JP2009019172A - Pressure-sensitive adhesive, pressure-sensitive adhesive sheet and optical film with pressure-sensitive adhesive - Google Patents
Pressure-sensitive adhesive, pressure-sensitive adhesive sheet and optical film with pressure-sensitive adhesive Download PDFInfo
- Publication number
- JP2009019172A JP2009019172A JP2007184710A JP2007184710A JP2009019172A JP 2009019172 A JP2009019172 A JP 2009019172A JP 2007184710 A JP2007184710 A JP 2007184710A JP 2007184710 A JP2007184710 A JP 2007184710A JP 2009019172 A JP2009019172 A JP 2009019172A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- mass
- adhesive
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 86
- 239000012788 optical film Substances 0.000 title claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 112
- 230000001070 adhesive effect Effects 0.000 claims abstract description 112
- 239000000178 monomer Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 43
- 210000002858 crystal cell Anatomy 0.000 abstract description 29
- 230000001678 irradiating effect Effects 0.000 abstract description 4
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- 239000010408 film Substances 0.000 description 40
- -1 2-ethylhexyl Chemical group 0.000 description 31
- 239000010410 layer Substances 0.000 description 27
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
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- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
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- 229920000728 polyester Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
Description
本発明は、粘着剤、粘着シート及び粘着剤付き光学フィルムに関する。さらに詳しくは、本発明は、偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板に、又は偏光板に位相差板が積層される場合に好適に適用され、該偏光板を液晶セルに耐久性よく接着し得ると共に、得られた液晶表示装置が、高温高湿環境下でも光漏れが生じにくいなどの特性を有し、さらに貼合を誤った際などに容易に再剥離可能な粘着剤、粘着シート及び粘着剤付き光学フィルムに関するものである。 The present invention relates to an adhesive, an adhesive sheet, and an optical film with an adhesive. More specifically, the present invention is preferably applied to a polarizing plate, particularly a polarizing plate integrated with a viewing angle widening film or the like, or when a retardation plate is laminated on the polarizing plate. The resulting liquid crystal display device has characteristics such that light leakage is less likely to occur even in a high temperature and high humidity environment, and can be easily peeled off when the bonding is mistaken. The present invention relates to an adhesive, an adhesive sheet, and an optical film with an adhesive.
従来、ガラス、セラミックス、金属などの被着体に、粘着剤を介して有機材料からなるシートを貼合した場合、経時により、シート端部が剥がれてきたり、浮きが生じるなど、好ましくない事態がしばしば生じる。
このような事態を解決するために、一般的には、粘着剤を構成する成分の分子量を上げたり、架橋密度を高めるなどして、粘着性能を高めた強粘着性材料を用いることが行われている。しかしながら、このような強粘着性材料を用いた場合、保持力は向上するものの、高温高湿条件下では、有機材料からなるシートの収縮や膨潤によって発生する形状変化に、粘着剤が追従できなくなり、様々なトラブルの発生要因となっている。
Conventionally, when a sheet made of an organic material is bonded to an adherend such as glass, ceramics, or metal via an adhesive, an unfavorable situation occurs such that the sheet edge peels off or floats with time. Often occurs.
In order to solve such a situation, in general, it is performed to use a highly adhesive material with improved adhesion performance by increasing the molecular weight of the component constituting the adhesive or increasing the crosslinking density. ing. However, when such a strong adhesive material is used, the holding power is improved, but under high temperature and high humidity conditions, the adhesive cannot follow the shape change caused by the shrinkage or swelling of the sheet made of organic material. This is a cause of various troubles.
ところで、光学部品の中には、その表面に偏光板を貼合して使用するものがあり、その代表例として液晶表示装置（ＬＣＤ）の液晶セルが挙げられる。以下、図１を用いて説明する。
この液晶セル１３は、一般に配向層を形成した２枚の透明電極基板の配向層を内側にして、スペーサにより所定の間隔になるように配置し、その周辺をシールして、該間隔に液晶材料を挟持させると共に、上記２枚の透明電極基板に、それぞれ粘着剤１２を介して、偏光板１１が配置された構造を有している。前記偏光板は、一般的にポリビニルアルコール系偏光子の両面に、光学的等方性フィルム、例えばトリアセチルセルロース（ＴＡＣ）フィルムなどを貼り合わせた３層構造を有する偏光フィルムからなり、さらにその片面には、液晶セルなどの光学部品に貼着することを目的に粘着剤層が設けられている。
また、図２に示す模式図のように、視野角特性の改善を図るため、偏光板２１と液晶セル２３の間に粘着剤２２及び２５を介して位相差板２４が配置される場合もある。
Incidentally, some optical components are used by attaching a polarizing plate to the surface thereof, and a typical example thereof is a liquid crystal cell of a liquid crystal display (LCD). Hereinafter, a description will be given with reference to FIG.
The
In addition, as shown in the schematic diagram of FIG. 2, a
上述のような構成の偏光板を液晶セルなどの光学部品に貼着した場合、又は偏光板と位相差板を貼着した場合、異種材料の多層構造となり、材料特性から寸法安定性が乏しく、特に高温高湿環境下では、収縮や膨潤による寸法変化が大きい。該偏光板には粘着剤として、一般に前述の強粘着性のものが用いられているため、偏光板の寸法変化に伴う浮きや剥がれは抑制することができるが、該偏光板の寸法変化に伴う応力を粘着剤層で吸収することができず、偏光板における残留応力が不均一になる。その結果、ＴＮ液晶セルでは、いわゆる「光漏れ」が、ＳＴＮ液晶では「色むら」が発現しやすくなるという問題が生じる。 When the polarizing plate having the above-described configuration is attached to an optical component such as a liquid crystal cell, or when a polarizing plate and a retardation plate are attached, it becomes a multilayer structure of different materials, and the dimensional stability is poor from the material characteristics. Particularly in a high temperature and high humidity environment, the dimensional change due to shrinkage and swelling is large. Since the above-mentioned strong adhesive is generally used as the pressure-sensitive adhesive for the polarizing plate, it is possible to suppress floating and peeling accompanying the dimensional change of the polarizing plate, but with the dimensional change of the polarizing plate. The stress cannot be absorbed by the adhesive layer, and the residual stress in the polarizing plate becomes non-uniform. As a result, there is a problem that so-called “light leakage” is likely to occur in the TN liquid crystal cell and “color unevenness” is likely to occur in the STN liquid crystal.
このような問題を解決するために、例えば粘着剤に可塑剤などの低分子量体を添加することで、適度に軟らかくして応力緩和性を付与する技術が開示されている（例えば、特許文献１参照）。しかしながら、低分子量体の添加は、偏光板を剥離した際に液晶セルを汚染する原因となる上、保持力を低下させることとなり、経時による浮きや剥がれが発生しやすくなる。 In order to solve such a problem, for example, a technique has been disclosed in which a low molecular weight material such as a plasticizer is added to an adhesive to moderately soften and impart stress relaxation properties (for example, Patent Document 1). reference). However, the addition of a low molecular weight substance causes the liquid crystal cell to be contaminated when the polarizing plate is peeled off, and also reduces the holding power, and is likely to be lifted or peeled off over time.
一方、アクリル系共重合体と側鎖に放射線重合性基を有するアクリル系重合体を、重量比１００：１〜１００：１００の割合で含むものを放射線架橋してなる感圧接着剤シートが開示されている（例えば、特許文献２参照）。
この公報においては、偏光板用として実施例が記載されているが、いずれの実施例においても、光漏れ性について、評価サンプルのサイズに関する記載がない。本発明者らが、該公報の実施例に記載された感圧接着剤を用いて光漏れ性を１５インチサイズの偏光板で評価した結果は、十分に満足し得るものでなかった。
このように、偏光板用粘着剤においては、接着耐久性と光漏れ防止性を両立させることは困難であり、それを両立させることが課題となっていた。
特に、車載用途などより過酷な耐久性が要求される場合には、接着耐久性と光漏れ防止性を両立させることはさらに困難になる。
On the other hand, a pressure-sensitive adhesive sheet formed by radiation-crosslinking an acrylic copolymer and an acrylic polymer having a radiation polymerizable group in a side chain at a weight ratio of 100: 1 to 100: 100 is disclosed. (For example, refer to Patent Document 2).
In this publication, examples are described for polarizing plates. However, in any of the examples, there is no description regarding the size of the evaluation sample for light leakage. The results of evaluation of light leakage by a 15-inch size polarizing plate using the pressure-sensitive adhesive described in Examples of the publication by the present inventors were not sufficiently satisfactory.
Thus, in the pressure-sensitive adhesive for polarizing plates, it is difficult to achieve both adhesion durability and light leakage prevention properties, and it has been a challenge to achieve both.
In particular, when severe durability is required such as in-vehicle use, it becomes more difficult to achieve both adhesion durability and light leakage prevention.
また、液晶ディスプレイ等の製造工程において、偏光板を液晶セルなどの光学部品に貼合するに際し、貼合位置にずれが生じた場合など、貼合からある時間が経過した後に偏光板を剥離し、高価な液晶セルを再利用することが必要となる場合がある。従って、偏光板に塗布されている粘着剤を介して貼合した後、例えば１週間、もしくはそれ以上の長い期間が経過した後であっても液晶セルから剥離することが行われる場合がある。このような、長期間経過した後でも容易に剥離することができる粘着剤が求められていた。これは、接着耐久性を付与するための強粘着力化とは相反する性質であって、これらを両立することが課題であった。 Also, in the manufacturing process of liquid crystal displays, etc., when the polarizing plate is bonded to an optical component such as a liquid crystal cell, the polarizing plate is peeled off after a certain period of time has elapsed, such as when the bonding position has shifted. It may be necessary to reuse expensive liquid crystal cells. Therefore, after bonding through the pressure-sensitive adhesive applied to the polarizing plate, peeling from the liquid crystal cell may be performed even after a long period of time, for example, for one week or longer. There has been a demand for an adhesive that can be easily peeled even after a long period of time has passed. This is a property that is contrary to strong adhesion for imparting adhesion durability, and it has been a problem to achieve both.
本発明は、このような状況下で、例えば、偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板に、又は偏光板に位相差板が積層される場合に好適に適用され、該偏光板を液晶セルに耐久性よく接着し得ると共に、得られた液晶表示装置が、高温高湿環境下でも光漏れが生じにくいなどの特性を有し、かつ貼合からある時間が経過した後であっても、液晶セルから剥離すること（以下「再剥離」ということがある。）が容易にできる粘着剤、該粘着剤を用いた粘着シート、及び該粘着剤を用いた粘着剤付き光学フィルムを提供することを目的とするものである。 Under such circumstances, the present invention is suitably applied to, for example, a polarizing plate integrated with a polarizing plate, particularly a viewing angle widening film, or when a retardation plate is laminated on the polarizing plate, After the polarizing plate can be bonded to the liquid crystal cell with good durability, the obtained liquid crystal display device has characteristics such that light leakage hardly occurs even in a high-temperature and high-humidity environment, and after a certain period of time has passed since bonding. Even so, a pressure-sensitive adhesive that can be easily peeled off from the liquid crystal cell (hereinafter sometimes referred to as “re-peeling”), a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive, and an optical with a pressure-sensitive adhesive using the pressure-sensitive adhesive The object is to provide a film.
一般的に再剥離性粘着剤の特性としては、貼付してから粘着力上昇が極力少なく、低粘着力であっても耐久性に優れることが必要とされる。特に、偏光板用途では、低粘着力かつ耐久性に優れることが強く望まれる。しかしながら、実際のディスプレイ構成において、低粘着力で長期間高耐久性が維持されるかという点は不安材料として残る。そこで、本発明者らは、徐々に粘着力上昇は起こるが、その上昇速度が低いため、再剥離性が必要とされる貼付後１４日間は１０Ｎ／２５ｍｍ程度の再剥離可能な粘着力領域にあり、その後、強粘着剤へと変化する粘着剤を開発することが重要であると認識した。なお、本発明において、このように貼合後の所定期間は再剥離可能な粘着力領域にあり、その後、強粘着力領域へと変化する性質を「リワーク性」という。
そして、該リワーク性を有する粘着剤を開発すべく鋭意研究を重ねた結果、２種類の特定のアクリル系重合体と、活性エネルギー線硬化型化合物を含む粘着性材料に、活性エネルギー線を照射してなる粘着剤が、その目的に適合し得ることを見出した。
本発明は、かかる知見に基づいて完成したものである。
In general, as a characteristic of a releasable pressure-sensitive adhesive, an increase in adhesive force is extremely small after being applied, and it is required to have excellent durability even with a low adhesive force. In particular, for polarizing plate applications, it is strongly desired to have low adhesive strength and excellent durability. However, in an actual display configuration, whether high durability is maintained for a long time with a low adhesive strength remains as an anxious material. Therefore, the present inventors gradually increase the adhesive force, but since the rate of increase is low, the re-removable adhesive force region of about 10 N / 25 mm is required for 14 days after the application when re-removability is required. Yes, and then recognized that it is important to develop a pressure sensitive adhesive that changes into a strong pressure sensitive adhesive. In addition, in this invention, it exists in the adhesive force area | region which can be peeled again for the predetermined period after bonding in this way, and the property which changes into a strong adhesive force area | region after that is called "rework property."
As a result of intensive research to develop a pressure-sensitive adhesive having reworkability, an adhesive material containing two kinds of specific acrylic polymers and an active energy ray-curable compound was irradiated with active energy rays. It has been found that the pressure-sensitive adhesive can be adapted to the purpose.
The present invention has been completed based on such findings.
すなわち、本発明は、
（１）（Ａ）水酸基含有モノマーをモノマー組成比で０．０１〜５質量％含み、かつ、カルボキシル基含有モノマーをモノマー組成比で０．０１質量％以上２．０質量％未満含むモノマー組成物を重合してなる重量平均分子量１００万以上のアクリル系共重合体、（Ｂ）水酸基含有モノマーがモノマー組成比で０．０１質量％未満であり、かつ、カルボキシル基含有モノマーをモノマー組成比で０．０１〜１５．０質量％含むモノマー組成物を重合してなる重量平均分子量１００万以上のアクリル系共重合体、及び（Ｃ）活性エネルギー線硬化型化合物を含む粘着性材料に活性エネルギー線を照射してなる粘着剤であって、成分（Ａ）と成分（Ｂ）の質量比が１００：１〜１００：３０であり、かつ、２３℃における貯蔵弾性率（Ｇ’）が、０．３ＭＰａ以上である粘着剤、
（２）成分（Ａ）と成分（Ｃ）の質量比が１００：１〜１００：４０である上記（１）に記載の粘着剤、
（３）成分（Ａ）が重量平均分子量１５０万以上のアクリル系共重合体である上記（１）又は（２）に記載の粘着剤、
（４）さらに、（Ｄ）ポリイソシアネート化合物及び（Ｅ）シランカップリング剤を含有し、成分（Ａ）中の水酸基含有モノマーと成分（Ｄ）のモル比が０．８：１．２〜１．２：０．８であって、かつ、成分（A）と成分（Ｅ）の質量比が１００：０．１〜１００：０．５である上記（１）〜（３）のいずれかに記載の粘着剤、
（５）２３℃における貯蔵弾性率（Ｇ’）が、０．３〜１５ＭＰａである上記（１）〜（４）のいずれかに記載の粘着剤、
（６）８０℃における貯蔵弾性率（Ｇ’）が、０．１〜１５ＭＰａである上記（１）〜（５）のいずれかに記載の粘着剤、
（７）剥離シートの剥離層上に上記（１）〜（６）のいずれかに記載の粘着剤からなる粘着性材料層を有する粘着シート、
（８）２枚の剥離シートの剥離層側に接するように上記（１）〜（６）のいずれかに記載の粘着剤を挟持してなる粘着シート、
（９）光学フィルム上に上記（１）〜（６）のいずれかに記載の粘着剤からなる粘着性材料層を有する粘着剤付き光学フィルム、及び
（１０）前記光学フィルムが偏光板である上記（９）に記載の粘着剤付き光学フィルム、
を提供するものである。
That is, the present invention
(1) (A) A monomer composition containing a hydroxyl group-containing monomer in a monomer composition ratio of 0.01 to 5 mass% and a carboxyl group-containing monomer in a monomer composition ratio of 0.01 mass% or more and less than 2.0 mass%. An acrylic copolymer having a weight average molecular weight of 1,000,000 or more, and (B) the hydroxyl group-containing monomer is less than 0.01% by mass in the monomer composition ratio, and the carboxyl group-containing monomer is 0 in the monomer composition ratio. Active energy rays are applied to a pressure-sensitive adhesive material containing an acrylic copolymer having a weight average molecular weight of 1,000,000 or more obtained by polymerizing a monomer composition containing 0.01 to 15.0% by mass and (C) an active energy ray-curable compound. Irradiated pressure-sensitive adhesive, the mass ratio of the component (A) and the component (B) is 100: 1 to 100: 30, and the storage elastic modulus (G ′) at 23 ° C. is 0. A pressure-sensitive adhesive having a pressure of 3 MPa or more,
(2) The pressure-sensitive adhesive according to (1), wherein the mass ratio of the component (A) to the component (C) is 100: 1 to 100: 40,
(3) The pressure-sensitive adhesive according to (1) or (2), wherein the component (A) is an acrylic copolymer having a weight average molecular weight of 1.5 million or more,
(4) Further, (D) a polyisocyanate compound and (E) a silane coupling agent are contained, and the molar ratio of the hydroxyl group-containing monomer in component (A) to component (D) is 0.8: 1.2 to 1. .2: 0.8, and the mass ratio of component (A) to component (E) is 100: 0.1 to 100: 0.5. The adhesive,
(5) The pressure-sensitive adhesive according to any one of (1) to (4), wherein the storage elastic modulus (G ′) at 23 ° C. is 0.3 to 15 MPa,
(6) The pressure-sensitive adhesive according to any one of (1) to (5), wherein the storage elastic modulus (G ′) at 80 ° C. is 0.1 to 15 MPa,
(7) A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive material layer made of the pressure-sensitive adhesive according to any one of (1) to (6) above on the release layer of the release sheet,
(8) A pressure-sensitive adhesive sheet obtained by sandwiching the pressure-sensitive adhesive according to any one of (1) to (6) so as to be in contact with the release layer side of two release sheets,
(9) The optical film with an adhesive which has an adhesive material layer which consists of an adhesive in any one of said (1)-(6) on an optical film, and (10) The said optical film is a polarizing plate. (9) The optical film with an adhesive according to
Is to provide.
本発明によれば、例えば、偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板に、又は偏光板に位相差板が積層される場合に好適に適用され、該偏光板を液晶セルに耐久性よく接着し得ると共に、得られた液晶表示装置が、高温高湿環境下でも光漏れが生じにくいなどの特性を有し、かつリワーク性を有する粘着剤、粘着シート、粘着剤付き光学フィルム、及び粘着剤付き偏光板を提供することができる。 According to the present invention, for example, it is suitably applied to a polarizing plate, particularly a polarizing plate integrated with a viewing angle widening film, or when a retardation plate is laminated on the polarizing plate. Adhesive, pressure-sensitive adhesive sheet, and pressure-sensitive adhesive with a rework property, such that the obtained liquid crystal display device has a property such that light leakage does not easily occur even in a high-temperature and high-humidity environment. A film and a polarizing plate with an adhesive can be provided.
本発明の粘着剤は、成分（Ａ）として、官能基を有しない（メタ）アクリル酸エステル（主モノマー）、水酸基含有モノマー及びカルボキシル基含有モノマーを構成単位として含むアクリル系共重合体と、成分（Ｂ）として、官能基を有しない（メタ）アクリル酸エステル（主モノマー）及びカルボキシル基含有モノマーを構成単位として含み、水酸基含有モノマーを構成単位として実質的に含まないアクリル系共重合体を組み合わせて用いることが重要である。
このような組み合わせをとることで、貼合の優れた耐久性を実現しながら、貼合の後の粘着力の上昇速度を抑制することができ、再剥離性が要求される期間は再剥離領域の粘着力を示すようなリワーク性を有する粘着剤を得ることができることを見出したものである。
The pressure-sensitive adhesive of the present invention comprises, as component (A), an acrylic copolymer containing (meth) acrylic acid ester (main monomer) having no functional group, a hydroxyl group-containing monomer and a carboxyl group-containing monomer as constituent units, and a component. As (B), a (meth) acrylic acid ester (main monomer) having no functional group and a carboxyl group-containing monomer are included as structural units, and an acrylic copolymer that is substantially free of a hydroxyl group-containing monomer as a structural unit is combined. It is important to use them.
By taking such a combination, it is possible to suppress the rate of increase in adhesive strength after bonding while realizing excellent durability of bonding, and during the period when removability is required, the re-peeling area It has been found that a pressure-sensitive adhesive having a reworking property exhibiting the above adhesive strength can be obtained.
より具体的には、本発明の粘着剤は、（Ａ）水酸基含有モノマーをモノマー組成比で０．０１〜５質量％含み、かつ、カルボキシル基含有モノマーをモノマー組成比で０．０１質量％以上２．０質量％未満含むモノマー組成物を重合してなる重量平均分子量１００万以上のアクリル系共重合体、（Ｂ）水酸基含有モノマーがモノマー組成比で０．０１質量％未満であり、かつ、カルボキシル基含有モノマーをモノマー組成比で０．０１〜１５．０質量％含むモノマー組成物を重合してなる重量平均分子量１００万以上のアクリル系共重合体、及び（Ｃ）活性エネルギー線硬化型化合物を含む粘着性材料に活性エネルギー線を照射してなる粘着剤である。 More specifically, the pressure-sensitive adhesive of the present invention contains (A) a hydroxyl group-containing monomer in a monomer composition ratio of 0.01 to 5% by mass, and a carboxyl group-containing monomer in a monomer composition ratio of 0.01% by mass or more. An acrylic copolymer having a weight average molecular weight of 1,000,000 or more obtained by polymerizing a monomer composition containing less than 2.0% by mass, (B) the hydroxyl group-containing monomer is less than 0.01% by mass in terms of monomer composition, and An acrylic copolymer having a weight average molecular weight of 1,000,000 or more obtained by polymerizing a monomer composition containing a carboxyl group-containing monomer in a monomer composition ratio of 0.01 to 15.0 mass%, and (C) an active energy ray-curable compound. Is an adhesive formed by irradiating active energy rays to an adhesive material containing
成分（Ａ）のアクリル系共重合体は、（メタ）アクリル酸メチルや（メタ）アクリル酸ブチル等の官能基を有しない（メタ）アクリル酸エステルを主モノマーとし、これと架橋性官能基として水酸基を含有するモノマーとカルボキシル基を含有するモノマーとの共重合体である。成分（Ａ）のアクリル系共重合体は、本発明の粘着剤に対して、再剥離性を付与し、貼付した後の経時的な粘着力の変化を制御する重要な構成要素である。
なお、本発明において、（メタ）アクリル酸エステルとは、アクリル酸エステル及びメタクリル酸エステルの両方を意味する。他の類似用語も同様である。
The acrylic copolymer of component (A) has (meth) acrylic acid ester having no functional group such as methyl (meth) acrylate and butyl (meth) acrylate as a main monomer, and as a crosslinkable functional group. It is a copolymer of a monomer containing a hydroxyl group and a monomer containing a carboxyl group. The acrylic copolymer of component (A) is an important component for imparting removability to the pressure-sensitive adhesive of the present invention and controlling the change in adhesive strength over time after being applied.
In the present invention, (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
上記成分（Ａ）において、官能基を有しない（メタ）アクリル酸エステルモノマーとしては特に制限はなく、例えば、エステル部分のアルキル基の炭素数が１〜２０の（メタ）アクリル酸エステルを好ましく挙げることができる。ここで、エステル部分のアルキル基の炭素数が１〜２０の（メタ）アクリル酸エステルの例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、（メタ）アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
これらの化合物のうち、特に、（メタ）アクリル酸ブチルが、適度な粘着性能を得ることができるのと、重量平均分子量１００万以上の（メタ）アクリル酸エステル重合体を容易に製造できる点で好ましい。
In the said component (A), there is no restriction | limiting in particular as a (meth) acrylic acid ester monomer which does not have a functional group, For example, the C1-C20 (meth) acrylic acid ester whose carbon number of the ester part is mentioned preferably is mentioned. be able to. Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, ( Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
Among these compounds, in particular, butyl (meth) acrylate can obtain an appropriate pressure-sensitive adhesive performance, and can easily produce a (meth) acrylate polymer having a weight average molecular weight of 1 million or more. preferable.
上記成分（Ａ）における水酸基含有モノマーの具体例としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチルなどの（メタ）アクリル酸ヒドロキシアルキルエステルなどが挙げられ、これらのうち特に（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチルが、重量部平均分子量１００万以上の（メタ）アクリル酸重合体を容易に製造できる点から好ましい。 Specific examples of the hydroxyl group-containing monomer in the component (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Examples include 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid hydroxyalkyl esters such as 4-hydroxybutyl (meth) acrylic acid, etc. Among them, (meth) acrylic acid 2- Hydroxyethyl and 4-hydroxybutyl (meth) acrylate are preferred from the viewpoint that a (meth) acrylic acid polymer having a weight part average molecular weight of 1,000,000 or more can be easily produced.
上記成分（Ａ）において、水酸基含有モノマーの含有量はモノマー組成比で０．０１〜５質量％の範囲である。０．０１質量％未満であると、高温下での耐久性に劣る点で不都合であり、５質量％を超えると、高温・高湿下での耐久性が不十分となる。以上の観点から、水酸基含有モノマーの含有量はモノマー組成比で０．１〜４質量％の範囲が好ましく、０．５〜３質量％の範囲がさらに好ましい。 In the said component (A), content of a hydroxyl-containing monomer is the range of 0.01-5 mass% by monomer composition ratio. If it is less than 0.01% by mass, it is inconvenient in that it is inferior in durability at high temperatures, and if it exceeds 5% by mass, durability at high temperatures and high humidity will be insufficient. From the above viewpoint, the content of the hydroxyl group-containing monomer is preferably in the range of 0.1 to 4% by mass and more preferably in the range of 0.5 to 3% by mass in terms of the monomer composition ratio.
上記成分（Ａ）におけるカルボキシル基含有モノマーの具体例としては、（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などが挙げられ、重量平均分子量１００万以上の（メタ）アクリル酸エステル共重合体を容易に製造できる点から、（メタ）アクリル酸が好ましい。 Specific examples of the carboxyl group-containing monomer in the component (A) include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like, and (meth) acrylic acid having a weight average molecular weight of 1 million or more. (Meth) acrylic acid is preferred because an ester copolymer can be easily produced.
また、成分（Ａ）において、カルボキシル基含有モノマーの含有量はモノマー組成比で０．０１質量％以上、２．０質量％未満である。０．０１質量％未満であると、粘着力を上昇させることができず、再剥離を要求される期間を過ぎても十分な粘着力を有するものとはならない。また、２．０質量％以上であると、再剥離を要求される期間での粘着力上昇が大きく、リワーク性を発揮できない。以上の観点から、カルボキシル基含有モノマーの含有量はモノマー組成比で０．１〜１．５質量％の範囲が好ましく、０．２〜１．０質量％の範囲がさらに好ましい。 In Component (A), the content of the carboxyl group-containing monomer is 0.01% by mass or more and less than 2.0% by mass in terms of the monomer composition ratio. If it is less than 0.01% by mass, the adhesive force cannot be increased, and the adhesive force is not sufficient even after the period required for re-peeling. Moreover, when it is 2.0 mass% or more, the adhesive force raise in the period as which a re-peeling is requested | required is large, and rework property cannot be exhibited. From the above viewpoint, the content of the carboxyl group-containing monomer is preferably in the range of 0.1 to 1.5% by mass and more preferably in the range of 0.2 to 1.0% by mass in terms of the monomer composition ratio.
また、成分（Ａ）のアクリル系共重合体は、重量平均分子量が１００万以上である。重量平均分子量が１００万未満であると、被着体との密着性や高温・高湿下での接着耐久性が不十分となり、浮きや剥がれなどが生じる場合がある。密着性及び接着耐久性などを考慮すると、この重量平均分子量は、１２０万〜２２０万のものが好ましく、特に１５０万〜２００万のものが好ましい。また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比率を表す分子量分布（Ｍｗ／Ｍｎ）は２０以下が好ましい。分子量分布が２０以下であると、十分な接着耐久性が得られる。
なお、重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定したポリスチレン換算の値である。
当該粘着性材料においては、この成分（Ａ）のアクリル系共重合体は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
Moreover, the acrylic copolymer of the component (A) has a weight average molecular weight of 1,000,000 or more. When the weight average molecular weight is less than 1,000,000, adhesion to an adherend and adhesion durability under high temperature and high humidity may be insufficient, and floating or peeling may occur. In view of adhesion and adhesion durability, the weight average molecular weight is preferably 1.2 million to 2,200,000, particularly preferably 1,500,000 to 2,000,000. Further, the molecular weight distribution (Mw / Mn) representing the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 20 or less. When the molecular weight distribution is 20 or less, sufficient adhesion durability can be obtained.
In addition, a weight average molecular weight and a number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
In the said adhesive material, the acrylic copolymer of this component (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
次に、成分（Ｂ）のアクリル系共重合体は、官能基を有しない（メタ）アクリル酸エステルを主モノマーとし、これと主に架橋性官能基としてカルボキシル基を含有するモノマーとの共重合体である。官能基を有しない（メタ）アクリル酸エステル及びカルボキシル基を含有するモノマーの具体例については、上記成分（Ａ）において記載したものと同様である。 Next, the acrylic copolymer of component (B) is a copolymer of (meth) acrylic acid ester having no functional group as a main monomer and a monomer mainly containing a carboxyl group as a crosslinkable functional group. It is a coalescence. Specific examples of the (meth) acrylic acid ester having no functional group and the monomer containing a carboxyl group are the same as those described in the component (A).
成分（Ｂ）においては、カルボキシル基含有モノマーの含有量は、モノマー組成比で０．０１〜１５．０質量％の範囲である。０．０１質量％未満であると高温下での耐久性の点で不十分であり、１５．０質量％を超えると、高温・高湿下での耐久性が不十分となる。以上の観点から、成分（Ｂ）におけるカルボキシル基含有モノマーの含有量は、モノマー組成比で０．１〜８質量％の範囲が好ましく、特に、十分な耐久性に加えて、リワーク性のバランスを向上させる観点から、３〜７質量％の範囲がさらに好ましい。 In the component (B), the content of the carboxyl group-containing monomer is in the range of 0.01 to 15.0% by mass in terms of the monomer composition ratio. If it is less than 0.01% by mass, the durability at high temperature is insufficient, and if it exceeds 15.0% by mass, the durability at high temperature and high humidity becomes insufficient. From the above viewpoint, the content of the carboxyl group-containing monomer in the component (B) is preferably in the range of 0.1 to 8% by mass in terms of the monomer composition ratio, and in particular, the balance of reworkability in addition to sufficient durability. From the viewpoint of improving, the range of 3 to 7% by mass is more preferable.
また、成分（Ｂ）においては、水酸基含有モノマーは実質的に含まれず、モノマー組成比で０．０１質量％未満である。水酸基含有モノマーの含有量を０．０１質量％以下とすることで、ガラスに対する急激な粘着力の上昇を抑制する効果が得られる。以上の観点から、成分（Ｂ）において、水酸基含有モノマーは含有されないことが好ましい。 Moreover, in a component (B), a hydroxyl-containing monomer is not contained substantially and it is less than 0.01 mass% by monomer composition ratio. By setting the content of the hydroxyl group-containing monomer to 0.01% by mass or less, an effect of suppressing an abrupt increase in adhesive strength to glass can be obtained. From the above viewpoint, it is preferable that the component (B) does not contain a hydroxyl group-containing monomer.
成分（Ｂ）のアクリル系共重合体は、重量平均分子量が１００万以上である。重量平均分子量が１００万未満であると、成分（Ａ）において記載したのと同様に、被着体との密着性や高温・高湿下での接着耐久性が不十分となり、浮きや剥がれなどが生じる場合がある。密着性及び接着耐久性などを考慮すると、この重量平均分子量は、１２０万〜２２０万のものが好ましく、特に１５０万〜２００万のものが好ましい。また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比率を表す分子量分布（Ｍｗ／Ｍｎ）についても、成分（Ａ）と同様に２０以下が好ましい。分子量分布が２０以下であると、十分な接着耐久性が得られる。
なお、当該粘着性材料においては、この成分（Ｂ）のアクリル系重合体は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The acrylic copolymer of component (B) has a weight average molecular weight of 1,000,000 or more. When the weight average molecular weight is less than 1,000,000, as described in the component (A), adhesion to the adherend and adhesion durability under high temperature and high humidity become insufficient, and floating and peeling are caused. May occur. In view of adhesion and adhesion durability, the weight average molecular weight is preferably 1.2 million to 2,200,000, particularly preferably 1,500,000 to 2,000,000. Also, the molecular weight distribution (Mw / Mn) representing the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 20 or less, as in the component (A). When the molecular weight distribution is 20 or less, sufficient adhesion durability can be obtained.
In addition, in the said adhesive material, the acrylic polymer of this component (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明の粘着性材料においては、上記成分（Ａ）と成分（Ｂ）の質量比（成分（Ａ）：成分（Ｂ））は１００：１〜１００：３０の範囲である。この質量比が１００：１未満、すなわち成分（Ｂ）の含有量が成分（Ａ）１００質量部に対して１質量部未満であると、十分な接着耐久性が得られず、特に過酷な耐久性が要求される場合に、接着性が不十分となる。一方、上記質量比が１００：３０を越える、すなわち成分（Ｂ）の含有量が成分（Ａ）１００質量部に対して３０質量部を超えると、十分な再剥離性が得られない。以上の観点から、成分（Ａ）：成分（Ｂ）は、１００：５〜１００：２０の範囲が好ましい。 In the adhesive material of the present invention, the mass ratio of the component (A) to the component (B) (component (A): component (B)) is in the range of 100: 1 to 100: 30. When the mass ratio is less than 100: 1, that is, the content of the component (B) is less than 1 part by mass with respect to 100 parts by mass of the component (A), sufficient adhesion durability cannot be obtained, and particularly severe durability is obtained. When the property is required, the adhesion is insufficient. On the other hand, when the mass ratio exceeds 100: 30, that is, when the content of the component (B) exceeds 30 parts by mass with respect to 100 parts by mass of the component (A), sufficient removability cannot be obtained. From the above viewpoint, the component (A): component (B) is preferably in the range of 100: 5 to 100: 20.
上記成分（Ａ）及び成分（Ｂ）には、本発明の効果を損なわない範囲であれば、構成成分として共重合可能な成分を含んでいてもよい。具体的には、官能基として、アミド基、アミノ基などを含むモノマーであり、具体例としては、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミドなどのアクリルアミド類；（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、（メタ）アクリル酸モノエチルアミノプロピルなどの（メタ）アクリル酸モノアルキルアミノアルキルなどが挙げられる。これらのモノマーは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In the said component (A) and component (B), if it is a range which does not impair the effect of this invention, the component which can be copolymerized may be included as a structural component. Specifically, it is a monomer containing an amide group, an amino group, or the like as a functional group. Specific examples include acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, and N-methylol (meth) acrylamide. ; (Meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl, etc. (meth) acrylic acid monoalkylaminoalkyl, etc. Is mentioned. These monomers may be used independently and may be used in combination of 2 or more type.
本発明の粘着性材料において、成分（Ｃ）として用いられる活性エネルギー線硬化型化合物としては、２官能から６官能までの種々の多官能（メタ）アクリレートモノマーを用いることができ、特に分子量１０００未満の多官能（メタ）アクリレート系モノマーを好ましく挙げることができる。
多官能（メタ）アクリレート系モノマーとしては、例えば１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、ジ（メタ）アクリロキシエチルイソシアヌレート、アリル化シクロヘキシルジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ジメチロールジシクロペンタンジ（メタ）アクリレート、エチレンオキサイド変性ヘキサヒドロフタル酸ジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、アダマンタンジ（メタ）アクリレートなどの２官能型；トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（メタ）アクリロキシエチルイソシアヌレートなどの３官能型；ジグリセリンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレートなどの４官能型；プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレートなどの５官能型；ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレートなどの６官能型などが挙げられる。
In the adhesive material of the present invention, as the active energy ray-curable compound used as the component (C), various polyfunctional (meth) acrylate monomers from bifunctional to hexafunctional can be used, and the molecular weight is particularly less than 1000. The polyfunctional (meth) acrylate monomer can be preferably mentioned.
Examples of the polyfunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di (meth). ) Acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol Cyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, adamantane di (meth) acrylate Bifunctional type such as: trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane Trifunctional type such as tri (meth) acrylate and tris (meth) acryloxyethyl isocyanurate; diglycerin tetra (meth) acrylate, pentae Tetrafunctional type such as sitolitol tetra (meth) acrylate; pentafunctional type such as propionic acid modified dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. The 6 functional type is mentioned.
本発明において、これらの多官能（メタ）アクリレート系モノマーは、１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよいが、これらの中で、骨格構造に環状構造を有するものを含有することが好ましい。環状構造は、炭素環式構造でも、複素環式構造でもよく、また、単環式構造でも多環式構造でもよい。このような多官能（メタ）アクリレート系モノマーとしては、例えばジ（メタ）アクリロキシエチルイソシアヌレート、トリス（メタ）アクリロキシエチルイソシアヌレートなどのイソシアヌレート構造を有するもの、ジメチロールジシクロペンタンジ（メタ）アクリレート、エチレンオキサイド変性ヘキサヒドロフタル酸ジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、アダマンタンジ（メタ）アクリレートなどが好適であり、特にイソシアヌレート構造を有するものが好ましい。 In the present invention, these polyfunctional (meth) acrylate monomers may be used alone or in combination of two or more. Among these, a cyclic structure is added to the skeleton structure. It is preferable to contain what it has. The cyclic structure may be a carbocyclic structure or a heterocyclic structure, and may be a monocyclic structure or a polycyclic structure. Examples of such polyfunctional (meth) acrylate monomers include those having an isocyanurate structure such as di (meth) acryloxyethyl isocyanurate, tris (meth) acryloxyethyl isocyanurate, dimethylol dicyclopentane di ( Suitable are meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, adamantane di (meth) acrylate, etc. In particular, those having an isocyanurate structure are preferred.
また、成分（Ｃ）として活性エネルギー線硬化型のアクリレート系オリゴマーを用いることができる。このアクリレート系オリゴマーは重量平均分子量５０，０００以下のものが好ましい。このようなアクリレート系オリゴマーの例としては、ポリエステルアクリレート系、エポキシアクリレート系、ウレタンアクリレート系、ポリエーテルアクリレート系、ポリブタジエンアクリレート系、シリコーンアクリレート系などが挙げられる。 Moreover, an active energy ray hardening-type acrylate-type oligomer can be used as a component (C). The acrylate oligomer preferably has a weight average molecular weight of 50,000 or less. Examples of such acrylate oligomers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, and silicone acrylate.
ここで、ポリエステルアクリレート系オリゴマーとしては、例えば多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を（メタ）アクリル酸でエステル化することにより、あるいは、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。エポキシアクリレート系オリゴマーは、例えば、比較的低分子量のビスフェノール型エポキシ樹脂やノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応させ、エステル化することにより得ることができる。また、このエポキシアクリレート系オリゴマーを部分的に二塩基性カルボン酸無水物で変性したカルボキシル変性型のエポキシアクリレートオリゴマーも用いることができる。ウレタンアクリレート系オリゴマーは、例えば、ポリエーテルポリオールやポリエステルポリオールとポリイソシアナートの反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸でエステル化することにより得ることができ、ポリオールアクリレート系オリゴマーは、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得ることができる。
上記アクリレート系オリゴマーの重量平均分子量は、ＧＰＣ法で測定した標準ポリメチルメタクリレート換算の値で、上述のように５０，０００以下が好ましく、より好ましくは５００〜５０，０００、さらに好ましくは３，０００〜４０，０００の範囲で選定される。
これらのアクリレート系オリゴマーは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Here, examples of the polyester acrylate oligomer include esterification of hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.
The weight average molecular weight of the acrylate oligomer is a value in terms of standard polymethyl methacrylate measured by GPC method, and is preferably 50,000 or less, more preferably 500 to 50,000, and still more preferably 3,000 as described above. It is selected in the range of ~ 40,000.
These acrylate oligomers may be used alone or in combination of two or more.
本発明においては、成分（Ｃ）として（メタ）アクリロイル基を有する基が側鎖に導入されたアダクトアクリレート系ポリマーを用いることもできる。このようなアダクトアクリレート系ポリマーは、例えば、前述の成分（Ａ）又は成分（Ｂ）において説明した（メタ）アクリル酸エステルと、分子内に官能基を有するモノマーとの共重合体を用い、該共重合体の官能基の一部に、（メタ）アクリロイル基及び該官能基と反応する基を有する化合物を反応させることにより得ることができる。該アダクトアクリレート系ポリマーの重量平均分子量は、ポリスチレン換算で、通常５０万〜２００万である。
本発明においては、成分（Ｃ）として、前記の多官能アクリレート系モノマー、アクリレート系オリゴマー及びアダクトアクリレート系ポリマーの中から、適宜１種を選び用いてもよく、２種以上を選び併用してもよい。
In the present invention, an adduct acrylate polymer in which a group having a (meth) acryloyl group is introduced into the side chain can also be used as the component (C). Such an adduct acrylate-based polymer uses, for example, a copolymer of the (meth) acrylic acid ester described in the above component (A) or component (B) and a monomer having a functional group in the molecule. It can be obtained by reacting a part of the functional group of the copolymer with a compound having a (meth) acryloyl group and a group that reacts with the functional group. The weight average molecular weight of the adduct acrylate polymer is usually 500,000 to 2,000,000 in terms of polystyrene.
In the present invention, as the component (C), one type may be appropriately selected from the above-mentioned polyfunctional acrylate monomers, acrylate oligomers, and adduct acrylate polymers, or two or more types may be used in combination. Good.
本発明においては、成分（Ｃ）の活性エネルギー線硬化型化合物の含有割合は、前記成分（Ａ）のアクリル系重合体に対して、得られる粘着剤の性能の面から、質量比（成分（Ａ）：成分（Ｃ））で、１００：１〜１００：４０の範囲であることが好ましい。
この範囲であると、成分（Ａ）及び成分（Ｂ）の特性を妨げずに活性エネルギー線照射後の粘着剤の貯蔵弾性率を最適な範囲に制御できる点で有利である。以上の観点から、成分（Ａ）：成分（Ｃ）は、１００：５〜１００：３０の範囲であることがさらに好ましい。
In the present invention, the content ratio of the active energy ray-curable compound of the component (C) is a mass ratio (component (component (C)) from the aspect of the performance of the pressure-sensitive adhesive obtained with respect to the acrylic polymer of the component (A). A): Component (C)), preferably in the range of 100: 1 to 100: 40.
Within this range, it is advantageous in that the storage elastic modulus of the pressure-sensitive adhesive after irradiation with active energy rays can be controlled within the optimum range without impairing the properties of the component (A) and the component (B). From the above viewpoints, the ratio of component (A): component (C) is more preferably in the range of 100: 5 to 100: 30.
本発明における粘着性材料には、所望により光重合開始剤を含有させることができる。この光重合開始剤としては、例えばベンソイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−２−（ヒドロキシ−２−プロピル）ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４，４’−ジエチルアミノベンゾフェノン、ジクロロベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリ−ブチルアントラキノン、２−アミノアントラキノン、２−メチルチオキサントン、２−エチルチオキサントン、２−クロロチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、ｐ−ジメチルアミノ安息香酸エステル、オリゴ［２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノン］、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイドなどが挙げられる。これらは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよく、また、その配合量は、前記成分（Ｃ）１００質量部に対して、通常０．２〜２０質量部の範囲で選ばれる。 The adhesive material in the present invention may contain a photopolymerization initiator as desired. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethyla Nobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the like. These may be used individually by 1 type, may be used in combination of 2 or more types, and the compounding quantity is 0.2-20 mass normally with respect to 100 mass parts of said components (C). Selected in the range of parts.
本発明における粘着性材料には、所望により、架橋剤を含有させることができる。この架橋剤としては、特に制限はなく、従来アクリル系粘着剤において架橋剤として慣用されているものの中から、任意のものを適宜選択して用いることができる。このような架橋剤としては、例えばポリイソシアネート化合物、エポキシ樹脂、メラミン樹脂、尿素樹脂、ジアルデヒド類、メチロールポリマー、アジリジン系化合物、金属キレート化合物、金属アルコキシド、金属塩などが挙げられるが、ポリイソシアネート化合物（成分（Ｄ））が好ましく用いられる。
ここで、（Ｄ）ポリイソシアネート化合物としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環式ポリイソシアネートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油などの低分子活性水素含有化合物との反応物であるアダクト体などを挙げることができる。
これらのうち、例えば、偏光板の表面材料として使用されるトリアセチルセルロース（ＴＡＣ）フィルムとの密着性を向上させ得る点から、イソシアネート系架橋剤が好ましい。
The adhesive material in the present invention can contain a crosslinking agent as desired. There is no restriction | limiting in particular as this crosslinking agent, Arbitrary things can be suitably selected and used from what was conventionally used as a crosslinking agent in an acrylic adhesive. Examples of such crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, and metal salts. A compound (component (D)) is preferably used.
Here, as (D) polyisocyanate compounds, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic rings such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Polyisocyanates and the like, and biurets, isocyanurates, and adducts that are a reaction product with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can be mentioned.
Among these, for example, an isocyanate-based cross-linking agent is preferable from the viewpoint of improving adhesion with a triacetyl cellulose (TAC) film used as a surface material of a polarizing plate.
本発明においては、上記架橋剤は１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、その使用量は、架橋剤の種類にもよるが、前記成分（Ａ）のアクリル系重合体１００質量部に対し、通常０．０１〜２０質量部、好ましくは、０．１〜１０質量部である。
また、（Ｄ）ポリイソシアネート化合物を用いる場合には、上記成分（Ａ）中の水酸基含有モノマーと（Ｄ）ポリイソシアネート化合物のモル比が０．８：１．２〜１．２：０．８の範囲であることが好ましい。当該モル比の範囲であると、成分（Ａ）及び成分（Ｂ）の特性を妨げずに活性エネルギー線照射後の粘着剤の貯蔵弾性率を最適な範囲に制御できる点で好ましい。
In this invention, the said crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although the usage-amount is based also on the kind of crosslinking agent, it is 0.01-20 mass parts normally with respect to 100 mass parts of acrylic polymers of the said component (A), Preferably, it is 0.1-10 mass. Part.
When (D) the polyisocyanate compound is used, the molar ratio of the hydroxyl group-containing monomer in the component (A) to the (D) polyisocyanate compound is 0.8: 1.2 to 1.2: 0.8. It is preferable that it is the range of these. The molar ratio is preferable in that the storage elastic modulus of the pressure-sensitive adhesive after irradiation with active energy rays can be controlled within an optimal range without disturbing the characteristics of the component (A) and the component (B).
本発明における粘着性材料には、所望により、成分（Ｅ）としてシランカップリング剤を含有させることができる。このシランカップリング剤を含有させることにより、偏光板などの光学フィルムを、例えば液晶セルなどに貼合する場合に、粘着剤と液晶セルの間の密着性がより良好となる。このシランカップリング剤としては、分子内にアルコキシシリル基を少なくとも１個有する有機ケイ素化合物であって、粘着剤成分との相溶性がよく、かつ光透過性を有するもの、例えば実質上透明なものが好適である。このようなシランカップリング剤の添加量は、成分（Ａ）と（Ｅ）シランカップリング剤の質量比が１００：０．１〜１００：０．５の範囲であることが好ましい。当該モル比の範囲であると、液晶セルなどの無アルカリガラスとの密着性と再剥離性を両立できる点で好ましい。 If desired, the adhesive material in the present invention can contain a silane coupling agent as the component (E). By including this silane coupling agent, when an optical film such as a polarizing plate is bonded to, for example, a liquid crystal cell, the adhesion between the pressure-sensitive adhesive and the liquid crystal cell becomes better. This silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, having good compatibility with the pressure-sensitive adhesive component, and having light transparency, for example, substantially transparent Is preferred. As for the addition amount of such a silane coupling agent, it is preferable that mass ratio of a component (A) and (E) silane coupling agent is the range of 100: 0.1-100: 0.5. When the molar ratio is within this range, it is preferable in terms of achieving both adhesiveness and removability with non-alkali glass such as a liquid crystal cell.
前記シランカップリング剤の具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有ケイ素化合物；３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ構造を有するケイ素化合物；３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン等のアミノ基含有ケイ素化合物；３−クロロプロピルトリメトキシシラン等が挙げられる。これらは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- Silicon compounds having an epoxy structure such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane and other amino group-containing silicon compounds; 3-chloropropyltrimethoxysilane and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
本発明の粘着剤は、このようにして得られた前記粘着性材料に、活性エネルギー線を照射してなるものである。
活性エネルギー線としては、例えば紫外線や電子線などが挙げられる。上記紫外線は、高圧水銀ランプ、無電極ランプ、キセノンランプなどで得られ、一方、電子線は電子線加速器などによって得られる。この活性エネルギー線の中では、特に紫外線が好適である。なお、電子線を使用する場合は、光重合開始剤を添加することなく、粘着剤を形成することができる。
当該粘着性材料に対する活性エネルギー線の照射量としては、好適な貯蔵弾性率、無アルカリガラスに対する粘着力を有する架橋化粘着剤が得られるように、適宜選定されるが、紫外線の場合は照度５０〜１０００ｍＷ／ｃｍ2、光量５０〜１０００ｍＪ／ｃｍ2、電子線の場合は１０〜１０００ｋｒａｄの範囲が好ましい。
The pressure-sensitive adhesive of the present invention is obtained by irradiating the pressure-sensitive adhesive material thus obtained with active energy rays.
Examples of the active energy rays include ultraviolet rays and electron beams. The ultraviolet rays are obtained with a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp or the like, while the electron beam is obtained with an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, an adhesive can be formed, without adding a photoinitiator.
The irradiation amount of the active energy ray for the adhesive material is appropriately selected so as to obtain a cross-linked adhesive having a suitable storage elastic modulus and an adhesive force to alkali-free glass. In the case of -1000mW / cm < 2 >, the light quantity 50-1000mJ / cm < 2 >, and an electron beam, the range of 10-1000krad is preferable.
本発明の粘着剤は、２３℃における貯蔵弾性率（G’）が、０．３ＭＰａ以上であることを必須とする。この貯蔵弾性率（Ｇ’）が０．３ＭＰａ以上であれば十分な光漏れ防止性が得られる。２３℃における貯蔵弾性率（G’）の上限については特に限定されないが、接着耐久性がより良好な粘着剤を得るためには、５０ＭＰａ以下であることが好ましく、さらに１５ＭＰａ以下であることが好ましい。以上の観点から特に好ましい２３℃の貯蔵弾性率（Ｇ’）は０．３５〜１２ＭＰａである。また、８０℃の貯蔵弾性率（Ｇ’）も、通常０．１ＭＰａ以上が好ましく、さらには０．１〜１５ＭＰａ、特には０．３〜１０ＭＰａであることが好ましい。
なお、前記貯蔵弾性率（Ｇ’）は、下記の方法で測定した値である。
＜貯蔵弾性率（Ｇ’）の測定方法＞
貯蔵弾性率（Ｇ’）は、厚さ３０μｍの粘着剤を積層し、８ｍｍφ×３ｍｍ厚の円柱状の試験片を作製し、ねじり剪断法により、下記の条件で測定する。
測定装置：レオメトリック社製動的粘弾性測定装置「ＤＹＮＡＭＩＣ ＡＮＡＬＹＺＥＲ ＲＤＡII」
周波数 ：１Ｈｚ
温度 ：２３℃、８０℃
The pressure-sensitive adhesive of the present invention essentially has a storage elastic modulus (G ′) at 23 ° C. of 0.3 MPa or more. If this storage elastic modulus (G ′) is 0.3 MPa or more, sufficient light leakage prevention properties can be obtained. The upper limit of the storage elastic modulus (G ′) at 23 ° C. is not particularly limited, but in order to obtain a pressure-sensitive adhesive having better adhesion durability, it is preferably 50 MPa or less, and more preferably 15 MPa or less. . From the above viewpoint, the storage elastic modulus (G ′) at 23 ° C. is particularly preferably 0.35 to 12 MPa. Further, the storage elastic modulus (G ′) at 80 ° C. is usually preferably 0.1 MPa or more, more preferably 0.1 to 15 MPa, and particularly preferably 0.3 to 10 MPa.
The storage elastic modulus (G ′) is a value measured by the following method.
<Method for measuring storage elastic modulus (G ′)>
The storage elastic modulus (G ′) is measured by the following conditions by laminating an adhesive having a thickness of 30 μm to produce a cylindrical test piece having a thickness of 8 mmφ × 3 mm and using a torsional shear method.
Measuring device: rheometric dynamic viscoelasticity measuring device "DYNAMIC ANALYZER RDAII"
Frequency: 1Hz
Temperature: 23 ° C, 80 ° C
また、本発明の粘着剤は、無アルカリガラスに対する粘着力を、貼合後１４日まで１０Ｎ／２５ｍｍに抑制することができる。従って、貼合から１４日経過後であっても、液晶セルにダメージを与えることなく再剥離が可能である。
なお、該粘着力の下限値については、通常０．２Ｎ／２５ｍｍ以上であることが好ましい。この粘着力が０．２Ｎ／２５ｍｍ以上であれば、偏光板を十分な粘着力で液晶セル等に貼合することができる。
Moreover, the adhesive of this invention can suppress the adhesive force with respect to an alkali free glass to 10 N / 25mm until 14 days after bonding. Therefore, even after 14 days have passed since pasting, re-peeling is possible without damaging the liquid crystal cell.
In addition, about the lower limit of this adhesive force, it is usually preferable that it is 0.2 N / 25mm or more. If this adhesive strength is 0.2 N / 25 mm or more, the polarizing plate can be bonded to a liquid crystal cell or the like with sufficient adhesive strength.
なお、上記粘着力は、下記の方法で測定した値である。
＜無アルカリガラスとの粘着力＞
粘着剤付き偏光板から、２５ｍｍ幅、１００ｍｍ長のサンプルを切り出し、剥離フィルムを剥がして（粘着剤層の厚さ２５μｍ）、無アルカリガラス［コーニング社製「１７３７」］に貼付したのち、栗原製作所製オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧する。その後、２３℃、５０％ＲＨ環境下で１４日間放置した後、引張試験機（オリエンテック社製「テンシロン」）を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で粘着力を測定する。
In addition, the said adhesive force is the value measured by the following method.
<Adhesive strength with non-alkali glass>
A 25 mm wide, 100 mm long sample was cut out from the polarizing plate with an adhesive, the release film was peeled off (the thickness of the adhesive layer was 25 μm), and pasted on an alkali-free glass [Corning “1737”], then Kurihara Seisakusho Pressurization is performed under the conditions of 0.5 MPa, 50 ° C., and 20 minutes in an autoclave. Then, after being left for 14 days in an environment of 23 ° C. and 50% RH, the adhesive strength was measured using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.) at a peeling speed of 300 mm / min and a peeling angle of 180 °. To do.
本発明の粘着剤はゲル分率が８５％以上であることが好ましい。すなわち、有機溶媒にて抽出される程度の低分子量成分が少ない場合は、加熱下や温熱下の環境で浮きや剥がれ、被着体への汚染が少なく、ゲル分率が８５％以上である粘着性材料は耐久性や安定性が高い。ゲル分率はさらに９０〜９９．９％であることが好ましい。 The pressure-sensitive adhesive of the present invention preferably has a gel fraction of 85% or more. In other words, when there are few low molecular weight components that can be extracted with an organic solvent, the adhesive is floated or peeled off under heating or in an environment of heat, has little contamination to the adherend, and has a gel fraction of 85% or more. Material is highly durable and stable. The gel fraction is preferably 90 to 99.9%.
本発明の粘着剤には、本発明の目的が損なわれない範囲で、所望によりアクリル系粘着剤に通常使用されている各種添加剤、例えば粘着付与剤、酸化防止剤、光安定剤、軟化剤、充填剤などを添加することができる。 In the pressure-sensitive adhesive of the present invention, various additives usually used in acrylic pressure-sensitive adhesives as desired, for example, tackifiers, antioxidants, light stabilizers, softeners, as long as the object of the present invention is not impaired. A filler or the like can be added.
本発明の粘着剤は、偏光フィルム単独からなる偏光板に適用して、該偏光板を、例えば液晶セルに接着させるのに用いることができるが、特に偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板に適用し、この偏光板を、例えば液晶セルに接着させるのに、好ましく用いることができる。
前記偏光フィルムと視野角拡大フィルムとが一体化してなる偏光板としては、例えばポリビニルアルコール系偏光子の両面に、それぞれトリアセチルセルロース（ＴＡＣ）フィルムを貼り合わせてなる偏光フィルムの片面に、例えばディスコティック液晶からなる視野角拡大機能層（視野角拡大フィルム）を塗布により設けたもの、あるいは視野角拡大フィルムを接着剤で貼り合わせたものなどを挙げることができる。この場合、粘着剤は、前記視野角拡大機能層又は視野角拡大フィルム側に設ける。
また、偏光板としてはポリビニルアルコール系偏光子の片面にトリアセチルセルロース（ＴＡＣ）フィルムを貼り合わせ、もう一方の面にシクロオレフィン系フィルムやポリカーボネートフィルムなどからなる位相差フィルムを貼り合わせたものでもよい。この場合、粘着剤は位相差フィルム側に設ける。
The pressure-sensitive adhesive of the present invention can be applied to a polarizing plate composed of a polarizing film alone and used to adhere the polarizing plate to, for example, a liquid crystal cell. In particular, a polarizing film and a viewing angle widening film are integrated. For example, the polarizing plate can be preferably used for bonding to a liquid crystal cell.
As the polarizing plate in which the polarizing film and the viewing angle widening film are integrated, for example, on one side of a polarizing film obtained by bonding a triacetyl cellulose (TAC) film to each side of a polyvinyl alcohol polarizer, for example, disco Examples thereof include those provided by applying a viewing angle widening functional layer (viewing angle widening film) made of a tick liquid crystal, or those obtained by bonding a viewing angle widening film with an adhesive. In this case, the adhesive is provided on the viewing angle widening functional layer or the viewing angle widening film side.
Moreover, as a polarizing plate, what stuck the triacetylcellulose (TAC) film on the single side | surface of the polyvinyl alcohol type polarizer, and bonded the retardation film which consists of a cycloolefin type film, a polycarbonate film, etc. on the other side may be used. . In this case, the adhesive is provided on the retardation film side.
また、図２に示すように偏光板と液晶セルの間に位相差板がある場合にも、本発明の粘着剤は好適に使用し得る。すなわち、偏光フィルム単独からなる偏光板と位相差板を本発明の粘着剤で貼合して光学フィルムを製造し、該光学フィルムの位相差板と液晶セルを粘着剤で貼合するものである。ここで位相差板と液晶セルを貼合する粘着剤としては特に限定されず、通常偏光板と液晶セルの貼合に用いられる粘着剤を使用することができる。具体的には、特開平１１−１３１０３３に開示されるアクリル系共重合体、架橋剤及びシランカップリング剤からなる粘着性材料などが挙げられる。なお、偏光板と液晶セルの貼合に、本発明の粘着剤を用いることもできる。
本発明の粘着剤を用いて、前記のようにして液晶セル又は位相差板に偏光板を接着させることにより作製した液晶表示装置は、高温高湿環境下でも光漏れが生じにくい上、偏光板と液晶セルとの接着耐久性に優れている。
Moreover, also when there exists a phase difference plate between a polarizing plate and a liquid crystal cell as shown in FIG. 2, the adhesive of this invention can be used conveniently. That is, an optical film is produced by laminating a polarizing plate consisting of a polarizing film and a retardation plate with the adhesive of the present invention, and laminating the retardation plate of the optical film and a liquid crystal cell with an adhesive. . Here, the pressure-sensitive adhesive for bonding the retardation plate and the liquid crystal cell is not particularly limited, and a pressure-sensitive adhesive usually used for bonding the polarizing plate and the liquid crystal cell can be used. Specific examples thereof include an adhesive material composed of an acrylic copolymer, a crosslinking agent and a silane coupling agent disclosed in JP-A-11-133103. In addition, the adhesive of this invention can also be used for bonding of a polarizing plate and a liquid crystal cell.
A liquid crystal display device produced by adhering a polarizing plate to a liquid crystal cell or a retardation plate as described above using the pressure-sensitive adhesive of the present invention is less susceptible to light leakage even in a high temperature and high humidity environment. Excellent adhesion durability between LCD and liquid crystal cell.
本発明はまた、光学フィルム上、例えば偏光板上に、前述の本発明の粘着剤からなる層を有する粘着剤付き光学フィルムをも提供する。この偏光板としては、前述したように、偏光フィルム単独からなるものであってもよいが、図１に示すような構成の場合には、偏光フィルムと視野角拡大フィルムとが一体化してなるものが好ましい。
また、前記の粘着剤からなる粘着剤層の厚さは、通常５〜１００μｍ程度、好ましくは１０〜５０μｍ、さらに好ましくは１０〜３０μｍである。
The present invention also provides an optical film with a pressure-sensitive adhesive having a layer made of the pressure-sensitive adhesive of the present invention described above on an optical film, for example, a polarizing plate. As described above, the polarizing plate may be composed of a polarizing film alone, but in the case of the configuration shown in FIG. 1, the polarizing film and the viewing angle widening film are integrated. Is preferred.
The thickness of the pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive is usually about 5 to 100 μm, preferably 10 to 50 μm, and more preferably 10 to 30 μm.
この粘着剤付き光学フィルムの製造方法については、偏光板などの光学フィルム上に本発明の粘着剤からなる層が設けられたものが得られる方法であればよく、特に制限はないが、以下に示す本発明の方法によれば、効率よく所望の粘着剤付き光学フィルムを製造することができる。 About the manufacturing method of this optical film with an adhesive, what is necessary is just a method by which what was provided with the layer which consists of an adhesive of the present invention on optical films, such as a polarizing plate, although there is no restriction in particular, According to the method of the present invention shown, a desired optical film with a pressure-sensitive adhesive can be efficiently produced.
本発明の方法においては、剥離シートの剥離層上に設けられた粘着性材料層に、偏光板を貼合した後、該剥離シート側から活性エネルギー線を、前記粘着性材料層が、前述の所定の特性を有する本発明の粘着剤から構成される層になるように照射することによって、本発明の粘着剤付き光学フィルムが得られる。 In the method of the present invention, after the polarizing plate is bonded to the adhesive material layer provided on the release layer of the release sheet, the active energy ray is applied from the release sheet side, and the adhesive material layer is the above-described adhesive material layer. By irradiating so that it may become a layer comprised from the adhesive of this invention which has a predetermined characteristic, the optical film with an adhesive of this invention is obtained.
前記剥離シートとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルムなどのプラスチックフィルムに、シリコーン樹脂などの剥離剤を塗布し剥離層を設けたものなどが挙げられる。この剥離シートの厚さについては特に制限はないが、通常２０〜１５０μｍ程度である。
また、粘着性材料及び活性エネルギー線の照射条件については、前述の本発明の粘着剤において説明したとおりである。
Examples of the release sheet include a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., a plastic film such as a polyolefin film such as polypropylene or polyethylene, and a release layer such as a silicone resin applied to the release film. Is mentioned. Although there is no restriction | limiting in particular about the thickness of this peeling sheet, Usually, it is about 20-150 micrometers.
Moreover, about the irradiation conditions of an adhesive material and an active energy ray, it is as having demonstrated in the above-mentioned adhesive of this invention.
剥離シート上に粘着性材料層を設ける方法としては、例えばバーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などを用いて、好ましくは溶剤を加えた粘着性材料をコーティングして塗膜を形成させ、乾燥させる方法を用いることができる。乾燥条件は特に制限されないが、通常５０〜１５０℃で１０秒〜１０分程度である。また、用いる溶剤としても特に限定されず、トルエン、酢酸エチル、メチルエチルケトンなどが挙げられる。 As a method of providing an adhesive material layer on a release sheet, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, etc., preferably a solvent added adhesive A method of coating the material to form a coating film and drying can be used. The drying conditions are not particularly limited, but are usually about 10 seconds to 10 minutes at 50 to 150 ° C. Moreover, it does not specifically limit as a solvent to be used, Toluene, ethyl acetate, methyl ethyl ketone, etc. are mentioned.
また、図１に示すような構成の場合には、偏光板としては、偏光フィルム単独からなるものである場合が多く、粘着剤からなる粘着剤層の厚さは前記と同様である。図１に示すような構成における粘着剤付き偏光板の製造方法についても、上記と同様に偏光板上に本発明の粘着剤からなる粘着剤層が設けられたものが得られる方法であればよく、特に制限はない。上記した本発明の製造方法によって効率的に製造することができる。 In the case of the configuration shown in FIG. 1, the polarizing plate is often made of a polarizing film alone, and the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive is the same as described above. The production method of the polarizing plate with the pressure sensitive adhesive in the configuration as shown in FIG. 1 may be any method as long as the pressure sensitive adhesive layer comprising the pressure sensitive adhesive of the present invention is provided on the polarizing plate as described above. There is no particular limitation. It can manufacture efficiently by the manufacturing method of the above-mentioned this invention.
さらに、図２に示すような構成の場合には、２枚の剥離シートの剥離層側に接するように上述の粘着剤を挟持してなる粘着シートを作製しておき、該粘着シートを用いて偏光板と位相差板を貼合することができる。ここで活性エネルギー線は２枚の剥離シートに粘着性材料を挟持した後に照射してもよいし、一方の剥離シートに粘着性材料層を設け、活性エネルギー線を照射した後に他の剥離シートで挟持してもよい。なお、活性エネルギー線の照射条件は、前述の所定の特性を有する本発明の粘着剤から構成される層になるように選択される。
この粘着シートを用いて本発明の光学フィルムを製造する場合には、粘着シートの剥離シートが剥がされ、通常の方法により偏光板と貼合される。
Further, in the case of the configuration as shown in FIG. 2, a pressure-sensitive adhesive sheet is prepared by sandwiching the above-mentioned pressure-sensitive adhesive so as to be in contact with the release layer side of the two release sheets. A polarizing plate and a retardation plate can be bonded together. Here, the active energy ray may be irradiated after the adhesive material is sandwiched between two release sheets, or an adhesive material layer is provided on one release sheet, and after the active energy ray is irradiated, It may be pinched. In addition, the irradiation conditions of an active energy ray are selected so that it may become a layer comprised from the adhesive of this invention which has the above-mentioned predetermined characteristic.
When manufacturing the optical film of this invention using this adhesive sheet, the peeling sheet of an adhesive sheet is peeled off and it bonds with a polarizing plate by a normal method.
本発明においては、粘着シートから剥離シートを剥離する際の剥離力が３０ｍ／分の速度で剥離した場合に１００ｍＮ／２５ｍｍ以下であることが好ましい。剥離力が１００ｍＮ／２５ｍｍ以下であると剥離帯電が生じにくく、本発明の偏光板等を作製する際に異物を巻き込むことがない。特に大型テレビなどの用途に用いる場合には有効である。
なお、偏光板以外に、本発明のリワーク性を有する粘着剤を適用できる光学フィルムとしては、位相差フィルム、及びプラズマディスプレイパネルや液晶ディスプレイパネル等のディスプレイ表面の保護フィルム等が挙げられるが、これらに限定されるものではない。
In this invention, when peeling force at the time of peeling a peeling sheet from an adhesive sheet peels at the speed | rate of 30 m / min, it is preferable that it is 100 mN / 25mm or less. When the peeling force is 100 mN / 25 mm or less, peeling electrification hardly occurs and no foreign matter is involved when the polarizing plate of the present invention is produced. This is particularly effective when used for applications such as large televisions.
In addition to the polarizing plate, examples of the optical film to which the reworkable pressure-sensitive adhesive of the present invention can be applied include retardation films and protective films for display surfaces such as plasma display panels and liquid crystal display panels. It is not limited to.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、実施例１〜７及び比較例１〜６で得られた粘着剤の性能及び粘着剤付き偏光板の性能を、以下に示す要領で求めた。
（１）粘着剤の貯蔵弾性率
明細書本文に記載の方法に従って、２３℃及び８０℃における貯蔵弾性率を測定した。
（２）粘着力（無アルカリガラスとの粘着力）
明細書本文に記載の方法に従って、無アルカリガラスとの粘着力を測定した。粘着力の測定は、オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧した後、２３℃、５０％ＲＨ環境下で、１日、１４日、及び２１日間、それぞれ放置した後のものを測定した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the performance of the adhesive obtained in Examples 1-7 and Comparative Examples 1-6 and the performance of the polarizing plate with an adhesive were calculated | required in the way shown below.
(1) Storage elastic modulus of adhesive The storage elastic modulus at 23 ° C. and 80 ° C. was measured according to the method described in the specification text.
(2) Adhesive strength (adhesive strength with non-alkali glass)
The adhesion with non-alkali glass was measured according to the method described in the specification text. The measurement of the adhesive strength was carried out in an autoclave under conditions of 0.5 MPa, 50 ° C. and 20 minutes, and then allowed to stand for 1 day, 14 days and 21 days in an environment of 23 ° C. and 50% RH. The latter was measured.
（３）ゲル分率
各実施例及び比較例における成分（Ａ）〜成分（Ｅ）からなる粘着剤組成物を秤量し（初期質量）、これを酢酸エチル中に投入し、ソックスレー抽出装置を用いて１６時間以上還流を行った後、不溶分のみを取り出した。該不溶分に含まれている溶剤を乾燥除去した後、秤量し（不溶分質量）、以下の式によってゲル分率を求めた。
ゲル分率（％）＝（不溶分質量／初期質量）×１００
(3) Gel fraction The pressure-sensitive adhesive composition comprising the components (A) to (E) in each Example and Comparative Example was weighed (initial mass), and this was put into ethyl acetate, using a Soxhlet extraction apparatus. After refluxing for 16 hours or more, only the insoluble matter was taken out. After the solvent contained in the insoluble matter was removed by drying, the solvent was weighed (insoluble matter mass), and the gel fraction was determined by the following formula.
Gel fraction (%) = (insoluble mass / initial mass) × 100
（４）粘着剤付き偏光板の耐久性
粘着剤付き偏光板を、裁断装置（荻野精機製作所社製スーパーカッター「ＰＮ１−６００」）により、２３３ｍｍ×３０９ｍｍサイズに調整したのち、無アルカリガラス［コーニング社製「１７３７」］に貼合後、栗原製作所社製オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧した。その後、下記の各耐久条件の環境下に投入し、２００時間後に、１０倍率ルーペを用いて観察を行い、以下の判定基準で耐久性を評価した。
◎：４辺において、外周端部から０．３ｍｍ以上に欠点がないもの。
○：４辺において、外周端部から０．６ｍｍ以上に欠点がないもの。
△：４辺のいずれか１辺に、外周端部から０．６ｍｍ以上に浮き、剥がれ、発泡、スジなどの０．１ｍｍ未満の粘着剤の外観異常欠点があるもの。
×：４辺のいずれか１辺に、外周端部から０．６ｍｍ以上に浮き、剥がれ、発泡、スジなどの０．１ｍｍ以上の粘着剤の外観異常欠点があるもの。
＜耐久条件＞
８０℃ドライ環境、９０℃ドライ環境、６０℃・相対湿度９０％環境
−２０℃⇔６０℃の各３０分のヒートショック試験、２００サイクル
(4) Durability of polarizing plate with pressure-sensitive adhesive A polarizing plate with pressure-sensitive adhesive is adjusted to a size of 233 mm × 309 mm using a cutting device (Super cutter “PN1-600” manufactured by Sugano Seiki Seisakusho Co., Ltd.), and then alkali-free glass [Corning After being bonded to “1737” manufactured by Kogyo Co., Ltd., pressure was applied in an autoclave manufactured by Kurihara Seisakusho under the conditions of 0.5 MPa, 50 ° C., and 20 minutes. Then, it put into the environment of each following durability conditions, and after 200 hours observed using a 10 magnification loupe, and evaluated durability with the following criteria.
A: There are no defects on the four sides 0.3 mm or more from the outer peripheral edge.
◯: There are no defects on the four sides 0.6 mm or more from the outer peripheral edge.
Δ: Any one of the four sides has an abnormal appearance defect of an adhesive of less than 0.1 mm such as floating, peeling, foaming, or streaking from the outer peripheral edge to 0.6 mm or more.
X: One of the four sides has an abnormal appearance defect of an adhesive of 0.1 mm or more such as floating, peeling, foaming, or streaking from the outer peripheral end portion to 0.6 mm or more.
<Durability conditions>
80 ° C dry environment, 90 ° C dry environment, 60 ° C and 90% relative humidity environment – 20 ° C to 60 ° C heat shock test for 30 minutes each, 200 cycles
（５）光漏れ性能
粘着剤付き偏光板を、裁断装置（荻野精機製作所製スーパーカッター「ＰＮ１−６００」）により、２３３ｍｍ×３０９ｍｍサイズに調整したのち、無アルカリガラス［コーニング社製「１７３７」］に貼合後、栗原製作所製オートクレーブにて、０．５ＭＰａ、５０℃、２０分間の条件で加圧した。なお、上記貼合は、無アルカリガラスの表裏に、粘着剤付き偏光板を偏光軸がクロスニコル状態になるように行った。この状態で８０℃ドライ環境下、２００時間放置後、以下に示す方法で光漏れ性を評価した。
大塚電子社製ＭＣＰＤ−２０００を用い、図３に示す各領域の明度を測定し、明度ΔＬ*を、式
ΔＬ*＝［（ｂ＋ｃ＋ｄ＋ｅ）／４］−ａ
（ただし、ａ、ｂ、ｃ、ｄ及びｅは、それぞれＡ領域、Ｂ領域、Ｃ領域、Ｄ領域及びＥ領域のあらかじめ定められた測定点（各領域の中央部１箇所）における明度である。）で求め、光漏れ性とする。ΔＬ*の値が小さいほど、光漏れが少ないことを示し、通常４．０未満であれば、液晶表示装置用として使用が可能である。
(5) Light leakage performance A polarizing plate with an adhesive is adjusted to a size of 233 mm × 309 mm with a cutting device (Super cutter “PN1-600” manufactured by Sugano Seiki Seisakusho), and then alkali-free glass [“1737” manufactured by Corning] After pasting, it was pressurized under the conditions of 0.5 MPa, 50 ° C., and 20 minutes in an autoclave manufactured by Kurihara Seisakusho. In addition, the said bonding was performed so that a polarizing axis might be in a crossed Nicol state on the front and back of an alkali free glass with an adhesive. In this state, after leaving in an 80 ° C. dry environment for 200 hours, light leakage was evaluated by the following method.
The brightness of each region shown in FIG. 3 was measured using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and the brightness ΔL * was expressed by the formula ΔL * = [(b + c + d + e) / 4] −a
(Where a, b, c, d, and e are the lightness values at predetermined measurement points (one central portion of each region) in the A region, B region, C region, D region, and E region, respectively. ) To obtain light leakage. A smaller value of ΔL * indicates that there is less light leakage. Usually, if it is less than 4.0, it can be used for a liquid crystal display device.
実施例１〜７及び比較例１〜６
第１表に示すモノマー組成（固形分換算）を用いて、第１表に示す物性を有する、アクリル系共重合体（成分（Ａ））及びアクリル系共重合体（成分（Ｂ））を調製した。これに多官能アクリレート系モノマー（成分（Ｃ））、光重合開始剤、ポリイソシアネート化合物（成分（Ｄ））、シランカップリング剤（成分（Ｅ））を第１表に記載する配合量にて配合し、さらに溶剤としてトルエンを加えて固形分２０質量％の塗工液を得た。該塗工液を用いて、剥離フィルムとして厚さ３８μｍのポリエチレンテレフタレート製剥離フィルム［リンテック社製「ＳＰ−ＰＥＴ３８１１」］の剥離層上に、乾燥後の厚さが２５μｍとなるように、ナイフ式塗工機で塗布した後、９０℃で１分間乾燥処理して粘着性材料層を形成した。
Examples 1-7 and Comparative Examples 1-6
An acrylic copolymer (component (A)) and an acrylic copolymer (component (B)) having the physical properties shown in Table 1 were prepared using the monomer composition (solid content conversion) shown in Table 1. did. A polyfunctional acrylate monomer (component (C)), a photopolymerization initiator, a polyisocyanate compound (component (D)), and a silane coupling agent (component (E)) are added in the amounts shown in Table 1. Further, toluene was added as a solvent to obtain a coating liquid having a solid content of 20% by mass. Using this coating solution, a knife-type film is formed on a release layer of a release film made of polyethylene terephthalate having a thickness of 38 μm as a release film [“SP-PET3811” manufactured by Lintec Corporation] so that the thickness after drying is 25 μm. After applying with a coating machine, it was dried at 90 ° C. for 1 minute to form an adhesive material layer.
次いで、ディスコティック液晶層（視野角拡大機能層）付偏光フィルムからなる偏光板を、粘着性材料層とディスコティック液晶層が接するように貼合した。貼合してから１時間後に剥離フィルム側から、紫外線（ＵＶ）を下記の条件で照射し、粘着剤付き偏光板を作製した。
＜ＵＶ照射条件＞
・フュージョン社製無電極ランプ Ｈバルブ使用
・照度６００ｍＷ／ｃｍ2、光量１５０ｍＪ／ｃｍ2
ＵＶ照度・光量計は、アイグラフィックス社製「ＵＶＰＦ−３６」を使用した。
粘着剤の性能及び粘着剤付き偏光板の性能の評価結果を第２表に示す。
Subsequently, the polarizing plate which consists of a polarizing film with a discotic liquid crystal layer (viewing angle expansion functional layer) was bonded so that an adhesive material layer and a discotic liquid crystal layer may contact | connect. One hour after bonding, ultraviolet rays (UV) were irradiated from the release film side under the following conditions to produce a polarizing plate with an adhesive.
<UV irradiation conditions>
Fusion Co. electrodeless lamp H bulb used, illuminance 600 mW / cm 2, light quantity 150 mJ / cm 2
“UVPF-36” manufactured by Eye Graphics Co., Ltd. was used as the UV illuminance / light meter.
Table 2 shows the evaluation results of the performance of the pressure-sensitive adhesive and the performance of the polarizing plate with the pressure-sensitive adhesive.
＊１ ＢＡ；アクリル酸ブチル
＊２ ＨＥＡ；アクリル酸２−ヒドロキシエチル
＊３ ＡＡ；アクリル酸
＊４ Ｍ−３１５；トリス（アクリロキシエチル）イソシアヌレート、分子量＝４２３、３官能型（東亜合成社製、商品名「アロニックスＭ−３１５」）
＊５ Ｒ−６８４；トリシクロデカンジメタノールアクリレート（日本化薬社製「ＫＡＹＡＲＡＤ Ｒ−６８４」、分子量＝３３６）
＊６ 光重合開始剤；ベンゾフェノンと１−ヒドロキシシクロヘキシルフェニルケトンとの質量比１：１の混合物、チバ・スペシャルティ・ケミカルズ社製「イルガキュア５００」
＊７ ポリイソシアネート化合物；（架橋剤、密着性改良剤）：トリメチロールプロパン変性トリレンジイソシアネート（日本ポリウレタン社製「コロネートＬ」）
＊８ シランカップリング剤：３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製「ＫＢＭ−４０３」）
* 1 BA; butyl acrylate * 2 HEA; 2-hydroxyethyl acrylate * 3 AA; acrylic acid * 4 M-315; tris (acryloxyethyl) isocyanurate, molecular weight = 423, trifunctional (manufactured by Toagosei Co., Ltd.) Product name "Aronix M-315")
* 5 R-684; tricyclodecane dimethanol acrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., molecular weight = 336)
* 6 Photopolymerization initiator; a mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1: 1, “Irgacure 500” manufactured by Ciba Specialty Chemicals
* 7 Polyisocyanate compound; (crosslinking agent, adhesion improver): trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane)
* 8 Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)
本発明の粘着剤は、例えば、偏光板、特に視野角拡大フィルムなどと一体化してなる偏光板に、又は偏光板に位相差板が積層される場合に好適に適用され、該偏光板を液晶セルに耐久性よく接着し得ると共に、得られた液晶表示装置が、高温高湿環境下でも光漏れが生じにくいなどの特性を有している。また、リワーク性に優れるため、貼合位置にずれが生じた場合など、貼合から一定期間は再度剥離することができ、正確に貼合された場合には、一定期間経過することにより、液晶セルに十分に貼合することができる。従って、高価な液晶セルを再利用することができる。 The pressure-sensitive adhesive of the present invention is suitably applied to, for example, a polarizing plate integrated with a polarizing plate, particularly a viewing angle widening film, or when a retardation plate is laminated on the polarizing plate. In addition to being able to adhere to the cell with good durability, the obtained liquid crystal display device has characteristics such that light leakage hardly occurs even in a high temperature and high humidity environment. In addition, because it has excellent reworkability, it can be peeled again for a certain period from pasting, such as when there is a shift in the pasting position. Can be fully bonded to the cell. Therefore, expensive liquid crystal cells can be reused.
１，２；液晶表示装置
１１，２１；偏光板
１２，２２，２５；粘着剤
１３，２３；ガラス（液晶セル）
２４；位相差板
1, 2; Liquid
24; retardation plate
Claims (10)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007184710A JP4991421B2 (en) | 2007-07-13 | 2007-07-13 | Adhesive, adhesive sheet and optical film with adhesive |
| CN2008101330925A CN101343517B (en) | 2007-07-13 | 2008-07-08 | Adhesive, adhesive sheet and optical functional film with adhesive |
| TW097126006A TWI421318B (en) | 2007-07-13 | 2008-07-10 | Adhesive, adhesion sheet and optical film with adhesive |
| KR20080066928A KR101496461B1 (en) | 2007-07-13 | 2008-07-10 | Adhesive, adhesive sheet and optical film with adhesive |
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| JP2007184710A JP4991421B2 (en) | 2007-07-13 | 2007-07-13 | Adhesive, adhesive sheet and optical film with adhesive |
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| JP2012105752A Division JP5567619B2 (en) | 2012-05-07 | 2012-05-07 | Adhesive, adhesive sheet and optical film with adhesive |
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| JP2009019172A true JP2009019172A (en) | 2009-01-29 |
| JP4991421B2 JP4991421B2 (en) | 2012-08-01 |
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| JP (1) | JP4991421B2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20090007222A (en) | 2009-01-16 |
| KR101496461B1 (en) | 2015-02-26 |
| JP4991421B2 (en) | 2012-08-01 |
| CN101343517A (en) | 2009-01-14 |
| CN101343517B (en) | 2012-06-06 |
| TW200911939A (en) | 2009-03-16 |
| TWI421318B (en) | 2014-01-01 |
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