Transparent electroconductive laminate
The purpose of the present invention is to provide a transparent electroconductive laminate having extremely high visibility. A transparent electroconductive laminate in which a hard coat layer, a color difference adjustment layer, and a transparent electroconductive layer are formed in this order, wherein (1) the hard coat layer being obtained by applying and curing a hard coating composition including (A) a phenol Novolac-type acrylate having two or more acrylate groups and (B) an aromatic-group-containing mono- or poly(meth)acrylate compound having 1-2 moles of a C2 or C3 alkylene oxide structure in the molecule thereof, (2) and the color difference adjustment layer includes a cured resin component (i), and metal oxide particles (ii) having an average primary particle diameter of 100 nm or less and/or metal fluoride particles (iii); having an average primary particle diameter of 100 nm or less, where the total mass of particles (ii) and (iii) in the color difference adjustment layer is 0-200 parts by mass with respect to 100 parts by mass of the cured resin component (i).
1. A transparent electroconductive laminate in which a hard coat layer, a color difference adjusting layer, and a transparent electrically conducting layer are formed in this order on at least one surface of a transparent polymer substrate, wherein
(1) the hard coat layer is obtained by applying and curing a hard coating composition comprising (A) a phenolic novolac acrylate having two or more acrylate groups and (B) an aromatic group-containing mono or poly (meth)acrylate having 1 or 2 alkylene oxide structures comprising two or three carbon atoms in each molecule, wherein
the hard coating composition comprises 60 to 85 parts by mass of the phenolic novolac acrylate (A) and 15 to 30 parts by mass of the (meth)acrylate (B), providing that 100 parts by mass of a resin content in the hard coating composition, and
(2) the color difference adjusting layer comprises a curing resin component (i), and metal oxide particles having an average primary particle diameter of 100 nm or less (ii) and/or metal fluoride particles having an average primary particle diameter of 100 nm or less (iii), and where the total mass of particles (ii) and (iii) in the color difference adjusting layer is 0-200 parts by mass with respect to 100 parts by mass of the curing resin component (i), and
(3) a difference ΔR of R1 and R2 is not greater than 1, wherein R1 is a reflectance obtained by irradiation with a light source having a wavelength in a range of 500 to 750 nm toward the transparent electroconductive laminate, and R2 is a reflectance obtained by irradiation with a light source having a wavelength in a range of 500 to 750 nm toward a transparent electroconductive laminate after immersion into a strong acid aqueous solution at 40° C. for three minutes and dried, wherein the strong acid aqueous solution is obtained by a mixing of 12 N hydrochloric acid, 16 N nitric acid and water in a mass ratio of 12 N hydrochloric acid:16 N nitric acid:water being 3.3:1.0:7.6.
2. The transparent electroconductive laminate according to claim 1 , wherein
the curing resin component (i) in the color difference adjusting layer is an ultraviolet curing resin, and
a difference ΔH of H1 and H2 is not greater than 0.3%, wherein H1 is a haze value of the transparent electroconductive laminate, and H2 is a haze value of a transparent electroconductive laminate after immersion into a strong acid aqueous solution at 40° C. for three minutes and dried, wherein the strong acid aqueous solution is obtained by a mixing of 12 N hydrochloric acid, 16 N nitric acid and water in a mass ratio of 12 N hydrochloric acid:16 N nitric acid:water being 3.3: 1.0: 7.6.
3. The transparent electroconductive laminate according to claim 1 , wherein
the phenolic novolac acrylate (A) is represented by the following formula (I):
wherein R 1 represents H or CH 2 OH, R 2 represents H or OH, n represents a number of 2 to 5 and m represents a number of 0 to 5.
4. The transparent electroconductive laminate according to claim 1 , wherein the (meth)acrylate (B) is an aromatic group-containing (meth)acrylate having a refractive index within a range of 1.56 to 1.64.
5. The transparent electroconductive laminate according to claim 1 , wherein
the hard coat layer is obtained by applying and curing the hard coating composition further comprising (C) a fluorene unit-containing (meth)acrylate having two or more (meth)acrylate groups in addition to the components (A) and (B), wherein
the hard coating composition comprises 60 to 70 parts by mass of the phenolic novolac acrylate (A), 15 to 30 parts by mass of the (meth)acrylate (B) and 15 to 40 parts by mass of the fluorene unit-containing (meth)acrylate (C), providing that 100 parts by mass of a resin content in the hard coating composition.
6. The transparent electroconductive laminate according to claim 5 , wherein the fluorene unit-containing (meth)acrylate (C) is represented by the following formula (II):
wherein each of R 3 independently represents H or CH 3 , R 4 represents -A-OC(O)CR═CH 2 , wherein A each represents OCH 2 CH 2 —, —OCH 2 CH 2 CH 2 —, —OCH(CH 3 )CH 2 — or OCH 2 CH(CH 3 )— and R each represents H or CH 3 .
7. The transparent electroconductive laminate according to claim 1 , wherein a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium tin oxide in the hard coat layer is less than or equal to 0.0001% by mass.
8. The transparent electroconductive laminate according to claim 1 , wherein
the hard coat layer has a refractive index within a range of 1.565 to 1.620.
9. The transparent electroconductive laminate according to claim 1 , wherein
the curing resin component (i) in the color difference adjusting layer is a (meth)acrylate having two or more acrylate groups and a molecular weight of 1400 to 1800, and the curing resin component (i) has a hydroxyl value of 60 to 100 mgKOH/g, and
a thickness of the color difference adjusting layer is within a range of 50 nm to 200 nm.
10. The transparent electroconductive laminate according to claim 1 , wherein
the transparent electrically conducting layer is a crystalline layer comprising indium oxide, and
the transparent electrically conducting layer has a thickness within a range of 5 to 50 nm.
11. The transparent electroconductive laminate according to claim 1 , wherein
the transparent electroconductive laminate has a metal oxide layer between the color difference adjusting layer and the transparent electrically conducting layer, and
the metal oxide layer has a thickness within a range of 0.5 to 5.0 nm.
12. The transparent electroconductive laminate according to claim 1 , wherein
the hard coat layer, the color difference adjusting layer, and the transparent electrically conducting layer are formed in this order on one side of the transparent polymer substrate, and
an antiblocking layer is formed on the other side of the transparent polymer substrate.
13. The transparent electroconductive laminate according to claim 12 , wherein
the antiblocking layer is obtained by applying and curing a composition for forming an antiblocking layer comprising a first component and a second component, wherein
the first component is an unsaturated double bond containing acrylic copolymer, and
the second component comprises a polyfunctional acrylate, and
a difference of solubility parameter values (ΔSP) of the first component (SP1) and the second component (SP2) is within a range of 1 to 2, and
phase separation occurs between the first component and the second component after the composition for forming an antiblocking layer is applied, to form an antiblocking layer having a microscopic convexoconcave on its surface.
14. A touch panel having the transparent electroconductive laminate according to claim 1 .
15. A transparent electroconductive laminate in which a high refractive index antiblocking layer, a color difference adjusting layer, and a transparent electrically conducting layer are formed in this order on at least one surface of a transparent polymer substrate, wherein
(1) the high refractive index antiblocking layer has a refractive index within a range of 1.565 to 1.620, and is obtained by applying a composition for forming a high refractive index antiblocking layer comprising a first component and a second component, wherein
the first component is an unsaturated double bond containing acrylic copolymer, and
the second component comprises
(A) a phenolic novolac acrylate having two or more acrylate groups, and
(B) an aromatic group-containing mono or poly (meth)acrylate having 1 or 2 alkylene oxide structures comprising two or three carbon atoms in each molecule, wherein
the second component comprises 60 to 85 parts by mass of the phenolic novolac acrylate (A) and 15 to 30 parts by mass of the (meth)acrylate (B), providing that 100 parts by mass of the second component, and
a difference of solubility parameter values (ΔSP) of the first component (SP1) and the second component (SP2) is within a range of 1 to 4, and
a mass ratio of the first component to the second component in the composition is from 0.5:99.5 to 20:80, and
phase separation occurs between the first component and the second component after the composition for forming a high refractive index antiblocking layer is applied, to form an antiblocking layer having a microscopic convexoconcave on its surface,
(2) the color difference adjusting layer comprises a curing resin component (i), and metal oxide particles having an average primary particle diameter of 100 nm or less (ii) and/or metal fluoride particles having an average primary particle diameter of 100 nm or less (iii), and where the total mass of particles (ii) and (iii) in the color difference adjusting layer is 0-200 parts by mass with respect to 100 parts by mass of the curing resin component (i), and
(3) a difference ΔR of R1 and R2 is not greater than 1, wherein R1 is a reflectance obtained by irradiation with a light source having a wavelength in a range of 500 to 750 nm toward the transparent electroconductive laminate, and R2 is a reflectance obtained by irradiation with a light source having a wavelength in a range of 500 to 750 nm toward a transparent electroconductive laminate after immersion into a strong acid aqueous solution at 40° C. for three minutes and dried, wherein the strong acid aqueous solution is obtained by a mixing of 12 N hydrochloric acid, 16 N nitric acid and water in a mass ratio of 12 N hydrochloric acid:16 N nitric acid:water being 3.3:1.0:7.6.
16. The transparent electroconductive laminate according to claim 15 , wherein
the curing resin component (i) in the color difference adjusting layer is an ultraviolet curing resin, and
a difference ΔH of H1 and H2 is not greater than 0.3%, wherein H1 is a haze value of the transparent electroconductive laminate, and H2 is a haze value of a transparent electroconductive laminate after immersion into a strong acid aqueous solution at 40° C. for three minutes and dried, wherein the strong acid aqueous solution is obtained by a mixing of 12 N hydrochloric acid, 16 N nitric acid and water in a mass ratio of 12 N hydrochloric acid:16 N nitric acid:water being 3.3:1.0:7.6.
17. The transparent electroconductive laminate according to claim 15 , wherein
the phenolic novolac acrylate (A) is represented by the following formula (I):
wherein R 1 represents H or CH 2 OH, R 2 represents H or OH, n represents a number of 2 to 5 and m represents a number of 0 to 5.
18. The transparent electroconductive laminate according to claim 15 , wherein the (meth)acrylate (B) is an aromatic group-containing (meth)acrylate having a refractive index within a range of 1.56 to 1.64.
19. The transparent electroconductive laminate according to claim 15 , wherein a total content of ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 and indium tin oxide in the high refractive index antiblocking layer is less than or equal to 0.0001% by mass.
20. The transparent electroconductive laminate according to claim 15 , wherein
the high refractive index antiblocking layer has an arithmetic average roughness (Ra) of 0.001 to 0.09 μm and a ten-point average roughness (Rz) of 0.01 to 0.5 μm.
21. The transparent electroconductive laminate according to claim 15 , wherein the high refractive index antiblocking layer has a thickness within a range of 0.05 to 10 μm.
22. The transparent electroconductive laminate according to claim 15 , wherein
the transparent electrically conducting layer is a crystalline layer comprising indium oxide, and
the transparent electrically conducting layer has a thickness within a range of 5 to 50 nm.
23. The transparent electroconductive laminate according to claim 15 , wherein
the transparent electroconductive laminate has a metal oxide layer between the color difference adjusting layer and the transparent electrically conducting layer, and
the metal oxide layer has a thickness within a range of 0.5 to 5.0 nm.
24. The transparent electroconductive laminate according to claim 15 , wherein
the high refractive index antiblocking layer, the color difference adjusting layer, and the transparent electrically conducting layer are formed in this order on one side of the transparent polymer substrate, and
an antiblocking layer is formed on the other side of the transparent polymer substrate.
25. The transparent electroconductive laminate according to claim 12 , wherein
the antiblocking layer is obtained by applying and curing a composition for forming an antiblocking layer comprising a first component and a second component, wherein
the first component is an unsaturated double bond containing acrylic copolymer, and
the second component comprises a polyfunctional acrylate, and
a difference of solubility parameter values (ΔSP) of the first component (SP1) and the second component (SP2) is within a range of 1 to 2, and
phase separation occurs between the first component and the second component after the composition for forming an antiblocking layer is applied, to form an antiblocking layer having a microscopic convexoconcave on its surface.
26. A touch panel having the transparent electroconductive laminate according to claim 15 .