JP2011219665A - Transparent self-adhesive sheet, and image display device - Google Patents
Transparent self-adhesive sheet, and image display device Download PDFInfo
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- JP2011219665A JP2011219665A JP2010091931A JP2010091931A JP2011219665A JP 2011219665 A JP2011219665 A JP 2011219665A JP 2010091931 A JP2010091931 A JP 2010091931A JP 2010091931 A JP2010091931 A JP 2010091931A JP 2011219665 A JP2011219665 A JP 2011219665A
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- adhesive layer
- sensitive adhesive
- adhesive sheet
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- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、透明な粘着シートに関する。例えばモバイル端末、ＰＤＡ、ゲーム機、ＴＶ、タッチパネル、ペンタブレットなどＬＣＤ、ＰＤＰ、ＥＬを用いた平面型画像表示装置において、画像表示パネルに保護パネル等の透明パネルを貼り合わせるのに好適に用いることができる透明粘着シートに関する。 The present invention relates to a transparent pressure-sensitive adhesive sheet. For example, in a flat image display device using LCD, PDP, EL such as a mobile terminal, PDA, game machine, TV, touch panel, pen tablet, etc., it is preferably used for bonding a transparent panel such as a protection panel to the image display panel. The present invention relates to a transparent adhesive sheet that can be used.
平面型画像表示装置はテレビ、パソコン、携帯電話（モバイル）など様々な分野で応用され、急激に市場が拡大をしている。この種の平面型画像表示装置において、表示パネルやタッチパネルの破損を防止するため、表示パネルやタッチパネル上に保護パネルを配置することがあり、従来は、画像表示パネルと保護パネルとの間に空間を設けて積層することで緩衝性を高めて、画像表示パネルのキズや割れを防止していた。しかし、保護パネルと空間との界面で反射が生じて画像の視認性が低下し、特に屋外において画像が見難くなるという問題があった。また、空間を設けることによって薄型化することが困難になるという問題もあった。
そこで、薄型化と視認性の両方を改善する方法として、画像表示パネルと保護パネルとを透明な粘着剤乃至シートを介して直接積層することが提案（下記参照）されている。
Flat-type image display devices are applied in various fields such as televisions, personal computers, and mobile phones (mobiles), and the market is rapidly expanding. In this type of flat-type image display device, a protection panel may be disposed on the display panel or touch panel in order to prevent damage to the display panel or touch panel. Conventionally, there is a space between the image display panel and the protection panel. By providing and laminating, the buffering property was improved and the image display panel was prevented from being scratched or cracked. However, reflection occurs at the interface between the protective panel and the space, and the visibility of the image is lowered. In particular, there is a problem that it is difficult to view the image outdoors. Moreover, there also existed a problem that it became difficult to reduce in thickness by providing space.
Therefore, as a method for improving both thinning and visibility, it has been proposed (see below) that the image display panel and the protection panel are directly laminated via a transparent adhesive or sheet.
例えば特許文献１には、加熱仮接着やオートクレーブによる高温・高圧処理を必要とせず、室温にてガラス板を貼り合わせることができる粘着シートとして、第１の感圧接着層と、その両面に形成された第２の感圧接着層と、両感圧接着層の接着面に付着された離型フィルムとを備え、第１の感圧接着層は、測定温度２０℃、周波数１Ｈｚでの貯蔵弾性率Ｇ'(１Ｈｚ)が５×１０3〜５×１０5 Ｐａで、基準温度２０℃、周波数１０-7Ｈｚでの貯蔵弾性率Ｇ'(１０-7Ｈｚ)が５×１０1〜５×１０3 Ｐａの粘弾性特性を有する感圧接着剤で形成し、第２の感圧接着層は、測定温度２０℃の貯蔵弾性率Ｇ'(１Ｈｚ)が１×１０4 〜５×１０6Ｐａで、基準温度２０℃の貯蔵弾性率Ｇ'(１０-7Ｈｚ)が１×１０4〜１×１０6Ｐａの粘弾性特性を有する感圧接着剤で形成する粘着シートが開示されている。 For example, Patent Document 1 does not require high-temperature and high-pressure treatment by heat temporary bonding or autoclave, and forms a first pressure-sensitive adhesive layer and both surfaces thereof as an adhesive sheet capable of bonding glass plates at room temperature. The second pressure-sensitive adhesive layer and a release film attached to the adhesive surfaces of the two pressure-sensitive adhesive layers, and the first pressure-sensitive adhesive layer has a storage elasticity at a measurement temperature of 20 ° C. and a frequency of 1 Hz. The rate G ′ (1 Hz) is 5 × 10 3 to 5 × 10 5 Pa, the storage elastic modulus G ′ (10 −7 Hz) at a reference temperature of 20 ° C. and a frequency of 10 −7 Hz is 5 × 10 1 to 5 ×. The second pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive having viscoelastic properties of 10 3 Pa, and the storage elastic modulus G ′ (1 Hz) at a measurement temperature of 20 ° C. is 1 × 10 4 to 5 × 10 6 Pa. And a pressure sensitive contact having a viscoelastic property with a storage elastic modulus G ′ (10 −7 Hz) at a reference temperature of 20 ° C. of 1 × 10 4 to 1 × 10 6 Pa. A pressure-sensitive adhesive sheet formed with an adhesive is disclosed.
また、特許文献２には、紫外線架橋前は、低凝集力の粘着層（測定温度２０℃、周波数１Ｈｚでの貯蔵弾性率Ｇ’が５×１０3〜５×１０5Ｐａであり、且つ、基準温度２０℃、周波数１０-7Ｈｚでの貯蔵弾性率Ｇ’が５×１０1〜５×１０3 Ｐａ）として形成することにより、パネル同士を気泡なく密着させ、密着後に保護パネル面越しに紫外線（ＵＶ）照射して硬化させることにより、その粘弾性を、測定温度２０℃、周波数１Ｈｚでの貯蔵弾性率Ｇ’が１×１０4〜１×１０6Ｐａであり、且つ、基準温度２０℃、周波数１０-7Ｈｚでの貯蔵弾性率Ｇ’が１×１０4Ｐａ以上とする方法が開示されている。 Patent Document 2 discloses that an adhesive layer having a low cohesive force (a storage elastic modulus G ′ at a measurement temperature of 20 ° C. and a frequency of 1 Hz is 5 × 10 3 to 5 × 10 5 Pa before UV crosslinking) By forming the storage elastic modulus G ′ at a reference temperature of 20 ° C. and a frequency of 10 −7 Hz as 5 × 10 1 to 5 × 10 3 Pa), the panels are brought into close contact with each other without bubbles, and after contact, over the protective panel surface By curing by ultraviolet (UV) irradiation, the viscoelasticity is measured at a temperature of 20 ° C., a storage elastic modulus G ′ at a frequency of 1 Hz is 1 × 10 4 to 1 × 10 6 Pa, and a reference temperature of 20 A method is disclosed in which the storage elastic modulus G ′ at 1 ° C. and a frequency of 10 −7 Hz is 1 × 10 4 Pa or more.
また、特許文献３には、凝集力の異なる２種類の粘着層をガスバリヤー基材の表裏に配置した構成とし、低凝集力の第１粘着層でパネル同士の気泡なく密着させると共に、保護パネルからの揮発成分の攻撃をガスバリヤー基材と高凝集力の第２粘着層で遮断する構成が開示されている。 In Patent Document 3, two types of adhesive layers having different cohesive forces are arranged on the front and back of the gas barrier substrate, and the first adhesive layer having a low cohesive force is adhered to the panels without bubbles between the panels. The structure which shields the attack of the volatile component from a gas barrier base material and the 2nd adhesion layer of high cohesion force is disclosed.
特許文献４には、ＰＤＰ等の表示装置の各種光学部材を貼合するための粘着シートであって、変形回復力に優れたものとして、２３℃×５０％ＲＨの環境下において、１００ｍｍ/ｍｉｎの引張速度で５０％伸長し、同速度で元に戻した時の歪復元率が６０％以上であることを特徴とする光学部材貼合用粘着シートが開示されている。 Patent Document 4 discloses a pressure-sensitive adhesive sheet for bonding various optical members of a display device such as a PDP, which is excellent in deformation recovery force, in an environment of 23 ° C. × 50% RH, 100 mm / min. A pressure-sensitive adhesive sheet for bonding optical members is disclosed in which the strain recovery rate is 50% or more when the film is stretched 50% at a tensile speed of 5% and returned to the original speed at the same speed.
特許文献５には、同じくＰＤＰ等の表示装置の各種光学部材を貼合するための粘着シートであって、画面表面を押圧しても変形し難く、変形しても凹みが回復し易い粘着シートとして、１種類以上の（メタ）アクリル酸エステル系重合体を含むベースポリマーと、アクリル系架橋モノマーと、架橋開始剤とを含有する粘着剤組成物を架橋してなる粘着シートであって、２０℃基準マスターカーブの周波数１０-1Ｈｚ〜１０-5Ｈｚのいずれにおいても、貯蔵剪断弾性率は１．０×１０4Ｐａを超えて１．０×１０5Ｐａ以下の範囲内にあり、且つ周波数１０-3Ｈｚにおけるｔａｎδが１．０×１０-1以下である物性を備えた粘着シートが開示されている。 Patent Document 5 discloses a pressure-sensitive adhesive sheet for bonding various optical members of a display device such as a PDP. The pressure-sensitive adhesive sheet is not easily deformed even when the screen surface is pressed, and the dent is easily recovered even when deformed. As a pressure-sensitive adhesive sheet obtained by cross-linking a pressure-sensitive adhesive composition containing a base polymer containing at least one (meth) acrylic acid ester-based polymer, an acrylic crosslinking monomer, and a crosslinking initiator, The storage shear modulus is in the range of more than 1.0 × 10 4 Pa and 1.0 × 10 5 Pa or less at any of the frequencies of 10 −1 Hz to 10 −5 Hz of the ° C reference master curve, and An adhesive sheet having physical properties such that tan δ at a frequency of 10 −3 Hz is 1.0 × 10 −1 or less is disclosed.
従来開示されていたこの種の粘着剤乃至粘着シートは、この粘着剤乃至粘着シートを介して積層してなる積層体をカットした場合、カット後暫くするとカット端面がベタつくようになり、生産設備に付着して生産工程の支障となったり、カット端面に異物やホコリ等が付着して汚染の原因となったりする心配があった。 This type of pressure-sensitive adhesive or pressure-sensitive adhesive sheet that has been disclosed in the past, when a laminated body laminated through this pressure-sensitive adhesive or pressure-sensitive adhesive sheet is cut, the cut end surface becomes sticky after a while, and this is a problem in production equipment. There was a concern that it would interfere with the production process due to adhesion, or foreign matter or dust would adhere to the cut end face and cause contamination.
また、例えば携帯電話の表示画面などでは、図１に示すように、液晶パネルディスプレイ（ＬＣＤ）上に偏光フィルム等を積層し、その上に粘着剤乃至シートを介してプラスチック製の保護パネルを積層する構成が採用されることがあり、該保護パネルの裏面には周縁部に黒色印刷部（厚さ５μｍ〜２０μｍ程度）が付設されていることが通常である。このような場合、黒色印刷部の縁に形成される段差部の入隅部内にまで粘着剤が十分に入り込まないと気泡が残留して画面の視認性が低下することになる。また、保護パネルがプラスチック製である場合には、この保護パネルからガスが発生することがあるため（アウトガスと呼ばれる）、粘着剤乃至シートがこのガス圧に対して対抗できるだけの粘着力及び凝集力を有していないと、粘着剤乃至シート内にガスが残留して高温になると残留ガスが発泡して画面の視認性を低下させることになる。
このようなアウトガス対策としては、例えば前述の特許文献２のように、低凝集力の粘着剤として形成しておいて、気泡が残留しないようにパネル同士を密着させた後、保護パネル越しに紫外線を照射して架橋させる方法が提案されているが、保護パネルを貼りあわせた後に架橋させる必要があるため、生産性の点で問題があった。また、前述の特許文献３にように、アウトガスバリアー層を設ける方法が提案されているが、厚さや重さが増したり、透明性が低下したりするなどの問題があった。
Further, for example, in a display screen of a mobile phone, as shown in FIG. 1, a polarizing film or the like is laminated on a liquid crystal panel display (LCD), and a plastic protective panel is laminated thereon with an adhesive or a sheet. In general, a black printed portion (thickness of about 5 μm to 20 μm) is attached to the periphery of the back surface of the protective panel. In such a case, if the adhesive does not sufficiently enter the inside corner of the stepped portion formed at the edge of the black print portion, bubbles remain and the visibility of the screen decreases. Further, when the protective panel is made of plastic, gas may be generated from the protective panel (referred to as outgas), so that the adhesive or the cohesive force that the adhesive or sheet can counteract this gas pressure. Otherwise, when the gas remains in the pressure-sensitive adhesive or sheet and the temperature rises, the residual gas is foamed and the visibility of the screen is lowered.
As a countermeasure against such outgas, for example, as in the above-mentioned Patent Document 2, it is formed as a low cohesive adhesive, and after the panels are brought into close contact so that no bubbles remain, ultraviolet rays are passed through the protective panel. However, there is a problem in terms of productivity because it is necessary to crosslink after bonding the protective panel. Further, as described in Patent Document 3, a method of providing an outgas barrier layer has been proposed, but there are problems such as an increase in thickness and weight and a decrease in transparency.
そこで本発明の目的は、粘着シートを介して貼り合せた積層体をカットした際、カット後に経時的にカット端面がベタツクことがなく、しかも被着面に５μｍ〜２０μｍ程度の凹凸があっても気泡を残留させることなく貼着することができ、さらには、被着体がプラスチック等のアウトガスを発生する材料のものであっても、例えば８０℃程度の高温環境下において発泡することがないように貼着することができる、新たな透明粘着シートを提供することにある。 Therefore, the object of the present invention is to cut the laminated body bonded through the pressure-sensitive adhesive sheet so that the cut end face does not become sticky with time after the cut, and the adherend surface has unevenness of about 5 μm to 20 μm. It can be stuck without leaving bubbles, and even if the adherend is made of a material that generates outgas such as plastic, it will not foam in a high temperature environment of about 80 ° C., for example. An object of the present invention is to provide a new transparent pressure-sensitive adhesive sheet that can be attached to a sheet.
本発明は、各層ともに、ベースポリマーとしての（メタ）アクリル酸エステル系共重合体と架橋開始剤とを含有する粘着剤組成物を架橋してなり、且つ、異なる粘弾性挙動を有する第１粘着層及び第２粘着層を積層し一体化してなる構成を備えた粘着シートであって、
周波数１Ｈｚの温度分散で測定した動的剪断貯蔵弾性率Ｇ’の値が下記範囲内にあるという特徴と、
下記引張試験方法による引張弾性率が０．２０ＭＰａ以上であり、且つ、引張破断時伸びが４００％以上であるという特徴と、を有する透明粘着シートを提案するものである。
・Ｇ’（２０℃）が２×１０４〜５×１０５Ｐａ。
・Ｇ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
引張試験方法：試験試料として粘着シートを幅２０ｍｍ、長さ８０ｍｍに切り出し、試験機チャック間距離４０ｍｍで試料をチャックにはさんで引張速度３００ｍｍ／ｍｉｎで引張試験を行う。
In the present invention, the first pressure-sensitive adhesive is obtained by cross-linking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer and a crosslinking initiator in each layer, and having different viscoelastic behaviors. A pressure-sensitive adhesive sheet having a structure in which a layer and a second pressure-sensitive adhesive layer are laminated and integrated,
The characteristic that the value of the dynamic shear storage modulus G ′ measured by temperature dispersion at a frequency of 1 Hz is within the following range:
The present invention proposes a transparent pressure-sensitive adhesive sheet having the characteristics that the tensile modulus by the following tensile test method is 0.20 MPa or more and the elongation at tensile break is 400% or more.
G ′ (20 ° C.) is 2 × 10 4 to 5 × 10 5 Pa.
G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
Tensile test method: As a test sample, an adhesive sheet is cut into a width of 20 mm and a length of 80 mm, and a tensile test is performed at a tensile speed of 300 mm / min with a distance between the chucks of the tester of 40 mm between the tester and the chuck.
粘着シートが上記のような粘弾性挙動を備えていれば、この粘着シートを介して貼合せた積層体をカットした場合、経時的にカット端面がベタツクことがなく、しかも、被着面に５μｍ〜２０μｍ程度の凹凸があっても気泡が残留することなく貼着することができ、さらには、被着体がプラスチック等のアウトガスを発生する材料からなるものであっても、例えば８５℃程度の高温環境下においても発泡することがないように貼着することができる。
被着面に凹凸がある場合に気泡を残留させることなく貼着するためには、一般的には粘着剤乃至シートを柔らかくて濡れ易いものとすればよい。しかし、単純に柔らかいだけでは、カット端面がベタついてしまうばかりか、アウトガスのガス圧に対して対抗できるだけの凝集力を有さないために、ガスが内部に残留して高温状態になると残留ガスが発泡して視認性を低下させることになってしまう。他方、粘着剤乃至シートを硬くしたのでは、被着面に凹凸があると気泡が残留するようになり視認性を低下させることになる。
そこで本発明は、粘着シートを単純に柔らかくしたり硬くしたりするのではなく、異なる粘弾性挙動を有する第１粘着層及び第２粘着層を積層することとし、しかも２０℃と１５０℃という全く異なる温度領域での動的剪断貯蔵弾性率Ｇ’の値を規定することにより、両立の難しい特性、すなわち、カット端面がカット後に経時的にベタつくことがない特性と、被着面に凹凸があっても気泡を残留させることなく貼着することができる特性と、さらには、アウトガスに十分に耐えることができて高温環境下でも発泡することがないように貼着できる特性と、を兼ね備えたものとすることができたのである。
さらに、引張弾性率を０．２０ＭＰａ以上と規定すると共に、引張破断時伸びを４００％以上と規定することにより、伸び特性と引張弾性率を両方兼ね備えたものとなり、ハンドリング性を高めることができるばかりか、ヒートショックなどの急激な環境変化に対する耐久性にも優れたものとすることができる。
If the pressure-sensitive adhesive sheet has the above viscoelastic behavior, when the laminated body laminated through this pressure-sensitive adhesive sheet is cut, the cut end face does not become sticky with time, and the adhesion surface has a thickness of 5 μm. Even if there are irregularities of about 20 μm, it is possible to stick without leaving bubbles, and even if the adherend is made of a material that generates outgas such as plastic, for example, about 85 ° C. It can be stuck so as not to foam even in a high temperature environment.
In order to adhere without leaving air bubbles when there is unevenness on the adherend surface, in general, the adhesive or sheet should be soft and easy to wet. However, simply by being soft, not only will the cut end face be sticky, but it will not have a cohesive force that can counteract the gas pressure of the outgas. Foaming will reduce visibility. On the other hand, if the pressure-sensitive adhesive or sheet is hardened, if there are irregularities on the adherend surface, bubbles will remain and visibility will be reduced.
Therefore, in the present invention, the pressure-sensitive adhesive sheet is not simply softened or hardened, but the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer having different viscoelastic behaviors are laminated, and 20 ° C. and 150 ° C. are completely different. By defining the value of the dynamic shear storage modulus G ′ in different temperature ranges, it is difficult to achieve compatibility, that is, the cut end surface does not become sticky with time after cutting, and the adherend surface has irregularities. Even if it has the characteristics that it can be stuck without leaving any bubbles, and furthermore, it has the characteristics that it can sufficiently withstand outgas and can be stuck so that it will not foam even in a high temperature environment It was possible to.
Furthermore, by defining the tensile modulus as 0.20 MPa or more and by defining the elongation at tensile break as 400% or more, both the elongation characteristics and the tensile modulus can be obtained, and handling properties can be improved. Or it can be excellent in durability against rapid environmental changes such as heat shock.
このような本発明の透明粘着シートを形成する手段としては、第１粘着層及び第２粘着層それぞれについて周波数１Ｈｚの温度分散で測定した動的剪断貯蔵弾性率Ｇ’の値が下記（ａ）、（ｂ）の範囲内になるように形成するのが好ましく、特に２０℃及び１５０℃における動的剪断貯蔵弾性率Ｇ’の値が第１粘着層よりも第２粘着層の方が高い場合がより好ましい。
（ａ） 第１粘着層のＧ’（２０℃）が２×１０４〜５×１０５Ｐａであり、かつＧ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
（ｂ） 第２粘着層のＧ’（２０℃）が２×１０５〜５×１０６Ｐａであり、かつＧ’（１５０℃）が５×１０４〜５×１０５Ｐａ。
As a means for forming such a transparent adhesive sheet of the present invention, the value of the dynamic shear storage modulus G ′ measured by temperature dispersion at a frequency of 1 Hz for each of the first adhesive layer and the second adhesive layer is the following (a): , (B) is preferably formed so that the value of the dynamic shear storage modulus G ′ at 20 ° C. and 150 ° C. is higher in the second adhesive layer than in the first adhesive layer. Is more preferable.
(A) G ′ (20 ° C.) of the first adhesive layer is 2 × 10 4 to 5 × 10 5 Pa, and G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
(B) G ′ (20 ° C.) of the second adhesive layer is 2 × 10 5 to 5 × 10 6 Pa, and G ′ (150 ° C.) is 5 × 10 4 to 5 × 10 5 Pa.
異なる粘弾性挙動を有する第１粘着層及び第２粘着層を備える透明粘着シートの場合、透明粘着シート全体としては、より柔らかい粘着層の粘弾性挙動が支配的に現れることになる。すなわち、上記の透明粘着シートを剪断法で低温側から動的粘弾性測定すると、弾性率の小さい第１粘着層が先に変形し（ズレ）、第２粘着層は比較的硬いため変形し難い状態となり、透明粘着シート全体としては柔らかい第１粘着層の粘弾性挙動が支配的に現れるようになる。そこで、第１粘着層を第２粘着層よりも柔らかい粘着層とすると共に、第１粘着層における２０℃と１５０℃という全く異なる温度域の動的剪断貯蔵弾性率Ｇ’をそれぞれ規定することにより、本発明の透明粘着シートを形成するようにしたものである。 In the case of a transparent pressure-sensitive adhesive sheet comprising a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer having different viscoelastic behaviors, the viscoelastic behavior of a softer pressure-sensitive adhesive layer appears predominantly as the whole transparent pressure-sensitive adhesive sheet. That is, when the above-mentioned transparent adhesive sheet is subjected to dynamic viscoelasticity measurement from the low temperature side by the shearing method, the first adhesive layer having a small elastic modulus is deformed first (displacement), and the second adhesive layer is relatively hard and thus hardly deformed. As a whole, the viscoelastic behavior of the soft first pressure-sensitive adhesive layer appears dominant in the entire transparent pressure-sensitive adhesive sheet. Therefore, by making the first adhesive layer an adhesive layer softer than the second adhesive layer, and defining the dynamic shear storage elastic modulus G ′ in a completely different temperature range of 20 ° C. and 150 ° C. in the first adhesive layer, respectively. The transparent adhesive sheet of the present invention is formed.
以下、本発明の実施形態の一例について説明するが、本発明が下記実施形態に制限されるものではない。 Hereinafter, although an example of embodiment of the present invention is explained, the present invention is not limited to the following embodiment.
本実施形態に係る透明粘着シート（以下「本粘着シート」と称する。）は、各層ともに、ベースポリマーとしての（メタ）アクリル酸エステル系共重合体と架橋開始剤とを含有する粘着剤組成物を架橋してなり、且つ異なる粘弾性挙動を有する第１粘着層と第２粘着層とをそれぞれ１層以上備え、かつこれらの層を積層し一体化してなる構成を備えた粘着シートである。 The transparent pressure-sensitive adhesive sheet according to the present embodiment (hereinafter referred to as “the pressure-sensitive adhesive sheet”) includes a (meth) acrylate copolymer as a base polymer and a crosslinking initiator in each layer. Is a pressure-sensitive adhesive sheet having a structure in which one or more first pressure-sensitive adhesive layers and second pressure-sensitive adhesive layers each having different viscoelastic behavior are laminated and these layers are laminated and integrated.
本粘着シートは、次のような粘弾性特性（ａ）（ｂ）を備えた第１粘着層及び第２粘着層をそれぞれ１層以上積層して一体化することにより形成することができる。この場合、２０℃及び１５０℃での動的剪断貯蔵弾性率Ｇ’の値が第１粘着層よりも第２粘着層の方が高い方が好ましい。 This pressure-sensitive adhesive sheet can be formed by laminating and integrating one or more first pressure-sensitive adhesive layers and second pressure-sensitive adhesive layers each having the following viscoelastic properties (a) and (b). In this case, the value of the dynamic shear storage elastic modulus G ′ at 20 ° C. and 150 ° C. is preferably higher in the second adhesive layer than in the first adhesive layer.
（ａ） 第１粘着層：周波数１Ｈｚの温度分散で測定した２０℃での動的剪断貯蔵弾性率Ｇ’（２０℃）が２×１０４〜５×１０５Ｐａであり、１５０℃での動的剪断貯蔵弾性率Ｇ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
（ｂ） 第２粘着層：周波数１Ｈｚの温度分散で測定した２０℃での動的剪断貯蔵弾性率Ｇ’（２０℃）が２×１０５〜５×１０６Ｐａであり、１５０℃での動的剪断貯蔵弾性率Ｇ’（１５０℃）が５×１０４〜５×１０５Ｐａ。
(A) 1st adhesion layer: Dynamic shear storage elastic modulus G '(20 degreeC) in 20 degreeC measured by the temperature dispersion of frequency 1Hz is 2 * 10 < 4 > -5 * 10 < 5 > Pa, 150 degreeC The dynamic shear storage elastic modulus G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
(B) 2nd adhesion layer: The dynamic shear storage elastic modulus G '(20 degreeC) in 20 degreeC measured by the temperature dispersion of frequency 1Hz is 2 * 10 < 5 > -5 * 10 < 6 > Pa, 150 degreeC The dynamic shear storage modulus G ′ (150 ° C.) is 5 × 10 4 to 5 × 10 5 Pa.
第１粘着層のＧ’（２０℃）は、２×１０４〜５×１０５Ｐａであればよく、好ましくは２×１０４〜８×１０４Ｐａである。
第１粘着層のＧ’（２０℃）が２．０×１０４Ｐａ未満では、この粘着シートを介して貼り合せた積層体をカットした場合、カット端面でのベタつきが室温でも大きく、例えばトムソン刃でカットした際に刃にくっつくなどカット性に劣り、カット後もベタついて生産機械にくっつくなどハンドリング性も劣ることになる。他方、５×１０５Ｐａを超えると、柔軟性が低下し、例えば裏面に印刷段差を有する保護パネルを貼り合わせる場合など、この段差部の入隅部内に粘着剤が入り込めなくて気泡が残留する可能性がある。
G ′ (20 ° C.) of the first adhesive layer may be 2 × 10 4 to 5 × 10 5 Pa, and preferably 2 × 10 4 to 8 × 10 4 Pa.
If G ′ (20 ° C.) of the first adhesive layer is less than 2.0 × 10 4 Pa, when the laminated body bonded through this adhesive sheet is cut, the stickiness at the cut end face is large even at room temperature. When cutting with a blade, it will be inferior in cutting properties, such as sticking to the blade, and will be inferior in handling properties, such as sticking to the production machine after cutting. On the other hand, when it exceeds 5 × 10 5 Pa, the flexibility is lowered, and for example, when a protective panel having a printed step is pasted on the back surface, the pressure-sensitive adhesive cannot enter into the corner of the stepped portion, and bubbles remain. there's a possibility that.
第１粘着層のＧ’（１５０℃）は、１×１０４〜１×１０５Ｐａであればよく、好ましくは２×１０４〜５×１０４Ｐａである。
第１粘着層のＧ’（１５０℃）が１×１０４Ｐａ未満では、高温環境下で粘着層ズレや粘着材ハミダシが起こる可能性がある。
他方、１×１０５Ｐａを超えると粘性が低下し弾性回復する傾向があり、例えば保護パネル裏面の印刷段差部の入隅部内に空隙を発生する可能性がある。
G ′ (150 ° C.) of the first adhesive layer may be 1 × 10 4 to 1 × 10 5 Pa, and preferably 2 × 10 4 to 5 × 10 4 Pa.
When G ′ (150 ° C.) of the first pressure-sensitive adhesive layer is less than 1 × 10 4 Pa, there is a possibility that a pressure-sensitive adhesive layer shift or a pressure-sensitive adhesive material may occur in a high temperature environment.
On the other hand, when it exceeds 1 × 10 5 Pa, the viscosity tends to decrease and elastic recovery tends to occur. For example, a void may be generated in the corner of the printed step on the back of the protective panel.
第２粘着層のＧ’（２０℃）は、２×１０５〜５×１０６Ｐａであればよく、好ましくは５×１０５〜２×１０６Ｐａである。
２×１０５Ｐａ未満では、アウトガスに十分に耐えることができずに発泡する一方、５×１０６Ｐａを超えて大きいと、硬くて被着体表面に十分に濡れが進行しないなどの問題が発生する可能性がある。
第２粘着層のＧ’（１５０℃）は、５×１０４〜５×１０５であればよく、好ましくは１×１０５〜３×１０５Ｐａである。
５×１０４Ｐａ未満ではアウトガスに十分に耐えることができずに発泡することになる一方、５×１０５Ｐａを超えると十分な密着力が得られないなどの問題が発生する可能性がある。
G ′ (20 ° C.) of the second adhesive layer may be 2 × 10 5 to 5 × 10 6 Pa, preferably 5 × 10 5 to 2 × 10 6 Pa.
If it is less than 2 × 10 5 Pa, it will not be able to withstand outgas sufficiently, and foaming will occur. On the other hand, if it exceeds 5 × 10 6 Pa, it will be hard and will not sufficiently wet the adherend surface. May occur.
G ′ (150 ° C.) of the second adhesive layer may be 5 × 10 4 to 5 × 10 5 , and preferably 1 × 10 5 to 3 × 10 5 Pa.
If it is less than 5 × 10 4 Pa, it will not be able to withstand outgas sufficiently, and foaming will occur. On the other hand, if it exceeds 5 × 10 5 Pa, problems such as insufficient adhesion may occur. .
さらに、第１粘着層及び第２粘着層は、周波数１Ｈｚの温度分散で測定した動的Ｔａｎδ極大値を示す温度（；Ｔｇ）がそれぞれ下記範囲内であるのが好ましい。
・第１粘着層のＴｇ（１）が−１０℃未満。
・第２粘着層のＴｇ（２）が−１０℃以上。
Furthermore, it is preferable that the first adhesive layer and the second adhesive layer each have a temperature (; Tg) showing a dynamic Tan δ maximum value measured by temperature dispersion at a frequency of 1 Hz within the following range.
-Tg (1) of a 1st adhesion layer is less than -10 degreeC.
-Tg (2) of a 2nd adhesion layer is -10 degreeC or more.
第１粘着層のＴｇ（１）は−１０℃未満であることが好ましく、−２０℃以下であれば柔軟性が向上してさらに好ましい。Ｔｇ（１）が−１０℃以上になると、柔軟性が低下するため、例えば被着面に凹凸や印刷段差等がある場合、気泡が残留して視認性が低下するようになる。
他方、第２粘着層のＴｇ（２）は−１０℃以上であるのが好ましく、Ｔｇ（２）が−１０℃以上１０℃未満であれば高接着性が得られてより好ましい。Ｔｇ（２）が−１０℃未満の場合は、接着力が不足し、被着体がプラスチック等のアウトガスを発生する材料からなる場合には、アウトガスのガス圧に負けて粘着剤内にガスが残留し、高温になると残留ガスが発泡する可能性がある。逆にＴｇ（２）が１０℃以上の場合は、硬すぎて被貼着面に対して濡れ難くなり、接着不足になる可能性がある。この場合、加温接着する方法もあるがコストアップ要因となるので好ましくはない。
The Tg (1) of the first adhesive layer is preferably less than −10 ° C., and more preferably −20 ° C. or less, further improving flexibility. When Tg (1) is −10 ° C. or higher, the flexibility is lowered. For example, when there are irregularities or printing steps on the adherend surface, bubbles remain and visibility is lowered.
On the other hand, the Tg (2) of the second adhesive layer is preferably −10 ° C. or higher, and if the Tg (2) is −10 ° C. or higher and lower than 10 ° C., high adhesiveness is obtained, which is more preferable. When Tg (2) is less than −10 ° C., the adhesive force is insufficient, and when the adherend is made of a material that generates outgas such as plastic, the gas is lost in the pressure-sensitive adhesive against the gas pressure of outgas. Residual gas may be foamed when the temperature is high. On the other hand, when Tg (2) is 10 ° C. or higher, it is too hard to wet the adherend surface, which may result in insufficient adhesion. In this case, there is a method of heating and bonding, but this is not preferable because it causes a cost increase.
以上のように第１粘着層と第２粘着層のＴｇが異なり、第１粘着層のＴｇ（１）が第２粘着層のＴｇ（２）に比べて低いことが好ましい。特にＴｇ（１）とＴｇ（２）の差が１０℃以上であるのが好ましく、中でも２０℃以上、その中でも４０℃以上であるのがより好ましい。 As described above, the Tg of the first adhesive layer and the second adhesive layer are different, and it is preferable that Tg (1) of the first adhesive layer is lower than Tg (2) of the second adhesive layer. In particular, the difference between Tg (1) and Tg (2) is preferably 10 ° C. or more, more preferably 20 ° C. or more, and particularly preferably 40 ° C. or more.
またさらに、第１粘着層及び第２粘着層は、それぞれの厚さが下記範囲内であることが好ましい。すなわち、第１粘着層の厚さが第２粘着層の厚さに比べて大きいことが好ましい。
・第１粘着層の厚さが５０μｍ〜２０００μｍ。
・第２粘着層の厚さが５μｍ〜５０μｍ。
Furthermore, it is preferable that each thickness of the first adhesive layer and the second adhesive layer is within the following range. That is, it is preferable that the thickness of the first adhesive layer is larger than the thickness of the second adhesive layer.
-The thickness of the 1st adhesion layer is 50 micrometers-2000 micrometers.
-The thickness of a 2nd adhesion layer is 5 micrometers-50 micrometers.
第１粘着層は、表面凹凸を充填するために必要な厚さを有していることが好ましいため、被着材の厚さ、表面凹凸に合わせて第１粘着層の厚さを適宜選択する必要がある。例えば被着面が表面凹凸の少ないフィルムやシートであれば、５０μｍ〜５００μｍであるのが好ましく、さらに１００μｍ〜５００μｍであるのが好ましい。他方、ガラスのような剛性のある板材や、比較的大きな印刷段差を有する被着体などの場合には５００μｍ〜２０００μｍであるのがより好ましい。
他方、第２粘着層の厚さは、接着性を確保するため、５μｍ〜５０μｍであるのが好ましく、１５μｍ〜３０μｍであるのがより好ましい。この際、５μｍ未満では接着不足になる可能性があり、厚さが５０μｍを超えてもあまり接着性能に影響せずコストアップ要因となるばかりなので好ましくない。
Since the first adhesive layer preferably has a thickness necessary for filling the surface irregularities, the thickness of the first adhesive layer is appropriately selected according to the thickness of the adherend and the surface irregularities. There is a need. For example, if the adherend is a film or sheet with little surface irregularities, it is preferably 50 μm to 500 μm, and more preferably 100 μm to 500 μm. On the other hand, in the case of a rigid plate material such as glass or an adherend having a relatively large printing level difference, it is more preferably 500 μm to 2000 μm.
On the other hand, the thickness of the second adhesive layer is preferably 5 μm to 50 μm, and more preferably 15 μm to 30 μm, in order to ensure adhesion. At this time, if the thickness is less than 5 μm, there is a possibility of insufficient adhesion, and if the thickness exceeds 50 μm, the adhesion performance is not affected so much and it is only a factor for increasing the cost.
（第１粘着層及び第２粘着層の材料）
第１粘着層及び第２粘着層はいずれも、粘着性、透明性及び耐候性などの観点から、（メタ）アクリル酸エステル系重合体（共重合体を含む意で、以下「アクリル酸エステル系（共）重合体」と称する。）をベース樹脂として用い、これに架橋モノマー、必要に応じて架橋開始剤や反応触媒などを配合して、架橋反応させて形成するのが好ましい。
(Material of the first adhesive layer and the second adhesive layer)
The first adhesive layer and the second adhesive layer are both (meth) acrylic acid ester-based polymers (including copolymers, from the viewpoints of adhesiveness, transparency, weather resistance, and the like. (Co) polymer ”) is used as a base resin, and a crosslinking monomer, a crosslinking initiator, a reaction catalyst, and the like are blended in the resin, and a crosslinking reaction is preferably performed.
アクリル酸エステル重合体（共重合体を含む）は、これを重合するために用いられるアクリルモノマーやメタクリルモノマーの種類、組成比率、さらには重合条件等によって、ガラス転移温度（Ｔｇ）等の特性を適宜調整することが可能である。 Acrylic acid ester polymers (including copolymers) have properties such as glass transition temperature (Tg) depending on the types and composition ratios of acrylic monomers and methacrylic monomers used to polymerize them, and polymerization conditions. It is possible to adjust appropriately.
アクリル酸エステル重合体を重合するために用いられるアクリルモノマーやメタクリルモノマーとしては、例えば２−エチルヘキシルアクリレート、ｎ−オクチルアクリート、ｎ−ブチルアクリレート、エチルアクリレート、メチルメタクリレート等を挙げることができる。これらに親水基や有機官能基などを共重合させた酢酸ビニル、ヒドロキシエチルアクリレート、アクリル酸、グリシジルアクリレート、アクリルアミド、アクリルニトリル、メタクリルニトリル、フッ素アクリレート、シリコーンアクリレートなども用いることができる。 Examples of the acrylic monomer and methacrylic monomer used for polymerizing the acrylate polymer include 2-ethylhexyl acrylate, n-octyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, and the like. Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc., which are copolymerized with a hydrophilic group or an organic functional group, can also be used.
アクリル酸エステル重合体の中でも、(メタ)アクリル酸アルキルエステル系共重合体が特に好ましい。
(メタ)アクリル酸アルキルエステル系共重合体を形成するために用いる（メタ）アクリレート、即ち、アルキルアクリレート又はアルキルメタクリレート成分としては、アルキル基がｎ−オクチル、イソオクチル、２−エチルヘキシル、ｎ−ブチル、イソブチル、メチル、エチル、イソプロピルのうちのいずれか１つであるアルキルアクリレート又はアルキルメタクリレートの１種又はこれらから選ばれた２種以上の混合物であるのが好ましい。
その他の成分として、カルボキシル基、水酸基、グリシジル基等の有機官能基を有するアクリレート又はメタクリレートを共重合させてもよい。具体的には、前記アルキル（メタ）アクリレート成分と有機官能基を有する（メタ）アクリレート成分とを適宜に選択的に組み合わせたモノマー成分を出発原料として加熱重合して(メタ)アクリル酸エステル系共重合体ポリマーを得ることができる。
中でも好ましくは、イソ−オクチルアクリレート、ｎ−オクチルアクリレート、ｎ−ブチルアクリレート、２−エチルヘキシルアクリレート等のアルキルアクリレートの１種又はこれらから選ばれた２種以上の混合物か、或いは、イソ−オクチルアクリレート、ｎ−オクチルアクリレート、ｎ−ブチルアクリレート、２−エチルヘキシルアクリレート等から少なくとも１種類以上と、アクリル酸とを共重合させたものを挙げることができる。
Among the acrylic ester polymers, (meth) acrylic acid alkyl ester copolymers are particularly preferable.
The (meth) acrylate used for forming the (meth) acrylic acid alkyl ester copolymer, that is, as the alkyl acrylate or alkyl methacrylate component, the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl, One of alkyl acrylate or alkyl methacrylate which is any one of isobutyl, methyl, ethyl and isopropyl, or a mixture of two or more selected from these is preferable.
As other components, an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group may be copolymerized. Specifically, a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material is subjected to heat polymerization to form a (meth) acrylate ester copolymer. A polymer polymer can be obtained.
Among them, preferably, an alkyl acrylate such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate, Examples thereof include those obtained by copolymerizing at least one kind of n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like with acrylic acid.
これらのモノマーを用いた重合処理としては、溶液重合、乳化重合、塊状重合、懸濁重合などの公知の重合方法が採用可能であり、その際に重合方法に応じて熱重合開始剤や光重合開始剤などの重合開始剤を用いることによりアクリル酸エステル共重合体を得ることができる。 As the polymerization treatment using these monomers, known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like can be employed. In this case, a thermal polymerization initiator or photopolymerization is used according to the polymerization method. An acrylic ester copolymer can be obtained by using a polymerization initiator such as an initiator.
ベースポリマーのガラス転移温度（Ｔｇ）は−１０℃以下、特に−８０℃〜−１０℃であるのが好ましく、その１３０℃における溶融粘度は５万ｍＰａ・ｓ以上、特に１０万ｍＰａ・ｓ〜５０万ｍＰａ・ｓ、中でも特に１０万ｍＰａ・ｓ〜３０万ｍＰａ・ｓであるのが好ましい。 The glass transition temperature (Tg) of the base polymer is preferably −10 ° C. or less, particularly preferably −80 ° C. to −10 ° C., and its melt viscosity at 130 ° C. is not less than 50,000 mPa · s, particularly 100,000 mPa · s to It is preferably 500,000 mPa · s, particularly 100,000 mPa · s to 300,000 mPa · s.
なお、ベースポリマーのガラス転移温度（Ｔｇ）は、粘弾性測定装置、例えばレオメトリックス社製の粘弾性測定装置「ダイナミックアナライザーＲＤＡII」を用いて測定することができる。その際、Ｔｇはパラレルプレート２５ｍｍφ、歪み０．５％、周波数１Ｈｚで測定した時のＴａｎδの極大値を示す温度を読みとればよい。
溶融粘度は、粘弾性測定装置、例えばレオロジ社製「レオメータ ＭＲ−３００Ｔ」用いて測定することができる。その際、コーンプレート４０ｍｍφ、コーン角２°、温度１３０℃、歪み（角度）０．７°、周波数０．０２Ｈｚで測定した時の粘度η*値を読みとればよい。
The glass transition temperature (Tg) of the base polymer can be measured using a viscoelasticity measuring device, for example, a viscoelasticity measuring device “Dynamic Analyzer RDAII” manufactured by Rheometrics. In that case, Tg should just read the temperature which shows the maximum value of Tan (delta) when it measures by parallel plate 25mm (phi), distortion 0.5%, and frequency 1Hz.
The melt viscosity can be measured using a viscoelasticity measuring apparatus, for example, “Rheometer MR-300T” manufactured by Rheology. At that time, the viscosity η * value measured at a cone plate of 40 mmφ, a cone angle of 2 °, a temperature of 130 ° C., a strain (angle) of 0.7 °, and a frequency of 0.02 Hz may be read.
アクリル酸エステル重合体の質量平均分子量は１０万〜７０万、特に２０万〜５０万、中でも特に２５万〜５０万であるのが好ましい。
また、本用途においては、アクリル酸エステル重合体の質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）は比較的大きい方が好ましく、５〜１０が好ましく、特に６〜９であるのがさらに好ましい。
The mass average molecular weight of the acrylic ester polymer is 100,000 to 700,000, particularly 200,000 to 500,000, and particularly preferably 250,000 to 500,000.
In this application, the mass average molecular weight (MW) / number average molecular weight (MN) of the acrylate polymer is preferably relatively large, preferably 5 to 10, and more preferably 6 to 9. .
アクリル酸エステル重合体を架橋する際に用いる架橋モノマー（「架橋剤」とも称する）としては、（メタ）アクリロイル基を２個以上有する多官能（メタ）アクリレート、イソシアネート基、エポキシ基、メラミン基、グリコール基、シロキサン基、アミノ基などの有機官能基を２個以上有する多官能有機官能基樹脂、亜鉛、アルミ、ナトリウム、ジルコニウム、カルシウムなどの金属錯体を有する有機金属化合物を用いることができる。
上記の多官能（メタ）アクリレートの例を挙げると、例えば１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレート、トリメチロールプロパントリアクリレートなどを挙げることができる。
架橋モノマーの含有量は、所望の保持力が得られるよう他の要因と併せて調整すればよいが、一般的にはベースポリマー１００質量部に対し０．０１〜４０．０質量部、好ましくは０．１〜３０．０質量部、中でも０．５〜３０．０質量部の割合の範囲内で調整するのがよい。但し、他の要素とのバランスでこの範囲を超えてもよい。
As a crosslinking monomer (also referred to as “crosslinking agent”) used for crosslinking the acrylic ester polymer, a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, an isocyanate group, an epoxy group, a melamine group, A polyfunctional organic functional resin having two or more organic functional groups such as a glycol group, a siloxane group, and an amino group, and an organometallic compound having a metal complex such as zinc, aluminum, sodium, zirconium, or calcium can be used.
Examples of the above polyfunctional (meth) acrylates include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, and the like. be able to.
The content of the crosslinking monomer may be adjusted in combination with other factors so as to obtain a desired holding force, but is generally 0.01 to 40.0 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the base polymer. It is good to adjust within the range of the ratio of 0.1-30.0 mass parts, especially 0.5-30.0 mass parts. However, this range may be exceeded in balance with other elements.
また、アクリル酸エステル重合体を架橋する際には、架橋開始剤（過酸化開始剤、光開始剤）や反応触媒（三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物など）を適宜添加すると効果的である。 In addition, when the acrylic ester polymer is crosslinked, a crosslinking initiator (peroxidation initiator, photoinitiator) or reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) is added. It is effective to add appropriately.
紫外線照射架橋（「ＵＶ架橋」とも称する）場合には、光開始剤を配合するのが好ましい。
光開始剤としては、開裂型光開始剤及び水素引抜型光開始剤のいずれを使用してもよいが、両者を併用してもよい。
開裂型光開始剤としては、例えばベンゾインブチルエーテル、ベンジルジメチルケタール、ヒドロキシアセトフェノンなどを挙げることができる。
他方、水素引抜型光開始剤としては、例えばベンゾフェノン、ミヒラーケトン、ジベンゾスベロン、２−エチルアントラキノン、イソブチルチオキサンソンなどを挙げルことができる。
但し、前記に挙げた物質に限定するものではない。
光開始剤の添加量は、上記貯蔵せん断弾性率が所定範囲内に入るように調整すればよいが、一般的にはベースポリマー１００質量部に対し０．０５〜５．０質量部の割合の範囲内で調整するのがよく、水素引抜型と開裂型の各光開始剤を１：１の割合で併用するのが良い。但し、他の要素とのバランスでこの範囲を超えてもよい。
In the case of ultraviolet irradiation crosslinking (also referred to as “UV crosslinking”), it is preferable to incorporate a photoinitiator.
As the photoinitiator, either a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator may be used, but both may be used in combination.
Examples of the cleavage type photoinitiator include benzoin butyl ether, benzyl dimethyl ketal, and hydroxyacetophenone.
On the other hand, examples of the hydrogen abstraction type photoinitiator include benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, and isobutylthioxanthone.
However, it is not limited to the substances listed above.
The addition amount of the photoinitiator may be adjusted so that the storage shear modulus falls within a predetermined range, but generally the ratio of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the base polymer. It is preferable to adjust within the range, and it is preferable to use hydrogen abstraction type and cleavage type photoinitiators in a ratio of 1: 1. However, this range may be exceeded in balance with other elements.
（他の添加剤）
上記成分のほか、必要に応じて、近赤外線吸収特性を有する顔料や染料などの色素、粘着付与剤、酸化防止剤、老化防止剤、吸湿剤、紫外線吸収剤、シランカップリング剤、天然物や合成物の樹脂類、ガラス繊維やガラスビーズなどの各種の添加剤を適宜配合することもできる。
(Other additives)
In addition to the above components, pigments such as pigments and dyes having near-infrared absorption characteristics, tackifiers, antioxidants, antioxidants, hygroscopic agents, ultraviolet absorbers, silane coupling agents, natural products, Various additives such as synthetic resins, glass fibers and glass beads can be appropriately blended.
（積層構成）
本粘着シートは、第１粘着層と第２粘着層とをそれぞれ１層以上備え、かつこれらの層を積層し一体化してなる構成を備えた粘着シートである。よって、本粘着シートが採用し得る積層構成としては、例えば、第１粘着層（以降「第１」と称する）／第２粘着層（以降「第２」と称する）、第１／第２／第１、第２／第１／第２、第１／第２／第１／第２などの積層構成を採用することができる。第１／第２からなる２層構成の場合、第２粘着層側を粘着力が大きい粘着面とし、第１粘着層側を粘着力が比較的低い剥離面として利用することができる。
以上の中でも、第２／第１／第２からなる３層構成などのように、第１粘着層を中間層として備え、当該第１粘着層よりも動的剪断貯蔵弾性率Ｇ’の値が高い第２粘着層を表裏層として備えた構成が特に好ましい。
(Laminated structure)
This pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having a configuration in which one or more first pressure-sensitive adhesive layers and second pressure-sensitive adhesive layers are provided, and these layers are laminated and integrated. Therefore, as a laminated structure that can be adopted by the present adhesive sheet, for example, a first adhesive layer (hereinafter referred to as “first”) / second adhesive layer (hereinafter referred to as “second”), first / second / Layered configurations such as first, second / first / second, first / second / first / second, etc. may be employed. In the case of the two-layer configuration composed of the first and second layers, the second adhesive layer side can be used as an adhesive surface with a high adhesive force, and the first adhesive layer side can be used as a release surface with a relatively low adhesive force.
Among the above, the first adhesive layer is provided as an intermediate layer, such as a three-layer configuration composed of 2 / first / second, and the value of the dynamic shear storage elastic modulus G ′ is higher than that of the first adhesive layer. The structure provided with the high 2nd adhesion layer as a front and back layer is especially preferable.
また、第１粘着層と第２粘着層との間に他の層を介在させることは可能である。但し、本粘着シートは、アウトガスバリアー層を設けなくても高温環境下での発泡を防止できる点に特徴であるから、少なくともアウトガスバリアー層が介在しない積層構成であるのが好ましい。 Moreover, it is possible to interpose another layer between the first adhesive layer and the second adhesive layer. However, since this pressure-sensitive adhesive sheet is characterized in that foaming in a high-temperature environment can be prevented without providing an outgas barrier layer, it is preferably a laminated structure in which at least the outgas barrier layer is not interposed.
（本粘着シートの粘弾性）
以上のようにして、異なる粘弾性挙動を有する第１粘着層及び第２粘着層をそれぞれ１層以上有し、且つ、これらの層を積層し一体化してなる構成を備えた粘着シートであって、周波数１Ｈｚの温度分散で測定した動的剪断貯蔵弾性率Ｇ’の値が下記範囲内であることを特徴とする本透明粘着シートを形成することができる。
・Ｇ’（２０℃）が２×１０４〜５×１０５Ｐａ。
・Ｇ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
(Viscoelasticity of this adhesive sheet)
A pressure-sensitive adhesive sheet having a configuration in which one or more first pressure-sensitive adhesive layers and second pressure-sensitive adhesive layers each having different viscoelastic behaviors are formed as described above, and these layers are laminated and integrated. The transparent adhesive sheet can be formed in which the value of the dynamic shear storage modulus G ′ measured by temperature dispersion at a frequency of 1 Hz is within the following range.
G ′ (20 ° C.) is 2 × 10 4 to 5 × 10 5 Pa.
G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
本粘着シートの動的剪断貯蔵弾性率Ｇ’（２０℃）は２×１０４〜５×１０５Ｐａであるのが重要であり、好ましくは５×１０４〜５×１０５、特に好ましくは１×１０５〜３×１０５である。
ここで、本粘着シートの動的剪断貯蔵弾性率Ｇ’（２０℃）が２．０×１０４未満であると、カット端面でのベタつきが室温でも大きく、例えばトムソン刃でカットした際に刃にくっつくなどカット性に劣り、カット後もベタついて生産機械にくっつくなどハンドリング性も劣ることになる。５×１０５Ｐａより大きいと柔軟性や粘着性が低下し、例えば裏面に印刷段差を有する保護パネルを貼り合わせる場合など、段差部分に粘着剤が入り込めなくて気泡が残留する可能性がある。
また、本粘着シートの動的剪断貯蔵弾性率Ｇ’（１５０℃）は１×１０４〜１×１０５Ｐａであるのが重要であり、好ましくは２×１０４〜６×１０４、特に好ましくは２×１０４〜５×１０４である。
ここで、本粘着シートの動的剪断貯蔵弾性率Ｇ’（１５０℃）が１×１０４未満であると、高温環境下で粘着層ズレや粘着材ハミダシが起こる可能性がある。１×１０５Ｐａより大きいと粘性が低下し弾性回復する傾向があり、例えば保護パネル裏面の印刷段差部の入隅部内に空隙を発生する可能性がある。
It is important that the dynamic shear storage elastic modulus G ′ (20 ° C.) of the pressure-sensitive adhesive sheet is 2 × 10 4 to 5 × 10 5 Pa, preferably 5 × 10 4 to 5 × 10 5 , particularly preferably. 1 × a 10 5 ~3 × 10 5.
Here, when the dynamic shear storage elastic modulus G ′ (20 ° C.) of the pressure-sensitive adhesive sheet is less than 2.0 × 10 4 , the stickiness at the cut end face is large even at room temperature, and the blade is cut when cut with a Thomson blade, for example. It will be inferior in cutting properties such as sticking, and will be inferior in handling properties such as sticking to the production machine after cutting. When it is higher than 5 × 10 5 Pa, flexibility and adhesiveness are lowered, and for example, when a protective panel having a printed step is pasted on the back surface, the adhesive may not enter the stepped portion and air bubbles may remain. .
The dynamic shear storage modulus G ′ (150 ° C.) of the pressure-sensitive adhesive sheet is important to be 1 × 10 4 to 1 × 10 5 Pa, preferably 2 × 10 4 to 6 × 10 4 , particularly preferably from 2 × 10 4 ~5 × 10 4 .
Here, when the dynamic shear storage elastic modulus G ′ (150 ° C.) of the pressure-sensitive adhesive sheet is less than 1 × 10 4 , there is a possibility that a pressure-sensitive adhesive layer shift or a pressure-sensitive adhesive material may occur in a high-temperature environment. If it exceeds 1 × 10 5 Pa, the viscosity tends to decrease and elastic recovery tends to occur. For example, there is a possibility that voids are generated in the corners of the printed steps on the back surface of the protective panel.
（本粘着シートの引張弾性率・引張破断時伸び）
本粘着シートは、引張弾性率が０．２０ＭＰａ以上であって、かつ引張破断時伸びが４００％以上であるのが好ましい。このような粘着シートであれば、伸び特性と引張弾性率を両方兼ね備えているから、ハンドリング性に優れているばかりか、ヒートショックなどの急激な環境変化に対する耐久性にも優れたものとなる。
このような観点から、本粘着シートの引張弾性率は０．６０ＭＰａ以下であるのがより一層好ましく、特に０．３０ＭＰａ以上、或いは０．５０ＭＰａ以下であるのがさらに好ましい。
また、本粘着シートの引張破断時伸びは、柔軟性と段差追従性の観点から、８００％以上、或いは１３００％以下であるのがより一層好ましく、中でも１０００％以下であるのがさらに好ましい。
(The tensile modulus of elasticity and the elongation at break of this adhesive sheet)
The pressure-sensitive adhesive sheet preferably has a tensile elastic modulus of 0.20 MPa or more and an elongation at break of 400% or more. Such a pressure-sensitive adhesive sheet has both elongation characteristics and tensile elastic modulus, so that it is excellent not only in handling properties but also in durability against rapid environmental changes such as heat shock.
From such a viewpoint, the tensile elastic modulus of the pressure-sensitive adhesive sheet is more preferably 0.60 MPa or less, and particularly preferably 0.30 MPa or more, or 0.50 MPa or less.
Further, the elongation at break of the pressure-sensitive adhesive sheet is more preferably 800% or more or 1300% or less, more preferably 1000% or less, from the viewpoint of flexibility and step following ability.
（製造方法）
本粘着シートの第１粘着層及び第２粘着層のいずれも、例えば、ベースポリマーとしてアクリル酸エステル重合体を選択し、架橋剤及び反応開始剤或いは反応触媒等を添加して攪拌混合し、離型フィルム上に目的の厚さになるように製膜し、加熱乾燥或いは紫外線照射して架橋させることで、第１粘着層形成シート又は第２粘着層形成シートを得ることができる。
(Production method)
For each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer of the present pressure-sensitive adhesive sheet, for example, an acrylate polymer is selected as the base polymer, and a cross-linking agent and a reaction initiator or a reaction catalyst are added and stirred and mixed. A first pressure-sensitive adhesive layer-forming sheet or a second pressure-sensitive adhesive layer-formed sheet can be obtained by forming a film on a mold film so as to have a desired thickness, and crosslinking by heat drying or ultraviolet irradiation.
この際、第１粘着層は、ベースポリマーとしての（メタ）アクリル酸エステル系共重合体と架橋剤と光重合開始剤とを含有する粘着剤組成物を、ＵＶ架橋して形成するのが好ましい。
他方、第２粘着層は、ベースポリマーとしての（メタ）アクリル酸エステル系共重合体と架橋開始剤とを含有する粘着剤組成物を、加熱反応架橋して形成するのが好ましい。
At this time, the first pressure-sensitive adhesive layer is preferably formed by UV-crosslinking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer, a crosslinking agent, and a photopolymerization initiator. .
On the other hand, the second pressure-sensitive adhesive layer is preferably formed by subjecting a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer and a crosslinking initiator to heat reaction crosslinking.
このようにして第１粘着層形成シート及び第２粘着層形成シートをそれぞれ作製しておき、後工程で重ね合わせて透明両面粘粘着シートを作製することもできる。
また、どちらか一方のシートを作製しておき、このシートに他方の組成物をコートして透明両面粘粘着シートを作製することもできる。
また、離型フィルム上に、順番に第１粘着層形成用組成物及び第２粘着層形成用組成物を多段コートして透明両面粘粘着シートを作製することもできる。
さらにまた、第１粘着層形成用組成物および第２粘着層形成用組成物を共押出することにより透明両面粘粘着シートを作製することもできる。
Thus, the 1st adhesion layer formation sheet and the 2nd adhesion layer formation sheet are each produced, and it can pile up at a post process and can also produce a transparent double-sided adhesive sheet.
Moreover, either one sheet | seat is produced and the other composition can be coat | covered with this sheet | seat, and a transparent double-sided adhesive sheet can also be produced.
Alternatively, a transparent double-sided pressure-sensitive adhesive sheet can be prepared by applying a multistage coating of the first pressure-sensitive adhesive layer forming composition and the second pressure-sensitive adhesive layer forming composition on the release film in order.
Furthermore, a transparent double-sided adhesive sheet can also be produced by co-extruding the first adhesive layer forming composition and the second adhesive layer forming composition.
このようにして第１粘着層付シートと第２粘着層付シートをそれぞれ作製しておき、後工程で重ね合わせて積層シートを形成することもできるし、また、どちらか一方の粘着層付シートを作製しておき、この粘着層付シートに他方の粘着層組成物をコートするようにして積層シートを形成することもできる。また、離型フィルム上に順番に第１粘着層形成用組成物、第２粘着層形成用組成物を多段コートするようにして積層シートを形成することもできる。さらに、第１粘着層形成用組成物および第２粘着層形成用組成物を共押出することにより積層シートを形成することもできる。粘着剤の性状や架橋方法によって適宜選択して製造することが可能である。 In this way, the first adhesive layer-attached sheet and the second adhesive layer-attached sheet are respectively prepared, and can be laminated in a subsequent process to form a laminated sheet, or either one of the adhesive layer-attached sheets. A laminated sheet can also be formed by coating the other adhesive layer composition on this adhesive layer-attached sheet. Moreover, a laminated sheet can also be formed by carrying out multi-step coating of the 1st adhesion layer formation composition and the 2nd adhesion layer formation composition on a release film in order. Furthermore, a laminated sheet can also be formed by coextrusion of the first adhesive layer forming composition and the second adhesive layer forming composition. It can be appropriately selected and manufactured depending on the properties of the pressure-sensitive adhesive and the crosslinking method.
粘着シートの特定温度での貯蔵弾性率は、ベースポリマーであるアクリル酸エステル共重合体の構成成分である重合性モノマーの種類、組成比率及び重合条件のほか、架橋剤および架橋開始剤の種類、量、架橋条件によって調整が可能である。 The storage elastic modulus at a specific temperature of the pressure-sensitive adhesive sheet is the type of polymerizable monomer that is a constituent component of the acrylate copolymer that is the base polymer, the composition ratio and the polymerization conditions, as well as the type of crosslinking agent and crosslinking initiator The amount can be adjusted depending on the crosslinking conditions.
特に粘着層のＧ’（２０℃）値はベースポリマーのＴｇ値に影響を受け、ベースポリマーのＴｇが低いほど、Ｇ’（２０℃）値は小さくなる傾向となり、Ｔｇが高いほどＧ’（２０℃）値は大きくなる傾向がある。
よって、例えば第１粘着層は、ベースポリマーのＴｇが−１０℃未満になるように、共重合するモノマー種類や組成比率を調整することにより、第１粘着層のＧ’（２０℃）を本発明の範囲に調製することができる。具体的には、例えばベースポリマーのアクリル酸共重合体を形成する共重合モノマー成分にｎ−ブチルアクリレートモノマーや２エチルヘキシルアクリレートモノマー等の比較的Ｔｇの低いモノマー比率を多くし、メチルメタアクリレート、アクリル酸や酢酸ビニル等の比較的Ｔｇの高いモノマー比率を少なくしてランダム共重合することで、好ましい第１粘着層のベースポリマーを調製することができ、その結果としてＴｇが−１０℃未満の特定温度における特定範囲の貯蔵弾性率を有する第１粘着層を作製することが可能である。
逆に、第２粘着層は、ベースポリマーのＴｇが−１０℃以上になるように、共重合するモノマー種類や組成比率を調整することにより、第２粘着層のＧ’（２０℃）を本発明の範囲に調製することができる。具体的には、ベースポリマーのアクリル酸共重合体を形成する共重合モノマー成分にｎ−ブチルアクリレートモノマーや２エチルヘキシルアクリレートモノマー等の比較的Ｔｇの低いモノマー比率を少なくし、メチルメタアクリレート、アクリル酸や酢酸ビニル等の比較的Ｔｇの高いモノマー比率を多くしてランダム共重合することで、好ましい第２粘着層のベースポリマーを調製することができ、その結果としてＴｇが−１０℃以上の特定温度における特定範囲の貯蔵弾性率を有する第２粘着層を作製することが可能である。
In particular, the G ′ (20 ° C.) value of the adhesive layer is affected by the Tg value of the base polymer. The lower the Tg of the base polymer, the smaller the G ′ (20 ° C.) value tends to be. The higher the Tg, the G ′ ( 20 ° C.) value tends to increase.
Thus, for example, in the first adhesive layer, G ′ (20 ° C.) of the first adhesive layer is adjusted by adjusting the monomer type and composition ratio to be copolymerized so that the Tg of the base polymer is less than −10 ° C. It can be prepared within the scope of the invention. Specifically, for example, the copolymer monomer component that forms the acrylic acid copolymer of the base polymer is increased in the ratio of monomers having a relatively low Tg such as n-butyl acrylate monomer and 2-ethylhexyl acrylate monomer, so that methyl methacrylate, acrylic A preferred base polymer of the first adhesive layer can be prepared by random copolymerization by reducing the proportion of monomers having a relatively high Tg such as acid and vinyl acetate, and as a result, a specific Tg of less than −10 ° C. It is possible to produce the 1st adhesion layer which has the storage elastic modulus of the specific range in temperature.
On the other hand, the second adhesive layer is made of G ′ (20 ° C.) of the second adhesive layer by adjusting the type of monomer to be copolymerized and the composition ratio so that the Tg of the base polymer is −10 ° C. or higher. It can be prepared within the scope of the invention. Specifically, the copolymer monomer component forming the acrylic copolymer of the base polymer has a relatively low Tg monomer ratio such as n-butyl acrylate monomer and 2-ethylhexyl acrylate monomer to reduce methyl methacrylate and acrylic acid. The base polymer of the preferable second adhesive layer can be prepared by increasing the proportion of the monomer having a relatively high Tg, such as vinyl acetate, and the like, and as a result, a specific temperature having a Tg of −10 ° C. or higher can be prepared. It is possible to produce the 2nd adhesion layer which has the storage elastic modulus of a specific range in.
粘着層のＧ’（１５０℃）値はベースポリマーの分子量、架橋後の架橋点間分子量や絡み合い点間分子量に影響を受ける。ベースポリマーの分子量、架橋点間分子量や絡み合い点間分子量が大きいほどＧ’(１５０℃）値は大きくなる傾向がある。
よって、Ｇ’（１５０℃）の範囲からすると、第１粘着層は、厚さが必要なためベースポリマーを無溶剤で溶融成形するために必要な分子量（Ｍｗ：２〜６×１０5）のものを使用し、且つベタツキを抑制するため架橋剤および光開始剤の量を多くして調製するのが好ましい。
また、第２粘着層は、強接着性を付与するため、架橋剤量を少なくして架橋点間分子量を大きくして柔軟かつ高凝集力の粘弾性挙動を得ることが好ましい。
The G ′ (150 ° C.) value of the adhesive layer is affected by the molecular weight of the base polymer, the molecular weight between crosslink points after crosslinking, and the molecular weight between entangled points. The G ′ (150 ° C.) value tends to increase as the molecular weight of the base polymer, the molecular weight between cross-linking points, or the molecular weight between entanglement points increases.
Therefore, considering the range of G ′ (150 ° C.), the first adhesive layer has a molecular weight (Mw: 2 to 6 × 10 5 ) necessary for melt-molding the base polymer without solvent since the thickness is required. In order to suppress stickiness, it is preferable to prepare by increasing the amount of the crosslinking agent and the photoinitiator.
In order to provide strong adhesion, the second pressure-sensitive adhesive layer preferably has a soft and highly cohesive viscoelastic behavior by reducing the amount of crosslinking agent and increasing the molecular weight between crosslinking points.
（用途）
本粘着シートは、例えば、表裏に離型フィルムを設けた透明粘着シートとして提供することができる。
この際、離型フィルムは、ポリエステル系、ポリプロピレン系、ポリエチレン系のキャストフィルムや延伸フィルムにシリコーン離型処理したものや、離型紙から選択でき、特に剥離力の異なる離型フィルムや厚さの異なる離型フィルムを粘着シートの表裏に用いるのが好ましい。
(Use)
This pressure-sensitive adhesive sheet can be provided, for example, as a transparent pressure-sensitive adhesive sheet having a release film on the front and back.
At this time, the release film can be selected from polyester-type, polypropylene-type, polyethylene-type cast film and stretched film obtained by silicone release treatment, or release paper, and in particular, release films with different release forces and different thicknesses. It is preferable to use a release film on the front and back of the pressure-sensitive adhesive sheet.
本粘着シートまた、例えば、保護パネルの裏面に積層することで粘着付き保護パネル体として提供することができる。
本粘着シート製造時に保護パネルに直接積層することで、保護パネルと粘着シートとの界面を強固に密着させて耐久性を向上させることができ、この際、離型フィルム側に本粘着シートを先に積層させた後、直ちに保護パネル裏面に密着させて養生させればよい。
この際の養生条件は、特に限定するものではないが、例えば室温で７日間静置したり、４０℃で３日間静置したりすればよい。
The pressure-sensitive adhesive sheet can also be provided as a pressure-sensitive protective panel by laminating the back surface of the protective panel, for example.
By directly laminating the protective panel during the production of the adhesive sheet, the interface between the protective panel and the adhesive sheet can be firmly adhered to improve the durability. At this time, the adhesive sheet is first placed on the release film side. After being laminated, the substrate is immediately brought into close contact with the protective panel and cured.
The curing conditions at this time are not particularly limited, but may be, for example, left at room temperature for 7 days or left at 40 ° C. for 3 days.
被着体である保護パネルとしては、ガラス、アクリル樹脂、ポリカーボネート樹脂、脂環式ポリオレフィン樹脂、塩化ビニル樹脂、ナイロン樹脂、エポキシ樹脂、スチレン樹脂から選択することができ、保護パネルの表裏には反射防止処理、飛散防止処理やハードコート処理や意匠（切削、印刷）加工、タッチパネル機能が予め施されていてもよい。
本粘着シートは、被着体がアウトガスを発生する材料からなるものであっても、高温で発泡することなく貼着することができるから、被着体である保護パネルは、アウトガスを発生し得るプラスチック、すなわちアクリル樹脂、ポリカーボネート樹脂、脂環式ポリオレフィン樹脂、塩化ビニル樹脂、ナイロン樹脂、エポキシ樹脂、スチレン樹脂等であれば、本発明の効果をより享受できる。
The protective panel that is the adherend can be selected from glass, acrylic resin, polycarbonate resin, alicyclic polyolefin resin, vinyl chloride resin, nylon resin, epoxy resin, and styrene resin. Prevention processing, scattering prevention processing, hard coat processing, design (cutting, printing) processing, and touch panel function may be performed in advance.
Even if the adherend is made of a material that generates outgas, the pressure-sensitive adhesive sheet can be attached without foaming at a high temperature. Therefore, the protective panel that is the adherend can generate outgas. The effects of the present invention can be further enjoyed with plastics, that is, acrylic resins, polycarbonate resins, alicyclic polyolefin resins, vinyl chloride resins, nylon resins, epoxy resins, styrene resins, and the like.
このような透明粘着シート又は粘着付き保護パネルを用いて画像表示装置を作製することができる。
粘着付き保護パネルを用いると、画像表示装置の製造工程を削減でき、より生産性が向上できる。
また、上記透明粘着シート又は上記粘着付き保護パネルは、カット後に経時的にベタつかないから、画像表示パネルに合わせて予めカットしておくのが好ましい。
この際のカット方法は、トムソン刃による打ち抜き、スーパーカッターやレーザーでのカットが一般的であり、離型フィルムを剥がし易いように表裏どちらか一方の離型フィルムを額縁状に残してハーフカットするのがより好ましい。
An image display apparatus can be produced using such a transparent adhesive sheet or a protective panel with adhesive.
When the protective panel with adhesive is used, the manufacturing process of the image display device can be reduced, and the productivity can be further improved.
Moreover, since the said transparent adhesive sheet or the said protection panel with adhesion does not become sticky with time after cutting, it is preferable to cut beforehand according to an image display panel.
The cutting method at this time is generally punched with a Thomson blade, cut with a super cutter or laser, and half-cuts leaving either the front or back release film in a frame shape so that the release film can be easily peeled off. Is more preferable.
（語句の説明など）
なお、一般的に「シート」とは、ＪＩＳにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう（日本工業規格ＪＩＳＫ６９００）。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シートおよびフィルムを包含するものである。
また、本発明において「主成分」と表現した場合には、特に記載しない限り、当該主成分の機能を妨げない範囲で他の成分を含有することを許容する意を包含するものである。この際、特に当該主成分の含有割合を特定するものではないが、その成分（２成分以上が主成分である場合には、これらの合計量）が組成物中で５０質量％以上、特に７０質量％以上、中でも９０質量％以上（１００％含む）を占めるのが一般的である。
(Explanation of words)
In general, “sheet” refers to a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width. In general, “film” is compared to the length and width. A thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
In addition, the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet, and a film.
In addition, the expression “main component” in the present invention includes the meaning of allowing other components to be contained within a range that does not hinder the function of the main component, unless otherwise specified. At this time, the content ratio of the main component is not particularly specified, but the component (when two or more components are the main components, the total amount thereof) is 50% by mass or more, particularly 70% in the composition. In general, it accounts for 90% by mass or more (including 100%).
本明細書において、「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と記載した場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含するものである。
また、「Ｘ以上」（Ｘは任意の数字）と記載した場合、特にことわらない限り「好ましくはＸより大きい」の意を包含し、「Ｙ以下」（Ｙは任意の数字）と記載した場合、特にことわらない限り「好ましくはＹより小さい」の意も包含するものである。
In the present specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included.
Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is also included.
次に、実施例を挙げてより具体的に説明する。
なお、以下において「部」とは「質量部」を意味するものとする。
Next, an example is given and it demonstrates more concretely.
In the following, “parts” means “parts by mass”.
＜Ｇ’及びＴｇの測定＞
動的粘弾性挙動は、レオメトリックス社製の粘弾性測定装置「ダイナミックアナライザーＲＤＡＩＩ」を用いて剪断法で以下の条件で測定した。
・治具：Φ２５ｍｍパラレルプレート
・歪み：０．５％
・周波数：１Ｈｚ
・温度：−７０〜２００℃（−７０℃から昇温速度３℃／ｍｉｎで測定）
・試料厚さ：２５０μｍ
<Measurement of G ′ and Tg>
The dynamic viscoelastic behavior was measured by the shearing method using the viscoelasticity measuring device “Dynamic Analyzer RDAII” manufactured by Rheometrics Co., Ltd. under the following conditions.
・ Jig: Φ25mm parallel plate ・ Strain: 0.5%
・ Frequency: 1 Hz
-Temperature: -70 to 200 ° C (measured from -70 ° C at a heating rate of 3 ° C / min)
・ Sample thickness: 250 μm
第１粘着層形成用シート、第２粘着層形成用シート、これら第１粘着層形成用シート及び第２粘着層形成用シートを積層一体化してなる粘着シートを、それぞれ測定サンプルとした。そして、この測定サンプル（粘着シート）の２０℃および１５０℃の貯蔵弾性率Ｇ’の値と、Ｔａｎδの最大値(＝Ｔｇ)とを読み取った。 A first adhesive layer forming sheet, a second adhesive layer forming sheet, and an adhesive sheet formed by laminating and integrating the first adhesive layer forming sheet and the second adhesive layer forming sheet were used as measurement samples, respectively. And the value of the storage elastic modulus G 'of 20 degreeC and 150 degreeC of this measurement sample (adhesive sheet) and the maximum value (= Tg) of Tan (delta) were read.
＜積算光量の測定＞
ウシオ電機製紫外線積算光量計「ＵＩＴ−１５０」に受光器「ＵＶＤ-Ｓ３６５」を取付けて波長３６５ｎｍの積算光量を測定した。
<Measurement of integrated light intensity>
A photoreceiver “UVD-S365” was attached to a UV integrated light meter “UIT-150” manufactured by USHIO ELECTRIC CO., LTD, and the integrated light amount at a wavelength of 365 nm was measured.
＜カット性＞
実施例・比較例で得た粘着シートを、トムソン打ち抜き機を用いて１分間に３０ショットの速度でカットした際に、該粘着シートがトムソン刃に付着せずに打ち抜けるか否かを観察した。
○：付着しなかったもの。
×：付着したもの。
<Cutability>
When the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut at a rate of 30 shots per minute using a Thomson punching machine, it was observed whether or not the pressure-sensitive adhesive sheet was punched out without adhering to the Thomson blade. .
○: Not attached.
X: Attached.
＜加熱耐久性＞
５３×８３ｍｍのソーダライムガラスの周縁部に、幅３ｍｍ、厚み２０μｍの印刷を施し、周縁部に２０μｍの印刷段差をもつ評価用ガラス基板を作製した。実施例・比較例で得た粘着シートを、ガラス基板の印刷段差部を覆うようにハンドローラにて貼着した。そして、ソーダライムガラスを減圧下（−０．１ＭＰａ）にてプレス貼合した後、オートクレーブ処理（６０℃０．３ＭＰａ）を施して仕上貼着し、積層体を作製した。
前記積層体を、常態（温度２３℃湿度５０％）で一日静置した後、温度８０℃湿度８５％の恒温恒湿機にて３日間保管した。保管後の外観を目視観察した。そして、印刷段差付近の発泡、剥離、粘着材のはみ出しを観察した。
○：発泡、剥離、はみ出しのなかったもの。
×：発泡、剥離、はみ出しのあったもの。
<Heating durability>
An evaluation glass substrate having a printing step of 3 μm in width and 20 μm in thickness was printed on the periphery of 53 × 83 mm soda lime glass, and a 20 μm print step was formed in the periphery. The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were attached with a hand roller so as to cover the printing step portion of the glass substrate. And soda-lime glass was press-bonded under reduced pressure (−0.1 MPa), and then autoclaved (60 ° C., 0.3 MPa) to finish and paste to produce a laminate.
The laminate was allowed to stand for one day in a normal state (temperature 23 ° C., humidity 50%), and then stored for 3 days in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 85%. The appearance after storage was visually observed. Then, foaming, peeling, and protrusion of the adhesive material in the vicinity of the printing step were observed.
○: No foaming, peeling, or protrusion.
X: A thing with foaming, peeling, and protrusion.
＜引張試験＞
実施例・比較例で得た粘着シートを、幅２０ｍｍ、長さ８０ｍｍに切り出し、これを図２（Ａ）に示すような型紙（６０ｍｍ×８０ｍｍ、中央部は窓部）に貼り付け、引張試験機（インテスコ社製「２０５型試験機」）に型紙上下をチャックした後、図２（Ｂ）に示すように、型紙の両横に斜めに切り込みを入れて型紙の上下を分断し、チャック間距離４０ｍｍ、引張速度３００ｍｍ／ｍｉｎで引張試験を行った。そして、引張弾性率（ＭＰａ）を算出すると共に、引張破断時伸び（％）を算出した。
<Tensile test>
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were cut into a width of 20 mm and a length of 80 mm, and this was attached to a paper pattern (60 mm × 80 mm, the central part being a window part) as shown in FIG. After chucking the upper and lower sides of the paper pattern with a machine ("205 type testing machine" manufactured by Intesco), as shown in Fig. 2 (B), the upper and lower sides of the paper pattern are cut into two sides to cut the upper and lower sides of the paper pattern. A tensile test was performed at a distance of 40 mm and a tensile speed of 300 mm / min. And while calculating | requiring the tensile elasticity modulus (MPa), elongation (%) at the time of a tensile fracture was calculated.
＜ヒートショック試験＞
実施例・比較例で得た粘着シートを、厚さ０．９ｍｍのフロートガラスの間に挟んで試験試料とし、ヒートショック試験（−２０℃×３０分⇔８０℃×３０分、１００回）を行い、外観を目視で比較確認し、次の基準で評価した。
○：発泡、剥離、はみ出しのなかったもの。
×：発泡、剥離、はみ出しがあったもの。
<Heat shock test>
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples are sandwiched between 0.9 mm-thick float glass and used as test samples, and a heat shock test (−20 ° C. × 30 minutes⇔80 ° C. × 30 minutes, 100 times) is performed. The appearance was compared and confirmed visually, and evaluated according to the following criteria.
○: No foaming, peeling, or protrusion.
X: A thing with foaming, peeling, and protrusion.
［実施例１］
（第１粘着層付シートの作製）
予め重合されたアクリル酸エステル共重合体Ａ：１００質量部に対して、光開始剤（商品名エザキュアＴＺＴ：日本シーベルヘグナー社製）：２．０質量部および架橋剤（４官能アクリレート（商品名ＮＫエステルＡＴＭ−４ＰＬ：新中村化学社製）：２０質量部を溶融攪拌して均一に混合して粘着剤組成物を調製した。
この粘着剤組成物を、厚さ５０μｍのシリコーン離型ＰＥＴフィルム（商品名ＭＲＦ５０：三菱化学ポリエステル社製）の離型面にホットメルトコーターを用いて塗布した後、シリコーン離型ＰＥＴフィルム（商品名ＭＲＦ５０：三菱化学ポリエステル社製）を重ねて、２枚のシリコーン離型ＰＥＴフィルムの間に粘着剤組成物を挟み込んで厚さ２００μｍのシート状に成形した後、ＰＥＴフィルム越しに高圧水銀ランプの紫外線を表裏両側からそれぞれ１０００ｍＪ／ｃｍ2照射（波長３６５ｍｍ換算）して前記粘着剤組成物を紫外線架橋させて、第１粘着層付シートを作製した。
[Example 1]
(Preparation of sheet with first adhesive layer)
Prepolymerized acrylate copolymer A: 100 parts by mass, photoinitiator (trade name Ezacure TZT: manufactured by Nippon Sebel Hegner): 2.0 parts by mass and cross-linking agent (tetrafunctional acrylate (trade name) NK ester ATM-4PL (manufactured by Shin-Nakamura Chemical Co., Ltd.): An adhesive composition was prepared by melting and stirring 20 parts by mass and mixing uniformly.
This adhesive composition was applied to the release surface of a 50 μm-thick silicone release PET film (trade name MRF50: manufactured by Mitsubishi Chemical Polyester) using a hot melt coater, and then a silicone release PET film (trade name) MRF50 (manufactured by Mitsubishi Chemical Polyester Co., Ltd.) and the adhesive composition is sandwiched between two silicone release PET films to form a 200 μm thick sheet, and then UV light from a high-pressure mercury lamp is passed through the PET film. Were irradiated from the front and back sides by 1000 mJ / cm 2 (wavelength 365 mm conversion), and the pressure-sensitive adhesive composition was UV-crosslinked to prepare a sheet with a first pressure-sensitive adhesive layer.
前記アクリル酸エステル共重合体Ａは、２−エチルヘキシルアクリレート：８５質量％、メチルメタクリレート１５質量％の組成比で溶液重合した後、脱溶剤したものを用いた。
前記アクリル酸エステル共重合体ＡをＧＰＣで測定した分子量および分子量分布は、質量平均分子量（ＭＷ）：２．７×１０5、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：６．３であった。
As the acrylic ester copolymer A, a solvent-polymerized one obtained by solution polymerization at a composition ratio of 2-ethylhexyl acrylate: 85 mass% and methyl methacrylate 15 mass% was used.
The molecular weight and molecular weight distribution of the acrylic ester copolymer A measured by GPC were as follows: mass average molecular weight (MW): 2.7 × 10 5 , mass average molecular weight (MW) / number average molecular weight (MN): 6.3 Met.
（第２粘着層付シートの作製）
市販溶剤タイプのアクリル系粘着剤（ベース樹脂：アクリル酸エステル共重合体、商品名ＳＫダイン１８８２：綜研化学社製）１０００質量部に対して、イソシアネート系硬化剤（商品名Ｌ−４５：綜研化学社製）１．８５質量部およびエポキシ系硬化剤（商品名Ｅ−５ＸＭ：綜研化学社製）０．５質量部を均一混合して粘着剤溶液を調製した。
この粘着剤溶液を、厚さ５０μｍのシリコーン離型ＰＥＴフィルム（商品名ＭＲＦ５０：三菱化学ポリエステル社製）の離型面に、厚さ２５μｍとなるようにホットメルトコーターを用いて塗布し、溶剤を乾燥（加熱温度８０℃、乾燥時間５分）させるようにして加熱反応架橋させ、厚さ２５μｍの粘着層を備えた第２粘着層付シートを２枚作製した。
(Preparation of sheet with second adhesive layer)
Commercially available solvent-type acrylic pressure-sensitive adhesive (base resin: acrylate copolymer, trade name SK Dyne 1882: manufactured by Soken Chemical Co., Ltd.) with respect to 1000 parts by mass, an isocyanate-based curing agent (trade name L-45: Soken Chemical) 1.85 parts by mass) and 0.5 parts by mass of an epoxy curing agent (trade name E-5XM: manufactured by Soken Chemical Co., Ltd.) were uniformly mixed to prepare an adhesive solution.
This adhesive solution was applied to a release surface of a 50 μm-thick silicone release PET film (trade name MRF50: manufactured by Mitsubishi Chemical Polyester) using a hot melt coater so as to have a thickness of 25 μm. Two sheets of the second pressure-sensitive adhesive layer-attached sheet provided with a pressure-sensitive adhesive layer having a thickness of 25 μm were prepared by drying by heating (heating temperature 80 ° C., drying time 5 minutes).
（第１粘着層および第２粘着層の一体化）
第１粘着層付シートの表裏両側の離型ＰＥＴを剥がし、第１粘着層の両側面に、溶剤を乾燥させた直後の第２粘着層付シートの粘着層をそれぞれ密着一体化して、室温（２３℃）で７日間放置熟成し、厚さ２５０μｍの２種３層（第２／第１／第２）の粘着層を備えた粘着シートを得た。
(Integration of the first adhesive layer and the second adhesive layer)
The release PET on both the front and back sides of the sheet with the first pressure-sensitive adhesive layer is peeled off, and the pressure-sensitive adhesive layers of the sheet with the second pressure-sensitive adhesive layer immediately after drying the solvent are adhered and integrated on both sides of the first pressure-sensitive adhesive layer, respectively. The pressure-sensitive adhesive sheet was aged at 23 ° C. for 7 days, and was provided with two types and three layers (second / first / second) adhesive layers having a thickness of 250 μm.
［実施例２］
実施例１のアクリル酸エステル共重合体Ａの代わりに、アクリル酸エステル共重合体Ｂを用いた以外は、実施例１同様にして粘着シートを得た。
[Example 2]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic ester copolymer B was used in place of the acrylic ester copolymer A of Example 1.
前記アクリル酸エステル共重合体Ｂは、２−エチルヘキシルアクリレート：７０質量％、酢酸ビニル：２５質量％およびアクリル酸：５．０質量％の組成比で溶液重合した後、脱溶剤して用いた。
前記アクリル酸エステル共重合体ＢをＧＰＣで測定した分子量および分子量分布は、質量平均分子量（ＭＷ）：５×１０5、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：９．０であった。
The acrylic ester copolymer B was subjected to solution polymerization at a composition ratio of 2-ethylhexyl acrylate: 70% by mass, vinyl acetate: 25% by mass and acrylic acid: 5.0% by mass, and then used after removing the solvent.
The molecular weight and molecular weight distribution of the acrylic acid ester copolymer B measured by GPC were: mass average molecular weight (MW): 5 × 10 5 , mass average molecular weight (MW) / number average molecular weight (MN): 9.0. It was.
［実施例３］
実施例１のアクリル酸エステル共重合体Ａの代わりに、アクリル酸エステル共重合体Ｃを用いた以外は、実施例１同様にして粘着シートを得た。
[Example 3]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the acrylic ester copolymer C was used in place of the acrylic ester copolymer A of Example 1.
アクリル酸エステル共重合体Ｃは、２−エチルヘキシルアクリレート：７７．０質量％、酢酸ビニル：１９質量％およびアクリル酸：４．０質量％の組成比で溶液重合した後、脱溶剤して用いた。
前記アクリル酸エステル共重合体ＣをＧＰＣで測定した分子量および分子量分布は、質量平均分子量（ＭＷ）：４×１０5、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：８．０であった。
Acrylic ester copolymer C was used after solvent polymerization at a composition ratio of 2-ethylhexyl acrylate: 77.0% by mass, vinyl acetate: 19% by mass and acrylic acid: 4.0% by mass, and then removing the solvent. .
The molecular weight and molecular weight distribution of the acrylate copolymer C measured by GPC were: mass average molecular weight (MW): 4 × 10 5 , mass average molecular weight (MW) / number average molecular weight (MN): 8.0 It was.
［実施例４]
（第１粘着層付シートの作製）
実施例３で調製した第１粘着層用の粘着剤組成物を、実施例３と同様に２枚のシリコーン離型ＰＥＴフィルムの間に挟み込んで粘着層の厚さ１３５μｍに成形した後、ＰＥＴフィルム越しに高圧水銀ランプの紫外線を表裏両側からそれぞれ１０００ｍＪ／ｃｍ2照射（波長３６５ｍｍ換算）して紫外線架橋させて、第１粘着層付シートを作製した。
[Example 4]
(Preparation of sheet with first adhesive layer)
The pressure-sensitive adhesive composition for the first pressure-sensitive adhesive layer prepared in Example 3 was sandwiched between two silicone release PET films in the same manner as in Example 3 to form a pressure-sensitive adhesive layer having a thickness of 135 μm, and then a PET film. A sheet with a first pressure-sensitive adhesive layer was produced by irradiating ultraviolet rays from a high-pressure mercury lamp through both sides of the front and back sides at 1000 mJ / cm 2 (wavelength 365 mm conversion).
（第２粘着層付シートの作製）
市販溶剤タイプのアクリル系粘着剤（ベース樹脂：アクリル酸エステル共重合体、商品名ＳＫダイン１８８２：綜研化学社製）１０００質量部に対して、イソシアネート系硬化剤（商品名Ｌ−４５：綜研化学社製）１．８５質量部およびエポキシ系硬化剤（商品名Ｅ−５ＸＭ：綜研化学社製）０．５質量部を均一混合して粘着剤溶液を調製した。
この粘着剤溶液を、厚さ５０μｍのシリコーン離型ＰＥＴフィルム（商品名ＭＲＦ５０：三菱化学ポリエステル社製）の離型面に、厚さ２０μｍとなるようにホットメルトコーターを用いて塗布し、溶剤を乾燥（加熱温度８０℃、乾燥時間５分）させるようにして加熱反応架橋させて、厚さ２０μｍの粘着層を備えた第２粘着層付シートを２枚作製した。
(Preparation of sheet with second adhesive layer)
Commercially available solvent-type acrylic pressure-sensitive adhesive (base resin: acrylate copolymer, trade name SK Dyne 1882: manufactured by Soken Chemical Co., Ltd.) with respect to 1000 parts by mass, an isocyanate-based curing agent (trade name L-45: Soken Chemical) 1.85 parts by mass) and 0.5 parts by mass of an epoxy curing agent (trade name E-5XM: manufactured by Soken Chemical Co., Ltd.) were uniformly mixed to prepare an adhesive solution.
This adhesive solution was applied to the release surface of a 50 μm thick silicone release PET film (trade name MRF50: manufactured by Mitsubishi Chemical Polyester) using a hot melt coater so as to have a thickness of 20 μm. Two sheets of the second pressure-sensitive adhesive layer-attached sheet each having a pressure-sensitive adhesive layer having a thickness of 20 μm were prepared by drying by heating (heating temperature 80 ° C., drying time 5 minutes).
（第１粘着層および第２粘着層の一体化）
第１粘着層付シートの表裏両側の離型ＰＥＴを剥がし、第１粘着層の両側面に、溶剤を乾燥させた直後の第２粘着層付シートの粘着層をそれぞれ密着一体化して、室温（２３℃）で７日間放置熟成し、厚さ１７５μｍの２種３層（第２／第１／第２）の粘着層を備えた粘着シートを得た。
(Integration of the first adhesive layer and the second adhesive layer)
The release PET on both the front and back sides of the sheet with the first pressure-sensitive adhesive layer is peeled off, and the pressure-sensitive adhesive layers of the sheet with the second pressure-sensitive adhesive layer immediately after drying the solvent are adhered and integrated on both sides of the first pressure-sensitive adhesive layer, respectively. The pressure-sensitive adhesive sheet was aged at 23 ° C. for 7 days to obtain a 175 μm-thick two-type three-layer (second / first / second) pressure-sensitive adhesive layer.
［実施例５]
実施例４において、第１粘着層の厚さを１１０μｍとして粘着シート全体の厚さを１５０μｍとした以外は、実施例４と同様に粘着シートを得た。
[Example 5]
In Example 4, an adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the first adhesive layer was 110 μm and the thickness of the entire adhesive sheet was 150 μm.
［実施例５]
実施例４において、第１粘着層の厚さを２１０μｍとして粘着シート全体の厚さを２５０μｍとした以外は、実施例４と同様に粘着シートを得た。
[Example 5]
In Example 4, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the first pressure-sensitive adhesive layer was 210 μm and the thickness of the entire pressure-sensitive adhesive sheet was 250 μm.
［比較例１］
特開２００２−３４８１５０の実施例１に準じて、次のようにして粘着シートを作製した。
アクリル酸エステル共重合体１００質量部に対し、有機官能基含有（メタ）アクリレートモノマーとして２−イソシアナートエチルメタクリレート：２．０質量部、光重合開始剤として１−ヒドロキシ−シクロヘキシル−フェニルケトン：２．０質量部、金属化合物としてアセチルアセトン亜鉛塩：２．０質量部を溶融攪拌した後、離型フィルム間に厚み２５０μｍのシート状に成形して紫外線未照射の単層粘着シートを得た。
[Comparative Example 1]
A pressure-sensitive adhesive sheet was produced as follows in accordance with Example 1 of JP-A-2002-348150.
With respect to 100 parts by mass of the acrylic ester copolymer, 2-isocyanatoethyl methacrylate as an organic functional group-containing (meth) acrylate monomer: 2.0 parts by mass, and 1-hydroxy-cyclohexyl-phenylketone as a photopolymerization initiator: 2 0.0 parts by mass and 2.0 parts by mass of acetylacetone zinc salt as a metal compound were melted and stirred, and then formed into a sheet having a thickness of 250 μm between release films to obtain a single-layer adhesive sheet not irradiated with ultraviolet rays.
用いたアクリル酸エステル共重合体の組成は、ｎ−ブチルアクリレート：７８．４質量％、２−エチルヘキシルアクリレート：１９．６質量％及びアクリル酸：２．０質量％を共重合させたもので、アクリル酸エステル共重合体のＧＰＣで測定した分子量及び分子量分布は、質量平均分子量（ＭＷ）：２．２７×１０６、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：３．６であった。 The composition of the acrylic ester copolymer used was obtained by copolymerizing n-butyl acrylate: 78.4% by mass, 2-ethylhexyl acrylate: 19.6% by mass and acrylic acid: 2.0% by mass, The molecular weight and molecular weight distribution measured by GPC of the acrylate copolymer were: mass average molecular weight (MW): 2.27 × 10 6 , mass average molecular weight (MW) / number average molecular weight (MN): 3.6. It was.
［比較例２］
ＷＯ２００６／１１２３１１の実施例１に準じて、次のようにして粘着シートを作製した。
無機酸化物層を形成したシートとして、厚さ２５μｍの２軸延伸ポリエステルシートの片面に、アルミナを蒸着したシート（麗光社製商品名：ファインバリヤーＡＴ）。
一面側に形成する層の接着剤として、以下の紫外線で架橋した接着剤を用いた。
ｎ−ブチルアクリレート：７８．４質量部、２−エチルヘキシルアクリレート：１９．６質量部、アクリル酸：２．０質量部からなるアクリルモノマーを、酢酸エチル溶剤中で重合開始剤（ナカライテスク社製１級試薬）を用いてランダム共重合させてポリマー溶液を調製し、この溶液から酢酸エチルを脱溶剤して固形のアクリル酸エステル重合体ポリマーを得た。
このポリマーは、ＧＰＣで測定した分子量および分子量分布は質量平均分子量（ＭＷ）：２．２７×１０６、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：３．６であった。
[Comparative Example 2]
A pressure-sensitive adhesive sheet was produced as follows in accordance with Example 1 of WO2006 / 112311.
As a sheet on which an inorganic oxide layer is formed, a sheet obtained by vapor-depositing alumina on one side of a 25-μm thick biaxially stretched polyester sheet (trade name: Fine Barrier AT, manufactured by Reiko Co., Ltd.).
As an adhesive for the layer formed on the one surface side, the following UV-crosslinked adhesive was used.
An acrylic monomer composed of n-butyl acrylate: 78.4 parts by mass, 2-ethylhexyl acrylate: 19.6 parts by mass, and acrylic acid: 2.0 parts by mass was used as a polymerization initiator (1 manufactured by Nacalai Tesque, Inc.) in an ethyl acetate solvent. The polymer solution was prepared by random copolymerization using a grade reagent, and ethyl acetate was removed from the solution to obtain a solid acrylate polymer polymer.
This polymer had a molecular weight and molecular weight distribution measured by GPC of mass average molecular weight (MW): 2.27 × 10 6 and mass average molecular weight (MW) / number average molecular weight (MN): 3.6.
このポリマーの固形分１００質量部に対して、水素引き抜き型光開始剤０．３質量部及び２官能モノマー（大阪有機化学者製商品名ビスコート２６０）０．１質量部を添加して溶融攪拌した。これを、厚さ５０μｍのシリコーン離型ＰＥＴ（商品名ＭＲＦ５０：三菱化学ポリエステル社製）の離型面に厚さ２００μｍとなるようにホットメルトコーターを用いて塗布し、無機酸化物膜層を形成したシートのアルミナを蒸着してない面側に密着積層させ、両側から高圧水銀ランプを用いて積算光量２０００ｍＪ／ｃｍ2の紫外線エネルギー（波長３６５ｍｍ換算）を照射し、紫外線で架橋した。 With respect to 100 parts by mass of the solid content of this polymer, 0.3 part by mass of a hydrogen abstraction type photoinitiator and 0.1 part by mass of a bifunctional monomer (trade name Biscoat 260 manufactured by Osaka Organic Chemist) were added and melted and stirred. . This is applied to a release surface of a 50 μm thick silicone release PET (trade name MRF50: manufactured by Mitsubishi Chemical Polyester) using a hot melt coater so as to have a thickness of 200 μm to form an inorganic oxide film layer. The laminated sheet was adhered and laminated on the side of the surface where alumina was not deposited, and irradiated with ultraviolet energy (wavelength 365 mm equivalent) with an integrated light amount of 2000 mJ / cm 2 from both sides using a high-pressure mercury lamp, and crosslinked with ultraviolet rays.
他面側に形成する層の接着剤として、以下の湿気で架橋した接着剤を用いた。
アクリル系接着剤（商品名ＳＫダイン１８８２：綜研化学社製）１０００質量部に対して、イソシアネート系硬化剤（商品名Ｌ−４５：綜研化学社製）１．８５質量部およびエポキシ系硬化剤（商品名Ｅ−５ＸＭ：綜研化学社製）０．５質量部を均一混合して粘着剤溶液を調製した。この粘着剤溶液を、厚さ３８μｍのシリコーン離型ＰＥＴフィルム（商品名ＭＲＦ５０：三菱化学ポリエステル社製）の離型面に、厚さ２５μｍとなるようにホットメルトコーターを用いて塗布し、無機酸化物膜層を形成したシートのアルミナを蒸着した面側に密着積層させ、室温（２３℃）で７日間放置熟成し、十分に架橋した。
As the adhesive for the layer formed on the other surface side, the following moisture-crosslinked adhesive was used.
1.85 parts by mass of an isocyanate curing agent (trade name L-45: manufactured by Soken Chemical Co., Ltd.) and an epoxy curing agent (trade name SK Dyne 1882: manufactured by Soken Chemical Co., Ltd.) (Product name E-5XM: manufactured by Soken Chemical Co., Ltd.) 0.5 parts by mass was uniformly mixed to prepare an adhesive solution. This pressure-sensitive adhesive solution was applied to the release surface of a 38 μm-thick silicone release PET film (trade name MRF50: manufactured by Mitsubishi Chemical Polyester) using a hot melt coater so as to have a thickness of 25 μm. The sheet on which the material film layer was formed was closely laminated on the surface on which the alumina was vapor-deposited and aged for 7 days at room temperature (23 ° C.) to sufficiently crosslink.
［比較例３］
特開２００１−２３４１２９の実施例１に準じて、次のように粘着シートを作製した。
[Comparative Example 3]
According to Example 1 of JP2001-234129, an adhesive sheet was prepared as follows.
（第１粘着層付シートの作製）
アクリル酸エステル共重合体を金属化合物で架橋させて、第１の感圧接着層として厚さ２００μｍの感圧接着シートを形成した。
より詳細には、アクリル酸エステル共重合体１００質量部に対し、金属化合物としてアセチルアセトン亜鉛塩：０．５質量部及びアセチルアセトンアルミ塩：０．７質量部を溶融攪拌した後、離型フィルム間に所定厚みでシート状に成形して得た。
(Preparation of sheet with first adhesive layer)
The acrylic ester copolymer was crosslinked with a metal compound to form a pressure-sensitive adhesive sheet having a thickness of 200 μm as the first pressure-sensitive adhesive layer.
More specifically, after 100 parts by mass of acrylic acid ester copolymer is melt-stirred with 0.5 parts by mass of acetylacetone zinc salt and 0.7 parts by mass of acetylacetone aluminum salt as metal compounds, between the release films. It was obtained by molding into a sheet with a predetermined thickness.
（第２粘着層付シートの作製）
また、前記未架橋のアクリル酸エステル共重合体を酢酸エチルで固形分４０質量％に調整した溶液：１００質量部に対し、架橋剤としてトリレンジイソシアネート（ＴＤＩ）を酢酸エチルで２５質量％に調整した溶液：９．０質量部を混合攪拌して、離型フィルム上に塗工して、溶剤を乾燥後、厚さ２５μｍの第２の感圧接着層を得た。
前記第１の感圧接着シートを第２の感圧接着層で挟むように重ね合わせて、表裏両面に離型フィルムを備えた厚さ２５０μｍの粘着シートを得た。
(Preparation of sheet with second adhesive layer)
In addition, a solution in which the uncrosslinked acrylate copolymer is adjusted to 40% by mass with ethyl acetate: Tolylene diisocyanate (TDI) is adjusted to 25% by mass with ethyl acetate as a crosslinking agent for 100 parts by mass. The prepared solution: 9.0 parts by mass was mixed and stirred, applied onto a release film, and after drying the solvent, a second pressure-sensitive adhesive layer having a thickness of 25 μm was obtained.
The first pressure-sensitive adhesive sheet was overlapped so as to be sandwiched between the second pressure-sensitive adhesive layers to obtain a pressure-sensitive adhesive sheet having a thickness of 250 μm having release films on both the front and back surfaces.
前記アクリル酸エステル共重合体は、ｎ−ブチルアクリレート：７８．４質量％、２−エチルヘキシルアクリレート：１９．６質量％及びアクリル酸：２．０質量％を共重合させたもので、アクリル酸エステル共重合体のＧＰＣで測定した分子量及び分子量分布は、質量平均分子量（ＭＷ）：２．２７×１０6 、質量平均分子量（ＭＷ）／数平均分子量（ＭＮ）：３．６であった。 The acrylic ester copolymer is obtained by copolymerizing n-butyl acrylate: 78.4% by mass, 2-ethylhexyl acrylate: 19.6% by mass and acrylic acid: 2.0% by mass. The molecular weight and molecular weight distribution measured by GPC of the copolymer were: mass average molecular weight (MW): 2.27 × 10 6 , mass average molecular weight (MW) / number average molecular weight (MN): 3.6.
（考察）
表１から明らかなように、実施例１−６の粘着シートを用いると、カット性が良く、打ち抜き機での加工性に優れていることが分かった。また、加工後の粘着シートで貼合したサンプルの加熱テストでも、発泡、剥離、はみ出し等がなく、実際の使用上に優れることが分かった。これに対して、比較例１−３の粘着シートでは、ベタつきで打ち抜き加工性を満足することができないか、或いは、加熱耐久性を満足することができないか、いずれかが劣ることが分かった。
(Discussion)
As is apparent from Table 1, it was found that when the pressure-sensitive adhesive sheet of Example 1-6 was used, the cutability was good and the workability with a punching machine was excellent. Further, even in the heat test of the sample bonded with the processed pressure-sensitive adhesive sheet, it was found that there was no foaming, peeling, protrusion, etc., and that it was excellent in actual use. On the other hand, it was found that the pressure-sensitive adhesive sheet of Comparative Example 1-3 was inferior, either stickiness and punching workability could not be satisfied, or heating durability could not be satisfied.
なお、アクリル系樹脂の分解温度は２００℃付近であるから、アクリル系樹脂を主剤とする粘着剤について、１５０℃での粘弾性特性を規定すること自体、通常は考えられないことであった。 In addition, since the decomposition temperature of acrylic resin is around 200 ° C., it is usually unthinkable to prescribe the viscoelastic property at 150 ° C. itself for an adhesive mainly composed of acrylic resin.
Claims (9)
周波数１Ｈｚの温度分散で測定した動的剪断貯蔵弾性率Ｇ’の値が下記範囲内にあるという特徴と、
下記引張試験方法による引張弾性率が０．２０ＭＰａ以上であり、且つ、引張破断時伸びが４００％以上であるという特徴とを有する透明粘着シート。
・Ｇ’（２０℃）が２×１０４〜５×１０５Ｐａ。
・Ｇ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
引張試験方法：試験試料としての粘着シートを幅２０ｍｍ、長さ８０ｍｍに切り出し、試験機チャック間距離４０ｍｍで該試料をチャックにはさんで引張速度３００ｍｍ／ｍｉｎで引張試験を行う。 Each layer is formed by crosslinking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer and a crosslinking initiator, and has a different viscoelastic behavior and a second pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet having a configuration in which a pressure-sensitive adhesive layer is laminated and integrated,
The characteristic that the value of the dynamic shear storage modulus G ′ measured by temperature dispersion at a frequency of 1 Hz is within the following range:
The transparent adhesive sheet which has the characteristics that the tensile elasticity modulus by the following tension test method is 0.20 Mpa or more, and elongation at the time of a tensile fracture is 400% or more.
G ′ (20 ° C.) is 2 × 10 4 to 5 × 10 5 Pa.
G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
Tensile test method: A pressure-sensitive adhesive sheet as a test sample is cut into a width of 20 mm and a length of 80 mm, and a tensile test is performed with a distance of 40 mm between chucks of the tester between the chucks and a tensile speed of 300 mm / min.
（ａ） 第１粘着層のＧ’（２０℃）が２×１０４〜５×１０５Ｐａであり、かつＧ’（１５０℃）が１×１０４〜１×１０５Ｐａ。
（ｂ） 第２粘着層のＧ’（２０℃）が２×１０５〜５×１０６Ｐａであり、かつＧ’（１５０℃）が５×１０４〜５×１０５Ｐａ。 The dynamic shear storage modulus G ′ measured by temperature dispersion at a frequency of 1 Hz for each of the first adhesive layer and the second adhesive layer is within the following ranges (a) and (b). The transparent adhesive sheet as described in 2.
(A) G ′ (20 ° C.) of the first adhesive layer is 2 × 10 4 to 5 × 10 5 Pa, and G ′ (150 ° C.) is 1 × 10 4 to 1 × 10 5 Pa.
(B) G ′ (20 ° C.) of the second adhesive layer is 2 × 10 5 to 5 × 10 6 Pa, and G ′ (150 ° C.) is 5 × 10 4 to 5 × 10 5 Pa.
・第１粘着層のＴｇ（１）が−１０℃未満。
・第２粘着層のＴｇ（２）が−１０℃以上。 The temperature (; Tg) showing the dynamic Tan δ maximum value measured by temperature dispersion at a frequency of 1 Hz for each of the first adhesive layer and the second adhesive layer is within the following range. The transparent adhesive sheet of description.
-Tg (1) of a 1st adhesion layer is less than -10 degreeC.
-Tg (2) of a 2nd adhesion layer is -10 degreeC or more.
第２粘着層は、ベースポリマーとしての（メタ）アクリル酸エステル系共重合体と架橋開始剤とを含有する粘着剤組成物を加熱反応架橋して形成されたものであることを特徴とする請求項１〜４の何れかに記載の透明粘着シート。 The first pressure-sensitive adhesive layer is formed by UV-crosslinking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer, a crosslinking agent, and a photopolymerization initiator,
The second pressure-sensitive adhesive layer is formed by heat-reactive crosslinking of a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a base polymer and a crosslinking initiator. Item 5. The transparent adhesive sheet according to any one of Items 1 to 4.
・第１粘着層の厚さが５０μｍ〜２０００μｍ。
・第２粘着層の厚さが５μｍ〜５０μｍ。 The transparent adhesive sheet according to any one of claims 1 to 5, wherein the thickness of each of the first adhesive layer and the second adhesive layer is within the following range.
-The thickness of the 1st adhesion layer is 50 micrometers-2000 micrometers.
-The thickness of a 2nd adhesion layer is 5 micrometers-50 micrometers.
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