Photo-curable resin composition

• US 6,127,085 A
• Filed: 10/17/1997
• Issued: 10/03/2000
• Est. Priority Date: 10/14/1996
• 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): Hamilton, Cynthia
• Application Number:
  US08/953,633
• Time in Patent Office: 1,082 Days
• Field of Search: 430/280.1, 430/177, 430/171, 522/170, 522/169, 522/15, 522/25
• US Class Current: 430/177
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• 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 novel photo-curable resin composition. The resin composition capable of providing a cured product having excellent mechanical strength, high dimensional accuracy, and excellent toughness. The resin composition is capable of providing a cured product which experiences little change in mechanical strength over time. The resin composition is capable of forming, by photo-fabricating, a three-dimensional object which can be used for a long period of time in a humid atmosphere. The composition comprises, (A) an epoxy compound having a cyclohexene oxide, (B) a cationic photo-initiator, (C) an ethylenically unsaturated monomer, (D) a radical photo-initiator, and (E) a polyol.

Claims

1. A photo-curable resin composition comprising:

(A) a compound represented by formula (1), ##STR3## (B) a cationic photo-initiator, (C) a monomer comprising at least one ethylenically unsaturated bond per molecule;

(D) a radical photo-initiator, and

(E) a polyol;

wherein R¹ and R², which may be the same or different, individually represent a hydrogen atom, methyl group, ethyl group, isopropyl group, n-butyl group, sec-butyl group, or tert-butyl group, s is an integer from 1-7, and t is an integer from 1-20, provided that when there are two or more groups of R¹ or R² present, a plurality of R¹ or R² may be either the same or different; and

wherein at least 60% of the ethylenically unsaturated monomer, relative to the total amount of ethylenically unsaturated monomer, has three or more ethylenically unsaturated bonds per molecule.

2. The photo-curablc resin composition of claim 1, wherein the amount of component (A) present in said photo-curable resin composition is 5-60% by weight.

3. The photo-curable resin composition of claim 1, wherein the cationic photo-initiator (B) comprises at least one onium salt of formula 2:

space="preserve" listing-type="equation">[R.sup.3.sub.a R.sup.4.sub.b R.sup.5.sub.c R.sup.6.sub.d Z].sup. m [MX.sub.n ].sup.-m (

     2)

wherein the cation is onium;

Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N.tbd.N;

R³, R⁴, R⁵, and R⁶ represent individually the same or a different organic group;

a, b, c, and d represent individually an integer from 0 to 3, and the sum of a, b, c, and d (=a b c d) is equal to the valence number of Z;

M represents a metal or metalloid selected from the group consisting of B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co and X is a halogen atom;

m represents an integer of at least 1 and n represents an integer of at least 1.

4. The photo-curable resin composition of claim 3, wherein the anion complex is selected from the group consisting of tetrafluoroborate(BF₃^-), hexafluorophosphate (PF₆^-), hexafluoroantimonate (SbF₆^-), hexafluoroarsenate (AsF₆^-), and hexachloroantimonate (SbCL₆^-).

5. The photo-curable resin compound of claim 3, wherein the cationic photo-initiator (B) is an onium salt containing an anion selected from the group consisting perchloric acid ion (ClO₄^-), trifluoromethane sulfonate ion (CF₃ SO₃^-), fluorosulfonate ion (FSO₃^-), toluene sulfonate anion, trinitrobenzene sulfonate anion and trinitrotoluene sulfonate anion.

6. The photo-curable resin composition of claim 1, wherein the photo-initiator (B) is an onium salt containing an anion represented by the general formula

7. The photo-curable resin composition of claim 1, wherein the photo-initiator (B) is present in an amount of 0.1-10% by weight.

8. The photo-curable resin composition of claim 1, wherein the ethylenically unsaturated monomer (C) is present in an amount of 5-40% by weight of the total composition.

9. The photo-curable resin composition of claim 1, wherein the radical photo-initiator (D) is present in an amount of 0.01-10% by weight.

10. A photo-curable resin composition comprising:

(A) a compound represented by formula (1), ##STR4## (B) a cationic photo-initiator, (C) an ethylenically unsaturated monomer,

(D) a radical photo-initiator, and

(E) a polyol having 2-6 hydroxyl groups per molecule;

wherein R¹ and R², which may be the same or different, individually represent a hydrogen atom, methyl group, ethyl group, isopropyl group, n-butyl group, sec-butyl group, or tert-butyl group, s is an integer from 1-7, and t is an integer from 1-20, provided that when there are two or more groups of R¹ or R² present, a plurality of R¹ or R² may be either the same or different.

11. A photo-curable resin composition comprising:

(A) a compound represented by formula (1), ##STR5## (B) a cationie photo-initiator, (C) an ethylenically unsaturated monomer,

(D) a radical photo-initiator, and

(E) a polyol;

(F) one or more cationically polymerizable compounds selected from the group consisting of oxetane compounds, oxalan compounds, cyclic acetal compounds, lactone compounds, thiirane compounds, thietane compounds, vinylether compounds and spiro-ortho ester compounds;

wherein R¹ and R², which may be the same or different, individually represent a hydrogen atom, methyl group, ethyl group, isopropyl group, n-butyl group, sec-butyl group, or tert-butyl group, s is an integer from 1-7, and t is an integer from 1-20, provided that when there are two or more groups of R¹ or R² present, a plurality of R¹ or R² may be either the same or different.