Photocurable composition, a hydrogel and a molded product thereof

Patent metadata

Field	Value
Publication number	US-11987688-B2
Application number	US-201816644860-A
Country	US
Kind code	B2
Filing date	Aug 21, 2018
Priority date	Sep 7, 2017
Publication date	May 21, 2024
Grant date	May 21, 2024

Abstract

A photocurable composition including the following components (A) to (D), (A) a monomer having one (meth)acryloyl structure, (B) a crosslinking agent having two or more (meth)acryloyl structures, (C) an inorganic ultraviolet-blocking agent having a 50% volume cumulative particle size of 1 to 50 nm, and (D) a photopolymerization initiator in an amount of 0.05 to 1 part by weight, relative to total 100 parts by weight of components (A) and (B), wherein a part or all of component (A) is a hydrophilic monomer, and a content of the hydrophilic monomer is 70% by weight or more, relative to the total weight of components (A) and (B).

First claim

The invention claimed is:

1. A photocurable composition comprising the following components (A) to (D),
(A) a monomer having one (meth)acryloyl structure,
(B) a crosslinking agent having two or more (meth)acryloyl structures in an amount of 0.1 to 10 parts by weight, relative to total 100 parts by weight of components (A) and (B),
(C) an inorganic ultraviolet-blocking agent having a 50% volume cumulative particle size of 1 to 50 nm in the particle size distribution as determined according to a dynamic light scattering method, wherein the inorganic ultraviolet-blocking agent has a core-shell structure composed of a core of a titanium oxide-containing metal oxide and a silicon oxide shell outside the core, in an amount of 0.5 to 10 parts by weight, relative to total 100 parts by weight of components (A) and (B), and
(D) a photopolymerization initiator in an amount of 0.05 to 1 part by weight, relative to total 100 parts by weight of components (A) and (B),
wherein a part or all of component (A) is a hydrophilic monomer, and a content of the hydrophilic monomer is 70% by weight or more, relative to the total weight of components (A) and (B).

2. The photocurable composition according to claim 1 , wherein the hydrophilic monomer is a compound represented by the following formula (I):
CH 2 ═CR 1 COR 2   (I)

wherein R 1 is a hydrogen atom or a methyl group, R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a group represented by —OH, —OR 3 , —NH 2 , —NHR 3 or —NR 3 R 4 , and R 3 and R 4 are, independently of each other, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

3. The photocurable composition according to claim 1 , wherein the metal oxide particle includes tetragonal titanium oxide particles which is a solid solution with at least one of tin and manganese, wherein a molar ratio of titanium to tin (Ti/Sn) is 10 to 1,000 and a molar ratio of titanium to manganese (Ti/Mn) is 10 to 1,000.

4. The photocurable composition according to claim 1 , wherein at least a part of the surface of the inorganic ultraviolet-blocking agent has a coating layer composed of a surface treatment agent comprising a compound represented by the following general formula (II):
R 5 Si(OR 6 ) 3   (II)

wherein R 5 is a monovalent hydrocarbon group having 1 to 15 carbon atoms and R 6 is
a linear or branched alkyl group having 1 to 4 carbon atoms, and/or a hydrolysis condensation product thereof.

5. A cured product obtained by curing the photocurable composition according to claim 1 .

6. A hydrogel comprising the cured product according to claim 5 and water.

7. A molded product comprising the hydrogel according to claim 6 .

8. A photocurable composition comprising the following components (A) to (D),
(A) a monomer having one (meth)acryloyl structure,
(B) a crosslinking agent having two or more (meth)acryloyl structures in an amount of 0.1 to 10 parts by weight, relative to total 100 parts by weight of components (A) and (B),
(C) an inorganic ultraviolet-blocking agent having a 50% volume cumulative particle size of 1 to 50 nm in the particle size distribution as determined according to a dynamic light scattering method,
wherein the metal oxide particle includes tetragonal titanium oxide particles which is a solid solution with at least one of tin and manganese, wherein a molar ratio of titanium to tin (Ti/Sn) is 10 to 1,000 and a molar ratio of titanium to manganese (Ti/Mn) is 10 to 1,000,
in an amount of 0.5 to 10 parts by weight, relative to total 100 parts by weight of components (A) and (B),
and
(D) a photopolymerization initiator in an amount of 0.05 to 1 part by weight, relative to total 100 parts by weight of components (A) and (B),
wherein a part or all of component (A) is a hydrophilic monomer, and a content of the hydrophilic monomer is 70% by weight or more, relative to the total weight of components (A) and (B).

9. The photocurable composition according to claim 8 , wherein the hydrophilic monomer is a compound represented by the following formula (I):
CH 2 ═CR 1 COR 2   (I)

wherein R 1 is a hydrogen atom or a methyl group, R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a group represented by —OH, —OR 3 , —NH 2 , —NHR 3 or —NR 3 R 4 , and R 3 and R 4 are, independently of each other, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

10. The photocurable composition according to claim 8 , wherein at least a part of the surface of the inorganic ultraviolet-blocking agent has a coating layer composed of a surface treatment agent comprising a compound represented by the following general formula (II):
R 5 Si(OR 6 ) 3   (II)

wherein R 5 is a monovalent hydrocarbon group having 1 to 15 carbon atoms and R 6 is
a linear or branched alkyl group having 1 to 4 carbon atoms, and/or a hydrolysis condensation product thereof.

11. A cured product obtained by curing the photocurable composition according to claim 8 .

12. A cured product obtained by curing the photocurable composition according to claim 9 .

13. A cured product obtained by curing the photocurable composition according to claim 10 .

14. A hydrogel comprising the cured product according to claim 11 and water.

15. A molded product comprising the hydrogel according to claim 12 .

Assignees

• Shinetsu Chemical Co

Inventors

• Yoshii Ryosuke
• Masuda Kohei
• Hagiwara Mamoru
• Kimura Tsuneo

Classifications

• C08K3/22 Primary

  of metals · CPC title

• C08F292/00

  Macromolecular compounds obtained by polymerising monomers on to inorganic materials · CPC title

• G02B1/043

  Contact lenses · CPC title

• G02B27/0006

  with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation (G02B1/18 takes precedence; cleaning in general B08B) · CPC title

• C08K2003/2231

  of tin · CPC title