JP2024050734A - Laminate, polarizer protective film, and polarizing plate - Google Patents
Laminate, polarizer protective film, and polarizing plate Download PDFInfo
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- JP2024050734A JP2024050734A JP2024012761A JP2024012761A JP2024050734A JP 2024050734 A JP2024050734 A JP 2024050734A JP 2024012761 A JP2024012761 A JP 2024012761A JP 2024012761 A JP2024012761 A JP 2024012761A JP 2024050734 A JP2024050734 A JP 2024050734A
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- Prior art keywords
- meth
- curable composition
- acrylate
- acrylic polymer
- laminate
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 98
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 85
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 77
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 239000003999 initiator Substances 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000031700 light absorption Effects 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 34
- 238000000034 method Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- -1 polyol acrylate Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229920002284 Cellulose triacetate Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 5
- 238000010558 suspension polymerization method Methods 0.000 description 5
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YWEJNVNVJGORIU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-hydroxy-2-phenylacetate Chemical compound OCCOCCOC(=O)C(O)C1=CC=CC=C1 YWEJNVNVJGORIU-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
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- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
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- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
【課題】基材の（メタ）アクリル系重合体を含む表面に耐擦傷性、表面硬度及び平滑性等を付与するハードコート層を有する積層体において、前記基材とハードコート層との密着性、ハードコート層の表面硬度及び表面平滑性に優れた積層体、この積層体からなる偏光子保護フィルム、及びこの偏光子保護フィルムを偏光子に貼り合せてなる偏光板を提供することを目的とする。【解決手段】硬化性組成物の硬化物を含むハードコート層が、基材の（メタ）アクリル系重合体（Ｓ）を含む表面に直接積層されている積層体であって、前記硬化性組成物が、ラジカル重合可能な二重結合を３個以上有する（メタ）アクリレート（Ｍ）と、質量平均分子量が１０００以上７００００以下の（メタ）アクリル系重合体（Ｐ）を含む硬化性組成物である、積層体。【選択図】 なし[Problem] The objective of the present invention is to provide a laminate having a hard coat layer that imparts scratch resistance, surface hardness, smoothness, etc. to a surface of a substrate containing a (meth)acrylic polymer, the laminate having excellent adhesion between the substrate and the hard coat layer, and excellent surface hardness and surface smoothness of the hard coat layer, a polarizer protective film made of the laminate, and a polarizing plate obtained by bonding the polarizer protective film to a polarizer. [Solution] A laminate in which a hard coat layer containing a cured product of a curable composition is directly laminated on a surface of a substrate containing a (meth)acrylic polymer (S), the curable composition being a curable composition containing a (meth)acrylate (M) having three or more double bonds capable of radical polymerization, and a (meth)acrylic polymer (P) having a mass average molecular weight of 1,000 or more and 70,000 or less. [Selected Figure] None
Description
本発明は、基材の（メタ）アクリル系重合体を含む表面に耐擦傷性、表面硬度及び平滑性等を付与するハードコート層を有する積層体、この積層体からなる偏光子保護フィルム、及びこの偏光子保護フィルムを偏光子に貼り合せてなる偏光板に関する。 The present invention relates to a laminate having a hard coat layer that imparts scratch resistance, surface hardness, smoothness, etc. to the surface of a substrate containing a (meth)acrylic polymer, a polarizer protective film made of this laminate, and a polarizing plate obtained by bonding this polarizer protective film to a polarizer.
従来、液晶表示装置に用いられる偏光板の保護フィルムには、トリアセチルセルロース（ＴＡＣ）フィルムが使用されてきた。トリアセチルセルロース（ＴＡＣ）フィルムは一般的に表面硬度が低く、傷付き防止を目的としてＴＡＣフィルムの表面にはハードコート層が形成されている。 Traditionally, triacetyl cellulose (TAC) film has been used as a protective film for polarizing plates used in liquid crystal display devices. Triacetyl cellulose (TAC) film generally has low surface hardness, so a hard coat layer is formed on the surface of the TAC film to prevent scratches.
近年、液晶表示装置の大型化あるいは薄型化に伴い、ＴＡＣフィルムよりも透湿防止性の高い（メタ）アクリル系重合体からなる（メタ）アクリル系フィルムを偏光板保護フィルムとして使用する検討がなされている。 In recent years, as liquid crystal displays have become larger and thinner, the use of (meth)acrylic films made of (meth)acrylic polymers, which have higher moisture permeability resistance than TAC films, as polarizing plate protective films has been considered.
また、携帯電話、スマートフォン等の液晶表示装置を有する電子機器においては、デザインの多様化、薄型化、大面積化の進展に伴い、その液晶表示装置のカバー自体にも薄型化、軽量化、安価化等の要求が高まっている。この表示体カバーとしてはガラス基材が一般的に使用されているが、表示体カバーそれ自体の薄型化、軽量化、安価化等の要求に伴い、現在では（メタ）アクリルシートの使用が検討されている。 In addition, with the trend toward more diverse designs, thinner designs, and larger screen sizes for electronic devices with liquid crystal displays, such as mobile phones and smartphones, there is an increasing demand for thinner, lighter, and less expensive covers for the liquid crystal display devices themselves. Glass substrates are generally used for these display covers, but with the demand for thinner, lighter, less expensive displays themselves, the use of (meth)acrylic sheets is currently being considered.
しかしながら、基材の（メタ）アクリル系重合体を含む表面は、ＴＡＣ基材やポリカーボネート基材の表面と比較してハードコート層との密着性が低いという問題がある。このため（メタ）アクリル系重合体を含む表面とハードコート層との密着性を改善する検討が行われている。 However, there is a problem in that the surface of the substrate containing the (meth)acrylic polymer has poor adhesion to the hard coat layer compared to the surfaces of TAC substrates and polycarbonate substrates. For this reason, studies are being conducted to improve the adhesion between the surface containing the (meth)acrylic polymer and the hard coat layer.
たとえば特許文献１には（メタ）アクリル系基材にゴム粒子等の密着付与成分を混ぜ込むことでハードコート層との密着性を改善する方法が記載されている。特許文献２には（メタ）アクリル系基材とハードコート層の間にプライマー層を積層する方法が記載されている。特許文献３には透明プラスチックフィルムにポリオールアクリレートを含むハードコート層を積層する方法が記載されている。 For example, Patent Document 1 describes a method of improving adhesion with a hard coat layer by mixing an adhesion-imparting component such as rubber particles into a (meth)acrylic substrate. Patent Document 2 describes a method of laminating a primer layer between a (meth)acrylic substrate and a hard coat layer. Patent Document 3 describes a method of laminating a hard coat layer containing a polyol acrylate onto a transparent plastic film.
しかしながら、特許文献１から３の方法は、いずれも基材あるいはプライマー層に柔軟な成分が用いられるため、積層体としての表面硬度が低下するという問題があった。本発明はこれらの問題点を解決することを目的とする。
即ち、本発明は、基材の（メタ）アクリル系重合体を含む表面に耐擦傷性、表面硬度及び平滑性等を付与するハードコート層を有する積層体において、前記基材とハードコート層との密着性、ハードコート層の表面硬度及び表面平滑性に優れた積層体、この積層体からなる偏光子保護フィルム、及びこの偏光子保護フィルムを偏光子に貼り合せてなる偏光
板を提供することを目的とする。
However, the methods of Patent Documents 1 to 3 all have a problem in that the surface hardness of the laminate is reduced because soft components are used in the substrate or primer layer. The object of the present invention is to solve these problems.
That is, the present invention aims to provide a laminate having a hard coat layer that imparts scratch resistance, surface hardness, smoothness, etc. to a surface of a substrate containing a (meth)acrylic polymer, the laminate having excellent adhesion between the substrate and the hard coat layer, and excellent surface hardness and surface smoothness of the hard coat layer, a polarizer protective film made of this laminate, and a polarizing plate obtained by bonding the polarizer protective film to a polarizer.
前記課題は本発明によって解決される。
本発明の要旨は以下の［１］から［８］にある。
The above problems are solved by the present invention.
The gist of the present invention lies in the following [1] to [8].
［１］硬化性組成物の硬化物を含むハードコート層が、基材の（メタ）アクリル系重合体（Ｓ）を含む表面に直接積層されている積層体であって、前記硬化性組成物が、ラジカル重合可能な二重結合を３個以上有する（メタ）アクリレート（Ｍ）と、質量平均分子量が１０００以上７００００以下の（メタ）アクリル系重合体（Ｐ）を含む硬化性組成物である、積層体。
［２］前記硬化性組成物中の前記（メタ）アクリレート（Ｍ）及び前記（メタ）アクリル系重合体（Ｐ）の合計質量が７０質量％以上である［１］に記載の積層体。
［３］前記硬化性組成物中の前記（メタ）アクリル系重合体（Ｐ）のガラス転移温度（Ｔｇ）が６０℃以上である［１］又は［２］に記載の積層体。
［４］前記硬化性組成物中の前記（メタ）アクリル系重合体（Ｐ）の配合量が、前記（メタ）アクリレート（Ｍ）１００質量部に対して、１０質量部以上２００質量部以下である［１］から［３］のいずれか１項に記載の積層体。
［５］前記硬化性組成物が、さらに光重合開始剤を含む［１］から［４］のいずれか１項に記載の積層体。
［６］前記光重合開始剤が、光吸収スペクトルの２００ｎｍ以上２８０ｎｍ以下の領域に極大吸収波長を有する化合物である[５]に記載の積層体。
［７］前記光重合開始剤がベンゾフェノンである［６］に記載の積層体。
［８］前記（メタ）アクリレート（Ｍ）のラジカル重合可能な二重結合の数が４から１５である［１］から［７］のいずれか１項に記載の積層体。
［９］前記基材に含まれる（メタ）アクリル系重合体（Ｓ）の構成単位の８０％以上がメタクリル酸メチルに由来する構成単位である［１］から［８］のいずれか１項に記載の積層体。
［１０］前記基材がフィルム状であり、その片面だけに前記ハードコート層を有している［１］から［９］のいずれか１項に記載の積層体からなる偏光子保護フィルム。
［１１］［１０］記載の偏光子保護フィルムのハードコート層を有していない面を偏光子に貼り合わせてなる偏光板。
[1] A laminate in which a hard coat layer containing a cured product of a curable composition is directly laminated on a surface of a substrate containing a (meth)acrylic polymer (S), the curable composition being a curable composition containing a (meth)acrylate (M) having three or more radically polymerizable double bonds and a (meth)acrylic polymer (P) having a mass average molecular weight of 1,000 or more and 70,000 or less.
[2] The laminate according to [1], wherein the total mass of the (meth)acrylate (M) and the (meth)acrylic polymer (P) in the curable composition is 70 mass% or more.
[3] The laminate according to [1] or [2], wherein the (meth)acrylic polymer (P) in the curable composition has a glass transition temperature (Tg) of 60° C. or higher.
[4] The laminate according to any one of [1] to [3], wherein the blending amount of the (meth)acrylic polymer (P) in the curable composition is 10 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the (meth)acrylate (M).
[5] The laminate according to any one of [1] to [4], wherein the curable composition further contains a photopolymerization initiator.
[6] The laminate according to [5], wherein the photopolymerization initiator is a compound having a maximum absorption wavelength in the region of 200 nm or more and 280 nm or less in the light absorption spectrum.
[7] The laminate according to [6], wherein the photopolymerization initiator is benzophenone.
[8] The laminate according to any one of [1] to [7], wherein the (meth)acrylate (M) has 4 to 15 radically polymerizable double bonds.
[9] The laminate according to any one of [1] to [8], wherein 80% or more of the structural units of the (meth)acrylic polymer (S) contained in the base material are structural units derived from methyl methacrylate.
[10] A polarizer protective film comprising the laminate according to any one of [1] to [9], wherein the substrate is in the form of a film and has the hard coat layer on only one side thereof.
[11] A polarizing plate obtained by attaching the surface of the polarizer protective film according to [10] that does not have a hard coat layer to a polarizer.
本発明によれば、表面が（メタ）アクリル系重合体を含む基材と当該（メタ）アクリル系重合体を含む基材の表面にハードコート層が直接積層されている積層体において、前記基材とハードコート層との密着性、ハードコート層の表面硬度及び表面平滑性に優れた積層体、この積層体からなる偏光子保護フィルム、及びこの偏光子保護フィルムを偏光子に貼り合せてなる偏光板を提供することができる。 According to the present invention, it is possible to provide a laminate in which a substrate having a surface containing a (meth)acrylic polymer and a hard coat layer is directly laminated on the surface of the substrate containing the (meth)acrylic polymer, the laminate having excellent adhesion between the substrate and the hard coat layer, and excellent surface hardness and surface smoothness of the hard coat layer, a polarizer protective film made of this laminate, and a polarizing plate obtained by bonding this polarizer protective film to a polarizer.
本発明において、「（メタ）アクリレート」という表現を用いる場合、「アクリレート」及び「メタクリレート」の一方又は両方を意味するものとする。「（メタ）アクリロイル」という表現を用いる場合、「アクリロイル」及び「メタクリロイル」の一方又は両方を意味するものとする。「（メタ）アクリル」という表現を用いる場合、「アクリル」及び「メタクリル」の一方又は両方を意味するものとする。 In the present invention, when the term "(meth)acrylate" is used, it means one or both of "acrylate" and "methacrylate". When the term "(meth)acryloyl" is used, it means one or both of "acryloyl" and "methacryloyl". When the term "(meth)acrylic" is used, it means one or both of "acrylic" and "methacrylic".
本発明の積層体は、硬化性組成物の硬化物を含むハードコート層（以下、単に「ハードコート層」ともいう。）が基材の（メタ）アクリル系重合体（Ｓ）を含む表面に直接積層されている積層体である。 The laminate of the present invention is a laminate in which a hard coat layer (hereinafter, also simply referred to as "hard coat layer") containing a cured product of a curable composition is laminated directly on a surface of a substrate containing a (meth)acrylic polymer (S).
［ハードコート層］
本発明の積層体におけるハードコート層は、ラジカル重合可能な二重結合を３個以上有する（メタ）アクリレート（Ｍ）と、質量平均分子量が１０００以上７００００以下の（メタ）アクリル系重合体（Ｐ）を含む硬化性組成物の硬化物を含む。
[Hard coat layer]
The hard coat layer in the laminate of the present invention contains a cured product of a curable composition containing a (meth)acrylate (M) having three or more radically polymerizable double bonds and a (meth)acrylic polymer (P) having a mass average molecular weight of 1,000 or more and 70,000 or less.
前記硬化性組成物は（メタ）アクリレート（Ｍ）を含むことで硬化性組成物の硬化物を含む層の表面硬度が良好となる。 The curable composition contains (meth)acrylate (M), which improves the surface hardness of the layer containing the cured product of the curable composition.
（メタ）アクリレート（Ｍ）としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、ポロポキシ化トリメチロールプロパントリ（メタ）アクリレート、トリス－２－ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、グリセリントリ（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、ジペンタエリスリトールトリ（メタ）アクリレート、ジ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テトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパンペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンヘキサ（メタ）アクリレート等の３官能以上の多官能（メタ）アクリレート；これらの（メタ）アクリレートの一部をアルキル基やε－カプロラクトンで置換した多官能（メタ）アクリレート化合物の変性物；イソシアヌレート構造を有する多官能（メタ）アクリレート等の窒素原子含有複素環構造を有する多官能（メタ）アクリレート；デンドリマー構造を有する多官能（メタ）アクリレート、ハイパーブランチ構造を有する多官能（メタ）アクリレート等の多分岐樹脂状構造を有する多官能（メタ）アクリレート；イソシアネートやトリイソシアネート、イソシアヌレートに、例えば、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の水酸基を有する（メタ）アクリレートが付加したウレタン（メタ）アクリレート等が挙げられる。これらの中でも、前記（メタ）アクリル系重合体（Ｐ）との相溶性の点から、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートが好ましく、鉛筆硬度の点から、ジペンタエリスリトールペンタアクリレートとヘキサメチレンジイソシアネートの３量体の付加物であるウレタン（メタ）アクリレート、ジペンタエリスリトールペンタアクリレートとイソホロンジイソシアネートの付加物であるウレタン（メタ）アクリレートが好ましい。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 Examples of (meth)acrylates (M) include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris-2-hydroxyethyl isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, Examples of the polyfunctional (meth)acrylate include polyfunctional (meth)acrylates having three or more functional groups such as acrylates; modified polyfunctional (meth)acrylate compounds in which a portion of these (meth)acrylates is substituted with an alkyl group or ε-caprolactone; polyfunctional (meth)acrylates having a nitrogen atom-containing heterocyclic structure such as polyfunctional (meth)acrylates having an isocyanurate structure; polyfunctional (meth)acrylates having a multi-branched resin structure such as polyfunctional (meth)acrylates having a dendrimer structure and polyfunctional (meth)acrylates having a hyperbranched structure; and urethane (meth)acrylates in which a (meth)acrylate having a hydroxyl group, such as pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, is added to an isocyanate, triisocyanate, or isocyanurate. Among these, from the viewpoint of compatibility with the (meth)acrylic polymer (P), pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred, and from the viewpoint of pencil hardness, urethane (meth)acrylate, which is an adduct of a trimer of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, and urethane (meth)acrylate, which is an adduct of dipentaerythritol pentaacrylate and isophorone diisocyanate, are preferred. These may be used alone or in combination of two or more.
（メタ）アクリレート（Ｍ）のラジカル重合可能な二重結合の数は、ハードコート層の硬度の点から４から１５が好ましい。 The number of radically polymerizable double bonds in the (meth)acrylate (M) is preferably 4 to 15 in terms of the hardness of the hard coat layer.
前記硬化性組成物中の（メタ）アクリレート（Ｍ）の含有量は、（メタ）アクリレート（Ｍ）と（メタ）アクリル系重合体（Ｐ）との合計１００質量％に対して、１０質量％以上９０質量％以下が好ましく、２０質量％以上８０質量％以下がより好ましく、３０質量％以上７０質量％以下がさらに好ましい。（メタ）アクリレート（Ｍ）の含有量は、多いほどハードコート層の硬度が高くなり、少ないほどハードコート層と基材との密着性が高くなる。 The content of (meth)acrylate (M) in the curable composition is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less, based on 100% by mass of the total of (meth)acrylate (M) and (meth)acrylic polymer (P). The higher the content of (meth)acrylate (M), the higher the hardness of the hard coat layer, and the lower the content, the higher the adhesion between the hard coat layer and the substrate.
また本発明では、前記硬化性組成物が（メタ）アクリル系重合体（Ｐ）を含むことで、ハードコート層の平滑性と表面硬度が良好となる。（メタ）アクリル系重合体（Ｐ）の質量平均分子量は１０００以上７００００以下であり、３０００以上５００００以下が好ましく、５０００以上３００００以下がより好ましい。 In the present invention, the curable composition contains a (meth)acrylic polymer (P), which improves the smoothness and surface hardness of the hard coat layer. The mass average molecular weight of the (meth)acrylic polymer (P) is 1,000 or more and 70,000 or less, preferably 3,000 or more and 50,000 or less, and more preferably 5,000 or more and 30,000 or less.
（メタ）アクリル系重合体（Ｐ）の質量平均分子量が１０００未満ではハードコート層の表面硬度が低下することがある。また、（メタ）アクリル系重合体（Ｐ）の質量平均分子量が７００００を超えるとハードコート層の平滑性が低下することがある。 If the mass average molecular weight of the (meth)acrylic polymer (P) is less than 1,000, the surface hardness of the hard coat layer may decrease. If the mass average molecular weight of the (meth)acrylic polymer (P) is more than 70,000, the smoothness of the hard coat layer may decrease.
（メタ）アクリル系重合体（Ｐ）は、（メタ）アクリル酸アルキルエステルを主な構成単位とする重合体である。前記（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル及び（メタ）アクリル酸ｎ－ヘキシル等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。これらの中でも、（メタ）アクリル系重合体（Ｐ）の（メタ）アクリレート（Ｍ）との相溶性、ハードコート層の耐熱性の点から、（メタ）アクリル酸メチルが好ましい。
（メタ）アクリル系重合体（Ｐ）はラジカル重合可能な二重結合を有するものであってもよい。
The (meth)acrylic polymer (P) is a polymer having a (meth)acrylic acid alkyl ester as a main constituent unit. Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, and n-hexyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, methyl (meth)acrylate is preferred from the viewpoints of the compatibility of the (meth)acrylic polymer (P) with the (meth)acrylate (M) and the heat resistance of the hard coat layer.
The (meth)acrylic polymer (P) may have a radically polymerizable double bond.
（メタ）アクリル系重合体（Ｐ）のガラス転移温度（Ｔｇ）は、ハードコート層の機械特性を良好にする点から、６０℃以上が好ましく、８０℃以上がより好ましく、９０℃以上がさらに好ましい。また、そのガラス転移温度（Ｔｇ）はハードコート層を積層させた積層体の加工性を良好にする点から、１４０℃以下が好ましく、１３０℃以下がより好ましく、１２０℃以下がさらに好ましい。 The glass transition temperature (Tg) of the (meth)acrylic polymer (P) is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, from the viewpoint of improving the mechanical properties of the hard coat layer. In addition, the glass transition temperature (Tg) is preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower, from the viewpoint of improving the processability of the laminate in which the hard coat layer is laminated.
ガラス転移温度（Ｔｇ）は、（メタ）アクリル系重合体（Ｐ）を形成する単量体の種類および質量分率から、下記のＦｏｘの式より求められる。
１／Ｔｇ＝Σ（Ｗｉ／Ｔｇｉ）
この式で、Ｔｇは（メタ）アクリル系重合体（Ｐ）のガラス転移温度（単位はＫ）、Ｗｉは（メタ）アクリル系重合体（Ｐ）を構成する単量体ｉ由来の単量体単位の質量分率、Ｔｇｉは単量体ｉの単独重合体のガラス転移温度（単位はＫ）を示す。Ｔｇｉの値は、ＰＯＬＹＭＥＲＨＡＮＤＢＯＯＫ Ｖｏｌｕｍｅ １（ＷＩＬＥＹ－ＩＮＴＥＲＳＣＩＥＮＣＥ）に記載の値を用いることができる。
The glass transition temperature (Tg) can be calculated from the type and mass fraction of the monomers forming the (meth)acrylic polymer (P) by the following Fox formula.
1/Tg=Σ(Wi/Tg i )
In this formula, Tg represents the glass transition temperature (unit: K) of the (meth)acrylic polymer (P), W i represents the mass fraction of the monomer unit derived from the monomer i constituting the (meth)acrylic polymer (P), and Tg i represents the glass transition temperature (unit: K) of a homopolymer of the monomer i. As the value of Tg i , the value described in POLYMER HANDBOOK Volume 1 (WILEY-INTERSCIENCE) can be used.
前記硬化性組成物中の（メタ）アクリル系重合体（Ｐ）の配合量は、ハードコート層の硬度の点から、（メタ）アクリレート（Ｍ）１００質量部に対して、５質量部以上２００質量部以下が好ましく、１０質量部以上１００質量部以下がより好ましい。 The amount of the (meth)acrylic polymer (P) in the curable composition is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the (meth)acrylate (M) in terms of the hardness of the hard coat layer.
前記硬化性組成物中の（メタ）アクリレート（Ｍ）及び（メタ）アクリル系重合体（Ｐ）の合計質量は、ハードコート層の硬度と、ハードコート層と基材との密着性が良好となる点から、７０質量％以上が好ましく、８０質量％以上がより好ましい。 The total mass of the (meth)acrylate (M) and the (meth)acrylic polymer (P) in the curable composition is preferably 70% by mass or more, and more preferably 80% by mass or more, in order to improve the hardness of the hard coat layer and the adhesion between the hard coat layer and the substrate.
（メタ）アクリル系重合体（Ｐ）の製造方法としては、例えば、溶液重合法、懸濁重合法及び乳化重合が挙げられる。（メタ）アクリル系重合体（Ｐ）の質量平均分子量は、重合開始剤、連鎖移動剤、固形分濃度又は反応条件等により調整することができる。 Methods for producing the (meth)acrylic polymer (P) include, for example, solution polymerization, suspension polymerization, and emulsion polymerization. The mass average molecular weight of the (meth)acrylic polymer (P) can be adjusted by the polymerization initiator, chain transfer agent, solids concentration, reaction conditions, etc.
本発明で用いる前記硬化性組成物には、有機溶媒を含んでいてもよい。その場合、（メタ）アクリル系重合体（Ｐ）は、有機溶媒に容易に溶解することができる点から、粒子形状のものを用いることが好ましい。粒子形状の（メタ）アクリル系重合体（Ｐ）の製造方法としては懸濁重合法が好ましい。 The curable composition used in the present invention may contain an organic solvent. In that case, it is preferable to use a particulate (meth)acrylic polymer (P) because it can be easily dissolved in an organic solvent. A suspension polymerization method is preferable as a method for producing a particulate (meth)acrylic polymer (P).
懸濁重合法による（メタ）アクリル系重合体（Ｐ）の製造方法としては、例えば、水、
分散剤及び単量体を含む水性懸濁液中に重合開始剤を添加した後にこれを加熱して懸濁重合を実施し、次いで、重合後の水性懸濁液を濾過、洗浄、脱水及び乾燥する方法が挙げられる。
The (meth)acrylic polymer (P) can be produced by suspension polymerization using, for example, water,
An example of such a method is a method in which a polymerization initiator is added to an aqueous suspension containing a dispersant and a monomer, the suspension is heated to carry out suspension polymerization, and then the aqueous suspension after polymerization is filtered, washed, dehydrated and dried.
前記懸濁重合法で用いる分散剤としては、例えば、ポリ（メタ）アクリル酸アルカリ金属塩、（メタ）アクリル酸アルカリ金属塩と（メタ）アクリル酸メチルの共重合体、ケン化度７０％以上１００％以下のポリビニルアルコ－ル及びメチルセルロ－ス等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 Examples of dispersants used in the suspension polymerization method include poly(alkali metal (meth)acrylate), copolymers of alkali metal (meth)acrylate and methyl (meth)acrylate, polyvinyl alcohol and methyl cellulose having a degree of saponification of 70% to 100%, etc. These may be used alone or in combination of two or more.
前記懸濁重合法における分散剤の添加量としては、懸濁重合における分散安定性並びに得られる粒子形状の重合体の洗浄性、脱水性、乾燥性及び流動性が向上する点から、重合させる全単量体１００質量部に対して０．００５質量部以上５質量部以下が好ましく、０．０１質量部以上１質量部以下がより好ましい。 The amount of dispersant added in the suspension polymerization method is preferably 0.005 parts by mass or more and 5 parts by mass or less, and more preferably 0.01 parts by mass or more and 1 part by mass or less, per 100 parts by mass of the total monomers to be polymerized, in order to improve the dispersion stability in the suspension polymerization and the washability, dewaterability, drying property and flowability of the resulting particulate polymer.
前記懸濁重合法では分散安定性向上を目的として、水性懸濁液中に炭酸ナトリウム、硫酸ナトリウム、硫酸マンガン等の電解質を加えることもできる。 In the suspension polymerization method, electrolytes such as sodium carbonate, sodium sulfate, and manganese sulfate can be added to the aqueous suspension to improve dispersion stability.
前記懸濁重合法で用いる重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等のアゾ化合物；ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ｔ－ブチルパーオキシ２－エチルヘキサノエート、ｔ－ヘキシルパーオキシ２－エチルヘキサノエート、１，１，３，３－テトラメチルブチルパーオキシ２－エチルヘキサノエート、ｔ－ヘキシルハイドロパーオキサイド等の有機過酸化物；及び過酸化水素、過硫酸ナトリウム、過硫酸アンモニウム等の無機過酸化物が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 Examples of polymerization initiators used in the suspension polymerization method include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, and t-hexyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, sodium persulfate, and ammonium persulfate. These may be used alone or in combination of two or more.
（メタ）アクリル系重合体（Ｐ）を製造する際、連鎖移動剤を使用することができる。連鎖移動剤としては、例えば、ｎ－ドデシルメルカプタン等のメルカプタン、チオグリコール酸オクチル等のチオグリコール酸エステル、ビス（ボロンジフルオロジフェニルグリオキシメイト）コバルト（ＩＩ）等のコバルト金属錯体、α－メチルスチレンダイマー及びターピノーレンが挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。これらの中で、前記硬化性組成物の臭気や前記硬化性組成物の硬化物の耐候性の点から、ビス（ボロンジフルオロジフェニルグリオキシメイト）コバルト（ＩＩ）等のコバルト金属錯体が好ましい。 When producing the (meth)acrylic polymer (P), a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, cobalt metal complexes such as bis(boron difluorodiphenyl glyoximate) cobalt (II), α-methylstyrene dimer, and terpinolene. These may be used alone or in combination of two or more. Among these, cobalt metal complexes such as bis(boron difluorodiphenyl glyoximate) cobalt (II) are preferred from the viewpoints of odor of the curable composition and weather resistance of the cured product of the curable composition.
（メタ）アクリル系重合体（Ｐ）を製造する際の重合温度としては、短時間での重合及び重合安定性の点から、５０℃以上１３０℃以下が好ましく、６０℃以上１００℃以下がより好ましい。 The polymerization temperature when producing the (meth)acrylic polymer (P) is preferably 50°C or higher and 130°C or lower, more preferably 60°C or higher and 100°C or lower, from the viewpoints of short-term polymerization and polymerization stability.
また本発明では、前記硬化性組成物はさらに光重合開始剤を含むことが好ましい。 In the present invention, it is also preferable that the curable composition further contains a photopolymerization initiator.
前記光重合開始剤は、硬化性組成物に添加しておくことで光照射によって重合反応を惹起する触媒作用を有するので、硬化性組成物の硬化性向上が期待できる。前記光重合開始剤としては例えば、光ラジカル発生剤、光酸発生剤等が挙げられる。 The photopolymerization initiator, when added to the curable composition, has a catalytic effect of inducing a polymerization reaction by irradiation with light, and is therefore expected to improve the curability of the curable composition. Examples of the photopolymerization initiator include a photoradical generator and a photoacid generator.
前記光ラジカル発生剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとそのアルキルエーテル類；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン［例えば、商品名「Ｏｍｎｉｒａｄ（登録商
標）１８４」、ＩＧＭ製］、オキシ－フェニル－アセチックアシッド２－［２－オキソ－２－フェニル-アセトキシ－エトキシ]－エチルエステルとオキシ－フェニル－アセチックアシッド２－［２－ヒドロキシ－エトキシ]－エチルエステルとの混合物［例えば、商品
名「Ｏｍｎｉｒａｄ（登録商標）７５４」、ＩＧＭ製］、２－ヒドロキシ－１－｛４－[
４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル]－フェニル｝－２－メ
チル－プロパン－１－オン［例えば、商品名「Ｏｍｎｉｒａｄ（登録商標）１２７」、ＩＧＭ製］、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン［例えば、商品名「Ｏｍｎｉｒａｄ（登録商標）２９５９」、ＩＧＭ製］、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ン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－１－ブタノン等のアセトフェノン類；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シド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド等のホスフィンオキシド類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、１－クロロアントラキノン、２－アミルアントラキノン等のアントラキノン類；ベンゾフェノン及びその誘導体からなるベンゾフェノン類；ベンゾイルギ酸メチル、ベンゾイルギ酸エチル等のギ酸誘導体等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。
Examples of the photoradical generator include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone [e.g., trade name "Omnirad (registered trademark) 184", manufactured by IGM], a mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester [e.g., trade name "Omnirad (registered trademark) 754", manufactured by IGM], 2-hydroxy-1-{4-[
4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one [e.g., trade name "Omnirad (registered trademark) 127", manufactured by IGM], 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one [e.g., trade name "Omnirad (registered trademark) 2959", manufactured by IGM], 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 acetophenones such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc.; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, etc.; benzophenones consisting of benzophenone and derivatives thereof; formic acid derivatives such as methyl benzoylformate, ethyl benzoylformate, etc. These may be used alone or in combination of two or more.
前記光酸発生剤としては公知のものが使用可能であるが、例えば、ジアリールヨードニウム塩、トリアリールスルホニウム塩等が挙げられる。具体的には、ＰＦ６塩、ＳｂＦ５塩、テトラキス（パーフルオロフェニル）ボレート塩等のジ（アルキル置換）フェニルヨードニウムのアニオン塩が挙げられる。これらの中でも、硬化性、酸発生効率が良好である点から、ジアルキルフェニルヨードニウムのＰＦ６塩［商品名「Ｏｍｎｉｃａｔ（登録商標）２５０」、ＩＧＭ製］が好ましい。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 The photoacid generator may be any known one, such as diaryliodonium salts and triarylsulfonium salts. Specific examples include anion salts of di(alkyl-substituted)phenyliodonium, such as PF6 salt, SbF5 salt, and tetrakis(perfluorophenyl)borate salt. Among these, PF6 salt of dialkylphenyliodonium [trade name "Omnicat (registered trademark) 250", manufactured by IGM] is preferred because of its good curing properties and acid generation efficiency. These may be used alone or in combination of two or more.
光重合開始剤としては、基材に塗布した硬化性組成物に活性エネルギー線を照射して硬化物を含む層を形成する際に塗膜の深部の硬化が表面より遅延するため硬化物を含む層と基材の（メタ）アクリル系重合体（Ｓ）を含む表面との密着性が高くなることから、光吸収スペクトルの２００ｎｍ以上３１５ｎｍ以下の波長帯の領域に極大吸収波長を有する光ラジカル発生剤が好ましく、２００ｎｍ以上２８０ｎｍ以下の短波長帯の領域に極大吸収波長を有する光ラジカル発生剤（以下、このような光ラジカル発生剤を特に「光ラジカル発生剤（Ｘ）」という。）がより好ましい。光ラジカル発生剤（Ｘ）としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン、オキシ－フェニル－アセチックアシッド２－［２－オキソ－２－フェニル-アセトキシ－エトキシ]－エチルエステルとオキシ－フェニル－アセチックアシッド２－［２－ヒドロキシ－エトキシ]－エチルエステルの混合
物、２－ヒドロキシ－１－｛４－[４－（２－ヒドロキシ－２－メチル－プロピオニル）
－ベンジル]－フェニル｝－２－メチル－プロパン－１－オン、１－［４－（２－ヒドロ
キシエトキシ）フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、ベンゾフェノン類、アセトフェノン類が挙げられる。
As the photopolymerization initiator, a photoradical generator having a maximum absorption wavelength in the wavelength band region of 200 nm or more and 315 nm or less in the light absorption spectrum is preferred, and a photoradical generator having a maximum absorption wavelength in the short wavelength band region of 200 nm or more and 280 nm or less (hereinafter, such a photoradical generator will be particularly referred to as "photoradical generator (X)") is more preferred, because when a layer containing a cured product is formed by irradiating an active energy ray to a curable composition applied to a substrate, curing of the deeper part of the coating film is delayed compared to the surface, thereby increasing adhesion between the layer containing the cured product and the surface of the substrate containing the (meth)acrylic polymer (S). Examples of the photoradical generator (X) include 1-hydroxycyclohexyl phenyl ketone, a mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)
-benzyl]-phenyl}-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, benzophenones, and acetophenones.
前記硬化性組成物中の前記光重合開始剤の含有量は、硬化性を向上させる点から、硬化性組成物中の（メタ）アクリロイル基を有する化合物の合計１００質量部に対して、０．１質量部以上が好ましく、０．５質量部以上がより好ましく、１．０質量部以上がさらに好ましい。また、硬化性組成物の安定性が良好である点から、１５質量部以下が好ましく、１０質量部以下がより好ましく、７質量部以下さらに好ましい。また、前記光重合開始剤中に光ラジカル発生剤（Ｘ）が占める比率は、密着性の観点から５質量％以上が好ましく、３０質量％以上がより好ましく、７０質量％以上がさらに好ましい。９０質量％以上が特に好ましい。 The content of the photopolymerization initiator in the curable composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, based on 100 parts by mass of the total of the compounds having a (meth)acryloyl group in the curable composition, from the viewpoint of improving the curability. Also, from the viewpoint of good stability of the curable composition, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. Also, the ratio of the photoradical generator (X) in the photopolymerization initiator is preferably 5% by mass or more, more preferably 30% by mass or more, and even more preferably 70% by mass or more, from the viewpoint of adhesion. 90% by mass or more is particularly preferable.
さらに本発明における硬化性組成物は、本発明の効果を阻害しない範囲で、前記（メタ）アクリレート（Ｍ）、前記（メタ）アクリル系重合体（Ｐ）及び光重合開始剤以外の「その他の成分」を含んでいてもよい。その他の成分としては、有機溶媒、紫外線吸収剤、ヒンダートアミン系光安定剤、充填剤、シランカップリング剤、前記（メタ）アクリレート（Ｍ）以外の（メタ）アクリレート等の重合性希釈剤、帯電防止剤、有機顔料、有機粒子、無機粒子、レベリング剤、分散剤、チクソトロピー性付与剤（増粘剤）、消泡剤、酸化防止剤等が挙げられる。 Furthermore, the curable composition of the present invention may contain "other components" other than the (meth)acrylate (M), the (meth)acrylic polymer (P) and the photopolymerization initiator, to the extent that the effect of the present invention is not impaired. Examples of other components include organic solvents, ultraviolet absorbers, hindered amine light stabilizers, fillers, silane coupling agents, polymerizable diluents such as (meth)acrylates other than the (meth)acrylate (M), antistatic agents, organic pigments, organic particles, inorganic particles, leveling agents, dispersants, thixotropic agents (thickeners), defoamers, antioxidants, etc.
前記有機溶媒としては、特に限定されるものではなく、前記硬化性組成物に含まれる成分の種類等を考慮して適宜選択することができる。有機溶媒の具体例としては、例えば、トルエン、キシレン等の芳香族系溶媒；メチルエチルケトン（ＭＥＫ）、アセトン、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン等のケトン系溶媒；ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル（ＰＧＭ）、アニソール、フェネトール等のエーテル系溶媒；酢酸エチル、酢酸ブチル、酢酸イソプロピル、エチレングリコールジアセテート等のエステル系溶媒；ジメチルホルムアミド、ジエチルホルムアミド、Ｎ－メチルピロリドン等のアミド系溶媒；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等のセロソルブ系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒等が挙げられる。 The organic solvent is not particularly limited, and may be appropriately selected in consideration of the types of components contained in the curable composition. Specific examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform.
有機溶媒は１種のみで用いても２種以上を組み合わせて用いてもよい。これらの中でも、（メタ）アクリレート（Ｍ）と（メタ）アクリル系重合体（Ｐ）との相溶性が良好となる点から、エステル系溶媒、エーテル系溶媒、アルコール系溶媒及びケトン系溶媒が好ましい。 The organic solvent may be used alone or in combination of two or more. Among these, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred because they provide good compatibility between the (meth)acrylate (M) and the (meth)acrylic polymer (P).
有機溶媒の使用量は特に制限はなく、硬化性組成物の塗布性、液の粘度・表面張力、固形分との相溶性等を考慮して適宜決定される。前記硬化性組成物の固形分濃度は、有機溶媒の量により調整される。前記硬化性組成物の固形分濃度は、２０質量％以上９５質量％以下が好ましく、２５質量％以上８０質量％以下がより好ましい。ここで、硬化性組成物における「固形分」とは硬化性組成物中の溶媒以外の成分を意味する。 The amount of organic solvent used is not particularly limited, and is appropriately determined in consideration of the coatability of the curable composition, the viscosity and surface tension of the liquid, and compatibility with the solid content. The solid content concentration of the curable composition is adjusted by the amount of organic solvent. The solid content concentration of the curable composition is preferably 20% by mass or more and 95% by mass or less, and more preferably 25% by mass or more and 80% by mass or less. Here, the "solid content" in the curable composition means the components other than the solvent in the curable composition.
前記硬化性組成物の粘度は、塗装性とハードコート層の平滑性が良好となる点から、３０ｍＰａ・ｓ以下が好ましく、２５ｍＰａ・ｓ以下がより好ましい。 The viscosity of the curable composition is preferably 30 mPa·s or less, and more preferably 25 mPa·s or less, in order to improve the coatability and smoothness of the hard coat layer.
前記硬化性組成物の製造方法は特に制限されないが、例えば、（メタ）アクリレート（Ｍ）、（メタ）アクリル系重合体（Ｐ）、及び必要により、重合開始剤、有機溶媒、その他の成分等を混合する方法が挙げられる。各成分の混合に際しては、通常使用されるディスパーザー、撹拌機等で均一に混合することが好ましい。 The method for producing the curable composition is not particularly limited, but examples thereof include a method of mixing (meth)acrylate (M), (meth)acrylic polymer (P), and, if necessary, a polymerization initiator, an organic solvent, other components, etc. When mixing the components, it is preferable to mix them uniformly using a disperser, a stirrer, etc. that are commonly used.
［基材］
本発明の積層体における基材は、ハードコート層が積層されている表面に（メタ）アクリル系重合体（Ｓ）を含む。基材の形状はシート形状、フィルム形状等が挙げられる。
[Base material]
The substrate in the laminate of the present invention contains a (meth)acrylic polymer (S) on the surface on which the hard coat layer is laminated. The shape of the substrate may be a sheet shape, a film shape, or the like.
（メタ）アクリル系重合体（Ｓ）は（メタ）アクリル酸及び（メタ）アクリル酸の誘導体から選ばれる少なくとも１種の単量体を主な構成単位とする重合体を意味する。前記（メタ）アクリル酸の誘導体としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）ア
クリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸４－ｔ－ブチルシクロヘキシル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸ジシクロペンタジエニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸γ－ブチロラクトン等の（メタ）アクリル酸エステル類等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。これらの中でも前記基材の透明性及び光学特性が良好となる点から、メタクリル酸メチルが好ましく、前記基材の機械特性、耐熱性が良好となる点から、（メタ）アクリル酸γ－ブチロラクトンが好ましい。
The (meth)acrylic polymer (S) means a polymer having at least one monomer selected from (meth)acrylic acid and derivatives of (meth)acrylic acid as a main constituent unit. Examples of the derivatives of (meth)acrylic acid include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, adamantyl (meth)acrylate, and γ-butyrolactone (meth)acrylate. These may be used alone or in combination of two or more. Among these, methyl methacrylate is preferred from the viewpoint of improving the transparency and optical properties of the substrate, and γ-butyrolactone (meth)acrylate is preferred from the viewpoint of improving the mechanical properties and heat resistance of the substrate.
また、（メタ）アクリル系重合体（Ｓ）は、耐熱性、透明性、表面硬度を損なわない範囲で（メタ）アクリル酸及び（メタ）アクリル酸の誘導体以外のその他の単量体の構成単位を含んでいてもよい。その他の単量体としては、例えば、芳香族ビニル化合物、ジエン系化合物、不飽和カルボン酸、不飽和カルボン酸無水物、マレイミド類、（メタ）アクリルアミド誘導体等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 The (meth)acrylic polymer (S) may also contain structural units of other monomers other than (meth)acrylic acid and derivatives of (meth)acrylic acid, as long as the heat resistance, transparency, and surface hardness are not impaired. Examples of other monomers include aromatic vinyl compounds, diene compounds, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimides, (meth)acrylamide derivatives, and the like. These may be used alone or in combination of two or more.
これらの中でも、前記基材の耐熱性の点から、不飽和カルボン酸無水物、マレイミド類が好ましい。不飽和カルボン酸無水物としては、無水マレイン酸等が挙げられる。マレイミド類としては、マレイミド、Ｎ－フェニルマレイミド等が挙げられる。（メタ）アクリルアミド誘導体としては（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド等が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。これらの中でも、前記基材の機械特性、耐熱性が良好となる点から、マレイミドが好ましい。 Among these, unsaturated carboxylic anhydrides and maleimides are preferred from the viewpoint of the heat resistance of the substrate. Examples of unsaturated carboxylic anhydrides include maleic anhydride. Examples of maleimides include maleimide and N-phenylmaleimide. Examples of (meth)acrylamide derivatives include (meth)acrylamide and N,N-dimethyl(meth)acrylamide. These may be used alone or in combination of two or more. Among these, maleimides are preferred from the viewpoint of providing good mechanical properties and heat resistance of the substrate.
本発明において、前記（メタ）アクリル系重合体（Ｓ）中の前記（メタ）アクリル酸及び（メタ）アクリル酸の誘導体の構成単位の含有量は基材の機械特性や光学特性を良好にする点から、前記（メタ）アクリル系重合体（Ｓ）１００質量％に対し８０質量％以上１００質量％以下が好ましく、９０質量％以上１００質量％以下がより好ましく、９７質量％以上１００質量％以下がさらに好ましい。 In the present invention, the content of the structural units of the (meth)acrylic acid and (meth)acrylic acid derivatives in the (meth)acrylic polymer (S) is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 97% by mass or more and 100% by mass or less, relative to 100% by mass of the (meth)acrylic polymer (S), in order to improve the mechanical properties and optical properties of the substrate.
前記（メタ）アクリル系重合体（Ｓ）の質量平均分子量は（Ｍｗ）は、基材の靱性が十分に得られる点から、７万以上が好ましく、１０万以上がより好ましく、１５万以上がさらに好ましく、２０万以上が特に好ましい。また、（メタ）アクリル系重合体（Ｓ）の質量平均分子量（Ｍｗ）は、基材の溶融粘度を低くして成型加工性を良好にできる点から、１５０万以下が好ましく、１００万以下がより好ましく、７０万以下がさらに好ましい。 The mass average molecular weight (Mw) of the (meth)acrylic polymer (S) is preferably 70,000 or more, more preferably 100,000 or more, even more preferably 150,000 or more, and particularly preferably 200,000 or more, in order to obtain sufficient toughness of the substrate. The mass average molecular weight (Mw) of the (meth)acrylic polymer (S) is preferably 1,500,000 or less, more preferably 1,000,000 or less, and even more preferably 700,000 or less, in order to reduce the melt viscosity of the substrate and improve moldability.
また、前記基材のハードコート層を直接積層する表面以外の部分、例えば基材の内部や反対側の面は、（メタ）アクリル系重合体（Ｓ）とは異なる材質であってもよい。そのような異なる材質としては、例えば、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリビニルアルコール樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリシクロオレフィン樹脂、トリアセチルセルロース樹脂、（メタ）アクリル系重合体（Ｓ）とは異なる（メタ）アクリル系重合体などが挙げられる。これらの中でも透明性及び耐熱性が良好である点から、ポリカーボネート樹脂が好ましく、耐薬品性が良好である点からポリビニルアルコール樹脂が好ましい。そのため、基材としては、これら樹脂の層に（メタ）アクリル系重合体（Ｓ）の層を積層したものが好ましい。 In addition, the portion of the substrate other than the surface on which the hard coat layer is directly laminated, for example, the inside of the substrate or the opposite surface, may be made of a material different from the (meth)acrylic polymer (S). Examples of such different materials include polyester resin, polycarbonate resin, polyurethane resin, polyamide resin, polyimide resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, polycycloolefin resin, triacetyl cellulose resin, and a (meth)acrylic polymer different from the (meth)acrylic polymer (S). Among these, polycarbonate resin is preferred because of its good transparency and heat resistance, and polyvinyl alcohol resin is preferred because of its good chemical resistance. Therefore, the substrate is preferably one in which a layer of the (meth)acrylic polymer (S) is laminated on a layer of these resins.
本明細書において「質量平均分子量」は、Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ法で測定されたポリスチレン換算の質量平均分子量を意味するものとする。 In this specification, "mass average molecular weight" refers to the polystyrene equivalent mass average molecular weight measured by the gel permeation chromatography method.
（メタ）アクリル系重合体（Ｓ）のガラス転移温度（Ｔｇ）は、基材の耐屈曲性が良好となる点から、８０℃以上１５０℃以下が好ましく、９０℃以上１４５℃以下がより好ましく、１００℃以上１４０℃以下がさらに好ましい。 The glass transition temperature (Tg) of the (meth)acrylic polymer (S) is preferably 80°C or higher and 150°C or lower, more preferably 90°C or higher and 145°C or lower, and even more preferably 100°C or higher and 140°C or lower, in order to provide a good bending resistance to the substrate.
本発明の基材の（メタ）アクリル系重合体（Ｓ）を含む表面は、（メタ）アクリル系重合体（Ｓ）以外に、本発明の効果を損なわない範囲でその他の重合体を含んでいてもよい。前記その他の重合体としては、例えば、アセテート系重合体、ポリエステル系重合体、ポリエーテルスルホン系重合体、ポリスルホン系重合体、ポリカーボネート系重合体、ポリアミド系重合体、ポリイミド系重合体、ポリオレフィン系重合体、ノルボルネン系重合体等の環状オレフィン系重合体、ポリアリレート系重合体、ポリスチレン系重合体、ポリビニルアルコール系重合体、およびこれらの混合物が挙げられる。また、（メタ）アクリル系、ウレタン系、（メタ）アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性重合体または紫外線硬化性重合体も用いることができる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。 The surface of the substrate of the present invention containing the (meth)acrylic polymer (S) may contain other polymers in addition to the (meth)acrylic polymer (S) as long as the effect of the present invention is not impaired. Examples of the other polymers include acetate polymers, polyester polymers, polyethersulfone polymers, polysulfone polymers, polycarbonate polymers, polyamide polymers, polyimide polymers, polyolefin polymers, cyclic olefin polymers such as norbornene polymers, polyarylate polymers, polystyrene polymers, polyvinyl alcohol polymers, and mixtures thereof. Thermosetting polymers or ultraviolet-curing polymers such as (meth)acrylic, urethane, (meth)acrylic urethane, epoxy, and silicone may also be used. These may be used alone or in combination of two or more.
前記（メタ）アクリル系重合体（Ｓ）は、前述の単量体の混合物を重合することにより製造することができる。重合にはアゾ系重合開始剤を用いることが好ましい。アゾ系重合開始剤を用いると、過酸化物系重合開始剤を用いた場合と比較して基材の耐熱性が向上する。 The (meth)acrylic polymer (S) can be produced by polymerizing a mixture of the above-mentioned monomers. It is preferable to use an azo-based polymerization initiator for the polymerization. When an azo-based polymerization initiator is used, the heat resistance of the substrate is improved compared to when a peroxide-based polymerization initiator is used.
前記アゾ系重合開始剤としては、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、２,２'－アゾビス（４－メトキシ－２,４－ジメチルバレロニトリル）、２,２'
－アゾビス（２,４－ジメチルバレロニトリル）、２,２'－アゾビス（２－メチルブチロ
ニトリル）、１,１'－アゾビス（シクロヘキサン－１－カルボニトリル）、２－（カルバモイルアゾ）イソブチロニトリル、２,２'－アゾビス［２－メチル－Ｎ－｛１,１－ビス
（ヒドロキシメチル）－２－ヒドロキシエチル｝プロピオンアミド］、２,２'－アゾビス［２－メチル－Ｎ－｛２－（１－ヒドロキシブチル）｝プロピオンアミド］、２,２'－アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）－プロピオンアミド］、２,２'－アゾビス［Ｎ－（２－プロペニル）－２－メチルプロピオンアミド］、２,２'－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２,２'－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）、２,２'－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジハイドロクロライド、２,２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジハイドロクロライド、２,２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジサルフェート・ジハイドレート、２,２'－アゾビス［２－（３,４,５,６－テトラヒドロピリミジン－２－イル）プロパン］ジハイドロクロ
ライド、２,２'－アゾビス［２－｛１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル｝プロパン］ジハイドロクロライド、２,２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２,２'－アゾビス（２－メチルプロピオンアミジン）ジハイドロクロライド、２,２'－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチル－プロピオンアミジン］、２,２'－アゾビス（２－メチルプロピオンアミドキシム）、ジメチル２,２'－アゾビスブチレート、４,４'－アゾビス（４－シアノペンタノイックアシッド）、２,２'－アゾビス（２,４,４－トリメチルペンタン）が挙げられる。これらは１種のみで用いても２種以上を組み合わせて用いてもよい。
The azo-based polymerization initiator may be, for example, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'
-Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis[2-methyl-N-{1,1-bis(hydroxymethyl)-2-hydroxyethyl}propionamide], 2,2'-azobis[2-methyl-N-{2-(1-hydroxybutyl)}propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis[N-(2-propenyl)-2-methyl 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride amide, 2,2'-azobis[2-{1-(2-hydroxyethyl)-2-imidazolin-2-yl}propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methyl-propionamidine], 2,2'-azobis(2-methylpropionamidoxime), dimethyl 2,2'-azobisbutyrate, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2,4,4-trimethylpentane). These may be used alone or in combination of two or more.
基材は、例えば、（メタ）アクリル系重合体（Ｓ）をインフレーション法、Ｔダイ法等の溶融押出成形法、溶液流延法、カレンダー法等任意の方法で成形して製造することがで
きる。また、必要に応じて１軸もしくは２軸延伸処理を行ってもよい。
The substrate can be produced, for example, by molding the (meth)acrylic polymer (S) by any method such as a melt extrusion molding method such as an inflation method or a T-die method, a solution casting method, a calendar method, etc. Furthermore, uniaxial or biaxial stretching treatment may be performed as necessary.
基材には、（メタ）アクリル系重合体（Ｓ）以外に機能性重合体、紫外線吸収剤、酸化防止剤、可塑剤、離型剤、着色防止剤、着色剤、帯電防止剤、難燃剤、位相差低減剤、無機粒子、有機粒子等の添加剤を配合してもよい。 In addition to the (meth)acrylic polymer (S), the substrate may contain additives such as functional polymers, ultraviolet absorbers, antioxidants, plasticizers, release agents, coloring inhibitors, colorants, antistatic agents, flame retardants, retardation reducers, inorganic particles, and organic particles.
［積層体の製造方法］
本発明の積層体の製造方法は特に制限されないが、例えば、基材の（メタ）アクリル系重合体（Ｓ）を含む表面に前記硬化性組成物を塗布して硬化させる方法を挙げることができる。なお、本発明の積層体は、基材の一部の表面、例えば基材がシート状やフィルム状の場合は一方の面にハードコート層が形成されていてもよく、他の面、例えば基材がシート状やフィルム状の場合は裏面にもハードコート層が形成されていてもよい。
[Method of manufacturing laminate]
The method for producing the laminate of the present invention is not particularly limited, and may be, for example, a method of applying the curable composition to the surface of the substrate containing the (meth)acrylic polymer (S) and curing the composition. The laminate of the present invention may have a hard coat layer formed on a part of the substrate surface, for example, on one side when the substrate is in the form of a sheet or film, or may have a hard coat layer formed on the other side, for example, on the back side when the substrate is in the form of a sheet or film.
前記硬化性組成物を基材に塗布する方法としては、例えば、リバースコート法、グラビアコート法、ロッドコート法、バーコート法、マイヤーバーコート法、ダイコート法、スプレーコート法等が挙げられる。 Methods for applying the curable composition to a substrate include, for example, reverse coating, gravure coating, rod coating, bar coating, Mayer bar coating, die coating, spray coating, etc.
基材に塗布した硬化性組成物を硬化する方法としては、例えば、４０℃以上１００℃以下で乾燥させた後、４０℃以上１００℃以下で活性エネルギー線を照射する方法が挙げられる。活性エネルギー線としては、紫外線、電子線、Ｘ線、赤外線及び可視光線が挙げられる。これらの中でも、前記硬化性組成物の硬化性及び基材の劣化防止の点から、紫外線及び電子線が好ましい。 As a method for curing the curable composition applied to the substrate, for example, a method of drying at 40°C or more and 100°C or less, and then irradiating with active energy rays at 40°C or more and 100°C or less can be mentioned. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible light. Among these, ultraviolet rays and electron beams are preferred from the viewpoints of the curability of the curable composition and prevention of deterioration of the substrate.
活性エネルギー線として紫外線を用いる場合、種々の紫外線照射装置を用いることができる。前記紫外線照射装置の光源としては、キセノンランプ、高圧水銀灯、メタルハライドランプ、ＬＥＤ－ＵＶランプ等を使用することができる。 When ultraviolet light is used as the active energy ray, various ultraviolet light irradiation devices can be used. As the light source of the ultraviolet light irradiation device, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, etc. can be used.
紫外線の照射量は、硬化工程で必要とされる（メタ）アクリロイル基の反応率に応じて適宜決定されるが、通常１０ｍＪ／ｃｍ２以上１００００ｍＪ／ｃｍ２以下である。前記硬化性組成物の硬化性、前記硬化物の可撓性等の点から、１５ｍＪ／ｃｍ２以上５０００ｍＪ／ｃｍ２以下が好ましく、２０ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下がより好ましい。 The amount of ultraviolet light irradiation is appropriately determined depending on the reaction rate of the (meth)acryloyl group required in the curing step, but is usually 10 mJ/cm 2 or more and 10,000 mJ/cm 2 or less. From the viewpoints of the curability of the curable composition and the flexibility of the cured product, the amount of ultraviolet light irradiation is preferably 15 mJ/cm 2 or more and 5,000 mJ/cm 2 or less, and more preferably 20 mJ/cm 2 or more and 3,000 mJ/cm 2 or less.
また、活性エネルギー線として電子線を用いる場合、種々の電子線照射装置を使用することができる。電子線の照射量は、硬化工程で必要とされる（メタ）アクリロイル基の反応率に応じて適宜決定されるが、通常、０．５Ｍｒａｄ以上２０Ｍｒａｄ以下である。前記硬化性組成物の硬化性、前記硬化物の可撓性、基材の損傷防止等の点から、１Ｍｒａｄ以上１５Ｍｒａｄ以下が好ましい。 When electron beams are used as the active energy rays, various electron beam irradiation devices can be used. The dose of electron beams is appropriately determined depending on the reaction rate of the (meth)acryloyl group required in the curing process, but is usually 0.5 Mrad to 20 Mrad. From the viewpoints of the curability of the curable composition, the flexibility of the cured product, and prevention of damage to the substrate, it is preferably 1 Mrad to 15 Mrad.
ハードコート層の形成において、前記硬化性組成物の塗布及び硬化は１回のみ行ってもよいし、複数回行ってもよい。塗布及び硬化を複数回繰り返すことで、基材の反りを防止することができる。 In forming the hard coat layer, the application and curing of the curable composition may be performed only once or multiple times. By repeating the application and curing multiple times, warping of the substrate can be prevented.
ハードコート層の厚さは、得られる積層体の鉛筆硬度や耐擦傷性の点から、１μｍ以上が好ましく、３μｍ以上がより好ましく、４μｍ以上がさらに好ましい。また、耐クラック性の点から、５０μｍ以下が好ましく、３０μｍ以下がより好ましく、２０μｍ以下がさらに好ましい。 From the viewpoint of the pencil hardness and scratch resistance of the resulting laminate, the thickness of the hard coat layer is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. From the viewpoint of crack resistance, the thickness is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less.
本発明の積層体に用いる基材の厚さは任意である。基材がフィルム状の場合、その厚さは、１０μｍ以上３ｍｍ以下が好ましく、１５μｍ以上２ｍｍ以下より好ましく、２０μ
ｍ以上１ｍｍ以下がさらに好ましい。
The thickness of the substrate used in the laminate of the present invention is arbitrary. When the substrate is in the form of a film, the thickness is preferably 10 μm or more and 3 mm or less, more preferably 15 μm or more and 2 mm or less, and more preferably 20 μm or more and 3 mm or less.
It is more preferable that the length is from 1 m to 1 mm.
また、本発明の積層体の厚さも任意である。フィルム状の積層体の場合、各層が各々の機能を十分に発揮させる必要性から、積層体の厚さは１０μｍ以上が好ましく、２０μｍ以上がより好ましく、３０μｍ以上がさらに好ましい。また、前記積層体が適用される製品の薄型化、軽量化の要請の点から、積層体の厚さは３ｍｍ以下が好ましく、２ｍｍ以下がより好ましく、１ｍｍ以下がさらに好ましい。 The thickness of the laminate of the present invention is also arbitrary. In the case of a film-like laminate, the thickness of the laminate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, because each layer needs to fully exert its respective function. Furthermore, in view of the demand for thinner and lighter products to which the laminate is applied, the thickness of the laminate is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less.
本発明の積層体は、基材の（メタ）アクリル系重合体（Ｓ）を含む表面に（メタ）アクリレート（Ｍ）及び（メタ）アクリル系重合体（Ｐ）を含む硬化性組成物の硬化物を含むハードコート層を直接積層した積層体であり、基材とハードコート層との密着性及び表面硬度等に優れた積層体である。このため、本発明の積層体は、タッチパネル、液晶テレビ等の光学ディスプレイ用部品；ランプ関連物品、ウインドウ関連物品（リアウィンドウ、サイドウィンドウ、天窓等）等の自動車関連部品；各種電気機器の筐体、化粧板、家具等の生活関連物品等の幅広い物品の表面カバーに好適に用いることができる。これらの中でも光学ディスプレイ用部品として好適であり、特にディスプレイ用偏光板の製造において偏光子に貼りあわせて用いる偏光子保護フィルム、ディスプレイ用保護フィルムに好適に用いることができる。 The laminate of the present invention is a laminate in which a hard coat layer containing a cured product of a curable composition containing a (meth)acrylate (M) and a (meth)acrylic polymer (P) is directly laminated on the surface of a substrate containing a (meth)acrylic polymer (S), and is a laminate excellent in adhesion between the substrate and the hard coat layer and surface hardness. For this reason, the laminate of the present invention can be suitably used for surface covers of a wide range of items, such as optical display parts such as touch panels and liquid crystal televisions; automobile-related parts such as lamp-related items and window-related items (rear windows, side windows, skylights, etc.); housings for various electrical devices, decorative panels, furniture, and other lifestyle-related items. Among these, it is suitable as an optical display part, and can be particularly suitable for use as a polarizer protective film and a display protective film that are attached to a polarizer in the manufacture of a polarizing plate for a display.
本発明の偏光子保護フィルムは、本発明の積層体における基材がフィルム状であり、その片面だけに前記ハードコート層を有したものである。
本発明の偏光板は本発明の偏光子保護フィルムのハードコート層を有していない面を偏光子に貼り合わせたものである。偏光子保護フィルムは、偏光子の片側または両側に貼り合せることができる。貼り合せには接着剤や粘着剤等を用いることができる。
The polarizer protective film of the present invention is such that the substrate in the laminate of the present invention is in the form of a film and has the hard coat layer on only one side thereof.
The polarizing plate of the present invention is obtained by laminating the surface of the polarizer protective film of the present invention, which does not have a hard coat layer, to a polarizer. The polarizer protective film can be laminated to one side or both sides of the polarizer. An adhesive, a pressure sensitive adhesive, or the like can be used for lamination.
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.
［（メタ）アクリル系重合体（Ｐ）の質量平均分子量（Ｍｗ）］
ゲル透過クロマトグラフィー（ＧＰＣ）「ＨＬＣ－８１２０」（東ソー（株）製）を用いて測定した。カラムとしては、ＴＳＫｇｅｌ Ｇ５０００ＨＸＬ＊ＧＭＨＸＬ－Ｌ（東ソー（株）製）を使用した。また、標準ポリスチレンとして、Ｆ２８８／Ｆ８０／Ｆ４０／Ｆ１０／Ｆ４／Ｆ１／Ａ５０００／Ａ１０００／Ａ５００（東ソー（株）製）及びスチレンを使用して検量線を作成した。
重合体をテトラヒドロフランに濃度が０．４％になるように溶解した溶液１００μｌを使用してカラムオーブン温度４０℃で測定を行った。標準ポリスチレン換算にて質量平均分子量（Ｍｗ）を算出した。
[Weight average molecular weight (Mw) of (meth)acrylic polymer (P)]
Measurements were performed using a gel permeation chromatography (GPC) "HLC-8120" (manufactured by Tosoh Corporation). As the column, TSKgel G5000HXL*GMHXL-L (manufactured by Tosoh Corporation) was used. In addition, a calibration curve was created using F288/F80/F40/F10/F4/F1/A5000/A1000/A500 (manufactured by Tosoh Corporation) and styrene as standard polystyrene.
The polymer was dissolved in tetrahydrofuran to a concentration of 0.4%, and 100 μl of the solution was used for the measurement at a column oven temperature of 40° C. The mass average molecular weight (Mw) was calculated in terms of standard polystyrene.
実施例及び比較例の評価は以下の方法で行った。 The examples and comparative examples were evaluated as follows:
［粘度］
Ｂ型粘度計「東機産業株式会社製ＢＬ粘度計」にて、２５℃における硬化性組成物の粘度を測定し、以下の基準で評価した。
（粘度の評価基準）
○：粘度が１５ｍＰａ・ｓ以下と低く、塗工性に優れる。
△：粘度が１５ｍＰａ・ｓよりも大きく３５ｍＰａ・ｓ以下で塗工しにくい。
×：粘度が３５ｍＰａ・ｓよりも大きく塗工に長時間を要し塗工性に劣る。
[viscosity]
The viscosity of the curable composition at 25° C. was measured using a Brookfield viscometer (BL viscometer manufactured by Toki Sangyo Co., Ltd.), and evaluated according to the following criteria.
(Viscosity Evaluation Criteria)
◯: The viscosity is low at 15 mPa·s or less, and the coating properties are excellent.
Δ: Viscosity is greater than 15 mPa·s and equal to or less than 35 mPa·s, making application difficult.
×: Viscosity is greater than 35 mPa·s, so coating takes a long time and coatability is poor.
［平滑性］
得られた積層体のハードコート層の外観を目視確認し、以下の基準で評価した。
（平滑性の評価基準）
○：ハードコート層にバーコーター跡が無い。
△：ハードコート層にバーコーター跡が薄く残る。
×：ハードコート層の全面にバーコーター跡が明確に残る。
[Smoothness]
The appearance of the hard coat layer of the obtained laminate was visually inspected and evaluated according to the following criteria.
(Smoothness Evaluation Criteria)
◯: No bar coater marks were found on the hard coat layer.
Δ: Light bar coater marks remain on the hard coat layer.
×: Bar coater marks are clearly visible on the entire surface of the hard coat layer.
［密着性］
得られた積層体をＪＩＳ Ｋ－５４００の碁盤目剥離試験（碁盤目数：１００個）に準じて評価し、剥離試験後に残ったマス目に応じて以下の基準で評価した。
（密着性の評価基準）
◎：試験後に残ったマス目の数が１００個（＝剥離したマス目が無い）。
○：試験後に残ったマス目の数が７０個以上９９個以下。
△：試験後に残ったマス目の数が１０個以上６９個以下。
×：試験後に残ったマス目の数が０個以上９個以下。
[Adhesion]
The obtained laminate was evaluated according to the cross-cut peel test of JIS K-5400 (number of cross-cuts: 100), and was evaluated according to the following criteria according to the number of cross-cuts remaining after the peel test.
(Adhesion Evaluation Criteria)
⊚: 100 squares remained after the test (= no peeled squares).
○: The number of squares remaining after the test is 70 to 99.
△: The number of squares remaining after the test is between 10 and 69.
×: The number of squares remaining after the test is 0 to 9.
［鉛筆硬度］
得られた積層体の硬化性組成物の硬化物の表面に対して、ＪＩＳ準拠鉛筆硬度計を用い、ＪＩＳ Ｋ－５４００に準じて、荷重５００ｇで傷の入らない鉛筆硬度を測定し、以下の基準で評価した。
（鉛筆硬度の評価基準）
○：鉛筆硬度がＦランク以上で優れている。
×：鉛筆硬度がＦランク未満で劣る。
[Pencil hardness]
The surface of the cured product of the curable composition of the obtained laminate was measured for pencil hardness without scratching under a load of 500 g using a JIS pencil hardness tester in accordance with JIS K-5400, and evaluated according to the following criteria.
(Evaluation Criteria for Pencil Hardness)
A: The pencil hardness is excellent, being rank F or higher.
×: The pencil hardness is inferior, being less than rank F.
[（メタ）アクリレート（Ｍ）]
ラジカル重合可能な二重結合を３個以上有する（メタ）アクリレート（Ｍ）として、以下の市販品を使用した。
（Ｂ－１Ｉ） ビスコート＃３００（大阪有機化学工業株式会社製）
ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物
（Ｂ－１ＩＩ） カヤラッドＤＰＨＡ（日本化薬株式会社製）
ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物
（Ｂ－１ＩＩＩ） ＫＲＭ８４５２（ダイセルオルネクス株式会社製）
ジペンタエリスリトールペンタアクリレート２当量とヘキサメチレンジイソシアネート１当量の反応物（１０官能ウレタンアクリレート）とジペンタエリスリトールヘキサアクリレートの混合物
（Ｂ－１ＩＶ）ＵＶ１７００Ｂ（三菱ケミカル株式会社製）
ジペンタエリスリトールペンタアクリレート２当量とイソホロンジイソシアネート１当量の反応物（１０官能ウレタンアクリレート）とジペンタエリスリトールヘキサアクリレートの混合物
（Ｂ－１Ｖ） ＮＫオリゴＵ－１５ＨＡ（新中村化学工業株式会社製）
ジペンタエリスリトールペンタアクリレート３当量とヘキサメチレンジイソシアネートの３量体１当量との反応物（１５官能ウレタンアクリレート）とジペンタエリスリトールヘキサアクリレートの混合物
[(Meth)acrylate (M)]
As the (meth)acrylate (M) having three or more radically polymerizable double bonds, the following commercially available products were used.
(B-1I) Viscoat #300 (Osaka Organic Chemical Industry Ltd.)
Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (B-1II) KAYARADD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (B-1III) KRM8452 (manufactured by Daicel Allnex Corporation)
Mixture of dipentaerythritol pentaacrylate (10-functional urethane acrylate) and dipentaerythritol hexaacrylate (B-1IV) UV1700B (manufactured by Mitsubishi Chemical Corporation)
Mixture of dipentaerythritol pentaacrylate (2 equivalents) and isophorone diisocyanate (10-functional urethane acrylate) and dipentaerythritol hexaacrylate (B-1V) NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A mixture of a reaction product of 3 equivalents of dipentaerythritol pentaacrylate with 1 equivalent of a trimer of hexamethylene diisocyanate (15-functional urethane acrylate) and dipentaerythritol hexaacrylate
比較のためにラジカル重合可能な二重結合を１個有する（メタ）アクリレートとして、以下の市販品を比較例で使用した。
（Ｂ－１ＶＩ） ＨＥＡ（大阪有機化学工業株式会社製）
２－ヒドロキシエチルアクリレート
For comparison, the following commercially available products were used as (meth)acrylates having one radically polymerizable double bond in the Comparative Examples.
(B-1VI) HEA (Osaka Organic Chemical Industry Ltd.)
2-Hydroxyethyl acrylate
［（メタ）アクリル系重合体（Ｐ）］
質量平均分子量が１０００以上７００００以下の（メタ）アクリル系重合体（Ｐ）として、以下の製造例１－１～１－３に記載の方法で製造した重合体（Ｂ－２Ｉ）を使用した。
[(Meth)acrylic polymer (P)]
As the (meth)acrylic polymer (P) having a mass average molecular weight of 1,000 or more and 70,000 or less, a polymer (B-2I) produced by the method described in the following Production Examples 1-1 to 1-3 was used.
［製造例１－１］分散剤（Ｘ）の製造
撹拌機、冷却管及び温度計を備えたフラスコ中に脱イオン水９００部、メタクリル酸２－スルホエチルナトリウム６０部、メタクリル酸カリウム１０部及びメタクリル酸メチル１２部を入れて撹拌し、フラスコ内を窒素置換しながら５０℃に昇温した。次いで、フラスコ中に重合開始剤として２，２'－アゾビス（２－メチルプロピオンアミジン）二塩酸
塩０.０８部を添加し、更に６０℃に昇温した。昇温後、滴下ポンプを使用して、メタク
リル酸メチル１８部を０.２４部／分の速度で連続的に滴下した。得られた反応溶液を６
０℃で６時間保持した後、室温に冷却して、透明な水溶液である固形分１０％の分散剤（Ｘ）を得た。
[Production Example 1-1] Production of Dispersant (X) 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate were placed in a flask equipped with a stirrer, a cooling tube, and a thermometer, and the mixture was stirred and heated to 50°C while replacing the atmosphere in the flask with nitrogen. Next, 0.08 parts of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added as a polymerization initiator to the flask, and the mixture was further heated to 60°C. After the temperature was raised, 18 parts of methyl methacrylate was continuously dropped at a rate of 0.24 parts/min using a dropping pump. The resulting reaction solution was stirred for 6 hours.
After keeping at 0° C. for 6 hours, the mixture was cooled to room temperature to obtain a transparent aqueous solution of Dispersant (X) having a solid content of 10%.
［製造例１－２］連鎖移動剤（Ｙ）の製造
撹拌装置を備えたフラスコ中に、窒素雰囲気下で、酢酸コバルト（ＩＩ）四水和物１．００ｇ、ジフェニルグリオキシム１．９３ｇ及び予め窒素バブリングにより脱酸素したジエチルエーテル８０ｍｌを入れ、室温で３０分間攪拌した。次いで、三フッ化ホウ素ジエチルエーテル錯体１０ｍｌを加え、更に６時間攪拌した。得られた反応物を濾過し、固形分をジエチルエーテルで洗浄し、１５時間真空乾燥して、赤褐色固体の連鎖移動剤（Ｙ）２．１２ｇを得た。
[Production Example 1-2] Production of chain transfer agent (Y) In a flask equipped with a stirrer, 1.00 g of cobalt (II) acetate tetrahydrate, 1.93 g of diphenylglyoxime, and 80 ml of diethyl ether previously deoxygenated by nitrogen bubbling were placed under a nitrogen atmosphere and stirred at room temperature for 30 minutes. Then, 10 ml of boron trifluoride diethyl ether complex was added and stirred for another 6 hours. The resulting reaction product was filtered, the solid content was washed with diethyl ether, and vacuum dried for 15 hours to obtain 2.12 g of chain transfer agent (Y) as a reddish brown solid.
［製造例１－３］重合体（Ｂ－２Ｉ）の製造
撹拌機、冷却管及び温度計を備えたフラスコ中に、脱イオン水１４５部、硫酸ナトリウム０．１部及び分散剤（Ｘ）０．２５部を入れて撹拌し、均一な水溶液とした。次いで、フラスコ中にメタクリル酸メチル１００部、連鎖移動剤（Ｙ）０．００５部及び２，２’－アゾビス（２－メチルブチロニトリル）０．４部の単量体混合物を加え、水性懸濁液とした。次に、フラスコ内を窒素置換し、８０℃に昇温して約１時間反応させ、更に重合率を上げるため、９３℃に昇温して１時間保持した。次に、反応液を４０℃に冷却して、水性重合体懸濁液を得た。この水性重合体懸濁液を目開き４５μｍのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、４０℃で１６時間乾燥することで、重合体（Ｂ－２Ｉ）を得た。重合体（Ｂ－２Ｉ）のガラス転移温度（Ｔｇ）は８２℃、質量平均分子量（Ｍｗ）は７８００であった。
[Production Example 1-3] Production of polymer (B-2I) 145 parts of deionized water, 0.1 parts of sodium sulfate, and 0.25 parts of dispersant (X) were added to a flask equipped with a stirrer, a cooling tube, and a thermometer, and stirred to obtain a uniform aqueous solution. Next, a monomer mixture of 100 parts of methyl methacrylate, 0.005 parts of a chain transfer agent (Y), and 0.4 parts of 2,2'-azobis(2-methylbutyronitrile) was added to the flask to obtain an aqueous suspension. Next, the atmosphere in the flask was replaced with nitrogen, the temperature was raised to 80°C, and the reaction was carried out for about 1 hour, and in order to further increase the polymerization rate, the temperature was raised to 93°C and maintained for 1 hour. Next, the reaction solution was cooled to 40°C to obtain an aqueous polymer suspension. This aqueous polymer suspension was filtered through a nylon filter cloth with a mesh size of 45 μm, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain polymer (B-2I). The polymer (B-2I) had a glass transition temperature (Tg) of 82° C. and a mass average molecular weight (Mw) of 7,800.
重合体（Ｂ－２ＩＩ）から（Ｂ－２Ｖ）
実施例で（メタ）アクリル系重合体（Ｐ）として使用した重合体（Ｂ－２ＩＩ）から（Ｂ－２ＩＶ）、比較例で使用した重合体（Ｂ－２Ｖ）は、以下の市販品を使用した。
Polymers (B-2II) to (B-2V)
The polymers (B-2II) to (B-2IV) used as the (meth)acrylic polymer (P) in the examples and the polymer (B-2V) used in the comparative examples were the following commercially available products.
（Ｂ－２ＩＩ）ＡＡ６（東亞合成株式会社製）
質量平均分子量（Ｍｗ）１２０００、ガラス転移温度（Ｔｇ）９５℃の重合体
（Ｂ－２ＩＩＩ）ＢＲ８７（三菱ケミカル株式会社製）
質量平均分子量（Ｍｗ）２５０００、ガラス転移温度（Ｔｇ）１０６℃の重合体
（Ｂ－２ＩＶ）ＢＲ８３（三菱ケミカル株式会社製）
質量平均分子量（Ｍｗ）４００００、ガラス転移温度（Ｔｇ）１０５℃の重合体
（Ｂ－２Ｖ）ＢＲ８０（三菱ケミカル株式会社製）
質量平均分子量（Ｍｗ）１０００００、ガラス転移温度（Ｔｇ）１０４℃の重合体
(B-2II) AA6 (manufactured by Toagosei Co., Ltd.)
Polymer (B-2III) BR87 (manufactured by Mitsubishi Chemical Corporation) having a mass average molecular weight (Mw) of 12,000 and a glass transition temperature (Tg) of 95°C
Polymer (B-2IV) BR83 (manufactured by Mitsubishi Chemical Corporation) having a mass average molecular weight (Mw) of 25,000 and a glass transition temperature (Tg) of 106°C
A polymer (B-2V) BR80 (manufactured by Mitsubishi Chemical Corporation) having a mass average molecular weight (Mw) of 40,000 and a glass transition temperature (Tg) of 105°C.
A polymer having a mass average molecular weight (Mw) of 100,000 and a glass transition temperature (Tg) of 104°C.
光重合開始剤として、以下の市販品を実施例と比較例で使用した。
（Ｃ－１）ベンゾフェノン（大同化成工業株式会社製）
（Ｃ－２）Ｏｍｎｉｒａｄ－１８４（ＩＧＭ社製）
１－ヒドロキシシクロヘキシルフェニルケトン
As the photopolymerization initiator, the following commercially available products were used in the examples and comparative examples.
(C-1) Benzophenone (manufactured by Daido Chemical Industry Co., Ltd.)
(C-2) Omnirad-184 (manufactured by IGM)
1-Hydroxycyclohexyl phenyl ketone
[実施例１]
フラスコに、（メタ）アクリレート（Ｍ）として「Ｂ－１Ｉ」を３０質量部、「Ｂ－１ＩＩ」を７０質量部、（メタ）アクリル系重合体（Ｐ）として「Ｂ－２Ｉ」を２０質量部、光重合開始剤としてＣ－１を５質量部混合し、これにイソプロピルアルコール（ＩＰＡ）とメチルイソブチルケトン（ＭＩＢＫ）の５０：５０（重量比）の混合溶媒により、固形分濃度３５質量％となるように希釈して硬化性組成物を得た。
[Example 1]
A flask was charged with 30 parts by mass of "B-1I" as the (meth)acrylate (M), 70 parts by mass of "B-1II", 20 parts by mass of "B-2I" as the (meth)acrylic polymer (P), and 5 parts by mass of C-1 as a photopolymerization initiator, and this was diluted with a 50:50 (weight ratio) mixed solvent of isopropyl alcohol (IPA) and methyl isobutyl ketone (MIBK) to a solids concentration of 35% by mass, thereby obtaining a curable composition.
得られた硬化性組成物を、基材となるメタクリル酸メチルに由来する構成単位が１００％のメタクリル系重合体とポリカーボネート樹脂の積層シート（ＡＷ－２０Ｕ、株式会社シャインテクノ製；厚さ＝０．２ｍｍ）のメタクリル系重合体側の表面に、バーコーター＃１２を用いて乾燥後の塗膜厚さが５μｍになるように塗布し、８０℃で２分間加熱乾燥した。硬化性組成物の塗膜に高圧水銀灯を光源とした岩崎電気株式会社製「ＵＳ５－Ｘ０４０１」を使用して積算光量が３００ｍＪ／ｃｍ２となるように紫外線を１パス照射することで硬化性組成物を硬化させ、基材のメタクリル系重合体を含む表面にハードコート層を積層した。得られた積層体について、前述の平滑性、密着性及び鉛筆硬度の評価を行った。硬化性組成物の組成（単位は質量部）を表１に、評価結果を表２に示した。 The obtained curable composition was applied to the surface of the methacrylic polymer side of a laminate sheet (AW-20U, Shine Techno Co., Ltd.; thickness = 0.2 mm) of a methacrylic polymer having 100% structural units derived from methyl methacrylate as a substrate and a polycarbonate resin, using a bar coater #12 so that the coating thickness after drying was 5 μm, and then heated and dried at 80 ° C. for 2 minutes. The coating film of the curable composition was irradiated with ultraviolet light in one pass using Iwasaki Electric Co., Ltd.'s "US5-X0401" with a high pressure mercury lamp as a light source so that the accumulated light amount was 300 mJ / cm 2 , and the curable composition was cured, and a hard coat layer was laminated on the surface containing the methacrylic polymer of the substrate. The obtained laminate was evaluated for smoothness, adhesion and pencil hardness as described above. The composition of the curable composition (unit: parts by mass) is shown in Table 1, and the evaluation results are shown in Table 2.
[実施例２から実施例１４]
表１に示すように硬化性組成物の組成を変更した以外は実施例１と同様にして各硬化性組成物を得た後、塗工、硬化することで基材の表面にハードコート層を積層した。得られた積層体について、前述の平滑性、密着性及び鉛筆硬度の評価を行った。評価結果を表２に記載した。
[Examples 2 to 14]
Each curable composition was obtained in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 1, and then the composition was coated and cured to laminate a hard coat layer on the surface of the substrate. The obtained laminate was evaluated for smoothness, adhesion, and pencil hardness as described above. The evaluation results are shown in Table 2.
[実施例１５および実施例１６]
表１に示すように硬化性組成物の組成を変更し、バーコーター＃１０を用いて乾燥後の塗膜の厚さが５μｍになるように塗布した以外は実施例１と同様にして積層体を得て評価を行った。評価結果を表２に記載した。
[Examples 15 and 16]
Laminates were obtained and evaluated in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 1 and coating was performed using a bar coater #10 so that the coating thickness after drying would be 5 μm. The evaluation results are shown in Table 2.
[比較例１]
表３に示すように硬化性組成物の組成を変更した以外は実施例１と同様にして硬化性組成物を得た。硬化性組成物を硬化する際、実施例１と同じ積算光量では硬化が不十分であったため、硬化条件を積算光量４００ｍＪ／ｃｍ２で紫外線を１パス照射するよう変更した以外は実施例１と同様にして硬化性組成物を塗工、硬化することで基材の表面にハードコート層を積層した。得られた積層体について、前述の平滑性、密着性及び鉛筆硬度の評価を行った。評価結果を表４に記載した。
[Comparative Example 1]
A curable composition was obtained in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 3. When the curable composition was cured, the curing was insufficient with the same cumulative light amount as in Example 1. Therefore, the curing conditions were changed to one pass of ultraviolet irradiation with a cumulative light amount of 400 mJ/ cm2. The curable composition was coated and cured in the same manner as in Example 1, to laminate a hard coat layer on the surface of the substrate. The obtained laminate was evaluated for smoothness, adhesion, and pencil hardness as described above. The evaluation results are shown in Table 4.
[比較例２、比較例３]
表３に示すように硬化性組成物の組成を変更した以外は実施例１と同様にして各硬化性組成物を得た後、塗工、硬化することで基材の表面にハードコート層を積層した。得られた積層体について、前述の平滑性、密着性及び鉛筆硬度の評価を行った。評価結果を表４に記載した。
[Comparative Example 2 and Comparative Example 3]
Each curable composition was obtained in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 3, and then the composition was coated and cured to form a hard coat layer on the surface of the substrate. The obtained laminate was evaluated for smoothness, adhesion, and pencil hardness as described above. The evaluation results are shown in Table 4.
[比較例４]
表３に示すように硬化性組成物の組成を変更した以外は実施例１と同様にして硬化性組成物を得た。硬化性組成物を硬化する際、実施例１と同じ積算光量では硬化が不十分であったため、硬化条件を積算光量６００ｍＪ／ｃｍ２で紫外線を１パス照射するよう変更した以外は実施例１と同様にして硬化性組成物を塗工、硬化することで基材の表面にハード
コート層を積層した。得られた積層体について、前述の平滑性、密着性及び鉛筆硬度の評価を行った。評価結果を表４に記載した。
[Comparative Example 4]
A curable composition was obtained in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 3. When the curable composition was cured, the curing was insufficient with the same cumulative light amount as in Example 1. Therefore, the curing conditions were changed to one pass of ultraviolet irradiation with an cumulative light amount of 600 mJ/ cm2. The curable composition was coated and cured in the same manner as in Example 1, to laminate a hard coat layer on the surface of the substrate. The obtained laminate was evaluated for smoothness, adhesion, and pencil hardness as described above. The evaluation results are shown in Table 4.
表４に示すとおり、比較例１は（メタ）アクリル系重合体（Ｐ）を含まない硬化性組成
物を使用したため、密着性が悪かった。比較例２と比較例３は本願規定の範囲外の質量平均分子量の（メタ）アクリル系重合体を含む硬化性組成物を使用したため、硬化性組成物の粘度が高く、ハードコート層の平滑性が悪かった。比較例４はラジカル重合可能な二重結合を３個以上有さない（メタ）アクリレートを含む硬化性組成物を使用したため、鉛筆硬度が悪かった。
As shown in Table 4, Comparative Example 1 used a curable composition that did not contain a (meth)acrylic polymer (P), and therefore had poor adhesion. Comparative Examples 2 and 3 used curable compositions that contained a (meth)acrylic polymer with a mass average molecular weight outside the range specified in the present application, and therefore had high viscosity of the curable composition and poor smoothness of the hard coat layer. Comparative Example 4 used a curable composition that contained a (meth)acrylate that did not have three or more radically polymerizable double bonds, and therefore had poor pencil hardness.
本発明の積層体は、液晶ディスプレイ、有機エレクトロルミネッセスディスプレイ、電子ペーパー、タッチパネル、スマートフォン等のディスプレイ等に広く適用できる。特にディスプレイ用偏光板の製造において偏光子に貼りあわせて用いる偏光子保護フィルム、ディスプレイ用保護フィルムに好適に用いることができる。
The laminate of the present invention can be widely applied to displays such as liquid crystal displays, organic electroluminescence displays, electronic paper, touch panels, and smartphones. In particular, it can be suitably used as a polarizer protective film to be attached to a polarizer in the production of a polarizing plate for a display, or a protective film for a display.
Claims (11)
A polarizing plate obtained by laminating the surface of the polarizer protective film according to claim 10 that does not have a hard coat layer to a polarizer.
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| JP2018100183 | 2018-05-25 | ||
| JP2018100183 | 2018-05-25 | ||
| JP2019097651A JP2019206178A (en) | 2018-05-25 | 2019-05-24 | Laminate, polarizer protective film and polarizing plate |
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| JP2019097651A Division JP2019206178A (en) | 2018-05-25 | 2019-05-24 | Laminate, polarizer protective film and polarizing plate |
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| JP2019097651A Pending JP2019206178A (en) | 2018-05-25 | 2019-05-24 | Laminate, polarizer protective film and polarizing plate |
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| JP4452107B2 (en) * | 2004-03-16 | 2010-04-21 | 日本ウェーブロック株式会社 | Metallic decorative sheet for molding |
| JP2005306992A (en) * | 2004-04-21 | 2005-11-04 | Dainippon Ink & Chem Inc | Functional cured film |
| CN101410247B (en) * | 2006-03-31 | 2012-10-17 | 大日本印刷株式会社 | Optical laminated body and method for manufacturing optical laminated body |
| US20090176077A1 (en) * | 2006-03-31 | 2009-07-09 | Dai Nippon Printing Co., Ltd. | Optical layered body |
| JP2009154372A (en) * | 2007-12-26 | 2009-07-16 | Mitsubishi Plastics Inc | Laminating sheet and optical recording medium |
| JP5397686B2 (en) * | 2009-10-28 | 2014-01-22 | Ｄｉｃ株式会社 | Fluorine-containing curable resin, active energy ray-curable coating composition and cured product thereof |
| JP2017058693A (en) * | 2011-04-22 | 2017-03-23 | 日東電工株式会社 | Optical laminate |
| JP5181056B2 (en) * | 2011-11-28 | 2013-04-10 | 新日鉄住金化学株式会社 | Hard coat film or sheet, optical element, and image display device |
| JP2015034832A (en) * | 2011-11-30 | 2015-02-19 | 日本製紙株式会社 | Hard coat film and manufacturing method therefor |
| JP6098225B2 (en) * | 2013-02-26 | 2017-03-22 | 三菱化学株式会社 | Laminate and roll laminate |
| JP6071108B2 (en) * | 2013-03-13 | 2017-02-01 | 荒川化学工業株式会社 | Photocurable resin composition and optical film obtained using the same |
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