JP2018053208A - Adhesive composition for optical member protective film, and optical member protective film - Google Patents
Adhesive composition for optical member protective film, and optical member protective film Download PDFInfo
- Publication number
- JP2018053208A JP2018053208A JP2016194488A JP2016194488A JP2018053208A JP 2018053208 A JP2018053208 A JP 2018053208A JP 2016194488 A JP2016194488 A JP 2016194488A JP 2016194488 A JP2016194488 A JP 2016194488A JP 2018053208 A JP2018053208 A JP 2018053208A
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- Japan
- Prior art keywords
- meth
- protective film
- monomer
- optical member
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 230000001681 protective effect Effects 0.000 title claims abstract description 85
- 230000003287 optical effect Effects 0.000 title claims abstract description 76
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 88
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- 125000002947 alkylene group Chemical group 0.000 claims abstract description 31
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
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- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、光学部材保護フィルム用粘着剤組成物及び光学部材保護フィルムに関する。 The present invention relates to an adhesive composition for an optical member protective film and an optical member protective film.
液晶表示装置や有機エレクトロルミネッセンス（ＥＬ）表示装置は、薄型軽量であること、消費電力が少なくて済むことなどから、近年、各種の情報関連機器、例えばテレビジョン、ノ−ト型パソコン、スマートフォン、タブレット端末、カーナビゲーションなどの画面表示装置として利用されている。
このような表示装置、例えば液晶表示装置には、本体である液晶を内包した液晶セル（ガラスセル）と共に、偏光フィルム、位相差フィルム、透明導電膜、輝度向上フィルムに代表される各種の光学部材が用いられている。
In recent years, liquid crystal display devices and organic electroluminescence (EL) display devices are thin and light and consume less power. Therefore, various information-related devices such as televisions, notebook computers, smartphones, It is used as a screen display device for tablet terminals and car navigation systems.
In such a display device, for example, a liquid crystal display device, various optical members represented by a polarizing film, a retardation film, a transparent conductive film, and a brightness enhancement film, as well as a liquid crystal cell (glass cell) containing liquid crystal as a main body. Is used.
これらの光学部材は、通常、打抜加工、検査、輸送、表示板の組立などの各工程を経る間にその表面が汚染されたり損傷したりしないよう、粘着フィルムを貼りつけて保護することが行われる。このような光学部材の表面を保護するために用いられる粘着フィルムは、光学部材保護フィルム（以下、「保護フィルム」ともいう。）と呼ばれる。
保護フィルムが備える粘着剤層には、光学部材の保護が必要とされる間は光学部材の表面上でのずれや光学部材の表面から意図せぬ剥落がない程度の粘着力を有し、かつ、光学部材の保護が不要となった段階では光学部材から剥離しやすいこと（以下、「剥離性」ともいう。）が求められる。
These optical members are usually protected by sticking an adhesive film so that the surface is not contaminated or damaged during each process such as punching, inspection, transportation, and display panel assembly. Done. The pressure-sensitive adhesive film used for protecting the surface of such an optical member is called an optical member protective film (hereinafter also referred to as “protective film”).
The pressure-sensitive adhesive layer provided in the protective film has an adhesive force that does not cause deviation on the surface of the optical member or unintentional peeling from the surface of the optical member while protection of the optical member is required, and When the protection of the optical member is no longer necessary, it is required to be easily peeled from the optical member (hereinafter also referred to as “peelability”).
近年、保護フィルムと光学部材とを貼り合せた積層体の状態で、更に加熱を伴った加工を施す場合がある。例えばＩＴＯフィルムを製造する場合、結晶化のために１５０℃で1時間程度加熱処理されることがある。一般に、保護フィルムは、保護フィルムと光学部材とを貼り合せた状態で加熱処理すると、保護フィルムが備える粘着剤層の光学部材に対する粘着力が過度に上昇するため、光学部材から剥がし難くなる。また、加熱処理により光学部材に対する保護フィルムが備える粘着剤層の濡れ性にばらつきが生じるため、光学部材から保護フィルムを剥離する際に音が発生したり、光学部材側に剥離した際の保護フィルムの剥離痕（ジッピングライン）が見えたりする、いわゆるジッピングが問題となる。
このため、保護フィルムには、加熱処理前にくわえ加熱処理後の剥離性が良好であることが求められる。
一般に、保護フィルム用粘着剤組成物は、被着体である光学部材に対する濡れ性を高めることでジッピングを抑制できることが知られている。例えば、粘着剤組成物の架橋密度を低くすれば、光学部材に対する濡れ性が良好となる。
In recent years, there is a case where a process with further heating is performed in the state of a laminated body in which a protective film and an optical member are bonded together. For example, when manufacturing an ITO film, it may be heat-treated at 150 ° C. for about 1 hour for crystallization. In general, when the protective film is heat-treated in a state where the protective film and the optical member are bonded together, the adhesive force of the pressure-sensitive adhesive layer included in the protective film is excessively increased, so that it is difficult to peel off from the optical member. In addition, since the wettability of the pressure-sensitive adhesive layer included in the protective film for the optical member varies due to the heat treatment, sound is generated when the protective film is peeled off from the optical member, or the protective film is peeled off on the optical member side. In other words, so-called zipping, in which peeling marks (zipping lines) are visible, becomes a problem.
For this reason, the protective film is required to have good peelability after the heat treatment before the heat treatment.
Generally, it is known that the adhesive composition for protective films can suppress zipping by improving the wettability with respect to the optical member which is a to-be-adhered body. For example, if the crosslink density of the pressure-sensitive adhesive composition is lowered, the wettability with respect to the optical member is improved.
光学部材保護フィルム用粘着剤組成物は広く知られている。
例えば、特許文献１には、（メタ）アクリル酸アルキレンオキサイド付加物を特定量の範囲で含み（メタ）アクリル系ポリマーを架橋せしめて得られる表面保護シート用粘着剤組成物が開示されている。特許文献１によれば、高接着力でありながら、高速剥離時に低速剥離時よりも低い力で剥離でき、濡れ性が良好である旨が記載されている。なお、特許文献１の実施例の粘着剤組成物は、架橋剤としてイソシアネート系架橋剤、より詳しくはトリレンジイソシアネートとトリメチロールプロパンの付加物、が用いられている。
Adhesive compositions for optical member protective films are widely known.
For example, Patent Document 1 discloses a pressure-sensitive adhesive composition for a surface protective sheet obtained by crosslinking a (meth) acrylic polymer containing a (meth) acrylic acid alkylene oxide adduct in a specific range. According to Patent Document 1, it is described that, although it has a high adhesive force, it can be peeled with a lower force at the time of high-speed peeling than at the time of low-speed peeling and has good wettability. In addition, the adhesive composition of the Example of patent document 1 uses the isocyanate type crosslinking agent as a crosslinking agent, and the adduct of tolylene diisocyanate and a trimethylol propane more specifically.
また、光学部材保護フィルムには、光学部材から保護フィルムを剥離した後に光学部材表面に保護フィルムが備える粘着剤層に由来する残渣が残らないこと、いわゆる耐汚染性が求められる。このような残渣は、例えば粘着剤組成物が含有する共重合体の低分子成分に由来する。
なお、光学部材保護フィルムにおいて、前述した粘着剤層に由来する残渣は、被着体と共に加熱処理した後に多く発生する傾向が見られる。
In addition, the optical member protective film is required to have a residue derived from the pressure-sensitive adhesive layer included in the protective film on the surface of the optical member after peeling the protective film from the optical member, so-called contamination resistance. Such a residue originates from the low molecular component of the copolymer which an adhesive composition contains, for example.
In addition, in the optical member protective film, there is a tendency that a large amount of the residue derived from the pressure-sensitive adhesive layer described above is generated after the heat treatment with the adherend.
保護フィルム用粘着剤組成物の耐汚染性は、粘着剤組成物の架橋密度を高めることや、例えばカルボキシ基に代表される官能基を有する単量体に由来する構成単位を粘着剤組成物が含有する共重合体に含有させることで改善できる。
これに対して、特許文献１には、粘着剤組成物が含む架橋剤の種類の変更に伴い粘着剤組成物の架橋密度を高めることで耐汚染性が改善できることについて何ら記載がない。また、特許文献１には、表面保護シート用粘着剤組成物の加熱処理後の使用について何ら記載がない。
さらに、特許文献１に記載の粘着剤組成物は、耐汚染性について何ら検討されていない。そのため、特許文献１に記載されているような従来の粘着剤組成物における加熱処理後の物性、すなわちジッピングの抑制、剥離性及び耐汚染性は、それぞれ十分といえない場合がある。
Contamination resistance of the pressure-sensitive adhesive composition for protective film is such that the pressure-sensitive adhesive composition can increase the crosslinking density of the pressure-sensitive adhesive composition, for example, a structural unit derived from a monomer having a functional group represented by a carboxy group. It can improve by making it contain in the copolymer to contain.
On the other hand, Patent Document 1 has no description that the stain resistance can be improved by increasing the crosslinking density of the pressure-sensitive adhesive composition in accordance with the change in the type of the crosslinking agent contained in the pressure-sensitive adhesive composition. Moreover, in patent document 1, there is no description about the use after heat processing of the adhesive composition for surface protection sheets.
Furthermore, the pressure-sensitive adhesive composition described in Patent Document 1 has not been studied at all for stain resistance. Therefore, the physical properties after the heat treatment in the conventional pressure-sensitive adhesive composition as described in Patent Document 1, that is, suppression of zipping, peelability and stain resistance may not be sufficient.
本発明は、前述した事情に鑑みてなされたものであり、加熱処理後のジッピングを十分に抑制し、加熱処理前及び加熱処理後の剥離性を維持し、かつ、耐汚染性が優れる光学部材保護フィルムを製造し得る粘着剤組成物を提供することを課題とする。
また、本発明は、前記粘着剤組成物に由来する粘着剤層を備え、加熱処理後のジッピングを十分に抑制し、加熱処理前及び加熱処理後の剥離性を維持し、かつ、耐汚染性が優れる光学部材保護フィルムを提供することを課題とする。
The present invention has been made in view of the above-described circumstances, and is an optical member that sufficiently suppresses zipping after heat treatment, maintains releasability before and after heat treatment, and has excellent contamination resistance. It aims at providing the adhesive composition which can manufacture a protective film.
In addition, the present invention includes a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition, sufficiently suppresses zipping after heat treatment, maintains releasability before and after heat treatment, and is resistant to contamination. It is an object of the present invention to provide an optical member protective film excellent in.
課題を解決するための具体的手段には、以下の態様が含まれる。
＜１＞酸性基を有する単量体に由来する構成単位と、
アルキレンオキシド鎖を有する単量体に由来する構成単位と、を含む、（メタ）アクリル系共重合体と、
エポキシ系架橋剤と、を含有し、
前記（メタ）アクリル系共重合体の全構成単位１００質量％に対して、前記酸性基を有する単量体に由来する構成単位を３〜９質量％含む、
光学部材保護フィルム用粘着剤組成物。
Specific means for solving the problems include the following aspects.
<1> a structural unit derived from a monomer having an acidic group;
A structural unit derived from a monomer having an alkylene oxide chain, and a (meth) acrylic copolymer,
An epoxy-based crosslinking agent,
Containing 3 to 9% by mass of a structural unit derived from the monomer having an acidic group with respect to 100% by mass of all the structural units of the (meth) acrylic copolymer,
An adhesive composition for an optical member protective film.
＜２＞前記アルキレンオキシド鎖を有する単量体が、エチレンオキシド鎖を有する単量体である＜１＞に記載の光学部材保護フィルム用粘着剤組成物。
＜３＞前記エチレンオキシド鎖を有する単量体において、エチレンオキシド鎖におけるエチレンオキシド単位の平均付加モル数が１モル以上９モル以下である＜２＞に記載の光学部材保護フィルム用粘着剤組成物。
＜４＞前記酸性基を有する単量体が、（メタ）アクリル酸である＜１＞〜＜３＞のいずれか一つに記載の光学部材保護フィルム用粘着剤組成物。
<2> The pressure-sensitive adhesive composition for an optical member protective film according to <1>, wherein the monomer having an alkylene oxide chain is a monomer having an ethylene oxide chain.
<3> The pressure-sensitive adhesive composition for an optical member protective film according to <2>, wherein the monomer having an ethylene oxide chain has an average addition mole number of ethylene oxide units in the ethylene oxide chain of 1 mol or more and 9 mol or less.
<4> The pressure-sensitive adhesive composition for an optical member protective film according to any one of <1> to <3>, wherein the monomer having an acidic group is (meth) acrylic acid.
＜５＞基材と、
＜１＞〜＜４＞のいずれか一つに記載の光学部材保護フィルム用粘着剤組成物に由来する粘着剤層と、を備えた光学部材保護フィルム。
<5> a base material;
An optical member protective film comprising: an adhesive layer derived from the adhesive composition for an optical member protective film according to any one of <1> to <4>.
本発明によれば、加熱処理後のジッピングを十分に抑制し、加熱処理前及び加熱処理後の剥離性を維持し、かつ、耐汚染性が優れる光学部材保護フィルムを製造し得る粘着剤組成物を提供できる。
また、本発明によれば、前記粘着剤組成物に由来する粘着剤層を備え、加熱処理後のジッピングを十分に抑制し、加熱処理前及び加熱処理後の剥離性を維持し、かつ、耐汚染性が優れる光学部材保護フィルムを提供できる。
According to the present invention, a pressure-sensitive adhesive composition capable of producing an optical member protective film that sufficiently suppresses zipping after heat treatment, maintains releasability before and after heat treatment, and is excellent in stain resistance. Can provide.
Further, according to the present invention, the pressure-sensitive adhesive composition is provided with a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition, sufficiently suppresses zipping after the heat treatment, maintains the peelability before the heat treatment and after the heat treatment, and has a high resistance. An optical member protective film having excellent contamination can be provided.
以下、本発明の具体的な実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜、変更を加えて実施できる。 Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. it can.
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を意味する。
本明細書において、組成物中の各成分の量は、各成分に該当する物質が組成物中に複数存在する場合には、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as a minimum value and a maximum value, respectively.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
本明細書において、「粘着剤組成物」とは、（メタ）アクリル系共重合体と、エポキシ系架橋剤とを混合した後から、架橋反応が終了する前の液状又はペースト状の物質を意味する。
本明細書において、「粘着剤層」とは、粘着剤組成物の架橋反応が終了した後の物質を意味する。
本明細書において「（メタ）アクリレート」は、アクリレート及びメタクリレートの両方を包含する用語であり、「（メタ）アクリル」は、アクリル及びメタクリルの両方を包含する用語である。
In the present specification, the “pressure-sensitive adhesive composition” means a liquid or pasty substance after the (meth) acrylic copolymer and the epoxy crosslinking agent are mixed and before the crosslinking reaction is completed. To do.
In the present specification, the “pressure-sensitive adhesive layer” means a substance after the crosslinking reaction of the pressure-sensitive adhesive composition is completed.
In the present specification, “(meth) acrylate” is a term including both acrylate and methacrylate, and “(meth) acryl” is a term including both acrylic and methacrylic.
［光学部材保護フィルム用粘着剤組成物］
本発明の光学部材保護フィルム粘着剤組成物（以下、単に粘着剤組成物とも称する。）は、酸性基を有する単量体に由来する構成単位と、アルキレンオキシド鎖を有する単量体に由来する構成単位と、を含む、（メタ）アクリル系共重合体と、エポキシ系架橋剤と、を含有し、前記（メタ）アクリル系共重合体の全構成単位１００質量％に対して、前記酸性基を有する単量体に由来する構成単位を３〜９質量％含む。
[Adhesive composition for protective film for optical member]
The optical member protective film pressure-sensitive adhesive composition of the present invention (hereinafter also simply referred to as a pressure-sensitive adhesive composition) is derived from a structural unit derived from a monomer having an acidic group and a monomer having an alkylene oxide chain. A (meth) acrylic copolymer and an epoxy-based crosslinking agent, and the acidic group with respect to 100% by mass of all the structural units of the (meth) acrylic copolymer. 3 to 9 mass% of a structural unit derived from a monomer having
本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、酸性基を有する単量体に由来する構成単位を特定量、具体的には（メタ）アクリル系共重合体１００質量％に対し、酸性基を有する単量体に由来する構成単位を３質量％以上含むため、耐汚染性が優れる。
なお、本明細書において、「耐汚染性が優れる」とは、被着体への汚染を抑制する、すなわち保護フィルムの被着体上に残る粘着剤層に由来する残渣を低減できることを意味する。
通常、（メタ）アクリル系共重合体の製造の際、分子量が例えば数百〜２万程度の低分子ポリマー（オリゴマー）が生成する。そのため、一般に（メタ）アクリル系共重合体を含有する粘着剤組成物は、前記低分子ポリマーも含有する。このような低分子ポリマーは、粘着剤組成物において経時で粘着剤層の界面付近にブリードアウトする傾向がある。このようなブリードアウトは、水酸基、酸性基及びアミノ基に代表される官能基を有する単量体に由来する構成単位量が少ない低分子ポリマーが含まれている場合、（メタ）アクリル系共重合体と低分子ポリマーとがそれぞれ有する官能基間での相互作用が小さくなるため顕著である。保護フィルム用粘着剤組成物では、保護フィルムを保護する被着体に貼付後、被着体から剥離すると、被着体表面に低分子ポリマーが残渣として残り、被着体を汚染する一因となっている。さらに、このような残渣は、被着体と共に加熱処理した後に多く発生する傾向が見られる。
本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、酸性基を有する単量体に由来する構成単位を特定量以上含むため、（メタ）アクリル系共重合体が含む前述した低分子ポリマーも酸性基を有する単量体に由来する構成単位を特定量以上含む。そのため、粘着剤組成物中で酸性基を有する単量体に由来する構成単位を共に有している（メタ）アクリル系共重合体と前述した低分子ポリマーとが相互作用し、前述した粘着剤層の界面付近への低分子ポリマーのブリードアウトが抑制される。したがって、本発明の粘着剤組成物は、保護フィルムに用いた際の被着体すなわち光学部材への耐汚染性が優れる。
くわえて、本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、（メタ）アクリル系共重合体１００質量％に対し、酸性基を有する単量体に由来する構成単位を３質量％以上含み、かつ、エポキシ系架橋剤を含むため、架橋密度が高くなる。本発明の粘着剤組成物は、架橋密度が高いため、前述した界面付近への低分子ポリマーのブリードアウトが抑制されることで保護フィルムに用いた際の光学部材への耐汚染性が優れる。
なお、例えば特許文献１に記載の表面保護シート用粘着剤組成物のように、（メタ）アクリル酸アルキレンオキサイド付加物を特定量の範囲で含み（メタ）アクリル系ポリマーをイソシアネート系架橋剤で架橋した粘着剤組成物は、前述した低分子ポリマーのブリードアウトが多くなる傾向がある。
The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention has a specific amount of a structural unit derived from a monomer having an acidic group, specifically, 100 mass of the (meth) acrylic copolymer. %, The structural unit derived from the monomer having an acidic group is contained in an amount of 3% by mass or more, so that the stain resistance is excellent.
In the present specification, “excellent stain resistance” means that the contamination of the adherend can be suppressed, that is, the residue derived from the pressure-sensitive adhesive layer remaining on the adherend of the protective film can be reduced. .
Usually, when a (meth) acrylic copolymer is produced, a low molecular polymer (oligomer) having a molecular weight of, for example, about several hundred to 20,000 is generated. Therefore, generally the adhesive composition containing a (meth) acrylic-type copolymer also contains the said low molecular weight polymer. Such a low molecular weight polymer tends to bleed out in the pressure-sensitive adhesive composition near the interface of the pressure-sensitive adhesive layer over time. Such a bleed-out is a (meth) acrylic copolymer, when a low molecular weight polymer having a small amount of structural units derived from a monomer having a functional group represented by a hydroxyl group, an acidic group and an amino group is contained. This is remarkable because the interaction between the functional groups of the polymer and the low molecular polymer is small. In the protective film pressure-sensitive adhesive composition, after being attached to an adherend that protects the protective film, if peeled off from the adherend, a low molecular polymer remains as a residue on the adherend surface, and this is a cause of contaminating the adherend. It has become. Furthermore, such a residue tends to be generated after heat treatment with the adherend.
The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention contains a specific amount or more of a structural unit derived from a monomer having an acidic group. The low molecular weight polymer also contains a specific amount or more of a structural unit derived from a monomer having an acidic group. Therefore, the (meth) acrylic copolymer having both a structural unit derived from a monomer having an acidic group in the pressure-sensitive adhesive composition interacts with the low-molecular polymer described above, and the pressure-sensitive adhesive described above. Bleed out of the low molecular weight polymer near the interface of the layer is suppressed. Therefore, the pressure-sensitive adhesive composition of the present invention is excellent in stain resistance to an adherend, that is, an optical member when used in a protective film.
In addition, the (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention comprises a structural unit derived from a monomer having an acidic group with respect to 100% by mass of the (meth) acrylic copolymer. Since it contains 3 mass% or more and contains an epoxy-based crosslinking agent, the crosslinking density is increased. Since the pressure-sensitive adhesive composition of the present invention has a high crosslinking density, the low molecular weight polymer bleed-out to the vicinity of the interface described above is suppressed, so that the stain resistance to the optical member when used for the protective film is excellent.
For example, as in the pressure-sensitive adhesive composition for a surface protective sheet described in Patent Document 1, a (meth) acrylic acid alkylene oxide adduct is included in a specific amount range and a (meth) acrylic polymer is cross-linked with an isocyanate cross-linking agent. The above-mentioned pressure-sensitive adhesive composition tends to increase the bleed-out of the low-molecular polymer described above.
また、本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、アルキレンオキシド鎖を有する単量体に由来する構成単位を含むため、加熱処理後のジッピングを十分抑制できる。
前述したとおり、本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、酸性基を有する単量体に由来する構成単位を特定量含み、かつ、エポキシ系架橋剤を含むため、架橋密度が高い。一般に、架橋密度が高い粘着剤組成物は、被着体への濡れ性が小さい。そのため、架橋密度が高い粘着剤組成物に由来する粘着剤層では、特に保護フィルムと光学部材とを貼り合せた積層体を加熱処理した後にジッピングが生じやすい傾向が見られる。
本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、架橋密度が高くても、アルキレンオキシド鎖を有する単量体に由来する構成単位を含むことで、被着体すなわち光学部材への濡れ性が向上し、加熱処理前にくわえ加熱処理後の剥離性を維持し、前述した加熱処理後に生じるジッピングを抑制できる。
つまり、本発明によれば、加熱処理後のジッピングを十分に抑制し、加熱処理前にくわえ加熱処理後の剥離性を維持し、かつ、耐汚染性が優れる光学部材保護フィルムを製造し得る粘着剤組成物を提供できる。
Moreover, since the (meth) acrylic-type copolymer which the adhesive composition of this invention contains contains the structural unit derived from the monomer which has an alkylene oxide chain, the zipping after heat processing can fully be suppressed.
As described above, the (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention contains a specific amount of a structural unit derived from a monomer having an acidic group and contains an epoxy-based crosslinking agent. High crosslink density. In general, a pressure-sensitive adhesive composition having a high crosslinking density has low wettability to an adherend. Therefore, in the pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition having a high crosslink density, there is a tendency that zipping is likely to occur particularly after the laminated body in which the protective film and the optical member are bonded together.
The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention contains a constitutional unit derived from a monomer having an alkylene oxide chain, even if the crosslink density is high. The wettability to the member is improved, the peelability after the heat treatment is maintained before the heat treatment, and zipping that occurs after the heat treatment described above can be suppressed.
That is, according to the present invention, the adhesive that can sufficiently suppress the zipping after the heat treatment, maintain the peelability after the heat treatment before the heat treatment, and produce an optical member protective film having excellent contamination resistance. An agent composition can be provided.
＜（メタ）アクリル系共重合体＞
本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、酸性基を有する単量体に由来する構成単位と、アルキレンオキシド鎖を有する単量体に由来する構成単位とを含む。前記酸性基を有する単量体に由来する構成単位の含有量は、（メタ）アクリル系共重合体１００質量％に対し３〜９質量％である。
<(Meth) acrylic copolymer>
The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention includes a structural unit derived from a monomer having an acidic group and a structural unit derived from a monomer having an alkylene oxide chain. . Content of the structural unit derived from the monomer which has the said acidic group is 3-9 mass% with respect to 100 mass% of (meth) acrylic-type copolymers.
本明細書において、「酸性基を有する単量体に由来する構成単位」とは、酸性基を有する単量体が付加重合して形成される構成単位を意味する。
また、本明細書において、「アルキレンオキシド鎖を有する単量体に由来する構成単位」とは、アルキレンオキシド鎖を有する単量体が付加重合して形成される構成単位を意味する。
In the present specification, the “structural unit derived from a monomer having an acidic group” means a structural unit formed by addition polymerization of a monomer having an acidic group.
In the present specification, the “structural unit derived from a monomer having an alkylene oxide chain” means a structural unit formed by addition polymerization of a monomer having an alkylene oxide chain.
本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、１種のみであってもよく、単量体の組成、重量平均分子量等が異なる２種以上であってもよい。 The (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention may be only one type, or two or more types having different monomer compositions, weight average molecular weights, and the like.
（メタ）アクリル系共重合体が酸性基を有する単量体に由来する構成単位を含むことで、前述したとおりエポキシ系架橋剤によって架橋される。
酸性基を有する単量体に由来する構成単位の含有量が（メタ）アクリル系共重合体１００質量％に対し３質量％以上であるため、前述したとおり被着体である光学部材への耐汚染性が優れ、また、９質量％以下であるため、架橋密度が過度に高くならず、加熱処理後に生じるジッピングを抑制できる。さらに、酸性基を有する単量体に由来する構成単位の影響による光学部材の劣化を抑制できる。
Since the (meth) acrylic copolymer contains a structural unit derived from a monomer having an acidic group, it is crosslinked by an epoxy crosslinking agent as described above.
Since the content of the structural unit derived from the monomer having an acidic group is 3% by mass or more with respect to 100% by mass of the (meth) acrylic copolymer, as described above, the resistance to the optical member as the adherend is Since the contamination property is excellent and it is 9% by mass or less, the crosslinking density is not excessively high, and zipping that occurs after the heat treatment can be suppressed. Furthermore, the deterioration of the optical member due to the influence of the structural unit derived from the monomer having an acidic group can be suppressed.
酸性基を有する単量体の種類は、特に制限はない。
酸性基を有する単量体としては、例えば、カルボキシ基を有する単量体、スルホ基を有する単量体等が挙げられる。
酸性基を有する単量体は、１種を単独で使用してもよく、２種以上を併用してもよい。
There is no restriction | limiting in particular in the kind of monomer which has an acidic group.
Examples of the monomer having an acidic group include a monomer having a carboxy group and a monomer having a sulfo group.
The monomer which has an acidic group may be used individually by 1 type, and may use 2 or more types together.
カルボキシ基を有する単量体としては、例えば、（メタ）アクリル酸、カルボキシ基を有するポリアルキレングリコール（メタ）アクリレート、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、桂皮酸、コハク酸モノヒドロキシエチル（メタ）アクリレート、マレイン酸モノヒドロキシエチル（メタ）アクリレート、フマル酸モノヒドロキシエチル（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート、１，２−ジカルボキシシクロヘキサンモノヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ダイマー及びω−カルボキシ-ポリカプロラクトンモノ（メタ）アクリレートが挙げられる。スルホ基を有する単量体としては、２−アクリルアミド−２−メチルプロパンスルホン酸等が挙げられる。
本発明において、酸性基を有する単量体に由来する構成単位としては、その他の単量体との共重合性の観点と、架橋剤との反応性の観点から、（メタ）アクリル酸、が好ましく、アクリル酸がより好ましい。
Examples of the monomer having a carboxy group include (meth) acrylic acid, polyalkylene glycol (meth) acrylate having a carboxy group, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, and cinnamon. Acid, monohydroxyethyl (meth) acrylate succinate, monohydroxyethyl (meth) acrylate maleate, monohydroxyethyl (meth) acrylate fumarate, monohydroxyethyl (meth) acrylate phthalate, 1,2-dicarboxycyclohexane mono Examples include hydroxyethyl (meth) acrylate, (meth) acrylic acid dimer and ω-carboxy-polycaprolactone mono (meth) acrylate. Examples of the monomer having a sulfo group include 2-acrylamido-2-methylpropanesulfonic acid.
In the present invention, the structural unit derived from the monomer having an acidic group includes (meth) acrylic acid from the viewpoint of copolymerization with other monomers and the reactivity with the crosslinking agent. Acrylic acid is preferred.
（メタ）アクリル系共重合体がアルキレンオキシド鎖を有する単量体に由来する構成単位を含むことで、本発明の粘着剤組成物は、被着体への濡れ性を制御できる。
アルキレンオキシド鎖としては、例えば、エチレンオキシド鎖、プロピレンオキシド鎖が挙げられる。
アルキレンオキシド鎖を有する単量体に由来する構成単位の含有量が（メタ）アクリル系共重合体１００質量％に対し０．１質量％以上、好ましくは１質量％以上であれば、前述したとおり光学部材への濡れ性が向上し、加熱処理後に生じるジッピングをより抑制できるため好ましく、また、３０質量％以下、好ましくは１０質量％以下であれば、加熱処理後の粘着力が過度に高くならず、保護フィルムと光学部材とを貼り合せた積層体の加熱処理後の剥離性がより適正となるため好ましい。
さらに、アルキレンオキシド鎖を有する単量体がエチレンオキシド鎖を有する単量体であれば、より被着体への濡れ性が適度な範囲となり、加熱処理後に生じるジッピングをより抑制できるため好ましい。
When the (meth) acrylic copolymer contains a structural unit derived from a monomer having an alkylene oxide chain, the pressure-sensitive adhesive composition of the present invention can control wettability to an adherend.
Examples of the alkylene oxide chain include an ethylene oxide chain and a propylene oxide chain.
As described above, if the content of the structural unit derived from the monomer having an alkylene oxide chain is 0.1% by mass or more, preferably 1% by mass or more with respect to 100% by mass of the (meth) acrylic copolymer. It is preferable because the wettability to the optical member is improved and zipping occurring after the heat treatment can be further suppressed, and is preferably 30% by mass or less, preferably 10% by mass or less, if the adhesive strength after the heat treatment is excessively high. However, the peelability after the heat treatment of the laminate in which the protective film and the optical member are bonded together is more preferable.
Furthermore, if the monomer having an alkylene oxide chain is a monomer having an ethylene oxide chain, the wettability to the adherend is in an appropriate range, and zipping that occurs after heat treatment can be further suppressed, which is preferable.
アルキレンオキシド鎖を有する単量体の種類は、特に制限はない。
アルキレンオキシド鎖を有する単量体は、１種を単独で使用してもよく、２種以上を併用してもよい。
There is no restriction | limiting in particular in the kind of monomer which has an alkylene oxide chain.
Monomers having an alkylene oxide chain may be used alone or in combination of two or more.
アルキレンオキシド鎖を有する単量体としては、例えば、メトキシエチル（メタ）アクリレート、２−（エトキシエトキシ）エチルアクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート及びメトキシポリエチレングリコール（メタ）アクリレートが挙げられる。
これらの中でも、被着体への濡れ性を適正に制御でき、加熱処理後に生じるジッピングを抑制できる観点から、メトキシポリエチレングリコール（メタ）アクリレート又はメトキシポリプロピレングリコール（メタ）アクリレートが好ましく、メトキシポリエチレングリコール（メタ）アクリレートがより好ましく、メトキシポリエチレングリコールメタクリレートがさらに好ましい。
Examples of the monomer having an alkylene oxide chain include methoxyethyl (meth) acrylate, 2- (ethoxyethoxy) ethyl acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. , Methoxypolypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate.
Among these, methoxypolyethylene glycol (meth) acrylate or methoxypolypropylene glycol (meth) acrylate is preferable from the viewpoint of being able to appropriately control the wettability to the adherend and suppressing zipping that occurs after the heat treatment. (Meth) acrylate is more preferred, and methoxypolyethylene glycol methacrylate is more preferred.
アルキレンオキシド鎖におけるアルキレンオキシド単位の平均付加モル数としては、１モル〜２５モルが好ましく、被着体への濡れ性を適正に制御でき、加熱処理後に生じるジッピングを抑制できる観点から、１モル〜９モルがより好ましい。
なお、アルキレンオキシド鎖におけるアルキレンオキシド単位の平均付加モル数とは、含有される単量体におけるアルキレンオキシドの付加モル数の平均値を意味する。
The average number of added moles of alkylene oxide units in the alkylene oxide chain is preferably 1 to 25 moles, from the viewpoint of being able to properly control the wettability to the adherend and suppressing zipping that occurs after the heat treatment. 9 moles is more preferred.
In addition, the average addition mole number of the alkylene oxide unit in an alkylene oxide chain means the average value of the addition mole number of the alkylene oxide in the monomer to contain.
アルキレンオキシド鎖を有する単量体は市販品を使用できる。
アルキレンオキシド鎖を有する単量体であるメトキシポリエチレングリコール（メタ）アクリレートの市販品は、例えば、新中村化学工業社製、商品名Ｍ−９０Ｇ（エチレンオキシド鎖におけるアルキレンオキシド単位の平均付加モル数が９）、Ｍ−２３０Ｇ（同平均付加モル数が２３）、共栄社化学社製、商品名ライトアクリレート１３０Ａ（同平均付加モル数が９）日油株式会社製、商品名ブレンマーＰＭＥ２００（同平均付加モル数が４）、商品名ブレンマーＰＭＥ４００（同平均付加モル数が９）、商品名ブレンマーＰＭＥ１０００（同平均付加モル数が２３）、として市販されている。
A commercially available product can be used as the monomer having an alkylene oxide chain.
A commercially available product of methoxypolyethylene glycol (meth) acrylate, which is a monomer having an alkylene oxide chain, is, for example, trade name M-90G manufactured by Shin-Nakamura Chemical Co., Ltd. (average added mole number of alkylene oxide units in ethylene oxide chain is 9). ), M-230G (same average addition mole number is 23), manufactured by Kyoeisha Chemical Co., Ltd., trade name Light Acrylate 130A (same average addition mole number is 9), manufactured by NOF Corporation, trade name Blemmer PME200 (same average addition mole number) 4), trade name Blemmer PME400 (same average added mole number is 9), and trade name Blemmer PME1000 (same average added mole number is 23).
さらに、本発明の粘着剤組成物が含有する（メタ）アクリル系共重合体は、アルキル（メタ）アクリレートに由来する構成単位を含むことが好ましい。（メタ）アクリル系共重合体がアルキル（メタ）アクリレートに由来する構成単位を含むことで、粘着力すなわち加熱処理前及び加熱処理後の剥離性を容易に調整できる。 Furthermore, it is preferable that the (meth) acrylic copolymer contained in the pressure-sensitive adhesive composition of the present invention includes a structural unit derived from an alkyl (meth) acrylate. When the (meth) acrylic copolymer contains a structural unit derived from an alkyl (meth) acrylate, it is possible to easily adjust the adhesive strength, that is, the peelability before and after the heat treatment.
本明細書において、「アルキル（メタ）アクリレートに由来する構成単位」とは、アルキル（メタ）アクリレートに由来する構成単位が付加重合して形成される構成単位を意味する。 In the present specification, the “structural unit derived from alkyl (meth) acrylate” means a structural unit formed by addition polymerization of a structural unit derived from alkyl (meth) acrylate.
（メタ）アクリル系共重合体がアルキル（メタ）アクリレートに由来する構成単位を含む場合、アルキル（メタ）アクリレートは、無置換のアルキル（メタ）アクリレートが好ましく、その種類は特に制限されない。アルキル（メタ）アクリレートのアルキル基は、直鎖状、分岐鎖状又は環状のいずれであってもよい。また、アルキル基の炭素数は、１〜１８の範囲が好ましく、１〜１２の範囲がより好ましく、１〜８の範囲がさらに好ましい。アルキル基の炭素数が前述した範囲内であると、粘着力すなわち加熱処理前と加熱処理後のそれぞれの剥離性をより制御しやすく、保護フィルムとしたときの被着体との濡れ性がより優れる。
アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート及びイソボルニル（メタ）アクリレートが挙げられる。
アルキル（メタ）アクリレートは、１種を単独で使用してもよく、２種以上を併用してもよい。
When the (meth) acrylic copolymer includes a structural unit derived from an alkyl (meth) acrylate, the alkyl (meth) acrylate is preferably an unsubstituted alkyl (meth) acrylate, and the type thereof is not particularly limited. The alkyl group of the alkyl (meth) acrylate may be linear, branched or cyclic. Moreover, the range of 1-18 is preferable, as for carbon number of an alkyl group, the range of 1-12 is more preferable, and the range of 1-8 is more preferable. When the carbon number of the alkyl group is within the above-mentioned range, it is easier to control the adhesive strength, that is, the releasability before and after the heat treatment, and the wettability with the adherend when it is used as a protective film is more Excellent.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth). Acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl ( Examples include meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Alkyl (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.
アルキル（メタ）アクリレートは、粘着力すなわち加熱処理前及び加熱処理後の剥離性をより容易に制御できるとともに、保護フィルムとしたときの被着体への濡れ性の観点から、２−エチルヘキシル（メタ）アクリレート及びｎ−ブチル（メタ）アクリレートが好ましく、２−エチルヘキシルアクリレート及びｎ−ブチルアクリレートがより好ましい。 Alkyl (meth) acrylate can more easily control adhesive strength, that is, peelability before and after heat treatment, and 2-ethylhexyl (meta) from the viewpoint of wettability to an adherend when it is used as a protective film. ) Acrylate and n-butyl (meth) acrylate are preferred, and 2-ethylhexyl acrylate and n-butyl acrylate are more preferred.
（メタ）アクリル系共重合体の全構成単位に占めるアルキル（メタ）アクリレートに由来する構成単位の含有量の割合は、被着体から容易に剥落しない程度に十分な粘着力を粘着剤層に付与できる観点から、全構成単位に対して５５質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上がさらに好ましい。
（メタ）アクリル系共重合体は、アルキル（メタ）アクリレートに由来する構成単位を全構成単位に対して５５質量％以上含むことで、共重合性が良好となり、酸性基を有する単量体に由来する構成単位を共重合体中により均一に分布させ得るため、架橋のムラがより抑制され、被着体への耐汚染性をより改善できる。
The ratio of the content of the structural unit derived from the alkyl (meth) acrylate in the total structural unit of the (meth) acrylic copolymer is sufficient for the pressure-sensitive adhesive layer so that it does not easily peel off from the adherend. From the viewpoint that it can be imparted, 55% by mass or more is preferable, 70% by mass or more is more preferable, and 80% by mass or more is more preferable with respect to all structural units.
The (meth) acrylic copolymer contains 55% by mass or more of a structural unit derived from an alkyl (meth) acrylate with respect to all structural units, whereby the copolymerizability is improved and the monomer having an acidic group is used. Since the derived structural unit can be more uniformly distributed in the copolymer, unevenness in crosslinking is further suppressed, and the stain resistance to the adherend can be further improved.
（メタ）アクリル系共重合体は、本発明の効果が発揮される範囲内において、酸性基を有する単量体に由来する構成単位、アルキレンオキシド鎖を有する単量体に由来する構成単位及びアルキル（メタ）アクリレートに由来する構成単位以外の構成単位（以下、「その他の構成単位」ともいう。）を含んでもよい。
その他の構成単位を構成する単量体の種類は、特に制限されない。
その他の構成単位を構成する単量体としては、例えば、例えば、ベンジル（メタ）アクリレートに代表される芳香族環を有する（メタ）アクリル系単量体、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートに代表される水酸基を有する（メタ）アクリル系単量体、グリシジル（メタ）アクリレートに代表されるグリシジル基を有する（メタ）アクリル系単量体、アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレートに代表される窒素原子を有する（メタ）アクリル系単量体、スチレン、α−メチルスチレンに代表される芳香族モノビニル単量体、アクリロニトリル、メタクリロニトリルに代表されるシアン化ビニル単量体や、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニルに代表されるカルボン酸ビニル単量体が挙げられる。
The (meth) acrylic copolymer is a structural unit derived from a monomer having an acidic group, a structural unit derived from a monomer having an alkylene oxide chain, and an alkyl within the range in which the effects of the present invention are exhibited. A structural unit other than the structural unit derived from (meth) acrylate (hereinafter, also referred to as “other structural unit”) may be included.
The type of monomer constituting other structural units is not particularly limited.
Examples of the monomer constituting the other structural unit include, for example, (meth) acrylic monomers having an aromatic ring represented by benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4 -(Meth) acrylic monomer having a hydroxyl group represented by hydroxybutyl (meth) acrylate, (meth) acrylic monomer having a glycidyl group represented by glycidyl (meth) acrylate, aminoethyl (meth) Acrylate, (meth) acrylic monomer having nitrogen atom typified by dimethylaminoethyl (meth) acrylate, styrene, aromatic monovinyl monomer typified by α-methylstyrene, acrylonitrile, methacrylonitrile Vinyl cyanide monomer, vinyl formate, vinyl acetate, vinyl propionate Carboxylic acid vinyl monomers are exemplified as represented by.
（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）は、被着体への汚染を抑制する観点からは、１０００００以上が好ましく、２０００００以上がより好ましい。また、（メタ）アクリル系共重合体の重量平均分子量は、加熱処理後に生じるジッピングを抑制できる観点及び粘着剤組成物塗工時の揮発性溶媒量を少なくする観点からは、１５０００００以下が好ましく、１００００００以下がより好ましい。（メタ）アクリル系共重合体の数平均分子量（Ｍｎ）に対する（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）の比で表される分散度（Ｍｗ／Ｍｎ）は、特に制限されない。例えば、被着体への汚染を抑制する観点からは、（メタ）アクリル系共重合体の分散度（Ｍｗ／Ｍｎ）は、１〜３０の範囲が好ましい。 The weight average molecular weight (Mw) of the (meth) acrylic copolymer is preferably 100,000 or more and more preferably 200,000 or more from the viewpoint of suppressing contamination of the adherend. In addition, the weight average molecular weight of the (meth) acrylic copolymer is preferably 1500000 or less from the viewpoint of suppressing zipping that occurs after the heat treatment and reducing the amount of volatile solvent at the time of coating the pressure-sensitive adhesive composition. 1000000 or less is more preferable. The dispersity (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) of the (meth) acrylic copolymer to the number average molecular weight (Mn) of the (meth) acrylic copolymer is not particularly limited. For example, from the viewpoint of suppressing contamination of the adherend, the dispersity (Mw / Mn) of the (meth) acrylic copolymer is preferably in the range of 1-30.
なお、（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）は、下記の（１）〜（３）に従って測定される値である。
（１）（メタ）アクリル系共重合体の溶液を剥離紙に塗布し、１００℃で２分間乾燥し、フィルム状の（メタ）アクリル系共重合体を得る。
（２）上記（１）で得られたフィルム状の（メタ）アクリル系共重合体とテトラヒドロフランとを用いて、固形分濃度が０．２質量％である試料溶液を得る。
（３）下記条件にて、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、標準ポリスチレン換算値として、（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）を測定する。
（条件）
ＧＰＣ ：ＨＬＣ−８２２０ ＧＰＣ〔東ソー株式会社製〕
カラム ：ＴＳＫ−ＧＥＬ ＧＭＨＸＬ ４本使用
移動相溶媒：テトラヒドロフラン
流速 ：０．６ｍＬ／分
カラム温度：４０℃
In addition, the weight average molecular weight (Mw) of a (meth) acrylic-type copolymer is a value measured according to following (1)-(3).
(1) A solution of a (meth) acrylic copolymer is applied to release paper and dried at 100 ° C. for 2 minutes to obtain a film-like (meth) acrylic copolymer.
(2) Using the film-like (meth) acrylic copolymer obtained in (1) above and tetrahydrofuran, a sample solution having a solid content concentration of 0.2% by mass is obtained.
(3) The weight average molecular weight (Mw) of the (meth) acrylic copolymer is measured as a standard polystyrene equivalent value using gel permeation chromatography (GPC) under the following conditions.
(conditions)
GPC: HLC-8220 GPC [manufactured by Tosoh Corporation]
Column: 4 TSK-GEL GMHXL used Mobile phase solvent: Tetrahydrofuran Flow rate: 0.6 mL / min Column temperature: 40 ° C
粘着剤組成物における（メタ）アクリル系共重合体の含有率は、目的に応じて適宜選択することができる。（メタ）アクリル系共重合体の含有率は、粘着剤組成物の固形分総質量中に、８０質量％〜９９質量％が好ましく、８５質量％〜９９質量％がより好ましく、９０質量％〜９８質量％が更に好ましい。なお、固形分総質量とは、粘着剤組成物から、溶剤などの揮発性成分を除いた残渣の総質量を意味する。 The content rate of the (meth) acrylic-type copolymer in an adhesive composition can be suitably selected according to the objective. The content of the (meth) acrylic copolymer is preferably 80% by mass to 99% by mass, more preferably 85% by mass to 99% by mass, and more preferably 90% by mass to the total solid content of the pressure-sensitive adhesive composition. 98 mass% is still more preferable. In addition, solid content total mass means the total mass of the residue remove | excluding volatile components, such as a solvent, from an adhesive composition.
（メタ）アクリル系共重合体の製造方法は、特に制限されない。例えば、溶液重合、乳化重合、懸濁重合及び塊状重合に代表される公知の重合方法で、単量体を重合して製造できる。これらの重合方法の中でも、処理方法が比較的簡単であり、かつ、短時間で行える点で溶液重合が好ましい。 The method for producing the (meth) acrylic copolymer is not particularly limited. For example, it can be produced by polymerizing monomers by a known polymerization method represented by solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization. Among these polymerization methods, solution polymerization is preferable because the treatment method is relatively simple and can be performed in a short time.
溶液重合は、一般に、重合槽内に所定の有機溶媒、単量体、重合開始剤、触媒及び必要に応じて連鎖移動剤を仕込み、窒素気流中又は有機溶媒の還流下で、撹拌しながら数時間加熱反応させることで行う。前記重合開始剤としては、特に制限されるものではなく、例えばアゾ系化合物を用いることができる。
なお、前述した（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、反応温度、反応時間、有機溶媒量、触媒の種類や量を調整することにより、所望の分子量に調整できる。
In solution polymerization, a predetermined organic solvent, a monomer, a polymerization initiator, a catalyst, and a chain transfer agent as necessary are generally charged in a polymerization tank, and the number is stirred in a nitrogen stream or under reflux of the organic solvent. The reaction is performed by heating for a period of time. The polymerization initiator is not particularly limited, and for example, an azo compound can be used.
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic copolymer described above are desired by adjusting the reaction temperature, the reaction time, the amount of the organic solvent, and the type and amount of the catalyst. The molecular weight can be adjusted.
＜エポキシ系架橋剤＞
本発明の粘着剤組成物は、エポキシ系架橋剤を含有する。
また、本発明の粘着剤組成物は、前述した（メタ）アクリル系共重合体１００質量部に対し、０．１〜２０質量部のエポキシ系架橋剤を含有することが好ましい。
本発明の粘着剤組成物は、（メタ）アクリル系共重合体１００質量部に対し、エポキシ系架橋剤を０．１質量部以上、より好ましくは１質量部以上、さらに好ましくは５質量部以上含有すれば、前述したとおり（メタ）アクリル系共重合体が含む酸性基を有する単量体に由来する構成単位が架橋するため、本発明の粘着剤組成物の架橋密度が高くなり、被着体である光学部材への汚染をより抑制できるため好ましく、また、２０質量部以下、より好ましくは１０質量部以下、さらに好ましくは８質量部以下含有すれば、架橋密度が過度に高くなりすぎず、前述した加熱処理後に生じるジッピングをより抑制できるため好ましい。
通常エポキシ系架橋剤は、溶液状態で使用される。上記したエポキシ系架橋剤の質量部は、固形分換算値である。
なお、（メタ）アクリル系共重合体のエポキシ系架橋剤による架橋は、例えばイソシアネート系架橋剤を用いた架橋よりも架橋密度が高くなる傾向がある。
<Epoxy-based crosslinking agent>
The pressure-sensitive adhesive composition of the present invention contains an epoxy crosslinking agent.
Moreover, it is preferable that the adhesive composition of this invention contains 0.1-20 mass parts epoxy type crosslinking agent with respect to 100 mass parts of (meth) acrylic-type copolymers mentioned above.
In the pressure-sensitive adhesive composition of the present invention, the epoxy-based crosslinking agent is 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 5 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic copolymer. If contained, since the structural unit derived from the monomer having an acidic group contained in the (meth) acrylic copolymer is crosslinked as described above, the crosslinking density of the pressure-sensitive adhesive composition of the present invention is increased, It is preferable because contamination to the optical member which is a body can be further suppressed, and is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, so that the crosslinking density does not become excessively high. It is preferable because zipping that occurs after the heat treatment described above can be further suppressed.
Usually, the epoxy-based crosslinking agent is used in a solution state. The mass part of the above-described epoxy-based crosslinking agent is a solid content conversion value.
In addition, the crosslinking with an epoxy-based crosslinking agent of a (meth) acrylic copolymer tends to have a higher crosslinking density than a crosslinking using, for example, an isocyanate-based crosslinking agent.
エポキシ系架橋剤としては、例えば、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、レゾルシンジグリシジルエーテル、２，２−ジブロモネオペンチルグリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリトリトールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、アジピン酸ジグリシジルエステル、フタル酸ジグリシジルエステル、トリス（グリシジル）イソシアヌレート、トリス（グリシドキシエチル）イソシアヌレート、１，３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）シクロヘキサン及びＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミンが挙げられる。これらのエポキシ系架橋剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 Examples of the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2 -Dibromoneopentyl glycol diglycidyl ester Ter, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate, tris (glycidoxyethyl) isocyanurate, 1 , 3-bis (N, N-glycidylaminomethyl) cyclohexane and N, N, N ′, N′-tetraglycidyl-m-xylylenediamine. These epoxy crosslinking agents may be used alone or in combination of two or more.
エポキシ系架橋剤が、トリス（グリシジル）イソシアヌレート、トリス（グリシドキシエチル）イソシアヌレート、１，３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）シクロヘキサン及びＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミンから成る群より選ばれる少なくとも１種であれば、粘着剤組成物の透明性がより優れることで光学部材保護フィルム用粘着剤組成物としてより好適となる。 Epoxy crosslinking agents include tris (glycidyl) isocyanurate, tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane and N, N, N ′, N′-tetra. If it is at least 1 sort (s) chosen from the group which consists of glycidyl-m-xylylenediamine, it will become more suitable as an adhesive composition for optical member protective films because the transparency of an adhesive composition is more excellent.
エポキシ系架橋剤は市販品を使用できる。
エポキシ系架橋剤の市販品は、例えば、三菱ガス化学社製 商品名テトラッド−Ｃ、テトラッド−Ｘが挙げられる。
A commercial item can be used for an epoxy type crosslinking agent.
Examples of commercially available epoxy-based crosslinking agents include trade names Tetrad-C and Tetrad-X manufactured by Mitsubishi Gas Chemical Company.
本発明の粘着剤組成物は、本発明の効果が発揮される範囲内において、エポキシ系架橋剤以外の架橋剤、例えば、イソシアネート系架橋剤、金属キレート系架橋剤を含有してもよい。 The pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent other than the epoxy-based crosslinking agent, for example, an isocyanate-based crosslinking agent or a metal chelate-based crosslinking agent within the range in which the effects of the present invention are exhibited.
＜その他の成分＞
本発明の粘着剤組成物は、本発明の効果が発揮される範囲内において、（メタ）アクリル系共重合体及びエポキシ系架橋剤以外の成分を含有してもよい。
前述した（メタ）アクリル系共重合体及びエポキシ系架橋剤以外の成分としては、例えば、溶剤、耐候性安定剤、タッキファイアー、架橋触媒、可塑剤、軟化剤、剥離助剤、染料、顔料、無機充填剤、界面活性剤、帯電防止剤、シランカップリング剤、（メタ）アクリル系共重合体以外のポリマー、重量平均分子量が数百から３万程度のオリゴマー及びポリエーテル変性シリコーンに代表されるシリコーン系剥離調整剤等が挙げられる。
<Other ingredients>
The pressure-sensitive adhesive composition of the present invention may contain components other than the (meth) acrylic copolymer and the epoxy-based crosslinking agent within the range in which the effects of the present invention are exhibited.
Examples of the components other than the (meth) acrylic copolymer and the epoxy crosslinking agent described above include, for example, a solvent, a weather resistance stabilizer, a tackifier, a crosslinking catalyst, a plasticizer, a softening agent, a peeling aid, a dye, a pigment, Typical examples include inorganic fillers, surfactants, antistatic agents, silane coupling agents, polymers other than (meth) acrylic copolymers, oligomers having a weight average molecular weight of about several hundred to 30,000, and polyether-modified silicones. Examples include silicone-based release modifiers.
[光学部材保護フィルム]
本発明の光学部材保護フィルムは、基材と、前記基材上に設けられ本発明の粘着剤組成物に由来する粘着剤層と、を備える。すなわち、本発明の光学部材保護フィルムは、基材と、本発明の粘着剤組成物に由来する粘着剤層と、が積層されている。本発明の光学部材保護フィルムは、本発明の粘着剤組成物に由来する粘着剤層を備えることで、加熱処理後のジッピングを十分に抑制でき、かつ、耐汚染性も優れる。
[Optical member protective film]
The optical member protective film of the present invention includes a base material and a pressure-sensitive adhesive layer provided on the base material and derived from the pressure-sensitive adhesive composition of the present invention. That is, the optical member protective film of the present invention is formed by laminating a base material and a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition of the present invention. By providing the pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition of the present invention, the optical member protective film of the present invention can sufficiently suppress zipping after heat treatment, and is excellent in stain resistance.
本発明の保護フィルムを構成する基材の材料は、特に制限されない。基材の材料としては、透視による光学部材の検査及び管理の観点から、例えば、ポリエステル系樹脂、アセテート系樹脂、ポリエーテルサルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂及びアクリル系樹脂が挙げられる。これらの中でも、基材の材料としては、表面保護性能の観点からは、ポリエステル系樹脂が好ましく、透明性及び耐熱性の観点からは、ポリエチレンテレフタレート系樹脂がより好ましい。 The material of the base material constituting the protective film of the present invention is not particularly limited. As a material of the base material, from the viewpoint of inspection and management of optical members by fluoroscopy, for example, polyester resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, etc. Resin and acrylic resin are mentioned. Among these, as the base material, a polyester resin is preferable from the viewpoint of surface protection performance, and a polyethylene terephthalate resin is more preferable from the viewpoint of transparency and heat resistance.
基材の厚みは、特に制限されず、例えば、５μｍ〜５００μｍの範囲が好ましく、１０μｍ〜２００μｍの範囲がより好ましい。 The thickness in particular of a base material is not restrict | limited, For example, the range of 5 micrometers-500 micrometers is preferable, and the range of 10 micrometers-200 micrometers is more preferable.
基材の片面又は両面には、帯電防止層や易接着処理層を設けてもよい。また基材の、粘着剤層が設けられる側の表面には、粘着剤層との密着性を向上させるためにコロナ放電処理等が施されていてもよい。 An antistatic layer or an easy adhesion treatment layer may be provided on one side or both sides of the substrate. The surface of the substrate on the side where the pressure-sensitive adhesive layer is provided may be subjected to a corona discharge treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer.
基材上には、本発明の粘着剤組成物に由来する粘着剤層が設けられている。
粘着剤層の形成方法としては、例えば、粘着剤組成物を、そのままで又は必要に応じて適宜の溶媒で希釈し、これを基材に塗布した後、乾燥して溶媒を除去する方法を採用することができる。
また、先ず、シリコーン樹脂等により離型処理が施された紙又はポリエステルフィルム等の適宜のフィルムからなる剥離シートの上に粘着剤組成物を塗布し、加熱乾燥して粘着剤層を形成し、次に、剥離シートの粘着剤層側を基材に圧接して、粘着剤層を基材に転写させる方法を採用することもできる。
On the base material, a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition of the present invention is provided.
As a method for forming the pressure-sensitive adhesive layer, for example, a method is adopted in which the pressure-sensitive adhesive composition is diluted as it is or with an appropriate solvent as necessary, and this is applied to a substrate and then dried to remove the solvent. can do.
First, the pressure-sensitive adhesive composition is applied onto a release sheet made of an appropriate film such as paper or polyester film that has been subjected to a release treatment with a silicone resin or the like, and dried by heating to form a pressure-sensitive adhesive layer. Next, it is also possible to employ a method in which the pressure-sensitive adhesive layer side of the release sheet is pressed against the base material and the pressure-sensitive adhesive layer is transferred to the base material.
本発明における粘着剤層は、架橋剤によって、（メタ）アクリル系共重合体が架橋されてなる粘着剤層である。（メタ）アクリル系共重合体をエポキシ系架橋剤で架橋する条件は特に制限されない。例えば、２３℃、５０％ＲＨの環境下で、４〜１４日間養生することで、粘着剤組成物の架橋反応が終了し、粘着剤層が形成される。 The pressure-sensitive adhesive layer in the present invention is a pressure-sensitive adhesive layer obtained by crosslinking a (meth) acrylic copolymer with a crosslinking agent. Conditions for crosslinking the (meth) acrylic copolymer with an epoxy crosslinking agent are not particularly limited. For example, by curing for 4 to 14 days in an environment of 23 ° C. and 50% RH, the crosslinking reaction of the pressure-sensitive adhesive composition is completed, and a pressure-sensitive adhesive layer is formed.
基材上に形成される粘着剤層の厚さは、光学部材保護フィルムに求められる粘着力、光学部材の表面粗さ等に応じて適宜設定することができる。粘着剤層の厚さとしては、一般に、１μｍ〜１００μｍであり、好ましくは５μｍ〜５０μｍ、更に好ましくは１５μｍ〜３０μｍ程度を例示することができる。 The thickness of the pressure-sensitive adhesive layer formed on the substrate can be appropriately set according to the adhesive force required for the optical member protective film, the surface roughness of the optical member, and the like. The thickness of the pressure-sensitive adhesive layer is generally 1 μm to 100 μm, preferably 5 μm to 50 μm, more preferably about 15 μm to 30 μm.
粘着剤層のゲル分率は、粘着力の観点から、８０質量％以上１００質量％以下の範囲が好ましく、９０質量％以上１００質量％以下の範囲がより好ましい。 The gel fraction of the pressure-sensitive adhesive layer is preferably in the range of 80% by mass to 100% by mass and more preferably in the range of 90% by mass to 100% by mass from the viewpoint of adhesive strength.
本発明の保護フィルムは、被着体である光学部材に積層して用いられる。被着体である光学部材は、液晶表示装置や有機エレクトロルミネッセンス（ＥＬ）表示装置に代表される各種表示装置を構成する部材又はタッチパネルに代表される各種入力装置機器に用いられる部材が挙げられる。このような光学部材は、例えば、偏光板、波長板、位相差板、光学補償フィルム、輝度向上フィルム、光拡散フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム（ＩＴＯフィルム）、意匠フィルム、装飾フィルム、ハードコートフィルム、カラーフィルター、センサー付きガラス基板、フレキシブルプリント基板及びリジッドプリント配線基板が挙げられる。
なお、各種光学部材の材質は特に制限はない。例えば偏光板表面の材質としては、トリアセチルセルロース（ＴＡＣ）、ポリエチレンテレフタレートに代表されるポリエステル樹脂、アクリル樹脂、ノルボルネン系樹脂が挙げられる。
The protective film of the present invention is used by being laminated on an optical member that is an adherend. Examples of the optical member that is an adherend include members constituting various display devices typified by liquid crystal display devices and organic electroluminescence (EL) display devices, and members used in various input device devices typified by touch panels. Such optical members include, for example, a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light diffusion film, a light guide plate, a reflection film, an antireflection film, a transparent conductive film (ITO film), and a design. Examples include films, decorative films, hard coat films, color filters, glass substrates with sensors, flexible printed boards, and rigid printed wiring boards.
In addition, the material of various optical members is not particularly limited. For example, examples of the material for the polarizing plate surface include triacetyl cellulose (TAC), polyester resins typified by polyethylene terephthalate, acrylic resins, and norbornene resins.
本発明の保護フィルムは、光学部材と積層後、例えば１００℃〜２５０℃の範囲で加熱処理して用いられることが好ましい。本発明の保護フィルムは、例えば１００℃〜２５０℃の加熱処理工程においては光学部材の表面を保護又は補強し、加熱処理工程後においてはジッピングを生じることなく容易に剥がすことができる。 The protective film of the present invention is preferably used after being laminated with the optical member, for example, by heat treatment in the range of 100 ° C to 250 ° C. The protective film of the present invention protects or reinforces the surface of the optical member in a heat treatment step of, for example, 100 ° C. to 250 ° C., and can be easily peeled off without causing zipping after the heat treatment step.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はその主旨を超えない限り、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
（製造例Ａ−１）
温度計、攪拌機、窒素導入管及び逐次滴下装置を備えた反応容器内に、酢酸エチル７０質量部を入れた。また、別の容器に単量体としてｎ−ブチルアクリレート（ＢＡ）８９質量部、酸性基を有する単量体としてアクリル酸（ＡＡ）６質量部、アルキレンオキシド鎖を有する単量体としてメトキシポリエチレングリコールアクリレート[共栄社化学社製、商品名ライトアクリレート１３０Ａ]５質量部を入れ、混合して単量体混合物とした。この単量体混合物の中の２０質量％を反応容器中に加え、次いで反応容器の空気を窒素ガスで置換した後、重合開始剤としてアゾビスイソブチロニトリル（以下、「ＡＩＢＮ」ともいう。）０．０１質量部を添加して、攪拌下に窒素雰囲気中で、前記反応容器内の混合物温度を８６℃に昇温させて、初期反応を開始させた。初期反応がほぼ終了した後、残りの単量体混合物８０質量％、酢酸エチル２０質量部及びＡＩＢＮ０．０７質量部の混合物をそれぞれ逐次添加しながら約２時間反応させ、引き続いて、さらに２時間反応させた。その後、酢酸エチル２５質量部にＡＩＢＮ０．１２質量部を溶解させた溶液を１時間かけて滴下し、さらに１．５時間反応させた。反応終了後、トルエン６０質量部を添加し、その後攪拌することで、（メタ）アクリル系共重合体（Ａ−１）の溶液を得た。（メタ）アクリル系共重合体（Ａ−１）の溶液の固形分は４０．０質量％であった。また、重量平均分子量は５０万であった。
なお、「固形分」とは（メタ）アクリル系共重合体の溶液から溶媒を除去した残渣である。
(Production Example A-1)
70 mass parts of ethyl acetate was put in the reaction container provided with the thermometer, the stirrer, the nitrogen introducing tube, and the sequential dripping apparatus. In another container, 89 parts by mass of n-butyl acrylate (BA) as a monomer, 6 parts by mass of acrylic acid (AA) as a monomer having an acidic group, and methoxypolyethylene glycol as a monomer having an alkylene oxide chain 5 parts by mass of acrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name Light Acrylate 130A] was added and mixed to obtain a monomer mixture. 20% by mass of the monomer mixture is added to the reaction vessel, and then the air in the reaction vessel is replaced with nitrogen gas. Then, azobisisobutyronitrile (hereinafter also referred to as “AIBN”) is used as a polymerization initiator. ) 0.01 parts by mass was added, and the temperature of the mixture in the reaction vessel was raised to 86 ° C. in a nitrogen atmosphere with stirring to initiate an initial reaction. After the initial reaction was almost completed, the mixture was reacted for about 2 hours while sequentially adding the remaining 80% by weight of the monomer mixture, 20 parts by weight of ethyl acetate and 0.07 parts by weight of AIBN, and then the reaction was continued for another 2 hours. I let you. Thereafter, a solution prepared by dissolving 0.12 parts by mass of AIBN in 25 parts by mass of ethyl acetate was added dropwise over 1 hour, and the mixture was further reacted for 1.5 hours. After completion of the reaction, 60 parts by mass of toluene was added, followed by stirring to obtain a solution of (meth) acrylic copolymer (A-1). The solid content of the solution of the (meth) acrylic copolymer (A-1) was 40.0% by mass. The weight average molecular weight was 500,000.
The “solid content” is a residue obtained by removing the solvent from the solution of the (meth) acrylic copolymer.
[製造例（Ａ−２）〜（Ａ−９）]
製造例（Ａ−１）において、表１に示す単量体組成に変更し、開始剤量他を適宜調整したこと以外は、製造例（Ａ−１）と同様にして、（メタ）アクリル系共重合体（Ａ−２）〜（Ａ−９）の溶液を製造した。
[Production Examples (A-2) to (A-9)]
In Production Example (A-1), the (meth) acrylic type was changed in the same manner as in Production Example (A-1) except that the monomer composition shown in Table 1 was changed and the initiator amount and the like were appropriately adjusted. Solutions of copolymers (A-2) to (A-9) were produced.
表１における略号は以下のとおりである。なお、表１中の「−」は、該当の成分を含まないことを示す。
・２ＥＨＡ：２−エチルヘキシルアクリレート
・ＢＡ：ｎ−ブチルアクリレート
・ＡＡ：アクリル酸
・ＭｅＰＥＧＡ：メトキシポリエチレングリコールアクリレート（アルキレンオキシド単位の平均付加モル数は９）
Abbreviations in Table 1 are as follows. In addition, "-" in Table 1 indicates that the corresponding component is not included.
2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate AA: acrylic acid MePEGA: methoxypolyethylene glycol acrylate (average number of moles of alkylene oxide units added is 9)
＜実施例１＞
攪拌羽根、温度計、冷却器、滴下ロートを備えた四つ口フラスコに製造例Ａ−１で調製した、（メタ）アクリル系共重合体（Ａ−１）の溶液（固形分４０．０質量％）を２５０．０質量部（固形分として１００質量部）、エポキシ系架橋剤としてＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン[三菱ガス化学社製 商品名テトラッド−Ｘ、固形分２０質量％]３０．０質量部（固形分換算６．０質量部）を添加し、十分に攪拌して粘着剤組成物溶液を得た。実施例１の粘着剤組成物における酸性基を有する単量体に対する架橋剤当量は０．７２である。
この粘着剤組成物溶液を用いて、以下の試験用保護フィルムの作製方法に従い、試験用保護フィルムを作製し、各種物性試験を行った。得られた結果を表２に示す。
<Example 1>
A solution of (meth) acrylic copolymer (A-1) prepared in Production Example A-1 in a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel (solid content: 40.0 mass %) 250.0 parts by mass (100 parts by mass as a solid content), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine [trade name Tetrad- manufactured by Mitsubishi Gas Chemical Co., Ltd.] as an epoxy-based crosslinking agent X, solid content 20% by mass] 30.0 parts by mass (6.0 parts by mass in terms of solid content) was added and sufficiently stirred to obtain an adhesive composition solution. The crosslinking agent equivalent with respect to the monomer which has an acidic group in the adhesive composition of Example 1 is 0.72.
Using this pressure-sensitive adhesive composition solution, a test protective film was prepared according to the following method for preparing a test protective film, and various physical property tests were performed. The obtained results are shown in Table 2.
[評価]
（１）試験用保護フィルムの作製
基材として、ポリエチレンテレフタレート（ＰＥＴ）フィルム（商品名：ルミラーＵ３５、東レ社製、厚み１２５μｍ）上に、乾燥後の塗工量が２０ｇ／ｍ２となるように粘着剤組成物を塗工し、１００℃で６０秒間熱風循環式乾燥機にて乾燥させた。次いで、粘着剤組成物を塗工したＰＥＴフィルムと、シリコーン系離型剤で表面処理された離型フィルム（商品名：フィルムバイナ１００Ｅ−００１０ＮＯ２３、厚み１００μｍ、藤森工業社製）とを、粘着剤組成物が塗工された面が離型フィルムの表面処理面に接するように重ね合せて積層体とした。この積層体を加圧ニップロール対に通して圧着して貼り合わせた後、２３℃、５０％ＲＨの条件下で７日間、架橋反応が完了するまで養生して試験用保護フィルムを作製した。
[Evaluation]
(1) Preparation of test protective film As a base material, on a polyethylene terephthalate (PET) film (trade name: Lumirror U35, manufactured by Toray Industries, Inc., thickness 125 μm), the coating amount after drying is 20 g / m 2. The pressure-sensitive adhesive composition was applied to the film and dried at 100 ° C. for 60 seconds with a hot air circulation dryer. Next, the PET film coated with the pressure-sensitive adhesive composition and the release film surface-treated with a silicone-based release agent (trade name: film binder 100E-0010NO23, thickness 100 μm, manufactured by Fujimori Kogyo Co., Ltd.) The laminate was laminated so that the surface coated with the composition was in contact with the surface-treated surface of the release film. The laminate was pressed and bonded through a pair of pressure nip rolls, and then cured under conditions of 23 ° C. and 50% RH for 7 days until the crosslinking reaction was completed, thereby producing a test protective film.
（２）剥離性
上記で作製した試験用保護フィルムを２５ｍｍ×１５０ｍｍの大きさに切断し、得られた試験用保護フィルム片から離型フィルムを剥がし、ハードコート処理されたＰＥＴフィルム（商品名：ＫＢフィルムＧ０１Ｓ、きもと社製）のハードコート処理された面に貼り合わせ、２ｋｇのゴムローラーを１往復して圧着し、試験片を得た。この試験片を２３℃、５０％ＲＨ環境下で１時間放置して、加熱処理前の剥離性の試験片とした。また、別の試験片を準備し、同様に２３℃、５０％ＲＨ環境下で１時間放置後、１５０℃環境下で６０分間加熱処理を行い、続いて２３℃、５０％ＲＨ環境下で１時間放置して加熱処理後の剥離性の試験片とした。
それぞれの試験片について、長辺（１５０ｍｍ）方向に剥離した場合の１８０°剥離における粘着力（単位：Ｎ／２５ｍｍ）を剥離速度１０ｍ／分の条件で測定し、以下の評価基準に従って、剥離性を評価した。評価結果を表２に示す。粘着力の大きさにより、加熱処理後の剥離性の優劣を評価した。加熱処理前及び加熱処理後のいずれにおいても、試験用保護フィルムの粘着力が過度に高い場合、被着体から剥離できず、剥離性が劣り、保護フィルムとして不適である。また、粘着力が過度に低い場合、被着体から意図せぬ剥落が生じやすく、剥離性が劣り、保護フィルムとして不適である。
なお、「／」を挟んで２つの値が記載されている評価結果は、ジッピングにより２つの値の間で粘着力が変動したことを示している。
(2) Peelability The protective film for test prepared above was cut into a size of 25 mm × 150 mm, the release film was peeled off from the obtained protective film piece for test, and a hard-coated PET film (trade name: Bonded to the surface of the KB film G01S (produced by Kimoto Co., Ltd.) that had been hard-coated, and a 2 kg rubber roller was reciprocated once for pressure bonding to obtain a test piece. This test piece was left for 1 hour in an environment of 23 ° C. and 50% RH to obtain a peelable test piece before heat treatment. In addition, another test piece was prepared, similarly, left for 1 hour in an environment of 23 ° C. and 50% RH, and then heat-treated in an environment of 150 ° C. for 60 minutes, followed by 1 in an environment of 23 ° C. and 50% RH. It was left for a period of time to obtain a peelable test piece after heat treatment.
About each test piece, the adhesive force (unit: N / 25mm) in 180 degree peeling at the time of peeling in a long side (150mm) direction was measured on condition of peeling speed 10m / min, and peelability according to the following evaluation criteria Evaluated. The evaluation results are shown in Table 2. The superiority or inferiority of the peelability after the heat treatment was evaluated according to the magnitude of the adhesive strength. Before and after the heat treatment, if the adhesive strength of the test protective film is excessively high, the test film cannot be peeled off from the adherend, and the peelability is poor, making it unsuitable as a protective film. Moreover, when adhesive force is too low, it will be easy to produce unintentional peeling from a to-be-adhered body, peelability is inferior, and it is unsuitable as a protective film.
In addition, the evaluation result in which two values are described with “/” interposed therebetween indicates that the adhesive force varies between the two values due to zipping.
−評価基準−
（剥離性）
ＡＡ：加熱処理前及び加熱処理後の粘着力がいずれも０．０５Ｎ／２５ｍｍ以上かつ０．５Ｎ／２５ｍｍ未満であり、加熱処理前及び加熱処理後のいずれも剥離性に優れる。
Ａ：上記ＡＡの基準を満たさず、加熱処理前及び加熱処理後の粘着力がいずれも０．０５Ｎ／２５ｍｍ以上かつ１．０Ｎ／２５ｍｍ未満であり、加熱処理前及び加熱処理後のいずれも剥離性が良好である。
Ｂ：加熱処理前または加熱処理後の少なくとも一方の粘着力が１．０Ｎ／２５ｍｍ以上であり、加熱処理前及び加熱処理後の少なくとも一方の剥離性が劣り、保護フィルムとして不適である。
Ｃ：加熱処理前または加熱処理後の少なくとも一方の粘着力が０．０５Ｎ／２５ｍｍ未満であり、加熱処理前及び加熱処理後の少なくとも一方の剥離性が劣り、保護フィルムとして不適である。
-Evaluation criteria-
(Peelability)
AA: The adhesive strength before heat treatment and after heat treatment is both 0.05 N / 25 mm or more and less than 0.5 N / 25 mm, and both the heat treatment before and after heat treatment are excellent in peelability.
A: The adhesive strength before and after the heat treatment does not satisfy the above AA standard, and both are 0.05 N / 25 mm or more and less than 1.0 N / 25 mm, and both before and after the heat treatment are peeled off. Good properties.
B: At least one adhesive strength before heat treatment or after heat treatment is 1.0 N / 25 mm or more, and at least one peelability before heat treatment and after heat treatment is inferior, and is unsuitable as a protective film.
C: At least one adhesive strength before heat treatment or after heat treatment is less than 0.05 N / 25 mm, and at least one peelability before heat treatment and after heat treatment is inferior, and is unsuitable as a protective film.
（３）ジッピング
上記の「（２）剥離性」において、加熱処理後の粘着力測定後における被着体の状態を、以下の基準で評価した。評価結果を表２に示す。
(3) Zipping In the above “(2) peelability”, the state of the adherend after the measurement of the adhesive strength after the heat treatment was evaluated according to the following criteria. The evaluation results are shown in Table 2.
−評価基準−
（ジッピング）
Ａ：加熱処理後の粘着力測定時に剥離音が発生せず、測定後の被着体に息を吹きかけた後の状態を目視で観察したところ、試験用保護フィルムの剥離痕（ジッピングライン）が見えない。
Ｂ：加熱処理後の粘着力測定時に剥離音が発生し、測定後の被着体に息を吹きかけた後の状態を目視で観察したところ、試験用保護フィルムの剥離痕（ジッピングライン）が見える。
-Evaluation criteria-
(Zipping)
A: No peeling sound was generated during the measurement of the adhesive strength after the heat treatment, and the state after blowing on the adherend after the measurement was visually observed. The peeling mark (zipping line) of the test protective film I can't see.
B: A peeling sound was generated during the measurement of the adhesive strength after the heat treatment, and when the state after blowing on the adherend after the measurement was visually observed, peeling marks (zipping lines) of the test protective film were found. appear.
（４）耐汚染性
上記の「（２）剥離性」において、試験片から試験用保護フィルムを剥離した後のハードコート処理されたＰＥＴフィルムのハードコート処理面上に、２μＬの純水を滴下し、滴下から３０秒後に、接触角測定装置（装置名：Ｄｒｏｐ Ｍａｓｔｅｒ ＤＭ−７０１、協和界面科学社製）を用いて、水の接触角（θ１）を測定した。
得られた値を耐汚染性の指標とし、以下の基準に従って評価した。評価結果を表２に示す。
(4) Contamination resistance In the above “(2) Peelability”, 2 μL of pure water is dropped onto the hard coat treated surface of the hard coat treated PET film after the test protective film is peeled from the test piece. Then, 30 seconds after the dropping, the contact angle (θ1) of water was measured using a contact angle measuring device (device name: Drop Master DM-701, manufactured by Kyowa Interface Science Co., Ltd.).
The obtained value was used as an index of contamination resistance and evaluated according to the following criteria. The evaluation results are shown in Table 2.
−評価基準−
Ａ：θ１が７５°以下であり、耐汚染性が優れる。
Ｂ：θ１が８０°未満であり、耐汚染性が劣る。
Ｃ：θ１が８０°以上であり、耐汚染性が非常に劣る。
-Evaluation criteria-
A: θ1 is 75 ° or less, and the stain resistance is excellent.
B: θ1 is less than 80 ° and the stain resistance is poor.
C: θ1 is 80 ° or more, and the stain resistance is very poor.
＜実施例２〜５及び比較例１〜４＞
各実施例２〜５及び各比較例１〜４では、実施例１における（メタ）アクリル系共重合体の組成及びエポキシ系架橋剤の部数を表２に示すものにした以外は、実施例１と同様にして粘着剤組成物を得た。
なお、表２におけるエポキシ系架橋剤の部数は、固形分換算値である。
得られた粘着剤組成物を用い、実施例１と同様にして、試験用保護フィルムを作製した。そして、作製した試験用保護フィルムについて、実施例１と同様にして、加熱処理前及び加熱処理後のそれぞれの剥離性、ジッピング、耐汚染性の評価を行った。評価結果を表２に示す。
<Examples 2-5 and Comparative Examples 1-4>
In each of Examples 2 to 5 and Comparative Examples 1 to 4, Example 1 except that the composition of the (meth) acrylic copolymer and the number of parts of the epoxy-based crosslinking agent in Example 1 are those shown in Table 2. In the same manner as above, a pressure-sensitive adhesive composition was obtained.
In addition, the number of parts of the epoxy-based crosslinking agent in Table 2 is a solid content conversion value.
A test protective film was produced in the same manner as in Example 1 using the obtained pressure-sensitive adhesive composition. And about the produced test protective film, it carried out similarly to Example 1, and evaluated each peelability before heat processing, and after heat processing, zipping, and stain resistance. The evaluation results are shown in Table 2.
表２に示すように、実施例１〜５の粘着剤組成物は、いずれも、加熱処理後のジッピングを十分抑制でき、加熱処理前及び加熱処理後の剥離性が良好で、かつ、耐汚染性が優れるため、光学部材保護フィルム用の粘着剤組成物として適している。
一方、アルキレンオキシド鎖を有する単量体に由来する構成単位を含まない（メタ）アクリル系共重合体を含有する比較例１の粘着剤組成物は、加熱処理前及び加熱処理後のそれぞれの粘着力が過度に小さく剥離性が劣り、加熱処理後にジッピングが生じたため、光学部材保護フィルム用の粘着剤組成物として不適であった。
また、アルキレンオキシド鎖を有する単量体に由来する構成単位を含まない（メタ）アクリル系共重合体を含有する比較例２の粘着剤組成物は、加熱処理後にジッピングが生じたため、光学部材保護フィルム用の粘着剤組成物として不適であった。
また、酸性基を有する単量体に由来する構成単位の含有量が（メタ）アクリル系共重合体１００質量％に対し３質量％未満である比較例３の粘着剤組成物は、粘着力が過度に高く加熱処理後の剥離性が劣り、かつ耐汚染性が劣るため、光学部材保護フィルム用の粘着剤組成物として不適であった。
さらに、酸性基を有する単量体に由来する構成単位の含有量が（メタ）アクリル系共重合体１００質量％に対し９質量％を超える比較例４の粘着剤組成物は、加熱処理前及び加熱処理後の粘着力が過度に小さく剥離性が劣り、かつ加熱処理後にジッピングが生じたため、光学部材保護フィルム用の粘着剤組成物として不適であった。
As shown in Table 2, each of the pressure-sensitive adhesive compositions of Examples 1 to 5 can sufficiently suppress zipping after heat treatment, has good peelability before and after heat treatment, and is resistant to contamination. Due to its excellent properties, it is suitable as a pressure-sensitive adhesive composition for an optical member protective film.
On the other hand, the pressure-sensitive adhesive composition of Comparative Example 1 containing a (meth) acrylic copolymer that does not contain a structural unit derived from a monomer having an alkylene oxide chain is the pressure-sensitive adhesive before and after the heat treatment. Since the force was excessively small and the peelability was poor, and zipping occurred after the heat treatment, it was unsuitable as a pressure-sensitive adhesive composition for an optical member protective film.
In addition, the pressure-sensitive adhesive composition of Comparative Example 2 containing a (meth) acrylic copolymer not containing a structural unit derived from a monomer having an alkylene oxide chain was protected from optical members because zipping occurred after heat treatment. It was unsuitable as an adhesive composition for films.
Moreover, the pressure-sensitive adhesive composition of Comparative Example 3 in which the content of the structural unit derived from the monomer having an acidic group is less than 3% by mass with respect to 100% by mass of the (meth) acrylic copolymer has an adhesive strength. Since it was excessively high and the peelability after heat treatment was poor and the stain resistance was poor, it was unsuitable as a pressure-sensitive adhesive composition for an optical member protective film.
Furthermore, the pressure-sensitive adhesive composition of Comparative Example 4 in which the content of the structural unit derived from the monomer having an acidic group exceeds 9% by mass with respect to 100% by mass of the (meth) acrylic copolymer, Since the adhesive strength after the heat treatment was excessively small and the peelability was poor, and zipping occurred after the heat treatment, it was unsuitable as a pressure-sensitive adhesive composition for an optical member protective film.
Claims (5)
アルキレンオキシド鎖を有する単量体に由来する構成単位と、を含む、（メタ）アクリル系共重合体と、
エポキシ系架橋剤と、を含有し、
前記（メタ）アクリル系共重合体の全構成単位１００質量％に対して、前記酸性基を有する単量体に由来する構成単位を３〜９質量％含む、
光学部材保護フィルム用粘着剤組成物。 A structural unit derived from a monomer having an acidic group;
A structural unit derived from a monomer having an alkylene oxide chain, and a (meth) acrylic copolymer,
An epoxy-based crosslinking agent,
Containing 3 to 9% by mass of a structural unit derived from the monomer having an acidic group with respect to 100% by mass of all the structural units of the (meth) acrylic copolymer,
An adhesive composition for an optical member protective film.
請求項１〜請求項４のいずれか１項に記載の光学部材保護フィルム用粘着剤組成物に由来する粘着剤層と、を備えた光学部材保護フィルム。 A substrate;
An optical member protective film comprising: a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition for an optical member protective film according to any one of claims 1 to 4.
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| JP2005200540A (en) * | 2004-01-15 | 2005-07-28 | Nitto Denko Corp | Pressure sensitive adhesive composition and surface protection film using it |
| JP2005314579A (en) * | 2004-04-30 | 2005-11-10 | Nitto Denko Corp | Adhesive composition and adhesive sheets |
| WO2016027787A1 (en) * | 2014-08-18 | 2016-02-25 | 日本合成化学工業株式会社 | Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking |
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| JP2005200540A (en) * | 2004-01-15 | 2005-07-28 | Nitto Denko Corp | Pressure sensitive adhesive composition and surface protection film using it |
| JP2005314579A (en) * | 2004-04-30 | 2005-11-10 | Nitto Denko Corp | Adhesive composition and adhesive sheets |
| WO2016027787A1 (en) * | 2014-08-18 | 2016-02-25 | 日本合成化学工業株式会社 | Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking |
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| WO2020021920A1 (en) * | 2018-07-23 | 2020-01-30 | 東洋インキＳｃホールディングス株式会社 | Adhesive agent and adhesive sheet |
| CN112449649A (en) * | 2018-07-23 | 2021-03-05 | 东洋油墨Sc控股株式会社 | Adhesive and adhesive sheet |
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