯啉陽離子、1-乙基-2-苯基吲哚陽離子、1,2-二甲基吲哚陽離子、1-乙基咔唑陽離子、N-乙基-N-甲基嗎啉鎓陽離子等。 Specific examples thereof include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl-4. -methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, 1-B -1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidine Ruthenium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1 - butyl pyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, pyrrolidin-2-one cation, 1-propyl Piperidinium cation, 1-pentylpiperidinium cation, 1,1-dimethylpiperidinium cation 1-methyl-1-acetate Isopiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidine Ruthenium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropyl Isopiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dibutylpiperidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2- Phenylhydrazine cation, 1,2-dimethylhydrazine cation, 1-ethylcarbazole cation, N-ethyl-N-methylmorpholinium cation, and the like.
作為式(C2)所示之陽離子,例如可列舉:咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子等。 Examples of the cation represented by the formula (C2) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
作為具體例,例如可列舉:1,3-二甲基咪唑鎓陽離子、1,3-二乙基咪唑鎓陽離子、1-乙基-3-甲基咪唑鎓陽離子、1-丁基-3-甲基咪唑鎓陽離子、1-己基-3-甲基咪唑鎓陽離子、1-辛基-3-甲基咪唑鎓陽離子、1-癸基-3-甲基咪唑鎓陽離子、1-十二烷基-3-甲基咪唑鎓陽離子、1-十四烷基-3-甲基咪唑鎓陽離子、1,2-二甲基-3-丙基咪唑鎓陽離子、1-乙基-2,3-二甲基咪唑鎓陽離子、1-丁基-2,3-二甲基咪唑鎓陽離子、1-己基-2,3-二甲基咪唑鎓陽離子、1-(2-甲氧基乙基)-3-甲基咪唑鎓陽離子、1,3-二甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3-三甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3,5-四甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,3-二甲基-1,4-二氫嘧啶鎓陽離子、1,3-二甲基-1,6-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,4-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,6-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,6-二氫嘧啶鎓陽離子等。 Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-dodecyl 3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-di Methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-(2-methoxyethyl)-3 -methylimidazolium cation, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidine Ruthenium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetra Hydroquinone cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl -1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3 , 4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like.
作為式(C3)所示之陽離子,例如可列舉:吡唑鎓陽離子、吡唑啉鎓陽離子等。 Examples of the cation represented by the formula (C3) include a pyrazolium cation, a pyrazolinium cation, and the like.
作為具體例,例如可列舉:1-甲基吡唑鎓陽離子、3-甲基吡唑鎓陽離子、1-乙基-2-甲基吡唑啉鎓陽離子、1-乙基-2,3,5-三甲基吡唑鎓陽離子、1-丙基-2,3,5-三甲基吡唑鎓陽離子、1-丁基-2,3,5-三甲基吡唑鎓陽離子、1-乙基-2,3,5-三甲基吡唑啉鎓陽離子、1-丙基-2,3,5-三甲基吡唑啉鎓陽離子、1-丁基-2,3,5-三甲基吡唑啉鎓陽離子等。 Specific examples include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, and 1-ethyl-2,3. 5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1- Ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-three Methylpyrazolium cations and the like.
作為式(C4)所示之陽離子,例如可列舉:四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子、或上述烷基之一部分經烯基、或烷氧基、進而環氧基取代之陽離子等。 The cation represented by the formula (C4) may, for example, be a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the above alkyl group via an alkenyl group, an alkoxy group, or an epoxy group. a cation or the like substituted by a base.
作為具體例,例如可列舉:四甲基銨陽離子、四乙基銨陽離子、四丁基銨陽離子、四戊基銨陽離子、四己基銨陽離子、四庚基銨陽離子、三乙基甲基銨陽離子、三丁基乙基銨陽離子、三甲基癸基銨陽離子、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、縮水甘油基三甲基銨陽離子、三甲基鋶陽離子、三乙基鋶陽離子、三丁基鋶陽離子、三己基鋶陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子、四甲基鏻陽離子、四乙基鏻陽離子、四丁基鏻陽離子、四己基鏻陽離子、四辛基鏻陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻陽離子、二烯丙基二甲基銨陽離子、三丁基-(2-甲氧基乙基)鏻陽離子等。其中,較佳使用三乙基甲基銨陽離子、三丁基乙基銨陽離子、三甲基癸基銨陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻陽離子等非對稱之四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子、或N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、縮水甘油基三甲基銨陽離子、二烯丙基二甲基銨陽離子、N,N-二甲基-N-乙基-N-丙基銨陽離子、N,N-二甲基-N-乙基-N-丁基銨陽離子、N,N-二甲基-N-乙基-N-戊基銨陽離子、N,N-二甲基-N-乙基-N-己基銨陽離子、N,N-二甲基-N- 乙基-N-庚基銨陽離子、N,N-二甲基-N-乙基-N-壬基銨陽離子、N,N-二甲基-N,N-二丙基銨陽離子、N,N-二乙基-N-丙基-N-丁基銨陽離子、N,N-二甲基-N-丙基-N-戊基銨陽離子、N,N-二甲基-N-丙基-N-己基銨陽離子、N,N-二甲基-N-丙基-N-庚基銨陽離子、N,N-二甲基-N-丁基-N-己基銨陽離子、N,N-二乙基-N-丁基-N-庚基銨陽離子、N,N-二甲基-N-戊基-N-己基銨陽離子、N,N-二甲基-N,N-二己基銨陽離子、三甲基庚基銨陽離子、N,N-二乙基-N-甲基-N-丙基銨陽離子、N,N-二乙基-N-甲基-N-戊基銨陽離子、N,N-二乙基-N-甲基-N-庚基銨陽離子、N,N-二乙基-N-丙基-N-戊基銨陽離子、三乙基丙基銨陽離子、三乙基戊基銨陽離子、三乙基庚基銨陽離子、N,N-二丙基-N-甲基-N-乙基銨陽離子、N,N-二丙基-N-甲基-N-戊基銨陽離子、N,N-二丙基-N-丁基-N-己基銨陽離子、N,N-二丙基-N,N-二己基銨陽離子、N,N-二丁基-N-甲基-N-戊基銨陽離子、N,N-二丁基-N-甲基-N-己基銨陽離子、三辛基甲基銨陽離子、N-甲基-N-乙基-N-丙基-N-戊基銨陽離子。 Specific examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, tetraheptyl ammonium cation, and triethylmethylammonium cation. , tributylethylammonium cation, trimethylsulfonium ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethyl Ammonium cation, trimethyl phosphonium cation, triethyl phosphonium cation, tributyl phosphonium cation, trihexyl phosphonium cation, diethyl methyl phosphonium cation, dibutyl ethyl phosphonium cation, dimethyl fluorenyl cation, Tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethylmethyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl fluorenyl a phosphonium cation, a diallyldimethylammonium cation, a tributyl-(2-methoxyethyl)phosphonium cation, and the like. Among them, triethylmethylammonium cation, tributylethylammonium cation, trimethylsulfonium ammonium cation, diethylmethyl phosphonium cation, dibutylethyl phosphonium cation, dimethyl fluorenyl group are preferably used. An asymmetric tetraalkylammonium cation such as a phosphonium cation, a triethylmethyl phosphonium cation, a tributylethyl phosphonium cation, a trimethylsulfonium cation, a trialkyl phosphonium cation, a tetraalkyl phosphonium cation, or N , N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, diallyldimethylammonium cation, N,N-di Methyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N- Amyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexyl ammonium cation, N,N-dimethyl-N- Ethyl-N-heptyl ammonium cation, N,N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl -N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N- Diethyl-N-butyl-N-heptyl ammonium cation, N,N-dimethyl-N-pentyl-N-hexyl ammonium cation, N,N-dimethyl-N,N-dihexylammonium a cation, a trimethylheptyl ammonium cation, a N,N-diethyl-N-methyl-N-propylammonium cation, an N,N-diethyl-N-methyl-N-amyl ammonium cation, N,N-Diethyl-N-methyl-N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-amyl ammonium cation, triethyl propyl ammonium cation, triethyl Yl amyl ammonium cation, triethylheptyl ammonium cation, N,N-dipropyl-N-methyl-N-ethyl ammonium cation, N,N-dipropyl-N-methyl-N-pentyl Alkyl ammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N- Methyl-N-amyl ammonium Cationic, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-amylammonium cation .
作為式(C5)所示之陽離子,例如可列舉鋶陽離子等。此外,作為上述式(E)中之RP之具體例,可列舉:甲基、乙基、丙基、丁基、己基、辛基、壬基、癸基、十二烷基、十三烷基、十四烷基、十八烷基等。 Examples of the cation represented by the formula (C5) include a phosphonium cation. Further, specific examples of R P in the above formula (E) include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, decyl group, dodecyl group, and tridecane. Base, tetradecyl, octadecyl and the like.
另一方面,作為陰離子成分,只要能形成離子液體則無特別限定,例如可使用:Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、C4F9SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N-、C9H19COO-、(CH3)2PO4 -、(C2H5)2PO4 -、CH3OSO3 -、C2H5OSO3 -、 C4H9OSO3 -、C6H13OSO3 -、C8H17OSO3 -、CH3(OC2H4)2OSO3 -、C6H4(CH3)SO3 -、(C2F5)3PF3 -、CH3CH(OH)COO-、(FSO2)2N-、B(CN)4 -、C(CN)3 -、N(CN)2 -、對甲苯磺酸酯陰離子、2-(2-甲氧基乙基)乙基硫酸酯陰離子等。其中,特別是含有氟原子之陰離子成分由於可獲得低熔點之離子液體、或可獲得與(甲基)丙烯酸系聚合物(a)、或(甲基)丙烯酸系聚合物(B)等之相容性優異的離子液體,故而較佳使用。 On the other hand, the anion component is not particularly limited as long as it can form an ionic liquid, and for example, Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , SCN can be used. - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , C 4 F 9 SO 3 - , (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , (C 3 F 7 SO 2 ) 2 N - , (C 4 F 9 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , F(HF) n - , (CN) 2 N - , C 4 F 9 SO 3 - , (C 2 F 5 SO 2 ) 2 N - , C 3 F 7 COO - , (CF 3 SO 2 )(CF 3 CO)N - , C 9 H 19 COO - , (CH 3 ) 2 PO 4 - , (C 2 H 5 ) 2 PO 4 - , CH 3 OSO 3 - , C 2 H 5 OSO 3 - , C 4 H 9 OSO 3 - , C 6 H 13 OSO 3 - , C 8 H 17 OSO 3 - , CH 3 (OC 2 H 4 ) 2 OSO 3 - , C 6 H 4 ( CH 3 )SO 3 - , (C 2 F 5 ) 3 PF 3 - , CH 3 CH(OH)COO - , (FSO 2 ) 2 N - , B(CN) 4 - , C(CN) 3 - , N (CN) 2 - , p-toluenesulfonate anion, 2-(2-methoxyethyl) ethyl sulfate anion, and the like. Among them, in particular, an anionic component containing a fluorine atom can obtain an ionic liquid having a low melting point, or can be obtained by phase with a (meth)acrylic polymer (a) or a (meth)acrylic polymer (B). It is preferably used because it has an excellent ionic liquid.
此外,作為陰離子成分,亦可進而使用下述式(C6)所示之陰離子等。 Further, as the anion component, an anion or the like represented by the following formula (C6) can be further used.
[式(C6)中之R1~R4分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烯基、可具有取代基之炔基、可具有取代基之芳基及可具有取代基之雜環基。上述取代基之氫原子可進而經其他取代基(吸電子性基之取代基等)取代。] In the [formula (C6) R 1 ~ R 4 each independently represent a hydrogen atom, an optionally substituted alkyl group, the alkenyl group may have a substituent group, the alkynyl group may have a substituent group, the group may have a substituent group of the aryl And a heterocyclic group which may have a substituent. The hydrogen atom of the above substituent may be further substituted with another substituent (substituent such as an electron withdrawing group). ]
此外,作為陰離子成分,亦可使用下述式(C7)所示之陰離子等。 Further, as the anion component, an anion or the like represented by the following formula (C7) can also be used.
作為上述陰離子成分,其中特別是含有氟原子之陰離子成分由於可獲得低熔點之離子液體、或可獲得與(甲基)丙烯酸系聚合物(a)、或(甲基)丙烯酸系聚合物(B)等之相容性優異的離子液體,故而較佳使用。 As the above anionic component, among them, an anion component containing a fluorine atom in particular, a ionic liquid having a low melting point or a (meth)acrylic polymer (a) or a (meth)acrylic polymer (B) can be obtained. It is preferably used because it is an ionic liquid excellent in compatibility.
作為本發明中使用之離子液體之具體例,可自上述陽離子成分與陰離子成分之組合中適當選擇使用,例如可列舉:1-丁基吡啶鎓四氟硼酸鹽、1-丁基吡啶鎓六氟磷酸鹽、1-丁基-3-甲基吡啶鎓四氟硼酸鹽、1-丁基-3-甲基吡啶鎓三氟甲磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓雙(五氟乙磺醯基)醯亞胺、1-己基吡啶鎓四氟硼酸鹽、1,1-二甲基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基哌 啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基- 1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、2-甲基-1-吡咯啉四氟硼酸鹽、1-乙基-2-苯基吲哚四氟硼酸鹽、1,2-二甲基吲哚四氟硼酸鹽、1-乙基咔唑四氟硼酸鹽、1-乙基-3-甲基咪唑鎓四氟硼酸鹽、1-乙基-3-甲基咪唑鎓乙酸鹽、1-乙基-3-甲基咪唑鎓三氟乙酸鹽、1-乙基-3-甲基咪唑鎓七氟丁酸鹽、1-乙基-3-甲基咪唑鎓三氟甲磺酸鹽、1-乙基-3-甲基咪唑鎓全氟丁磺酸鹽、1-乙基-3-甲基咪唑鎓二氰胺、1-乙基-3-甲基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三(三氟甲磺醯基)甲基化物、1-丁基-3-甲基咪唑鎓四氟硼酸鹽、1-丁基-3-甲基咪唑鎓六氟磷酸鹽、1-丁基-3-甲基咪唑鎓三氟乙酸鹽、1-丁基-3-甲基咪唑鎓七氟丁酸鹽、1-丁基-3-甲基咪唑鎓三氟甲磺酸鹽、1-丁基-3-甲基咪唑鎓全氟丁磺酸鹽、1-丁基-3-甲基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓溴化物、1-己基-3-甲基咪唑鎓氯化物、1-己基-3-甲基咪唑鎓四氟硼酸鹽、1-己基-3-甲基咪唑鎓六氟磷酸鹽、1-己基-3-甲基咪唑鎓三氟甲磺酸鹽、1-辛基-3-甲基咪唑鎓四氟硼酸鹽、1-辛基-3-甲基咪唑鎓六氟磷酸鹽、1-己基-2,3-二甲基咪唑鎓四氟硼酸鹽、1,2-二甲基-3-丙基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-甲基吡唑鎓四氟硼酸鹽、2-甲基吡唑鎓四氟硼酸鹽、1-乙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)三氟乙醯胺、1-丙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)三氟乙醯胺、 1-丁基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)三氟乙醯胺、1-乙基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑啉鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑啉鎓雙(五氟乙磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑啉鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)三氟乙醯胺、1-丙基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)三氟乙醯胺、1-丁基-2,3,5-三甲基吡唑啉鎓雙(三氟甲磺醯基)三氟乙醯胺、四戊基銨三氟甲磺酸鹽、四戊基銨雙(三氟甲磺醯基)醯亞胺、四己基銨三氟甲磺酸鹽、四己基銨雙(三氟甲磺醯基)醯亞胺、四庚基銨三氟甲磺酸鹽、四庚基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨四氟硼酸鹽、二烯丙基二甲基銨三氟甲磺酸鹽、二烯丙基二甲基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨雙(五氟乙磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨四氟硼酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨三氟甲磺酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(五氟乙磺醯基)醯亞胺、縮水甘油基三甲基銨三氟甲磺酸鹽、縮水甘油基三甲基銨雙(三氟甲磺醯基)醯亞胺、縮水甘油基三甲基銨雙(五氟乙磺醯基)醯亞胺、四辛基鏻三氟甲磺酸鹽、四辛基鏻雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丁基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-壬基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-丁基 銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-戊基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、三甲基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基丙基銨雙(三氟甲磺醯基)醯亞胺、三乙基戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-乙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-己基銨雙(三氟甲磺醯基)醯亞胺、三辛基甲基銨雙(三氟甲磺醯基)醯亞胺、N-甲基-N-乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、1-丁基吡啶鎓(三氟甲磺醯基)三氟乙醯胺、1-丁基-3-甲基吡啶鎓(三氟甲磺醯基)三氟乙醯胺、1-乙基-3-甲基咪唑鎓(三氟甲磺醯基)三氟乙醯胺、N-乙基-N-甲基嗎啉鎓硫氰酸鹽、4-乙基-4-甲基嗎啉鎓甲基碳酸鹽等。 Specific examples of the ionic liquid used in the present invention can be appropriately selected from the combination of the above cationic component and anionic component, and examples thereof include 1-butylpyridinium tetrafluoroborate and 1-butylpyridinium hexafluorophosphate. Phosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis ( Trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 1,1-di Methylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1- Propyl pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1- Amylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-glycol Pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butene Kipyrrole Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis ( Trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(trifluoro Methanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 ,1-Dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1,1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl 1-heptylpiper Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylperidine Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidine Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidine bismuth (Trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis (three Fluoromethanesulfonyl) quinone imine, 1,1-dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonate Indenylamine, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis ( Fluoroethinyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis (five Fluoroethinyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoro Ethylsulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonate Indole, quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Ethyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Butyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1- Hexyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1- 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-B -1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl - 1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1- Butyl piperidine bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 2-methyl-1-pyrroline Tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl 3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methyl Imidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl- 3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1- Butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl 3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl 3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2 - dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-methylpyrazolium tetrafluoroborate, 2-methylpyrazolium tetrafluoroborate, 1- Ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethyl) Sulfhydryl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-three Methylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonate Iridium imine, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethyl Pyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-2,3,5-trimethylpyrazoline Bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-2 ,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazoline bis(pentafluoroethanesulfonate) Iridium imine, 1-propyl-2,3,5-trimethylpyrazolinium bis(pentafluoroethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethyl Pyrithione bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)trifluoroacetamide , 1-propyl-2,3,5-trimethylpyrazolinium bis(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazole Ruthenium bis(trifluoromethanesulfonyl)trifluoroacetamide, tetraamyl ammonium triflate, tetraamylammonium bis(trifluoromethanesulfonyl) ruthenium, tetrahexylammonium trifluoride Methanesulfonate, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, tetraheptyl ammonium trifluoromethanesulfonate, tetraheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, two Allyldimethylammonium IV Borate, diallyldimethylammonium triflate, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium double (five Fluoroethinyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N- Methyl-N-(2-methoxyethyl)ammonium triflate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium double (three Fluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, glycidol Trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl)pyrene Amine, tetraoctylfluorene triflate, tetraoctylphosphonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-propyl ammonium bis ( Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl- N-ethyl-N-amyl ammonium bis(trifluoromethanesulfonyl) fluorene imine, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl) fluorene Imine N,N-Dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium (Trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N -propyl-N-butyl Ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-di Methyl-N-propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonate Iridium imine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N -heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N - dimethyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl --N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonate Iridium imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl- N-amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl amyl ammonium bis(trifluoromethanesulfonate) Iridium imine, triethylheptyl ammonium bis(trifluoromethanesulfonyl)pyrene , N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-amyl ammonium Bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl -N,N-dihexylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonyl) fluorene Amine, N,N-dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine , N-methyl-N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoro Acetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl)trifluoro Ethylamine, N-ethyl-N-methylmorpholinium thiocyanate, 4-ethyl-4-methylmorpholinium methyl carbonate, and the like.
如上述之離子液體可使用市售之產品,亦可以如下方式來合成。作為離子液體之合成方法,只要可獲得目標離子液體則無特別限定,通常使用如文獻《離子液體-開發之最前線及未來-》[CMC出版發行]中記載之鹵化物法、氫氧化物法、酸酯法、錯合形成法以及中 和法等。 As the ionic liquid described above, a commercially available product can be used, and it can also be synthesized in the following manner. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and a halide method or a hydroxide method as described in the literature "Iron Liquid - The Forefront and Future of Development -" [CMC Publishing] is generally used. , acid ester method, mismatch formation method and medium And law.
以下對於鹵化物法、氫氧化物法、酸酯法、錯合形成法以及中和法,以含氮鎓鹽為例表示其合成方法,而對於其他之含硫鎓鹽、含磷鎓鹽等其他離子液體,亦可藉由同樣之方法獲得。 Hereinafter, for the halide method, the hydroxide method, the acid ester method, the mismatch formation method, and the neutralization method, the synthesis method of the nitrogen-containing phosphonium salt is exemplified, and other sulfur-containing phosphonium salts, phosphorus-containing phosphonium salts, etc. Other ionic liquids can also be obtained by the same method.
鹵化物法係藉由如下述式(1)~(3)所示之反應來進行的方法。首先使三級胺與鹵化烷基反應獲得鹵化物(反應式(1),使用氯、溴、碘作為鹵素)。使所得之鹵化物與具有目標離子液體之陰離子結構(A-)之酸(HA)或鹽(MA、M為銨、鋰、鈉、鉀等與目標陰離子形成鹽之陽離子)反應而獲得目標離子液體(R4NA)。 The halide method is a method which is carried out by a reaction represented by the following formulas (1) to (3). First, a tertiary amine is reacted with a halogenated alkyl group to obtain a halide (reaction formula (1), using chlorine, bromine, or iodine as a halogen). The obtained halide is reacted with an acid (HA) or a salt (MA, M is a cation which forms a salt with a target anion such as ammonium, lithium, sodium or potassium) having an anionic structure (A - ) of a target ionic liquid to obtain a target ion. Liquid (R 4 NA).
[化25](1)R3N+RX→R4NX(X:Cl,Br,I) (2)R4NX+HA→R4NA+HX (3)R4NX+MA→R4NA+MX(M:NH4,Li,Na,K,Ag等) (1) R 3 N+RX→R 4 NX(X:Cl, Br, I) (2) R 4 NX+HA→R 4 NA+HX (3)R 4 NX+MA→R 4 NA+MX (M: NH 4 , Li, Na, K, Ag, etc.)
氫氧化物法係藉由如(4)~(8)所示之反應來進行的方法。首先對於鹵化物(R4NX),藉由離子交換膜法電解(反應式(4))、OH型離子交換樹脂法(反應式(5))或與氧化銀(Ag2O)之反應(反應式(6))獲得氫氧化物(R4NOH)(使用氯、溴、碘,作為鹵素)。與上述鹵化法同樣,對所得之氫氧化物使用反應式(7)~(8)之反應獲得目標離子液體(R4NA)。 The hydroxide method is a method carried out by a reaction as shown in (4) to (8). First, for halide (R 4 NX), electrolysis by ion exchange membrane method (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag 2 O) The reaction formula (6)) obtains hydroxide (R 4 NOH) (using chlorine, bromine, iodine as a halogen). The target ionic liquid (R 4 NA) is obtained by reacting the obtained hydroxides with the reaction formulas (7) to (8) in the same manner as the above halogenation method.
[化26](4)R4NX+H2O→R4NOH+1/2H2+1/2X2(X:Gl,Br,l) (5)R4NX+P-OH→R4NOH+P-X(P-OH:OH型離子交換樹脂) (6)R4NX+1/2Ag2O+1/2H2O→R4NOH+AgX (7)R4NOH+HA→R4NA+H2O (8)R4NOH+MA→R4NA+MOH(M:NH4,Li,Na,K,Ag等) (4) R 4 NX+H 2 O→R 4 NOH+1/2H 2 +1/2X 2 (X:Gl,Br,l) (5)R 4 NX+P-OH→R 4 NOH+PX (P-OH: OH type ion exchange resin) (6) R 4 NX+1/2Ag 2 O+1/2H 2 O→R 4 NOH+AgX (7)R 4 NOH+HA→R 4 NA +H 2 O (8)R 4 NOH+MA→R 4 NA+MOH(M:NH 4 ,Li,Na,K,Ag, etc.)
酸酯法係藉由如(9)~(11)所示之反應來進行的方法。首先使三級胺(R3N)與酸酯反應而獲得酸酯物(反應式(9),使用硫酸、亞硫酸、磷酸、亞磷酸、碳酸等無機酸之酯、或甲磺酸、甲基膦酸、甲酸等有機酸之酯等,作為酸酯)。與上述鹵化法同樣,對所得之酸酯物使用反應式(10)~(11)之反應獲得目標離子液體(R4NA)。此外,亦可藉由使用甲基三氟甲磺酸鹽、甲基三氟乙酸鹽等作為酸酯而直接獲得離子液體。 The acid ester method is a method carried out by a reaction as shown in (9) to (11). First, a tertiary amine (R 3 N) is reacted with an acid ester to obtain an acid ester (reaction formula (9), using an ester of a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid, or methanesulfonic acid, A An ester of an organic acid such as phosphinic acid or formic acid as an acid ester). The target ionic liquid (R 4 NA) is obtained by reacting the obtained acid ester with the reaction formulas (10) to (11) in the same manner as the above halogenation method. Further, an ionic liquid can be directly obtained by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester.
錯合形成法係藉由如(12)~(15)所示之反應來進行的方法。首先使四級銨之鹵化物(R4NX)、四級銨之氫氧化物(R4NOH)、四級銨之碳酸酯化物(R4NOCO2CH3)等與氟化氫(HF)、或氟化銨(NH4F)反應獲得氟化四級銨鹽(反應式(12)~(14))。藉由所得之氟化四級銨鹽與BF3、AlF3、PF5、AsF5、SbF5、NbF5、TaF5等氟化物之錯合形成反應,可獲得離子液體(反應式(15))。 The mismatch formation method is a method carried out by a reaction as shown in (12) to (15). First, a quaternary ammonium halide (R 4 NX), a quaternary ammonium hydroxide (R 4 NOH), a quaternary ammonium carbonate (R 4 NOCO 2 CH 3 ), etc., and hydrogen fluoride (HF), or Ammonium fluoride (NH 4 F) is reacted to obtain a fluorinated quaternary ammonium salt (reaction formula (12) to (14)). An ionic liquid can be obtained by forming a reaction between the obtained fluorinated quaternary ammonium salt and a fluoride such as BF 3 , AlF 3 , PF 5 , AsF 5 , SbF 5 , NbF 5 or TaF 5 (reaction formula (15) ).
[化28] (12)R4NX+HF→R4NF+HX(X:Cl,Br,I) (13)R4NY+HF→R4NF+HY(Y:OH,OCO2CH3) (14)R4NY+NH4F→R4NF+NH3+HY(Y:OH,OCO2CH3) (15)R4NF+MFn-1→R4NMFn(MFn-1:BF3,AlF3,PF5,AsF6,SbF5,NbF5,TaF5等) (12) R 4 NX+HF→R 4 NF+HX(X:Cl,Br,I) (13)R 4 NY+HF→R 4 NF+HY(Y:OH, OCO 2 CH 3 (14) R 4 NY+NH 4 F→R 4 NF+NH 3 +HY(Y:OH, OCO 2 CH 3 ) (15)R 4 NF+MF n-1 →R 4 NMF n (MF n- 1 : BF 3 , AlF 3 , PF 5 , AsF 6 , SbF 5 , NbF 5 , TaF 5 , etc.)
中和法係藉由如(16)所示之反應來進行之方法。可藉由使三級胺與HBF4、HPF6、CH3COOH、CF3COOH、CF3SO3H、(CF3SO2)2NH、(CF3SO2)3CH、(C2F5SO2)2NH等有機酸反應而獲得。 The neutralization method is carried out by a reaction as shown in (16). By subjecting the tertiary amine to HBF 4 , HPF 6 , CH 3 COOH, CF 3 COOH, CF 3 SO 3 H, (CF 3 SO 2 ) 2 NH, (CF 3 SO 2 ) 3 CH, (C 2 F 5 SO 2 ) 2 NH and other organic acids are obtained by reaction.
[化29](16)R3N+HZ→R3HN+Z-[HZ:HBF4,HPF6,CH3COOH,CF3COOH,GF3SO3H,(CF3SO2)2NH,(CF3SO2)3CH,(C2F6SO2)2NH等有機酸] (16) R 3 N+HZ→R 3 HN + Z - [HZ:HBF 4 ,HPF 6 ,CH 3 COOH,CF 3 COOH,GF 3 SO 3 H,(CF 3 SO 2 ) 2 NH , (CF 3 SO 2 ) 3 CH, (C 2 F 6 SO 2 ) 2 NH and other organic acids]
上述式(1)~(16)中記載之R表示氫或碳原子數1~20之烴基,上述烴基之一部分亦可為經雜原子取代之官能基。 R in the above formulas (1) to (16) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
另外,上述離子液體可單獨使用,亦可混合2種以上使用。 Further, the ionic liquid may be used singly or in combination of two or more.
此外,對上述離子性化合物(C)之含量並無特別限制,例如相對於上述聚合物(A)100質量份,較佳為0.005~2質量份,更佳為0.01~1.5質量份,進而較佳為0.05~1質量份,最佳為0.07~0.8質量份。若在上述範圍內,則所得之黏著劑層(黏著片)能夠發揮優異之接著強度(黏著力)及抗靜電性,較為有用。 Further, the content of the ionic compound (C) is not particularly limited, and is, for example, preferably 0.005 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, based on 100 parts by mass of the polymer (A). Preferably, it is 0.05 to 1 part by mass, and most preferably 0.07 to 0.8 parts by mass. When it is in the above range, the obtained adhesive layer (adhesive sheet) can exhibit excellent adhesive strength (adhesion) and antistatic property, and is useful.
本發明之藥液處理用黏著劑層較佳為上述黏著劑組合物含有上述具有聚氧伸烷基鏈之化合物(D),只要為具有聚氧伸烷基鏈之化合物則並無特別限定,例如,作為氧伸烷基單元,可列舉具有碳數1~6 之伸烷基之單元,可列舉氧亞甲基、氧伸乙基、氧伸丙基、氧伸丁基等。構成上述氧伸烷基鏈之烴基可為直鏈,亦可為支鏈。例如可列舉:聚乙二醇、聚丙二醇(二元醇型)、聚丙二醇(三元醇型)、聚四亞甲基醚二醇、甲氧基聚乙二醇、乙氧基聚乙二醇以及上述聚合物之衍生物、或共聚物。該等可單獨使用,亦可混合2種以上使用。上述聚氧伸烷基鏈藉由與離子性化合物相互作用,可於促進離子解離同時利用鏈之分子運動搬運離子,因此可獲得提高離子傳導性之效果。 In the adhesive composition for treating a chemical solution of the present invention, the above-mentioned adhesive composition preferably contains the compound (D) having a polyoxyalkylene chain, and is not particularly limited as long as it is a compound having a polyoxyalkylene chain. For example, as the oxygen-extended alkyl unit, a carbon number of 1 to 6 can be cited. Examples of the unit of the alkyl group include an oxymethylene group, an oxygen-extended ethyl group, an oxygen-extended propyl group, and an oxygen-extended butyl group. The hydrocarbon group constituting the above oxygen alkyl chain may be a straight chain or a branched chain. For example, polyethylene glycol, polypropylene glycol (glycol type), polypropylene glycol (triol type), polytetramethylene ether glycol, methoxy polyethylene glycol, ethoxy polyethylene polyethylene An alcohol and a derivative or copolymer of the above polymer. These may be used singly or in combination of two or more. The polyoxyalkylene chain interacts with the ionic compound to promote ion detachment while transporting ions by molecular motion of the chain, thereby obtaining an effect of improving ion conductivity.
作為上述具有聚氧伸烷基鏈之化合物之分子量,較佳為數量平均分子量為100000以下,更佳為200~50000。若分子量超過100000,則對被接著體之污染增加,故而不佳。 The molecular weight of the compound having a polyoxyalkylene chain is preferably a number average molecular weight of 100,000 or less, more preferably 200 to 50,000. If the molecular weight exceeds 100,000, the contamination of the adherend is increased, which is not preferable.
此外,對於上述具有聚氧伸烷基鏈之化合物(D),較佳為上述具有聚氧伸烷基鏈之化合物(D)為具有聚氧伸烷基鏈之有機聚矽氧烷,更佳為上述具有聚氧伸烷基鏈之有機聚矽氧烷為下述通式(D1)~(D3)所示之具有聚氧伸烷基鏈的有機聚矽氧烷。 Further, in the above compound (D) having a polyoxyalkylene chain, it is preferred that the compound (D) having a polyoxyalkylene chain is an organopolyoxane having a polyoxyalkylene chain, more preferably The organopolyoxane having the polyoxyalkylene chain is an organopolyoxane having a polyoxyalkylene chain represented by the following formulas (D1) to (D3).
上述式(D1)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m及n為0~1000之整數。但,m、n不同時為0。a及b為0~1000之整數。但,a、b不同時為0。 R 1 in the above formula (D1) is a monovalent organic group, R 2 , R 3 and R 4 are an alkylene group, R 5 is a hydrogen or an organic group, and m and n are integers of 0 to 1000. However, m and n are not 0 at the same time. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.
上述式(D2)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m為1~2000之整數。a及b為0~1000之整數。但,a、b不同時為0。 In the above formula (D2), R 1 is a monovalent organic group, R 2 , R 3 and R 4 are an alkylene group, R 5 is a hydrogen or an organic group, and m is an integer of from 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.
上述式(D3)中之R1為1價有機基,R2、R3及R4為伸烷基,R5為氫或有機基,m為1~2000之整數。a及b為0~1000之整數。但,a、b不同時為0。 In the above formula (D3), R 1 is a monovalent organic group, R 2 , R 3 and R 4 are an alkylene group, R 5 is a hydrogen or an organic group, and m is an integer of from 1 to 2,000. a and b are integers from 0 to 1000. However, a and b are not 0 at the same time.
作為上述具有聚氧伸烷基鏈之有機聚矽氧烷,例如可使用如以下之構成。具體而言,式中之R1為以甲基、乙基、丙基等烷基、苯基、甲苯基等芳基、或苄基、苯乙基等芳烷基例示之1價有機基,可各自具有羥基等取代基。R2、R3及R4可使用亞甲基、伸乙基、伸丙基等碳數1~8之伸烷基。此處,R3及R4為不同之伸烷基,R2可與R3或R4相同亦可不同。為了提高能溶解於其聚氧伸烷基側鏈中之離子性化合物之濃度,R3及R4較佳為其中任一者為伸乙基或伸丙基。R5可為以甲基、乙基、丙基等烷基、或乙醯基、丙醯基等醯基例示之1價有機基,亦可各自具有羥基等取代基。該等化合物可單獨使用,亦可混合2種以上使用。另外,分子中亦可具有(甲基)丙烯醯基、烯丙基、羥基等反應性取代基。 As the above organopolyoxyalkylene having a polyoxyalkylene chain, for example, the following constitution can be used. Specifically, R 1 in the formula is an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a tolyl group, or a monovalent organic group exemplified by an aralkyl group such as a benzyl group or a phenethyl group. Each may have a substituent such as a hydroxyl group. As R 2 , R 3 and R 4 , a methylene group having a carbon number of 1 to 8 such as a methylene group, an exoethyl group or a propyl group can be used. Here, R 3 and R 4 are different alkylene groups, and R 2 may be the same as or different from R 3 or R 4 . In order to increase the concentration of the ionic compound which can be dissolved in the polyoxyalkylene side chain, R 3 and R 4 are preferably either an exoethyl or a propyl group. R 5 may be a monovalent organic group exemplified by an alkyl group such as a methyl group, an ethyl group or a propyl group, or a fluorenyl group such as an ethyl group or a propyl group, and each may have a substituent such as a hydroxyl group. These compounds may be used singly or in combination of two or more. Further, the molecule may have a reactive substituent such as a (meth)acrylinyl group, an allyl group or a hydroxyl group.
作為上述具有聚氧伸烷基鏈之有機聚矽氧烷之市售品,例如可列舉:商品名KF-351A、KF-353、KF-945、KF-6011、KF-889、KF-6004(以上為信越化學工業公司製造),FZ-2122、FZ-2164、FZ-7001、SH8400、SH8700、SF8410、SF8422(以上為東麗道康寧公司製造),TSF-4440、TSF-4445、TSF-4452、TSF-4460(Momentive Performance Materials公司製造),BYK-333、BYK-377、BYK- UV3500、BYK-UV3570(BYK-Chemie Japan公司製造)等。該等可單獨使用,亦可混合2種以上使用。 As a commercial item of the above-mentioned organopolyoxane having a polyoxyalkylene chain, for example, trade names KF-351A, KF-353, KF-945, KF-6011, KF-889, KF-6004 (for example) The above are manufactured by Shin-Etsu Chemical Co., Ltd., FZ-2122, FZ-2164, FZ-7001, SH8400, SH8700, SF8410, SF8422 (above is manufactured by Toray Dow Corning), TSF-4440, TSF-4445, TSF-4452, TSF-4460 (manufactured by Momentive Performance Materials), BYK-333, BYK-377, BYK- UV3500, BYK-UV3570 (manufactured by BYK-Chemie Japan Co., Ltd.), and the like. These may be used singly or in combination of two or more.
對上述具有聚氧伸烷基鏈之化合物(D)之含量並無特別限制,就黏著劑層之接著強度(黏著力)及抗靜電性之觀點而言,相對於上述聚合物(A)100質量份,較佳為0.005~1質量份,更佳為0.01~0.8質量份,進而較佳為0.03~0.5質量份。 The content of the above compound (D) having a polyoxyalkylene chain is not particularly limited, and is relative to the above polymer (A) 100 from the viewpoint of the adhesive strength (adhesion) and antistatic property of the adhesive layer. The mass part is preferably 0.005 to 1 part by mass, more preferably 0.01 to 0.8 part by mass, still more preferably 0.03 to 0.5 part by mass.
本發明中使用之黏著劑組合物除了上述聚合物(A)、(甲基)丙烯酸系聚合物(B)、離子性化合物(C)及具有聚氧伸烷基鏈之化合物(D)以外,亦可含有於黏著劑領域中通常之各種添加劑作為任意成分。作為該任意成分,除上述添加劑,亦可例示其他增黏樹脂、交聯劑、觸媒、塑化劑、軟化劑、填充劑、著色劑(顏料、染料等)、抗氧化劑、流平劑、穩定劑、防腐劑、抗靜電劑等。此種添加劑可根據常規方法使用先前公知者。 The adhesive composition used in the present invention is in addition to the above polymer (A), (meth)acrylic polymer (B), ionic compound (C), and compound (D) having a polyoxyalkylene chain. It is also possible to contain various additives which are usually used in the field of adhesives as optional components. As the optional component, in addition to the above additives, other tackifying resins, crosslinking agents, catalysts, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, and the like may be exemplified. Stabilizers, preservatives, antistatic agents, etc. Such an additive can be used in a conventional manner according to a conventional method.
為了調整本發明之黏著劑層之凝聚力,上述黏著劑組合物亦可含有交聯劑。交聯劑可使用通常於黏著劑領域中使用之交聯劑,例如可列舉:異氰酸酯系交聯劑、環氧系交聯劑、矽酮系交聯劑、噁唑啉系交聯劑、氮丙啶系交聯劑、矽烷系交聯劑、三聚氰胺系交聯劑(烷基醚化三聚氰胺系交聯劑等)、金屬螯合物系交聯劑等。此外,亦可將上述之可作為上述(甲基)丙烯酸系聚合物(a)之單體成分使用的上述多官能性單體用作交聯劑。尤其,可較佳地使用異氰酸酯系交聯劑、環氧系交聯劑、金屬螯合物系交聯劑。該等化合物可單獨使用,亦可將2種以上組合使用。 In order to adjust the cohesive force of the adhesive layer of the present invention, the above adhesive composition may also contain a crosslinking agent. As the crosslinking agent, a crosslinking agent which is usually used in the field of adhesives can be used, and examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an anthrone crosslinking agent, an oxazoline crosslinking agent, and nitrogen. A propidium crosslinking agent, a decane crosslinking agent, a melamine crosslinking agent (such as an alkyl etherified melamine crosslinking agent), a metal chelate crosslinking agent, and the like. Further, the above-mentioned polyfunctional monomer which can be used as a monomer component of the above (meth)acrylic polymer (a) can also be used as a crosslinking agent. In particular, an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent can be preferably used. These compounds may be used singly or in combination of two or more.
作為上述異氰酸酯系交聯劑(異氰酸酯化合物),例如可列舉:亞丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類,伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等 脂環族異氰酸酯類,2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類,三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(商品名CORONATE L,日本聚胺酯工業公司製造)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(商品名CORONATE HL,日本聚酯工業公司製造)、六亞甲基二異氰酸酯之異氰脲酸酯體(商品名CORONATE HX,日本聚胺酯工業公司製造)等異氰酸酯加成物等。或者,1分子中具有至少1個以上異氰酸基及1個以上之不飽和鍵之化合物,具體而言(甲基)丙烯酸2-異氰酸基乙酯等亦可作為異氰酸酯系交聯劑使用。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the isocyanate-based crosslinking agent (isocyanate compound) include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophora. Ketone diisocyanate, etc. Alicyclic isocyanates, aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzenedimethyl diisocyanate, trimethylolpropane/toluene diisocyanate terpolymer Adduct (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: CORONATE HL, manufactured by Japan Polyester Industries Co., Ltd.), Liuya An isocyanate adduct such as an isocyanurate body (trade name: CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) of methyl diisocyanate. Or a compound having at least one or more isocyanato groups and one or more unsaturated bonds in one molecule, and specifically, 2-isocyanatoethyl (meth)acrylate may be used as an isocyanate crosslinking agent. use. These compounds may be used singly or in combination of two or more.
作為上述環氧系交聯劑(環氧化合物),例如可列舉:雙酚A、環氧氯丙烷型之環氧系樹脂、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二胺縮水甘油基胺、N,N,N',N'-四縮水甘油基間苯二甲胺(商品名TETRAD-X,三菱瓦斯化學公司製造)或1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷(商品名TETRAD-C,三菱瓦斯化學公司製造)等。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the epoxy-based crosslinking agent (epoxy compound) include bisphenol A, an epichlorohydrin-based epoxy resin, ethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. Glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidylamine, N, N, N', N'-tetraglycidyl meta-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like. These compounds may be used singly or in combination of two or more.
作為上述三聚氰胺系交聯劑,可列舉六羥甲基三聚氰胺等。此外,作為上述氮丙啶系交聯劑(氮丙啶衍生物),例如可列舉作為市售品之商品名HDU(相互藥工公司製造)、商品名TAZM(相互藥工公司製造)、商品名TAZO(相互藥工公司製造)等。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the melamine-based crosslinking agent include hexamethylol melamine and the like. In addition, as the above-mentioned aziridine-based crosslinking agent (aziridine derivative), for example, the product name of the commercial product is HDU (manufactured by Mutual Pharmaceutical Co., Ltd.), the product name is TAZM (manufactured by Mutual Pharmaceutical Co., Ltd.), and the product is used. Named TAZO (manufactured by Mutual Pharmaceutical Co., Ltd.). These compounds may be used singly or in combination of two or more.
作為上述金屬螯合物系交聯劑(金屬螯合物化合物),作為金屬成分,可列舉鋁、鐵、錫、鈦、鎳等,作為螯合物成分,可列舉乙炔、乙醯乙酸甲酯、乳酸乙酯等。該等化合物可單獨使用,亦可將2種以 上組合使用。 Examples of the metal chelate-based crosslinking agent (metal chelate compound) include aluminum, iron, tin, titanium, and nickel. Examples of the chelate component include acetylene and ethyl acetacetate. , ethyl lactate, and the like. These compounds may be used alone or in combination of two Used in combination.
對本發明中使用之交聯劑之含量並無特別限制,例如相對於上述聚合物(A)100質量份,較佳含有0.001~0.8質量份,更佳含有0.01~0.7質量份。於上述交聯劑之含量未達0.001質量份之情形時,存在黏著劑(層)之凝聚力減小、發生藥液浸入的情況。另一方面,於上述交聯劑之含量超過0.8質量份之情形時,存在黏著劑(層)之凝聚力增大、流動性降低、對被接著體之潤濕不充分、接著強度(黏著力)降低之虞。 The content of the crosslinking agent to be used in the present invention is not particularly limited. For example, it is preferably 0.001 to 0.8 parts by mass, more preferably 0.01 to 0.7 parts by mass, per 100 parts by mass of the polymer (A). When the content of the above-mentioned crosslinking agent is less than 0.001 part by mass, the cohesive force of the adhesive (layer) may be reduced, and the infiltration of the chemical solution may occur. On the other hand, when the content of the above-mentioned crosslinking agent exceeds 0.8 parts by mass, the cohesive force of the adhesive (layer) increases, the fluidity decreases, the wetting of the adherend is insufficient, and the strength (adhesion) Reduce the embarrassment.
此外,上述多官能性單體之含量根據與欲交聯之聚合物之平衡,進而根據黏著劑層(黏著片、表面保護片)之使用用途而適當選擇。另外,為藉由黏著劑(層)之凝聚力獲得充分之耐熱性,於使用上述聚合物(A)(例如上述(甲基)丙烯酸系聚合物(a))之情形時,相對於上述聚合物(A)100質量份,較佳為以0.001~1.0質量份進行調配。此外,就柔軟性、接著性方面而言,相對於上述聚合物(A)100質量份,更佳為以0.5質量份以下進行調配。 Further, the content of the above polyfunctional monomer is appropriately selected depending on the balance with the polymer to be crosslinked, and further depending on the use of the adhesive layer (adhesive sheet, surface protective sheet). Further, in order to obtain sufficient heat resistance by the cohesive force of the adhesive (layer), in the case of using the above polymer (A) (for example, the above (meth)acrylic polymer (a)), the above polymer is used. (A) 100 parts by mass, preferably 0.001 to 1.0 part by mass. In addition, in terms of flexibility and adhesion, it is more preferably 0.5 parts by mass or less based on 100 parts by mass of the above polymer (A).
另外,於使用上述多官能性單體作為交聯劑之情形時,為了進行交聯反應,可照射放射線。作為上述放射線,例如可列舉:紫外線、雷射線、α射線、β射線、γ射線、X射線、電子束等,就控制性及操作性之良好程度、成本之方面而言,較佳使用紫外線。更佳使用波長200~400nm之紫外線。紫外線可使用高壓水銀燈、微波激發型燈、化學燈等適當光源進行照射。此外,於使用紫外線作為放射線之情形時,於黏著劑組合物中可同樣調配、添加上述可於調製(聚合)上述(甲基)丙烯酸系聚合物(a)時使用之光聚合起始劑(光起始劑)以及光聚合起始助劑。另外,於使用上述多官能性單體作為交聯劑之情形時,可進行放射線照射,作為該情形時使用之上述光聚合起始劑,為對應於放射線反應性成分之種類、藉由照射能夠引起其聚合反應之合 適波長之紫外線而生成自由基或陽離子之物質即可。 Further, when the above polyfunctional monomer is used as the crosslinking agent, radiation can be irradiated in order to carry out the crosslinking reaction. Examples of the radiation include ultraviolet rays, thunder rays, α rays, β rays, γ rays, X rays, and electron beams, and ultraviolet rays are preferably used in terms of controllability and workability, and cost. It is better to use ultraviolet rays having a wavelength of 200 to 400 nm. The ultraviolet light can be irradiated with a suitable light source such as a high pressure mercury lamp, a microwave excitation lamp, or a chemical lamp. Further, when ultraviolet rays are used as the radiation, the photopolymerization initiator which can be used for preparing (polymerizing) the (meth)acryl-based polymer (a) can be similarly added and added to the adhesive composition ( Photoinitiator) and photopolymerization initiation aid. In the case where the above-mentioned polyfunctional monomer is used as the crosslinking agent, radiation irradiation can be performed, and the photopolymerization initiator used in this case can be used in accordance with the type of the radiation-reactive component and by irradiation. Causing the polymerization It is sufficient to generate a radical or a cation by ultraviolet rays of a suitable wavelength.
相對於上述聚合物(A)100質量份,上述光聚合起始劑通常調配0.1~10質量份,較佳為以0.2~7質量份之範圍調配。若在上述範圍內,則就容易控制聚合反應、獲得適度之分子量之觀點而言較佳。 The photopolymerization initiator is usually formulated in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 7 parts by mass, based on 100 parts by mass of the polymer (A). When it is in the above range, it is preferable from the viewpoint of easily controlling the polymerization reaction and obtaining an appropriate molecular weight.
於添加有上述光聚合起始劑之情形時,藉由將上述黏著劑組合物直接塗覆於被接著體(被保護體)上,或者塗覆於隔離體等特定之被塗佈體上之後,或者塗覆於支持體(基材)上的單面之後,進行光照射,使交聯反應進行,可獲得黏著劑層。通常,藉由以光量200~4000mJ/cm2左右照射波長300~400nm下之照度為1~200mW/cm2的紫外線進行光聚合,可獲得黏著劑層。 In the case where the above photopolymerization initiator is added, by applying the above-mentioned adhesive composition directly to the adherend (protected body) or after coating it on a specific coated body such as a separator After coating on one side of the support (substrate), light irradiation is performed to carry out a crosslinking reaction, and an adhesive layer can be obtained. In general, an adhesive layer can be obtained by photopolymerizing ultraviolet rays having an illuminance of from 1 to 200 mW/cm 2 at a wavelength of from 300 to 400 nm at a light amount of about 200 to 4000 mJ/cm 2 .
此外,本發明中使用之上述黏著劑組合物可進而含有交聯促進劑。交聯促進劑之種類可根據所使用之交聯劑之種類而適當選擇。另外,於本說明書中交聯促進劑係指用以提高利用交聯劑之交聯反應之速度的觸媒。作為該交聯促進劑,例如可例示:二月桂酸二辛基錫、二月桂酸二丁基錫、二乙酸二丁基錫、二乙醯丙酮二丁基錫、四正丁基錫、三甲基氫氧化錫等含錫(Sn)化合物;N,N,N',N'-四甲基己二胺、或三乙基胺等胺類、咪唑類等含氮(N)化合物。其中,較佳為含Sn化合物。上述黏著劑組合物中含有之交聯促進劑之量相對於上述聚合物(A)100質量份,例如可為0.0001~1.0質量份左右(較佳為0.001~0.5質量份左右)。 Further, the above-mentioned adhesive composition used in the present invention may further contain a crosslinking accelerator. The kind of the crosslinking accelerator can be appropriately selected depending on the kind of the crosslinking agent to be used. Further, in the present specification, the crosslinking accelerator means a catalyst for increasing the rate of crosslinking reaction by a crosslinking agent. Examples of the crosslinking accelerator include tin-containing dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetate, tetra-n-butyltin, trimethyltin hydroxide, and the like. (Sn) compound; N, N, N', N'-tetramethylhexanediamine, or an amine such as triethylamine, or a nitrogen-containing (N) compound such as an imidazole. Among them, a Sn-containing compound is preferred. The amount of the crosslinking accelerator to be contained in the above-mentioned adhesive composition is, for example, about 0.0001 to 1.0 part by mass (preferably about 0.001 to 0.5 part by mass) based on 100 parts by mass of the polymer (A).
本發明中使用之上述黏著劑組合物可進而含有產生酮-烯醇互變異構之化合物。例如,於含有交聯劑之黏著劑組合物或可調配交聯劑使用之黏著劑組合物中,可較佳採用含有上述產生酮-烯醇互變異構之化合物之態樣。藉此,能夠實現抑制交聯劑調配後之黏著劑組合物之過度黏度上升、或凝膠化,延長黏著劑組合物之使用壽命的效果。於至少使用異氰酸酯化合物作為上述交聯劑之情形時,含有產生酮- 烯醇互變異構之化合物特別有意義。該技術可較佳應用於例如上述黏著劑組合物為有機溶劑溶液或無溶劑形態之情況。 The above adhesive composition used in the present invention may further contain a compound which produces keto-enol tautomerism. For example, in the adhesive composition used for the adhesive composition containing a crosslinking agent or the adjustable crosslinking agent, the aspect containing the above-described compound which produces the keto-enol tautomerization can be preferably used. Thereby, it is possible to achieve an effect of suppressing an excessive increase in viscosity or gelation of the adhesive composition after the crosslinking agent is blended, and prolonging the service life of the adhesive composition. In the case where at least an isocyanate compound is used as the above crosslinking agent, it contains a ketone- Enol tautomeric compounds are of particular interest. This technique can be preferably applied, for example, to the case where the above-mentioned adhesive composition is in an organic solvent solution or a solventless form.
作為上述產生酮-烯醇互變異構之化合物,可使用各種β-二羰基化合物。作為具體例,可列舉:乙醯丙酮、2,4-己二酮、3,5-庚二酮、2-甲基己烷-3,5-二酮、6-甲基庚烷-2,4-二酮、2,6-二甲基庚烷-3,5-二酮等β-二酮類;乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸異丙酯、乙醯乙酸第三丁酯等乙醯乙酸酯類;丙醯乙酸乙酯、丙醯乙酸異丙酯、丙醯乙酸第三丁酯等丙醯乙酸酯類;異丁醯乙酸乙酯、異丁醯乙酸乙酯、異丁醯乙酸異丙酯、異丁醯乙酸第三丁酯等異丁醯乙酸酯類;丙二酸甲酯、丙二酸乙酯等丙二酸酯類等。其中,作為較佳之化合物,可列舉乙醯丙酮及乙醯乙酸酯類。該產生酮-烯醇互變異構之化合物可單獨使用,亦可將2種以上組合使用。 As the above compound which produces keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetamidine acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane-2. Β-diketones such as 4-dione and 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl acetate, isopropyl acetate, acetonitrile Acetyl acetate such as tert-butyl ester; acetonitrile acetate such as ethyl acetate, isopropyl acetate, and butyl phthalate; ethyl acetate and isobutyl phthalate Examples include isobutyl phthalate esters such as ester, isopropyl isobutyl phthalate acetate and tributyl butyl acetoacetate; malonic esters such as methyl malonate and ethyl malonate. Among them, preferred examples of the compound include acetamidineacetone and acetamidine acetate. The keto-enol tautomerization compound may be used singly or in combination of two or more.
相對於上述聚合物(A)100質量份,上述產生酮-烯醇互變異構之化合物之含量例如可為0.1~20質量份,通常為0.5~15質量份(例如1~10質量份)較為適當。若上述化合物之量過少,則存在難以發揮充分之使用效果的情況。另一方面,若超過必需使用上述化合物,則存在殘留於黏著劑層、降低凝聚力之情況。 The content of the keto-enol tautomerizing compound may be, for example, 0.1 to 20 parts by mass, and usually 0.5 to 15 parts by mass (for example, 1 to 10 parts by mass) per 100 parts by mass of the polymer (A). appropriate. When the amount of the above compound is too small, it may be difficult to exhibit a sufficient use effect. On the other hand, if it is necessary to use the above compound, it may remain in the adhesive layer and the cohesive force may be lowered.
上述黏著劑組合物可根據需要而含有增黏樹脂。上述(甲基)丙烯酸系共聚物(B)於本發明之黏著劑層中具有作為增黏樹脂的功能,進而,作為其他增黏樹脂,可無特別限定地使用先前公知之樹脂。例如可列舉:萜烯系增黏樹脂、酚系增黏樹脂、松香系增黏樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、共聚系石油樹脂、脂環族系石油樹脂、二甲苯樹脂、環氧系增黏樹脂、聚醯胺系增黏樹脂、酮系增黏樹脂、彈性體系增黏樹脂。該等可單獨使用1種或將2種以上組合使用。於使用增黏樹脂之情形時,就不降低上述聚合物(A)、或(甲基)丙烯酸系聚合物(B)等之性質、充分獲得增黏樹脂之效果之觀點而言,其含 量較佳為相對於聚合物(A)100質量份為20質量份以下(典型為0.01~10質量份)。 The above adhesive composition may contain a tackifying resin as needed. The (meth)acrylic copolymer (B) has a function as a tackifying resin in the adhesive layer of the present invention, and as the other tackifying resin, a conventionally known resin can be used without particular limitation. For example, a terpene type tackifying resin, a phenol type tackifying resin, a rosin type tackifying resin, an aliphatic petroleum resin, an aromatic petroleum resin, a copolymerization petroleum resin, an alicyclic petroleum resin, and a xylene resin are mentioned. , epoxy-based tackifying resin, polyamine-based tackifying resin, ketone-based tackifying resin, elastic system tackifying resin. These may be used alone or in combination of two or more. In the case of using a tackifying resin, it does not lower the properties of the above polymer (A), or (meth)acrylic polymer (B), and the effect of sufficiently obtaining a tackifying resin. The amount is preferably 20 parts by mass or less (typically 0.01 to 10 parts by mass) based on 100 parts by mass of the polymer (A).
上述黏著劑組合物可為於上述聚合物(A)中根據需要而調配其他聚合物(任意聚合物)所調製者。此種任意聚合物例如可為了提高黏著劑之凝聚力而調配。黏著劑之凝聚力提高有助於防止藥液自黏著片(表面保護片)之外緣浸入的防藥液浸入性(典型而言防止主要起因於黏著劑因藥液而膨潤之藥液浸入的性能)之提高。 The above adhesive composition may be prepared by blending other polymers (any polymer) as needed in the above polymer (A). Such an arbitrary polymer can be formulated, for example, in order to increase the cohesive force of the adhesive. The cohesive force of the adhesive helps to prevent the immersion of the chemical solution from the outer edge of the adhesive sheet (surface protection sheet) (typically preventing the infiltration of the liquid mainly due to the swelling of the adhesive due to the liquid medicine) ) improvement.
本發明之黏著劑層可為黏著劑組合物之硬化層。例如,上述黏著劑層可藉由於將黏著劑組合物賦予(例如塗佈、塗覆)至合適之支持體之後適當實施硬化處理而形成。於支持體為經抗靜電處理之塑膠基材之情形時,亦可於抗靜電層上形成黏著劑層,亦可於未經抗靜電處理之面形成黏著劑層。於進行2種以上之硬化處理(乾燥、交聯、聚合等)之情形時,該等可同時或分多階段進行。對於使用部分聚合物(丙烯酸系聚合物漿液)之黏著劑組合物,典型而言進行最終之共聚反應(使部分聚合物進行進一步之共聚反應而形成完全聚合物)作為上述硬化處理。例如,若為光硬化性之黏著劑組合物,則實施光照射。可根據需要而實施交聯、乾燥等硬化處理。例如,為光硬化性黏著劑組合物且需要乾燥之情形時,於乾燥後進行光硬化即可。對於使用完全聚合物之黏著劑組合物,典型而言,根據需要實施乾燥(加熱乾燥)、交聯等處理作為上述硬化處理。 The adhesive layer of the present invention may be a hardened layer of the adhesive composition. For example, the above adhesive layer can be formed by appropriately applying a hardening treatment after imparting (for example, coating, coating) an adhesive composition to a suitable support. When the support is an antistatically treated plastic substrate, an adhesive layer may be formed on the antistatic layer, or an adhesive layer may be formed on the surface not subjected to the antistatic treatment. In the case where two or more kinds of hardening treatments (drying, crosslinking, polymerization, etc.) are carried out, these may be carried out simultaneously or in multiple stages. For the adhesive composition using a partial polymer (acrylic polymer slurry), the final copolymerization reaction (to further copolymerize a part of the polymer to form a complete polymer) is typically carried out as the above hardening treatment. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Hardening treatment such as crosslinking or drying can be carried out as needed. For example, when it is a photocurable adhesive composition and it needs to dry, it can be hard-hardened after drying. For the adhesive composition using a complete polymer, a treatment such as drying (heat drying), crosslinking, or the like is typically performed as the above-described hardening treatment as needed.
上述黏著劑組合物(黏著劑組合物溶液)之塗佈、塗覆可使用例如凹版輥式塗佈機、逆轉輥式塗佈機、接觸輥式塗佈機、浸漬輥式塗佈機、棒塗佈機、刮刀塗佈機、噴霧塗佈機等常用之塗佈機來實施。另外,可直接將黏著劑組合物賦予至支持體(基材)來形成黏著劑層,亦可將形成於剝離襯墊上之黏著劑層轉印至支持體。 The coating and coating of the above adhesive composition (adhesive composition solution) may be, for example, a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, or a rod. It is implemented by a usual coater such as a coater, a knife coater, or a spray coater. Further, the adhesive composition may be directly applied to the support (substrate) to form an adhesive layer, and the adhesive layer formed on the release liner may be transferred to the support.
對上述黏著劑層之厚度並無特別限定,可根據目的而適當調整。黏著劑層之厚度例如可為1~100μm左右。另外,就與被接著體表面之密著性之觀點而言,較佳之厚度為2μm以上,更佳為3μm以上(例如為5μm以上,典型而言為7μm以上)。此外,就剝離作業性之觀點而言,黏著劑層之厚度較佳為90μm以下,更佳為70μm以下,典型而言為50μm以下。就抑制黏著劑之膨潤引起之藥液浸入之觀點而言,亦較佳為黏著劑層之厚度不過大。 The thickness of the above-mentioned pressure-sensitive adhesive layer is not particularly limited and may be appropriately adjusted depending on the purpose. The thickness of the adhesive layer can be, for example, about 1 to 100 μm. Further, from the viewpoint of adhesion to the surface of the adherend, the thickness is preferably 2 μm or more, more preferably 3 μm or more (for example, 5 μm or more, and typically 7 μm or more). Further, from the viewpoint of peeling workability, the thickness of the adhesive layer is preferably 90 μm or less, more preferably 70 μm or less, and typically 50 μm or less. It is also preferable that the thickness of the adhesive layer is not too large from the viewpoint of suppressing the infiltration of the chemical solution caused by the swelling of the adhesive.
上述黏著劑層之表面(黏著面即與被接著體之貼附面)之算術平均表面粗糙度較佳為1μm以下,更佳為在約0.05~0.75μm(例如約0.05~0.5μm,典型而言為約0.1~0.3μm)之範圍。若黏著面之平滑性提高,則黏著面與被接著體界面之密著性提高。由此,能夠更好地防止藥液自黏著劑與被接著體之界面浸入。此外,平滑性較高之黏著劑層由於自被接著體表面剝離時應力之分佈不均較小,因此能夠更好地避免產生因局部應力導致一部分黏著劑破裂而殘留於被接著體側等之現象。因此,於支持體(基材)上具有該黏著劑層之黏著片(表面保護片)能夠順利地自被接著體剝離而不於被接著體表面產生糊劑殘留等污染。 The arithmetic mean surface roughness of the surface of the adhesive layer (adhesive surface, that is, the attachment surface to the adherend) is preferably 1 μm or less, more preferably about 0.05 to 0.75 μm (for example, about 0.05 to 0.5 μm, typically It is a range of about 0.1 to 0.3 μm). When the smoothness of the adhesive surface is improved, the adhesion between the adhesive surface and the interface of the adherend is improved. Thereby, it is possible to better prevent the chemical solution from entering from the interface between the adhesive and the adherend. Further, since the unevenness of the stress distribution due to the peeling of the adhesive layer having a high smoothness from the surface of the adherend is small, it is possible to better prevent the partial adhesive from being broken and remaining on the side of the adherend due to local stress. phenomenon. Therefore, the adhesive sheet (surface protective sheet) having the adhesive layer on the support (substrate) can be smoothly peeled off from the adherend without causing contamination such as paste residue on the surface of the adherend.
另外,黏著面之算術平均表面粗糙度可使用通常之表面粗糙度測定裝置(例如Veeco公司製造之非接觸三維表面形狀測定裝置,型號「Wyko NT-3300」)進行測定。 Further, the arithmetic mean surface roughness of the adhesive surface can be measured using a usual surface roughness measuring device (for example, a non-contact three-dimensional surface shape measuring device manufactured by Veeco Co., Ltd., model "Wyko NT-3300").
此外,本發明之黏著劑層之溶劑不溶成分率(凝膠率)為50~90質量%,較佳為55~87質量%,更佳為60~85質量%。若溶劑不溶成分率超過90質量%,則接著強度(黏著力)降低,於低於50質量%之情形時,黏著劑(層)之凝聚力降低,有可能產生糊劑殘留。另外,關於溶劑不溶成分率之評價方法,根據下述之實施例中記載之方法、條件進行測定。 Further, the solvent-insoluble component ratio (gel fraction) of the adhesive layer of the present invention is 50 to 90% by mass, preferably 55 to 87% by mass, more preferably 60 to 85% by mass. When the solvent-insoluble component ratio exceeds 90% by mass, the strength (adhesion) decreases, and when it is less than 50% by mass, the cohesive force of the adhesive (layer) is lowered, and the paste may remain. Further, the method for evaluating the solvent insoluble component ratio was measured according to the methods and conditions described in the following examples.
此外,上述黏著劑層之表面電阻率為103~1013Ω/□,較佳為104~1013Ω/□,更佳為106~1013Ω/□。若在上述範圍內,則可抑制剝離靜電壓,即可賦予抗靜電性,較為有用。另外,關於上述表面電阻率之評價方法,根據下述之實施例中記載之方法、條件進行測定。 Further, the surface resistivity of the above adhesive layer is 10 3 to 10 13 Ω/□, preferably 10 4 to 10 13 Ω/□, more preferably 10 6 to 10 13 Ω/□. When it is in the above range, it is useful to suppress the peeling static voltage and to impart antistatic properties. Further, the method for evaluating the surface resistivity was measured according to the methods and conditions described in the following examples.
本發明之藥液處理用黏著片較佳為於支持體之至少單面形成上述黏著劑層。具有上述黏著劑層之黏著片由於防藥液浸入性及抗靜電性優異故而較為有用。另外,作為上述黏著片(表面保護片)中使用之支持體(基材),可適當選擇使用公知之薄膜狀、或片狀等支持體。對支持體之材質並無特別限定。例如可使用由金屬材料(鋁等)形成之支持體、由樹脂材料形成之支持體、由該等之複合材料形成之支持體(例如於單面蒸鍍有金屬之塑膠薄膜)等。 The adhesive sheet for chemical treatment of the present invention preferably forms the above-mentioned adhesive layer on at least one side of the support. The adhesive sheet having the above adhesive layer is useful because it is excellent in chemical solution immersion property and antistatic property. In addition, as a support (base material) used for the above-mentioned adhesive sheet (surface protection sheet), a support such as a known film shape or a sheet shape can be appropriately selected and used. The material of the support is not particularly limited. For example, a support formed of a metal material (aluminum or the like), a support formed of a resin material, a support formed of the composite material (for example, a plastic film on which a metal is vapor-deposited on one side), or the like can be used.
作為此處所揭示之技術中之支持體(基材)的較佳例,可列舉包含下述樹脂材料之支持體(塑膠薄膜):聚乙烯(PE)、聚丙烯(PP)、乙丙橡膠(EPR)、乙烯-丙烯-丁烯共聚物、乙烯-丙烯酸乙酯共聚物等聚烯烴樹脂;聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯等聚酯樹脂;聚醯胺樹脂(PA);聚醯亞胺樹脂(PI);聚苯硫醚樹脂(PPS);聚碳酸酯樹脂(PC);聚胺基甲酸酯樹脂(PU);乙烯-乙酸乙烯酯樹脂(EVA);聚四氟乙烯(PTFE)等氟樹脂;丙烯酸系樹脂等。可為包含單獨含有此種樹脂之1種的樹脂材料之支持體,亦可為包含摻合有2種以上之此種之樹脂之樹脂材料的支持體(塑膠薄膜)。 Preferred examples of the support (substrate) in the technology disclosed herein include a support (plastic film) comprising the following resin materials: polyethylene (PE), polypropylene (PP), and ethylene propylene rubber ( Polyolefin resin such as EPR), ethylene-propylene-butene copolymer, ethylene-ethyl acrylate copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene Polyester resin such as ethylene dicarboxylate; polyamine resin (PA); polyimine resin (PI); polyphenylene sulfide resin (PPS); polycarbonate resin (PC); polyurethane Resin (PU); ethylene-vinyl acetate resin (EVA); fluororesin such as polytetrafluoroethylene (PTFE); acrylic resin. The support may be a support containing a resin material containing one type of the resin alone, or a support (plastic film) containing a resin material containing two or more of such resins.
此處,塑膠薄膜典型而言係指非多孔之塑膠膜,係區別於織布、或不織布之概念。作為此處所揭示之黏著片(表面保護片)之支持體,無延伸塑膠薄膜及延伸(單軸延伸或雙軸延伸)塑膠薄膜中之任一種均可使用。 Here, the plastic film generally refers to a non-porous plastic film, which is distinguished from the concept of a woven fabric or a non-woven fabric. As the support of the adhesive sheet (surface protective sheet) disclosed herein, any of the non-stretched plastic film and the stretch (uniaxially stretched or biaxially stretched) plastic film can be used.
該等之中,作為自具有適度之可撓性之觀點而言較佳之樹脂材料,可列舉聚烯烴樹脂(例如將PP、PE、EPR等聚烯烴樹脂中之1種單獨含有,或者為摻合有2種以上之聚烯烴樹脂)及聚酯樹脂(例如PET)。由於聚烯烴樹脂、或聚酯樹脂具有適度之可撓性,因此具備此種樹脂材料製之支持體之黏著片(表面保護片)即便於例如被接著體之表面存在階差之情形時亦容易追隨上述階差(即表面形狀追隨性較高)。因此,不容易於構成黏著片之黏著劑(層)與被接著體之間形成藥液之浸入路徑(空隙)。因此,較佳作為藥液處理用之黏著片(表面保護片)之支持體。 Among these, a resin material which is preferable from the viewpoint of having moderate flexibility is a polyolefin resin (for example, one of polyolefin resins such as PP, PE, and EPR is contained alone or blended. There are two or more kinds of polyolefin resins) and polyester resins (for example, PET). Since the polyolefin resin or the polyester resin has moderate flexibility, the adhesive sheet (surface protective sheet) having the support made of such a resin material is easy even when there is a step difference on the surface of the adherend, for example. Follow the above steps (ie, surface shape followability is higher). Therefore, it is not easy to form a immersion path (void) of the chemical solution between the adhesive (layer) constituting the adhesive sheet and the adherend. Therefore, it is preferable as a support for an adhesive sheet (surface protective sheet) for chemical liquid treatment.
另外,上述階差可來源於在被接著體之表面形成之結構物。作為具有此種結構物之被接著體,例如可列舉如平板型個人電腦、或手機、有機LED(發光二極體)等中使用之於表面部分性設置有透明導電膜(例如ITO(氧化銦錫)膜)、或柔性印刷基板(FPC)之玻璃基材。 Further, the above-described step difference may be derived from a structure formed on the surface of the adherend. Examples of the adherend having such a structure include a flat type personal computer, a mobile phone, an organic LED (light emitting diode), and the like, and a surface is partially provided with a transparent conductive film (for example, ITO (indium oxide). Tin) film, or a glass substrate of a flexible printed substrate (FPC).
作為此處所揭示之黏著片(表面保護片)之支持體(基材),可較佳採用包含耐酸性較高之樹脂材料之支持體。該支持體即便暴露於酸性之藥液(例如玻璃之蝕刻中使用之氫氟酸溶液、或鉻電鍍液、硫酸銅電鍍液、鎳電鍍液、酸性無電解鎳電鍍液、酸性錫電鍍液等酸性之電鍍液)亦不容易發生膨潤。因此,於阻止酸性之藥液使支持體膨潤而浸入至黏著片(表面保護片)並到達至被接著體(非處理對象部分)方面較為有利。就耐酸性及可撓性平衡優異之觀點而言,作為較佳之支持體,可例示包含聚烯烴樹脂之支持體。 As a support (substrate) of the adhesive sheet (surface protective sheet) disclosed herein, a support comprising a resin material having a high acid resistance can be preferably used. The support is exposed to acidic acid liquid (for example, hydrofluoric acid solution used in etching of glass, or chromium plating solution, copper sulfate plating solution, nickel plating solution, acid electroless nickel plating solution, acid tin plating solution, etc.) The plating solution is also not prone to swelling. Therefore, it is advantageous to prevent the acidic chemical solution from swelling the support and immersing it in the adhesive sheet (surface protective sheet) and reaching the adherend (non-treated portion). From the viewpoint of excellent acid resistance and flexibility balance, a support comprising a polyolefin resin can be exemplified as a preferred support.
上述支持體(基材)可為單層,亦可為二層以上之多層結構(例如三層結構)。例如,可使用包括上述薄膜之多層結構之樹脂薄膜(多層薄膜)作為支持體。於多層薄膜中,構成各層之樹脂材料可為單獨含有上述樹脂中之1種的樹脂材料,亦可為摻合有2種以上之樹脂之樹脂材料。 The support (substrate) may be a single layer or a multilayer structure of two or more layers (for example, a three-layer structure). For example, a resin film (multilayer film) including a multilayer structure of the above film can be used as a support. In the multilayer film, the resin material constituting each layer may be a resin material containing one of the above resins alone, or a resin material containing two or more kinds of resins.
於較佳之一態樣中,上述支持體(基材)為單層或多層之聚烯烴樹脂薄膜。此處,聚烯烴樹脂薄膜係指由含有聚烯烴樹脂(即以聚烯烴為主要成分之樹脂)之樹脂材料所形成的塑膠薄膜。聚烯烴樹脂於上述聚烯烴樹脂薄膜中之樹脂成分(聚合物成分)中所佔之比例較佳為超過50質量%,較佳為75質量%以上,進而較佳為90質量%以上。可為樹脂成分實質上包含聚烯烴樹脂之薄膜。或者,亦可為由下述樹脂材料所形成之薄膜,上述樹脂材料中,作為樹脂成分,除作為主要成分(例如樹脂成分中超過50質量%之成分)之聚烯烴樹脂外亦含有聚烯烴樹脂以外之樹脂成分(PA、PC、PU、EVA等)。 In a preferred embodiment, the support (substrate) is a single layer or a plurality of layers of a polyolefin resin film. Here, the polyolefin resin film refers to a plastic film formed of a resin material containing a polyolefin resin (that is, a resin containing a polyolefin as a main component). The proportion of the polyolefin resin in the resin component (polymer component) in the polyolefin resin film is preferably more than 50% by mass, preferably 75% by mass or more, and more preferably 90% by mass or more. It may be a film in which the resin component substantially contains a polyolefin resin. Alternatively, it may be a film formed of a resin material containing a polyolefin resin as a resin component in addition to a polyolefin resin as a main component (for example, a component of more than 50% by mass in the resin component). Resin components other than PA (PC, PC, PU, EVA, etc.).
作為上述聚烯烴樹脂,可單獨使用1種聚烯烴,或將2種以上之聚烯烴組合使用。上述聚烯烴例如可為α-烯烴之均聚物、2種以上之α-烯烴之共聚物、1種或2種以上之α-烯烴與其他乙烯單體之共聚物等。作為具體例,可列舉:PE、PP、EPR等乙烯-丙烯共聚物、乙烯-丙烯-丁烯共聚物、乙烯-丙烯酸乙酯共聚物等。低密度(LD)聚烯烴及高密度(HD)聚烯烴中之任一種均可使用。作為此種聚烯烴樹脂薄膜,可列舉:雙軸延伸聚丙烯(OPP)薄膜、低密度聚乙烯(LDPE)薄膜、直鏈狀低密度聚乙烯(LLDPE)薄膜、中密度聚乙烯(MDPE)薄膜、高密度聚乙烯(HDPE)薄膜、摻合有2種以上之聚乙烯(PE)之聚乙烯(PE)薄膜、摻合有聚丙烯(PP)及聚乙烯(PE)之PP/PE摻合薄膜、各種軟質聚烯烴薄膜等聚烯烴樹脂薄膜。 As the polyolefin resin, one type of polyolefin may be used alone or two or more types of polyolefins may be used in combination. The polyolefin may be, for example, a homopolymer of an α-olefin, a copolymer of two or more kinds of α-olefins, a copolymer of one or two or more kinds of α-olefins and another ethylene monomer, and the like. Specific examples thereof include an ethylene-propylene copolymer such as PE, PP, and EPR, an ethylene-propylene-butene copolymer, and an ethylene-ethyl acrylate copolymer. Any of low density (LD) polyolefin and high density (HD) polyolefin can be used. Examples of such a polyolefin resin film include a biaxially oriented polypropylene (OPP) film, a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, and a medium density polyethylene (MDPE) film. , high density polyethylene (HDPE) film, polyethylene (PE) film blended with two or more kinds of polyethylene (PE), PP/PE blended with polypropylene (PP) and polyethylene (PE) A polyolefin resin film such as a film or various soft polyolefin films.
上述PP可為以丙烯為主要單體(主要構成單體、即超過單體整體之50質量%之成分)的各種聚合物(丙烯系聚合物)。此處所謂丙烯系聚合物之概念包含例如以下之聚丙烯。 The above-mentioned PP may be various polymers (propylene-based polymers) containing propylene as a main monomer (mainly constituting a monomer, that is, a component exceeding 50% by mass of the entire monomer). The concept of a propylene-based polymer herein includes, for example, the following polypropylene.
丙烯之均聚物(即均聚丙烯)。例如等規立構聚丙烯、間規立構聚丙烯、無規立構聚丙烯。 A homopolymer of propylene (ie, homopolypropylene). For example, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene.
丙烯與其他α-烯烴(典型而言選自乙烯及碳原子數4~10之α-烯烴 中之1種或2種以上)的無規共聚物(無規聚丙烯)。例如使丙烯96~99.9莫耳%與其他α-烯烴(較佳為乙烯及/或丁烯)0.1~4莫耳%進行無規共聚而成的無規聚丙烯。 Propylene and other alpha-olefins (typically selected from ethylene and alpha-olefins having 4 to 10 carbon atoms) One or two or more kinds of random copolymers (random polypropylene). For example, a random polypropylene obtained by randomly copolymerizing 96 to 99.9 mol% of propylene with 0.1 to 4 mol% of other α-olefins (preferably ethylene and/or butene).
對丙烯嵌段共聚其他α-烯烴(典型而言選自乙烯及碳原子數4~10之α-烯烴中之1種或2種以上)而成的共聚物(嵌段聚丙烯)。該嵌段聚丙烯亦可含有作為副產物之以丙烯及上述其他α-烯烴中之至少1種作為成分的橡膠成分。例如含有對丙烯90~99.9莫耳%嵌段共聚其他α-烯烴(較佳為乙烯及/或丁烯)0.1~10莫耳%而成之聚合物、及含有作為副產物之以丙烯及其他α-烯烴中之至少1種作為成分的橡膠成分的嵌段聚丙烯。 A copolymer (block polypropylene) obtained by copolymerizing a propylene group with another α-olefin (typically one or more selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms). The block polypropylene may contain, as a by-product, a rubber component containing at least one of propylene and the other α-olefin as a component. For example, a polymer containing 0.1 to 10 mol% of other α-olefin (preferably ethylene and/or butene) copolymerized with 90 to 99.9 mol% of propylene, and propylene and others as a by-product. A block polypropylene having at least one rubber component as a component of the α-olefin.
上述PP樹脂可為樹脂成分中之主要成分為上述丙烯系聚合物並摻合有其他聚合物作為副成分之樹脂。上述其他聚合物可為丙烯以外之α-烯烴例如以碳原子數2或4~10之α-烯烴作為主要單體(主要構成單體、即超過單體整體之50質量%之成分)之聚烯烴的1種或2種以上。上述PP樹脂可為至少含有PE作為上述副成分之組成。例如相對於PP 100質量份,PE之含量可為3~50質量份(典型而言5~30質量份)。可為樹脂成分實質上包含PP及PE之PP樹脂。此外,亦可至少含有PE及EPR作為副成分之PP樹脂(例如樹脂成分實質上包含PP及PE及EPR之PP樹脂)。於該情況下,例如相對於PP100質量份,EPR之含量可為3~50質量份(典型而言為5~30質量份)。 The PP resin may be a resin in which the main component of the resin component is the propylene-based polymer and other polymers are blended as a subcomponent. The above-mentioned other polymer may be an a-olefin other than propylene, for example, agglomerates of an α-olefin having 2 or 4 to 10 carbon atoms as a main monomer (mainly constituting a monomer, that is, a component exceeding 50% by mass of the entire monomer) One type or two or more types of olefins. The PP resin may have a composition containing at least PE as the above-mentioned subcomponent. For example, the content of PE may be 3 to 50 parts by mass (typically 5 to 30 parts by mass) with respect to 100 parts by mass of PP. It may be a PP resin in which the resin component substantially contains PP and PE. Further, a PP resin having at least PE and EPR as an auxiliary component (for example, a PP resin in which a resin component substantially contains PP and PE and EPR) may be contained. In this case, for example, the EPR content may be 3 to 50 parts by mass (typically 5 to 30 parts by mass) based on 100 parts by mass of the PP.
上述PE可為乙烯之均聚物,亦可為作為主要單體之乙烯與其他α-烯烴(例如碳原子數3~10之α-烯烴)之共聚物。作為上述α-烯烴之較佳例,可列舉:丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯等。低密度聚乙烯(LDPE)、直鏈狀低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)中之任一種均可使用。例如可較佳採用LDPE及/或LLDPE。 The above PE may be a homopolymer of ethylene or a copolymer of ethylene as a main monomer and another α-olefin (for example, an α-olefin having 3 to 10 carbon atoms). Preferable examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Any of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE) can be used. For example, LDPE and/or LLDPE can be preferably used.
作為上述支持體(基材),亦可使用含有烯烴系聚合物合金及含羰 基單元之熱塑性樹脂之聚烯烴樹脂薄膜。此處,含羰基單元之熱塑性樹脂係指分子骨架中含有羰基(C=O)單元之熱塑性樹脂。此種聚烯烴樹脂薄膜實質上不含鹵素原子,可具有與聚氯乙烯(PVC)同等之柔軟性、耐熱性、阻燃性。 As the support (substrate), an olefin-based polymer alloy and a carbonyl group can also be used. A polyolefin resin film of a thermoplastic resin of a base unit. Here, the thermoplastic resin containing a carbonyl unit means a thermoplastic resin containing a carbonyl (C=O) unit in a molecular skeleton. Such a polyolefin resin film does not substantially contain a halogen atom, and has flexibility, heat resistance, and flame retardancy equivalent to those of polyvinyl chloride (PVC).
上述烯烴系聚合物合金係主要用以抑制支持體(基材)之熱變形之成分,較佳為含有乙烯成分及丙烯成分之聚合物合金。對聚合物合金之形態並無特別限定,例如可使用2種以上之聚合物進行物理性混合而成之聚合物摻雜物,2種以上之聚合物以共價鍵鍵結而成之嵌段共聚物、或接枝共聚物,2種以上之聚合物相互纏繞而不以共價鍵鍵結之IPN(Interpenetrating Polymer Network,互穿聚合物網絡)結構體等各種形態者。亦可為2種以上之聚合物相容而成之相容性聚合物合金、2種以上之聚合物非相容而形成相分離結構之非相容性聚合物合金中之任一種。 The olefin-based polymer alloy is mainly used for suppressing thermal deformation of a support (base material), and is preferably a polymer alloy containing an ethylene component and a propylene component. The form of the polymer alloy is not particularly limited. For example, a polymer dopant obtained by physically mixing two or more kinds of polymers may be used, and a block in which two or more kinds of polymers are covalently bonded is used. A copolymer or a graft copolymer, and various forms such as an IPN (Interpenetrating Polymer Network) structure in which two or more kinds of polymers are entangled with each other and are not covalently bonded. It may be any one of a compatible polymer alloy in which two or more kinds of polymers are compatible, and an incompatible polymer alloy in which two or more kinds of polymers are incompatible to form a phase-separated structure.
作為此種烯烴系聚合物合金,例如可列舉:聚丙烯(均聚丙烯、無規聚丙烯)與聚乙烯(含有乙烯及少量α-烯烴之共聚物)之聚合物摻雜物,丙烯/乙烯共聚物,丙烯與乙烯與該等以外之其他α-烯烴之三元共聚物(作為其他α-烯烴,可列舉1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯等,較佳為1-丁烯。)。 Examples of such an olefin-based polymer alloy include polymer dopants of polypropylene (homopolypropylene, atactic polypropylene) and polyethylene (copolymer containing ethylene and a small amount of α-olefin), propylene/ethylene. a copolymer, a terpolymer of propylene and ethylene with other α-olefins other than these (as other α-olefins, 1-butene, 1-pentene, 1-hexene, 4-methyl-1) -pentene, 1-heptene, 1-octene, etc., preferably 1-butene.).
於上述烯烴系聚合物合金為共聚物之情形時,較佳為藉由2級以上之多級聚合進行聚合而成之多級聚合烯烴共聚物(較佳為乙烯/丙烯共聚物)。作為該多級聚合烯烴共聚物,例如可列舉如日本專利特開2001-192629號公報中記載之聚合物合金。即,使用以丙烯為主要成分之單體混合物進行第1級之聚合,繼而於第2級及之後使丙烯與乙烯共聚而成之聚丙烯(第1級)/丙烯-乙烯共聚物(第2級及之後)的聚合物合金。第1級之聚合較佳為於鈦化合物觸媒及有機鋁化合物觸媒之存在下進行。第2級及之後的聚合較佳為於第1級之聚合中生成之含鈦聚烯 烴及有機鋁化合物觸媒之存在下進行。作為上述鈦化合物觸媒,例如可列舉將三氯化鈦與氯化鎂一起粉碎並經原鈦酸正丁酯、2-乙基己醇、對甲苯酸乙酯、四氯化矽、鄰苯二甲酸二異丁酯等處理而成之球狀且平均粒徑1~30μm之固體觸媒。作為有機鋁化合物觸媒,例如可列舉三乙基鋁等烷基鋁。另外,亦可進而於聚合層中添加二苯基二甲氧基矽烷等矽化合物,或添加碘化乙烷等碘化合物作為電子供體。 When the olefin-based polymer alloy is a copolymer, a multistage polymerized olefin copolymer (preferably an ethylene/propylene copolymer) obtained by polymerization of a plurality of stages of two or more stages is preferred. The polymer alloy described in JP-A-2001-192629 is exemplified as the multi-stage polymerized olefin copolymer. That is, a polymerization of the first stage using a monomer mixture containing propylene as a main component, followed by a polypropylene (grade 1)/propylene-ethylene copolymer obtained by copolymerizing propylene and ethylene at the second stage and thereafter (second Polymer alloys of grades and after). The polymerization of the first stage is preferably carried out in the presence of a titanium compound catalyst and an organoaluminum compound catalyst. The second and subsequent polymerizations are preferably titanium-containing polyolefins formed in the polymerization of the first stage. It is carried out in the presence of a hydrocarbon and an organoaluminum compound catalyst. Examples of the titanium compound catalyst include pulverization of titanium trichloride with magnesium chloride and n-butyl orthotitanate, 2-ethylhexanol, ethyl p-toluate, ruthenium tetrachloride, and phthalic acid. A solid catalyst having a spherical shape and an average particle diameter of 1 to 30 μm, which is treated with diisobutyl ester or the like. The organoaluminum compound catalyst may, for example, be an alkyl aluminum such as triethylaluminum. Further, an antimony compound such as diphenyldimethoxydecane may be added to the polymerization layer, or an iodine compound such as iodine iodide may be added as an electron donor.
就抑制熱變形之觀點而言,上述烯烴系聚合物合金較佳為顯示80℃下之動態儲存模數(E')為40MPa以上且未達180MPa(例如45MPa~160MPa)且顯示120℃下之動態儲存模數(E')為12MPa以上且未達70MPa(例如15MPa~65MPa)者。此外,考慮到於室溫附近之表面形狀追隨性、或作業性,較佳為23℃下之動態儲存模數(E')為200MPa以上且未達400MPa。上述動態儲存模數(E')係如下方式測定之值:製作由聚合物合金形成之試驗片(厚度0.2mm、寬度10mm、長度20mm),使用DMS200(Seiko Instruments股份有限公司製造)作為測定儀器於特定之測定條件(例如測定方法:拉伸模式、升溫速度:2℃/分鐘、頻率:1Hz)下測定該試驗片之由溫度分散引起之動態黏彈性行為。作為此種聚合物合金之例,可列舉SunAllomer股份有限公司製造之商品名「Catalloy KS-353P」、「Catalloy KS-021P」、「Catalloy C200F」、「Catalloy Q-200F」等。 From the viewpoint of suppressing thermal deformation, the olefin-based polymer alloy preferably exhibits a dynamic storage modulus (E') at 80 ° C of 40 MPa or more and less than 180 MPa (for example, 45 MPa to 160 MPa) and exhibits at 120 ° C. The dynamic storage modulus (E') is 12 MPa or more and less than 70 MPa (for example, 15 MPa to 65 MPa). Further, in consideration of surface shape followability or workability in the vicinity of room temperature, it is preferable that the dynamic storage modulus (E') at 23 ° C is 200 MPa or more and less than 400 MPa. The dynamic storage modulus (E') is a value measured by preparing a test piece (thickness: 0.2 mm, width: 10 mm, length: 20 mm) formed of a polymer alloy, and using DMS200 (manufactured by Seiko Instruments Co., Ltd.) as a measuring instrument. The dynamic viscoelastic behavior of the test piece caused by temperature dispersion was measured under specific measurement conditions (for example, measurement method: tensile mode, temperature increase rate: 2 ° C/min, frequency: 1 Hz). Examples of such a polymer alloy include the trade names "Catalloy KS-353P", "Catalloy KS-021P", "Catalloy C200F", and "Catalloy Q-200F" manufactured by Sun Allomer Co., Ltd., and the like.
上述含羰基單元之熱塑性樹脂係用以賦予支持體(基材)以適度之柔軟性及良好之伸長性者,係於分子骨架中含有羰基(C=O)單元之熱塑性樹脂。如下所述,於聚烯烴樹脂薄膜含有無機系阻燃劑之情形時,亦可作為使由無機系阻燃劑引起之阻燃性賦予作用活化之成分。作為該熱塑性樹脂,較佳為分子骨架中含有羰基單元之軟質聚烯烴系樹脂。例如可列舉將乙烯酯及/或α,β-不飽和羧酸或其衍生物用作單體或共聚單體進行合成而成之乙烯系共聚物(乙烯/乙烯酯共聚物、乙烯/ 不飽和羧酸共聚物等)、該等之金屬鹽等。對該熱塑性樹脂之熔點並無特別限定,較佳為120℃以下(典型而言40~100℃)。上述熔點可藉由通常之差示掃描熱量計(DSC)進行測定。 The thermoplastic resin containing a carbonyl group is a thermoplastic resin containing a carbonyl (C=O) unit in a molecular skeleton for imparting moderate flexibility and good elongation to a support (substrate). When the polyolefin resin film contains an inorganic flame retardant as described below, it may be used as a component for activating the flame retardancy imparted by the inorganic flame retardant. The thermoplastic resin is preferably a soft polyolefin-based resin containing a carbonyl unit in its molecular skeleton. For example, a vinyl copolymer obtained by using a vinyl ester and/or an α,β-unsaturated carboxylic acid or a derivative thereof as a monomer or a comonomer (ethylene/vinyl acetate copolymer, ethylene/ An unsaturated carboxylic acid copolymer or the like), a metal salt or the like. The melting point of the thermoplastic resin is not particularly limited, but is preferably 120 ° C or lower (typically 40 to 100 ° C). The above melting point can be measured by a usual differential scanning calorimeter (DSC).
作為上述乙烯系共聚物或其金屬鹽中之乙烯酯,可例示乙酸乙烯酯等羧酸乙烯酯。此外,作為α,β-不飽和羧酸或其衍生物,例如可列舉:丙烯酸、甲基丙烯酸、馬來酸、富馬酸、馬來酸酐、衣康酸酐等不飽和羧酸或其酸酐類;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十二烷基酯、馬來酸1-甲酯、馬來酸1-乙酯、馬來酸二乙酯、富馬酸1-甲酯、(甲基)丙烯酸縮水甘油酯等不飽和羧酸酯類。該等可單獨使用1種或將2種以上組合使用。其中,較佳為(甲基)丙烯酸烷基酯,更佳為丙烯酸乙酯。 The vinyl ester in the ethylene-based copolymer or the metal salt thereof may, for example, be a vinyl carboxylate such as vinyl acetate. Further, examples of the α,β-unsaturated carboxylic acid or a derivative thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. ; (methyl) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, cyclomethacrylate Ester, octadecyl (meth)acrylate, dodecyl (meth)acrylate, 1-methyl maleate, 1-ethyl maleate, diethyl maleate, fumaric acid Unsaturated carboxylic acid esters such as 1-methyl ester and glycidyl (meth)acrylate. These may be used alone or in combination of two or more. Among them, an alkyl (meth)acrylate is preferred, and ethyl acrylate is more preferred.
作為上述乙烯/乙烯酯共聚物及乙烯/不飽和羧酸共聚物之較佳例,可列舉:乙烯/丙烯酸共聚物、乙烯/甲基丙烯酸共聚物、乙烯/丙烯酸乙酯共聚物、乙烯/丙烯酸/丙烯酸乙酯共聚物、乙烯/乙酸乙烯酯共聚物、乙烯/乙酸乙烯酯/丙烯酸乙酯共聚物、乙烯/甲基丙烯酸縮水甘油酯共聚物、乙烯/甲基丙烯酸縮水甘油酯-丙烯酸乙酯共聚物以及該等之金屬鹽。該等可單獨使用1種或將2種以上組合使用。 Preferred examples of the ethylene/vinyl ester copolymer and the ethylene/unsaturated carboxylic acid copolymer include an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/ethyl acrylate copolymer, and an ethylene/acrylic acid. /ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl acetate/ethyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/glycidyl methacrylate-ethyl acrylate Copolymers and such metal salts. These may be used alone or in combination of two or more.
上述含有烯烴系聚合物合金及含羰基單元之熱塑性樹脂之聚烯烴樹脂薄膜中較佳為含有無機系阻燃劑。作為此種無機系阻燃劑,例如可列舉出:氫氧化鋁、氫氧化鎂、氫氧化鋯、氫氧化鈣、氫氧化鋇等金屬氫氧化物;鹼性碳酸鎂、碳酸鎂鈣、碳酸鈣、碳酸鋇、白雲石等金屬碳酸鹽;水滑石、硼砂等金屬水合物(金屬化合物之水合物);偏硼酸鋇、氧化鎂等無機金屬化合物。該等可單獨使用1種或將2種以上組合使用。其中,較佳為氫氧化鋁、氫氧化鎂、氫氧化鋯、氫氧化 鈣、氫氧化鋇等金屬氫氧化物,或鹼性碳酸鎂,水滑石。 The polyolefin resin film containing the olefin polymer alloy and the thermoplastic resin containing a carbonyl unit preferably contains an inorganic flame retardant. Examples of such an inorganic flame retardant include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, and barium hydroxide; and basic magnesium carbonate, calcium magnesium carbonate, and calcium carbonate. Metal carbonates such as barium carbonate and dolomite; metal hydrates such as hydrotalcite and borax (hydrates of metal compounds); inorganic metal compounds such as barium metaborate and magnesium oxide. These may be used alone or in combination of two or more. Among them, preferred are aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, and hydroxide. a metal hydroxide such as calcium or barium hydroxide, or basic magnesium carbonate or hydrotalcite.
此外,上述無機系阻燃劑較佳為實施利用矽烷系偶合劑進行之表面處理。藉此能夠進一步提高柔軟性、耐熱性、阻燃性等各種特性。作為此種矽烷系偶合劑之具體例,可列舉:乙烯基三乙氧基矽烷、乙烯基-三(2-甲氧基-乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷。該等可單獨使用1種或將2種以上組合使用。 Further, the inorganic flame retardant is preferably subjected to a surface treatment by a decane coupling agent. Thereby, various characteristics such as flexibility, heat resistance, and flame retardancy can be further improved. Specific examples of such a decane-based coupling agent include vinyltriethoxydecane, vinyl-tris(2-methoxy-ethoxy)decane, and γ-methylpropenyloxypropyltrimethyl. Oxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-β-(amino group Ethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltri Ethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane. These may be used alone or in combination of two or more.
對上述利用矽烷系偶合劑之無機金屬化合物之表面處理的方法並無特別限定,可適當採用例如乾式處理法、濕式處理法等先前公知之方法。矽烷系偶合劑於無機金屬化合物表面之附著量由於根據偶合劑之種類、無機金屬化合物之種類、比表面積等而有所不同,因此無法一概而論,相對於無機金屬化合物100質量份,通常為0.1~5.0質量份(例如0.3~3.0質量份)左右。 The method of surface treatment of the inorganic metal compound using the decane-based coupling agent is not particularly limited, and a conventionally known method such as a dry treatment method or a wet treatment method can be suitably employed. The amount of the decane-based coupling agent to the surface of the inorganic metal compound varies depending on the type of the coupling agent, the type of the inorganic metal compound, the specific surface area, and the like. Therefore, it cannot be generalized, and is usually 0.1 to 0.1 part by mass of the inorganic metal compound. 5.0 parts by mass (for example, 0.3 to 3.0 parts by mass).
對上述烯烴系聚合物合金與含羰基單元之熱塑性樹脂之調配比並無特別限定,就兼具耐熱性及阻燃性之觀點而言,例如以質量基準計較佳為90:10~20:80。此外,於調配無機系阻燃劑之情形時,就提高阻燃性及維持柔軟性之觀點而言,相對於聚合物成分(多級聚合烯烴共聚物與含羰基單元之熱塑性樹脂之合計)100質量份,其調配量較佳為10~200質量份(例如20~100質量份)左右。 The mixing ratio of the olefin polymer alloy to the carbonyl group-containing thermoplastic resin is not particularly limited, and from the viewpoint of heat resistance and flame retardancy, for example, it is preferably 90:10 to 20:80 on a mass basis. . Further, in the case of blending an inorganic flame retardant, the polymer component (the total of the multistage polymerized olefin copolymer and the thermoplastic resin containing a carbonyl unit) is 100 in terms of improving flame retardancy and maintaining flexibility. The blending amount is preferably from 10 to 200 parts by mass (e.g., from 20 to 100 parts by mass).
上述任一樹脂薄膜中均可根據需要而含有適合於黏著片(表面保護片)之用途之適當成分。例如可適當調配自由基捕捉劑、或紫外線吸收劑等光穩定劑、抗氧化劑、抗靜電劑、著色劑(染料、顏料等)、 填充材料、滑澤劑、抗黏連劑等添加劑。 Any of the above resin films may contain an appropriate component suitable for the use of the adhesive sheet (surface protective sheet) as needed. For example, a photo-trapping agent such as a radical scavenger or an ultraviolet absorber, an antioxidant, an antistatic agent, a coloring agent (dye, pigment, etc.) may be appropriately formulated. Additives such as fillers, slip agents, anti-blocking agents.
作為上述光穩定劑之例,可列舉以苯并三唑類、受阻胺類、苯甲酸酯類等作為有效成分者。 Examples of the light stabilizer include benzotriazoles, hindered amines, and benzoic acid esters as active ingredients.
作為上述抗氧化劑之例,可列舉以烷基酚類、伸烷基雙酚類、硫代丙烯酸酯類、有機亞磷酸酯類、胺類、氫醌類、羥基胺類等作為有效成分者。 Examples of the antioxidant include alkylphenols, alkylene bisphenols, thioacrylates, organic phosphites, amines, hydroquinones, hydroxylamines, and the like.
如上述之添加劑可分別僅單獨使用1種或將2種以上組合使用。上述添加劑之含量可根據表面保護片之用途(例如玻璃蝕刻用、電鍍遮罩用)而設定為與於該用途中作為表面保護片之支持體(基材)使用之樹脂薄膜之通常的含量(調配量)同等程度。 The above-mentioned additives may be used alone or in combination of two or more. The content of the above-mentioned additive can be set to a normal content of a resin film used as a support (substrate) of the surface protective sheet in the use according to the use of the surface protective sheet (for example, for glass etching or plating mask). The amount of blending is the same.
此種支持體(基材)(樹脂薄膜)可適當採用先前公知之通常之薄膜成型方法(擠出成型、吹脹成型等)製造。支持體中設置有黏著劑層側之表面(黏著劑層側表面、塗覆黏著劑之面)可實施用以提高與該黏著劑層之接著性之處理(用以獲得黏著劑之錨固性之處理),例如電暈放電處理、酸處理、紫外線照射處理、電漿處理、底塗劑(底漆)塗覆等表面處理。作為利用底漆塗覆之表面處理(底漆處理),較佳使用於丙烯酸系聚合物中調配異氰酸酯而成之底塗劑。支持體中與上述黏著劑層側表面相反側之面(背面)可根據需要而實施抗靜電處理、剝離處理等表面處理。作為剝離處理,例如可藉由於支持體之背面設置長鏈烷基系、矽酮系剝離處理層而減輕捲成輥狀之形態之表面保護片的退捲力。 Such a support (substrate) (resin film) can be suitably produced by a conventionally known conventional film forming method (extrusion molding, inflation molding, etc.). The surface on which the adhesive layer side is provided in the support (the side surface of the adhesive layer, the surface on which the adhesive is applied) may be subjected to treatment for improving the adhesion to the adhesive layer (to obtain the anchoring property of the adhesive) Treatment), for example, surface treatment such as corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, primer (primer) coating, and the like. As a surface treatment (primer treatment) by primer coating, it is preferred to use a primer obtained by blending an isocyanate in an acrylic polymer. The surface (back surface) of the support opposite to the side surface of the above-mentioned adhesive layer side can be subjected to surface treatment such as antistatic treatment or peeling treatment as needed. In the peeling treatment, for example, a long-chain alkyl-based or an oxime-based release-treated layer is provided on the back surface of the support to reduce the unwinding force of the surface protective sheet wound into a roll shape.
上述支持體(基材)之厚度可根據所使用之樹脂薄膜之可撓性(硬度)等而適當選擇。就對具有階差之表面之追隨性、或密著性之觀點而言,通常,支持體之厚度較佳為500μm以下(較佳為400μm以下,更佳為300μm以下,典型而言250μm以下,例如為200μm以下)。此外,就剝離作業性及其他操作性(處理性)之觀點而言,支持體之厚度 適當為10μm以上(較佳為20μm以上,更佳為25μm以上,例如為30μm以上)。此外,若支持體之厚度增大,則存在容易防止藥液自表面保護片表面膨潤浸入之傾向。 The thickness of the support (substrate) can be appropriately selected depending on the flexibility (hardness) of the resin film to be used and the like. The thickness of the support is preferably 500 μm or less (preferably 400 μm or less, more preferably 300 μm or less, and typically 250 μm or less, from the viewpoint of followability or adhesion of the surface having a step difference. For example, it is 200 μm or less). In addition, the thickness of the support is from the viewpoint of peeling workability and other operability (handling property) Suitably, it is 10 μm or more (preferably 20 μm or more, more preferably 25 μm or more, for example, 30 μm or more). Further, when the thickness of the support is increased, there is a tendency that the chemical liquid is easily prevented from being swollen from the surface of the surface protection sheet.
上述支持體中設置黏著劑層側之表面較佳為具有不影響黏著劑層之表面狀態(黏著面之表面粗糙度)的程度(即不構成使黏著面之算術平均表面粗糙度上升之主要原因之程度)的平滑性。例如,上述支持體較佳為其黏著劑層側表面之算術平均表面粗糙度為1μm以下,更佳為0.05~0.75μm(例如約0.05~0.5μm、典型而言約0.1~0.3μm)。藉由採用該構成,黏著面之平滑性亦提高。 The surface on the side where the adhesive layer is provided in the support preferably has a surface state (surface roughness of the adhesive surface) which does not affect the adhesive layer (that is, does not constitute a main cause of an increase in the arithmetic mean surface roughness of the adhesive surface). The degree of smoothness. For example, the support preferably has an arithmetic mean surface roughness of the side surface of the adhesive layer of 1 μm or less, more preferably 0.05 to 0.75 μm (e.g., about 0.05 to 0.5 μm, typically about 0.1 to 0.3 μm). By adopting this configuration, the smoothness of the adhesive surface is also improved.
亦可根據需要而對上述支持體進行利用矽酮系、氟系、長鏈烷基系或脂肪醯胺系之脫模劑、二氧化矽粉等之脫模及防污處理、或酸處理、鹼處理、底漆處理、電暈處理、電漿處理、紫外線處理等易接著處理、塗佈型、混練型、蒸鍍型等防靜電處理。 The support may be subjected to mold release, antifouling treatment, or acid treatment using an anthrone-based, fluorine-based, long-chain alkyl-based or fatty amide-based release agent, cerium oxide powder, or the like, as needed. Antistatic treatment such as alkali treatment, primer treatment, corona treatment, plasma treatment, ultraviolet treatment, etc., followed by easy treatment, coating type, kneading type, vapor deposition type, and the like.
此外,本發明之黏著片(表面保護片)中使用之支持體(塑膠薄膜)更佳為經過抗靜電處理。藉由進行抗靜電處理,能夠防止靜電產生,特別是於靜電會造成嚴重問題之光學、電子部件相關之技術領域中較為有用。作為對塑膠薄膜實施之抗靜電處理,並無特別限定,可使用通常使用之於薄膜之至少單面設置抗靜電層之方法、或將混練型抗靜電劑混練於塑膠薄膜中之方法。作為於薄膜之至少單面設置抗靜電層之方法,可列舉:塗佈由抗靜電劑及樹脂成分構成之抗靜電性樹脂、或導電性聚合物、含有導電性物質之導電性樹脂的方法,或者蒸鍍或電鍍導電性物質之方法。 Further, the support (plastic film) used in the adhesive sheet (surface protective sheet) of the present invention is preferably subjected to an antistatic treatment. By performing antistatic treatment, it is possible to prevent generation of static electricity, and it is particularly useful in the technical field related to optical and electronic components in which static electricity causes serious problems. The antistatic treatment applied to the plastic film is not particularly limited, and a method in which an antistatic layer is provided on at least one side of a film or a method in which a kneading antistatic agent is kneaded in a plastic film can be used. The method of providing an antistatic layer on at least one side of the film includes a method of applying an antistatic resin composed of an antistatic agent and a resin component, or a conductive polymer or a conductive resin containing a conductive material. Or a method of vaporizing or plating a conductive substance.
作為上述抗靜電性樹脂中含有之抗靜電劑,可列舉:四級銨鹽、吡啶鎓鹽、具有一級胺基、二級胺基、三級胺基等陽離子性官能基之陽離子型抗靜電劑,磺酸鹽、或硫酸酯鹽、膦酸鹽、磷酸酯鹽等具有陰離子性官能基之陰離子型抗靜電劑,烷基甜菜鹼及其衍生物、 咪唑啉及其衍生物、丙胺酸及其衍生物等兩性型抗靜電劑,胺基醇及其衍生物、甘油及其衍生物、聚乙二醇及其衍生物等非離子型抗靜電劑,進而將具有上述陽離子型、陰離子型、兩性離子型之離子導電性基之單體聚合或共聚而獲得之離子導電性聚合物。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the antistatic agent contained in the antistatic resin include a quaternary ammonium salt, a pyridinium salt, and a cationic antistatic agent having a cationic functional group such as a primary amine group, a secondary amino group or a tertiary amino group. An anionic antistatic agent having an anionic functional group such as a sulfonate or a sulfonate, a phosphonate or a phosphate ester, an alkylbetaine and a derivative thereof, Amphoteric antistatic agent such as imidazoline and its derivatives, alanine and its derivatives, nonionic antistatic agent such as amino alcohol and its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, Further, an ion conductive polymer obtained by polymerizing or copolymerizing a monomer having the above cationic, anionic or zwitterionic ionic conductive group. These compounds may be used singly or in combination of two or more.
具體而言,作為上述陽離子型之抗靜電劑,例如可列舉:烷基三甲基銨鹽、醯基醯胺丙基三甲基銨甲基硫酸鹽、烷基苄基甲基銨鹽、醯基氯化膽鹼、聚甲基丙烯酸二甲胺基乙酯等具有四級銨基之(甲基)丙烯酸酯共聚物,聚乙烯基苄基三甲基氯化銨等具有四級銨基之苯乙烯共聚物,聚二烯丙基二甲基氯化銨等具有四級銨基之二烯丙基胺共聚物等。該等化合物可單獨使用,亦可混合2種以上使用。 Specifically, examples of the cationic antistatic agent include an alkyltrimethylammonium salt, a mercaptoguanidinopropyltrimethylammonium methylsulfate, an alkylbenzylmethylammonium salt, and an anthracene. a (meth) acrylate copolymer having a quaternary ammonium group such as choline chloride or polydimethylaminoethyl methacrylate, and a quaternary ammonium group such as polyvinylbenzyltrimethylammonium chloride A styrene copolymer, a diallylamine copolymer having a quaternary ammonium group such as polydiallyldimethylammonium chloride or the like. These compounds may be used singly or in combination of two or more.
作為上述陰離子型之抗靜電劑,例如可列舉:烷基磺酸鹽、烷基苯磺酸鹽、烷基硫酸酯鹽、烷基乙氧基硫酸酯鹽、烷基磷酸酯鹽、含磺酸基之苯乙烯共聚物。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the anionic antistatic agent include an alkylsulfonate, an alkylbenzenesulfonate, an alkylsulfate, an alkylethoxysulfate, an alkyl phosphate, and a sulfonic acid. a styrene copolymer. These compounds may be used singly or in combination of two or more.
作為上述兩性離子型之抗靜電劑,例如可列舉:烷基甜菜鹼、烷基咪唑鎓甜菜鹼、羰基甜菜鹼(carbobetaine)接枝共聚物。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the amphoteric ion-type antistatic agent include an alkylbetaine, an alkylimidazolium betaine, and a carbobetaine graft copolymer. These compounds may be used singly or in combination of two or more.
作為上述非離子型之抗靜電劑,例如可列舉:脂肪酸羥烷基醯胺、二(2-羥基乙基)烷基胺、聚氧伸乙基烷基胺、脂肪酸甘油酯、聚氧乙二醇脂肪酸酯、山梨糖醇酐脂肪酸酯、聚氧伸乙基山梨糖醇酐脂肪酸酯、聚氧伸乙基烷基苯基醚、聚氧伸乙基烷基醚、聚乙二醇、聚氧伸乙基二胺、包含聚醚與聚酯與聚醯胺之共聚物、甲氧基聚乙二醇(甲基)丙烯酸酯等。該等化合物可單獨使用,亦可混合2種以上使用。 Examples of the nonionic antistatic agent include fatty acid hydroxyalkyl decylamine, bis(2-hydroxyethyl)alkylamine, polyoxyethylideneamine, fatty acid glyceride, and polyoxyethylene. Alcohol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene ethyl sorbitan fatty acid esters, polyoxyethylene ethyl phenyl ethers, polyoxyethylene ethyl ethers, polyethylene glycols Polyoxyethylene ethyl diamine, a copolymer comprising a polyether and a polyester and a polyamine, a methoxy polyethylene glycol (meth) acrylate, or the like. These compounds may be used singly or in combination of two or more.
作為上述導電性聚合物,例如可列舉:聚苯胺、聚吡咯、聚噻 吩等。 Examples of the conductive polymer include polyaniline, polypyrrole, and polythiophene. Order.
作為上述導電性物質,例如可列舉:氧化錫、氧化銻、氧化銦、氧化鎘、氧化鈦、氧化鋅、銦、錫、銻、金、銀、銅、鋁、鎳、鉻、鈦、鐵、鈷、碘化銅以及該等之合金或混合物。 Examples of the conductive material include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, and iron. Cobalt, copper iodide and alloys or mixtures thereof.
作為上述抗靜電性樹脂及導電性樹脂中使用之樹脂成分,可使用聚酯、丙烯酸、聚乙烯、胺基甲酸酯、三聚氰胺、環氧樹脂等通用樹脂。另外,於為高分子型抗靜電劑之情形時,亦可不含樹脂成分。此外,亦可於抗靜電樹脂成分中含有作為交聯劑之羥甲基化或羥烷基化之三聚氰胺系、尿素系、乙二醛系、丙烯醯胺系等化合物、環氧化合物、異氰酸酯系化合物。 As the resin component used in the antistatic resin and the conductive resin, a general-purpose resin such as polyester, acrylic, polyethylene, urethane, melamine or epoxy resin can be used. Further, in the case of a polymer type antistatic agent, a resin component may not be contained. In addition, a compound such as melamine or hydroxyalkylated melamine, urea, glyoxal or acrylamide may be contained in the antistatic resin component, and an epoxy compound or an isocyanate may be contained. Compound.
作為上述抗靜電層之形成方法,例如可以如下方式形成:藉由將上述抗靜電性樹脂、導電性聚合物、導電性樹脂用有機溶劑或水等溶劑稀釋,將該塗佈液塗佈於塑膠薄膜上並乾燥。 The method for forming the antistatic layer can be formed, for example, by diluting the antistatic resin, the conductive polymer, and the conductive resin with an organic solvent or a solvent such as water to apply the coating liquid to the plastic. The film is dried and dried.
作為上述抗靜電層之形成中使用之有機溶劑,例如可列舉:甲基乙基酮、丙酮、乙酸乙酯、四氫呋喃、二噁烷、環己酮、正己烷、甲苯、二甲苯、甲醇、乙醇、正丙醇、異丙醇等。該等溶劑可單獨使用,亦可混合2種以上使用。 Examples of the organic solvent used for the formation of the antistatic layer include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, and ethanol. , n-propanol, isopropanol, etc. These solvents may be used singly or in combination of two or more.
關於上述抗靜電層之形成中之塗佈方法,可適當使用公知之塗佈方法,具體而言,例如可列舉:輥塗法、凹版塗佈法、逆轉塗佈法、輥刷塗佈法、噴塗法、氣刀塗佈法、含浸塗佈法及淋幕式塗佈法。 A known coating method can be suitably used for the coating method in the formation of the antistatic layer. Specific examples thereof include a roll coating method, a gravure coating method, a reverse coating method, and a roll brush coating method. Spraying method, air knife coating method, impregnation coating method and curtain coating method.
作為上述抗靜電性樹脂層、導電性聚合物、導電性樹脂之厚度,通常為0.01~5μm,較佳為0.03~1μm左右。 The thickness of the antistatic resin layer, the conductive polymer, and the conductive resin is usually 0.01 to 5 μm, preferably about 0.03 to 1 μm.
作為導電性物質之蒸鍍或者電鍍之方法,例如可列舉:真空蒸鍍、濺射、離子鍍、化學蒸鍍、噴霧熱分解、化學鍍、電鍍法等。 Examples of the method of vapor deposition or plating of the conductive material include vacuum deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, electroless plating, and plating.
作為上述導電性物質層之厚度,通常為2~1000nm,較佳為5~ 500nm。 The thickness of the conductive material layer is usually 2 to 1000 nm, preferably 5 to 500nm.
此外,作為上述混練型抗靜電劑,可適當使用上述抗靜電劑。作為混練型抗靜電劑之含量(調配量),相對於作為支持體之塑膠薄膜之總質量,以20質量%以下、較佳為0.05~10質量%之範圍使用。作為混練方法,只要為能夠將上述抗靜電劑均勻地混合於用於塑膠薄膜之樹脂中之方法則無特別限定,例如可使用加熱輥、班伯里混合機、加壓捏合機、雙軸混練機等。 Further, as the kneading type antistatic agent, the above antistatic agent can be suitably used. The content (mixing amount) of the kneading-type antistatic agent is used in an amount of 20% by mass or less, preferably 0.05% to 10% by mass based on the total mass of the plastic film as the support. The kneading method is not particularly limited as long as it can uniformly mix the above antistatic agent in a resin for a plastic film, and for example, a heating roll, a Banbury mixer, a pressure kneader, and a biaxial kneading can be used. Machine and so on.
本發明之黏著片(表面保護片)於其使用前(貼附於被接著體前)可為於黏著劑層之表面上配置有剝離襯墊之附剝離襯墊之黏著片(表面保護片)的形態。於剝離襯墊配置於黏著面上且與該黏著面相對之表面(剝離面)平滑性優異之情形時,可更穩定地維持黏著劑表面(黏著面)之平滑性直至使用黏著片(表面保護片)時為止。 The adhesive sheet (surface protection sheet) of the present invention may be an adhesive sheet (surface protection sheet) with a release liner attached to the surface of the adhesive layer before use (before being attached to the adherend) Shape. When the release liner is disposed on the adhesive surface and the surface (peeling surface) facing the adhesive surface is excellent in smoothness, the smoothness of the adhesive surface (adhesive surface) can be more stably maintained until the adhesive sheet is used (surface protection) The film) is up to now.
作為上述剝離襯墊(隔離體),並無特別限定,可使用各種紙(可為於表面層壓有樹脂之紙)、樹脂薄膜等。於使用樹脂薄膜作為剝離襯墊之情形時,作為構成上述樹脂薄膜之樹脂成分之較佳例,可列舉:聚烯烴樹脂、PET等聚酯樹脂、聚醯胺樹脂、聚碳酸酯樹脂、聚胺基甲酸酯樹脂等。既可為包含單獨含有此種樹脂中之一種之樹脂材料的剝離襯墊,亦可為包含摻合有二種以上之樹脂(例如PE及PP)之樹脂材料的剝離襯墊。此種剝離襯墊用樹脂薄膜與支持體用之樹脂片同樣,可適當採用通常之薄膜成形方法來製造。剝離襯墊之結構可為單層,亦可為二層以上之多層結構。 The release liner (separator) is not particularly limited, and various papers (which may be paper having a resin laminated on the surface), a resin film, or the like can be used. In the case of using a resin film as a release liner, preferred examples of the resin component constituting the resin film include a polyolefin resin, a polyester resin such as PET, a polyamide resin, a polycarbonate resin, and a polyamine. Carbamate resin and the like. The release liner may be a release liner comprising a resin material containing one of the resins alone, or a release liner comprising a resin material in which two or more resins (for example, PE and PP) are blended. The resin film for such a release liner can be produced by a usual film forming method, similarly to the resin sheet for a support. The structure of the release liner may be a single layer or a multilayer structure of two or more layers.
於採用轉印法作為於支持體上設置黏著劑層之方法之情形時,轉印片及剝離襯墊可使用同一物質。例如,於形成於轉印片之剝離面上之黏著劑層上貼合支持體,將黏著劑層轉印至上述支持體,將該轉印片直接殘留於黏著劑層上而可作為剝離襯墊利用。就提高生產性、降低材料成本、削減廢棄物量等觀點而言,此種轉印片兼作剝離襯墊 之態樣較佳。 In the case where the transfer method is employed as a method of providing an adhesive layer on a support, the same substance can be used for the transfer sheet and the release liner. For example, the support is bonded to the adhesive layer formed on the release surface of the transfer sheet, and the adhesive layer is transferred to the support, and the transfer sheet is directly left on the adhesive layer to serve as a release liner. Pad utilization. The transfer sheet doubles as a release liner in terms of improving productivity, reducing material costs, and reducing waste. The situation is better.
對上述剝離襯墊之厚度並無特別限定,可為約5~500μm(例如約10~200μm、典型而言約20~200μm)。剝離襯墊之剝離面(與黏著面接觸配置之面)可根據需要而實施利用先前公知之剝離劑(例如通常之矽酮系、長鏈烷基系、氟系等)之剝離處理。上述剝離面之背面可實施剝離處理,亦可實施剝離處理以外之表面處理。 The thickness of the release liner is not particularly limited and may be about 5 to 500 μm (for example, about 10 to 200 μm, typically about 20 to 200 μm). The release surface of the release liner (the surface disposed in contact with the adhesive surface) may be subjected to a release treatment using a conventionally known release agent (for example, an ordinary anthrone type, a long-chain alkyl type, a fluorine type, or the like) as needed. The back surface of the peeling surface may be subjected to a peeling treatment, or a surface treatment other than the peeling treatment may be performed.
上述剝離襯墊中配置於黏著劑層之側之表面的算術平均表面粗糙度較佳為0.05~0.75μm(例如約0.05~0.5μm,典型而言約0.1~0.3μm)。由此,能夠維持較高之黏著劑表面(黏著面)之平滑性直至使用表面保護片時為止。黏著面之平滑性較高於防止藥液自黏著劑與被接著體之界面浸入方面較為有利。此外,就防止糊劑殘留之觀點而言亦較佳。就同樣之理由而言,藉由使黏著劑層之表面(黏著面)與支持體之背面抵接而保護黏著面直至使用表面保護片時為止之形態之表面保護片中,上述支持體之背面之算術平均表面粗糙度較佳為0.05~0.75μm(例如約0.05~0.5μm,典型而言約0.1~0.3μm)。 The arithmetic mean surface roughness of the surface of the release liner disposed on the side of the adhesive layer is preferably 0.05 to 0.75 μm (for example, about 0.05 to 0.5 μm, typically about 0.1 to 0.3 μm). Thereby, the smoothness of the surface (adhesive surface) of a high adhesive can be maintained until the surface protection sheet is used. The smoothness of the adhesive surface is higher than that of preventing the immersion of the chemical solution from the interface between the adhesive and the adherend. Further, it is also preferable from the viewpoint of preventing the residue of the paste. For the same reason, the surface of the adhesive layer is protected by abutting the surface (adhesive surface) of the adhesive layer against the back surface of the support to protect the adhesive surface until the surface protective sheet is used. The arithmetic mean surface roughness is preferably from 0.05 to 0.75 μm (e.g., from about 0.05 to 0.5 μm, typically from about 0.1 to 0.3 μm).
本發明之表面保護片較佳為包含上述藥液處理用黏著片。上述黏著片可貼附於被接著體之所期望之部位來作為用以保護該部位之表面保護片使用。該表面保護片中使用之黏著劑由於對被接著體之密著性較高,因此於表面保護片之外緣防止藥液(特別是水系之藥液,典型而言酸性之藥液)自黏著劑與被接著體之界面浸入之性能優異。由此,能夠可靠地阻止藥液浸入至不希望暴露於藥液之部位,保護其表面。 The surface protection sheet of the present invention preferably comprises the above-mentioned pressure-sensitive adhesive sheet for chemical liquid treatment. The above adhesive sheet can be attached to a desired portion of the adherend to be used as a surface protective sheet for protecting the portion. Since the adhesive used in the surface protection sheet has high adhesion to the adherend, the chemical protection liquid (especially the aqueous liquid medicine, typically acidic liquid) is adhered to the outer edge of the surface protection sheet. The agent is excellent in immersing in the interface with the adherend. Thereby, it is possible to reliably prevent the chemical solution from infiltrating into a portion where it is not desired to be exposed to the chemical liquid, and to protect the surface thereof.
本發明之表面保護片發揮此種長處例如可較佳地用於下述處理:為了減薄玻璃之厚度,或為了去除於玻璃之切斷端面形成之毛邊、或微裂紋而用藥液(蝕刻液)溶解玻璃之蝕刻處理;為了賦予裝 飾、或印刷性而用藥液(蝕刻液)部分性腐蝕金屬之表面之蝕刻處理;用藥液(電鍍液)部分性電鍍電路基板(印刷基板、柔性印刷基板(FPC)等)之連接端子部等之電鍍處理等。 The surface protection sheet of the present invention can be preferably used for such a treatment, for example, in order to reduce the thickness of the glass, or to remove the burrs or microcracks formed on the cut end surface of the glass (the etching liquid) Etching treatment of dissolved glass; Etching or printing of a chemical liquid (etching liquid) to partially etch the surface of the metal; and to connect the terminal portion of the printed circuit board (printed substrate, flexible printed circuit (FPC), etc.) with a chemical solution (plating solution) Plating treatment, etc.
此外,例如於包括被接著體之外緣之範圍貼附上述表面保護片並進行藥液處理之情形時,若藥液部分性自被接著體之外緣(貼附有表面保護片之區域之外緣)浸入,則存在被接著體之外緣(edge)之平滑性因藥液的影響而受損之虞。若被接著體之外緣之平滑性受損,則特別是如玻璃基板般之脆弱之被接著體會產生被接著體之強度降低等不利情況。此處所揭示之表面保護片由於防止藥液自上述表面保護片之外緣浸入的性能優異,因此能夠有效地防止被接著體之外緣之平滑性降低的現象。 Further, for example, when the surface protective sheet is attached to the outer edge of the adherend and the chemical liquid treatment is performed, if the chemical liquid is partially from the outer edge of the adherend (the area where the surface protective sheet is attached) When the outer edge is immersed, there is a flaw in the smoothness of the edge of the adherend due to the influence of the chemical solution. If the smoothness of the outer edge of the adherend is impaired, in particular, the adhering body which is weak as a glass substrate may cause disadvantages such as a decrease in the strength of the adherend. The surface protection sheet disclosed herein is excellent in the performance of preventing the chemical solution from entering from the outer edge of the surface protection sheet, and therefore it is possible to effectively prevent the phenomenon that the smoothness of the outer edge of the adherend is lowered.
本發明之附表面保護片之玻璃基板較佳為於玻璃基板上貼附有上述表面保護片。藉由將上述表面保護片貼附於玻璃基板,例如於為了調整玻璃之厚度、或去除於玻璃之切斷端面形成之毛邊等而進行用藥液(氫氟酸等強酸性之藥液)溶解玻璃之蝕刻處理等時,上述表面保護片由於具有防止藥液浸入至不需要利用上述藥液進行處理之玻璃表面的性質(防藥液浸入性、密封性),即與作為被接著體之玻璃表面無間隙密著之性質(不產生浮起、或剝離,優異之密著性)及接著強度(於藥液中之優異之黏著力)及於不再需要上述表面保護片之情形時能夠容易地剝離的性質(再剝離性)而較為有用。此外,上述表面保護片由於亦具有優異之抗靜電性,因此於不再需要上述表面保護片之階段將其剝離去除時能夠抑制於作為被接著體之玻璃表面產生之靜電,較為有用。玻璃基板可為如平板型個人電腦、或手機、有機LED(發光二極體)等中使用之於表面部分性設置有透明導電膜(例如ITO(氧化銦錫)膜)、或柔性印刷基板(FPC)之玻璃基材。 The glass substrate with a surface protection sheet of the present invention preferably has the surface protection sheet attached to the glass substrate. By attaching the surface protection sheet to the glass substrate, for example, in order to adjust the thickness of the glass or to remove the burrs formed on the cut end surface of the glass, the chemical solution (a highly acidic chemical solution such as hydrofluoric acid) is used to dissolve the glass. In the etching treatment or the like, the surface protective sheet has a property of preventing the chemical liquid from entering the surface of the glass which is not required to be treated by the chemical liquid (anti-drug immersion property, sealing property), that is, a glass surface as the adherend The property of no gap adhesion (no floating, or peeling, excellent adhesion) and the subsequent strength (excellent adhesion in the liquid) and the case where the above surface protection sheet is no longer needed can be easily It is useful for the property of peeling (repeelability). Further, since the surface protective sheet has excellent antistatic property, it is useful for suppressing static electricity generated on the surface of the glass as the adherend when the surface protective sheet is not required to be peeled off. The glass substrate may be, for example, a flat type personal computer, or a mobile phone, an organic LED (light emitting diode), or the like, partially provided with a transparent conductive film (for example, an ITO (Indium Tin Oxide) film) or a flexible printed substrate (for example). FPC) glass substrate.
以下對與本發明相關之若干實施例進行說明,但並非欲將本發明限定於該等具體例。另外,以下說明中之「份」及「%」只要無特別說明,則為質量基準。 In the following, several embodiments of the invention are described, but the invention is not intended to be limited to the specific examples. In addition, the "parts" and "%" in the following description are the quality standards unless otherwise specified.
將實施例1~15及比較例1~2之黏著劑組合物之成分示於表2,表3表示評價結果。 The components of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 and 2 are shown in Table 2, and Table 3 shows the evaluation results.
上述表2中之縮寫表示以下之化合物,份數表示固形物成分之質量份。 The abbreviations in Table 2 above indicate the following compounds, and the parts represent the parts by mass of the solid content.
2EHA:丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate
HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate
DCPMA:甲基丙烯酸二環戊酯 DCPMA: Dicyclopentyl Methacrylate
MMA:甲基丙烯酸甲酯 MMA: Methyl methacrylate
CHMA:甲基丙烯酸環己酯 CHMA: cyclohexyl methacrylate
BMP-TFSI:1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺 BMP-TFSI: 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone
EMI-FSI:1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺 EMI-FSI: 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine
KF6004:具有聚氧伸烷基鏈之有機聚矽氧烷 KF6004: organopolyoxane with polyoxyalkylene chain
Pluronic 25R-2:聚氧伸丙基-聚氧伸乙基-聚氧伸丙基嵌段共聚物 Pluronic 25R-2: polyoxypropylene propyl-polyoxyethylene ethyl-polyoxypropyl propyl block copolymer
Coronate L:三羥甲基丙烷/甲苯二異氰酸酯3聚物加成物 Coronate L: Trimethylolpropane/toluene diisocyanate 3-polymer adduct
Coronate HX:六亞甲基二異氰酸酯之異氰尿酸酯體 Coronate HX: isocyanurate body of hexamethylene diisocyanate
向具備攪拌葉片、溫度計、氮氣導入管、冷凝器、滴液漏斗之四口燒瓶中添加丙烯酸2-乙基己酯(2EHA)96質量份、丙烯酸2-羥基乙酯(HEA)4質量份、作為熱聚合起始劑之2,2'-偶氮雙異丁腈0.2質量份、以及乙酸乙酯150質量份,一面緩慢攪拌一面導入氮氣,將燒瓶內之液溫保持於65℃附近進行6小時聚合反應,調製(甲基)丙烯酸系聚合物(a)溶液(40質量%)。該(甲基)丙烯酸系聚合物(a)之根據Fox式算出之玻璃轉移溫度(Tg)為-68℃,重量平均分子量(Mw)為55萬。 96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) were added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel. 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator and 150 parts by mass of ethyl acetate, nitrogen gas was introduced while slowly stirring, and the liquid temperature in the flask was maintained at around 65 ° C. The polymerization reaction was carried out for an hour to prepare a (meth)acrylic polymer (a) solution (40% by mass). The glass transition temperature (Tg) of the (meth)acrylic polymer (a) calculated according to the Fox formula was -68 ° C, and the weight average molecular weight (Mw) was 550,000.
將乙酸乙酯100質量份、甲基丙烯酸二環戊基酯(DCPMA)(商品名:FA-513M,日立化成工業公司製造)60質量份、甲基丙烯酸甲酯(MMA)40質量份以及作為鏈轉移劑之α-硫代甘油3.5質量份投入至具 備攪拌葉片、溫度計、氮氣導入管、冷凝器、滴液漏斗之4口燒瓶中。繼而,於70℃下於氮氣氣氛下攪拌1小時之後,投入作為熱聚合起始劑之2,2'-偶氮雙異丁腈0.2質量份,於70℃下反應2小時,繼而於80℃下反應5小時。所得之(甲基)丙烯酸系聚合物1之根據Fox式算出之玻璃轉移溫度(Tg)為144℃,重量平均分子量(Mw)為4200。 100 parts by mass of ethyl acetate, 60 parts by mass of dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 40 parts by mass of methyl methacrylate (MMA), and 3.5 parts by mass of α-thioglycerol of the chain transfer agent A four-necked flask of a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel was prepared. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 2 hours, followed by 80 ° C. The reaction was carried out for 5 hours. The glass transition temperature (Tg) calculated from the Fox equation of the obtained (meth)acryl-based polymer 1 was 144 ° C, and the weight average molecular weight (Mw) was 4,200.
將乙酸乙酯100質量份、甲基丙烯酸環己酯(CHMA)60質量份、甲基丙烯酸甲酯(MMA)40質量份以及作為鏈轉移劑之α-硫代甘油3.5質量份投入至具備攪拌葉片、溫度計、氮氣導入管、冷凝器、滴液漏斗之4口燒瓶中。繼而,於70℃下於氮氣氣氛下攪拌1小時之後,投入作為熱聚合起始劑之2,2'-偶氮雙異丁腈0.2質量份,於70℃下反應2小時,繼而於80℃下反應5小時。所得之(甲基)丙烯酸系聚合物2之根據Fox式算出之玻璃轉移溫度(Tg)為81℃,重量平均分子量(Mw)為4100。 100 parts by mass of ethyl acetate, 60 parts by mass of cyclohexyl methacrylate (CHMA), 40 parts by mass of methyl methacrylate (MMA), and 3.5 parts by mass of α-thioglycerol as a chain transfer agent were supplied with stirring. A four-necked flask of a blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Then, after stirring at 70 ° C for 1 hour in a nitrogen atmosphere, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a thermal polymerization initiator was introduced, and the reaction was carried out at 70 ° C for 2 hours, followed by 80 ° C. The reaction was carried out for 5 hours. The glass transition temperature (Tg) calculated from the Fox equation of the obtained (meth)acrylic polymer 2 was 81 ° C, and the weight average molecular weight (Mw) was 4,100.
向用甲苯將上述(甲基)丙烯酸系聚合物(a)溶液(40質量%)稀釋至20質量%而成之溶液500質量份(固形物成分100質量份)中加入0.25質量份(甲基)丙烯酸系聚合物1,作為離子性化合物之1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺(BMP-TFSI)(商品名:CIL-312,Japan Carlit公司製造,25℃下為液態)0.5質量份,作為具有聚氧伸烷基鏈之化合物之具有聚氧伸烷基鏈之有機聚矽氧烷(商品名:KF6004,信越化學工業公司製造)0.05質量份,作為交聯劑之CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造)0.33質量份(固形物成分0.25質量 份),作為交聯觸媒之二月桂酸二辛基錫之固形物成分1質量%的乙酸乙酯溶液3質量份,於25℃下進行約5分鐘混合攪拌,調製黏著劑組合物(1)。 To 500 parts by mass of the solution (solid content: 100 parts by mass) of the solution obtained by diluting the (meth)acrylic polymer (a) solution (40% by mass) to 20% by mass with toluene, 0.25 parts by mass (methyl group) was added. Acrylic polymer 1, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) as an ionic compound (trade name: CIL-312, Japan Carlit) The company manufactures 0.5 parts by mass at 25 ° C, and is an organopolyoxane having a polyoxyalkylene chain as a compound having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 A mass fraction of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.33 parts by mass (solid form) Composition 0.25 mass 3 parts by mass of an ethyl acetate solution of 1% by mass of a solid content of dioctyltin dilaurate as a cross-linking catalyst, and mixing and stirring at 25 ° C for about 5 minutes to prepare an adhesive composition (1) ).
將上述黏著劑組合物(1)塗佈於作為支持體之聚乙烯薄膜(商品名:NSO Film,大倉工業公司製造,厚度150μm,表3中之「PE#150」)的電暈處理面,於80℃下加熱1分鐘,形成厚度25μm之黏著劑層。繼而,於作為剝離襯墊之上述黏著劑層之表面貼合聚乙烯薄膜(商品名:NSO FILM,大倉工業公司製造,厚度150μm)之與電暈處理面相反之一面,製作黏著片。 The adhesive composition (1) was applied to a corona-treated surface of a polyethylene film (trade name: NSO Film, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm, "PE #150" in Table 3) as a support. The film was heated at 80 ° C for 1 minute to form an adhesive layer having a thickness of 25 μm. Then, on the surface of the above-mentioned adhesive layer as a release liner, a surface of a polyethylene film (trade name: NSO FILM, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm) opposite to the corona-treated surface was bonded to each other to prepare an adhesive sheet.
使用0.15質量份上述(甲基)丙烯酸系聚合物1代替使用0.25質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例1同樣之方式調製黏著劑組合物(2)。 The adhesive composition (2) was prepared in the same manner as in Example 1 except that 0.15 parts by mass of the above (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.
使用上述黏著劑組合物(2)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (2) was used instead of the above-mentioned adhesive composition (1).
使用0.08質量份上述(甲基)丙烯酸系聚合物1代替使用0.25質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例1同樣之方式調製黏著劑組合物(3)。 The adhesive composition (3) was prepared in the same manner as in Example 1 except that 0.08 parts by mass of the above (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.
使用上述黏著劑組合物(3)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (3) was used instead of the above-mentioned adhesive composition (1).
使用0.25質量份六亞甲基二異氰酸酯之異氰脲酸酯體(商品名:CORONATE HX,日本聚胺酯工業公司製造)代替使用0.33質量份上述CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),除此以外以與實施例1同樣之方式調製黏著劑組合物(4)。 Instead of using 0.33 parts by mass of the above CORONATE L (trimethylolpropane/toluene diisocyanate trimer), 0.25 parts by mass of an isocyanurate body of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) was used. The adhesive composition (4) was prepared in the same manner as in Example 1 except that the solid content of the product was 75 mass% of an ethyl acetate solution (manufactured by Nippon Polyurethane Co., Ltd.).
使用上述黏著劑組合物(4)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (4) was used instead of the above-mentioned adhesive composition (1).
使用0.75質量份1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺(商品名:CIL-312,Japan Carlit公司製造,25℃下為液態)代替使用0.5質量份上述1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺(BMP-TFSI)(商品名:CIL-312,Japan Carlit公司製造,25℃下為液態),除此以外以與實施例4同樣之方式調製黏著劑組合物(5)。 Using 0.75 parts by mass of 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C) instead of using 0.5 mass The above 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C), Otherwise, the adhesive composition (5) was prepared in the same manner as in Example 4.
使用上述黏著劑組合物(5)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (5) was used instead of the above-mentioned adhesive composition (1).
使用0.1質量份作為具有聚氧伸烷基鏈之化合物之具有聚氧伸烷基鏈之有機聚矽氧烷(商品名:KF6004,信越化學工業公司製造),代替使用0.05質量份上述作為具有聚氧伸烷基鏈之化合物之具有聚氧伸烷基鏈之有機聚矽氧烷(商品名:KF6004,信越化學工業公司製造), 除此以外以與實施例4同樣之方式調製黏著劑組合物(6)。 0.1 parts by mass of an organopolysiloxane having a polyoxyalkylene chain as a compound having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.), instead of using 0.05 parts by mass as described above An organopolyoxane having a polyoxyalkylene chain of a compound having an alkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.), The adhesive composition (6) was prepared in the same manner as in Example 4 except the above.
使用上述黏著劑組合物(6)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (6) was used instead of the above-mentioned adhesive composition (1).
使用0.67質量份CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),代替使用0.33質量份上述CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),除此以外以與實施例2同樣之方式調製黏著劑組合物(7)。 Using 0.67 parts by mass of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.), instead of using 0.33 parts by mass of the above CORONATE L (Adhesive agent was prepared in the same manner as in Example 2 except that the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct was 75 mass% in ethyl acetate solution, manufactured by Japan Polyurethane Industrial Co., Ltd.) Composition (7).
使用上述黏著劑組合物(7)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (7) was used instead of the above-mentioned adhesive composition (1).
使用0.67質量份CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),代替使用0.33質量份上述CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),除此以外以與實施例3同樣之方式調製黏著劑組合物(8)。 Using 0.67 parts by mass of CORONATE L (75% by mass of a solid content of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Japan Polyurethane Industry Co., Ltd.), instead of using 0.33 parts by mass of the above CORONATE L (Adhesive agent was prepared in the same manner as in Example 3 except that the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct was 75 mass% in ethyl acetate solution, manufactured by Japan Polyurethane Industrial Co., Ltd.) Composition (8).
使用上述黏著劑組合物(8)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (8) was used instead of the above-mentioned adhesive composition (1).
使用0.15質量份(甲基)丙烯酸系聚合物2,代替使用0.15質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例2同樣之方式調製黏著劑組合物(9)。 The adhesive composition (9) was prepared in the same manner as in Example 2 except that 0.15 parts by mass of the (meth)acrylic polymer 2 was used instead of 0.15 parts by mass of the above (meth)acrylic polymer 1.
使用上述黏著劑組合物(9),代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (9) was used instead of the above-mentioned adhesive composition (1).
使用0.08質量份(甲基)丙烯酸系聚合物2,代替使用0.15質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例3同樣之方式調製黏著劑組合物(10)。 The adhesive composition (10) was prepared in the same manner as in Example 3 except that 0.08 parts by mass of the (meth)acrylic polymer 2 was used instead of 0.15 parts by mass of the above (meth)acrylic polymer 1.
使用上述黏著劑組合物(10),代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (10) was used instead of the above-mentioned adhesive composition (1).
使用0.1質量份聚氧伸丙基-聚氧伸乙基-聚氧伸丙基嵌段共聚物(商品名:Pluronic 25R-2,ADEKA公司製造),代替使用0.05質量份上述作為具有聚氧伸烷基鏈之化合物之具有聚氧伸烷基鏈之有機聚矽氧烷(商品名:KF6004,信越化學工業公司製造),除此以外以與實施例2同樣之方式調製黏著劑組合物(11)。 0.1 parts by mass of polyoxyl-propyl-polyoxyethylidene-polyoxypropyl propyl block copolymer (trade name: Pluronic 25R-2, manufactured by ADEKA Co., Ltd.), instead of using 0.05 parts by mass as described above as having a polyoxygen extension An adhesive composition (11) was prepared in the same manner as in Example 2 except that the organopolysiloxane having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the compound of the alkyl chain. ).
使用上述黏著劑組合物(11),代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (11) was used instead of the above-mentioned adhesive composition (1).
使用0.5質量份1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺(EMI-FSI)(第一工業製藥公司製造,IL-110),代替使用0.5質量份上述1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺(BMP-TFSI)(商品名:CIL-312,Japan Carlit公司製造,25℃下為液態),除此以外以與實施例2同樣之方式調製黏著劑組合物(12)。 0.5 parts by mass of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine (EMI-FSI) (manufactured by First Industrial Pharmaceutical Co., Ltd., IL-110) was used instead of 0.5 part by mass of the above 1 -butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (BMP-TFSI) (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., liquid at 25 ° C), except The adhesive composition (12) was prepared in the same manner as in Example 2.
使用上述黏著劑組合物(12),代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (12) was used instead of the above-mentioned adhesive composition (1).
不使用0.25質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例1同樣之方式調製黏著劑組合物(13)。 The adhesive composition (13) was prepared in the same manner as in Example 1 except that 0.25 parts by mass of the above (meth)acrylic polymer 1 was not used.
使用上述黏著劑組合物(13)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (13) was used instead of the above-mentioned adhesive composition (1).
使用1.0質量份(甲基)丙烯酸系聚合物1代替使用0.25質量份上述(甲基)丙烯酸系聚合物1,除此以外以與實施例1同樣之方式調製黏著劑組合物(14)。 The adhesive composition (14) was prepared in the same manner as in Example 1 except that 1.0 part by mass of the (meth)acrylic polymer 1 was used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1.
使用上述黏著劑組合物(14)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (14) was used instead of the above-mentioned adhesive composition (1).
塗佈於聚對苯二甲酸乙二酯薄膜(商品名:Lumirror S-105,東麗薄膜加工公司製造,厚度75μm,表3中之「PET#75」)之電暈處理面代替上述聚乙烯薄膜(商品名:NSO FILM,大倉工業公司製造,厚度150μm),於80℃下加熱1分鐘,形成厚度20μm之黏著劑層,除此以外以與實施例7同樣之方式製作黏著片。 The corona treatment surface coated on a polyethylene terephthalate film (trade name: Lumirror S-105, manufactured by Toray Film Processing Co., Ltd., thickness 75 μm, "PET #75" in Table 3) was used instead of the above polyethylene. An adhesive sheet was produced in the same manner as in Example 7 except that a film (trade name: NSO FILM, manufactured by Okura Industrial Co., Ltd., thickness: 150 μm) was heated at 80 ° C for 1 minute to form an adhesive layer having a thickness of 20 μm.
不使用上述(甲基)丙烯酸系聚合物1、1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺(商品名:CIL-312,Japan Carlit公司製造,25℃下為液態)、作為具有聚氧伸烷基鏈之化合物之具有聚氧伸烷基鏈之有機聚矽氧烷(商品名:KF6004,信越化學工業公司製造),除此以外以與實施例1同樣之方式調製黏著劑組合物(15)。 The above (meth)acrylic polymer 1, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine (trade name: CIL-312, manufactured by Japan Carlit Co., Ltd., 25) was not used. An organopolysiloxane having a polyoxyalkylene chain (trade name: KF6004, manufactured by Shin-Etsu Chemical Co., Ltd.) as a compound having a polyoxyalkylene chain, and other examples 1 The adhesive composition (15) was prepared in the same manner.
使用上述黏著劑組合物(15)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (15) was used instead of the above-mentioned adhesive composition (1).
使用0.15質量份(甲基)丙烯酸系聚合物1代替使用0.25質量份上述(甲基)丙烯酸系聚合物1,並且使用1.0質量份六亞甲基二異氰酸酯之異氰脲酸酯體(商品名:CORONATE HX,日本聚胺酯工業公司製造)代替0.33質量份作為交聯劑之CORONATE L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之固形物成分75質量%之乙酸乙酯溶液,日本聚胺酯工業公司製造),除此以外以與實施例1同樣之方式調製黏著劑組合物(16)。 0.15 parts by mass of (meth)acrylic polymer 1 is used instead of 0.25 parts by mass of the above (meth)acrylic polymer 1, and 1.0 part by mass of isocyanurate body of hexamethylene diisocyanate is used (trade name) :CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.) in place of 0.33 parts by mass of CORONATE L (75% by mass of the solid content of the trimethylolpropane/toluene diisocyanate trimer adduct as a crosslinking agent) The adhesive composition (16) was prepared in the same manner as in Example 1 except that the Japan Polyurethane Industry Co., Ltd. was used.
使用上述黏著劑組合物(16)代替上述黏著劑組合物(1),除此以外以與實施例1同樣之方式製作黏著片。 An adhesive sheet was produced in the same manner as in Example 1 except that the above-mentioned adhesive composition (16) was used instead of the above-mentioned adhesive composition (1).
聚合物及(甲基)丙烯酸系共聚物之重量平均分子量(Mw)係使用GPC裝置(東曹公司製造,HLC-8220GPC)進行測定。測定條件如下所述,並藉由標準聚苯乙烯換算求出分子量。‧樣品濃度:0.2質量%(四氫呋喃(THF)溶液)‧樣品注入量:10μl‧洗脫液:THF‧流速:0.6ml/min‧測定溫度:40℃‧管柱: 樣品柱:TSK guard column Super HZ-H(1根)+TSK gel Super HZM-H(2根) The weight average molecular weight (Mw) of the polymer and the (meth)acrylic copolymer was measured using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8220GPC). The measurement conditions were as follows, and the molecular weight was determined by standard polystyrene conversion. ‧ Sample concentration: 0.2% by mass (tetrahydrofuran (THF) solution) ‧ Sample injection amount: 10 μl ‧ Eluent: THF ‧ Flow rate: 0.6 ml / min ‧ Measurement temperature: 40 ° C ‧ Column: Sample column: TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2)
參照管柱:TSK gel Super H-RC(1根)‧檢測器:差示折射計(RI) Reference column: TSK gel Super H-RC (1) ‧ Detector: Differential Refractometer (RI)
溶劑不溶成分率(凝膠率)藉由將重量W1之測定樣品用四氟乙烯樹脂製多孔片包起來並於室溫下於乙酸乙酯中浸漬1週之後,乾燥該測定樣品並測量乙酸乙酯不溶解成分之重量W2,將W1及W2代入下式而求出:溶劑不溶成分率(凝膠率)[質量%]=W2/W1×100。 Solvent-insoluble component ratio (gel ratio) After the measurement sample of the weight W1 was wrapped with a porous sheet made of tetrafluoroethylene resin and immersed in ethyl acetate for 1 week at room temperature, the measurement sample was dried and the acetic acid B was measured. The weight W2 of the ester-insoluble component was determined by substituting W1 and W2 into the following formula: solvent insoluble component ratio (gel fraction) [% by mass] = W2 / W1 × 100.
更具體而言,可按以下方法測定溶劑不溶成分率(凝膠率)。即,將約0.1g測定樣品用平均孔徑0.2μm之四氟乙烯樹脂製多孔片包成束口袋狀,用風箏線將口綁緊。預先測量四氟乙烯樹脂製多孔片與風箏線之合計質量Wa(mg)。並且測量小包之質量(黏著劑層與小包之合計質量)Wb(mg)。將該小包放入至容量50mL之螺旋管(1個小包使用1根螺旋管),用乙酸乙酯填滿該螺旋管。將其於室溫(典型而言為23℃)下靜置7天之後,將上述小包取出於120℃下乾燥2小時,測量乾燥後之小包之質量Wc(mg)。該黏著劑層之溶劑不溶成分率(凝膠率)(質量%) 藉由將上述Wa、Wb及Wc代入下式而求出: 溶劑不溶成分率(凝膠率)[質量%]=(Wc-Wa)/(Wb-Wa)×100。 More specifically, the solvent insoluble component ratio (gel fraction) can be measured by the following method. Specifically, about 0.1 g of the measurement sample was wrapped in a bundle of tetrafluoroethylene resin having an average pore diameter of 0.2 μm, and the mouth was tied with a kite string. The total mass Wa (mg) of the porous sheet made of tetrafluoroethylene resin and the kite line was measured in advance. And the mass of the packet (the total mass of the adhesive layer and the packet) Wb (mg) was measured. The packet was placed in a spiral tube having a capacity of 50 mL (one spiral was used for one packet), and the spiral tube was filled with ethyl acetate. After allowing to stand at room temperature (typically 23 ° C) for 7 days, the above-mentioned packet was taken out and dried at 120 ° C for 2 hours, and the mass Wc (mg) of the dried packet was measured. Solvent-insoluble component ratio (gel fraction) (% by mass) of the adhesive layer By substituting the above Wa, Wb, and Wc into the following equation: Solvent-insoluble component ratio (gel fraction) [% by mass] = (Wc - Wa) / (Wb - Wa) × 100.
作為上述四氟乙烯樹脂製多孔片,可使用日東電工股份有限公司製造之商品名「NITOFLON(註冊商標)NTF1122」。另外,本發明之黏著劑層之溶劑不溶成分率為50~90質量%,較佳為55~87質量%,更佳為60~85質量%。若溶劑不溶成分率超過90質量%,則接著強度(黏著力)降低,於低於50質量%之情形,存在黏著劑(層)之凝聚力降低、產生糊劑殘留之可能性。另外,關於溶劑不溶成分率之評價方法,根據下述之實施例中記載之方法、條件進行測定。 As the porous sheet made of the above-mentioned tetrafluoroethylene resin, the trade name "NITOFLON (registered trademark) NTF1122" manufactured by Nitto Denko Corporation can be used. Further, the solvent-insoluble component ratio of the adhesive layer of the present invention is 50 to 90% by mass, preferably 55 to 87% by mass, more preferably 60 to 85% by mass. When the solvent-insoluble component ratio exceeds 90% by mass, the strength (adhesion) decreases, and when it is less than 50% by mass, the cohesive force of the adhesive (layer) may decrease and the paste may remain. Further, the method for evaluating the solvent insoluble component ratio was measured according to the methods and conditions described in the following examples.
將各實施例及比較例之黏著片於23℃×50%RH之環境下放置2小時之後,剝離隔離體,用表面電阻率測定裝置(三菱化學公司製造,Hiresta UP MCP-HT450型)測定黏著劑表面(糊面)之表面電阻率。以施加電壓100V、施加時間30秒進行。另外,本發明之黏著劑層之表面電阻率為103~1013Ω/□,較佳為104~1013Ω/□,更佳為106~1013Ω/□。若在上述範圍內,則可抑制剝離靜電壓,即可賦予抗靜電性,較為有用。 After the adhesive sheets of the respective examples and the comparative examples were allowed to stand in an environment of 23 ° C × 50% RH for 2 hours, the separator was peeled off, and adhesion was measured by a surface resistivity measuring device (manufactured by Mitsubishi Chemical Corporation, Hiresta UP MCP-HT450 type). Surface resistivity of the surface of the agent (pasta). The application was carried out with a voltage of 100 V and an application time of 30 seconds. Further, the surface resistivity of the adhesive layer of the present invention is 10 3 to 10 13 Ω/□, preferably 10 4 to 10 13 Ω/□, more preferably 10 6 to 10 13 Ω/□. When it is in the above range, it is useful to suppress the peeling static voltage and to impart antistatic properties.
將各實施例及比較例之黏著片切割成寬度10mm、長度60mm之尺寸,將剝離襯墊剝離之後,用2kg手壓輥壓接於玻璃(松浪硝子股份有限公司製造之商品名「MICROSLIDE GLASS」,寬度:70mm、長度:100mm、厚度:1.3mm)之表面,製作評價樣品。 The adhesive sheets of the respective examples and comparative examples were cut into a size of 10 mm in width and 60 mm in length, and the release liner was peeled off, and then pressed against a glass with a 2 kg hand roller (the product name "MICROSLIDE GLASS" manufactured by Matsunaga Glass Co., Ltd." The surface of the width: 70 mm, length: 100 mm, thickness: 1.3 mm), and an evaluation sample was produced.
上述層壓後,於23℃×50%RH之環境下放置30分鐘之後,將固定負載(3g)設置於黏著片1之單側之端部。以剝離角度成為90°之方式以固定負載開始剝離膠帶樣品。以長度10mm作為剩餘長度,測定直至剩餘之長度50mm之部分全部剝離為止之時間。測定係於23℃ ×50%RH之環境下進行。 After the above lamination, after standing for 30 minutes in an environment of 23 ° C × 50% RH, a fixed load (3 g) was placed on the one end side of the adhesive sheet 1. The tape sample was peeled off at a fixed load so that the peeling angle became 90°. The length of 10 mm was used as the remaining length, and the time until the remaining portion of 50 mm in length was peeled off was measured. The measurement is at 23 ° C It is carried out under the environment of ×50% RH.
於本發明中,固定負載下之剝離時間為2分鐘以上之評價為良好,未達2分鐘之評價為不良。若上述剝離時間為2分鐘以上,則具有可防止藥液浸入之接著性(密著性),較為有用。 In the present invention, the evaluation of the peeling time under a fixed load of 2 minutes or more was good, and the evaluation of less than 2 minutes was bad. When the peeling time is 2 minutes or longer, it is useful to prevent adhesion (adhesion) of the chemical solution.
將黏著片1切割成寬度70mm、長度120mm之尺寸,將剝離襯墊剝離之後,用手壓輥壓接於預先進行除靜電之玻璃20(松浪硝子股份有限公司製造之商品名「MICROSLIDE GLASS」,寬度:70mm、長度:100mm、厚度:1.3mm)之表面,以使單側之端部突出20mm。 The adhesive sheet 1 was cut into a size of 70 mm in width and 120 mm in length, and the release liner was peeled off, and then pressed by a hand-pressing roll to a glass 20 (Microslonide GLASS) manufactured by Songlang Glass Co., Ltd. The surface of the width: 70 mm, length: 100 mm, thickness: 1.3 mm) so that the end of one side protrudes by 20 mm.
於23℃×50%RH之環境下放置一天之後,如圖5所示將樣品設置於樣品固定台30之特定位置。將突出20mm之單側之端部固定於自動捲取機,以剝離角度150°、拉伸速度10m/min之方式進行剝離。用固定於特定位置之電位測定器40(春日電機公司製造,KSD-0103)測定此時所產生之玻璃20之表面之電位,作為剝離靜電壓之值。測定係於23℃×50%RH之環境下進行。另外,作為剝離靜電壓,絕對值較佳為1.0kV以下,更佳為0.9kV以下。若在前述範圍內,則可防止由靜電引起之集塵、或靜電危害,較為有用。 After standing for one day in an environment of 23 ° C × 50% RH, the sample was placed at a specific position of the sample fixing table 30 as shown in FIG. The end portion of the one side protruding by 20 mm was fixed to an automatic winder, and peeling was performed at a peeling angle of 150° and a stretching speed of 10 m/min. The potential of the surface of the glass 20 produced at this time was measured by a potential measuring device 40 (KSD-0103, manufactured by Kasuga Electric Co., Ltd.) fixed at a specific position as a value of the peeling static voltage. The measurement was carried out in an environment of 23 ° C × 50% RH. Further, as the peeling static voltage, the absolute value is preferably 1.0 kV or less, more preferably 0.9 kV or less. If it is within the above range, it is useful to prevent dust collection or electrostatic damage caused by static electricity.
如上述表3所示,確認到於所有實施例中,黏著劑層之溶劑不溶成分率與表面電阻率均在所期望之範圍內,能夠抑制剝離靜電壓,即抗靜電性優異,而且接著可靠性優異,即防藥液浸入性亦優異。 As shown in the above Table 3, it was confirmed that in all of the examples, the solvent insoluble component ratio and the surface resistivity of the adhesive layer were within a desired range, and it was possible to suppress the peeling static voltage, that is, excellent in antistatic property, and then be reliable. Excellent in properties, that is, excellent in immersion resistance.
另一方面,比較例1確認到表面電阻率超過1013Ω/□,亦未能充分抑制剝離靜電壓,抗靜電性較差,比較例2確認到黏著劑層之溶劑不溶成分率超過90質量%,接著可靠性不充分,防藥液浸入性較差。 On the other hand, in Comparative Example 1, it was confirmed that the surface resistivity exceeded 10 13 Ω/□, and the peeling static voltage was not sufficiently suppressed, and the antistatic property was inferior. In Comparative Example 2, it was confirmed that the solvent insoluble component ratio of the adhesive layer exceeded 90% by mass. Then, the reliability is insufficient, and the immersion resistance of the chemical solution is poor.
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TWI609058B (en) * | 2015-07-10 | 2017-12-21 | Lg化學股份有限公司 | Crosslinkable composition |
TWI797517B (en) * | 2020-12-11 | 2023-04-01 | 達邁科技股份有限公司 | Antistatic Adhesive Sheet |
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JP6815740B2 (en) * | 2016-03-29 | 2021-01-20 | 日東電工株式会社 | Masking sheet |
KR101862343B1 (en) * | 2016-09-26 | 2018-05-29 | 상명대학교 천안산학협력단 | Anion-exchange ionomer solution for polymer pulverization and method of manufacturing the same |
KR102366509B1 (en) * | 2018-06-15 | 2022-02-23 | 디아이씨 가부시끼가이샤 | Adhesive composition and laminated film using same |
KR101955595B1 (en) * | 2018-09-14 | 2019-03-07 | 노바테크인더스트리 주식회사 | Curved Display Pannel Etching System |
JP2021006491A (en) * | 2019-06-27 | 2021-01-21 | 日東電工株式会社 | Low-e glass plate, protective sheet for low-e glass plate, and method of using the same |
CN114634773A (en) * | 2020-12-16 | 2022-06-17 | 达迈科技股份有限公司 | Antistatic adhesive sheet |
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TWI609058B (en) * | 2015-07-10 | 2017-12-21 | Lg化學股份有限公司 | Crosslinkable composition |
US10851268B2 (en) | 2015-07-10 | 2020-12-01 | Lg Chem, Ltd. | Compound |
US10883020B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Pressure-sensitive adhesive polarizing plate |
US10883019B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Cross-linkable composition |
US10889735B2 (en) | 2015-07-10 | 2021-01-12 | Lg Chem, Ltd. | Cross-linkable composition |
TWI797517B (en) * | 2020-12-11 | 2023-04-01 | 達邁科技股份有限公司 | Antistatic Adhesive Sheet |
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