Layered body

Abstract

The present invention provides a layered body having high hardness and excellent flexibility and useful as a substitute material for glass, and the layered body includes a substrate film, a hard coat layer on one face of the substrate film, and a resin-cured layer on the other face of the substrate film. The layered body is not cracked when wound on a 30 mm-diameter cylinder and has a hardness of 0.5 to 1.5 GPa when an indenter is pushed in 500 nm by a nano-indentation method and/or a hardness of 0.29 to 1.10 GPa at 500 mN load using a micro-hardness tester.

Claims

1. A layered body comprising: a first substrate film; a hard coat layer on a first face of the first substrate film; a resin-cured layer on a second face of the first substrate film; and a second substrate film on the resin-cured layer, wherein the second face is opposing the first face, the resin-cured layer has a first surface and a second surface, the second surface of the resin-cured layer is opposing the first surface of the resin-cured layer, and the second surface of the resin-cured layer directly contacts the second substrate film, the first surface of the resin-cured layer directly contacts the second face of the first substrate film, the layered body is not cracked when wound on a 30 mm-diameter cylinder, the layered body has a hardness of 0.5 to 1.5 GPa measured by pushing an indenter in 500 nm in accordance with a nano-indentation method and/or a hardness of 0.29 to 1.10 GPa at 500 mN load using a micro-hardness tester, the resin-cured layer has a thickness in a range from 3 to 25 μm, the resin-cured layer is a cured layer of a composition whose monomer consists of at least one mono-functional acrylic monomer selected from the group consisting of acryloyl morpholine, N-acryloyloxyethyl hexahydrophthalimide, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate, hardnesses of the hard coat layer, the first substrate film, the resin-cured layer, and the second substrate film satisfy the following relationship: the hard coat layer>the resin-cured layer>the first substrate film and the second substrate film, the hardness is measured by pushing an indenter into cross sections of the hard coat layer, the resin-cured layer, and the first and second substrate films in the thickness direction of the layered body in accordance with the nano-indentation method, the thickness of the hard coat layer is 2.5 to 20.0 μm, and the hard coat layer contains fine particles having an average particle diameter of 5 to 100 nm.

2. The layered body according to claim 1, the first substrate film is a triacetyl cellulose substrate, poly(ethylene terephthalate) substrate, or olefin polymer substrate.

3. The layered body according to claim 1, wherein the second substrate film is a triacetylcellulose substrate, poly(ethylene terephthalate) substrate, or olefin polymer substrate, and the hard coat layer contains the fine particles and a binder resin.

4. The layered body according to claim 1, wherein the at least one mono-functional acrylic monomer is selected from the group consisting of acryloyl morpholine, N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl acrylate, and adamantyl acrylate.

Description

DESCRIPTION OF EMBODIMENTS

(1) The contents of the present invention will be described along with the following Examples, but the contents of the present invention is not be considered as being limited by the following illustrated embodiments.

Example 1

(2) As a substrate film, an 80 μm-thick triacetyl cellulose substrate (TD80ULN, manufactured by Fujifilm Corporation) was prepared and a composition 1 for hard coat layers as described below was applied to one face of the substrate film to form a coating. Next, the solvent in the coating was evaporated by circulating dry air at 70° C. for 45 seconds to the formed coating and the coating was cured by applying ultraviolet rays in nitrogen atmosphere (oxygen concentration, 200 ppm or lower) using an ultraviolet ray irradiation apparatus (light source H bulb manufactured by Fusion UV Systems Japan K.K.) such that the integrated light quantity was adjusted to be 200 mJ/cm.sup.2 to form a hard coat layer with a thickness of 15 μm (at the time of cured).

(3) (Composition 1 for Hard Coat Layers)

(4) TABLE-US-00001 Reactive nonspherical silica (ELCOM V8803, 50 parts by mass manufactured by JGC C&C) Dipentaerythritol hexaacrylate (DPHA, 50 parts by mass manufactured by Nippon Kayaku Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

(5) Next, a composition A for cured layers as described below was applied to the face of the substrate film in the side reverse to the side in which the hard coat layer was formed to form a coating such that the film thickness became 10 μm after curing and dry air at 70° C. was circulated for 45 seconds to evaporate the solvent in the coating. As another substrate film, an 80 μm-thick triacetyl cellulose substrate (TD80ULN, manufactured by Fujifilm Corporation) was prepared and the above-mentioned former substrate film was stuck to this substrate film through the coating.

(6) Thereafter, the coating was cured by applying ultraviolet rays from the another substrate film side in nitrogen atmosphere (oxygen concentration, 200 ppm or lower) using an ultraviolet ray irradiation apparatus (light source H bulb manufactured by Fusion ITV Systems Japan K.K.) such that the integrated light quantity was adjusted to be 600 mJ/cm.sup.2 to form a resin-cured layer with a thickness of 10 μm (at the time of cured) to produce a layered body.

(7) (Composition a for Cured Layers)

(8) TABLE-US-00002 Acryloylmorpholine (ACMO, manufactured by 100 parts by mass KOHJIN Film & Chemicals Co., Ltd.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK  20 parts by mass

Example 2

(9) A layered body was produced in the same manner as in Example 1, except that the thickness of the hard coat layer was 12 μm.

Example 3

(10) A layered body was produced in the same manner as in Example 1, except that the thickness of the hard coat layer was 10 μm.

Example 4

(11) A layered body was produced in the same manner as in Example 1, except that the thickness of the hard coat layer was 20 μm.

Example 5

(12) A layered body was produced in the same manner as in Example 1, except that a 40 μm-thick triacetyl cellulose substrate (KC4UA, manufactured by KONICA MINOLTA, INC.) was used as the substrate film and another substrate film.

Example 6

(13) A layered body was produced in the same manner as in Example 1, except that a 25 μm-thick triacetyl cellulose substrate (KC2UA, manufactured by KONICA MINOLTA, INC.) was used as the substrate film and another substrate film.

Example 7

(14) A layered body was produced in the same manner as in Example 1, except that a 40 μm-thick acrylic substrate was used as the substrate film.

Example 8

(15) A layered body was produced in the same manner as in Example 1, except that a 50 μm-thick poly (ethylene terepthalate) (PET) substrate (U48, manufactured by TORAY INDUSTRIES, INC.) was used as the substrate film.

Example 9

(16) A layered body was produced in the same manner as in Example 1, except that a 40 μm-thick acrylic substrate was used as another substrate film.

Example 10

(17) A layered body was produced in the same manner as in Example 1, except that a 50 μm-thick poly(ethylene terepthalate) (PET) substrate (U48, manufactured by TORAY INDUSTRIES, INC.) was used as another substrate film.

Example 11

(18) A layered body was produced in the same manner as in Example 1, except that a 50 μm-thick amorphous olefin polymer (COP) substrate (Zeonoa series, manufactured by Zeon Corporation) was used as another substrate film.

Example 12

(19) A layered body was produced in the same manner as in Example 5, except that the thickness of the resin-cured layer was 1 μm.

Example 13

(20) A layered body was produced in the same manner as in Example 5, except that the thickness of the resin-cured layer was 5 μm.

Example 14

(21) A layered body was produced in the same manner as in Example 5, except that the thickness of the resin-cured layer was 15 μm.

Example 15

(22) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick hard coat layer was formed using the following composition 2 for hard coat layers.

(23) (Composition 2 for Hard Coat Layers)

(24) TABLE-US-00003 Reactive nonspherical silica (ELCOM V8803, 40 parts by mass manufactured by JGC C&C) Dipentaerythritol hexaacrylate (DPHA, 60 parts by mass manufactured by Nippon Kayaku Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Example 16

(25) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick hard coat layer was formed using the following composition 3 for hard coat layers.

(26) (Composition 3 for Hard Coat Layers)

(27) TABLE-US-00004 Solid reactive silica (ELCOM V8802, particle size 50 parts by mass of 12 nm, manufactured by JGC C&C) Dipentaerythritol hexaacrylate (DPHA, 60 parts by mass manufactured by Nippon Kayaku Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Example 17

(28) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick hard coat layer was formed using the following composition 4 for hard coat layers.

(29) (Composition 4 for Hard Coat Layers)

(30) TABLE-US-00005 Reactive nonspherical silica (ELCOM V8803, 50 parts by mass manufactured by JGC C&C) Urethane acrylate (Shikoh UV 1700B, manufactured 50 parts by mass by The Nippon Synthetic Chemical Industry Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Example 18

(31) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick hard coat layer was formed using the following composition 5 for hard coat layers.

(32) (Composition 5 for Hard Coat Layers)

(33) TABLE-US-00006 Reactive nonspherical silica (ELCOM V8803, 50 parts by mass manufactured by JGC C&C) Pentaerythritol triacrylate (PETA30, manufactured by 50 parts by mass Nippon Kayaku Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Example 19

(34) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition B for cured layers.

(35) (Composition B for Cured Layers)

(36) TABLE-US-00007 Isobornyl acrylate (IBXA, manufactured by OSAKA 100 parts by mass ORGANIC CHEMICAL INDUSTRY LTD.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK  20 parts by mass

Example 20

(37) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition C for cured layers.

(38) (Composition C for Cured Layers)

(39) TABLE-US-00008 Phenoxyethyl acrylate (Light Acrylate PO-A, 100 parts by mass manufactured by KYOEISHA CHEMICAL Co., LTD.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK  20 parts by mass

Example 21

(40) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition D for cured layers.

(41) (Composition D for Cured Layers)

(42) TABLE-US-00009 Acryloylmorpholine (ACMO, manufactured by 90 parts by mass KOHJIN Film & Chemicals Co., Ltd.) Pentaerythritol triacrylate (PET30, manufactured by 10 parts by mass Nippon Kayaku Co., Ltd.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 20 parts by mass

Example 22

(43) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition E for cured layers.

(44) (Composition E for Cured Layers)

(45) TABLE-US-00010 Acryloylmorpholine (ACMO, manufactured by 90 parts by mass KOHJIN Film & Chemicals Co., Ltd.) Polyethylene glycol diacrylate(M240, manufactured by 10 parts by mass TOAGOSEI CO., LTD.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 20 parts by mass

Example 23

(46) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition F for cured layers.

(47) (Composition F for Cured Layers)

(48) TABLE-US-00011 Acryloylmorpholine (ACMO, manufactured by 95 parts by mass KOHJIN Film & Chemicals Co., Ltd.) Quaternary ammonium group-containing acrylic  5 parts by mass polymer (Acrit 1SX-1055F, manufactured by TAISEI FINE CHEMICAL CO., LTD.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 20 parts by mass

Example 24

(49) A layered body was produced in the same manner as in Example 5, except that a 15 μm-thick resin-cured layer was formed using the following composition G for cured layers.

(50) (Composition G for Cured Layers)

(51) TABLE-US-00012 Dimethylol tricyclodecane diacrylate (Light Acrylate 20 parts by mass DCP-A, manufactured by KYOEISHA CHEMICAL CO., LTD.) Adamantyl acrylate (ADA, manufactured by OSAKA 80 parts by mass ORGANIC CHEMICAL INDUSTRY LTD.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 20 parts by mass

Example 25

(52) A layered body was produced in the same manner as in Example 1, except that another substrate film was not stuck.

Example 26

(53) A layered body was produced in the same manner as in Example 7, except that another substrate film was not stuck.

Example 27

(54) A layered body was produced in the same manner as in Example 8, except that another substrate film was not stuck.

Comparative Example 1

(55) A layered body was produced in the same manner as in Example 1, except that a resin-cured layer was formed using the following composition H for cured layers.

(56) (Composition H for Cured Layers)

(57) TABLE-US-00013 Pentaerythritol triacrylate (PET30, manufactured by 100 parts by mass Nippon Kayaku Co., Ltd.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK  20 parts by mass

Comparative Example 2

(58) A layered body was produced in the same manner as in Comparative Example 1, except that a hard coat layer was formed using the following composition 6 for hard coat layers.

(59) (Composition 6 for Hard Coat Layers)

(60) TABLE-US-00014 Urethane acrylate (UV 1700B, manufactured by The 50 parts by mass Nippon Synthetic Chemical Industry Co., Ltd.) Polyester triacrylate (M9050, manufactured by 50 parts by mass TOAGOSEI CO., LTD.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Comparative Example 3

(61) A layered body was produced in the same manner as in Example 1, except that a resin-cured layer was formed using the following composition I for cured layers.

(62) (Composition I for Cured Layers)

(63) TABLE-US-00015 Urethane acrylate (UV 6300B, manufactured by The 100 parts by mass Nippon Synthetic Chemical Industry Co., Ltd.) Lucirin TPO (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK  20 parts by mass

Comparative Example 4

(64) A layered body was produced in the same manner as in Example 1, except that a adhesive (Panaclean PD-S1, manufactured by PANAC Co., Ltd.) was used in place of the composition A for cured layers and a 25 μm-thick adhesive layer was formed in place of the resin-cured layer.

Comparative Example 5

(65) A layered body was produced in the same manner as in Example 1, except that the composition A for cured layers was not applied and another substrate film and the substrate film were simply layered.

Comparative Example 6

(66) A layered body was produced in the same manner as in Example 1, except that a 30 μm-thick resin-cured layer was formed using the composition A for cured layers.

Reference Example 1

(67) A layered body was produced in the same manner as in Example 1, except that the thickness of the hard coat layer was 2 μm.

Reference Example 2

(68) A layered body was produced in the same manner as in Example 1, except that the thickness of the hard coat layer was 40 μm.

Reference Example 3

(69) A layered body was produced in the same manner as in Example 1, except that a 15 μm-thick hard coat layer was formed using the following composition 7 for hard coat layers.

(70) (Composition 7 for Hard Coat Layers)

(71) TABLE-US-00016 Urethane acrylate (UV 1700B, manufactured by The 50 parts by mass Nippon Synthetic Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate (DPHA, manufactured 50 parts by mass by Nippon Kayaku Co., Ltd.) Irgacure 184 (manufactured by BASF Japan Ltd.)  4 parts by mass MIBK 75 parts by mass MEK 75 parts by mass Fluorine non-reactive leveling agent (F477, 0.2 parts by mass  manufactured by DIC)

Reference Example 4

(72) A layered body was produced in the same manner as in Example 1, except that composition for cured layers was not cured.

(73) The following evaluations were carried out for layered bodies obtained in Examples, Comparative Examples, and Reference Examples and the results are shown in Table 1.

(74) (Nano-Indentation Hardness)

(75) Using TI950 Tribolndenter manufactured by HYSITRON, a Berkovich indenter (a trigonal pyramid) was pushed in 500 nm from the surface of the hard coat layer of each layered body and kept for a prescribed time to relax the residual stress and thereafter, the load was removed, and successively the maximum load was measured after relaxation and the nano-indentation hardness was calculated according to P.sub.max/A using the maximum load P.sub.max (μN) and the surface area A (nm.sup.2) of the dent with depth of 500 nm. In Table 1, it was expressed as Hardness 1.

(76) (Hardness at 500 mN Load Using Micro-Hardness Tester)

(77) Using PICODENTOR HM 500, manufactured by Fischer Instruments K.K., the hardness was measured by pushing in a Vickers indenter (a quadrangular pyramid) with a load of 500 mN from the surface of the hard coat layer of each layered body. At that time, the depth of the Vickers indenter (a quadrangular pyramid) pushed in was about 10 μm (8 to 11 μm) from the hard coat layer surface. In Table 1, it was expressed as “Hardness 2”.

(78) (Pencil Hardness)

(79) In the layered body production process in Examples, Comparative Examples, and Reference Examples, samples having a hard coat layer on a substrate film were separately prepared and the pencil hardness (1) of the samples and the pencil hardness (2) of the layered bodies of Examples, Comparative Examples, and Reference Examples were measured respectively according to JIS K5600-5-4 (1999).

(80) (Curl)

(81) The respective layered bodies of Examples, Comparative Examples, and Reference Examples were cut out in 100 mm×100 mm-square in an arbitrary direction and left in ambient environments at 25° C. and 50% humidity for 24 hours. The height of curl at 4 corners was measured and the average value was measured as curl.

(82) Good: less than 20 mm

(83) Poor: not lower than 20 mm and not higher than 30 mm or the state of becoming so cylindrical as to make measurement impossible

(84) (Bending Property)

(85) Samples in a size of 100 mm×150 mm were obtained from layered bodies of Examples, Comparative Examples, and Reference Examples and wound on a 30 mm-diameter cylinder in a manner that the hard coat layer side was in the outside and the bending property was evaluated according to the following standard.

(86) Good: No crack formation

(87) Poor: Cracks formed

(88) TABLE-US-00017 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 Hard coat Composition for 1 1 1 1 1 1 1 1 1 1 layer hard coat layer Thickness (μm) 15 12 10 20 15 15 15 15 15 15 Substrate Type TAC TAC TAC TAC TAC TAC Acryl PET TAC TAC film Thickness (μm) 80 80 80 80 40 25 40 50 40 40 Cured Composition for A A A A A A A A A A layer cured layer Thickness (μm) 10 10 10 10 10 10 10 10 10 10 Another Type TAC TAC TAC TAC TAC TAC TAC TAC Acryl PET substrate Thickness (μm) film 80 80 80 80 40 25 40 40 40 50 Hardness 1 (GPa) 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98 Hardness 2 (GPa) 0.77 0.71 0.68 0.87 0.71 0.73 0.68 0.72 0.70 0.72 Pencil hardness (1) 5H 5H 4H 6H 5H 5H 4H 5H 5H 5H Pencil hardness (2) 9H 9H 8H 9H 9H 9H 8H 9H 9H 9H Curl Good Good Good Good Good Good Good Good Good Good Bending property Good Good Good Good Good Good Good Good Good Good Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 11 ple 12 ple 13 ple 14 ple 15 ple 16 ple 17 ple 18 ple 19 ple 20 Hard coat Composition for 1 1 1 1 2 3 4 5 1 1 layer hard coat layer Thickness (μm) 15 15 15 15 15 15 15 15 15 15 Substrate Type TAC TAC TAC TAC TAC TAC TAC TAC TAC TAC film Thickness (μm) 40 40 40 40 40 40 40 40 40 40 Cured Composition for A A A A A A A A B C layer cured layer Thickness (μm) 10 1 5 15 10 10 10 10 15 15 Another Type COP TAC TAC TAC TAC TAC TAC TAC TAC TAC substrate Thickness (μm) film 50 40 40 40 40 40 40 40 40 40 Hardness 1 (GPa) 0.98 0.98 0.98 0.98 0.71 0.68 0.92 0.95 0.98 0.98 Hardness 2 (GPa) 0.64 0.65 0.71 0.82 0.70 0.65 0.70 0.71 0.77 0.75 Pencil hardness (1) 5H 5H 5H 5H 5H 4H 5H 5H 5H 5H Pencil hardness (2) 8H 8H 9H 9H 9H 8H 9H 9H 9H 9H Curl Good Good Good Good Good Good Good Good Good Good Bending property Good Good Good Good Good Good Good Good Good Good Compar- Compar- ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 21 ple 22 ple 23 ple 24 ple 25 ple 26 ple 27 ple 1 ple 2 Hard coat Composition for 1 1 1 1 1 1 1 1 6 layer hard coat layer Thickness (μm) 15 15 15 15 15 15 15 15 15 Substrate Type TAC TAC TAC TAC TAC Acryl PET TAC TAC film Thickness (μm) 40 40 40 40 80 40 50 80 80 Cured Composition for D E F G A A A H H layer cured layer Thickness (μm) 15 15 15 15 10 10 10 10 10 Another Type TAC TAC TAC TAC — — — TAC TAC substrate Thickness (μm) film 40 40 40 40 — — — 80 80 Hardness 1 (GPa) 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.40 Hardness 2 (GPa) 0.83 0.72 0.71 0.76 0.68 0.64 0.66 1.15 0.27 Pencil hardness (1) 5H 5H 5H 5H 4H 4H 4H 5H 3H Pencil hardness (2) 9H 9H 9H 9H 8H 7H 8H 9H 4H Curl Good Good Good Good Good Good Good Good Good Bending property Good Good Good Good Good Good Good Poor Poor Compar- Compar- Compar- Compar- Refer- Refer- Refer- Refer- ative ative ative ative ence ence ence ence Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 3 ple 4 ple 5 ple 6 ple 1 ple 2 ple 3 ple 4 Hard coat Composition for 1 1 1 1 1 1 7 1 layer hard coat layer Thickness (μm) 15 15 15 15 2 40 15 15 Substrate Type TAC TAC TAC TAC TAC TAC TAC TAC film Thickness (μm) 80 80 80 80 80 80 80 80 Cured Composition for I Adhe- — A A A A A layer cured layer sive Thickness (μm) 10 10 — 30 10 10 10 10 (un- cured) Another Type TAC TAC TAC TAC TAC TAC TAC TAC substrate Thickness (μm) film 80 80 80 80 80 80 80 80 Hardness 1 (GPa) 0.98 0.98 0.98 0.98 0.98 0.98 0.45 0.98 Hardness 2 (GPa) 0.22 0.15 0.25 0.91 0.25 1.25 0.26 0.25 Pencil hardness (1) 5H 5H 5H 5H 2H 8H 3H 5H Pencil hardness (2) 5H 3H 5H 9H 2H 9H 3H 5H Curl Good Good Good Good Good Poor Good Good Bending property Good Good Good Poor Good Poor Good Good

(89) As shown in Table 1, the layered bodies of Examples each having a prescribed cured layer on one face of a substrate film were found to have excellent hardness (nano-indentation hardness, hardness at 500 mN load measured using a micro-hardness tester, and pencil hardness) and an excellent bending property. The adhesive strength between the substrate film of each layered body of Examples and the resin-cured layer was as high as 10N/25 mm to 15N/25 mm when 180° peeling strength in width of 25 mm was measured at peeling speed of 300 mm/min and room temperature (23° C.). It was supposed that the substrate film and the resin-cured layer were sufficiently bonded and it contributed to the excellent hardness.

(90) On the other hand, the layered bodies of Comparative Examples 1 and 2 were inferior in the bending property and the layered bodies of Comparative Examples 3 and 4 were inferior in hardness, particularly in the evaluation of the pencil hardness (2). The adhesive strength between the substrate film and the resin-cured layer of the layered body of Comparative Example 3 was as extremely low as 0.05N/25 mm when 180° peeling strength in width of 25 mm was measured at peeling speed of 300 mm/min and room temperature (23° C.), and the substrate film and the resin-cured layer were not sufficiently bonded.

(91) The layered bodies of Reference Examples 1 and 3 were inferior in hardness, particularly in evaluation of pencil hardness (1) and (2): the layered body of Reference Example 2 was inferior in evaluation of the curl and the bending property: and the layered body of Reference Example 4 was inferior in hardness, particularly in evaluation of pencil hardness (2). Additionally, in the layered body of Reference Example 4, the substrate film and the resin-cured layer were not sufficiently bonded.

(92) In the case of the layered body of Comparative Example 4 in which the adhesive layer was formed in place of the resin-cured layer, the adhesive strength between the adhesive layer and the substrate film was as good as 13 N/25 mm when 180° peeling strength in width of 25 mm was measured at peeling speed of 300 mm/min and room temperature (23° C.) but the hardness was low. That is, the hardness balance was as to be hard coat layer> substrate film and another substrate film> resin-cured layer and therefore, no satisfactory hardness in the entire layered body was obtained. Further, the hardness means the hardness measured by pushing an indenter in the cross section of each layer appearing when each layered body was cut in the thickness direction by the above-described nano-indentation method in the cross section direction, or pencil hardness measured in the surface of the substrate film or another substrate film, or pencil hardness measured in the hard coat layer surface or the resin-cured layer surface after the hard coat layer or the resin-cured layer was formed on the substrate film or another substrate film.

(93) In the case where the resin-cured layer was not yet cured just like the layered body of Reference Example 4 or in the case where no resin-cured layer was formed just like the layered body of Reference Example 5, the adhesive strength between the substrate film and either the uncured coating or another substrate film was as extremely low as 0.02 to 0.03N/25 mm or very scarce when 180° peeling strength in width of 25 mm was measured at peeling speed of 300 mm/min and room temperature (23° C.). Further, the same hardness balance as that of the layered body of Comparative Example 4 in which the above-mentioned adhesive layer was formed and no hardness in the entire layered body was obtained.

INDUSTRIAL APPLICABILITY

(94) A layered body of the present invention can be used as a substitute material for glass and at the same time for thin, bendable, flexible type organic EL displays and flexible panels to be used for portable terminals such as smart phones and wrist watch type terminals, automotive interior display devices, wrist watches, etc., and also for image display devices such as liquid crystal display devices, touch panels, etc.