JP2015096579A - 光学フィルム用水分散型粘着剤組成物、粘着剤層、粘着型光学フィルム、及び、画像表示装置 - Google Patents
光学フィルム用水分散型粘着剤組成物、粘着剤層、粘着型光学フィルム、及び、画像表示装置 Download PDFInfo
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- JP2015096579A JP2015096579A JP2013237192A JP2013237192A JP2015096579A JP 2015096579 A JP2015096579 A JP 2015096579A JP 2013237192 A JP2013237192 A JP 2013237192A JP 2013237192 A JP2013237192 A JP 2013237192A JP 2015096579 A JP2015096579 A JP 2015096579A
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- optical film
- monomer
- acrylic copolymer
- acrylic
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- VEYCPJGKKJULEP-UHFFFAOYSA-N prop-2-enoic acid sulfuric acid Chemical compound OC(=O)C=C.OS(O)(=O)=O VEYCPJGKKJULEP-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
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- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SYYDEXILBJXXIA-UHFFFAOYSA-N trimethoxy(pent-4-enyl)silane Chemical compound CO[Si](OC)(OC)CCCC=C SYYDEXILBJXXIA-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
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Abstract
Description
前記(メタ)アクリル系共重合体(B)に含まれる芳香族環含有(メタ)アクリル系モノマーが、(メタ)アクリル系共重合体(A)及び(メタ)アクリル系共重合体(B)を構成する全モノマーに対して1〜28重量%であることを特徴とする光学フィルム用水分散型粘着剤組成物に関する。
本発明の光学フィルム用水分散型粘着剤組成物は、同一エマルション粒子内に、(メタ)アクリル酸アルキルエステルをモノマー単位として含有する(メタ)アクリル系共重合体(A)がコア層、芳香族環含有(メタ)アクリル系モノマー及び(メタ)アクリル酸アルキルエステルをモノマー単位として含有する(メタ)アクリル系共重合体(B)がシェル層として存在する、コアシェル構造のエマルション粒子を含有し、
前記(メタ)アクリル系共重合体(B)に含まれる芳香族環含有(メタ)アクリル系モノマーが、(メタ)アクリル系共重合体(A)及び(メタ)アクリル系共重合体(B)を構成する全モノマーに対して1〜28重量%であることを特徴とする。
FOXの式:
本発明の粘着剤層は、上記光学フィルム用水分散型粘着剤組成物により形成される。粘着剤層の形成は、支持基材(光学フィルム又は離型フィルム)に上記光学フィルム用水分散型粘着剤組成物を塗布した後、乾燥することより形成することができる。
本発明の粘着型光学フィルムは、光学フィルム片面又は両面に前記粘着剤層を積層したものである。本発明の粘着型光学フィルムは、前述の方法により、光学フィルム用水分散型粘着剤組成物を光学フィルム又は離型フィルムに塗布し、乾燥することにより形成される。粘着剤層を離型フィルムに形成した場合には、当該粘着剤層は光学フィルムに貼り合せて転写する。
本発明の粘着型光学フィルムは、液晶表示装置等の各種画像表示装置の形成などに好ましく用いることができる。液晶表示装置の形成は、従来に準じて行いうる。即ち、液晶表示装置は一般に、液晶セル等と粘着型光学フィルム、及び必要に応じての照明システム等の構成部品を適宜に組み立てて駆動回路を組み込むことなどにより形成されるが、本発明においては本発明による粘着型光学フィルムを用いる点を除いて特に限定は無く、従来に準じうる。液晶セルについても、例えばTN型やSTN型、π型、VA型、IPS型などの任意なタイプのものを用いうる。
エポクロスWS700((株)日本触媒製)を、イソプロピルアルコール(IPA)と水の混合液(IPA/水(重量比)=1/1)で希釈して、0.25重量%のエポクロスWS700溶液を調製した。これを偏光フィルム(商品名:SEG−DU、日東電工(株)製)にMayer rodにて塗布し、40℃で1分間加熱処理して、厚さ50nmの下塗り層を有する偏光フィルムを製造した。
(モノマーエマルション(1)の調製)
ガラス製のビーカーに、原料として、アクリル酸ブチル130部、メタクリル酸メチル800部、メタクリル酸シクロヘキシル50部、アクリル酸20部、3−メタクリロイルオキシプロピル−トリエトキシシラン(商品名:KBM−503、信越化学工業(株)製)0.4部、アクアロンHS−1025(25%水溶液、第一工業製薬(株)製)440部、および水4150部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルション(1)を調製した。
ガラス製のビーカーに、原料として、アクリル酸ブチル767部、アクリル酸ベンジル(商品名:ビスコート#160、大阪有機化学(株)製)100部、メタクリル酸シクロヘキシル50部、リン酸基含有モノマー(商品名:SipomerPAM200、ローディア日華(株)製)25部、アクリル酸58部、3−メタクリロイルオキシプロピル−トリエトキシシラン(商品名:KBM−503、信越化学工業(株)製)0.4部、アクアロンHS−1025(25%水溶液、第一工業製薬(株)製)40部、および水1080部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルション(2)を調製した。
冷却管、窒素導入管、温度計、滴下ロートおよび攪拌羽根を備えた反応容器に、上記で調製したモノマーエマルション(1)のうちの559部を仕込み、次いで、反応容器を十分窒素置換した後、内浴温度を65℃に調整した。次いで、アンモニウムペルオキソ硫酸ナトリウム(APS)水溶液(5%)を固形分で0.1部を添加した後、撹拌即150rpmで撹拌しながら一括重合(内浴温度:65℃、重合時間:2時間)を行った。一括重合後、アンモニウムペルオキソ硫酸ナトリウム(APS)水溶液(5%)固形分で0.5部を添加した後、内浴温度を65℃に保ちながら、10分重合し、コア層となる共重合体を得た。次いで、内浴温度を65℃に保ちながらモノマーエマルション(2)のうちの848部を3時間かけて滴下し、その後3時間重合してシェル層を形成し、コアシェル構造のポリマーエマルション粒子を含有する水分散液を得た。次いで、上記コアシェル構造のポリマーエマルション粒子を含有する水分散液を室温まで冷却した後、これに濃度10%のアンモニア水を添加してpH7.8に調整し、コアシェル構造のエマルション粒子を含有する水分散型粘着剤組成物を得た。得られたポリマーエマルション粒子の体積平均粒子径は、108nmであった。
調製した水分散型粘着剤組成物を、シリコーン系剥離剤を塗布した厚さ38μmのフィルム(商品名:MRF38、三菱化学ポリエステル(株)製)に、ダイ方式(塗工速度:5m/分)で塗工し、120℃で2分間乾燥して、厚さ25μmの粘着剤層を形成した。これを製造例1で得られた下塗り層を有する偏光フィルムの下塗り層上に転写して粘着型光学用フィルムを形成した。
実施例1の(モノマーエマルション(2)の調製)において、モノマーエマルション(2)の組成を表1に記載の組成に変更した以外は、実施例1と同様にして粘着型光学用フィルムを形成した。
(モノマーエマルションの調製)
容器に原料として、アクリル酸ブチル720部、メタクリル酸メチル160部、メタクリル酸シクロヘキシル50部、リン酸基含有モノマー(商品名:SipomerPAM200、ローディア日華(株)製)20部、アクリル酸50部、3−メタクリロイルオキシプロピル−トリエトキシシラン(商品名:KBM−503、信越化学工業(株)製)0.4部、アクアロンHS−1025(25%水溶液、第一工業製薬(株)製)40部、および水1080部を加えて、ホモミキサー(特殊機化工業(株)製)を用い、5分間、6000rpmで攪拌し、モノマーエマルション(3)を調製した。
冷却管、窒素導入管、温度計、滴下ロートおよび攪拌羽根を備えた反応容器に、水307部、アクアロンHS−1025(第一工業製薬(株)製)40部を添加し、窒素雰囲気下で60分、150rpmで撹拌した。次いで、上記で調製したモノマーエマルション(3)のうちの212部を添加して、内浴温度を65℃にして、アンモニウムペルオキソ硫酸ナトリウム(APS)水溶液(5%)を固形分で0.01部添加した後、撹拌速度150rpmで撹拌しながら一括重合(内浴温度:65℃、重合時間:2時間)を行った。一括重合後、アンモニウムペルオキソ硫酸ナトリウム(APS)水溶液(5%)を固形分で0.05部添加した後、内浴温度を65℃に保ちながら、10分重合し、コア層となる共重合体を得た。次いで、内浴温度を65℃に保ちながらモノマーエマルション(3)のうちの212部を3時間かけて滴下し、その後3時間重合してシェル層を形成し、コア層とシェル層が同じ組成であるコアシェル構造のポリマーエマルション粒子を含有する水分散液を得た。次いで、上記コアシェル構造のポリマーエマルション粒子を含有する水分散液を室温まで冷却した後、これに濃度10%のアンモニア水を添加してpH7.8に調整し、コアシェル構造のエマルション粒子を含有する水分散型粘着剤組成物を得た。得られたポリマーエマルション粒子の体積平均粒子径は、107nmであった。
調製した光学フィルム用水分散型粘着剤組成物を、シリコーン系剥離剤を塗布した厚さ38μmのフィルム(商品名:MRF38、三菱化学ポリエステル(株)製)に、ダイ方式(塗工速度5m/分)で塗工し、120℃で2分間加熱して、厚さ25μmの粘着剤層を形成した。これを製造例1で得られた下塗り層を有する偏光フィルムの下塗り層上に転写して粘着型光学用フィルムを形成した。
実施例1の(モノマーエマルション(1)の調製)、(モノマーエマルション(2)の調製)において、組成を表1に記載の組成に変更した以外は、実施例1と同様にして粘着型光学用フィルムを形成した。
各実施例で得られた光学フィルム用水分散型粘着剤組成物に含まれるエマルション粒子のコア層、シェル層を構成する(メタ)アクリル系共重合体のガラス転移温度は、以下に示す各モノマーのホモポリマーのガラス転移温度Tg(K)を用い、下記FOXの式で算出した。
BA:アクリル酸ブチル=219K
AA:アクリル酸=379.15K
CHMA:メタクリル酸シクロヘキシル=356K
MMA:メタクリル酸メチル=378.15K
BzA:ベンジルアクリレート=279.15K
FOXの式:
ポリマーエマルション粒子の体積平均粒子径は、調製したコアシェル構造のエマルション粒子を含有する水分散型粘着剤組成物を、蒸留水により固形分濃度が約1重量%となるように希釈したものを用いて下記装置にて測定した。
装置:ベックマンコールター製のLS13 320 PIDSモード
分散質の屈折率:1.48 ポリn−ブチルアクリレートを使用
分散媒の屈折率:1.333
2枚の粘着型光学フィルム(サイズ:80×50mm)(軸角度:0度、90度)をアルカリガラスの両面にクロスになるよう貼付し、50℃5気圧のオートクレーブ中に15分間処理した後、温度85℃の雰囲気下で75時間保存して、室温までアルカリガラスを冷却した後、暗室にて片面側からバックライトを照射して光学フィルムの端部やコーナー部の光漏れを目視観察により確認した。
各実施例および各比較例の粘着型光学フィルムを、230×310mmの大きさに切断し、これを、厚さ0.7mmのガラス板(EAGLE XG、コーニング(株)製)に貼着し、50℃5気圧のオートクレーブ中に15分間処理した後、温度60℃、湿度90%の雰囲気下で500時間保存して、粘着型光学フィルムの端部に発生する浮きや剥がれ欠陥の最大進入距離を目視観察により確認した。欠陥の評価については下記に示す。
○:最大進入距離が、0mm以上0.5mm以下である。
△:最大進入距離が、0.5mmより大きく、1.0mm以下である。
×:最大進入距離が、1.0mmより大きい。
Claims (6)
- 同一エマルション粒子内に、(メタ)アクリル酸アルキルエステルをモノマー単位として含有する(メタ)アクリル系共重合体(A)がコア層、芳香族環含有(メタ)アクリル系モノマー及び(メタ)アクリル酸アルキルエステルをモノマー単位として含有する(メタ)アクリル系共重合体(B)がシェル層として存在する、コアシェル構造のエマルション粒子を含有し、
前記(メタ)アクリル系共重合体(B)に含まれる芳香族環含有(メタ)アクリル系モノマーの含有量が、(メタ)アクリル系共重合体(A)及び(メタ)アクリル系共重合体(B)を構成する全モノマーに対して1〜28重量%であることを特徴とする光学フィルム用水分散型粘着剤組成物。 - 前記(メタ)アクリル系共重合体(A)のガラス転移温度が0℃以上180℃以下であり、前記(メタ)アクリル系共重合体(B)のガラス転移温度が−55℃以上0℃未満であることを特徴とする請求項1に記載の光学フィルム用水分散型粘着剤組成物。
- 前記芳香族環含有(メタ)アクリル系モノマーが、ベンジルアクリレートであることを特徴とする請求項1又は2に記載の光学フィルム用水分散型粘着剤組成物。
- 請求項1〜3のいずれかに記載の光学フィルム用水分散型粘着剤組成物から形成されることを特徴とする粘着剤層。
- 光学フィルムの少なくとも片面に、請求項4に記載の粘着剤層が積層されていることを特徴とする粘着型光学フィルム。
- 請求項5に記載の粘着型光学フィルムを備えることを特徴とする画像表示装置。
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JP2013237192A JP6251548B2 (ja) | 2013-11-15 | 2013-11-15 | 光学フィルム用水分散型粘着剤組成物、粘着剤層、粘着型光学フィルム、及び、画像表示装置 |
US15/036,646 US20160289516A1 (en) | 2013-11-15 | 2014-06-10 | Water-dispersible pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer, pressure-sensitive adhesive optical film, and image display device |
KR1020167011312A KR102328210B1 (ko) | 2013-11-15 | 2014-06-10 | 광학 필름용 수분산형 점착제 조성물, 점착제층, 점착형 광학 필름 및 화상 표시 장치 |
CN201480061950.3A CN105722936A (zh) | 2013-11-15 | 2014-06-10 | 光学膜用水分散型粘合剂组合物、粘合剂层、粘合型光学膜及图像显示装置 |
PCT/JP2014/065336 WO2015072168A1 (ja) | 2013-11-15 | 2014-06-10 | 光学フィルム用水分散型粘着剤組成物、粘着剤層、粘着型光学フィルム、及び、画像表示装置 |
TW103123519A TW201518450A (zh) | 2013-11-15 | 2014-07-08 | 光學膜用水分散型黏著劑組合物、黏著劑層、黏著型光學膜及圖像顯示裝置 |
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