Photo-curable resin composition and process for preparing resin-based mold

• US 5,874,041 A
• Filed: 05/30/1997
• Issued: 02/23/1999
• Est. Priority Date: 05/30/1996
• 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: Matsumura, Ayao, Watanabe, Tsuyoshi, Ukachi, Takashi, Haruta, Yuichi
• Primary Examiner(s): Tentoni, Leo B.
• Application Number:
  US08/865,781
• Time in Patent Office: 634 Days
• Field of Search: 264/308, 264/401
• US Class Current: 264/401
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Abstract

A photo-curable resin composition suitable as a material for optical molding. The composition can produce cured products with excellent mechanical strength and high heat resistance. Further disclosed is a process for molding a resin-based mold which provides superior molding dimensional precision and superb repetition durability. The composition contains a monomer component which contains (A) 20-80 wt % of a urethane-bond polyfunctional (meth)acrylate having a number average molecular weight of 1,000 or less and (B) 80-20 wt % of an ethylenically unsaturated monomer containing a cyclic structure and at least one ethylenically unsaturated bond in the molecule and of which the homopolymer has a glass transition temperature of 50° C. or higher; (C) a photopolymerization initiator; and (D) an inorganic filler having an average particle diameter or an average fiber length of 1-50 μm, wherein the ratio of the inorganic filler for 100 parts by volume of said monomer components and the photopolymerization initiator is 100-160 parts by volume, and the heat distortion temperature of the cured resin produced from the photo-curable resin composition is 80° C. or higher.

Claims

1. A process for the preparation of a resin-based three-dimensional object comprising the steps of:

forming a first layer of a photo-curable resin composition comprising;

as premixture ingredients;

a monomer component comprising,

at least one polyfunctional (meth)acrylate monomer represented by the following formula (1);

##STR3## wherein R1 independently represents a hydrogen atom or a methyl group, R2 independently represents a divalent hydrocarbon group comprising 2 to 10 carbon atoms, R3 represents an organic group with a valence of n and comprising 2 to 20 carbon atoms, n represents an integer of from 2 to 6, and

at least one ethylenically unsaturated monomer having at least one cyclic structure;

curing select portions of said first layer by radiation to form a first cured layer;

applying a second layer of said photo-curable resin composition, on top of said first cured layer;

curing select portions of said second layer by radiation to form a second cured layer; and

repeating said applying and curing steps a plurality of times to produce a resin-based three-dimensional object comprising a plurality of integrally laminated layers of cured resin.

2. A process for the preparation of a resin-based three-dimensional object according to claim 1, further comprising a step of washing said resin-based three-dimensional object with at least one washing agent.

3. A process for the preparation of a resin-based three-dimensional object according to claim 2, wherein said washing agent is at least one agent selected from the group consisting of alcohol, a low viscosity liquid thermosetting resin, and a low viscosity photo-curable resin.

4. A process for the preparation of a resin-based three-dimensional object according to claim 1, further comprising a step of irradiating said resin-based three-dimensional object with heat or light radiation.

5. The process of claim 1, wherein said photo-curable composition further comprises at least one inorganic filler and photopolymerization initiator.

6. The process of claim 5, wherein said at least one inorganic filler is selected from the group consisting of glass beads, hollow glass beads, and potassium titanate whisker.

7. The process of claim 5, wherein said inorganic filler is treated with at least one silane coupling agent.

8. The process of claim 7, wherein said filler is present in a volumetric ratio of from about 1:

1 to about 1.6;

1 with respect to a combination of said monomer component and said photopolymerization initiator.

9. The process of claim 5, wherein a heat distortion temperature of the cured photo-curable resin composition is at least 80°

C.

10. The process of claim 1, wherein said at least one ethylenically unsaturated monomer comprises from about 20 to 80 wt. % of said monomer component.

11. A process for making a three-dimensional object comprising the steps of:

forming and selectively curing a plurality of layers of a photo-curable resin composition comprising;

as premixture ingredients;

a monomer component comprising,

at least one polyfunctional urethane (meth)acrylate monomer, and

at least one ethylenically unsaturated monomer having at least one cyclic structure; and

repeating said forming and selectively curing steps a plurality of times to produce a resin-based three-dimensional object comprising a plurality of integrally laminated layers of cured resin.

12. The process of claim 11, wherein said polyfunctional urethane (meth)acrylate monomer is a compound represented by formula (1):

##STR4## wherein R1 independently represents a hydrogen atom or a methyl group,

R2 independently represents a divalent hydrocarbon group comprising 2 to 10 carbon atoms,

R3 represents an organic group with a valence of n and comprising 2 to 20 carbon atoms, and

n represents an integer from 2 to 6.

13. The process of claim 11, wherein said photo-curable composition further comprises at least one inorganic filler.

14. The process of claim 13, wherein said filler has an average particle diameter or an average fiber length of about 1 to about 50 μ

m.

15. The process of claim 13, wherein said at least one inorganic filler is selected from the group consisting of glass beads, hollow glass beads, and potassium titanate whisker.

16. The process of claim 13, wherein said inorganic filler is treated with at least one silane coupling agent.

17. The process of claim 13, wherein said composition further comprises a photopolymerization initiator.

18. The process of claim 17, wherein said filler is present in a volumetric ratio of from about 1:

1 to about 1.6;

1 with respect to a combination of said monomer component and said photopolymerization initiator.

19. The process of claim 11 wherein said polyfunctional urethane (meth)acrylate monomer is a product of a reaction between at least one hydroxyl group-containing (meth)acrylate and at least one polyisocyanate compound.

20. The process of claim 19, wherein said polyisocyanate includes at least one compound selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate.

21. The process of claim 19, wherein said polyisocyanate includes at least one compound selected from the group consisting of polymethylene polyphenyl isocyanate and triphenylmethane 4,4'"'"',4"-triisocyanate.

22. The process of claim 19 wherein said hydroxyl group-containing (meth)acrylate includes at least one compound selected from the group consisting of 2-hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate and trimethylolpropane di(meth)acrylate.

23. The process of claim 11, wherein said at least one ethylenically unsaturated monomer is selected from the group consisting of (meth)acryloyl morpholine, isobornyl (meth)acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, tricyclo 5.2.1.02,6!decanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and tricyclodecanediyldimethylene di(meth)acrylate.

24. The process of claim 11, wherein said at least one ethylenically unsaturated monomer comprises from about 20 to 80 wt. % of said monomer component.