JP5446015B2 - Adhesive composition and optical film using the same - Google Patents
Adhesive composition and optical film using the same Download PDFInfo
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- JP5446015B2 JP5446015B2 JP2011503906A JP2011503906A JP5446015B2 JP 5446015 B2 JP5446015 B2 JP 5446015B2 JP 2011503906 A JP2011503906 A JP 2011503906A JP 2011503906 A JP2011503906 A JP 2011503906A JP 5446015 B2 JP5446015 B2 JP 5446015B2
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- 239000000853 adhesive Substances 0.000 title claims description 76
- 230000001070 adhesive effect Effects 0.000 title claims description 76
- 239000000203 mixture Substances 0.000 title claims description 46
- 239000012788 optical film Substances 0.000 title claims description 42
- 239000010408 film Substances 0.000 claims description 120
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 37
- 125000001931 aliphatic group Chemical group 0.000 claims description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 32
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical group C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000012790 adhesive layer Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000003851 corona treatment Methods 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 14
- 125000005157 alkyl carboxy group Chemical group 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 125000004185 ester group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000003368 amide group Chemical group 0.000 claims description 8
- 125000000468 ketone group Chemical group 0.000 claims description 7
- 238000009832 plasma treatment Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920002799 BoPET Polymers 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920006289 polycarbonate film Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 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 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/02—Polyamines
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Description
本発明は接着剤組成物及びこれを用いた光学フィルムを提供する。具体的に、本発明は接着性に優れ、透明性を要する光学フィルムにも有用に用いることができる接着剤組成物及びこれを用いた光学フィルムを提供する。 The present invention provides an adhesive composition and an optical film using the same. Specifically, the present invention provides an adhesive composition that is excellent in adhesiveness and can be usefully used for an optical film that requires transparency, and an optical film using the same.
本出願は２００８年４月８日、韓国特許庁に提出された韓国特許出願第１０−２００８−００３２５６３号の出願日の利益を主張し、その全内容は本明細書に含まれる。 This application claims the benefit of the filing date of Korean Patent Application No. 10-2008-0032563 filed with the Korean Patent Office on April 8, 2008, the entire contents of which are included in this specification.
一般的に、偏光板はポリビニールアルコール（ＰＶＡ）成分の偏光子（偏光膜）の両面にトリアセチルセルロース（ｔｒｉａｃｅｔｙｌ ｃｅｌｌｕｌｏｓｅ、以下、ＴＡＣ）フィルムをＰＶＡ系水溶液から成る水系接着剤で積層させた構造を有する（図１）。このような構造の偏光板を別途の補償フィルムなしにＩＰＳ（Ｉｎ−Ｐｌａｎｅ Ｓｗｉｔｃｈｉｎｇ）モードの液晶表示装置に適用すると、視野角特性が脆弱であるため、従来用いられていた２枚のＴＡＣフィルムのうち１枚を厚さ方向及び面内（ｉｎ−ｐｌａｎｅ）における位相差（ｒｅｔａｒｄａｔｉｏｎ）が殆どないＴＡＣ（Ｚｅｒｏ Ｒｅｔａｒｄａｔｉｏｎ ＴＡＣ、以下、Ｚ−ＴＡＣ）フィルムに取り替えて視野角を改善して用いることもある。 In general, a polarizing plate has a structure in which a triacetyl cellulose (hereinafter referred to as TAC) film is laminated with an aqueous adhesive composed of a PVA aqueous solution on both sides of a polarizer (polarizing film) of a polyvinyl alcohol (PVA) component. (FIG. 1). When a polarizing plate having such a structure is applied to a liquid crystal display device in an IPS (In-Plane Switching) mode without a separate compensation film, the viewing angle characteristics are fragile, and thus two conventional TAC films are used. One of them may be used with an improved viewing angle by replacing it with a TAC (Zero TAC) (Z-TAC) film having almost no retardation in the thickness direction and in-plane. .
しかし、Ｚ−ＴＡＣは、基本的にＴＡＣ成分のフィルムが有する水分に対する脆弱性により、長期間使用すると、寸法の変化による耐久性の問題を引き起こす。このような短所を補うためにシクロオレフィン（Ｃｙｃｌｉｃ Ｏｌｅｆｉｎ）系樹脂またはアクリル系樹脂などのように水分に対する抵抗性が高く、低い位相差物性を有する組成のフィルムを適用しようと試されてきた。特に、アクリル系組成のフィルムは、光学的な特性と耐久性だけではなく、価格的な側面でも長所を有し得ると知られている。 However, Z-TAC basically causes a problem of durability due to dimensional changes when used for a long period of time due to the fragility of the TAC component film to moisture. In order to compensate for these disadvantages, attempts have been made to apply a film having a composition having a high resistance to moisture and low retardation properties such as a cycloolefin resin or an acrylic resin. In particular, it is known that a film having an acrylic composition can have advantages not only in optical properties and durability but also in terms of cost.
保護フィルムとして、ＴＡＣフィルムを用いて偏光板を製作する場合は、ＰＶＡ成分の偏光子との接着のために水系ＰＶＡ接着剤を主に使用してきた。この際、接着力を向上させるために、ＴＡＣフィルムの表面をアルカリ処理またはコロナー処理をして使用する。しかし、アクリルフィルムと水系ＰＶＡ接着剤を偏光板の製作に使用すると、アルカリ処理またはコロナー処理などで簡単に接着力を確保することが困難である。既存のＴＡＣフィルムは、アルカリ処理またはコロナー処理によりフィルムの表面にヒドロキシ（ｈｙｄｒｏｘｙ）基などの親水性基が導入されてＰＶＡ系接着剤との水素結合を通じて接着力が簡単に確保することができるが、アクリルフィルムは表面をコロナー処理またはプラズマ処理しても導入される親水性基の量が少ないため、ＰＶＡ系接着剤との水素結合が足りず、アクリルフィルムとＰＶＡ成分の偏光子との間に十分な接着力が確保されない。 When manufacturing a polarizing plate using a TAC film as a protective film, an aqueous PVA adhesive has been mainly used for bonding with a PVA component polarizer. At this time, in order to improve the adhesive strength, the surface of the TAC film is used after being subjected to alkali treatment or corona treatment. However, when an acrylic film and an aqueous PVA adhesive are used for the production of a polarizing plate, it is difficult to easily secure the adhesive force by alkali treatment or corona treatment. The existing TAC film has a hydrophilic group such as a hydroxy group introduced on the surface of the film by alkali treatment or corona treatment, and can easily secure the adhesive force through hydrogen bonding with the PVA adhesive. The acrylic film has a small amount of hydrophilic groups to be introduced even if the surface is corona-treated or plasma-treated, so there is not enough hydrogen bond with the PVA adhesive, and the acrylic film and the PVA component polarizer Sufficient adhesion is not secured.
アクリルフィルムと偏光子を付着するために、アクリル系ＵＶ硬化型接着剤を用いることができるが、下記のような幾つかの問題点が確認された。（１）一般的な偏光板の製造工程では水系接着剤が用いられているため、ＵＶ硬化型接着剤を使用する場合は、別途のＵＶ硬化工程が必要で、揮発性の引火性モノマーの使用などにより防爆設備がさらに必要であり、（２）既存の水系ＰＶＡ接着剤は固形分含量の調節及び工程の管理を通じて接着剤の厚さを１００ｎｍ内外に薄くできる一方、上記アクリル系ＵＶ硬化型接着剤は、一般的に接着層の厚さを１ｍｍ以下に調節することが困難で、接着層の脆性（ｂｒｉｔｔｌｅｎｅｓｓ）の増加による偏光板の折れなどの問題が発生することがあり、（３）アクリルフィルム側との接着は容易であるが、偏光子側との接着力を確保することは困難である。偏光子との接着力を確保するために、酸性反応基を多量に含ませることもあるが、酸による工程腐食及び作業環境の側面で好ましくない。 An acrylic UV curable adhesive can be used to attach the acrylic film and the polarizer, but some problems have been confirmed as follows. (1) Since a water-based adhesive is used in the manufacturing process of a general polarizing plate, when a UV curable adhesive is used, a separate UV curing process is required, and the use of a volatile flammable monomer is used. (2) The existing water-based PVA adhesive can be reduced to 100 nm in thickness by adjusting the solid content and managing the process, while the acrylic UV curable adhesive is used. In general, it is difficult to adjust the thickness of the adhesive layer to 1 mm or less, and the agent may cause problems such as bending of the polarizing plate due to an increase in brittleness of the adhesive layer. (3) Acrylic Adhesion with the film side is easy, but it is difficult to ensure adhesion with the polarizer side. In order to secure the adhesive strength with the polarizer, a large amount of acidic reactive groups may be contained, but this is not preferable in terms of process corrosion due to acid and working environment.
従って、アクリルフィルムを偏光子の保護フィルムとして用いる偏光板を製作するためには、既存工程への適用性及び安定的な偏光板の物性の提供が相対的に容易な水系接着剤の適用が相対的に多くの長所を有する。ここで、偏光板を含む光学フィルムに好ましい水系接着剤の開発が求められている。 Therefore, in order to produce a polarizing plate using an acrylic film as a protective film for a polarizer, it is relatively difficult to apply an aqueous adhesive which is relatively easy to apply to existing processes and to provide stable properties of the polarizing plate. It has many advantages. Here, development of the preferable aqueous adhesive for the optical film containing a polarizing plate is calculated | required.
本発明は、接着性に優れ、且つ光学フィルムに適用する際の光学フィルムの光学物性及び耐久性を阻害しない接着剤組成物であって、特にアクリルフィルムを偏光子の保護フィルムとして用いるとき、偏光子との優れた接着性を与え、その結果、製作される偏光板の光学物性及び耐久性を阻害しない接着剤組成物を提供することを目的とする。また、本発明は上記接着剤組成物を用いて製作された光学フィルム及び偏光板を提供することを目的とする。 The present invention is an adhesive composition that is excellent in adhesiveness and does not impair the optical properties and durability of an optical film when applied to an optical film, particularly when an acrylic film is used as a protective film for a polarizer. An object of the present invention is to provide an adhesive composition that gives excellent adhesion to a child and, as a result, does not impair the optical properties and durability of the manufactured polarizing plate. Moreover, this invention aims at providing the optical film and polarizing plate which were manufactured using the said adhesive composition.
上記目的を達成するために、本発明は下記化学式１で表されるアゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物を含む接着剤組成物を提供する。 In order to achieve the above object, the present invention provides an adhesive composition including a compound having an azetidinium functional group represented by the following chemical formula 1.
上記化学式１において、
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ１からＣ２０の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ−は１価陰イオンであり、
ｎは３０から７，０００である。
In the above chemical formula 1,
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Ｘ及びＹのうち少なくとも１つは親水性基を含むことが好ましい。上記化学式１の化合物は重量平均分子量が１万から２００万であることが好ましい。 It is preferable that at least one of X and Y contains a hydrophilic group. The compound of Formula 1 preferably has a weight average molecular weight of 10,000 to 2,000,000.
また、本発明は２層以上のフィルムが積層された構造を有する光学フィルムであって、上記フィルム間の少なくとも１つの界面にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする光学フィルムを提供する。 Further, the present invention is an optical film having a structure in which two or more films are laminated, and is formed using an adhesive composition containing a compound having an azetidinium functional group at at least one interface between the films. Provided is an optical film provided with an adhesive layer.
また、本発明は第１フィルム、偏光子及び第２フィルムが順に積層された構造を有する偏光板において、上記第１フィルム及び第２フィルムのうち少なくとも１つと偏光子との間にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする偏光板を提供する。 In the polarizing plate having a structure in which the first film, the polarizer, and the second film are sequentially laminated, an azetidinium functional group is provided between at least one of the first film and the second film and the polarizer. There is provided a polarizing plate comprising an adhesive layer formed using an adhesive composition containing a compound having the same.
また、本発明は上記光学フィルムまたは偏光板を含む電子素子を提供する。 Moreover, this invention provides the electronic device containing the said optical film or polarizing plate.
本発明による接着剤組成物は接着性に優れ、且つ光学フィルムの透明性を阻害しないながらも、既存の積層構造の光学フィルム工程に更なる工程や設備なしにそのまま適用できるため、光学フィルムの製造に有用に用いることができる。また、本発明による接着剤組成物を用いて製造された接着層を含む光学フィルムは耐久性に優れる。特に、本発明による接着剤組成物はアクリルフィルムを偏光子の保護フィルムとして使用すると、偏光子との優れた接着性を与え、その結果、製作される偏光板の光学物性及び耐久性を阻害しない。 Since the adhesive composition according to the present invention is excellent in adhesiveness and does not impair the transparency of the optical film, it can be applied as it is to the existing optical film process of a laminated structure without any further steps or equipment, so that an optical film can be produced. It can be usefully used. Moreover, the optical film containing the contact bonding layer manufactured using the adhesive composition by this invention is excellent in durability. In particular, when an acrylic film is used as a protective film for a polarizer, the adhesive composition according to the present invention provides excellent adhesion with the polarizer, and as a result, does not hinder the optical properties and durability of the manufactured polarizing plate. .
本発明による光学フィルムはアゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層を含むことを特徴とする。 The optical film according to the present invention includes an adhesive layer formed by using an adhesive composition including a compound having an azetidinium functional group.
上記アゼチジニウム官能基を有する化合物は、アゼチジニウム官能基が光学フィルムの表面のカルボキシル（ｃａｒｂｏｘｙｌ）基のような官能基と反応することができ、ポジティブ（＋）電荷を帯びるため、親水性基を有したり、コロナー処理、プラズマ処理などを通じてフィルムの表面にマイナス（−）電荷が豊かな光学フィルムへの濡れ性（ｗｅｔｔａｂｉｌｉｔｙ）に優れる。また、上記アゼチジニウム官能基が開環して親水性基が形成されることができ、この親水性基は偏光子のような光学フィルムの表面のヒドロキシ基と水素結合することができる。これに関し、上記アゼチジニウム官能基を有する化合物は、アゼチジニウム官能基の他にヒドロキシ基、カルボキシル基、アミン（ａｍｉｎｅ）基、アミド（ａｍｉｄｅ）基などの親水性基をさらに含むこともできる。このような理由から、アゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物は、ＰＶＡ系接着剤のような既存の接着剤に比べて優れた接着性を提供することができる。また、上記アゼチジニウム官能基を有する化合物は接着剤層内で自体架橋できるため、これにより接着剤層の耐水性が向上し、これを用いた偏光板を含む光学フィルムは耐久性が向上し、苛酷な環境におけるフィルム間の剥離を防ぐことができる。 The compound having an azetidinium functional group has a hydrophilic group because the azetidinium functional group can react with a functional group such as a carboxy group on the surface of the optical film and has a positive (+) charge. In addition, it is excellent in wettability to an optical film rich in negative (−) charges on the surface of the film through corona treatment, plasma treatment or the like. Further, the azetidinium functional group can be opened to form a hydrophilic group, and the hydrophilic group can hydrogen bond with a hydroxy group on the surface of an optical film such as a polarizer. In this regard, the compound having the azetidinium functional group may further include a hydrophilic group such as a hydroxy group, a carboxyl group, an amine group, and an amide group in addition to the azetidinium functional group. For these reasons, a compound having an azetidinium functional group can provide superior adhesiveness as compared to existing adhesives such as PVA adhesives. In addition, since the compound having the azetidinium functional group can be crosslinked within the adhesive layer, the water resistance of the adhesive layer is improved, and the optical film including the polarizing plate using the adhesive layer is improved in durability and severe. Peeling between films in a difficult environment can be prevented.
上記アゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物としては、下記化学式１の化合物を用いることができる。 As the compound having an azetidinium functional group, a compound represented by the following chemical formula 1 can be used.
上記化学式１において、
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ１からＣ２０の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ−は１価陰イオンであり、
ｎは３０から７，０００である。
In the above chemical formula 1,
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Ｘ及びＹのうち少なくとも１つは親水性基を含むことが好ましい。上記化学式１の化合物は重量平均分子量が１万から２００万であることが好ましい。 It is preferable that at least one of X and Y contains a hydrophilic group. The compound of Formula 1 preferably has a weight average molecular weight of 10,000 to 2,000,000.
上記化学式１の化合物は下記化学式２の化合物を含む。 The compound of Chemical Formula 1 includes the compound of Chemical Formula 2 below.
上記化学式２において、
Ｘ'、Ｘ"及びＹ'はそれぞれＣ１からＣ２０の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ１からＣ２０の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ−は１価陰イオンであり、
ｎは３０から７，０００である。
In the above chemical formula 2,
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
上記化学式２の化合物は下記化学式３のポリアミノアミド−エピクロルヒドリン（Ｐｏｌｙａｍｉｎｏａｍｉｄｅ−Ｅｐｉｃｈｌｏｒｏｈｙｄｒｉｎ、ＰＡＥ）を含む。 The compound of Chemical Formula 2 includes polyaminoamide-epichlorohydrin (PAE) of Chemical Formula 3 below.
上記化学式３において、ｎは３０から７，０００である。 In the above chemical formula 3, n is 30 to 7,000.
本発明による接着剤組成物は、接着剤層を形成するために、水のような溶媒をさらに含むことができる。この際、上記アゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物の濃度は０．１から３０重量％、好ましくは０．５から１０重量％である。 The adhesive composition according to the present invention may further include a solvent such as water in order to form an adhesive layer. At this time, the concentration of the compound having an azetidinium functional group is 0.1 to 30% by weight, preferably 0.5 to 10% by weight.
本発明による接着剤組成物はｐＨが２から１１で、４から１０に調整されることがより好ましい。本発明による接着剤組成物は、塩基を添加する方法などを利用してｐＨ調節をすることができる。塩基としては特に限定されないが、ＮａＯＨ、ＫＯＨ、ＮＨ４ＯＨなどが好ましい。 More preferably, the adhesive composition according to the present invention has a pH of 2 to 11 and is adjusted to 4 to 10. The adhesive composition according to the present invention can be adjusted in pH using a method of adding a base or the like. No particular limitation is imposed on the base, NaOH, KOH, etc. NH 4 OH is preferred.
本発明による接着剤組成物はポリビニールアルコール（ＰＶＡ）系樹脂をさらに含むことができる。ポリビニールアルコール系樹脂をさらに含むことで、ポリビニールアルコール系偏光子やＴＡＣフィルムのような光学フィルムとの接着性をより向上させることができる。特に、アセトアセチル（ａｃｅｔｏａｃｅｔｙｌ）基などを含む変性ＰＶＡを用いることが、接着性及び上記アゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物との架橋などに有利である。具体的な例としては、日本合成化学のＧｏｈｓｅｆｉｍｅｒ（商品名）Ｚ−１００、Ｚ−２００、Ｚ−２００Ｈ、Ｚ−２１０、Ｚ−２２０、Ｚ−３２０などを使用することができるが、これに限定されない。この際、ポリビニールアルコール系樹脂の重量比は特に限定されず、接着するフィルムの種類によってその範囲が多少変わる。例えば、ポリビニールアルコール系偏光子とアクリル系フィルムを接着する場合は、アゼチジニウム官能基を有する化合物１００重量部に対して、１０重量部以上１，０００重量部以下を使用することが好ましい。ポリビニールアルコール系樹脂が１０重量部未満の場合は、ポリビニールアルコール偏光素子やＴＡＣフィルムとの接着力が不良となり、１，０００重量部を超える場合には、アクリルフィルムとの接着力が不良であるという問題点がある。 The adhesive composition according to the present invention may further include a polyvinyl alcohol (PVA) resin. By further including a polyvinyl alcohol-based resin, it is possible to further improve the adhesiveness with an optical film such as a polyvinyl alcohol-based polarizer or a TAC film. In particular, the use of a modified PVA containing an acetoacetyl group or the like is advantageous for adhesiveness and crosslinking with a compound having the azetidinium functional group. As specific examples, Nippon Synthetic Chemical Co., Ltd.'s Gossefmer (trade name) Z-100, Z-200, Z-200H, Z-210, Z-220, Z-320, etc. can be used. It is not limited. At this time, the weight ratio of the polyvinyl alcohol-based resin is not particularly limited, and the range varies somewhat depending on the type of film to be bonded. For example, when a polyvinyl alcohol polarizer and an acrylic film are bonded, it is preferable to use 10 parts by weight or more and 1,000 parts by weight or less with respect to 100 parts by weight of the compound having an azetidinium functional group. When the polyvinyl alcohol-based resin is less than 10 parts by weight, the adhesive strength with the polyvinyl alcohol polarizing element or the TAC film is poor, and when it exceeds 1,000 parts by weight, the adhesive force with the acrylic film is poor. There is a problem that there is.
また、本発明は２層以上のフィルムが積層された構造を有する光学フィルムであって、上記フィルム間の少なくとも１つの界面にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする光学フィルムを提供する。本発明において、光学フィルムとは、光学的機能を行うフィルムのことであり、光透過率が８０％以上の狭意の透明フィルムだけではなく、偏光板のように特定の光学的機能を行うためのフィルムであれば、光透過率が５０％以下の光学フィルムも含む。 Further, the present invention is an optical film having a structure in which two or more films are laminated, and is formed using an adhesive composition containing a compound having an azetidinium functional group at at least one interface between the films. Provided is an optical film provided with an adhesive layer. In the present invention, an optical film refers to a film that performs an optical function, in order to perform a specific optical function such as a polarizing plate as well as a narrow transparent film having a light transmittance of 80% or more. In this case, an optical film having a light transmittance of 50% or less is included.
上記積層されるフィルムとしては特に限定されないが、アクリル系フィルム、ＰＥＴフィルム、特に、アクリル系プライマー処理されたＰＥＴフィルム、ＴＡＣフィルム、ＣＯＰフィルム、ＰＣ（ポリカーボネート）フィルム、ＰＮＢ（ポリノルボルネン）系フィルムなどを用いることができ、特に、アクリルフィルム、アクリル系プライマー処理されたＰＥＴフィルムの場合は、既存のポリビニールアルコール系接着剤を使用する場合に比べて接着力がより大きく向上する。上記積層されるフィルムは同一であるか、異なる材料から成ることができる。 Although it does not specifically limit as said film laminated | stacked, Acrylic-type film, PET film, especially PET film, TAC film, COP film, PC (polycarbonate) film, PNB (polynorbornene) -type film etc. which were acrylic primer-treated In particular, in the case of an acrylic film or an acrylic primer-treated PET film, the adhesive force is greatly improved as compared with the case where an existing polyvinyl alcohol-based adhesive is used. The laminated films can be the same or made of different materials.
上記積層されるフィルムは、必要に応じて、接着力を向上させるために表面処理されることができる。例えば、アルカリ処理、コロナー処理、プラズマ処理、プライマー処理などを行うことができる。 The laminated film can be subjected to a surface treatment to improve the adhesive force, if necessary. For example, alkali treatment, corona treatment, plasma treatment, primer treatment and the like can be performed.
また、本発明は第１フィルム、偏光子及び第２フィルムが順に積層された構造を有する偏光板において、上記第１フィルム及び第２フィルムのうち少なくとも１つと偏光子との間にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする偏光板を提供する。この際、上記第１フィルムまたは第２フィルムも上述のような表面処理を行うことができる。 In the polarizing plate having a structure in which the first film, the polarizer, and the second film are sequentially laminated, an azetidinium functional group is provided between at least one of the first film and the second film and the polarizer. There is provided a polarizing plate comprising an adhesive layer formed using an adhesive composition containing a compound having the same. At this time, the first film or the second film can also be subjected to the surface treatment as described above.
上記第１フィルム及び第２フィルムとしてはアクリル系フィルム、ＰＥＴフィルム、特に、アクリル系プライマー処理されたＰＥＴフィルム、ＴＡＣフィルム、ＣＯＰフィルム、ＰＣ（ポリカーボネート）フィルム、ＰＮＢ（ポリノルボルネン）系フィルムなどを用いることができる。上記第１フィルム及び第２フィルムは同一材料からなっても、異なる材料からなってもよい。例えば、上記第１フィルム及び第２フィルムは両方ともアクリル系フィルムまたはＴＡＣフィルムであることもでき（図２）、何れか１つがアクリル系フィルムで、他の１つがＴＡＣフィルムであることもできる（図３）。 As the first film and the second film, an acrylic film, a PET film, in particular, an acrylic primer-treated PET film, a TAC film, a COP film, a PC (polycarbonate) film, a PNB (polynorbornene) film, or the like is used. be able to. The first film and the second film may be made of the same material or different materials. For example, both the first film and the second film may be an acrylic film or a TAC film (FIG. 2), one of which may be an acrylic film and the other one may be a TAC film ( FIG. 3).
上記接着剤層は、上述の本発明による接着剤組成物を用いて形成されたものであり、具体的に上記接着剤組成物をフィルム上に直接塗布して乾燥したり、２種以上のフィルムの間に接着剤組成物を塗布し、圧着ロ−ルを利用して圧着した後に乾燥することで形成することができる。上記接着剤層の厚さは１０ｎｍから５００ｎｍであることが好ましく、２０ｎｍから２００ｎｍであることがより好ましい。 The adhesive layer is formed by using the above-described adhesive composition according to the present invention. Specifically, the adhesive composition is directly applied on the film and dried, or two or more kinds of films are used. It can be formed by applying an adhesive composition between the two and performing pressure bonding using a pressure-bonding roll and then drying. The thickness of the adhesive layer is preferably 10 nm to 500 nm, and more preferably 20 nm to 200 nm.
上記本発明による偏光板は３５から４５％の光透過率と、９８以上の偏光度を有することが好ましい。 The polarizing plate according to the present invention preferably has a light transmittance of 35 to 45% and a degree of polarization of 98 or more.
上記のように、本発明による光学フィルム及び偏光板などの光学物品はアゼチジニウム官能基を有する化合物を含む接着剤組成物の優れた光透過率により、製造された光学物品の光透過率の低下なしに、優れた光学物性などを保持することができ、優れた接着力で製造された光学物品の耐久性を向上させることができる。 As described above, the optical article such as the optical film and the polarizing plate according to the present invention has no decrease in the light transmittance of the manufactured optical article due to the excellent light transmittance of the adhesive composition containing the compound having an azetidinium functional group. In addition, it is possible to maintain excellent optical properties and the like, and it is possible to improve the durability of an optical article manufactured with an excellent adhesive force.
特に、偏光板に適用する場合、接着剤組成物による偏光子の光学物性、例えば、透過度、偏光度、色相などの変化が既存のポリビニールアルコール系接着剤を用いた時とほぼ類似するため、別途の工程条件の変化なしにも量産ラインに代えて適用できるという長所がある。 In particular, when applied to a polarizing plate, the optical properties of the polarizer due to the adhesive composition, for example, changes in transmittance, polarization degree, hue, etc. are almost similar to those when using an existing polyvinyl alcohol-based adhesive. Also, there is an advantage that it can be applied in place of the mass production line without any change in the separate process conditions.
本発明は上記光学フィルムまたは偏光板を含む電子素子を提供する。上記電子素子としては液晶表示素子などがあるが、上記のような光学フィルムまたは偏光板を要するものであれば、その種類は特に限定されない。上記電子素子は上述の本発明による接着剤組成物を用いて形成された接着剤層を含むことを除き、当技術分野に知られている構成を有する。例えば、上記電子素子は液晶セル、液晶セルの両面に備えられた本発明による偏光板及びバックライトユニットを含む液晶表示素子であることができる。 The present invention provides an electronic device including the optical film or polarizing plate. Examples of the electronic element include a liquid crystal display element, and the type of the electronic element is not particularly limited as long as the above optical film or polarizing plate is required. The electronic device has a configuration known in the art except that it includes an adhesive layer formed using the adhesive composition according to the present invention. For example, the electronic device may be a liquid crystal display device including a liquid crystal cell, a polarizing plate and a backlight unit according to the present invention provided on both surfaces of the liquid crystal cell.
以下では実施例を通じて本発明をより詳しく説明する。しかし、下記の実施例は本発明を例示するためのものであり、これにより本発明の範囲は限定されない。 Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereby.
実施例１
アゼチジニウム基とアミン基を有する化合物であるＫｙｍｅｎｅ−５５７Ｈ（Ｈｅｒｃｕｌｅｓ Ｋｏｒｅａ、１２．５ｗｔ％水溶液）を純水で希釈して６ｗｔ％水溶液を製造し、これを用いて偏光子の両面にコロナー処理をしたアクリル系フィルムを接着した。アクリル系フィルムとしては厚さ８０μｍのＯＰＴＥＳ社のＴ−ｆｉｌｍを使用し、フィルムの表面は５０Ｗ／ｍ２／ｍｉｎの条件でコロナー処理を行った。上記接着剤を偏光子とその両面のアクリル系フィルムの間に注入し、圧着ロ−ルを利用して圧着した後、温度８０℃で、５分間、熱風乾燥して偏光板を製造した。
Example 1
Kymene-557H (Hercules Korea, 12.5 wt% aqueous solution), which is a compound having an azetidinium group and an amine group, was diluted with pure water to produce a 6 wt% aqueous solution, which was used for corona treatment on both sides of the polarizer. Acrylic film was adhered. As the acrylic film, T-film of 80 μm in thickness of OPTES was used, and the surface of the film was subjected to corona treatment under the condition of 50 W / m 2 / min. The adhesive was injected between the polarizer and the acrylic film on both sides thereof, and pressure-bonded using a pressure-bonding roll, and then dried with hot air at a temperature of 80 ° C. for 5 minutes to produce a polarizing plate.
実施例２
Ｋｙｍｅｎｅ−５５７Ｈ（Ｈｅｒｃｕｌｅｓ Ｋｏｒｅａ、１２．５ｗｔ％水溶液、ｐＨ＝５）のｐＨが７になるようＮａＯＨ水溶液を添加した後、純水で希釈して製造された６ｗｔ％の接着剤組成物を用いて、偏光子の両面にコロナー処理をしたアクリル系フィルムを接着した。
Example 2
A 6 wt% adhesive composition produced by adding NaOH aqueous solution so that the pH of Kymene-557H (Hercules Korea, 12.5 wt% aqueous solution, pH = 5) is 7 and then diluting with pure water was used. Then, an acrylic film subjected to corona treatment was bonded to both sides of the polarizer.
実施例３
実施例２の接着剤組成物を用いて、偏光子の一面にはコロナー処理をしたアクリル系フィルムを、偏光子の他面にはアルカリ処理をしたＴＡＣフィルムを接着した。
Example 3
Using the adhesive composition of Example 2, a corona-treated acrylic film was bonded to one surface of the polarizer, and an alkali-treated TAC film was bonded to the other surface of the polarizer.
実施例４
変性ポリビニールアルコールレジンであるＧｏｈｓｅｆｉｍｅｒ Ｚ−２００（日本合成化学）をＫｙｍｅｎｅ−５５７Ｈ（Ｈｅｒｃｕｌｅｓ Ｋｏｒｅａ、１２．５ｗｔ％）１００重量部当たりに１００重量部の比で添加し、ｐＨが７になるようＮａＯＨ水溶液を添加した後、純水で希釈して製造された４．５ｗｔ％の接着剤組成物を用いて、偏光子の一面にはコロナー処理をしたアクリル系フィルムを、偏光子の他面にはアルカリ処理をしたＴＡＣフィルムを接着した。
Example 4
The modified polyvinyl alcohol resin Gohsfimmer Z-200 (Nippon Synthetic Chemical) is added at a ratio of 100 parts by weight per 100 parts by weight of Kymene-557H (Hercules Korea, 12.5 wt%), so that the pH becomes 7 After adding the aqueous solution, using a 4.5 wt% adhesive composition manufactured by diluting with pure water, one side of the polarizer is treated with a corona-treated acrylic film, and the other side of the polarizer is coated with an acrylic film. The alkali-treated TAC film was adhered.
比較例１
純水にポリビニールアルコールレジン（平均重合度２４００、鹸化度９９．９％）を溶かして３ｗｔ％のポリビニールアルコール水溶液を製造し、これを用いて偏光子の両面にコロナー処理をしたアクリル系フィルムを接着した。
Comparative Example 1
An acrylic film in which polyvinyl alcohol resin (average polymerization degree 2400, saponification degree 99.9%) is dissolved in pure water to produce a 3 wt% polyvinyl alcohol aqueous solution, and a corona treatment is applied to both sides of the polarizer using this. Glued.
比較例２
純水に変性ポリビニールアルコールレジンであるＧｏｈｓｅｆｉｍｅｒ Ｚ−２００（日本合成化学）を溶かして４．５ｗｔ％の変性ポリビニールアルコール水溶液を製造し、ここに、アミン系金属化合物架橋剤を変性ポリビニールアルコール１００重量部当たりに１０重量部を添加して接着剤を製造した。これを用いて偏光子の両面にコロナー処理をしたアクリル系フィルムを接着した。
Comparative Example 2
A modified polyvinyl alcohol resin, Ghosfemer Z-200 (Nippon Synthetic Chemical), is dissolved in pure water to produce a 4.5 wt% modified polyvinyl alcohol aqueous solution, and an amine-based metal compound cross-linking agent is used as the modified polyvinyl alcohol. An adhesive was produced by adding 10 parts by weight per 100 parts by weight. Using this, an acrylic film subjected to corona treatment was bonded to both surfaces of the polarizer.
比較例３
比較例２の接着剤を用いて、偏光子の一面にはコロナー処理をしたアクリル系フィルムを、偏光子の他面にはアルカリ処理をしたＴＡＣフィルムを接着した。
Comparative Example 3
Using the adhesive of Comparative Example 2, a corona-treated acrylic film was bonded to one surface of the polarizer, and an alkali-treated TAC film was bonded to the other surface of the polarizer.
［評価方法］
１．接着力
カッターを利用して偏光板の表面に切れ込みを入れてから、切れ込みの周辺の剥離された具合を百分率で示した（図４）。数値が低いほど、接着力は優れる。
[Evaluation method]
1. Adhesive strength After making a cut on the surface of the polarizing plate using a cutter, the percentage of peeling around the cut was shown as a percentage (FIG. 4). The lower the number, the better the adhesion.
２．耐水性
偏光板の片面を粘着剤を用いてガラス板に付着した後、温度６０℃の恒温槽に浸漬した状態で放置し、４時間及び４８時間後の偏光子の収縮及び保護フィルムの剥離有無で耐水性を評価した。
2. Water resistance After attaching one side of a polarizing plate to a glass plate using an adhesive, it was left immersed in a thermostatic bath at a temperature of 60 ° C., and the polarizer was shrunk and the protective film was peeled off after 4 hours and 48 hours. The water resistance was evaluated.
３．光学物性
偏光板の単体透過率（Ｔｓ）、平行透過率（Ｔｐ）、直交透過率（Ｔｃ）を分光光度計を利用して測定し、下記の式を用いて偏光度を計算した。
3. Optical properties The single transmittance (Ts), parallel transmittance (Tp), and orthogonal transmittance (Tc) of the polarizing plate were measured using a spectrophotometer, and the degree of polarization was calculated using the following equation.
［式１］
偏光度（Ｐ）＝√（Ｔｐ−Ｔｃ）／（Ｔｐ＋Ｔｃ）
[Formula 1]
Polarization degree (P) = √ (Tp−Tc) / (Tp + Tc)
［評価結果］
偏光板の接着力、耐水性、光学物性評価結果
[Evaluation results]
Evaluation results of adhesive strength, water resistance and optical properties of polarizing plate
・Ｋ１：６ｗｔ％ Ｋｙｍｅｎｅ−５５７Ｈ（ｐＨ＝５）
・Ｋ２：６ｗｔ％ Ｋｙｍｅｎｅ−５５７Ｈ（ｐＨ＝７）
・Ｋ３：４．５ｗｔ％ Ｋｙｍｅｎｅ−５５７Ｈ：Ｚ２００＝１：１（ｐＨ＝７）
・Ｐ１：３％ ＰＶＡ
・Ｐ２：４．５％ Ｚ２００：ｃｒｏｓｓｌｉｎｋｅｒ＝１０：１
［項目１］
下記化学式１で表されるアゼチジニウム（ａｚｅｔｉｄｉｎｉｕｍ）官能基を有する化合物を含む接着剤組成物。
［化１］
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目２］
上記化学式１の化合物は下記化学式２の化合物である、項目１に記載の接着剤組成物。
［化２］
Ｘ'、Ｘ"及びＹ'はそれぞれＣ １ からＣ ２０ の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目３］
上記化学式２の化合物は下記化学式３の化合物である、項目２に記載の接着剤組成物。
［化３］
［項目４］
ｐＨが４から１０である、項目１から３の何れか１項に記載の接着剤組成物。
［項目５］
塩基をさらに含む、項目１から４の何れか１項に記載の接着剤組成物。
［項目６］
ポリビニールアルコール系樹脂をさらに含む、項目１から５の何れか１項に記載の接着剤組成物。
［項目７］
２層以上のフィルムが積層された構造を有する光学フィルムであって、上記フィルム間の少なくとも１つの界面にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする光学フィルム。
［項目８］
上記アゼチジニウム官能基を有する化合物は下記化学式１で表される化合物である、項目７に記載の光学フィルム。
［化１］
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目９］
上記化学式１の化合物は下記化学式２である化合物である、項目８に記載の光学フィルム。
［化２］
Ｘ'、Ｘ"及びＹ'はそれぞれＣ １ からＣ ２０ の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目１０］
上記化学式２の化合物は下記化学式３の化合物である、項目９に記載の光学フィルム。
［化３］
［項目１１］
上記フィルムのうち少なくとも１つはアクリル系フィルム、ＰＥＴフィルム、アクリル系プライマー処理されたＰＥＴフィルム、ＴＡＣフィルム、ＣＯＰフィルム、ＰＣ（ポリカーボネート）フィルム及びＰＮＢ（ポリノルボルネン）系フィルムから選択される、項目７から１０の何れか１項に記載の光学フィルム。
［項目１２］
上記フィルムのうち少なくとも１つは少なくとも一面がアルカリ処理、コロナー処理、プラズマ処理及びプライマー処理から選択される１以上の表面処理が施された、項目７から１１の何れか１項に記載の光学フィルム。
［項目１３］
第１フィルム、偏光子及び第２フィルムが順に積層された構造を有する偏光板において、上記第１フィルム及び第２フィルムのうち少なくとも１つと偏光子との間にアゼチジニウム官能基を有する化合物を含む接着剤組成物を用いて形成された接着剤層が備えられていることを特徴とする偏光板。
［項目１４］
上記アゼチジニウム官能基を有する化合物は下記化学式１で表される化合物である、項目１３に記載の偏光板。
［化１］
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目１５］
上記化学式１の化合物は下記化学式２の化合物である、項目１４に記載の偏光板。
［化２］
Ｘ'、Ｘ"及びＹ'はそれぞれＣ １ からＣ ２０ の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。
［項目１６］
上記化学式２の化合物は下記化学式３の化合物である、項目１５に記載の偏光板。
［化３］
［項目１７］
上記第１または第２フィルムは、アクリル系フィルム、ＰＥＴフィルム、アクリル系プライマー処理されたＰＥＴフィルム、ＴＡＣフィルム、ＣＯＰフィルム、ＰＣ（ポリカーボネート）フィルム及びＰＮＢ（ポリノルボルネン）系フィルムから選択される、項目１３から１６の何れか１項に記載の偏光板。
［項目１８］
上記第１または第２フィルムは少なくとも一面がアルカリ処理、コロナー処理、プラズマ処理及びプライマー処理から選択される１以上の表面処理が施された、項目１３から１７の何れか１項に記載の偏光板。
［項目１９］
項目１３から項目１８の何れか１項に記載された偏光板を含む電子素子。
· K1: 6wt% Kymene-557H (pH = 5)
· K2: 6wt% Kymene-557H (pH = 7)
* K3: 4.5 wt% Kymene-557H: Z200 = 1: 1 (pH = 7)
・ P1: 3% PVA
· P2: 4.5% Z200: crosslinker = 10: 1
[Item 1]
An adhesive composition comprising a compound having an azetidinium functional group represented by the following chemical formula 1.
[Chemical 1]
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 2]
Item 2. The adhesive composition according to Item 1, wherein the compound of Formula 1 is a compound of Formula 2 below.
[Chemical 2]
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 3]
Item 3. The adhesive composition according to Item 2, wherein the compound of Chemical Formula 2 is a compound of Chemical Formula 3 below.
[Chemical formula 3]
[Item 4]
4. The adhesive composition according to any one of items 1 to 3, wherein the pH is 4 to 10.
[Item 5]
Item 5. The adhesive composition according to any one of items 1 to 4, further comprising a base.
[Item 6]
6. The adhesive composition according to any one of items 1 to 5, further comprising a polyvinyl alcohol-based resin.
[Item 7]
An optical film having a structure in which two or more films are laminated, and an adhesive layer formed using an adhesive composition containing a compound having an azetidinium functional group at at least one interface between the films. An optical film characterized by being made.
[Item 8]
8. The optical film according to item 7, wherein the compound having an azetidinium functional group is a compound represented by the following chemical formula 1.
[Chemical 1]
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 9]
Item 9. The optical film according to Item 8, wherein the compound of Formula 1 is a compound represented by Formula 2 below.
[Chemical 2]
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 10]
Item 10. The optical film according to Item 9, wherein the compound of Formula 2 is a compound of Formula 3 below.
[Chemical formula 3]
[Item 11]
Item 7 wherein at least one of the films is selected from an acrylic film, a PET film, an acrylic primer-treated PET film, a TAC film, a COP film, a PC (polycarbonate) film, and a PNB (polynorbornene) film. The optical film according to any one of 1 to 10.
[Item 12]
The optical film according to any one of items 7 to 11, wherein at least one of the films is subjected to at least one surface treatment selected from alkali treatment, corona treatment, plasma treatment and primer treatment. .
[Item 13]
In the polarizing plate having a structure in which a first film, a polarizer, and a second film are sequentially laminated, an adhesive containing a compound having an azetidinium functional group between at least one of the first film and the second film and the polarizer. A polarizing plate comprising an adhesive layer formed using an agent composition.
[Item 14]
14. The polarizing plate according to item 13, wherein the compound having an azetidinium functional group is a compound represented by the following chemical formula 1.
[Chemical 1]
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 15]
Item 15. The polarizing plate according to Item 14, wherein the compound of Chemical Formula 1 is a compound of Chemical Formula 2 below.
[Chemical 2]
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
[Item 16]
Item 16. The polarizing plate according to Item 15, wherein the compound of Chemical Formula 2 is a compound of Chemical Formula 3 below.
[Chemical formula 3]
[Item 17]
The first or second film is selected from an acrylic film, a PET film, an acrylic primer-treated PET film, a TAC film, a COP film, a PC (polycarbonate) film, and a PNB (polynorbornene) film, The polarizing plate according to any one of 13 to 16.
[Item 18]
18. The polarizing plate according to any one of items 13 to 17, wherein at least one surface of the first or second film is subjected to at least one surface treatment selected from alkali treatment, corona treatment, plasma treatment and primer treatment. .
[Item 19]
Item 19. An electronic device comprising the polarizing plate according to any one of Items 13 to 18.
Claims (15)
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。 An optical film having a structure in which two or more films are laminated, and formed using an adhesive composition containing a compound having an azetidinium functional group represented by the following chemical formula 1 at at least one interface between the films An optical film comprising an adhesive layer, wherein at least one of the films is an acrylic film.
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Ｘ'、Ｘ"及びＹ'はそれぞれＣ１からＣ２０の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ１からＣ２０の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ−は１価陰イオンであり、
ｎは３０から７，０００である。 The compound represented by Formula 1 is a compound which you express by the following Chemical Formula 2, an optical film according to claim 1:
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Ｘ及びＹは脂肪族炭化水素基で、Ｘ及びＹのうち少なくとも１つはアミン基、アミド基及びケトン基から１以上を含む脂肪族炭化水素基であり、ＸとＹは連結されて環を形成することができ、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ １ からＣ ２０ の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ − は１価陰イオンであり、
ｎは３０から７，０００である。 In the polarizing plate having a structure in which a first film, a polarizer, and a second film are sequentially laminated , an azetidinium function represented by the following chemical formula 1 is provided between at least one of the first film and the second film and the polarizer. A polarizing plate comprising an adhesive layer formed using an adhesive composition containing a group-containing compound, wherein at least one of the first film and the second film is an acrylic film .
X and Y are aliphatic hydrocarbon groups, and at least one of X and Y is an aliphatic hydrocarbon group containing one or more of an amine group, an amide group, and a ketone group, and X and Y are connected to form a ring. Can be formed,
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Ｘ'、Ｘ"及びＹ'はそれぞれＣ１からＣ２０の脂肪族炭化水素基であり、
Ｒ１からＲ６はそれぞれ水素、ヒドロキシル基、Ｃ１からＣ２０の脂肪族炭化水素基、アルキルカルボキシ酸エステル基及びシアン基から成る群から選択され、
Ａ−は１価陰イオンであり、
ｎは３０から７，０００である。 The compound represented by Formula 1 is a compound represented by the following Chemical Formula 2, polarizing plate according to claim 8:
X ′, X ″ and Y ′ are each a C 1 to C 20 aliphatic hydrocarbon group;
R1 to R6 each represents hydrogen, hydroxyl group, aliphatic hydrocarbon group having from C 1 C 20, selected from the group consisting of alkyl carboxy ester group and a cyano group,
A − is a monovalent anion;
n is 30 to 7,000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20080032563 | 2008-04-08 | ||
| KR10-2008-0032563 | 2008-04-08 | ||
| PCT/KR2009/001818 WO2009125980A2 (en) | 2008-04-08 | 2009-04-08 | Adhesive composition and optical film using the same |
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| JP5446015B2 true JP5446015B2 (en) | 2014-03-19 |
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| JP (1) | JP5446015B2 (en) |
| KR (1) | KR101057628B1 (en) |
| CN (2) | CN102015954B (en) |
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| KR20120032195A (en) * | 2010-09-28 | 2012-04-05 | 동우 화인켐 주식회사 | A polarizing plate and liquid crystal display comprising the same |
| MX366036B (en) * | 2012-06-14 | 2019-06-25 | Novartis Ag | Azetidinium-containing copolymers and uses thereof. |
| KR102246299B1 (en) * | 2019-03-12 | 2021-04-29 | 주식회사 온빛 | The manufacturing method of high-refraction polarizing lens |
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| US4528316A (en) * | 1983-10-18 | 1985-07-09 | Kimberly-Clark Corporation | Creping adhesives containing polyvinyl alcohol and cationic polyamide resins |
| JPH0345678A (en) * | 1989-07-14 | 1991-02-27 | Kuraray Co Ltd | Adhesive and glass base |
| ES2135849T3 (en) * | 1995-05-18 | 1999-11-01 | Fort James Corp | NEW FORMULATIONS OF CRESPADO ADHESIVE, CRESPADO METHOD AND CRESPADA FIBROUS BAND. |
| JP3704786B2 (en) * | 1996-03-18 | 2005-10-12 | 住友化学株式会社 | Polarizer |
| US5944954A (en) * | 1996-05-22 | 1999-08-31 | The Procter & Gamble Company | Process for creping tissue paper |
| US5865950A (en) * | 1996-05-22 | 1999-02-02 | The Procter & Gamble Company | Process for creping tissue paper |
| ZA983876B (en) | 1997-05-09 | 1999-01-08 | Procter & Gamble | Pigmented adhesive composition for laminating tissue paper products and methods for producing such compositions |
| US6677427B1 (en) * | 2000-06-13 | 2004-01-13 | Hercules Incorporated | Enzyme-catalyzed polyamides and compositions and processes of preparing and using the same |
| EP1180559A1 (en) * | 2000-08-04 | 2002-02-20 | Armstrong World Industries, Inc. | Binder composition for fibrous sheet |
| JP2004334168A (en) * | 2003-04-16 | 2004-11-25 | Sumitomo Chem Co Ltd | Polarizing plate and its manufacturing method |
| JP2005128294A (en) * | 2003-10-24 | 2005-05-19 | Sumitomo Chemical Co Ltd | Polarizing plate |
| WO2005113700A1 (en) * | 2004-04-20 | 2005-12-01 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives |
| CN100520453C (en) * | 2004-08-03 | 2009-07-29 | 捷时雅株式会社 | Polarizing plate and process for producing the same |
| JP2006235613A (en) * | 2005-01-25 | 2006-09-07 | Sumitomo Chemical Co Ltd | Compound polarizing plate |
| MY150700A (en) * | 2006-08-24 | 2014-02-28 | Hercules Inc | Adhesive composition of low molecular weight polyaminopolyamide-epichlorohydrin (pae) resin and protein |
| US7932349B2 (en) * | 2006-09-18 | 2011-04-26 | Hercules Incorporated | Membrane separation process for removing residuals polyamine-epihalohydrin resins |
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| WO2009125980A3 (en) | 2010-01-14 |
| WO2009125980A2 (en) | 2009-10-15 |
| KR101057628B1 (en) | 2011-08-19 |
| KR20090107444A (en) | 2009-10-13 |
| TWI386472B (en) | 2013-02-21 |
| CN102015954B (en) | 2013-11-13 |
| CN102015954A (en) | 2011-04-13 |
| CN103396756A (en) | 2013-11-20 |
| CN103396756B (en) | 2015-01-21 |
| JP2011519982A (en) | 2011-07-14 |
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