Photocurable resin composition, finely embossed pattern-forming sheet, finely embossed pattern transfer sheet, optical article, stamper and method of forming finely embossed pattern

• US 20030129385A1
• Filed: 06/24/2002
• Published: 07/10/2003
• Est. Priority Date: 06/28/2001
• Status: Active Grant

• Current Assignee: Dai Nippon Printing Company Limited
• Original Assignee: Dai Nippon Printing Company Limited
• Inventors: Yoshihara, Toshio, Hojo, Mikiko
• Granted Patent: US 7,420,005 B2
• Time in Patent Office: Days
• US Class Current: 428/323
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 2035/0877 using electron radiation, e.g. beta-rays
• CPC Class Codes: B29C 2059/023 Microembossing
• CPC Class Codes: B29C 37/0067 Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other separating agents B29C33/60
• CPC Class Codes: B29C 59/046 for layered or coated substantially flat surfaces
• CPC Class Codes: B29C 67/246 Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM] casting monomers B29C39/006, mixing construction B29B7/74
• CPC Class Codes: B29D 17/005 Producing optically read record carriers, e.g. optical discs
• CPC Class Codes: B29K 2105/16 Fillers
• CPC Class Codes: B29L 2031/7224 Holograms
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Abstract

The photocurable resin composition in the first aspect of the invention comprises, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form; the photocurable-resin composition in the second aspect comprises, as essential components, (C) a binder resin containing photopolymerizable functional groups and (D) hydrophobic fine silica particles; and the photocurable resin composition in the third aspect comprises, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate having photopolymerizable functional groups and (F) an organometallic coupling agent. These photocurable resin compositions are excellent not only in fitting to the shape of a cavity in a stamper complementary to a finely embossed pattern on an optical article, thus enabling rapidly and accurately shaping a finely embossed pattern, but also in form retention after shaping and resistance to blocking, thus enabling exposure to light after removal of the stamper and storage in a rolled form to achieve excellent successive producibility.

Claims

1. A photocurable resin composition comprising, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid.

2. The photocurable resin composition according to claim 1, wherein the inorganic superfine particles (B) are in a thin form.

3. The photocurable resin composition according to claim 1, wherein the inorganic superfine particles (B) are in the form of spheres of 1 to 300 nm in primary particle diameter.

4. The photocurable resin composition according to claim 1, wherein the content of the inorganic superfine particles (B) is in the range of 0.1 to 70% by weight relative to the total solids content.

5. The photocurable resin composition according to claim 1, wherein the inorganic superfine particles (B) are inorganic superfine particles having a surface rendered compatible with solvent.

6. The photocurable resin composition according to claim 1, wherein the polystyrene conversion molecular weight of the binder resin (A) is in the range of 2,000 to 600,000.

7. The photocurable resin composition according to claim 1, wherein the binder resin (A) comprises at least one member selected from the group consisting of acrylic resin, urethane acrylate resin and polyester acrylate resin.

8. The photocurable resin composition according to claim 1, which further comprises a monomer or oligomer having photopolymerizable functional groups.

9. The photocurable resin composition according to claim 1, which further comprises a releasing agent.

10. The photocurable resin composition according to claim 1, which further comprises an organometallic coupling agent.

11. The photocurable resin composition according to claim 1, which is used for formation of a finely embossed pattern on an optical article.

12. A finely embossed pattern-forming sheet provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid.

13. The finely embossed pattern-forming sheet according to claim 12, wherein the finely embossed pattern-forming sheet is in a rolled form.

14. A finely embossed pattern transfer sheet provided on a support in a transferable manner with a finely embossed pattern-forming layer comprising a photocurable resin composition comprisng, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid.

15. The finely embossed pattern transfer sheet according to claim 14, wherein the finely embossed pattern transfer sheet is in a rolled form.

16. The finely embossed pattern transfer sheet according to claim 14, which comprises at least a release layer, the finely embossed pattern-forming layer, a reflective layer selected from an opaque reflective layer and a transparent layer having refractive index different from that of the finely embossed pattern-forming layer, and an adhesive layer laminated in this order on the support.

17. An optical article comprising a surface structure having a finely embossed pattern formed thereon, said surface structure being made of a cured product of a photocurable resin composition comprising, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid.

18. The optical article according to claim 17, wherein the finely embossed pattern is a relief type hologram or a diffraction grating.

19. The optical article according to claim 17, wherein the finely embossed pattern is an optical element regulating at least one of reflection, transmission, scattering, polarization, convergence and interference of whole rays and/or a light at a specific wavelength.

20. The optical article according to claim 17, wherein the finely embossed pattern is a structure for recording information.

21. A stamper comprising a surface structure having a pattern complementary to a finely embossed pattern on an optical article, said surface structure being made of a cured product of a photocurable resin composition comprising, essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid.

22. A method of forming a finely embossed pattern, which comprises steps of providing an embossed pattern receiptor provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (A) a binder resin having photopolymerizable functional groups and (B) inorganic superfine particles in the order of sub-micron which can be dispersed in a colloidal form in a diluting solvent for preparation of a coating liquid, then pressing the surface of the embossed pattern receiptor with a stamper to form a finely embossed pattern thereon, and curing the finely embossed pattern-forming layer.

23. The method of forming a finely embossed pattern according to claim 22, wherein the finely embossed pattern-forming layer is cured after the stamper is removed therefrom.

24. The method of forming a finely embossed pattern according to claim 22, wherein the finely embossed pattern-forming layer cured on the support is transferred onto a second support.

25. A photocurable resin composition comprising, as essential components, (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles.

26. The photocurable resin composition according to claim 25, wherein the softening initiation temperature of the photocurable resin composition is lowered by the hydrophobic fine silica particles (D).

27. The photocurable resin composition according to claim 25, wherein the primary particle diameter of the hydrophobic fine silica particles (D) is 3 to 100 nm.

28. The photocurable resin composition according to claim 25, wherein the content of the hydrophobic fine silica particles (D) is in the range of 3 to 40% by weight relative to the total solids content.

29. The photocurable resin composition according to claim 25, wherein the polystyrene conversion molecular weight of the binder resin (C) is in the range of 2,000 to 600,000.

30. The photocurable resin composition according to claim 25, wherein the binder resin (C) comprises at least one member selected from the group consisting of acrylic resin, urethane acrylate resin and polyester acrylate resin.

31. The photocurable resin composition according to claim 25, which further comprises a monomer or oligomer having photopolymerizable functional groups.

32. The photocurable resin composition according to claim 25, which further comprises a release agent.

33. The photocurable resin composition according to claim 25, which further comprises an organometallic coupling agent.

34. The photocurable resin composition according to claim 25, which is used for formation of a finely embossed pattern on an optical article.

35. A finely embossed pattern-forming sheet provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles.

36. The finely embossed pattern-forming sheet according to claim 35, wherein the finely embossed pattern-forming sheet is in a rolled form.

37. A finely embossed pattern transfer sheet provided on a support in a transferable manner with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles.

38. The finely embossed pattern transfer sheet according to claim 37, wherein the finely embossed pattern transfer sheet is in a rolled form.

39. The finely embossed pattern transfer sheet according to claim 37, which comprises at least a release layer, the finely embossed pattern-forming layer, a reflective layer selected from an opaque reflective layer and a transparent layer having refractive index different from that of the finely embossed pattern-forming layer, and an adhesive layer laminated in this order on the support.

40. An optical article provided with a surface structure having a finely embossed pattern formed thereon, said surface structure being made of a cured product of a photocurable resin composition comprising, as essential component, (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles.

41. The optical article according to claim 40, wherein the finely embossed pattern is a relief type hologram or a diffraction grating.

42. The optical article according to claim 40, wherein the finely embossed pattern is an optical element regulating at least one of reflection, transmission, scattering, polarization, convergence and interference of whole rays and/or a light at a specific wavelength.

43. The optical article according to claim 40, wherein the finely embossed pattern is a structure for recording information.

44. As tamper provided with a surface structure having a pattern complementary to a finely embossed pattern on an optical article, said surface structure comprising a cured product of a photocurable resin composition comprising (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles as essential components.

45. A method of forming a finely embossed pattern, which comprises steps of providing an embossed pattern receiptor provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising (C) a binder resin having photopolymerizable functional groups and (D) hydrophobic fine silica particles as essential components, pressing the surface of the embossed pattern receiptor with a stamper to form an embossed pattern thereon, and curing the finely embossed pattern-forming layer.

46. The method of forming a finely embossed pattern according to claim 45, wherein the finely embossed pattern-forming layer is cured after the stamper is removed therefrom.

47. The method of forming a finely embossed pattern according to claim 45, wherein the finely embossed pattern-forming layer cured on the support is transferred onto a second support.

48. A photocurable resin composition comprising, as essential components, (E) a binder containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent.

49. The photocurable resin composition according to claim 48, wherein the organometallic coupling agent (F) is an aluminum coupling agent.

50. The photocurable resin composition according to claim 48, wherein the content of the organometallic coupling agent (F) is 0.1 to 20% by weight relative to the total solids content.

51. The photocurable resin composition according to claim 48, wherein the polystyrene conversion molecular weight of at least one kind in the binder resin (E) is in the range of 2,000 to 600,000.

52. The photocurable resin composition according to claim 48, which further comprises a monomer or oligomer having photopolymerizable functional groups.

53. The photocurable resin composition according to claim 48, which further comprises a release agent.

54. The photocurable resin composition according to claim 48, which is used for formation of a finely embossed pattern on an optical article.

55. A finely embossed pattern-forming sheet provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent.

56. The finely embossed pattern-forming sheet according to claim 55, wherein the finely embossed pattern-forming sheet is in a rolled form.

57. A finely embossed pattern transfer sheet provided on a support in a transferable manner with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent.

58. The finely embossed pattern transfer sheet according to claim 57, wherein the finely embossed pattern transfer sheet is in a rolled form.

59. The finely embossed pattern transfer sheet according to claim 57, which comprises at least a release layer, the finely embossed pattern-forming layer, a reflective layer selected from an opaque reflective layer and a transparent layer having refractive index different from that of the finely embossed pattern-forming layer, and an adhesive layer laminated in this order on the support.

60. An optical article provided with a surface structure having a finely embossed pattern formed thereon, said surface structure being made of a cured product of a photocurable resin composition comprising, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent.

61. The optical article according to claim 60, wherein the finely embossed pattern is a relief type hologram or a diffraction grating.

62. The optical article according to claim 60, wherein the finely embossed pattern is an optical element regulating at least one of reflection, transmission, scattering, polarization, convergence and interference of whole rays and/or a light at a specific wavelength.

63. The optical article according to claim 60, wherein the finely embossed pattern is a structure for recording information.

64. As tamper provided with a surface structure having a pattern complementary to a finely embossed pattern on an optical article, said surface structure being made of a cured product of a photocurable resin composition containing, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent.

65. A method of forming a finely embossed pattern, which comprises steps of providing an embossed pattern receiptor provided on a support with a finely embossed pattern-forming layer comprising a photocurable resin composition comprising, as essential components, (E) a binder resin containing acrylic resin and urethane acrylate resin and/or polyester acrylate resin having photopolymerizable functional groups and (F) an organometallic coupling agent, pressing the surface of the embossed pattern receiptor with a stamper to form an embossed pattern thereon, and curing the finely embossed pattern-forming layer.

66. The method of forming a finely embossed pattern according to claim 65, wherein the finely embossed pattern-forming layer is cured after the stamper is removed therefrom.

67. The method of forming a finely embossed pattern according to claim 65, wherein the finely embossed pattern-forming layer cured on the support is transferred onto a second support.