Curable resin composition

Patent metadata

Field	Value
Publication number	US-12297318-B2
Application number	US-202318351831-A
Country	US
Kind code	B2
Filing date	Jul 13, 2023
Priority date	Dec 13, 2017
Publication date	May 13, 2025
Grant date	May 13, 2025

Abstract

A curable resin composition includes (A) a specific curable resin and (C) a curing agent, and further includes (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on based on 100 parts by mass of the curable resin (A); (BII) a cyclic compound having 3 to 6 reactive groups and a reactive group equivalent of 100 g/eq or more and 300 g/eq or less; or (BIII) a specific oxetane compound in a mass ratio of the curable resin (A) to the oxetane compound (BIII) being 5:5 to 9:1.

First claim

What is claimed is:

1. A method of manufacturing a three-dimensional shaped article, comprising the steps of:
preparing a curable resin composition that comprises a first component, a second component and a curing agent;
forming a first layer of the curable resin composition;
photocuring the first layer of the curable resin composition based on a first slice data to shape a first part of the shaped article;
forming a second layer of the curable resin composition;
photocuring the second layer of the curable resin composition based on a second slice data to shape a second part of the shaped article; and
removing a part of the curable resin composition from a surface of a cured product including the first part and the second part, wherein
the second component is an oxetane compound, and
the first component is represented by formula (1)

where X 1 and X 2 are independently a divalent linking group containing an aromatic ring,
L 1 , L 2 , L 3 and L 4 are independently a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —CS—, an ester bond, a urethane bond, an ether bond, a thiourethane bond and a thioether bond,
Y 1 and Y 2 are independently an epoxy group, a cycloalkene oxide group or an oxetanyl group,
n is an average value of repeating structural units and is a real number of 0.1 to 10, and
X 3 is represented by formula (1-VIII)

where m is an integer selected so that the alkylene group has 4 to 18 carbon atoms,
R 1 and R 2 are hydrogen or a methyl group, and
* denotes a bond to L 1 or L 2 .

2. The method according to claim 1 ,
wherein the curable resin composition further comprises a cyclic compound.

3. The method according to claim 2 , wherein the cyclic compound has an epoxy group as a reactive group.

4. The method according to claim 2 , wherein the cyclic compound has 3 to 6 reactive groups and a reactive group equivalent of 100 g/eq to 300 g/eq.

5. The method according to claim 2 , wherein the cyclic compound has 1 to 6 cyclic structures selected from the group consisting of isocyanurate rings and aromatic rings.

6. The method according to claim 1 , wherein a viscosity of the curable resin composition at 25° C. is 50 to 10,000 mPa·s.

7. The method according to claim 1 , wherein the second component is an oxetane compound represented by formula (2)

where X 4 is a divalent linking group, which is linked by a carbon atom forming an aromatic ring,
X 5 and X 6 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
L 5 and L 6 are independently a divalent linking group containing a bond selected from the group consisting of —O—, —C—O—, an ester bond, and an ether bond, and
s is an average value of repeating structural units and is a real number of 0.1 to 10.

8. The method according to claim 7 , wherein the curable resin composition comprises a third component, which is a cation-polymerizable compound.

9. The method according to claim 8 , wherein the third component contains an epoxy resin or an oxetane compound.

10. The method according to claim 7 , wherein X 4 is a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, a diphenylpropanediyl group, a diphenyletherdiyl group, a diphenylsulfonediyl group, a triphenylethanediyl group or a tetraphenylmethanediyl group, which is optionally substituted.

11. The method according to claim 1 , wherein the second component is a cation-polymerizable compound.

12. The method according to claim 1 , wherein the curable resin composition comprises a polyhydric alcohol having 2 to 5 hydroxyl groups.

13. The method according to claim 12 , wherein the polyhydric alcohol has a molecular weight of 1,000 or less.

14. The method according to claim 1 , wherein the oxetane compound is represented by formula (4)

where X 8 is a dihydric alcohol residue, or a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, an ether bond, a carbonate bond, a urethane bond and a urea bond, and may optionally contain an aromatic ring.

15. The method according to claim 1 , wherein n is 0.2 to 5.

16. The method according to claim 1 , wherein X 1 and X 2 are independently a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, a diphenylpropanediyl group, a diphenyletherdiyl group, or a diphenylsulfonediyl group, which is optionally substituted.

17. The method according to claim 1 , wherein X 3 is an optionally substituted acyclic alkylene group having a straight chain or a branched chain structure.

18. The method according to claim 1 , wherein L 1 , L 2 , L 3 and L 4 independently contain a bond selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ether bond and a thioether bond.

19. The method according to claim 1 , wherein Y 1 and Y 2 are an epoxy group.

20. The method according to claim 1 , wherein the curing agent is a photoacid generator.

21. The method according to claim 1 , wherein the oxetane compound has two oxetanyl groups.

Assignees

• Canon Kk

Inventors

• Wada Kyohei
• Nishiura Chiaki
• Ogawa Ryo

Classifications

• C08G65/18

  Oxetanes · CPC title

• C08G59/3245

  containing only nitrogen as a heteroatom · CPC title

• C08G65/22

  Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring · CPC title

• B29C64/30

  Auxiliary operations or equipment · CPC title

• B29K2063/00

  Use of {EP, i.e.} epoxy resins {or derivatives thereof}, as moulding material · CPC title