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JP-7855522-B2 - Elastic material prepared from a curable liquid composition

JP7855522B2JP 7855522 B2JP7855522 B2JP 7855522B2JP-7855522-B2

Inventors

  • ザヒドゥル・アミン
  • 杉本 俊哉
  • ミンシン・ファン

Assignees

  • アルケマ フランス

Dates

Publication Date
20260508
Application Date
20210401
Priority Date
20200401

Claims (11)

  1. An elastic material having a rebound elasticity of more than 10% as measured in accordance with JIS K 6255:1996, and the elastic material having the following components a) and b): a) At least one urethane (meth)acrylate having a number-average molecular weight of at least 4,700 g/mol and containing oxybutylene units, in an amount of 30 to 90% by mass based on the total mass of components a) and b); b) An elastic material which is an energy curing reaction product of a curable composition comprising 10 to 70% by mass of at least one (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule, based on the total mass of components a) and b), Component a) comprises a urethane (meth)acrylate which is a reaction product of one or more diols, one or more aliphatic or alicyclic diisocyanates, and one or more hydroxylated mono( meth )acrylates, and at least one of the diols contains an oxybutylene repeating unit, Component b) contains a mono(meth)acrylate monomer having a glass transition temperature Tg greater than 20°C, and / or Component b) comprises a sterically hindered mono(meth)acrylate monomer containing a cyclic moiety and/or a tert-butyl group, Elastic material.
  2. The elastic material according to claim 1, wherein the mass content of oxybutylene units in the urethane (meth)acrylate is at least 45% based on the total mass of the urethane (meth)acrylate.
  3. The elastic material according to claim 1 or 2, wherein component a) comprises a urethane (meth)acrylate having at least one acrylate functional group.
  4. The elastic material according to any one of claims 1 to 3, wherein component a) comprises a urethane (meth)acrylate having a number-average molecular weight of 5,500 to 20,000 g/mol.
  5. Component a) is given by the following equation (I): (In the formula, Each A is independently a diol residue, and at least one A contains an oxybutylene unit; Each R is independently a residue of an aliphatic or alicyclic diisocyanate; Each B is independently a residue of a hydroxylated mono(meth)acrylate; Each X is independently either H or methyl; n is between 1 and 9 . An elastic material according to any one of claims 1 to 4, comprising a urethane (meth)acrylate having the following properties.
  6. The elastic material according to claim 5, wherein the diol is polytetramethylene ether glycol.
  7. The elastic material according to claim 5 or 6, wherein the diol has a number-average molecular weight of at least 1,100 g/mol.
  8. Component b) is tert-butyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, tricyclodecane methanol mono (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate An elastic material according to any one of claims 1 to 7, comprising a sterically hindered mono(meth)acrylate monomer selected from methacrylate (also called (5-ethyl-1,3-dioxan-5-yl)methyl (meth)acrylate), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, ( 2-ethyl-2-methyl-1,3-dioxolan-4-yl )methyl (meth)acrylate, glycerol formal methacrylate, alkoxylated derivatives thereof, and mixtures thereof.
  9. The elastic material according to any one of claims 1 to 8 , wherein the elastic material has an elongation greater than 300% as measured in accordance with JIS K 7127:1999.
  10. The elastic material according to any one of claims 1 to 9 , wherein the elastic material has a Shore A hardness of at least 15 as measured in accordance with JIS K 6253-3:2012.
  11. A method for producing an elastic material according to any one of claims 1 to 10 , comprising the step of curing a curable composition as defined in any one of claims 1 to 8 .

Description

This invention relates to an energy-cured elastic material having high rebound elasticity, obtained from a composition containing a specific urethane (meth)acrylate containing oxybutylene units. Energy curing (EC) refers to the conversion of a curable composition (sometimes called a "resin") into a polymer using an energy source such as an electron beam (EB), a light source (e.g., a visible light source, a near-ultraviolet light source, an ultraviolet lamp (UV), a light-emitting diode (LED), or an infrared light source) and/or heat. Compositions that can be polymerized by exposure to such energy sources are sometimes called energy-curable compositions. Materials prepared by polymerizing a curable composition with EB, a light source (e.g., visible light, near-ultraviolet light, ultraviolet LED, or infrared light) and/or heat can be considered energy-cured materials (energy-cured materials). Energy curing technology offers the potential to obtain a wide range of material properties. This breadth is evident in the numerous applications of energy-curable compositions: wood coatings, plastic coatings, glass coatings, metal coatings, finishing films, mechanical performance coatings, durable hard coats, inkjet inks, flexographic printing inks, screen printing inks, overprint varnishes, nail gel resins, dental materials, pressure-sensitive adhesives, bonding adhesives, electronic display components, photoresists, 3D printing resins, and more. However, the industry continues to strive to reach new "material property spaces" that have been previously unattainable in energy-curable compositions and materials prepared from them. A property space refers to a combination of different material properties under specific constraints. Elastic energy-curable materials are attracting significant interest for specific end-uses. However, energy-curable compositions capable of obtaining elastic materials through energy curing have not been widely explored or developed to date. To obtain the rebound elasticity required for elastomers, the material must 1) deform under stress and 2) quickly return to its original shape when the stress is removed. In polymer materials, crosslinking between polymer chains reduces the ability to deform. Therefore, too much crosslinking will result in a loss of rebound elasticity. On the other hand, crosslinking may be necessary for the material to return to its original shape after stress removal. For a given composition, there is an optimal crosslinking density that yields the best rebound elasticity. Similarly, the elongation of the material also largely depends on the crosslinking density, and crosslinking reduces elongation. The crosslinking density required for rebound is sufficient to significantly limit elongation. Therefore, the critical challenge when formulating energy-curable compositions that can produce elastic materials through curing is to simultaneously obtain high elongation and high rebound elasticity. U.S. Patent No. 6,265,476U.S. Patent No. 7,198,576U.S. Patent Application Publication No. 2012/0157564A1U.S. Patent No. 5,268,396International Publication No. 2014/126830International Publication No. 2014/126834International Publication No. 2014/126837 Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects," Science Vol. 347, No. 6228, pp. 1349-1352 (March 20, 2015). Detailed description of aspects of the present inventionDefinitions In this application, the term “comprise(s) a/an” means “comprise(s) one or more.” Unless otherwise stated, the mass percentage in a compound or composition is expressed based on the mass of the compound or composition. The term "X substantially does not contain Y" means that X contains Y in amounts less than 10% by mass, less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, less than 0.1% by mass, less than 0.01% by mass, and even 0% by mass. The term "Cα-Cβ group" (where α and β are integers) refers to a group having α to β carbon atoms. The term "elastic material" qualitatively refers to a material possessing one or more elastomer properties, such as high elongation, high rebound elasticity, high elasticity, and/or high elastic recovery. Furthermore, elastic materials may also possess appropriate toughness. Quantitatively, these properties vary depending on the specific end-use of the elastic material. Elongation refers to the total deformation until the sample breaks. High elongation may be greater than 200%, 300%, 400%, or 500% when measured according to the method defined herein. Rebound elasticity refers to the rebound height of an object bouncing off the surface of the material, expressed as a percentage of the object's original height. High rebound elasticity may be greater than 10%, 15%, 20%, 30%, or 40% when measured according to the method defined herein. Toughness refers to the integral value of the tensile stress-strain curve, and elasticity refers to the maximum deformation that a material