JP3749309B2 - Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition - Google Patents
Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition Download PDFInfo
- Publication number
- JP3749309B2 JP3749309B2 JP14233496A JP14233496A JP3749309B2 JP 3749309 B2 JP3749309 B2 JP 3749309B2 JP 14233496 A JP14233496 A JP 14233496A JP 14233496 A JP14233496 A JP 14233496A JP 3749309 B2 JP3749309 B2 JP 3749309B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- curable resin
- film
- weight
- meth
- 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.)
- Expired - Fee Related
Links
- 239000011342 resin composition Substances 0.000 title claims description 44
- 229920002284 Cellulose triacetate Polymers 0.000 title claims description 25
- 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 title claims description 25
- 239000000203 mixture Substances 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 5
- 229920000896 Ethulose Polymers 0.000 claims description 4
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 4
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 239000010408 film Substances 0.000 description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 230000004313 glare Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- -1 2-hydroxypropyl Chemical group 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012461 cellulose resin Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
- Polarising Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、エネルギー線硬化型樹脂組成物及び該組成物の硬化膜層を有するトリアセチルセルロースフィルム及び前述のフィルムを使用した偏光板、楕円偏光板に関する。本発明のフィルムは、ＬＣＤ、ＣＲＴ、プラズマディスプレイ等の各種表示体の表面に用いられる耐擦傷性フィルム、ノングレアフィルムとして有用である。
【０００２】
【従来の技術】
ＬＣＤ、ＣＲＴ、プラズマディスプレイの各種表示体は、その表面の保護基板（透明あるいはノングレア層を有する）を通して文字、図形等の視覚情報が観察されるようになっている。特に、液晶ディスプレイ等の表示体表面には、光シャッターの役目をする偏光素子が設けられているが、偏光素子自体が耐擦傷性に劣るため、透明プラスッチクフィルム（一般的にはトリアセチルセルロースフィルム、即ちＴＡＣフィルムが用いられる）により保護されている。しかしながら、この透明プラスッチクフィルム自体も耐擦傷性に劣り、近年、このような偏光板表面に耐擦傷性を持たせたものが開発されている。このような技術は、例えば特開平１−１０５７３８号公報、特開平６−１５７７９１号公報、特開平７−２９４７４０号公報に記載されている。
【０００３】
特開平１−１０５７３８号公報では、フィルム状の偏光素子に貼合して偏光板を構成するための、耐擦傷性、ノングレア性を付与した透明保護フィルムとしてトリアセチルセルロースフィルム（以降ＴＡＣフィルムと略す）が用いられている。このフィルムは、未ケン化のＴＡＣフィルムの片面に、紫外線硬化型エポキシアクリレート系樹脂からなる硬化塗膜を設けることにより耐擦傷性に優れたＴＡＣフィルムとしている。
【０００４】
特開平６−１５７７９１号公報では、電離放射線硬化型樹脂１００重量部に対して溶剤乾燥型樹脂としてセルロース系樹脂を１０重量部以上１００重量部以下を含む塗料組成物をＴＡＣフィルム上に塗布し、電離放射線を照射して塗膜を硬化させ耐擦傷性を付与している。しかし、セルロース系樹脂は塗膜とＴＡＣフィルムの密着性向上に寄与しており、１０重量部以上の添加はむしろ耐擦傷性を低下させることになる。
【０００５】
特開平７−２９４７４０号公報では、セルロース系樹脂の添加はＴＡＣフィルム上に形成したノングレア層との密着性には寄与するが、実施例では紫外線硬化型樹脂１００重量部に対して１．５重量部での塗布膜の硬度が示されている。しかし、高耐久性条件下での密着性向上のためには１．５重量部では不十分である。
【０００６】
【発明が解決しようとする課題】
従来、ＴＡＣフィルム上に、耐擦傷性を付与するためのハードコート層（フィラーを添加したノングレア層）を形成する際、ＴＡＣフィルムとの密着性を改善するために、ＴＡＣフィルムを溶解する酢酸エチル、メチルエチルケトン等の溶剤を用いてＴＡＣフィルムの表面を多少溶解しＴＡＣフィルムとハードコート層の密着性を向上させていたが、この方法ではＴＡＣフィルムの劣化、及びＴＡＣフィルムの白化により透明性を損ねる等の問題があった。
【０００７】
またハードコート層用の樹脂組成物として光拡散材を分散した樹脂組成物を使用する場合、ＴＡＣフィルムとの密着性が低下する問題があった。
【０００８】
【課題を解決するための手段】
本発明者らは、上記に鑑み鋭意検討の結果、ハードコート性を低下させることなく、ＴＡＣフィルムとの密着を大幅に改善されるエネルギー線硬化型樹脂組成物を見出し、本発明を完成するに至った。即ち、本発明は、
（１）官能基を５つ以上有するモノマーからなるエネルギー線硬化型樹脂１００重量部に対してセルロース系樹脂を２〜１０重量部含有するエネルギー線硬化型樹脂組成物、
（２）溶剤を除くエネルギー線硬化型樹脂組成物中の、官能基を５つ以上有するモノマーの含量が４０〜６５重量％である（１）又は（１４）のエネルギー線硬化型樹脂組成物、
（３）官能基を５つ以上有するモノマーがアクリル系モノマーである（１）又は
（２）又は（１４）のエネルギー線硬化型樹脂組成物、
（４）単官能（メタ）アクリル系モノマーを含有する（１）ないし（３）のエネルギー線硬化型樹脂組成物、
（５）溶剤を除くエネルギー線硬化型樹脂組成物中の、単官能（メタ）アクリル系モノマーの含量が５〜３０重量％である（４）又は（１４）のエネルギー線硬化型樹脂組成物、
（６）光拡散材を含有する（１）ないし（５）又は（１４）のエネルギー線硬化型樹脂組成物、
（７）光拡散材がシリカ粒子又は有機系ポリマー粒子である（６）又は（１４）のエネルギー線硬化型樹脂組成物、
（８）溶剤を除くエネルギー線硬化型樹脂組成物中の、光拡散材の含量が０．１〜３０重量％である（６）又は（７）又は（１４）のエネルギー線硬化型樹脂組成物、
（９）（１）ないし（８）又は（１４）のエネルギー線硬化型樹脂組成物の硬化膜層を有するトリアセチルセルロースフィルム、
（１０）硬化膜層に反射防止層を付与したことを特徴とする（９）のトリアセチルセルロースフィルム、
（１１）（９）又は（１０）のトリアセチルセルロースフィルム層を有する偏光板、
（１２）偏光板が楕円偏光板である（１１）の偏光板、
（１３）（１１）又は（１２）のフィルムを有する液晶表示装置、
に関する。
【０００９】
【発明の実施形態】
本発明のエネルギー線硬化型樹脂組成物は、紫外線や電子線等のエネルギー線の照射により硬化する樹脂組成物である。このエネルギー線硬化型樹脂組成物は、官能基を５つ以上有するモノマーとセルロース系樹脂を必須成分として含有する。官能基を５つ以上有するモノマーとしては、例えば５官能以上（メタ）アクリレート等の５官能以上アクリル系モノマーがあげられる。その具体例としてはジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ジペンタエリスリトールとε−カプロラクトンとを反応させたヘキサ（メタ）アクリレート、３官能以上（メタ）アクリレート（例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等）と有機ポリイソシアネート（例えば、トリレンジイソシアネート、キシリレンジイソシアネート等）との反応物等が挙げられる。５官能以上（メタ）アクリレートの樹脂組成物中における含有割合は４０〜６５重量％が好ましく、特に好ましくは４５〜６５重量％である。５官能以上（メタ）アクリレートが４０重量％未満である場合、その紫外線硬化皮膜の硬度、耐擦傷性が得られない。
【００１０】
本発明で使用するセルロース系樹脂の具体例としては、ニトロセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシエチルセルロース、アセチルセルロース、セルロースアセテートプロピオネート等が挙げられる。セルロース系樹脂の樹脂組成物中の含有割合は、密着性や硬化皮膜の硬度の点から２〜１０重量％、好ましくは２重量％より多く１０重量％未満、より好ましくは３重量％以上１０重量％未満、さらに好ましくは３〜９．５重量％程度がよい。またセルロース系樹脂の溶解溶剤としてトルエンを用いることができる。この溶剤は、ＴＡＣを溶解せずに密着性を向上できるため、ＴＡＣの白化を防止できる。
【００１１】
本発明のエネルギー線硬化型樹脂組成物には、例えば粘度を低下させる必要がある場合等、必要に応じ単官能（メタ）アクリル系モノマーを含有させることができる。単官能（メタ）アクリル系モノマーとしては、例えば２−ヒドロキシプロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、（メタ）アクリロイルモルホリン、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、ｔ−ブチルアミノエチル（メタ）アクリレート、２−シアノ（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアクリルアミド等が挙げらる。単官能（メタ）アクリレートの樹脂組成物中の含有割合は５〜３０重量％、好ましくは１０〜２５重量％である。単官能（メタ）アクリレートの含有割合が５重量％未満である場合、紫外線硬化皮膜の基材との密着性が不十分となり、３０重量％を越えると硬化皮膜の硬度が不十分となり好ましくない。
【００１２】
又、本発明のエネルギー線硬化型樹脂組成物には、例えばノングレア性の付与等、必要に応じ光拡散剤を含有することができる。光拡散剤としては、例えばシリカ粒子や有機系ポリマー粒子等があげられる。有機系ポリマー粒子としては、例えばポリメチルメタクリレート粒子、ポリスチレン粒子、ポリアミドイミド粒子、シリコーン粒子等があげられる。溶剤を除くエネルギー線硬化型樹脂組成物中の光拡散剤の含量は、使用する光拡散剤の粒径に応じ適宜定められるが、通常０．１〜３０重量％、好ましくは０．５〜２５重量％程度である。
【００１３】
本発明のエネルギー線硬化型樹脂組成物には、例えば紫外線硬化皮膜の硬度を保持し、カールを抑える必要がある場合等、必要に応じ２〜４官能（メタ）アクリル系モノマーを含有することができる。２官能（メタ）アクリル系モノマーとしては、例えばネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリプロピレンジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート等があげられる。３官能（メタ）アクリル系モノマーとしては、例えば３官能（メタ）アクリレートがあげられる。この具体例としては、例えばトリメチロールプロパン（メタ）トリアクリレート、ペンタエリスリトール（メタ）トリアクリレート等を挙げることができる。４官能（メタ）アクリル系モノマーとしては、例えばペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチルロールプロパンテトラ（メタ）アクリレート等があげられる。２〜４官能（メタ）アクリル系モノマーの樹脂組成物中の含有割合は１５〜２５重量％が好ましく、特に好ましくは２０〜２５重量％である。
【００１４】
本発明のエネルギー線硬化型樹脂組成物には、例えば紫外線硬化型とするための場合等、必要に応じ光重合開始剤を含有することができる。光重合開始剤としては、例えば、２−ヒドロキシ−２−メチルプロピオフェノン、４−イソプロピル−２−ヒドロキシ−２−メチルプロピオフェノン、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、ベンゾフェノン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルフォリノプロパノン−１、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。これらの光重合開始剤は、３級アミン類等の促進剤と併用することもできる。光重合開始剤の樹脂組成物中の含有割合は好ましくは０．５〜１０重量％、より好ましくは２〜７重量％程度である。
【００１５】
本発明のエネルギー線硬化型樹脂組成物を製造するには、例えば上記の各成分を、必要に応じ溶剤を使用して、混合（溶解又は分散）すればよい。溶剤としては、例えばトルエン、メチルエチルケトン、酢酸エチル、イソプロピルアルコール等があげられる。尚、本発明のエネルギー線硬化型樹脂組成物には、さらに性能改良のため、本来の特性を変えない範囲で、非反応性化合物（例えば、アクリルポリマー、スチレンポリマー等）、消泡剤、レベリング剤、帯電防止剤、難燃剤、酸化防止剤、光安定剤、紫外線吸収剤、カップリング剤、重合禁止剤等を含有せしめ最適化を図ることもできる。
【００１６】
本発明のトリアセチルセルロースフィルムは上記のエネルギー線硬化型樹脂組成物の硬化膜層を、少なくともその片面に有する。この硬化膜層は該組成物中に光拡散材が存在しない場合にハードコート層と呼ばれ、該組成物中に光拡散材が存在する場合にノングレア層と呼ばれる。この硬化膜層を有する本発明のトリアセチルセルロースフィルムを得るには、マイクログラビアコーター、グラビアコーター、メイヤーバーコーター、ディップコーター等の塗工装置を使用してトリアセチルセルロースフィルムの表面に上記のエネルギー線硬化型樹脂組成物を、乾燥後の厚さが２〜７μｍ、好ましくは３〜５μｍ程度になるように塗布し、次いでエネルギー線を照射すればよい。トリアセチルセルロースフィルムの厚さは５０〜２００μｍ程度が好ましい。
【００１７】
本発明のトリアセチルセルロースフィルムは、上記のエネルギー線硬化型樹脂組成物の硬化膜層の上に反射防止層、例えば低屈折率のフッ素系樹脂、二酸化珪素や金属化合物の薄膜を多数積層した多層反射防止膜（この多層反射防止膜上にさらにフッ素系樹脂を形成してもよい）、を形成することも可能である。光干渉効果によって反射光を低減するように光学設計された上記の層を設けることで、ハードコート層、ノングレア層表面で散乱する反射光を低減し、透過光を増加させることができる。従って、表示体等に用いた場合、この効果により、より鮮明な、見やすい表示画面となり好ましい。
【００１８】
本発明の偏光板は、例えば偏光子の片面に上記のハードコート層、必要に応じノングレア層及びそれらに反射防止層、を施したトリアセチルセルロースフィルムを、もう一方の面に単なるトリアセチルセルロースフィルムを接着剤で貼り張り合わせることで得られる。また本発明の楕円偏光板は、例えば上記の偏光板と位相差板を貼り合わせることにより得られる。
【００１９】
本発明で得られるトリアセチルセルロースフィルムから構成された偏光板は、ポリビニルアルコールより形成される偏光子との接着を改善するためのプライマー処理等を特別に施す必要はない。またノングレア層を設ける際も、ＴＡＣとの親和性が強いセルロース系樹脂を用いていることより密着性の低下を無視することができる。
【００２０】
本発明の液晶表示装置は、例えば上記の偏光板または楕円偏光板を表示体の前面に配置することにより得られる。この液晶表示装置の画面は、耐擦傷性に優れ、さらに外光の反射防止機能を有する。
【００２１】
【実施例】
本発明を実施例、比較例により具体的に説明するがこれに限定されるものではない。尚、実施例、比較例において部は重量部を意味する。
【００２２】
実施例１
厚さ８０μｍのトリアセチルセルロース上に下記樹脂組成物を、ディップコート方式により２ｍ／ｍｉｎの塗工速度でドライ換算で３．５ｇ／ｍ2 を塗布し、溶剤を蒸発後、８０Ｗ／ｃｍの高圧水銀ランプを用いて紫外線を照射、硬化させハードコート層を形成し、本発明のトリアセチルセルロースフィルムを得、ハードコート層の鉛筆硬度を測定した。又、この本発明のフィルムのトリアセチルセルロース面に粘着層を設けガラス板に貼合わせたものを８０℃−９０％ＲＨの湿熱条件下での密着性を評価した。鉛筆硬度の評価はＪＩＳ Ｋ５４００に準じて行った。密着性の評価はＪＩＳ Ｋ５４００碁盤目テープ法（すきま間隔１ｍｍ）に基づき実施し、一定時間経過後の密着性を判定した。結果は表１に示す。
（クリアーハードコート樹脂組成物）
・ジペンタエリスリトールヘキサアクリレート ５３部
・トリメチロールプロパントリアクリレート ２５部
・テトラヒドロフルフリルアクリレート ２２部
・エチルヒドロキシエチルセルロース ４．０部
・光重合開始剤 ５．０部
・トルエン １２０部
【００２３】
実施例２
実施例１の樹脂組成物に疎水処理シリカ（コールターカウンター法による平均粒子径１．５μｍ）を溶剤を除いた重量部に対して７．５部添加した以外は実施例１に準じて実施し、ノングレア層をトリアセチルセルロースフィルム上に形成しし、本発明のトリアセチルセルロースフィルムを得、ハードコート層の鉛筆硬度を測定した。又、この本発明のフィルムのトリアセチルセルロース面に粘着層を設けガラス板に貼合わせたものを８０℃−９０％ＲＨの湿熱条件下での密着性を評価した。結果は表１に示す。
【００２４】
比較例１
実施例１の樹脂組成物中のエチルヒドロキシエチルセルロースを除いた以外は、実施例１に準じて実施した。結果は表１に記載す。
【００２５】
比較例２
実施例２の樹脂組成物中のエチルヒドロキシエチルセルロースの重量部を１．０部とした以外は、実施例２に準じて実施した。結果は表１に記載す。
【００２６】
【表１】
【発明の効果】
本発明のエネルギー線硬化型樹脂組成物は、ハードコート性を低下させることなく、支持体であるトリアセチルセルロースフィルムとの密着性を大幅に改善することができ、耐久性等の信頼性を大きく向上することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an energy ray curable resin composition, a triacetyl cellulose film having a cured film layer of the composition, a polarizing plate using the above-described film, and an elliptically polarizing plate. The film of the present invention is useful as a scratch-resistant film or non-glare film used on the surface of various displays such as LCD, CRT, and plasma display.
[0002]
[Prior art]
Various display bodies such as LCDs, CRTs, and plasma displays allow visual information such as characters and figures to be observed through a protective substrate (having a transparent or non-glare layer) on the surface. In particular, a polarizing element that functions as an optical shutter is provided on the surface of a display body such as a liquid crystal display. However, since the polarizing element itself is inferior in scratch resistance, a transparent plastic film (generally a triacetyl cellulose film). That is, a TAC film is used). However, this transparent plastic film itself is also inferior in scratch resistance, and in recent years, such a polarizing plate surface having scratch resistance has been developed. Such a technique is described in, for example, Japanese Patent Application Laid-Open Nos. 1-1057738, 6-157791, and 7-294740.
[0003]
In JP-A-1-105738, a triacetyl cellulose film (hereinafter abbreviated as a TAC film) is used as a transparent protective film imparted with scratch resistance and non-glare properties for constituting a polarizing plate by bonding to a film-like polarizing element. ) Is used. This film is a TAC film having excellent scratch resistance by providing a cured coating film made of an ultraviolet curable epoxy acrylate resin on one surface of an unsaponified TAC film.
[0004]
In JP-A-6-157791, a coating composition containing 10 parts by weight or more and 100 parts by weight or less of a cellulose-based resin as a solvent-drying resin with respect to 100 parts by weight of an ionizing radiation curable resin is applied on a TAC film, Irradiation with ionizing radiation cures the coating and imparts scratch resistance. However, the cellulose-based resin contributes to improving the adhesion between the coating film and the TAC film, and the addition of 10 parts by weight or more rather reduces the scratch resistance.
[0005]
In JP-A-7-294740, the addition of a cellulose-based resin contributes to adhesion with a non-glare layer formed on a TAC film, but in the examples, 1.5 wt. The hardness of the coating film at the part is shown. However, 1.5 parts by weight is insufficient for improving adhesion under high durability conditions.
[0006]
[Problems to be solved by the invention]
Conventionally, when forming a hard coat layer (non-glare layer to which a filler is added) for imparting scratch resistance on a TAC film, ethyl acetate that dissolves the TAC film in order to improve adhesion to the TAC film The surface of the TAC film was slightly dissolved by using a solvent such as methyl ethyl ketone to improve the adhesion between the TAC film and the hard coat layer. However, this method deteriorates the transparency of the TAC film due to deterioration of the TAC film and whitening of the TAC film. There was a problem such as.
[0007]
Moreover, when using the resin composition which disperse | distributed the light-diffusion material as a resin composition for hard-coat layers, there existed a problem that adhesiveness with a TAC film fell.
[0008]
[Means for Solving the Problems]
As a result of intensive studies in view of the above, the present inventors have found an energy ray curable resin composition that can greatly improve the adhesion with a TAC film without reducing the hard coat properties, and to complete the present invention. It came. That is, the present invention
(1) An energy ray curable resin composition containing 2 to 10 parts by weight of a cellulose resin with respect to 100 parts by weight of an energy ray curable resin composed of a monomer having 5 or more functional groups,
(2) The energy ray curable resin composition according to (1) or (14), wherein the content of the monomer having 5 or more functional groups in the energy ray curable resin composition excluding the solvent is 40 to 65% by weight,
(3) The energy ray-curable resin composition according to (1), (2) or (14), wherein the monomer having 5 or more functional groups is an acrylic monomer,
(4) The energy ray-curable resin composition according to (1) to (3), which contains a monofunctional (meth) acrylic monomer,
(5) The energy ray curable resin composition according to (4) or (14), wherein the content of the monofunctional (meth) acrylic monomer in the energy ray curable resin composition excluding the solvent is 5 to 30% by weight,
(6) The energy beam curable resin composition according to (1) to (5) or (14), which contains a light diffusing material,
(7) The energy ray curable resin composition according to (6) or (14), wherein the light diffusing material is silica particles or organic polymer particles,
(8) The energy ray curable resin composition according to (6), (7) or (14), wherein the content of the light diffusing material in the energy ray curable resin composition excluding the solvent is 0.1 to 30% by weight. ,
(9) A triacetyl cellulose film having a cured film layer of the energy beam curable resin composition of (1) to (8) or (14),
(10) The triacetylcellulose film according to (9), wherein an antireflection layer is added to the cured film layer,
(11) A polarizing plate having the triacetyl cellulose film layer of (9) or (10),
(12) The polarizing plate according to (11), wherein the polarizing plate is an elliptical polarizing plate,
(13) A liquid crystal display device having the film of (11) or (12),
About.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The energy ray-curable resin composition of the present invention is a resin composition that is cured by irradiation with energy rays such as ultraviolet rays and electron beams. This energy beam curable resin composition contains a monomer having 5 or more functional groups and a cellulose resin as essential components. Examples of the monomer having five or more functional groups include five or more functional acrylic monomers such as five or more (meth) acrylates. Specific examples thereof include dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypentaacrylate, hexa (meth) acrylate obtained by reacting dipentaerythritol and ε-caprolactone, and trifunctional or higher (meth) acrylate (for example, And a reaction product of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.) and an organic polyisocyanate (eg, tolylene diisocyanate, xylylene diisocyanate, etc.). The content ratio of the pentafunctional or higher (meth) acrylate in the resin composition is preferably 40 to 65% by weight, particularly preferably 45 to 65% by weight. When the pentafunctional or higher (meth) acrylate is less than 40% by weight, the hardness and scratch resistance of the UV-cured film cannot be obtained.
[0010]
Specific examples of the cellulose resin used in the present invention include nitrocellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, acetylcellulose, cellulose acetate propionate and the like. The content ratio of the cellulose-based resin in the resin composition is 2 to 10% by weight, preferably more than 2% by weight and less than 10% by weight, more preferably 3% by weight or more and 10% by weight from the viewpoint of adhesion and hardness of the cured film. %, More preferably about 3 to 9.5% by weight. In addition, toluene can be used as a dissolving solvent for the cellulose resin. Since this solvent can improve adhesiveness without dissolving TAC, whitening of TAC can be prevented.
[0011]
The energy beam curable resin composition of the present invention may contain a monofunctional (meth) acrylic monomer as necessary, for example, when the viscosity needs to be lowered. Examples of monofunctional (meth) acrylic monomers include 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, Examples include caprolactone-modified tetrahydrofurfuryl (meth) acrylate, t-butylaminoethyl (meth) acrylate, 2-cyano (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide and the like. The The content ratio of the monofunctional (meth) acrylate in the resin composition is 5 to 30% by weight, preferably 10 to 25% by weight. When the content ratio of the monofunctional (meth) acrylate is less than 5% by weight, the adhesion of the ultraviolet curable film to the substrate becomes insufficient, and when it exceeds 30% by weight, the hardness of the cured film becomes insufficient.
[0012]
Further, the energy ray curable resin composition of the present invention may contain a light diffusing agent as necessary, for example, to impart non-glare properties. Examples of the light diffusing agent include silica particles and organic polymer particles. Examples of the organic polymer particles include polymethyl methacrylate particles, polystyrene particles, polyamideimide particles, and silicone particles. The content of the light diffusing agent in the energy ray curable resin composition excluding the solvent is appropriately determined according to the particle size of the light diffusing agent to be used, but is usually 0.1 to 30% by weight, preferably 0.5 to 25%. It is about wt%.
[0013]
The energy ray curable resin composition of the present invention may contain 2 to 4 functional (meth) acrylic monomers as necessary, for example, when it is necessary to maintain the hardness of the ultraviolet curable film and suppress curling. it can. Examples of the bifunctional (meth) acrylic monomer include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene di (meth) acrylate, and polyethylene glycol di (meth) acrylate. can give. Examples of the trifunctional (meth) acrylic monomer include trifunctional (meth) acrylate. Specific examples thereof include trimethylolpropane (meth) triacrylate and pentaerythritol (meth) triacrylate. Examples of the tetrafunctional (meth) acrylic monomer include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. As for the content rate in the resin composition of a 2-4 functional (meth) acrylic-type monomer, 15-25 weight% is preferable, Most preferably, it is 20-25 weight%.
[0014]
The energy beam curable resin composition of the present invention may contain a photopolymerization initiator as necessary, for example, in order to obtain an ultraviolet curable resin. Examples of the photopolymerization initiator include 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2- And methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide. These photopolymerization initiators can also be used in combination with accelerators such as tertiary amines. The content of the photopolymerization initiator in the resin composition is preferably about 0.5 to 10% by weight, more preferably about 2 to 7% by weight.
[0015]
In order to produce the energy beam curable resin composition of the present invention, for example, the above components may be mixed (dissolved or dispersed) using a solvent as necessary. Examples of the solvent include toluene, methyl ethyl ketone, ethyl acetate, isopropyl alcohol and the like. In addition, the energy ray curable resin composition of the present invention has a non-reactive compound (for example, an acrylic polymer, a styrene polymer, etc.), an antifoaming agent, and a leveling as long as the original characteristics are not changed for further performance improvement. It is also possible to optimize by adding an agent, an antistatic agent, a flame retardant, an antioxidant, a light stabilizer, an ultraviolet absorber, a coupling agent, a polymerization inhibitor and the like.
[0016]
The triacetyl cellulose film of the present invention has a cured film layer of the energy beam curable resin composition on at least one surface thereof. This cured film layer is called a hard coat layer when no light diffusing material is present in the composition, and is called a non-glare layer when a light diffusing material is present in the composition. In order to obtain the triacetyl cellulose film of the present invention having this cured film layer, the above-mentioned energy is applied to the surface of the triacetyl cellulose film using a coating apparatus such as a micro gravure coater, a gravure coater, a Mayer bar coater, or a dip coater. The wire curable resin composition may be applied so that the thickness after drying is 2 to 7 μm, preferably about 3 to 5 μm, and then irradiated with energy rays. The thickness of the triacetyl cellulose film is preferably about 50 to 200 μm.
[0017]
The triacetyl cellulose film of the present invention is a multilayer in which a number of antireflection layers, for example, a low refractive index fluorine-based resin, a thin film of silicon dioxide or a metal compound, are laminated on the cured film layer of the energy beam curable resin composition. It is also possible to form an antireflection film (a fluororesin may be further formed on the multilayer antireflection film). By providing the above-mentioned layer optically designed to reduce the reflected light by the light interference effect, the reflected light scattered on the hard coat layer and non-glare layer surfaces can be reduced and the transmitted light can be increased. Therefore, when used for a display body or the like, this effect is preferable because of a clearer and easier-to-see display screen.
[0018]
The polarizing plate of the present invention comprises, for example, a triacetyl cellulose film having the above-mentioned hard coat layer on one side of the polarizer, a non-glare layer if necessary, and an antireflection layer thereon, and a simple triacetyl cellulose film on the other side. Can be obtained by pasting together with an adhesive. The elliptically polarizing plate of the present invention can be obtained, for example, by laminating the above polarizing plate and a retardation plate.
[0019]
The polarizing plate composed of the triacetyl cellulose film obtained in the present invention does not need to be specially subjected to primer treatment or the like for improving adhesion with a polarizer formed from polyvinyl alcohol. Also, when the non-glare layer is provided, a decrease in adhesion can be ignored because a cellulose resin having a strong affinity with TAC is used.
[0020]
The liquid crystal display device of the present invention can be obtained, for example, by disposing the above polarizing plate or elliptically polarizing plate on the front surface of the display body. The screen of this liquid crystal display device is excellent in scratch resistance and further has a function of preventing reflection of external light.
[0021]
【Example】
The present invention will be specifically described with reference to examples and comparative examples, but is not limited thereto. In Examples and Comparative Examples, “part” means “part by weight”.
[0022]
Example 1
The following resin composition is applied onto triacetyl cellulose having a thickness of 80 μm by a dip coating method at a coating speed of 2 m / min, 3.5 g / m 2 in dry conversion, and after evaporation of the solvent, a high pressure of 80 W / cm. Ultraviolet rays were irradiated and cured using a mercury lamp to form a hard coat layer, to obtain a triacetyl cellulose film of the present invention, and the pencil hardness of the hard coat layer was measured. Moreover, the adhesiveness in the 80 degreeC-90% RH wet-heat conditions evaluated the thing which provided the adhesion layer on the triacetyl-cellulose surface of this film of this invention, and bonded together to the glass plate. The pencil hardness was evaluated according to JIS K5400. The evaluation of adhesion was carried out based on the JIS K5400 cross-cut tape method (gap spacing 1 mm), and the adhesion after a lapse of a certain time was determined. The results are shown in Table 1.
(Clear hard coat resin composition)
-53 parts of dipentaerythritol hexaacrylate-25 parts of trimethylolpropane triacrylate-22 parts of tetrahydrofurfuryl acrylate-4.0 parts of ethyl hydroxyethyl cellulose-5.0 parts of photopolymerization initiator-120 parts of toluene
Example 2
Except for adding 7.5 parts by weight of hydrophobically treated silica (average particle diameter of 1.5 μm by Coulter counter method) to the resin composition of Example 1 with respect to parts by weight excluding the solvent, this was carried out according to Example 1, A non-glare layer was formed on the triacetyl cellulose film to obtain the triacetyl cellulose film of the present invention, and the pencil hardness of the hard coat layer was measured. Moreover, the adhesiveness in the 80 degreeC-90% RH wet-heat conditions evaluated the thing which provided the adhesion layer on the triacetyl-cellulose surface of this film of this invention, and bonded together to the glass plate. The results are shown in Table 1.
[0024]
Comparative Example 1
The same procedure as in Example 1 was performed except that ethylhydroxyethylcellulose in the resin composition of Example 1 was removed. The results are listed in Table 1.
[0025]
Comparative Example 2
The same procedure as in Example 2 was performed except that 1.0 part by weight of ethylhydroxyethylcellulose in the resin composition of Example 2 was changed. The results are listed in Table 1.
[0026]
[Table 1]
【The invention's effect】
The energy ray curable resin composition of the present invention can greatly improve the adhesion with the triacetyl cellulose film as a support without degrading the hard coat property, and greatly increases the reliability such as durability. Can be improved.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14233496A JP3749309B2 (en) | 1996-05-14 | 1996-05-14 | Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14233496A JP3749309B2 (en) | 1996-05-14 | 1996-05-14 | Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09302144A JPH09302144A (en) | 1997-11-25 |
| JP3749309B2 true JP3749309B2 (en) | 2006-02-22 |
Family
ID=15312947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14233496A Expired - Fee Related JP3749309B2 (en) | 1996-05-14 | 1996-05-14 | Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3749309B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4521957B2 (en) * | 2000-09-28 | 2010-08-11 | 大日本印刷株式会社 | Film having hard coat layer, antireflection film, and production method thereof |
| JP4004886B2 (en) * | 2002-07-31 | 2007-11-07 | Ｔｄｋ株式会社 | Anti-reflection film and anti-reflection treated object |
| JP4501333B2 (en) * | 2002-09-04 | 2010-07-14 | 日本製紙株式会社 | Coating composition and hard coat film |
| JP2004099639A (en) * | 2002-09-04 | 2004-04-02 | Nippon Paper Industries Co Ltd | Coating composition and hard coat film |
| JP2005054100A (en) * | 2003-08-06 | 2005-03-03 | Konica Minolta Opto Inc | Cellulose ester film, hard coat film and antireflection film |
| JP4640762B2 (en) * | 2004-06-21 | 2011-03-02 | 日本化薬株式会社 | Hard coat film |
| JP5275550B2 (en) * | 2006-05-09 | 2013-08-28 | 三井化学株式会社 | Optical coating material and substrate |
| JP2009234059A (en) * | 2008-03-27 | 2009-10-15 | Konica Minolta Opto Inc | Hard coat film |
-
1996
- 1996-05-14 JP JP14233496A patent/JP3749309B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09302144A (en) | 1997-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4082965B2 (en) | Anti-glare hard coat film | |
| JP5313728B2 (en) | Optical film | |
| JP5149052B2 (en) | Anti-glare hard coat film and polarizing plate using the same | |
| JP4746863B2 (en) | Anti-glare hard coat layer forming material and anti-glare hard coat film | |
| JP5259334B2 (en) | Anti-glare hard coat film and polarizing plate using the same | |
| JP5486840B2 (en) | Antireflection film and polarizing plate using the same | |
| WO2011065246A1 (en) | Method for producing optical film, optical film, polarizing plate and display | |
| JP2004149631A (en) | Hard coat film | |
| JP5290046B2 (en) | Anti-glare hard coat film and polarizing plate using the same | |
| KR20130057413A (en) | Hard coat film, polarizing film, image display device, and hard coat film manufacturing method | |
| JP2001287308A (en) | Plastic laminate and image display protection film | |
| JP4266623B2 (en) | Hard coat film | |
| JP2009029126A (en) | Hard coat film and its manufacturing method | |
| JP5728191B2 (en) | Hard coat layer surface forming film, method for producing optical member with hard coat layer, and optical member with hard coat layer | |
| JP5690491B2 (en) | Anti-glare hard coat film and polarizing plate using the same | |
| JP3749309B2 (en) | Energy ray-curable resin composition and triacetyl cellulose film having a cured film layer of the composition | |
| JP2012048099A (en) | Antiglare-antistatic hard coat film and polarizer | |
| JP2002297042A (en) | Plastic layered body and image display protective member | |
| JP2022131260A (en) | hard coat film | |
| JP2006003676A (en) | Functional film for display screen and manufacturing method for same | |
| JP6721410B2 (en) | Protective film, film laminate, and polarizing plate | |
| CN103097923B (en) | Optical member and application of same | |
| JPH10128899A (en) | Film for preventing glass scattering having light diffusing function | |
| JP2004230562A (en) | Hard coat film | |
| JP5628617B2 (en) | Manufacturing method of optical member with hard coat layer, film for forming hard coat layer surface, and optical member with hard coat layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040401 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050613 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050804 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051128 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051201 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |