Process for producing resin substrate having hard coating layer, and resin substrate having hard coating layer

1. A process for producing a resin substrate having a hard coating layer on at least one side of a resin substrate, comprising, in the following order:

(1) applying a hard coating composition comprising an organopolysiloxane to at least one side of the resin substrate to form a coating film of the composition, and then applying a first heat treatment to the coating film to cure the organopolysiloxane, thereby forming a cured film, wherein said organopolysiloxane is present in an amount of 50 to 100 mass %, based on the total amount of the hard coating composition, excluding any solvent, and wherein in a interior of the cured film, a three dimensional crosslinking structure is formed by siloxane bonds, and on a surface of the cured film, structures of a monovalent organic group in which an alkyl group having 1 to 10 carbon atoms is bonded to a silicon atom, are present;

(2) irradiating the cured film having the three dimensional crosslinking structure with a Xe 2 excimer light having an irradiation energy of from 500 to 8,000 mJ/cm 2 , in an atmosphere having an oxygen concentration of at most 5 vol %, wherein at least some of the bonds between silicon atoms and carbon atoms present on the surface of the cured film are cleaved to form silicon radicals, such that a content of Si—CH 3 groups on the surface of the cured film measured by FT-IR after the Xe 2 excimer light irradiation treatment (A after ) is reduced compared with a content of Si—CH 3 groups on the surface of the cured film measured by FT-IR before the Xe 2 excimer light irradiation treatment (A initial ), and a degree of a reduction of Si—CH 3 groups shown by formula: 1−(A after /A initial ) is from 0.05 to 0.45; and

(3) applying an oxidation treatment to the cured film obtained by (2) wherein the silicon radicals on the surface of the cured film are oxidized to be in a state where a hydroxyl group is bonded to a silicon atom, thereby forming —SiOH moieties,

and then further applying a second heat treatment to form the hard coating layer, wherein the —SiOH moieties are reacted to form siloxane bonds,

wherein the hard coating layer has a hardness gradient in the depth direction of the hard coating layer such that the hard coating layer has a Martens hardness in a depth up to 150 nm from the surface of from 200 to 850 N/mm 2 , which is larger than a Martens hardness of an interior of the hard coating layer.

2. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the second heat treatment is a treatment of maintaining the cured film at a temperature of at least 80° C. and at most the heat deformation temperature of the resin substrate for from 5 to 120 minutes.

3. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the proportion in number of T units in the organopolysiloxane is from 70 to 100%.

4. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the organopolysiloxane is composed solely of T units and Q units, and the ratio in number of T:Q is from 90 to 100:10 to 0.

5. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein before the cured film forming step, a step of applying a primer composition to at least one side of the resin substrate and drying it to form a primer layer is further carried out, and in the cured film forming step, the hard coating composition is applied to the primer layer.

6. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the material of the resin substrate is a polycarbonate resin.

7. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the curing temperature is from 50 to 200° C. for the first heat treatment.

8. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the curing temperature is from 80 to 160° C. for the first heat treatment.

9. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the curing temperature is from 100 to 140° C. for the first heat treatment.

10. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein said oxygen concentration is at most 3 vol %.

11. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein said oxygen concentration is at most 1 vol %.

12. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein said organopolysiloxane is present in an amount of 60 to 95 mass %, based on the total amount of the hard coating composition, excluding any solvent.

13. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the degree of a reduction of Si—CH 3 groups shown by formula: 1−(A after /A initial ) is from 0.20 to 0.45.

14. The process for producing a resin substrate having a hard coating layer according to claim 1 , wherein the cured film having the three dimensional crosslinking structure is irradiated with a Xe 2 excimer light having an irradiation energy of from 1000 to 8,000 mJ/cm 2 .

15. A resin substrate having a hard coating layer obtained by the production process as defined in claim 1 .

16. The resin substrate having a hard coating layer according to claim 15 , wherein the ratio HM (0.005) /HM (0.5) of the Martens hardness (HM (0.005) ) measured at a loading/unloading rate F=0.005 mN/5 s with a creep C=5 s to the Martens hardness (HM (0.5) ) measured at a loading/unloading rate F=0.5 mN/5 s with a creep C=5 s, on the surface of the hard coating layer, is from 1.21 to 2.22.

17. The resin substrate having a hard coating layer according to claim 15 , wherein the ratio HM (0.01) /HM (0.5) of the Martens hardness (HM (0.01) ) measured at a loading/unloading rate F=0.01 mN/5 s with a creep C=5 s to the Martens hardness (HM (0.5) ) measured at a loading/unloading rate F=0.5 mN/5 s with a creep C=5 s, on the surface of the hard coating layer, is from 1.10 to 1.57.