Search

EP-4296295-B1 - RESIN COMPOSITION, AND PRINTING INK AND ELECTROCONDUCTIVE PASTE EACH USING SAME

EP4296295B1EP 4296295 B1EP4296295 B1EP 4296295B1EP-4296295-B1

Inventors

  • GOTO, Toshihito
  • OGAWA, NORIYOSHI

Dates

Publication Date
20260506
Application Date
20220210

Claims (17)

  1. A resin composition comprising a solvent represented by General formula (1) below and a polycarbonate resin containing a structural unit (a) represented by General formula (A) below (except for a polycarbonate homopolymer composed solely of a structural unit represented by Formula (i) below): wherein, R a represents hydrogen, or an optionally substituted C1-C20 alkyl group, C6-C20 aryl group, C2-C20 alkenyl group, C7-C20 aralkyl group or C2-C20 acyl group, R b represents an optionally substituted C1-C20 alkyl group, C6-C20 aryl group, C2-C20 alkenyl group, C7-C20 aralkyl group or C2-C20 acyl group, R c -R f each independently represent hydrogen or a C1-C3 alkyl group, and n represents an integer from 1 to 10); (wherein, R 1 -R 8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted C1-C7 alkyl group, C6-C12 aryl group, C2-C7 alkenyl group, C1-C7 alkoxy group or C7-C17 aralkyl group, and X represents -O-, -S-, -SO-, -SO 2 -, -CO-, or a divalent group represented by any of Formulae (2)-(4) below); (in Formulae (2)-(4), R 9 and R 10 each independently represent hydrogen, a halogen, or an optionally substituted C1-C20 alkyl group, C1-C5 alkoxy group, C6-C12 aryl group, C7-C17 aralkyl group or C2-C15 alkenyl group, or R 9 and R 10 bind to each other to form a C3-C20 carbon ring or a C1-C20 heterocyclic ring, c represents an integer from 0 to 20, R 11 and R 12 each independently represent hydrogen, a halogen, or an optionally substituted C1-C20 alkyl group, C1-C5 alkoxy group, C6-C12 aryl group, C7-C17 aralkyl group or C2-C15 alkenyl group, or R 11 and R 12 bind to each other to form a C3-C20 carbon ring or a C1-C20 heterocyclic ring, and R 13 -R 22 each independently represent hydrogen or a C1-C3 alkyl group, wherein General formula (A) above comprises one or more selected from the group consisting of Formulae (E)-(G) below:
  2. The resin composition according to Claim 1, wherein a mass ratio of the solvent to the polycarbonate resin (solvent/polycarbonate resin) is 99.99/0.01 to 50/50.
  3. The resin composition according to Claim 1 or 2, wherein a boiling point of the solvent is 140°C or higher.
  4. The resin composition according to any one of Claims 1 to 3, wherein, in General formula (1) above, R a represents hydrogen, a C1-C6 alkyl group, or a C2-C6 acyl group, R b represents a C1-C6 alkyl group, a C6-C10 aryl group, or a C2-C6 acyl group, R c -R f represent hydrogen or a methyl group, and n represents an integer from 1 to 4.
  5. The resin composition according to Claim 4, wherein n in General formula (1) above is 2 or 3.
  6. The resin composition according to any one of Claims 1 to 3, wherein the solvent represented by General formula (1) above comprises one or more selected from the group consisting of a glycol ether-based solvent, a glycol ester-based solvent, and a glyme-based solvent.
  7. A resin composition comprising a polycarbonate resin containing a structural unit (b) represented by General formula (A-1) below and a hydroxy compound, wherein the hydroxy compound is represented by General formula (1a) or General formula (1b) below: in Formula (1a), R a represents an optionally substituted C1-C20 alkyl group, C6-C20 aryl group, C2-C20 alkenyl group, C7-C20 aralkyl group or C2-C20 acyl group, R b -R e each independently represent hydrogen or a C1-C10 alkyl group, and n represents an integer from 1 to 10; in Formula (1b), R k represents an optionally branched C3-C20 alkyl group having a hydroxyl group, wherein the polycarbonate resin further comprises a structural unit (a) represented by General formula (A) below (except for the structural unit (b) represented by General formula (A-1) above): (in Formula (A), R 1 -R 8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted C1-C7 alkyl group, C6-C12 aryl group, C2-C7 alkenyl group, C1-C7 alkoxy group or C7-C17 aralkyl group, and X represents -O-, -S-, -SO-, -SO 2 -, -CO-, or a divalent group represented by any of Formulae (2)-(4) below); (in Formulae (2)-(4), R 9 and R 10 each independently represent hydrogen, a halogen, or an optionally substituted C1-C20 alkyl group, C1-C5 alkoxy group, C6-C12 aryl group, C7-C17 aralkyl group or C2-C15 alkenyl group, or R 9 and R 10 bind to each other to form a C3-C20 carbon ring or a C1-C20 heterocyclic ring, c represents an integer from 0 to 20, R 11 and R 12 each independently represent hydrogen, a halogen, or an optionally substituted C1-C20 alkyl group, C1-C5 alkoxy group, C6-C12 aryl group, C7-C17 aralkyl group or C2-C15 alkenyl group, or R 11 and R 12 bind to each other to form a C3-C20 carbon ring or a C1-C20 heterocyclic ring, and R 13 -R 22 each independently represent hydrogen or a C1-C3 alkyl group), wherein general formula (A) comprises one or more selected from the group consisting of Formulae (E)-(G) below:
  8. The resin composition according to Claim 7, wherein a content ratio of the structural unit (b) to the structural unit (a) [(b)/(a)] is 50/50 to 100/0 in mole ratio.
  9. The resin composition according to Claim 7 or 8, wherein a mass ratio of the polycarbonate resin to the hydroxy compound (polycarbonate resin/hydroxy compound) is 1/99 to 50/50.
  10. The resin composition according to any one of Claims 7 to 9, wherein a boiling point of the hydroxy compound is 50°C or higher.
  11. The resin composition according to any one of Claims 7 to 10, wherein the hydroxy compound is one or more selected from the group consisting of butyl carbitol, ethyl carbitol, butyl cellosolve, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-methoxy-2-butanol, 2-hydroxyethyl methacrylate, and diacetone alcohol.
  12. The resin composition according to any one of Claims 7 to 11, wherein the resin composition is a resin solution.
  13. A printing ink comprising the resin composition according to any one of Claims 1 to 12.
  14. A resin solution for 3D printers comprising the resin composition according to any one of Claims 1 to 12.
  15. An electroconductive paste comprising the resin composition according to any one of Claims 1 to 12.
  16. A coating solution comprising the resin composition according to any one of Claims 1 to 12.
  17. A film formed of the resin composition according to any one of Claims 1 to 12.

Description

TECHNICAL FIELD The present invention relates to a resin composition having low toxicity and excellent stability (no penetration) and uniformity on a base material when applied, to a more concentrated polycarbonate resin solution, and to a printing ink, resin solution for 3D printers, electroconductive paste, coating solution, and film using the same. BACKGROUND ART Certain polycarbonate resins dissolved in organic solvents are known for their use as inks and paints, and various organic solvents are used for this purpose. In recent years, there has been a shift from solvents with safety concerns for humans such as halogenated organic solvents, toluene, and 1,4-dioxane, to safer solvents (see Patent literature 1). Further compositions of polycarbonates with solvents or related components, are also described in Patent literatures 2, 3, 4 and 5. Furthermore, there is a need to improve the productivity of a coating film and the quality of a coating film including stability (no penetration) and uniformity on a base material. In addition, in order to take advantage of the property of a high-strength polycarbonate resin, a more concentrated polycarbonate resin solution is required. PRIOR ART LITERATURE Patent literature Patent literature 1: International Publication WO2018/123282Patent literature 2: CN 105 223 776 APatent literature 3: JP 2013 050699 APatent literature 4: JP 2014 160238 APatent literature 5: EP 1 116 751 A1 SUMMARY OF INVENTION Problem to be solved by the invention The present invention has an objective of providing a resin composition having low toxicity and excellent stability (no penetration) and uniformity on a base material when applied. The present invention also has an objective of providing a more concentrated polycarbonate resin solution. Means for solving the problem As a result of diligent study to solve the above problem, the present inventors have found that a resin composition with low toxicity and excellent stability (no penetration) and uniformity on a base material when applied can be obtained by dissolving a polycarbonate resin containing a specific structural unit in a specific organic solvent, thereby accomplishing the present invention. In addition, the present inventors found that a more concentrated polycarbonate resin solution can be obtained by combining a specific polycarbonate resin containing a fluorine atom with a specific hydroxy compound, thereby accomplishing the present invention. Thus, the present invention is as specified in the appended independent claims with preferred embodiments being specified in the appended dependent claims. EFFECTS OF THE INVENTION In a resin composition according to a preferred aspect of the present invention, a glycol-based solvent, which is a weak solvent, is used, and therefore, the resin composition is less likely to bite into a base material such as a polycarbonate (hereinafter, sometimes referred to as "PC") sheet, etc., when applied, and can form a precise and strong coating film surface with little bleed. In addition, glycol-based solvents are generally low in toxicity and odor, so they are advantageous for application to paints for screen printing and optical components from the viewpoint of working environment, and are suitable as various kinds of inks, paints, electroconductive pastes, and resin compositions for 3D printers. Furthermore, a resin composition according to another preferred aspect of the present invention can be used to provide a more concentrated polycarbonate resin solution, which is suitable for use in technical fields where high concentration is required. MODE FOR CARRYING OUT THE INVENTION [Resin composition of first embodiment] A resin composition of a first embodiment of the present invention comprises a solvent represented by General formula (1) below and a polycarbonate resin containing a structural unit (a) represented by General formula (A) below (except for a polycarbonate homopolymer composed solely of a structural unit represented by Formula (i) below.) As will be described in Comparative example 1 below, a polycarbonate homopolymer obtained by using 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes referred to as "BPA") alone as a raw material diol component is not soluble in a glycol-based solvent used in the present invention. Therefore, this resin cannot be used. However, as will be described in Example 8 below, even if BPA is used as a raw material diol component, when it is used together with other diol component defined by the present invention to make a polycarbonate copolymer, it is possible to use this copolymer. In General formula (A), R1-R8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted C1-C7 alkyl group, C6-C12 aryl group, C2-C7 alkenyl group, C1-C7 alkoxy group or C7-C17 aralkyl group.Herein, examples of a "substituent" implied by the phrase "optionally substituted" include "a fluorine atom, a chlorine atom, a bromine atom,