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JP-7856089-B2 - Resin composition, and printing ink and conductive paste using the same.

JP7856089B2JP 7856089 B2JP7856089 B2JP 7856089B2JP-7856089-B2

Inventors

  • 後藤 敏仁
  • 小川 典慶

Assignees

  • 三菱瓦斯化学株式会社

Dates

Publication Date
20260511
Application Date
20220210
Priority Date
20210217

Claims (17)

  1. A resin composition comprising a solvent represented by the following general formula (1) and a polycarbonate resin containing a constituent unit (a) represented by the following general formula (A) (excluding polycarbonate homopolymers consisting only of constituent units represented by the following formula (i)), (In the formula, Ra represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, each of which may have substituents; R b represents a C1-C20 alkyl group, a C6-C20 aryl group, a C2-C20 alkenyl group, a C7-C20 aralkyl group, or a C2-C20 acyl group, which may each have substituents; R c to R f each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms; n represents an integer between 1 and 10. (In the formulas, R1 to R8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, a C1-C7 alkyl group, a C6-C12 aryl group, a C2-C7 alkenyl group, a C1-C7 alkoxy group, or a C7-C17 aralkyl group, each of which may have substituents. X represents -O-, -S-, -SO-, -SO2- , -CO-, or a divalent group represented by any of the following formulas (2) to (4).) (In formulas (2) to (4), R9 and R10 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, which may each have substituents, R9 and R10 bond to each other to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; c represents an integer between 0 and 20; R11 and R12 each independently represent hydrogen, a halogen, a C1-C20 alkyl group which may have substituents, a C1-C5 alkoxy group which may have substituents, an aryl group which may have C6-C12, an aralkyl group which may have C7-C17, or an alkenyl group which may have C2-C15, or R11 and R12 bond to each other to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; R13 to R22 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. The resin composition wherein the general formula (A) comprises one or more selected from the group consisting of the following formulas (E) and (G).
  2. The resin composition according to claim 1, wherein the 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 the 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 the general formula (1), Ra represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms; Rb represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 2 to 6 carbon atoms; Rc to Rf 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 the general formula (1) is 2 or 3.
  6. The resin composition according to any one of claims 1 to 3, wherein the solvent represented by the general formula (1) contains one or more selected from the group consisting of glycol ether solvents, glycol ester solvents, and glyme solvents.
  7. A resin composition comprising a polycarbonate resin containing a constituent unit (b) represented by the following general formula (A-1), and a hydroxy compound, The hydroxy compound is represented by the following general formula (1a) or the following general formula (1b), (In formula (1a), Ra represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms, which may have substituents; R b to Re each independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms; n represents an integer between 1 and 10. (In formula (1b), R k represents a branched alkyl group having 3 to 20 carbon atoms and containing a hydroxyl group.) The polycarbonate resin further includes a constituent unit (a) represented by the following general formula (A) (excluding the constituent unit (b) represented by the general formula (A-1)), (In formula (A), R1 to R8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, a C1-C7 alkyl group, a C6-C12 aryl group, a C2-C7 alkenyl group, a C1-C7 alkoxy group, or a C7-C17 aralkyl group, each of which may have substituents. X represents -O-, -S-, -SO-, -SO2- , -CO-, or a divalent group represented by any of the following formulas (2) to (4).) (In formulas (2) to (4), R9 and R10 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, which may each have substituents, R9 and R10 bond to each other to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; c represents an integer between 0 and 20; R11 and R12 each independently represent hydrogen, a halogen, a C1-C20 alkyl group which may have substituents, a C1-C5 alkoxy group which may have substituents, an aryl group which may have C6-C12, an aralkyl group which may have C7-C17, or an alkenyl group which may have C2-C15, or R11 and R12 bond to each other to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; R13 to R22 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. The resin composition wherein the general formula (A) comprises one or more selected from the group consisting of the following formulas (E) to (G).
  8. The resin composition according to claim 7, wherein the content ratio of the constituent unit (b) to the constituent unit (a) [(b)/(a)] is 50/50 to 100/0 in molar ratio.
  9. The resin composition according to claim 7 or 8, wherein the 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 the 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 described in any one of claims 1 to 12.
  14. A resin solution for a 3D printer comprising the resin composition described in any one of claims 1 to 12.
  15. A conductive paste comprising the resin composition described in any one of claims 1 to 12.
  16. A coating solution comprising the resin composition described in any one of claims 1 to 12.
  17. A film molded from a resin composition according to any one of claims 1 to 12.

Description

This invention relates to a resin composition with low toxicity and excellent stability (no erosion) and uniformity on a substrate when applied, as well as a higher concentration polycarbonate resin solution, and printing inks, 3D printer resin solutions, conductive pastes, coating solutions, and films using the same. The use of certain polycarbonate resins dissolved in organic solvents as inks, paints, etc., is well known, and various organic solvents are used. In recent years, there has been a shift from solvents that raise concerns about human safety, such as halogenated organic solvents, toluene, and 1,4-dioxane, to solvents with higher safety (Patent Document 1). Furthermore, there is a demand for improved coating film productivity, stability on the substrate (absence of erosion), and uniformity. Additionally, to take advantage of the high-strength properties of polycarbonate resin, higher-concentration polycarbonate resin solutions are required. WO2018/123282 publication Potential for industrial use The present invention will be described in detail below with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as appropriate without departing from the spirit of the invention. [Resin composition of the first embodiment] The resin composition of the first embodiment of the present invention is a resin composition comprising a solvent represented by the above general formula (1) and a polycarbonate resin containing a constituent unit (a) represented by the following general formula (A) (excluding polycarbonate homopolymer consisting only of the constituent unit represented by the following formula (i)). As shown in Comparative Example 1 described later, a polycarbonate homopolymer obtained using only 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes referred to as "BPA") as the diol component of the raw material does not dissolve in the glycol-based solvent used in the present invention, and therefore cannot be used. However, as shown in Example 8 described later, even when BPA is used as the diol component of the raw material, if it is used together with other diol components specified in the present invention to form a polycarbonate copolymer, the copolymer can be used. In general formula (A), R1 to R8 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, a C1-C7 alkyl group, a C6-C12 aryl group, a C2-C7 alkenyl group, a C1-C7 alkoxy group, or a C7-C17 aralkyl group, which may each have substituents. In this specification, examples of "substituents" when referring to a group that "may have substituents" include "fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, C1-C7 alkyl groups, C6-C12 aryl groups, C2-C7 alkenyl groups, C1-C5 alkoxy groups, C7-C17 aralkyl groups," etc. (the same applies hereinafter). X represents a divalent group represented by -O-, -S-, -SO-, -SO₂- , -CO-, or any of the following formulas (2) to (4). In formulas (2) to (4), R9 and R10 each independently represent hydrogen, a halogen, a C1-C20 alkyl group which may each have substituents, a C1-C5 alkoxy group which may each have substituents, an aryl group which may each have substituents, a C6-C12 aralkyl group which may each have substituents, or a C2-C15 alkenyl group which may each have substituents, or R9 and R10 are bonded to each other to form a C3-C20 carbon ring or a C1-C20 heterocycle, c represents an integer between 0 and 20. R11 and R12 can each independently represent hydrogen, a halogen, a C1-C20 alkyl group which may have substituents, a C1-C5 alkoxy group which may have substituents, a C6-C12 aryl group which may have substituents, a C7-C17 aralkyl group which may have substituents, or a C2 - C15 alkenyl group which may be bonded to each other to form a C3-C20 carbon ring or a C1-C20 heterocycle which may have substituents. R13 to R22 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. In the first embodiment of the present invention, the constituent unit (a) represented by the general formula (A) preferably includes one or more selected from the group consisting of constituent units represented by the following formulas (B) to (G). <Polycarbonate resin> The polycarbonate resin used in the resin composition of the first embodiment of the present invention can be produced by reacting bisphenols that derive the constituent unit (a) represented by the general formula (A) with a carbonate ester-forming compound. Therefore, it can be produced using known methods used when producing polycarbonate resins derived from bisphenol A, such as the direct reaction of bisphenols with phosgene (phosgene method) or the transesterification reaction of bisphenols with bisaryl carbonate (transesterification method). The bisphenol compounds that serve as raw material monomers for the polycarbonate resin used in the resin composition of the first embodiment of