Polymer substrate with hardcoat layer, and manufacturing method for same
The present invention provides a polymer substrate with a hardcoat layer exhibiting excellent environmental resistance and wear resistance. A polymer substrate ( 60 ) is 1-20 mm thick and a hardcoat layer ( 70, 80 ) on the surface thereof comprises: an underlayer cured layer ( 70 ) with a thickness of 1-20 μm, and including 10-90 parts by weight of a multifunctional acrylate, and 90-10 parts by weight of inorganic oxide fine particles and/or a silicon compound hydrolytic condensate; and a silicon oxide layer ( 80 ) which is in direct contract with the underlayer cured layer, is formed by PE-CVD with an organosilicon compound as the starter material, and satisfies all of the following conditions (a)-(c): (a) the film thickness of the silicon oxide layer is 3.5-9.0 μm; (b) the maximum indentation depth of the surface of the silicon oxide layer by nanoindentation measurement at a maximum load of 1 mN is 150 nm or less; and (c) the limit compression ratio K of the silicon oxide layer is at most 0.975 in a 3-point bending test of the polymer substrate with a hardcoat layer having been subjected to indentation deformation that causes the surface on which the silicon oxide layer is layered to be indented.
1. A polymer substrate with hard coating layer comprising a polymer substrate having a thickness of 1 mm to 20 mm and a hard coating layer on the surface thereof; wherein,
the hard coating layer comprises:
a cured underlayer laminated on the surface of the polymer substrate, containing 10 to 90 parts by weight of multifunctional acrylate and 90 to 10 parts by weight of inorganic oxide fine particles and/or a hydrolysis-condensation product of an organic silicon compound, and having a thickness of 1 μm to 20 μm, and
a silicon oxide layer that makes direct contact with the cured underlayer on the opposite side from the polymer substrate, is formed by PE-CVD using an organic silicon compound selected from an organosiloxane, organosilane or (organo)silazane as raw material, and satisfies all of the following requirements (a) to (c):
(a) film thickness of the silicon oxide layer is within the range of 3.5 to 9.0 μm,
(b) maximum indentation depth of the surface of the silicon oxide layer, as determined by measuring nanoindentation under conditions of a maximum load of 1 mN, is 150 nm or less, and
(c) the value of critical compression ratio K of the silicon oxide layer, as defined by formula (1) in a 3-point bending test of the polymer substrate with hard coating layer that imparts indentation displacement in which the surface laminated with the silicon oxide layer becomes concave, is 0.975 or less:
K =( R−D/ 2)/ R −(0.00215× d ) Formula (1)
(wherein,
D represents the total thickness (mm) of the polymer substrate with hard coating layer,
d represents the film thickness (μm) of the silicon oxide layer, and
R represents the bend radius (mm) of the polymer substrate with hard coating layer, measured when the silicon oxide layer begins to separate from a cut line (separation starting line) drawn in advance at the location of the central fulcrum point where a weight is applied in a 3-point bending test),
wherein the ratio of infrared absorbance of the silicon oxide layer at a wave number of 1280 cm −1 to that at a wave number of 1020 cm −1 (α 1280 /α 1020 ) is within the range of 0.002 to 0.020, and
the inorganic oxide fine particles and/or the hydrolysis-condensation product of the organic silicon compound of the cured underlayer is reacted with a (meth)acrylic resin having alkoxysilyl groups, hydroxyl groups, amino groups, or carboxyl groups in a side chain thereof.
2. The polymer substrate with hard coating layer according to claim 1 , wherein the ratio of infrared absorbance of the silicon oxide layer at a wave number of 930 cm −1 to that at a wave number of 1020 cm −1 (α 930 /α 1020 ) is 0.30 or less.
3. The polymer substrate with hard coating layer according to claim 1 , wherein indentation hardness of the surface of the silicon oxide layer as determined by measuring nanoindentation under conditions of a maximum load of 1 mN is 3.0 GPa or more.
4. The polymer substrate with hard coating layer according to claim 1 , wherein surface roughness (Ra) of the silicon oxide layer when measured using the dynamic force mode (DFM) of a scanning probe microscope under conditions of observing by 5.0 μm square is 5.0 nm or less.
5. The polymer substrate with hard coating layer according to claim 1 , wherein the (meth)acrylic resin contains 0.1 to 5 mol/kg of the hydroxyl groups, amino groups, carboxyl groups, alkoxysilyl groups or a combination thereof in the compound thereof.
6. A method for producing the polymer substrate with hard coating layer according to claim 1 , comprising: forming the cured underlayer by coating a precursor material composition containing 10 to 90 parts by weight of a multi-functional acrylate and 90 to 10 parts by weight of an inorganic oxide fine particle and/or silicon compound hydrolysis-condensation product onto the polymer substrate followed by drying and heat curing or active energy ray curing.
7. The method for producing the polymer substrate with hard coating layer according to claim 6 , wherein the surface of the cured underlayer is adjusted by plasma excitation or colliding an ionized inert gas with the surface of the cured underlayer.
8. The method for producing the polymer substrate with hard coating layer according to claim 6 , wherein the silicon oxide layer is formed by making the average deposition rate (nm/sec) from the start of deposition to 30 seconds after the start of deposition to be 1 nm/sec or less.
9. The method for producing the polymer substrate with hard coating layer according to claim 8 , wherein the silicon oxide layer is formed by making the average deposition rate (nm/sec) starting from 30 seconds after the start of deposition to be 2 nm/sec or more.
10. The method for producing the polymer substrate with hard coating layer according to claim 9 , wherein the deposition rate of the silicon oxide layer is increased continuously or incrementally in two or more steps.