TWI634178B - Adhesive composition, adhesive and adhesive sheet - Google Patents
Adhesive composition, adhesive and adhesive sheet Download PDFInfo
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- TWI634178B TWI634178B TW103102888A TW103102888A TWI634178B TW I634178 B TWI634178 B TW I634178B TW 103102888 A TW103102888 A TW 103102888A TW 103102888 A TW103102888 A TW 103102888A TW I634178 B TWI634178 B TW I634178B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
本發明提供一種對於偏光板等的光學構件的密合性高，耐久性優異的黏接性組合物、黏接劑以及黏接片。為瞭解決上述課題，提供一種黏接性組合物，包含：作為構成聚合物的單體單元，含有具有脂環式結構的單體的(甲基)丙烯酸酯聚合物(A)，其重量平均分子量為80萬~300萬；架橋劑(B)；和矽烷偶聯劑(C)，其具有作為與有機材料反應的官能基的巰基。 The present invention provides an adhesive composition, an adhesive, and an adhesive sheet having high adhesion to optical members such as polarizing plates and excellent durability. In order to solve the above-mentioned problems, an adhesive composition is provided which includes, as a monomer unit constituting a polymer, a (meth) acrylate polymer (A) containing a monomer having an alicyclic structure, and having an average weight The molecular weight is from 800,000 to 3 million; the bridging agent (B); and the silane coupling agent (C) have a mercapto group as a functional group that reacts with an organic material.
Description
本發明是關於一種黏接性組合物、黏接劑(使黏接性組合物架橋的材料)以及黏接片，特別是關於一種適合作為偏光板等的光學構件用的黏接性組合物、黏接劑以及黏接片。 The present invention relates to an adhesive composition, an adhesive (a material that bridges the adhesive composition) and an adhesive sheet, and more particularly to an adhesive composition suitable for use as an optical member such as a polarizing plate, Adhesives and adhesive sheets.
近年在各種電子設備中，多使用兼具顯示裝置與輸入手段的觸控面板。觸控面板的種類主要有電阻式、電容式、光學式以及超聲波式。電阻式觸控面板有模擬數據電阻式以及母體電阻式。電容式觸控面板有表面型以及投影型。 In recent years, in various electronic devices, a touch panel having both a display device and an input means has been used. The types of touch panels are mainly resistive, capacitive, optical, and ultrasonic. Resistive touch panels include analog data resistive and matrix resistive. Capacitive touch panels are available in surface and projection types.
最近受到注目的智慧手機、平板電腦終端等移動式電子設備的觸控面板，多使用投影型電容式的觸控面板。作為上述移動電子機器的投影型電容式觸控面板，例如，有研究提出了從下向上按順序層疊液晶顯示裝置(LCD)、黏接劑層、透明導電膜(摻雜錫之氧化銦：ITO)、玻璃基板、透明導電膜(ITO)、及強化玻璃等保護層的觸控面板。 Recently, the touch panels of mobile electronic devices such as smartphones and tablet terminals have attracted attention. Projection-type capacitive touch panels are mostly used. As a projection type capacitive touch panel of the above-mentioned mobile electronic device, for example, research has proposed that a liquid crystal display device (LCD), an adhesive layer, and a transparent conductive film (tin-doped indium oxide: ITO) are sequentially stacked from the bottom to the top. ), A glass substrate, a transparent conductive film (ITO), and a touch panel with a protective layer such as tempered glass.
作為上述構成液晶顯示裝置的光學構件，一般使用液晶組件。液晶組件一般是將形成配向層的兩片透明電極基板的配向層作為內側，通過間隔片，以形成所定間隔的方式，進行配置，將其周邊密封，在兩片透明電極基板之間挾持液晶材料的組件。通常，在液晶組件中的兩片透明電極基板的外 側，分別利用黏接劑而黏接偏光板。 As the optical member constituting the liquid crystal display device, a liquid crystal module is generally used. In a liquid crystal module, an alignment layer of two transparent electrode substrates forming an alignment layer is generally used as an inner side, and a spacer is arranged to form a predetermined interval. The periphery is sealed, and a liquid crystal material is held between the two transparent electrode substrates. s component. Generally, the outer surface of two transparent electrode substrates in a liquid crystal module On the side, the polarizing plates are adhered with an adhesive, respectively.
作為在觸控面板中所使用的黏接劑，例如，已知有專利文獻1所示的黏接劑該黏接劑，作為單體單元，相對於具有碳原子數4~14的烷基的烷基(甲基)丙烯酸酯100重量份，含有將含有羧基的單體0.2重量份~20重量份作為共聚合成分而成的(甲基)丙烯類聚合物，以及相對於(甲基)丙烯類聚合物100重量份，作為架橋劑，含有過氧化物0.02重量份~2重量份，及含有環氧類架橋劑0.005重量份~5重量份。 As an adhesive used in a touch panel, for example, an adhesive shown in Patent Document 1 is known. The adhesive is known as a monomer unit with respect to an alkyl group having 4 to 14 carbon atoms. 100 parts by weight of an alkyl (meth) acrylate, a (meth) propylene polymer containing 0.2 to 20 parts by weight of a carboxyl group-containing monomer as a copolymerization component, and a content of (meth) propylene 100 parts by weight of a polymer based polymer, containing 0.02 to 2 parts by weight of a peroxide, and 0.005 to 5 parts by weight of an epoxy-based bridging agent.
【專利文獻1】日本特開2009-242786號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-242786
在如上所述的觸控面板中，最近，使用採用了聚環烯烴類的偏光板的情況在増加，而且，隨著近年的移動電子設備的薄型化，偏光板也被薄型化。但是，聚環烯烴類的材料缺乏與黏接劑的密合性，而且薄型偏光板的收縮率高，因此專利文獻1等以往的黏接劑耐久性低，由於經時或者在高溫條件下、濕熱條件下，有容易發生浮起、剝離這一問題。 In the touch panel as described above, the use of a polycycloolefin-based polarizing plate has recently been increasing, and in accordance with the reduction in thickness of mobile electronic devices in recent years, the polarizing plate has also been reduced in thickness. However, polycycloolefin-based materials lack adhesion to the adhesive, and the thin polarizer has a high shrinkage rate. Therefore, conventional adhesives such as Patent Document 1 have low durability. Due to aging or under high temperature conditions, Under the hot and humid conditions, there is a problem that floating and peeling easily occur.
本發明是鑒於這樣的現狀而進行的，目的在於提供一種適用於偏光板等的光學構件時，密合性高，耐久性也優異的黏接性組合物、黏接劑以及黏接片。 The present invention has been made in view of such a situation, and an object thereof is to provide an adhesive composition, an adhesive, and an adhesive sheet having high adhesion and excellent durability when applied to an optical member such as a polarizing plate.
為了達成上述目的，第一，本發明提供一種黏接 性組合物，其特徵在於：包含：重量平均分子量為80萬~300萬的(甲基)丙烯酸酯聚合物(A)，其作為構成聚合物的單體單元，含有具有脂環式結構的單體；架橋劑(B)；矽烷偶聯劑(C)，其具有巰基作為與有機材料反應的官能基(發明1)。 To achieve the above object, first, the present invention provides an adhesive A composition containing (meth) acrylate polymer (A) having a weight average molecular weight of 800,000 to 3,000,000 as a monomer unit constituting the polymer, containing a monomer having an alicyclic structure. Body; bridging agent (B); silane coupling agent (C), which has a mercapto group as a functional group that reacts with an organic material (Invention 1).
在上述發明(發明1)中，上述黏接性組合物的(甲基)丙烯酸酯聚合物，在具有脂環式結構的同時，該黏接性組合物通過含有具有巰基的矽烷偶聯劑，由於其上升效果所得到的黏接劑，對於偏光板等的光學構件的密合性高，耐久性也優異。 In the above invention (Invention 1), the (meth) acrylate polymer of the adhesive composition has an alicyclic structure, and the adhesive composition contains a silane coupling agent having a mercapto group. The adhesive obtained by its raising effect has high adhesiveness to optical members such as polarizing plates and excellent durability.
在上述發明(發明1)中，上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~30質量%的具有上述脂環式結構的單體(發明2)。 In the above invention (Invention 1), the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 30% by mass of a monomer having the alicyclic structure.体 (Invention 2).
在上述發明(發明1，發明2)中，上述脂環式結構優選含有環己基骨架、雙環戊二烯骨架、金剛烷骨架或異冰片骨架(發明3)。 In the above invention (Invention 1, Invention 2), the alicyclic structure preferably contains a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, or an isobornyl skeleton (Invention 3).
在上述發明(發明1~發明3)中，上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，進一步優選含有0.1質量%~10質量%的具有羥基的單體(發明4)。 In the above invention (Invention 1 to Invention 3), the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, more preferably contains 0.1 to 10% by mass of a monomer having a hydroxyl group.体 (Invention 4).
在上述發明(發明1~發明4)中，上述(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選實質上不含有具有羧基的單體(發明5)。 In the above invention (Invention 1 to Invention 4), the (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably does not substantially contain a monomer having a carboxyl group (Invention 5).
在上述發明(發明1~發明5)中，上述架橋劑(B)優選為異氰酸酯類架橋劑(發明6)。 In the above invention (Invention 1 to Invention 5), the bridging agent (B) is preferably an isocyanate bridging agent (Invention 6).
在上述發明(發明1~發明6)中，上述黏接性組合物中上述矽烷偶聯劑(C)的含有量，相對於上述(甲基)丙烯酸酯 聚合物(A)100質量份，優選為0.01質量份~5質量份(發明7)。 In the above invention (Invention 1 to Invention 6), the content of the silane coupling agent (C) in the adhesive composition is relative to the (meth) acrylate 100 parts by mass of the polymer (A), preferably 0.01 to 5 parts by mass (Invention 7).
第二，本發明提供一種將上述黏接性組合物(發明1~發明7)進行架橋而成的黏接劑(發明8)。 Secondly, the present invention provides an adhesive (Invention 8) obtained by bridging the above-mentioned adhesive composition (Invention 1 to Invention 7).
第三，本發明提供一種黏接片，其特徵在於：為具有基材和黏接劑層的黏接片，上述黏接劑層由上述黏接劑(發明8)構成(發明9)。 Third, the present invention provides an adhesive sheet, which is an adhesive sheet having a base material and an adhesive layer, and the adhesive layer is composed of the adhesive (invention 8) (invention 9).
在上述發明(發明9)中，上述基材優選為光學構件(發明10)。 In the said invention (invention 9), it is preferable that the said base material is an optical member (invention 10).
在上述發明(發明10)中，上述光學構件優選為偏光板(發明11)。 In the said invention (invention 10), it is preferable that the said optical member is a polarizing plate (invention 11).
第四，本發明提供一種黏接片，其特徵在於：其具備兩片剝離片和以上述兩片剝離片的剝離面相接的方式挾持上述剝離片的黏接劑層，上述黏接劑層由上述黏接劑(發明8)構成(發明12)。 Fourth, the present invention provides an adhesive sheet, which is characterized in that it includes two release sheets and an adhesive layer holding the release sheet in a manner that the release surfaces of the two release sheets are in contact with each other, and the adhesive layer is It consists of the said adhesive agent (invention 8) (invention 12).
本發明中所述的黏接性組合物的(甲基)丙烯酸酯聚合物，在含有脂環式結構的同時，該黏接性組合物通過含有具有巰基的矽烷偶聯劑，所得到的的黏接劑對於偏光板等的光學構件的密合性高，耐久性也優異。 The (meth) acrylate polymer of the adhesive composition according to the present invention contains an alicyclic structure, and the adhesive composition contains a silane coupling agent having a mercapto group. The adhesive has high adhesion to optical members such as a polarizing plate, and is also excellent in durability.
1A，1B‧‧‧黏接片 1A, 1B ‧‧‧ Adhesive Sheet
11‧‧‧黏接劑層 11‧‧‧Adhesive layer
12，12a，12b‧‧‧剝離片 12, 12a, 12b ‧‧‧ peeling sheet
13‧‧‧基材 13‧‧‧ substrate
圖1為本發明第1實施形態所有關的黏接片的剖面圖。 FIG. 1 is a cross-sectional view of an adhesive sheet according to a first embodiment of the present invention.
圖2為本發明第2實施形態所有關的黏接片的剖面圖。 Fig. 2 is a sectional view of an adhesive sheet according to a second embodiment of the present invention.
以下，關於本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
〔黏接性組合物〕 [Adhesive composition]
本實施形態所有關的黏接性組合物(以下稱為「黏接性組合物P」)，作為構成聚合物的單體單元，含有(甲基)丙烯酸酯聚合物(A)、架橋劑(B)和具有作為與有機材料反應的官能基的巰基的矽烷偶聯劑(C)，上述(甲基)丙烯酸酯聚合物(A)的重量平均分子量為80萬~300萬，其含有具有脂環式結構的單體(含有脂環式結構單體)。另外，本說明書中，所說的(甲基)丙烯酸酯，指丙烯酸酯以及甲基丙烯酸酯的兩方。其他的類似用語也同樣。另外，在「聚合物」中，也包括「共聚物」的概念。 The adhesive composition according to this embodiment (hereinafter referred to as "adhesive composition P") contains, as a monomer unit constituting a polymer, a (meth) acrylate polymer (A) and a bridging agent ( B) and a silane coupling agent (C) having a mercapto group as a functional group that reacts with an organic material. The weight average molecular weight of the (meth) acrylate polymer (A) is 800,000 to 3 million, and it contains a lipid A monomer having a cyclic structure (containing an alicyclic structure monomer). In addition, in this specification, a (meth) acrylate means both an acrylate and a methacrylate. The same applies to other similar terms. In addition, the term "copolymer" is also included in "polymer".
(1)(甲基)丙烯酸酯聚合物(A) (1) (meth) acrylate polymer (A)
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有具有脂環式結構的單體。在上述黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)通過含有具有上述脂環式結構的單體，由於與上述矽烷偶聯劑(C)的上升效果，該(甲基)丙烯酸酯聚合物(A)即使不含有酸成分，所得到的黏接劑對於偏光板等的光學構件，特別是對於聚環烯烴類的光學構件以及透明導電膜的密合性高，耐久性也優異。據推測這是因為脂環式結構與光學構件以及透明導電膜的親和性或相互作用較強，由此矽烷偶聯劑(C)也有效發揮作用。另外，本發明不排除(甲基)丙烯酸酯聚合物(A)含有酸成分。 The (meth) acrylate polymer (A) contains a monomer having an alicyclic structure as a monomer unit constituting the polymer. In the adhesive composition P, the (meth) acrylate polymer (A) contains a monomer having the alicyclic structure, and the (meth) acrylate polymer (A) has the effect of increasing with the silane coupling agent (C). Base) Acrylic polymer (A) Even if it does not contain an acid component, the obtained adhesive has high adhesion and durability to optical members such as polarizing plates, especially to polycycloolefin-based optical members and transparent conductive films. It is also excellent in properties. It is presumed that this is because the alicyclic structure has strong affinity or interaction with the optical member and the transparent conductive film, and thus the silane coupling agent (C) also effectively functions. In addition, the present invention does not exclude that the (meth) acrylate polymer (A) contains an acid component.
脂環式結構的碳原子環，既可以為飽和結構的碳原子環，也可以為含有不飽和鍵的碳原子環。而且，脂環式結構既可以是單環的脂環式結構，也可以是雙環、三環等的多環 脂環式結構。脂環式結構的碳原子數優選為5~20，特別優選為6~15，進一步優選為7~12。 The carbon atom ring of the alicyclic structure may be a carbon atom ring of a saturated structure or a carbon atom ring containing an unsaturated bond. Moreover, the alicyclic structure may be a monocyclic alicyclic structure, or a bicyclic or tricyclic polycyclic ring Alicyclic structure. The number of carbon atoms of the alicyclic structure is preferably 5 to 20, particularly preferably 6 to 15, and even more preferably 7 to 12.
作為脂環式結構，例如，可以列舉含有環己基骨架、雙環戊二烯骨架、金剛烷骨架、異冰片骨架、環烷烴骨架(環庚烷骨架、環辛烷骨架、環壬烷骨架、環癸烷骨架、環十一烷骨架、環十二烷骨架等)、環烯烴骨架(環庚烯骨架、環辛烯骨架等)、降冰片烯骨架、降冰片二烯骨架、多環式骨架(立方烷骨架、五環癸烷骨架、房烷骨架等)、螺環骨架等的脂環式結構，其中，優選發揮更優異提高密合性及耐久性效果的含有環己基骨架、雙環戊二烯骨架、金剛烷骨架或異冰片骨架的脂環式結構。 Examples of the alicyclic structure include a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, an isobornyl skeleton, a cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane). Alkane skeleton, cycloundecane skeleton, cyclododecane skeleton, etc.), cycloolefin skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornene diene skeleton, polycyclic skeleton (cubic Among alicyclic structures such as alkane skeleton, pentacyclodecane skeleton, and aventane skeleton), and spirocyclic skeleton, among them, a cyclohexyl skeleton and a dicyclopentadiene skeleton are preferred, which exhibit more excellent adhesion and durability effects. , Alicyclic structure of adamantane skeleton or isobornyl skeleton.
作為上述含有脂環式結構的單體，優選含有上述骨架的(甲基)丙烯酸酯單體，具體而言，可以舉出(甲基)丙烯酸環己基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸二環戊烯氧乙基酯等，其中，優選發揮更優異提高密合性及耐久性效果的(甲基)丙烯酸環己基酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯或(甲基)丙烯酸異冰片酯。這些可以單獨使用一種，也可以組合兩種以上使用。 As the alicyclic structure-containing monomer, a (meth) acrylate monomer containing the above-mentioned skeleton is preferable, and specifically, cyclohexyl (meth) acrylate and dicyclopentyl (meth) acrylate are mentioned. , Adamantyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc., among them, preferred Cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate or isobornyl (meth) acrylate exhibiting more excellent effects of improving adhesion and durability. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~30質量%的上述含有脂環式結構的單體，特別是優選含有0.2質量%~25質量%，進一步優選含有0.5質量%~20質量%。含有脂環式結構單體的含有量如果小於0.1質量%，則難以得到上述的提高密合性及耐久 性的效果。脂環式結構含有單體的含有量如果超過30質量%，則作為光學用途有得不到優選的黏接性的情況。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 30% by mass of the above-mentioned alicyclic structure-containing monomer, and particularly preferably contains 0.2% by mass to 25 mass%, more preferably 0.5 mass% to 20 mass%. If the content of the alicyclic structure-containing monomer is less than 0.1% by mass, it is difficult to obtain the above-mentioned improvement in adhesion and durability. Sexual effect. When the content of the alicyclic structure-containing monomer exceeds 30% by mass, the adhesiveness may not be obtained for optical applications.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，除上述含有脂環式結構單體之外，還優選含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，特別是優選作為主成分而含有。 The (meth) acrylic acid ester polymer (A), as the monomer unit constituting the polymer, in addition to the alicyclic structure-containing monomer described above, it is also preferable that the Alkyl) acrylate is particularly preferably contained as a main component.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，通過含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，可以表現優選的黏接性。作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如，可以列舉出(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸丙基酯、(甲基)丙烯酸正丁基酯、(甲基)丙烯酸正戊基酯、(甲基)丙烯酸正己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸正癸基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂基等。其中，從更加提高黏接性的觀點考慮，優選烷基的碳原子數為1~4的(甲基)丙烯酸酯，特別優選(甲基)丙烯酸甲酯及(甲基)丙烯酸正丁酯。而且，這些可以單獨使用，也可以組合兩種以上使用。 The (meth) acrylic acid ester polymer (A), as a monomer unit constituting the polymer, can exhibit preferable adhesion by an alkyl (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group. Sex. Examples of the alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Ester, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isomethacrylate Octyl ester, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, (methyl) ) Acrylic stearyl and the like. Among them, (meth) acrylates having 1 to 4 carbon atoms in the alkyl group are preferred from the viewpoint of further improving the adhesiveness, and methyl (meth) acrylate and n-butyl (meth) acrylate are particularly preferred. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有20質量%~99.8質量%的烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，特別優選含有60質量%~99.5質量%，進一步優選含有75質量%~99質量%。 The (meth) acrylic acid ester polymer (A) is preferably a (meth) acrylic acid alkyl group having 1 to 20 carbon atoms having 20 to 99.8% by mass of an alkyl group as a monomer unit constituting the polymer. The ester particularly preferably contains 60 to 99.5% by mass, and more preferably 75 to 99% by mass.
另外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚 合物的單體單元，優選含有具有羥基的單體(含有羥基單體)。羥基與架橋劑(B)的反應性官能基，特別是與異氰酸酯類架橋劑的異氰酸酯基反應性高，由於這些反應，(甲基)丙烯酸酯聚合物(A)由於架橋劑(B)被有效地架橋。由此架橋結構所得到的黏接劑，耐久性更優異。 In addition, a (meth) acrylate polymer (A), as a constituent of the polymer The monomer unit of the composition preferably contains a monomer having a hydroxyl group (a hydroxyl-containing monomer). The reactive functional group of the hydroxyl group and the bridging agent (B), especially the isocyanate group of the isocyanate-based bridging agent, has high reactivity. Due to these reactions, the (meth) acrylate polymer (A) is effective due to the bridging agent (B) Ground bridge. The adhesive obtained by the bridge structure is more excellent in durability.
作為含羥基單體，例如，可以例舉(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸3-羥基丙基酯、(甲基)丙烯酸2-羥基丁基酯、(甲基)丙烯酸3-羥基丁基酯、(甲基)丙烯酸4-羥基丁基酯等的(甲基)丙烯酸羥基烷基酯等，其中，從羥基的反應性以及共聚合性的觀點考慮，優選(甲基)丙烯酸2-羥基乙基酯。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (methyl) ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. From the viewpoint of reactivity and copolymerizability, 2-hydroxyethyl (meth) acrylate is preferred. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有0.1質量%~10質量%的含有羥基單體，特別是優選含有0.2質量%~8質量%，進一步優選含有0.3質量%~5質量%。含有羥基單體的含有量在上述範圍，則所形成的架橋結構良好，所得到的黏接劑具有更優異的耐久性。含有羥基單體的含有量如果小於0.1質量%，則架橋點過少，難以得到提高耐久性的効果。另一方面，含有羥基單體的含有量如果超過10質量%，則架橋點過多，所得到的黏接劑有不柔軟，應力緩和性有降低的可能性。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably contains 0.1 to 10% by mass of a hydroxyl group-containing monomer, and particularly preferably contains 0.2 to 8% by mass. Further, It is preferably contained in an amount of 0.3 to 5% by mass. When the content of the hydroxyl group-containing monomer is within the above range, the formed bridging structure is good, and the obtained adhesive has more excellent durability. When the content of the hydroxyl-containing monomer is less than 0.1% by mass, the number of bridge points is too small, and it is difficult to obtain the effect of improving durability. On the other hand, if the content of the hydroxyl-containing monomer exceeds 10% by mass, there will be too many bridging points, and the resulting adhesive may not be soft and the stress relaxation properties may be reduced.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選實質上不含有具有羧基的單體(含有羧基單體)。通過實質上不含有具有酸成分的羧基的單體，可以抑制 所得到的黏接劑的貼附對象由於酸所產生的不良，例如即使為透明導電膜或金屬膜等的情況，也可以抑制它們由於酸所產生的不良。特別是，在貼附對象為透明導電膜的情況時，可以抑制該透明導電膜被腐食或該透明導電膜的電阻值發生變化。而且，像後述的矽烷偶聯劑(C)那樣，不受酸影響的聚合物也有效地發揮作用。另外，通過實質上不含有具有羧基的單體，可以防止該羧基阻礙上述含有羥基單體的羥基與架橋劑(B)，特別是與異氰酸酯類架橋劑的反應。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably does not substantially contain a monomer having a carboxyl group (a carboxyl group-containing monomer). By substantially not containing a monomer having a carboxyl group having an acid component, it is possible to suppress Defects caused by the acid due to the adhered object of the obtained adhesive can be suppressed by the acid even in the case of a transparent conductive film or a metal film, for example. In particular, when the object to be attached is a transparent conductive film, it is possible to suppress the transparent conductive film from being rotten or to change the resistance value of the transparent conductive film. In addition, like the silane coupling agent (C) described later, polymers that are not affected by acids also effectively function. In addition, by not substantially containing a monomer having a carboxyl group, it is possible to prevent the carboxyl group from hindering the reaction between the hydroxyl group of the hydroxyl-containing monomer and the bridging agent (B), and in particular, with an isocyanate-based bridging agent.
(甲基)丙烯酸酯聚合物(A)除上述單體以外，根據需要，還可以含有其他的單體。作為其他單體，可以為具有羥基及羧基以外的反應性官能基的單體(含有反應性官能基單體)，也可以為非反應性的單體。 The (meth) acrylate polymer (A) may contain other monomers in addition to the above-mentioned monomers as necessary. The other monomer may be a monomer having a reactive functional group other than a hydroxyl group and a carboxyl group (a reactive functional group-containing monomer), or may be a non-reactive monomer.
作為含有反應性官能基的單體，例如，可以舉出具有氨基的單體(含有氨基單體)等。作為含有氨基的單體，例如，可以舉出(甲基)丙烯酸氨基乙基酯、(甲基)丙烯酸正丁基氨基乙基酯等。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the reactive functional group-containing monomer include a monomer having an amino group (amino-containing monomer) and the like. Examples of the amino group-containing monomer include aminoethyl (meth) acrylate and n-butylaminoethyl (meth) acrylate. These may be used alone or in combination of two or more.
作為非反應性單體，例如，可以舉出(甲基)丙烯酸甲氧基甲基酯、(甲基)丙烯酸甲氧基乙基酯、(甲基)丙烯酸乙氧基甲基酯、(甲基)丙烯酸乙氧基乙基酯等的含有烷氧基烷基(甲基)丙烯酸酯、(甲基)丙烯酸苯基酯等的具有芳香族環的(甲基)丙烯酸酯、丙烯醯胺、甲基丙烯醯胺等的非架橋性的丙烯醯胺、(甲基)丙烯酸N，N-二甲基氨基乙基酯、(甲基)丙烯酸N，N-二甲基氨基丙基酯等的具有非架橋性的3級氨基的(甲基)丙烯酸酯、乙酸乙烯酯、苯乙烯等。這些可以單獨使用， 也可以組合兩種以上使用。 Examples of the non-reactive monomer include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and (meth) (Meth) acrylates, such as ethoxyethyl acrylate, alkoxyalkyl (meth) acrylates, phenyl (meth) acrylates, etc., (meth) acrylates having aromatic rings, acrylamide, Non-bridged acrylamide such as methacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. Non-bridged tertiary amino (meth) acrylate, vinyl acetate, styrene, etc. These can be used individually, Two or more of them may be used in combination.
(甲基)丙烯酸酯聚合物(A)的聚合方式，可以為無規共聚物，也可以為嵌段共聚物。 The polymerization method of the (meth) acrylate polymer (A) may be a random copolymer or a block copolymer.
(甲基)丙烯酸酯聚合物(A)的重量平均分子量為80萬~300萬，優選為90萬~250萬，特別優選為120萬~200萬。另外，本說明書中的重量平均分子量，為根據凝膠滲透色譜法(GPC)法所測定的聚苯乙烯換算的值。 The weight average molecular weight of the (meth) acrylate polymer (A) is 800,000 to 3 million, preferably 900,000 to 2.5 million, and particularly preferably 1.2 to 2 million. In addition, the weight average molecular weight in this specification is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method.
(甲基)丙烯酸酯聚合物(A)重量平均分子量如果小於80萬，則所得到的黏接劑的耐久性差。而且，(甲基)丙烯酸酯聚合物(A)的重量平均分子量如果超過300萬，則所得到的黏接劑的黏接力降低。 If the weight average molecular weight of the (meth) acrylate polymer (A) is less than 800,000, the durability of the obtained adhesive will be inferior. When the weight average molecular weight of the (meth) acrylate polymer (A) exceeds 3 million, the adhesive force of the obtained adhesive is reduced.
另外，在黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)可以單獨使用一種，也可以組合兩種以上使用。而且，黏接性組合物P可以進一步含有不含有上述含有脂環式結構單體作為構成單體單元的(甲基)丙烯酸酯聚合物。 In addition, in the adhesive composition P, a (meth) acrylate polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. Further, the adhesive composition P may further contain a (meth) acrylate polymer that does not contain the alicyclic structure-containing monomer as a constituent monomer unit.
(2)架橋劑(B) (2) bridging agent (B)
作為架橋劑(B)，只要為對於(甲基)丙烯酸酯聚合物(A)所具有的反應性官能基(羥基、氨基等)，具有反應性的架橋劑即可，例如可以舉出異氰酸酯類架橋劑、環氧類架橋劑、胺類架橋劑、三聚氰胺類架橋劑、氮丙啶類架橋劑、肼類架橋劑、醛類架橋劑、惡唑啉類架橋劑、金屬醇鹽類架橋劑、金屬螯合物類架橋劑、金屬鹽類架橋劑、銨鹽類架橋劑等。其中，異氰酸酯類架橋劑與矽烷偶聯劑(C)所具有的巰基的反應性優異，而且，在(甲基)丙烯酸酯聚合物(A)具有羥基的情況時，具有與該 羥基的反應性優異的長處。架橋劑(B)可以單獨使用一種，或者也可以組合兩種以上使用。 The bridging agent (B) may be a reactive bridging agent with respect to a reactive functional group (such as a hydroxyl group and an amino group) of the (meth) acrylate polymer (A), and examples thereof include isocyanates. Bridging agent, epoxy bridging agent, amine bridging agent, melamine bridging agent, aziridine bridging agent, hydrazine bridging agent, aldehyde bridging agent, oxazoline bridging agent, metal alkoxide bridging agent, Metal chelate bridging agent, metal salt bridging agent, ammonium salt bridging agent, etc. Among them, the isocyanate-based bridging agent has excellent reactivity with the mercapto group of the silane coupling agent (C), and when the (meth) acrylate polymer (A) has a hydroxyl group, Advantages of excellent reactivity of a hydroxyl group. The bridging agent (B) may be used singly or in combination of two or more kinds.
異氰酸酯類架橋劑為至少含有聚異氰酸酯化合物的架橋劑。作為聚異氰酸酯化合物，例如，可以舉出甲次苯基二異氰酸酯、二苯甲烷二異氰酸酯、伸二甲苯二異氰酸酯等的芳香族聚異氰酸酯、六亞甲基二異氰酸酯等的脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯甲烷二異氰酸酯等的脂環式聚異氰酸酯等、及這些的雙縮脲體、異氰酸酯體、進一步可以列舉乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的作為與含有低分子活性氫化合物的反應物的加和物體等。其中，從與羥基的反應性方面考慮，優選三羥甲基丙烷改性的芳香族聚異氰酸酯，特別是優選三羥甲基丙烷改性伸二甲苯二異氰酸酯。 The isocyanate-based bridging agent is a bridging agent containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as methylenephenyl diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; and isophor Alicyclic polyisocyanates, such as keto diisocyanate, hydrogenated diphenylmethane diisocyanate, etc., and these bisureton bodies, isocyanate bodies, and further include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, Additives such as castor oil and the like as reactants with low-molecular active hydrogen compounds. Among these, from the viewpoint of reactivity with a hydroxyl group, a trimethylolpropane-modified aromatic polyisocyanate is preferred, and a trimethylolpropane-modified xylene diisocyanate is particularly preferred.
黏接性組合物P中架橋劑(B)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.05質量份~3質量份，特別優選為0.08質量份~1.5質量份，進一步優選為0.3~1質量份。架橋劑(B)的含有量如果為0.05質量份以上，則能夠得到由該架橋劑(B)所產生的提高耐久性的功效。架橋劑(B)的含有量如果超過3質量份，則架橋的程度過度，所得到的黏接劑的黏接力有可能降低。 The content of the bridging agent (B) in the adhesive composition P is preferably 0.05 parts by mass to 3 parts by mass, and particularly preferably 0.08 parts by mass to 100 parts by mass of the (meth) acrylate polymer (A). 1.5 parts by mass, and more preferably 0.3 to 1 part by mass. When the content of the bridging agent (B) is 0.05 parts by mass or more, the durability-improving effect of the bridging agent (B) can be obtained. When the content of the bridging agent (B) exceeds 3 parts by mass, the degree of bridging is excessive, and the adhesive force of the obtained adhesive may be reduced.
(3)矽烷偶聯劑(C) (3) Silane coupling agent (C)
本實施形態中，矽烷偶聯劑(C)具有能與有機材料反應的官能基巰基。將上述黏接性組合物P架橋，矽烷偶聯劑(C)的巰基與架橋劑(B)的反應性官能基反應。特別是在架橋劑(B)為 異氰酸酯類架橋劑的情況時，矽烷偶聯劑(C)的巰基，與異氰酸酯類架橋劑的異氰酸酯基容易形成硫代氨基甲酸酯鍵。另一方面，架橋劑(B)的其他反應性官能基(異氰酸酯類架橋劑的異氰酸酯基)，與(甲基)丙烯酸酯聚合物(A)的反應性官能基(羥基、氨基等)進行反應，將(甲基)丙烯酸酯聚合物(A)架橋，形成三維網絡結構。而且，矽烷偶聯劑(C)的烷氧基甲矽烷基，與(被架橋的)(甲基)丙烯酸酯聚合物(A)保持適宜的距離，成為懸掛在(甲基)丙烯酸酯聚合物(A)上的形態，由此發揮優異的偶聯效果。如上所得的黏接劑，黏接性優異，即使在高溫條件下或濕熱條件下，黏接耐久性也優異。 In this embodiment, the silane coupling agent (C) has a functional group mercapto group capable of reacting with an organic material. The adhesive composition P is bridged, and the thiol group of the silane coupling agent (C) is reacted with the reactive functional group of the bridge agent (B). Especially in the bridging agent (B) is In the case of an isocyanate-based bridging agent, the thiol group of the silane coupling agent (C) and the isocyanate group of the isocyanate-based bridging agent easily form a thiourethane bond. On the other hand, the other reactive functional groups of the bridging agent (B) (isocyanate groups of the isocyanate-based bridging agent) react with the reactive functional groups (such as a hydroxyl group and an amino group) of the (meth) acrylate polymer (A). The (meth) acrylate polymer (A) is bridged to form a three-dimensional network structure. In addition, the alkoxysilyl group of the silane coupling agent (C) is kept at a suitable distance from the (bridged) (meth) acrylate polymer (A), and becomes a (meth) acrylate polymer. (A), thereby exhibiting an excellent coupling effect. The adhesive obtained as described above is excellent in adhesiveness, and is excellent in adhesion durability even under high temperature conditions or wet heat conditions.
在架橋劑(B)為異氰酸酯類架橋劑的情況時，矽烷偶聯劑(C)具有的巰基，由於容易與異氰酸酯類架橋劑的異氰酸酯基發生反應，因此(甲基)丙烯酸酯聚合物(A)的反應性官能基，即使僅為在一般的矽烷偶聯劑中難以發揮作用的羥基((甲基)丙烯酸酯聚合物(A)作為反應性官能基可以不含有羧基)，也能得到來自矽烷偶聯劑(C)的偶聯效果。 When the bridging agent (B) is an isocyanate-based bridging agent, the thiol group of the silane coupling agent (C) easily reacts with the isocyanate group of the isocyanate-based bridging agent, so the (meth) acrylate polymer (A The reactive functional group of) can be obtained even if it is only a hydroxyl group ((meth) acrylate polymer (A) which does not contain a carboxyl group as a reactive functional group) which is difficult to function in a general silane coupling agent. Coupling effect of silane coupling agent (C).
作為矽烷偶聯劑(C)，為分子內至少具有一個巰基，至少具有一個烷氧基甲矽烷基的有機矽化合物，與黏接劑成分的相溶性良好，且具有光透過性，例如優選實質上為透明者。 The silane coupling agent (C) is an organosilicon compound having at least one mercapto group and at least one alkoxysilyl group in the molecule. It has good compatibility with the adhesive component and has light transparency. For example, it is preferably substantially Those who are transparent.
作為上述的矽烷偶聯劑(C)的具體例，可以舉出3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等的含有巰基的低分子型矽烷偶聯劑；3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、 0-巰基丙基二甲氧基甲基矽烷等的含有巰基的矽烷化合物與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等的含有烷基的矽烷化合物的共縮聚物等的含有巰基的寡聚物型矽烷偶聯劑等。其中，從提高耐久性的觀點考慮，優選為含有巰基的寡聚物型矽烷偶聯劑，特別優選為含有巰基的矽烷化合物與含有烷基矽烷化合物的共縮聚物，進一步優選為3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮聚物。這些可以單獨使用一種，也可以組合兩種以上使用。 Specific examples of the silane coupling agent (C) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane And other mercapto-containing low-molecular-weight silane coupling agents; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Mercapto-containing silane compounds such as 0-mercaptopropyldimethoxymethylsilane and methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, etc. A mercapto group-containing oligomeric silane coupling agent, such as a copolycondensate of an alkyl group-containing silane compound. Among these, from the viewpoint of improving durability, a mercapto-containing oligomeric silane coupling agent is preferred, a mercapto-containing silane compound and an alkylsilane compound-containing copolycondensate are particularly preferred, and 3-mercaptopropyl Copolymer of methyltrimethoxysilane and methyltriethoxysilane. These may be used alone or in combination of two or more.
在上述含有巰基的寡聚物型矽烷偶聯劑中，寡聚物中的巰基當量優選為100g/mol~1000g/mol，特別優選為200g/mol~900g/mol，進一步優選為300g/mol~700g/mol。巰基當量如果小於100g/mol，則耐久性能有可能降低。巰基當量如果超過1000g/mol，則有發生黏接力降低或剝離不良的可能性。 In the mercapto-containing oligomeric silane coupling agent, the thiol equivalent in the oligomer is preferably 100 g / mol to 1000 g / mol, particularly preferably 200 g / mol to 900 g / mol, and more preferably 300 g / mol to 700g / mol. If the mercapto equivalent is less than 100 g / mol, the durability may be reduced. When the mercapto equivalent is more than 1000 g / mol, there is a possibility that a decrease in adhesive strength or poor peeling may occur.
在黏接性組合物P中的矽烷偶聯劑(C)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.01質量份~5質量份，特別優選為0.02質量份~3質量份，進一步優選為0.2質量份~0.8質量份。矽烷偶聯劑(C)的含有量，如果小於0.01質量份，則難於得到由該矽烷偶聯劑(C)所帶來的効果。另一方面，矽烷偶聯劑(C)的含有量如果超過5質量份，則有可能發生與架橋劑(B)和(甲基)丙烯酸酯聚合物(A)反應降低的情況。 The content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate polymer (A), and particularly preferably 0.02 to 3 parts by mass, and more preferably 0.2 to 0.8 parts by mass. When the content of the silane coupling agent (C) is less than 0.01 parts by mass, it is difficult to obtain the effect by the silane coupling agent (C). On the other hand, when the content of the silane coupling agent (C) exceeds 5 parts by mass, the reaction with the bridging agent (B) and the (meth) acrylate polymer (A) may decrease.
(4)各種添加劑 (4) Various additives
黏接性組合物P，根據需要，可以添加在丙烯酸類黏接劑中通常使用的各種添加劑，例如帶電防止劑、黏接賦予劑、氧化防止劑、紫外線吸收劑、光穩定劑、軟化劑、充填劑、折射率調整劑等。 The adhesive composition P may be added with various additives generally used in acrylic adhesives, such as an antistatic agent, an adhesion-imparting agent, an oxidation inhibitor, an ultraviolet absorber, a light stabilizer, a softener, and the like, as necessary. Fillers, refractive index modifiers, etc.
作為帶電防止劑，例如可以舉出離子性液體、離子性固體、陰離子類介面活性劑、堿金屬鹽、陽離子類表面活性劑、非離子類表面活性劑等，其中優選使用從離子性液體、離子性固體以及堿金屬鹽所選出的至少一種。 Examples of the antistatic agent include ionic liquids, ionic solids, anionic surfactants, sulfonium metal salts, cationic surfactants, and nonionic surfactants. Among them, ionic liquids and ionic surfactants are preferably used. At least one selected from the group consisting of a solid solid and a rhenium metal salt.
作為離子性液體以及離子性固體，優選為含氮鎓鹽、含硫黃鎓鹽、含磷鎓鹽等。另外，作為堿金屬鹽優選為鋰鹽、鉀鹽等。這些可以單獨使用，也可以組合兩種以上使用。 As the ionic liquid and the ionic solid, a nitrogen-containing onium salt, a sulfur-containing xanthium salt, a phosphorus-containing onium salt, and the like are preferable. In addition, the phosphonium metal salt is preferably a lithium salt, a potassium salt, or the like. These may be used alone or in combination of two or more.
黏接性組合物P中的帶電防止劑的含有量，優選為0.5質量%~8質量%，特別優選為1質量%~5質量%。通過帶電防止劑的含有量在上述範圍內，則帶電防止性能與黏接劑的耐久性的平衡變得良好。 The content of the antistatic agent in the adhesive composition P is preferably 0.5% to 8% by mass, and particularly preferably 1% to 5% by mass. When the content of the antistatic agent is within the above range, the balance between the antistatic property and the durability of the adhesive becomes good.
〔黏接性組合物的製造方法〕 [Manufacturing method of adhesive composition]
黏接性組合物P可以通過製造(甲基)丙烯酸酯聚合物(A)，將所得的(甲基)丙烯酸酯聚合物(A)、架橋劑(B)和矽烷偶聯劑(C)進行混合，同時，根據需要，加入添加劑來製造。 The adhesive composition P can be produced by producing a (meth) acrylate polymer (A), and the obtained (meth) acrylate polymer (A), a bridging agent (B), and a silane coupling agent (C) Mix and, at the same time, add additives as needed to make.
(甲基)丙烯酸酯聚合物(A)，可以通過用通常的自由基聚合法，聚合構成聚合物的單體(共聚合物的情況為單體的混合物)來製造。(甲基)丙烯酸酯聚合物(A)的聚合，可以根據需要，使用聚合引發劑，由溶液聚合法等進行。作為聚合溶劑，例如可以舉出乙酸乙酯、乙酸正丁基酯、乙酸異丁基酯、 甲苯、丙酮、己烷、甲基乙基酮等，可以並用兩種以上。 The (meth) acrylate polymer (A) can be produced by polymerizing monomers (in the case of a copolymer, a mixture of monomers) constituting a polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate polymer (A) can be performed by a solution polymerization method or the like using a polymerization initiator as necessary. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, Toluene, acetone, hexane, methyl ethyl ketone and the like may be used in combination of two or more.
作為聚合引發劑，可以例舉偶氮類化合物、有機過氧化物等，可以同時使用兩種以上。作為偶氮類化合物，可以例舉2，2’-偶氮雙異丁腈、2，2’-偶氮雙(2-甲基丁腈)、1，1’-偶氮雙(環己烷1-腈)、2，2’-偶氮雙(2，4-二甲基戊腈)、2，2’-偶氮雙(2，4-二甲基-4-甲氧基戊腈)、二甲基2，2’-偶氮雙(2-甲基丙酸酯)、4，4’-偶氮雙(4-氰基纈草酸)、2，2’-偶氮雙(2-羥基甲基丙腈)、2，2’-偶氮雙〔2-(2-咪唑琳-2-基)丙烷〕等。 Examples of the polymerization initiator include an azo compound, an organic peroxide, and the like, and two or more of them may be used simultaneously. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). 1-nitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) , Dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methylpropionate) Hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and the like.
作為有機過氧化物，例如可以例舉出苯甲醯過氧化物、過氧苯甲酸叔丁基酯、異丙苯過氧化氫、二異丙基過氧二碳酸酯、二正丙基過氧二碳酸酯、二(2-乙氧基乙基)過氧二碳酸酯、過氧新葵酸叔丁基酯、過氧特戊酸叔丁基酯、(3，5，5-三甲基己醯基)過氧化物、二丙醯過氧化物、二乙醯過氧化物等。 Examples of the organic peroxide include benzamidine peroxide, tert-butyl peroxybenzoate, cumene hydrogen peroxide, diisopropylperoxydicarbonate, and di-n-propylperoxy. Dicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxynecaprylate, tert-butyl peroxypivalate, (3,5,5-trimethyl Hexamethylene) peroxide, dipropylhydrazone peroxide, diethylhydrazone peroxide, and the like.
另外，在上述聚合步驟中，通過搭配2-巰基乙醇等的鏈移動劑，可以對得到的聚合物的重量平均分子量進行調節。 Moreover, in the said polymerization process, the weight average molecular weight of the obtained polymer can be adjusted by mix | blending a chain shifting agent, such as 2-mercaptoethanol.
得到(甲基)丙烯酸酯聚合物(A)後，在(甲基)丙烯酸酯聚合物(A)的溶液中，添加架橋劑(B)、矽烷偶聯劑(C)、稀釋溶劑以及根據需要加入添加劑，進行充分混合，得到用溶劑稀釋了的黏接性組合物P(塗布溶液)。 After the (meth) acrylate polymer (A) is obtained, in a solution of the (meth) acrylate polymer (A), a bridging agent (B), a silane coupling agent (C), a diluent solvent, and if necessary, are added. Additives were added and mixed well to obtain an adhesive composition P (coating solution) diluted with a solvent.
作為對黏接性組合物P進行稀釋，得到塗布溶液的稀釋溶劑，可以使用己烷、庚烷、環己烷等的脂肪族烴；甲苯以及二甲苯等的芳香族烴；二氯甲烷以及二氯乙烷等的鹵代 烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇；丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等的酮類；乙酸乙酯以及乙酸丁基酯等的酯、乙基溶纖劑等的溶纖劑類溶劑等。 As a diluent for diluting the adhesive composition P to obtain a coating solution, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; dichloromethane and two Halogenated Hydrocarbons; alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, etc. Type; esters such as ethyl acetate and butyl acetate; solvents such as ethyl cellosolve;
作為如此調製的塗布溶液的濃度、黏度，只要為在塗布可能的範圍內即可，沒有特別的限制，可以根據情況進行適宜選擇。例如，黏接性組合物P的濃度可以稀釋到10質量%~40質量%。另外，得到塗布溶液時，稀釋溶劑等的添加不是必要條件，黏接性組合物P只要是塗布可能的黏度，稀釋溶劑不添加也可。該情況時黏接性組合物P可以直接作為塗布溶液。 The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as they are within the range possible for coating, and can be appropriately selected according to circumstances. For example, the concentration of the adhesive composition P may be diluted to 10% to 40% by mass. In addition, when a coating solution is obtained, the addition of a diluent solvent and the like is not necessary, and the adhesive composition P may be a viscosity that can be applied, and the diluent solvent may not be added. In this case, the adhesive composition P can be used as a coating solution as it is.
〔黏接劑〕 [Adhesive]
本實施形態所述的黏接劑由將黏接性組合物P架橋而得到。黏接性組合物P的架橋可以用加熱處理來進行。而且，此加熱處理還可兼作對黏接性組合物P的稀釋溶劑等進行揮發時的乾燥處理。 The adhesive according to this embodiment is obtained by bridging the adhesive composition P. The bridging of the adhesive composition P can be performed by heat treatment. In addition, this heat treatment can also serve as a drying treatment when the diluent solvent and the like of the adhesive composition P are volatilized.
在進行加熱處理的情況時，加熱溫度優選為50℃~150℃，特別優選為70℃~120℃。另外，加熱時間優選為10秒~10分，特別優選為50秒~2分。進一步優選為加熱處理後，在常溫(例如，23℃、50%RH)下放置1~2周的熟成期間。 When the heat treatment is performed, the heating temperature is preferably 50 ° C to 150 ° C, and particularly preferably 70 ° C to 120 ° C. The heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes. More preferably, it is a maturation period of 1 to 2 weeks after leaving it at normal temperature (for example, 23 ° C., 50% RH) after heat treatment.
通過上述加熱處理(及熟成)，(甲基)丙烯酸酯聚合物(A)架橋於架橋劑(B)，形成三維網絡結構。另外，矽烷偶聯劑(C)的巰基與架橋劑(B)的反應性官能基反應，該矽烷偶聯劑(C)的烷氧基甲矽烷基利用上述架橋劑(B)，與(甲基)丙烯酸 酯聚合物(A)乃至上述三維網絡結構保持適宜距離而存在，發揮優異的偶聯效果。 Through the heat treatment (and maturation) described above, the (meth) acrylate polymer (A) is bridged to the bridging agent (B) to form a three-dimensional network structure. The mercapto group of the silane coupling agent (C) reacts with the reactive functional group of the bridging agent (B). The alkoxysilyl group of the silane coupling agent (C) uses the bridging agent (B) and (methyl) Base) acrylic The ester polymer (A) and the above-mentioned three-dimensional network structure exist at an appropriate distance and exhibit excellent coupling effects.
將黏接性組合物P架橋所得到的的黏接劑，通過(甲基)丙烯酸酯聚合物(A)所具有的脂環式結構與矽烷偶聯劑(C)的作用，對於偏光板等的光學構件，特別是對於聚環烯烴類的光學構件與透明導電膜的密合性高，即使在高溫條件下或濕熱條件下，也能發揮優異的黏接耐久性。例如，在85℃的高溫條件下或60℃、90%RH的濕熱條件下，放置500小時也可以防止和抑制浮起、剝離、氣泡等的發生。 The adhesive obtained by bridging the adhesive composition P is used for a polarizing plate and the like through the action of the alicyclic structure of the (meth) acrylate polymer (A) and the silane coupling agent (C). The optical member, especially the polycycloolefin-based optical member, has high adhesiveness with the transparent conductive film, and can exhibit excellent adhesion durability even under high temperature conditions or wet heat conditions. For example, under high temperature conditions of 85 ° C. or humid conditions of 60 ° C. and 90% RH, 500 hours of standing can also prevent and suppress the occurrence of floating, peeling, and bubbles.
本實施形態所述的黏接劑的凝膠分率，優選為30%~95%，特別優選為40%~90%，進一步優選為70%~85%。如果凝膠分率小於30%，則黏接劑的凝集力不足，有耐久性以及再加工性降低的情況。另一方面，如果凝膠分率大於95%，則黏接力變得過低，有耐久性降低的情況。另外，上述凝膠分率是從黏接劑層形成時起，在23℃、50%RH的環境下，保管7天(熟成期間經過後)後的值。在不明是否為熟成期間的情況時，只要重新在23℃、50%RH的環境下保管7天後，如果凝膠分率在上述範圍內即可。 The gel fraction of the adhesive according to this embodiment is preferably 30% to 95%, particularly preferably 40% to 90%, and still more preferably 70% to 85%. When the gel fraction is less than 30%, the cohesive force of the adhesive is insufficient, and durability and reworkability may be reduced. On the other hand, if the gel fraction is more than 95%, the adhesion force becomes too low, and the durability may be reduced. The above-mentioned gel fraction is a value after storage for 7 days (after the maturation period has elapsed) under the environment of 23 ° C. and 50% RH from the time of formation of the adhesive layer. When it is unknown whether it is a maturation period, the gel fraction should be within the above range after re-storing for 7 days in an environment of 23 ° C. and 50% RH.
本實施形態所述的黏接劑，適宜用於光學構件，特別是適宜用於偏光板，例如，偏光板(偏光薄膜)和相位差板(相位差薄膜)等的光學構件之間的黏接，或偏光板(偏光薄膜)及相位差板(相位差薄膜)與玻璃基板的黏接。 The adhesive according to this embodiment is suitable for optical members, and particularly suitable for polarizing plates, for example, bonding between optical members such as polarizing plates (polarizing films) and retardation plates (phase difference films). , Or the adhesion of a polarizing plate (polarizing film) and a retardation plate (phase difference film) to a glass substrate.
在此，具備聚環烯烴類薄膜的偏光板(以下有稱為「COP偏光板」的情況)等，具有接觸角大(例如，95°以上)， 而且尺寸變化(收縮率)大的特性。因此，一般來說黏接劑的密合性低，並且在與黏接劑的介面上容易發生浮起、剝離的問題。但是，本實施形態所述的黏接劑，對於這種聚環烯烴類薄膜與COP偏光板等，也表現出優異的密合性以及耐久性。 Here, a polarizer including a polycycloolefin-based film (hereinafter referred to as a “COP polarizer”) and the like have a large contact angle (for example, 95 ° or more), In addition, it has a large dimensional change (shrinkage rate). Therefore, in general, the adhesiveness is low, and problems such as floating and peeling easily occur on the interface with the adhesive. However, the adhesive according to this embodiment also exhibits excellent adhesion and durability to such a polycycloolefin-based film and a COP polarizing plate.
〔黏接片〕 [Adhesive sheet]
如圖1所示，第1實施形態所述的黏接片1A，按照從下往上的順序，由剝離片12、層疊於剝離片12的剝離面上的黏接劑層11、及層疊於黏接劑層11上的基材13所構成。 As shown in FIG. 1, the adhesive sheet 1A according to the first embodiment is composed of a release sheet 12, an adhesive layer 11 laminated on a release surface of the release sheet 12, and The base material 13 on the adhesive layer 11 is configured.
另外，如圖2所示，第2實施形態所述的黏接片1B，由兩片剝離片12a、12b，以及以與這兩片剝離片12a、12b的剝離面相接的方式，被這兩片剝離片12a、12b所挾持的黏接劑層11所構成。另外，本說明書中所謂的剝離片的剝離面，是指剝離片中具有剝離性的面，包括實施了剝離處理的面以及即使未實施剝離處理也顯示出剝離性的面的兩者。 In addition, as shown in FIG. 2, the adhesive sheet 1B according to the second embodiment is composed of two peeling sheets 12 a and 12 b and is in contact with the peeling surfaces of the two peeling sheets 12 a and 12 b. The adhesive layer 11 held by the two release sheets 12a and 12b is configured. The release surface of the release sheet in the present specification refers to a surface having releasability in the release sheet, and includes both a surface subjected to a release treatment and a surface that exhibits releasability even without a release treatment.
在黏接片1A、1B的兩者中，黏接劑層11都是由架橋上述黏接性組合物P所成的黏接劑構成。 In both of the adhesive sheets 1A and 1B, the adhesive layer 11 is composed of an adhesive formed by bridging the above-mentioned adhesive composition P.
使用目的而適宜決定，但是通常為5μm~100μm，優選為10μm~60μm的範圍。例如，在作為光學構件，特別是作為偏光板用的黏接劑層使用的情況時，優選為10μm~50μm，特別優選為15μm~30μm。 The purpose of use is appropriately determined, but it is usually 5 μm to 100 μm, and preferably in a range of 10 μm to 60 μm. For example, when it is used as an optical member, especially as an adhesive layer for polarizing plates, it is preferable that it is 10 micrometers-50 micrometers, and it is especially preferable that it is 15 micrometers-30 micrometers.
作為基材13，沒有特別的限制，作為通常的黏接片的基材片所使用的基材都可以使用。例如，除所希望的光學構件之外，可以例舉出人造絲、丙烯以及聚酯等使用了纖維的織布或者不織布；合成紙；上質紙、玻璃紙、含浸紙、銅板紙 等的紙類；鋁、銅等的金屬箔；氨基甲酸酯發泡體、聚乙烯發泡體等的發泡體；聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二酸乙二醇酯等的聚酯薄膜；聚氨酯薄膜、聚乙烯薄膜、聚丙烯薄膜、三乙醯纖維素等的纖維素薄膜；聚氯乙烯薄膜、聚偏氯乙烯薄膜、聚乙烯基醇薄膜、乙烯-乙酸乙烯基共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、丙烯酸樹脂薄膜、降冰片烯類樹脂薄膜、環烯烴樹脂薄膜等的塑膠薄膜；這些的兩種以上的層疊體等。塑膠薄膜可以為單軸壓延的薄膜或者雙軸壓延的薄膜。 The base material 13 is not particularly limited, and any base material used as a base material sheet of a general adhesive sheet can be used. For example, in addition to desired optical members, woven or non-woven fabrics using fibers such as rayon, acrylic, and polyester; synthetic paper; high-quality paper, cellophane, impregnated paper, and copper paper And other papers; metal foils such as aluminum and copper; foams such as urethane foam and polyethylene foam; polyethylene terephthalate, polybutylene terephthalate Polyester films such as polyester, polyethylene naphthalate; cellulose films such as polyurethane films, polyethylene films, polypropylene films, and triethyl cellulose; polyvinyl chloride films, polyvinylidene chloride films, and polyethylene Plastic films such as vinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene resin film, cycloolefin resin film; two or more of these Laminates, etc. The plastic film may be a uniaxially rolled film or a biaxially rolled film.
作為光學構件，例如可以例舉出偏光板(偏光薄膜)、偏光子、相位差板(相位差薄膜)、視野角補償薄膜、提高輝度薄膜、提高對比度薄膜、液晶聚合物薄膜、擴散薄膜、半透過反射薄膜等。作為偏光板，使用在聚乙烯醇類偏光子的兩面黏接三乙醯纖維素(TAC)薄膜的偏光板，或將一側的TAC薄膜，變更為環烯烴聚合物薄膜的偏光板(COP偏光板)等。特別是聚環烯烴類薄膜或COP偏光板不僅容易收縮，尺寸變化大，而且接觸角大，密合性低，因此從密合性、耐久性的觀點考慮，適宜作為形成本實施形態的黏接劑(上述黏接劑層11)的對象。 Examples of the optical member include a polarizing plate (polarizing film), a polarizer, a retardation plate (a retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast enhancement film, a liquid crystal polymer film, a diffusion film, and a half Transmissive reflective film, etc. As the polarizing plate, a polarizing plate in which a triacetin cellulose (TAC) film is adhered to both sides of a polyvinyl alcohol-based polarizer, or a TAC film on one side is changed to a cycloolefin polymer film (COP polarizing film) Board) and so on. In particular, polycycloolefin-based films or COP polarizers are not only easy to shrink, have large dimensional changes, but also have large contact angles and low adhesion. Therefore, from the viewpoint of adhesion and durability, they are suitable for forming adhesives of this embodiment. Of the adhesive (the above-mentioned adhesive layer 11).
基材13的厚度，根據其種類而有所不同，但是，在例如光學構件的情況時，通常為10μm~500μm，優選為50μm~300μm，特別是優選為80μm~150μm。 The thickness of the base material 13 varies depending on the type, but in the case of an optical member, for example, it is usually 10 μm to 500 μm, preferably 50 μm to 300 μm, and particularly preferably 80 μm to 150 μm.
作為剝離片12，12a，12b可以使用例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯基薄膜、氯乙烯基共聚物薄膜、聚對苯二甲酸乙 二醇酯薄膜、聚萘二酸乙二醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜、聚氨酯薄膜、乙烯乙酸乙烯基薄膜、離聚物樹脂薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。另外，也可以使用這些的架橋薄膜。進一步，也可以為這些的疊層薄膜。 As the release sheets 12, 12a, 12b, for example, polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, Polyethylene terephthalate Glycol ester film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene- (meth) acrylic acid copolymer Film, ethylene- (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Moreover, these bridge films can also be used. Furthermore, these laminated films may be used.
上述剝離片的剝離面(特別是與黏接劑層11相接的面)，優選為實施有剝離處理。作為剝離處理所使用的剝離劑，例如可以列舉出醇酸類、矽酮類、氟類、不飽和聚酯類、聚烯烴類以及蠟類的剝離劑。 It is preferable that the peeling surface (especially the surface which contacts the adhesive layer 11) of the said peeling sheet is peeled. Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
關於剝離片12，12a，12b的厚度，沒有特別的限制，通常為20μm~150μm左右。 The thickness of the release sheets 12, 12a, and 12b is not particularly limited, but is usually about 20 μm to 150 μm.
在製造上述黏接片1A中，在剝離片12的剝離面上，將含有黏接性組合物的溶液(塗布溶液)進行塗布、加熱處理，在形成黏接劑層11後，在該黏接劑層11上，將基材13進行層疊。然後，保留熟成時間為優選。另外，關於加熱處理以及熟成的條件如上所述。 In the production of the above-mentioned adhesive sheet 1A, a solution (coating solution) containing an adhesive composition is applied and heat-treated on the release surface of the release sheet 12, and after the adhesive layer 11 is formed, the adhesive The base material 13 is laminated on the agent layer 11. Then, it is preferable to keep the aging time. The conditions for heat treatment and aging are as described above.
另外，在製造上述黏接片1B中，在一個剝離片12a(或者12b)的剝離面上，將含有上述黏接性組合物的塗布溶液進行塗布、加熱處理，在形成黏接劑層11後，在其黏接劑層11上，將另一個剝離片12b(或者12a)的剝離面聚合。 In addition, in the production of the adhesive sheet 1B, a coating solution containing the adhesive composition is applied and heat-treated on the release surface of one release sheet 12a (or 12b), and after the adhesive layer 11 is formed, On the adhesive layer 11, the release surface of the other release sheet 12 b (or 12 a) is polymerized.
作為塗布上述塗布溶液的方法，例如可以利用棒塗布法、刮刀塗布法、輥塗布法、板塗布法、模具塗布法、凹板塗布法等。 As a method of applying the coating solution, for example, a bar coating method, a blade coating method, a roll coating method, a plate coating method, a mold coating method, a gravure coating method, or the like can be used.
黏接片1A，1B中的黏接劑層11，霧度值(依據JIS K7136：2000測定而得到的值)優選為1.0%以下，特別是優選為0.9%以下，進一步優選為0.8%以下。如果霧度值為1.0%以下，則透明性非常高，成為適宜作為光學用途的黏接劑層。 The haze value (value measured in accordance with JIS K7136: 2000) of the adhesive layer 11 in the adhesive sheets 1A and 1B is preferably 1.0% or less, particularly preferably 0.9% or less, and still more preferably 0.8% or less. When the haze value is 1.0% or less, the transparency is very high, and it becomes an adhesive layer suitable for optical applications.
在此，例如，在製造由液晶組件和偏光板所構成的液晶顯示裝置中，作為黏接片1A的基材13，使用偏光板，將該黏接片1A的剝離片12剝離，將露出的黏接劑層11和液晶組件進行貼合即可。 Here, for example, in manufacturing a liquid crystal display device composed of a liquid crystal module and a polarizing plate, as the base material 13 of the adhesive sheet 1A, a polarizing plate is used, and the release sheet 12 of the adhesive sheet 1A is peeled off to expose the exposed The adhesive layer 11 may be bonded to the liquid crystal module.
另外，例如，製造在液晶組件和偏光板之間配置有相位差板的液晶顯示裝置中，作為一例，首先，將黏接片1B的一個剝離片12a(或者12b)剝離，將黏接片1B露出的黏接劑層11和相位差板進行貼合。然後，將作為基材13使用偏光板的黏接片1A的剝離片12剝離，將黏接片1A露出的黏接劑層11和上述相位差板進行貼合。進一步，從上述黏接片B的黏接劑層11，將另一個剝離片12b(或者12a)剝離，將黏接片B露出的黏接劑層11和液晶組件貼合。 In addition, for example, in a liquid crystal display device in which a retardation plate is disposed between a liquid crystal module and a polarizing plate, as an example, first, one peeling sheet 12a (or 12b) of the adhesive sheet 1B is peeled off, and the adhesive sheet 1B The exposed adhesive layer 11 and the retardation plate are bonded together. Then, the release sheet 12 of the adhesive sheet 1A using a polarizing plate as the base material 13 is peeled off, and the adhesive layer 11 exposed by the adhesive sheet 1A and the retardation plate are bonded together. Furthermore, the other peeling sheet 12b (or 12a) is peeled from the adhesive layer 11 of the said adhesive sheet B, and the adhesive layer 11 exposed by the adhesive sheet B and a liquid crystal element are bonded.
根據以上的黏接片1A，1B，黏接劑層11對於偏光板等的光學構件的密合性以及耐久性優異，因此表現出高黏接力，同時即使在高溫條件下或濕熱條件下，也可以防止和抑制浮起、剝離、發泡等的發生。 According to the above-mentioned adhesive sheets 1A and 1B, the adhesive layer 11 has excellent adhesion and durability to optical members such as a polarizing plate, and therefore exhibits high adhesive force, and it can be used even under high-temperature conditions or wet heat conditions. It can prevent and suppress the occurrence of floating, peeling, foaming, etc.
本實施形態所述的黏接片1A，1B，優選將透明導電膜作為被黏物。該種情況時，黏接性組合物P中的(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選為不含有含羧基單體。由此，可以抑制由於酸成分對透明導電膜帶 來不良影響。具體而言，為可以抑制透明導電膜發生腐食，或透明導電膜的電阻值發生變化。另外，本實施形態所述的黏接劑(黏接劑層11)，即使不包含羧基也能表現出上述優異的密合性以及耐久性。 In the adhesive sheets 1A and 1B according to this embodiment, a transparent conductive film is preferably used as an adherend. In this case, the (meth) acrylate polymer (A) in the adhesive composition P preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. This can suppress the transparent conductive film tape due to the acid component. To bad effects. Specifically, it is possible to suppress rottenness of the transparent conductive film or change in the resistance value of the transparent conductive film. In addition, the adhesive (adhesive layer 11) according to the present embodiment can exhibit the above-mentioned excellent adhesion and durability even if it does not contain a carboxyl group.
作為上述透明導電膜，例如可以列舉出鉑、金、銀、銅等的金屬；氧化錫、氧化銦、氧化鎘、氧化鋅、二氧化鋅等的氧化物；摻雜錫之氧化銦(ITO)、摻雜氧化鋅之氧化銦、摻雜氟之氧化銦、摻雜銻之氧化錫、摻雜氟之氧化錫、摻雜鋁之氧化鋅等的複合氧化物；硫化物、六硼化鑭、氮化鈦、碳化鈦等的非氧化化合物等所構成的透明導電膜。 Examples of the transparent conductive film include metals such as platinum, gold, silver, and copper; oxides of tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc dioxide; and tin-doped indium oxide (ITO) Compound oxides of zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, etc .; sulfide, lanthanum hexaboride, A transparent conductive film made of a non-oxidizing compound such as titanium nitride or titanium carbide.
作為基材13使用了偏光板的黏接片1A(以下有稱為「帶黏接劑層偏光板」的情況)，黏接力相對於無鹼玻璃，優選為0.1N/25mm~25N/25mm，特別優選為2N/25mm~20N/25mm。通過使黏接力在上述的範圍內，則在與玻璃板等的被黏物之間，可以防止浮起或剝離等。另外，在此所說的黏接力，基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品切成寬25mm、長100mm，使該測定樣品相對於被黏物，在0.5MPa、50℃，加壓20分貼附之後，以常壓23℃、50%RH的條件下放置24小時之後，以剝離速度300mm/min進行測定所得到的黏接力。 As the base material 13, an adhesive sheet 1A of a polarizing plate is used (hereinafter referred to as a "polarizing plate with an adhesive layer"), and the adhesive force is preferably 0.1N / 25mm to 25N / 25mm relative to alkali-free glass. It is particularly preferably 2N / 25mm to 20N / 25mm. When the adhesive force is within the above range, it is possible to prevent floating, peeling, and the like from being adhered to a glass plate or the like. In addition, the adhesive force referred to here basically refers to an adhesive force measured by a 180 ° peeling method based on JIS Z0237: 2009, but a measurement sample is cut into a width of 25 mm and a length of 100 mm so that the measurement sample is relatively The adhesive was adhered at 0.5 MPa and 50 ° C. for 20 minutes under pressure, and then left to stand for 24 hours under the conditions of normal pressure 23 ° C. and 50% RH, and then the obtained adhesion force was measured at a peeling speed of 300 mm / min.
而且，上述帶黏接劑層的偏光板貼附於上述被黏物，在常壓50℃、50%RH的條件下，放置2天後的黏接力優選為0.1N/25mm~25N/25mm，特別優選為2N/25mm~20N/25mm。像這樣由於經時所產生的黏接力的上升被抑制， 由此可以將上述帶黏接劑層的偏光板評價為再加工性優異的偏光板。此外，這裏所說的黏接力也基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品切成寬25mm、長100mm，使該測定樣品相對於被黏物，在0.5MPa、50℃，加壓20分貼附之後，在上述條件(常壓50℃、50%RH)下放置2天後，以剝離速度300mm/min進行測定所得到的黏接力。 In addition, the polarizing plate with an adhesive layer is attached to the adherend, and the adhesion force after being left for 2 days under the conditions of normal pressure 50 ° C and 50% RH is preferably 0.1N / 25mm ~ 25N / 25mm, It is particularly preferably 2N / 25mm to 20N / 25mm. In this way, the increase in the adhesive force due to the passage of time is suppressed, Thereby, the said polarizing plate with an adhesive layer can be evaluated as a polarizing plate excellent in reworkability. In addition, the adhesive force referred to here basically refers to the adhesive force measured by the 180 ° peeling method based on JIS Z0237: 2009, but the measurement sample is cut into a width of 25 mm and a length of 100 mm to make the measurement sample relatively adhered. The object was adhered at 0.5 MPa and 50 ° C. for 20 minutes under pressure, and then left under the above conditions (normal pressure 50 ° C., 50% RH) for 2 days, and the obtained adhesion force was measured at a peeling speed of 300 mm / min.
以上說明的實施形態，是為了易於對本發明的理解而記述的，並不是對本發明進行限定而進行的記述。因此，上述實施形態中所公開的各要素，也包括屬於本發明的技術範圍的所有設計變更以及均等物。 The embodiments described above are described for easy understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment includes all design changes and equivalents belonging to the technical scope of the present invention.
例如，黏接片1A的剝離片12可以省略，黏接片1B中的剝離片12a，12b中的任意一方也可以省略。 For example, the release sheet 12 of the adhesive sheet 1A may be omitted, and any one of the release sheets 12a and 12b in the adhesive sheet 1B may be omitted.
【實施例】 [Example]
以下，通過實施例等進一步對本發明進行具體說明，但是本發明的範圍並不受這些實施例等的限定。 Hereinafter, the present invention will be described in more detail through examples and the like, but the scope of the present invention is not limited by these examples and the like.
〔實施例1〕 [Example 1]
1.(甲基)丙烯酸酯聚合物的調製 1. Preparation of (meth) acrylate polymer
向包括攪拌機、溫度計、回流冷卻器、滴下裝置及氮氣導入管的反應容器中，裝入丙烯酸正丁基酯74質量份、丙烯酸甲基酯5質量份、丙烯酸異冰片酯(acrylic acid isobornyl)20質量份、丙烯酸2-羥乙基酯1質量份、乙酸乙酯(ethyl acetate)200質量份、及2，2'-偶氮二異丁腈0.08質量份，將上述反應容器內的空氣置換成氮氣。在該氮氣氣氛下一邊攪拌，一邊將反應 溶液升溫至60℃，使反應進行16小時後、冷卻至室溫。在此，將所得的溶液的一部分，用後述的方法測定分子量，確認到生成有重量平均分子量(Mw)185萬的(甲基)丙烯酸酯聚合物(A)。 Into a reaction vessel including a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, 74 parts by mass of n-butyl acrylate, 5 parts by mass of methyl acrylate, and acrylic acid isobornyl 20 were charged. Parts by mass, 1 part by mass of 2-hydroxyethyl acrylate, 200 parts by mass of ethyl acetate, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, replacing the air in the reaction vessel with Nitrogen. The reaction was stirred while stirring under this nitrogen atmosphere. The temperature of the solution was raised to 60 ° C, and the reaction was allowed to proceed for 16 hours, followed by cooling to room temperature. Here, a part of the obtained solution was measured for molecular weight by a method described later, and it was confirmed that a (meth) acrylate polymer (A) having a weight average molecular weight (Mw) of 1.85 million was formed.
2.黏接性組合物的調製 2. Preparation of adhesive composition
將在上述步驟(1)中獲得的(甲基)丙烯酸酯聚合物(A)100質量份(固體成分換算值；以下同)；作為架橋劑(B)，將三羥甲基丙烷改性伸二甲苯二異氰酸酯(綜研化學公司製，商品名「TD-75」)0.4質量份；作為矽烷偶聯劑(C)，其具有作為與有機材料反應的官能基的巰基，將3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮聚物(信越化學公司製，商品名「X41-1810」，巰基當量：450g/mol)0.3質量份，進行混合，充分地攪拌，通過用乙酸乙酯進行稀釋，獲得黏接性組合物的塗布溶液。 100 parts by mass of the (meth) acrylate polymer (A) obtained in the above step (1) (solid content conversion value; the same applies hereinafter); as a bridging agent (B), trimethylolpropane was modified 0.4 parts by mass of toluene diisocyanate (trade name "TD-75" manufactured by Soken Chemical Co., Ltd.); as the silane coupling agent (C), it has a mercapto group as a functional group that reacts with an organic material, and 3-mercaptopropyltrimethyl 0.3 parts by mass of a copolycondensate of oxysilane and methyltriethoxysilane (produced by Shin-Etsu Chemical Co., Ltd., "X41-1810", mercapto equivalent: 450 g / mol), mixed well, and stirred with acetic acid The ethyl ester was diluted to obtain a coating solution of the adhesive composition.
在此，將該黏接性組合物的搭配表示於表1。另外，表1所記載的縮寫符號等的詳細情況如下所述。 Here, the combination of this adhesive composition is shown in Table 1. The details of the abbreviations and the like described in Table 1 are as follows.
[(甲基)丙烯酸酯聚合物(A)] [(Meth) acrylate polymer (A)]
BA：丙烯酸正丁基酯 BA: n-butyl acrylate
MA：丙烯酸甲基酯 MA: methyl acrylate
HEA：丙烯酸2-羥基乙基酯 HEA: 2-hydroxyethyl acrylate
IBXA：丙烯酸異冰片酯 IBXA: Isobornyl Acrylate
ADMMA：甲基丙烯酸金剛烷基酯 ADMMA: Adamantyl Methacrylate
DCPA：丙烯酸二環戊酯 DCPA: Dicyclopentyl acrylate
CHA：丙烯酸環己基酯 CHA: cyclohexyl acrylate
PhEA：丙烯酸2-苯氧基乙基酯 PhEA: 2-phenoxyethyl acrylate
〔架橋劑(B)〕 〔Cross-linking agent (B)〕
XDI：三羥甲基丙烷改性伸二甲苯二異氰酸酯(綜研化學公司製，商品名「TD-75」) XDI: Trimethylolpropane modified xylene diisocyanate (manufactured by Soken Chemical Co., Ltd., trade name "TD-75")
TDI：三羥甲基丙烷改性甲次苯基二異氰酸酯(綜研化學公司製，商品名「L-45」) TDI: Trimethylolpropane modified methylenephenyl diisocyanate (manufactured by Soken Chemical Co., Ltd., trade name "L-45")
〔矽烷偶聯劑(C)〕 [Silane coupling agent (C)]
C1：3-巰基丙基三甲氧基矽烷和甲基三乙氧基矽烷的共縮聚物(信越化學工業公司製，商品名「X41-1810」，巰基當量：450g/mol) C1: Co-condensation product of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X41-1810", mercapto equivalent: 450 g / mol)
C2：3-巰基丙基三甲氧基矽烷(信越化學工業公司製，商品名「KBM-803」) C2: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-803")
C3：3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業公司製，商品名「KBM-403」) C3: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403")
3.帶有黏接劑層偏光板的製造 3. Manufacturing of polarizing plate with adhesive layer
將所得到的黏接性組合物的塗布溶液，在將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮類剝離劑進行了剝離處理的剝離片(琳得科株式公司製，SP-PET3811，厚度：38μm)的剝離處理面上，用刮刀塗布器進行塗布，使乾燥後的厚度為25μm後，用90℃進行1分鍾加熱處理而形成的黏接劑層。 The obtained coating solution of the adhesive composition was a peeling sheet (manufactured by Lindec Corporation, peeled off) on one side of a polyethylene terephthalate film with a silicone release agent, SP-PET3811 (thickness: 38 μm) was coated with a doctor blade applicator so that the thickness after drying was 25 μm, and then an adhesive layer was formed by heating at 90 ° C. for 1 minute.
接著，用三乙醯纖維素薄膜，保護聚乙烯基醇薄膜所構成的偏光子的一個面，用環烯烴聚合物薄膜保護另一個面所得的厚度為100μm的COP偏光板，貼合於上述黏接劑層，使上述黏接劑層的露出面與環烯烴聚合物薄膜的表面相接觸，之後在23℃、50%RH環境下放置7日進行熟成，由此得 到帶有黏接劑層的偏光板。 Next, a triethylammonium cellulose film was used to protect one side of a polarizer made of a polyvinyl alcohol film, and a cycloolefin polymer film was used to protect the other side of a COP polarizing plate having a thickness of 100 μm, which was bonded to the adhesive Adhesive layer, the exposed surface of the adhesive layer is in contact with the surface of the cycloolefin polymer film, and then aged at 23 ° C and 50% RH for 7 days for ripening, thereby obtaining To a polarizer with an adhesive layer.
〔實施例2~15，比較例1~3〕 [Examples 2 to 15, Comparative Examples 1 to 3]
除將構成(甲基)丙烯酸酯聚合物(A)的各單體的種類以及比例、(甲基)丙烯酸酯聚合物(A)的重量平均分子量以、架橋劑(B)及矽烷偶聯劑(C)的種類及搭配量，按照表1所示進行變更外，與實施例1同樣地進行操作，製造帶有黏接劑層的偏光板。另外，在實施例4及實施例12中，作為帶電防止劑，使用進一步搭配有吡啶鹽(廣榮化學公司製，商品名「IL-P18」)的黏接性組合物。 In addition to the types and proportions of each monomer constituting the (meth) acrylate polymer (A), the weight average molecular weight of the (meth) acrylate polymer (A), the bridging agent (B), and the silane coupling agent (C) The type and blending amount were changed as shown in Table 1, and the same operation as in Example 1 was performed to produce a polarizing plate with an adhesive layer. Moreover, in Example 4 and Example 12, as the antistatic agent, the adhesive composition further mix | blended with the pyridine salt (made by Kwong Young Chemical Co., Ltd., brand name "IL-P18") was used.
在此，上述的重量平均分子量(Mw)，為使用凝膠滲透色譜(GPC)在以下的條件下測定(GPC測定)的聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured (GPC measurement) under the following conditions using gel permeation chromatography (GPC).
<測定條件> <Measurement conditions>
‧GPC測定裝置：Tosoh公司製，HLC-8020 ‧GPC measurement device: manufactured by Tosoh Corporation, HLC-8020
‧GPC柱(以下的順序通過)：Tosoh公司製 ‧GPC column (passed in the following order): made by Tosoh
TSK guard column HXL-H TSK guard column HXL-H
TSK gel GMHXL(×2) TSK gel GMHXL (× 2)
TSK gel G2000HXL TSK gel G2000HXL
‧測定熔劑：四氫呋喃 ‧Determination of flux: tetrahydrofuran
‧測定溫度：40℃ ‧Measuring temperature: 40 ℃
〔試驗例1〕(凝膠分率的測定) [Test Example 1] (Measurement of gel fraction)
在實施例或者比較例中，代替製作帶有黏接劑層的偏光板所使用的偏光板，使用將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮類剝離劑進行了剝離處理的剝離片(琳得科株式公 司製，SP-PET3801，厚度：38μm)，進行黏接片的製作。具體而言，在用實施例或者比較例的製造過程所得到的的剝離片/黏接劑層(厚度：25μm)所構成的構成體的露出的黏接劑層上，以剝離處理面側相接的方式，將上述剝離片進行層疊。由此，來製作由剝離片/黏接劑層/剝離片的構成所形成的黏接片。 In Examples or Comparative Examples, instead of the polarizing plate used for the production of the polarizing plate with an adhesive layer, one surface of a polyethylene terephthalate film was peeled with a silicone-based release agent. Treated release sheet (Lintec) Co., Ltd., SP-PET3801, thickness: 38 μm), for the production of adhesive sheets. Specifically, on the exposed adhesive layer of the structure constituted by the release sheet / adhesive layer (thickness: 25 μm) obtained in the manufacturing process of the example or comparative example, the surface of the treated surface was peeled off. The above-mentioned peeling sheet is laminated. Thereby, the adhesive sheet which consists of a peeling sheet / adhesive layer / peeling sheet structure was produced.
將得到的黏接片，在23℃、50%RH的條件下進行7天熟成。之後，將該黏接片製成80mm×80mm尺寸的樣品，將其黏接劑層用聚酯製網(網尺寸200)包裹，僅將黏接劑的質量用精密天平進行稱量。將此時的質量作為M1。 The obtained adhesive sheet was aged for 7 days under the conditions of 23 ° C. and 50% RH. Then, the adhesive sheet was made into a sample having a size of 80 mm × 80 mm, and the adhesive layer was wrapped with a polyester mesh (mesh size 200), and only the mass of the adhesive was weighed with a precision balance. Let the mass at this time be M1.
接著，將上述聚酯製網包裹的黏接劑，在室溫下(23℃)下，在乙酸乙酯中進行24小時浸漬。之後將黏接劑取出，在溫度23℃、相對濕度50%的環境下，進行24小時風乾，進一步在80℃的烘箱中進行12小時乾燥。僅將乾燥後的黏接劑的質量用精密天平進行稱量。將此時的質量作為M2。凝膠分率(%)用(M2/M1)×100來表示。將結果示於表2。 Next, the polyester mesh-wrapped adhesive was impregnated in ethyl acetate at room temperature (23 ° C) for 24 hours. After that, the adhesive was taken out and air-dried for 24 hours under an environment of a temperature of 23 ° C and a relative humidity of 50%, and further dried in an oven at 80 ° C for 12 hours. Only the mass of the dried adhesive was weighed with a precision balance. Let the mass at this time be M2. The gel fraction (%) is represented by (M2 / M1) × 100. The results are shown in Table 2.
〔試驗例2〕(霧度值的測定) [Test Example 2] (Measurement of Haze Value)
作為測定樣品，準備與測定凝膠分率所用的黏接片同樣的黏接片(已經熟成7天)。關於該黏接片的黏接劑層(厚度：25μm)，使用霧度測量計(日本電色工業公司製，NDH2000)，基於JIS K7136：2000，對霧度值(%)進行測定。將結果示於表2。 As a measurement sample, an adhesive sheet similar to the adhesive sheet used for measuring the gel fraction was prepared (aged for 7 days). About the adhesive layer (thickness: 25 micrometers) of this adhesive sheet, the haze value (%) was measured based on JIS K7136: 2000 using the haze meter (made by Nippon Denshoku Industries, NDH2000). The results are shown in Table 2.
〔試驗例3〕(黏接力的測定) [Test Example 3] (Measurement of Adhesive Strength)
將在實施例或比較例中所得到的帶有黏接劑層的偏光板裁斷，製作寬25mm、長100mm的樣品。從該樣品上將剝離片剝離，通過露出的黏接劑層，在無鹼玻璃(康寧公司製，鷹XG) 上進行該樣品的貼附之後，用栗原製作所公司製的高壓鍋，在0.5MPa、50℃，加壓20分鍾。其後，在23℃、50%RH的條件下，放置24小時(1天)或放置14天後，使用拉伸試驗機(奧瑞公司製，Tensilon)，基於JIS Z0237：2009，以剝離速度300mm/min、剝離角度180°的條件，測定黏接力(貼附1天後及貼附14天後的黏接力；N/25mm)。將結果分別示於表2。 The polarizing plate with an adhesive layer obtained in the examples or comparative examples was cut to produce samples having a width of 25 mm and a length of 100 mm. The release sheet was peeled from the sample, and the exposed adhesive layer was passed through an alkali-free glass (made by Corning Corporation, Eagle XG). After attaching the sample, the pressure was applied using a pressure cooker manufactured by Kurihara Seisakusho Co., Ltd. at 0.5 MPa and 50 ° C for 20 minutes. Thereafter, under conditions of 23 ° C. and 50% RH, it was left for 24 hours (1 day) or after 14 days, and then a tensile tester (Tensilon, manufactured by Orion) was used at a peeling speed based on JIS Z0237: 2009. At 300 mm / min and a peeling angle of 180 °, the adhesive force (adhesive force after 1 day and 14 days after application; N / 25 mm) was measured. The results are shown in Table 2.
〔試驗例4〕(耐久性評價) [Test Example 4] (Durability Evaluation)
將在實施例或比較例中所得到的帶有黏接劑層的偏光板裁斷，製作233mm×309mm大小的樣品。作為樣品，從製作帶有黏接劑層的偏光板(形成黏接劑層)中，準備在23℃、50%RH的環境下保管7天後的樣品。從該樣品把剝離片剝離，通過露出的黏接劑層，在無鹼玻璃(康寧公司製，鷹XG)上進行貼附之後，用栗原製作所製的高壓鍋，在0.5MPa、50℃，加壓20分鍾。 The polarizing plate with an adhesive layer obtained in the examples or comparative examples was cut to produce a sample having a size of 233 mm × 309 mm. As a sample, from the production of a polarizing plate with an adhesive layer (adhesive layer formation), a sample after storage for 7 days in an environment of 23 ° C. and 50% RH was prepared. The peeling sheet was peeled from this sample, and after the exposed adhesive layer was adhered on alkali-free glass (King Ning Corporation, Eagle XG), it was pressurized with a pressure cooker made by Kurihara Seisakusho at 0.5 MPa and 50 ° C. 20 minutes.
之後，投入到下述的耐久條件的環境下，500小時後，使用10倍放大鏡，對浮起或者剝離的有無進行確認。評價基準如下。將結果示於表2。 After that, it was put into an environment with the following durable conditions, and 500 hours later, the presence or absence of floating or peeling was confirmed using a 10-fold magnifying glass. The evaluation criteria are as follows. The results are shown in Table 2.
◎：沒有確認到浮起或者剝離。 ：: No floating or peeling was observed.
○：確認到0.5mm以下大小的浮起或者剝離。 ○: Floating or peeling of a size of 0.5 mm or less was confirmed.
×：確認到0.6mm以上大小的浮起或者剝離。 ×: Floating or peeling of a size of 0.6 mm or more was confirmed.
<耐久條件> <Durable conditions>
‧85℃ dry ‧85 ℃ dry
‧60℃，相對濕度90%RH ‧60 ℃, relative humidity 90% RH
【表1】
由表2可知，在實施例所得到的黏接劑層的黏接 劑，具有高黏接力(密合性)，耐久性也優異。 As can be seen from Table 2, the adhesion of the adhesive layer obtained in the examples Agent with high adhesion (adhesiveness) and excellent durability.
本發明的黏接劑適宜於光學構件，特別是適宜於偏光板的黏接，而且，本發明的黏接片適宜作為光學構件用，特別是適宜作為偏光板用的黏接片。 The adhesive of the present invention is suitable for optical members, particularly for the adhesion of polarizing plates. In addition, the adhesive sheet of the present invention is suitable for use as an optical member, and particularly suitable as an adhesive sheet for polarizing plates.
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| JP2013025707A JP6112892B2 (en) | 2013-02-13 | 2013-02-13 | Adhesive composition, adhesive and adhesive sheet |
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| JP6609405B2 (en) * | 2014-08-26 | 2019-11-20 | 三星エスディアイ株式会社 | Adhesive composition, adhesive layer, adhesive optical film, adhesive polarizing plate, and image display device |
| JP6336897B2 (en) * | 2014-12-09 | 2018-06-06 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6550251B2 (en) * | 2015-03-03 | 2019-07-24 | リンテック株式会社 | Adhesive film with optical film |
| TWI767881B (en) * | 2015-03-31 | 2022-06-21 | 日商住友化學股份有限公司 | Optical laminate, liquid crystal display device, adhesive composition, and optical film with adhesive layer |
| CN106010383B (en) * | 2015-03-31 | 2019-08-02 | 住友化学株式会社 | Optical laminate and liquid crystal display device |
| JP6904926B2 (en) * | 2015-04-15 | 2021-07-21 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP2016204406A (en) * | 2015-04-15 | 2016-12-08 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| CN107614645B (en) * | 2015-06-30 | 2020-06-12 | 琳得科株式会社 | Adhesive composition, adhesive sheet and display |
| JP6826362B2 (en) * | 2015-06-30 | 2021-02-03 | リンテック株式会社 | Adhesive sheet |
| JP6632821B2 (en) * | 2015-07-01 | 2020-01-22 | リンテック株式会社 | Adhesive, adhesive sheet and optical film with adhesive layer |
| JP6776754B2 (en) * | 2016-09-14 | 2020-10-28 | 三菱ケミカル株式会社 | Adhesive composition for polarizing plate, pressure-sensitive adhesive for polarizing plate, polarizing plate with pressure-sensitive adhesive layer, and polarizing plate with pressure-sensitive adhesive layer with release film |
| JP6588596B2 (en) * | 2018-05-07 | 2019-10-09 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| KR102434825B1 (en) * | 2018-09-28 | 2022-08-22 | 주식회사 엘지화학 | Acryl-based adhesive composition, polarizing plate and display device |
| JP2019206726A (en) * | 2019-09-12 | 2019-12-05 | 藤森工業株式会社 | Adhesive layer and adhesive film |
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| JP4521520B2 (en) * | 2003-08-06 | 2010-08-11 | 綜研化学株式会社 | Adhesive for low polarity film |
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