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CN-121991295-A - Curable resin composition for photo-shaping, cured product, and three-dimensional shaped article

CN121991295ACN 121991295 ACN121991295 ACN 121991295ACN-121991295-A

Abstract

The invention provides a curable resin composition for optical stereolithography, which can form an optical stereolithography having sufficient toughness and heat resistance, a cured product thereof, and a stereolithography. The curable resin composition for photofabrication comprises a urethane resin (A) having two (meth) acryloyl groups, an alpha, beta-unsaturated carbonyl compound (B), and a photopolymerization initiator. The urethane resin (a) is prepared from a polycarbonate diol (a 1), a diisocyanate (a 2), and a compound (a 3) having a hydroxyl group and a (meth) acryloyl group as reaction raw materials. The polycarbonate diol (a 1) has a branched or linear aliphatic structure. The glass transition temperature (Tg) of the α, β -unsaturated carbonyl compound (B) as a monomer polymer is 50 ℃ or higher. The urethane resin (A) has a number average molecular weight (Mn) of 2000 or more.

Inventors

  • NISHIDA SHOKO
  • NISHI TAKASHI
  • DEGUCHI YOSHINOBU
  • MIKI TAKAYUKI

Assignees

  • DIC株式会社

Dates

Publication Date
20260508
Application Date
20251023
Priority Date
20241107

Claims (10)

  1. 1. A curable resin composition for photofabrication, comprising: a urethane resin (A) having two (meth) acryloyl groups, Alpha, beta-unsaturated carbonyl compound (B), and A photopolymerization initiator is used as a raw material, The urethane resin (A) is prepared from a polycarbonate diol (a 1), a diisocyanate (a 2) and a compound (a 3) having a hydroxyl group and a (meth) acryloyl group as reaction raw materials, The polycarbonate diol (a 1) has a branched or straight aliphatic structure, The glass transition temperature Tg of the alpha, beta-unsaturated carbonyl compound (B) as a monomer polymer is 50 ℃ or more, The urethane resin (A) has a number average molecular weight Mn of 2000 or more.
  2. 2. The curable resin composition for photofabrication according to claim 1, further comprising a compound (C) having two or more (meth) acryloyl groups, The compound (C) having two or more (meth) acryloyl groups has a glass transition temperature Tg of 60 ℃ or higher as a monomer polymer.
  3. 3. The curable resin composition for photofabrication according to claim 1, wherein the α, β -unsaturated carbonyl compound (B) is a compound having one (meth) acryloyl group.
  4. 4. The curable resin composition for light shaping according to any one of claims 1 to 3, wherein the urethane resin (a) has a (meth) acryloyl group content of 0.3 to mmol/g inclusive and 2.0 to mmol/g inclusive.
  5. 5. The curable resin composition for light shaping according to any one of claims 1 to 3, wherein the content of the urethane resin (a) is 1 mass% or more and 50 mass% or less.
  6. 6. The curable resin composition for photofabrication according to any one of claims 1 to 3, wherein the content of the α, β -unsaturated carbonyl compound (B) is 20 mass% or more and 90 mass% or less.
  7. 7. The curable resin composition for photofabrication according to claim 2, wherein when the compound (C) having two or more (meth) acryloyl groups is contained, the content of the compound (C) having two or more (meth) acryloyl groups is1 mass% or more and 50 mass% or less.
  8. 8. The curable resin composition for light shaping according to any one of claims 1 to 3, wherein the urethane resin (A) is a resin represented by the following formula (1), In the above-mentioned formula (1), R 1 、R 7 each independently represents a hydrogen atom or a methyl group, R 2 、R 6 independently represents-C 2 H 4 -、-C 3 H 6 -、-C 4 H 8 -or-C 2 H 4 O(COC 5 H 10 ) s -, wherein s is 1 to 4, R 3 、R 5 independently of one another represents-C 5 H 10 -、-C 6 H 12 -、-C 10 H 18 -or-C 9 H 18 -, R 4 represents one or more than two bivalent groups selected from- (CH 2 ) s -, and- (CH 2 ) s -CH(CH 3 )-(CH 2 ) t -), s in the- (CH 2 ) s -s is 2-12, s and t in the- (CH 2 ) s -CH(CH 3 )-(CH 2 ) t -s and t are 0 and s+t is 0-10, N represents an integer of 2 to 100.
  9. 9. A cured product which is a cured reaction product of the curable resin composition for photofabrication according to any one of claims 1 to 3.
  10. 10. A stereolithography article comprising the cured article of claim 9.

Description

Curable resin composition for photo-shaping, cured product, and three-dimensional shaped article Technical Field The present invention relates to a curable resin composition for photofabrication, a cured product, and a three-dimensional molded article. Background In recent years, as a method for producing a resin molded article, an optical stereolithography method (photo-patterning method) has been used in which a curable resin composition is selectively polymerized and cured by active energy rays such as ultraviolet rays based on three-dimensional shape data designed by a three-dimensional design system such as three-dimensional CAD, thereby producing a stereolithography article. The optical stereolithography method can also cope with complex shapes that are difficult to achieve in cutting, and is also short in manufacturing time and easy to handle, and therefore is widely used for manufacturing trial models of industrial products in addition to resin molded products. As a typical example of the optical stereolithography method, there is a method in which a dot-shaped ultraviolet laser beam controlled by a computer is irradiated from above onto a liquid photocurable resin placed in a container, one layer of a predetermined thickness is cured, the molded article is reduced by one layer, the liquid resin is supplied onto the layer, the irradiation curing is performed in the same manner as described above by using an ultraviolet laser beam, and lamination is performed, and this operation is repeated to obtain a stereomolded article. In addition to the dot pattern drawing method using dot-shaped ultraviolet laser, recently, an exposure method has been increased in which a plurality of digital micromirror shutters are arranged at intervals in a planar pattern drawing mask called a digital micromirror device (digital micromirror device, DMD) using a light source other than laser light such as LED, one layer of a predetermined cross-sectional pattern is cured by irradiation of ultraviolet light from below through a transparent container in which a photocurable resin is placed, and the resultant is lifted up by one layer, and the next layer is sequentially laminated by irradiation curing in the same manner as described above to obtain a three-dimensional pattern. The optical stereolithography method (optical stereolithography method) has been widely developed because of its high molding speed and high precision (for example, refer to patent document 1 and patent document 2). As a result, with the improvement of the photo-shaping machine and the photo-shaping material, the application range of the photo-shaping is gradually expanding from the trial product to the final product. However, it is still difficult to obtain an optical three-dimensional molded article having both sufficient toughness and heat resistance as a final product by using the conventional techniques for automobile parts, home electric appliances, and the like. Therefore, a curable resin composition for optical molding which can form an optical three-dimensional molded article having sufficient toughness and heat resistance is desired. Prior art literature Patent literature Patent document 1 Japanese patent application laid-open No. 2019-199448 Patent document 2 International publication No. 2022/209689 Disclosure of Invention Problems to be solved by the invention The purpose of the present invention is to provide a curable resin composition for optical stereolithography, which can form an optical stereolithography having sufficient toughness and heat resistance, a cured product thereof, and a stereolithography. Means for solving the problems The present invention includes the following modes. [1] A curable resin composition for photofabrication, comprising: a urethane resin (A) having two (meth) acryloyl groups, Alpha, beta-unsaturated carbonyl compound (B), and A photopolymerization initiator is used as a raw material, The urethane resin (A) is prepared from a polycarbonate diol (a 1), a diisocyanate (a 2), and a compound (a 3) having a hydroxyl group and a (meth) acryloyl group as reaction raw materials, The polycarbonate diol (a 1) has a branched or linear aliphatic structure, The glass transition temperature (Tg) of the α, β -unsaturated carbonyl compound (B) as a monomer polymer is 50 ℃ or higher, The urethane resin (A) has a number average molecular weight (Mn) of 2000 or more. [2] The curable resin composition for photofabrication according to [1], which further comprises a compound (C) having two or more (meth) acryloyl groups, The compound (C) having two or more (meth) acryloyl groups has a glass transition temperature (Tg) of 60 ℃ or higher as a monomer polymer. [3] The curable resin composition for photofabrication according to [1] or [2], wherein the α, β -unsaturated carbonyl compound (B) is a compound having one (meth) acryloyl group. [4] The curable resin composition for photofabrication according to any one of [1] to [3], wherein