Photo-curable resin composition

• US 6,096,796 A
• Filed: 12/10/1997
• Issued: 08/01/2000
• Est. Priority Date: 12/10/1996
• Status: Expired due to Term

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG), Japan Fine Coatings Co. Ltd. (JSR Corporation), JSR Corporation
• Original Assignee: DSM B.V., Japan Fine Coatings Co. Ltd. (JSR Corporation), JSR Corporation
• Inventors: Takeuchi, Akira, Watanabe, Tsuyoshi, Yamamura, Tetsuya, Ukachi, Takashi
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): McClendon, Sanza L.
• Application Number:
  US08/988,237
• Time in Patent Office: 965 Days
• Field of Search: 522/31, 522/29, 522/25, 522/97, 522/168, 522/170, 522/100, 427/517, 430/269, 430/270.1, 430/280.1, 430/281.1
• US Class Current: 522/100
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/029 Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021

Abstract

A photo-curable resin composition capable of providing a three-dimensional object having excellent mechanical strength and high dimensional accuracy when used in a photo-fabrication process. The resin composition is also capable of providing a three-dimensional object with excellent stability in shape and properties in a photo-fabrication process. The photo-curable composition includes:

(A) a compound represented by the formula (1) ##STR1## wherein R¹ and R² independently represent a hydrogen atom or a methyl group;

(B) a compound having a cyclohexene oxide structure;

(C) a cationic photo-initiator;

(D) an ethylenically unsaturated monomer;

(E) a radical photo-initiator; and

(F) a polyol having three or more hydroxyl groups.

Claims

1. A photo-curable resin composition comprising,

(A) an epoxy compound represented by the formula (1) ##STR4## wherein R¹ and R² independently represent a hydrogen atom or a methyl group,

(B) a compound having a cyclohexene oxide structure,

(C) a cationic photo-initiator,

(D) an ethylenically unsaturated monomer,

(E) a radical photo-initiator, and

(F) a polyol having three or more hydroxyl groups.

2. The photo-curable resin composition of claim 1, wherein said epoxy compound of formula (1) is selected from the group consisting of:

hydrogenated bisphenol A diglycidyl ethers, hydrogenated bisphenol F diglycidyl ethers, and hydrogenated bisphenol AD diglycidyl ethers.

3. The photo-curable resin composition of claim 1, wherein, relative to the total amount of resin composition:

component (A) is present in an amount from about 5 wt. % to about 40 wt. %;

component (B) is present in an amount from about 50 wt. % to 100 wt. %;

component (C) is present in an amount of about 0.1 wt. % to about 10 wt. %;

component (D) is present in an amount from about 5 wt. % to about 30 wt. %;

component (E) is present in an amount from about 0.01 wt. % to about 10 wt. %; and

component (F) is present in an amount from about 5 wt. % to about 30 wt. %.

4. The photo-curable resin composition of claim 1, wherein component (D) is a poly-functional ethylenically unsaturated monomer.

5. The photo-curable resin composition of claim 1, wherein component (D) is a poly-functional ethylenically unsaturated compound having at least three ethylenically unsaturated groups.

6. The photo-curable resin composition of claim 1, wherein said composition once cured, and after exposure to 95% relative humidity and 23°

C. for 30 days, displays a relative change in Young'"'"'s Modulus of not more than 20%.

7. The photo-curable resin composition of claim 1, wherein said composition after curing, and after exposure to water at 23°

C. for 30 days, displays a relative change in Young'"'"'s Modulus of not more than 50%.

8. The photo-curable resin composition of claim 1, wherein said composition after curing, has a rate of deformation of less than 0.10 mm after 30 days.

9. The photo-curable resin composition of claim 1, wherein said composition has a viscosity at 25°

C. of between 50 to 1,000 cps.

10. A three-dimensional object comprising a cured photo-curable resin composition comprising:

(A) an epoxy compound represented by the formula (1) ##STR5## wherein R¹ and R² independently represent a hydrogen atom or a methyl group,

(B) a compound having a cyclohexene oxide structure,

(C) a cationic photo-initiator,

(D) an ethylenically unsaturated monomer,

(E) a radical photo-initiator, and

(F) a polyol having three or more hydroxyl groups.

11. A process for photo-fabricating a three-dimensional object comprising the steps of selectively curing a photo-curable resin, wherein said photo-curable resin comprises:

(A) an epoxy compound represented by the formula(1) ##STR6## wherein R¹ and R² independently represent a hydrogen atom or a methyl group,

(B) a compound having a cyclohexene oxide structure,

(C) a cationic photo-initiator,

(D) an ethylenically unsaturated monomer,

(E) a radical photo-initiator, and

(F) a polyol having three or more hydroxyl groups.