Resin composition, and printing ink and conductive paste using the same

Abstract

The present application provides a resin composition comprising: a solvent represented by the following general formula (1); and a polycarbonate resin containing a structural unit (a) represented by the following general formula (A), wherein the polycarbonate resin does not include a polycarbonate homopolymer composed only of a structural unit represented by the following formula (i). In formula (1), R a represents hydrogen or the like; R b represents an alkyl group having 1 to 20 carbon atoms, which can have a substituent, or the like; R c ~R f each independently represents hydrogen or the like; and n represents an integer of 1 to 10. In formula (A), R1 to R8 each independently represent hydrogen or the like. X represents -O- or the like.

Description

Technical Field

[0001] The present invention relates to resin compositions with low toxicity and excellent stability (no erosion) and uniformity on substrates during coating, and higher concentration polycarbonate resin solutions, as well as printing inks, resin solutions for 3D printers, conductive pastes, coating solutions and films using the same. Background Technology

[0002] It is known to use specific polycarbonate resins dissolved in organic solvents as inks or coatings, and a wide variety of organic solvents are used. In recent years, there has been a push to replace halogenated organic solvents and solvents such as toluene and 1,4-dioxane, which have safety concerns regarding human health, with safer solvents (Patent Document 1).

[0003] Furthermore, there are requirements to improve the quality of the coating, including its productivity, stability to the substrate (no corrosion), and uniformity. In addition, to take advantage of the high strength properties of polycarbonate resin, higher concentrations of polycarbonate resin solutions are needed.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: WO2018 / 123282 Publication Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] The technical problem to be solved by this invention is to provide a resin composition with low toxicity and excellent stability (no corrosion) and uniformity to the substrate during coating. Furthermore, another technical problem to be solved by this invention is to provide a higher concentration of polycarbonate resin solution.

[0009] Technical solutions for solving technical problems

[0010] In order to solve the above-mentioned technical problems, the inventors of this invention conducted in-depth research and discovered that by dissolving a polycarbonate resin containing specific structural units in a specific organic solvent, a resin composition with low toxicity and excellent stability (no corrosion) and uniformity on the substrate during coating can be obtained, thus completing this invention. Furthermore, the inventors of this invention also discovered that by combining a specific polycarbonate resin containing fluorine atoms with a specific hydroxyl compound, a high-concentration polycarbonate resin solution can be obtained, thus completing this invention.

[0011] That is, the present invention is as follows.

[0012] <1> A resin composition comprising: a solvent represented by the following general formula (1); and a polycarbonate resin containing a structural unit (a) represented by the following general formula (A) (wherein, the polycarbonate resin does not include polycarbonate homopolymers consisting only of structural units represented by the following formula (i)).

[0013]

[0014] (where R is in the formula) a The groups represent hydrogen, and may have substituents, namely alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, aralkyl with 7 to 20 carbon atoms, or acyl with 2 to 20 carbon atoms;

[0015] R b The terms indicate that the substituents can be alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, aralkyl with 7 to 20 carbon atoms, or acyl with 2 to 20 carbon atoms.

[0016] R c ~R f Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0017] n represents an integer from 1 to 10.

[0018]

[0019] (In the formula, R1 to R8 independently represent hydrogen, fluorine, chlorine, bromine, iodine, and alkyl groups with 1 to 7 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkenyl groups with 2 to 7 carbon atoms, alkoxy groups with 1 to 7 carbon atoms, or aralkyl groups with 7 to 17 carbon atoms, which may have substituents. X represents -O-, -S-, -SO-, -SO2-, -CO-, or any divalent group represented by any of the formulas (2) to (4) below.)

[0020]

[0021] (In equations (2) to (4), R9 and R 10 Each can independently represent hydrogen, halogen, and alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 17 carbon atoms, or alkenyl groups having 2 to 15 carbon atoms, or

[0022] R9 and R 10 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms;

[0023] c represents an integer from 0 to 20;

[0024] R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 5 carbon atoms, aryl group with 6 to 12 carbon atoms, aralkyl group with 7 to 17 carbon atoms, or alkenyl group with 2 to 15 carbon atoms, or

[0025] R 11 and R 12 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms;

[0026] R 13 ~R 22 Each can be independently represented by either hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0027] <2> The resin composition as described in <1> above, wherein:

[0028] The mass ratio (solvent / polycarbonate resin) of the above solvent to the above polycarbonate resin is 99.99 / 0.01 to 50 / 50.

[0029] <3> The resin composition as described in <1> or <2> above, wherein:

[0030] The above general formula (A) includes one or more of the formulas (B) to (G) below.

[0031]

[0032] <4> The resin composition as described in any one of <1> to <3> above, wherein:

[0033] The boiling point of the above solvent is above 140℃.

[0034] <5> The resin composition as described in any one of <1> to <4> above, wherein:

[0035] In the above general formula (1), R a R represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. b R 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. c ~R f It represents hydrogen or methyl, and n represents an integer from 1 to 4.

[0036] <6> The resin composition as described in <5> above, wherein:

[0037] In the above general formula (1), n ​​is 2 or 3.

[0038] <7> The resin composition as described in any one of <1> to <4> above, wherein:

[0039] The solvent shown in the above general formula (1) contains one or more solvents selected from glycol ether solvents, glycol ester solvents and glycol dimethyl ether solvents.

[0040] <8> A resin composition, wherein:

[0041] The resin composition comprises: a polycarbonate resin containing structural unit (b) of the following general formula (A-1); and a hydroxyl compound,

[0042] The above-mentioned hydroxyl compounds are represented by the following general formula (1a) or the following general formula (1b).

[0043]

[0044] (In equation (1a), R) a It indicates that it may have substituents, namely alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, aralkyl with 7 to 20 carbon atoms, or acyl with 2 to 20 carbon atoms;

[0045] R b ~R e Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

[0046] n represents an integer from 1 to 10.

[0047]

[0048] (In equation (1b), R) k This refers to an alkyl group containing a hydroxyl group and may have a branched chain with 3 to 20 carbon atoms.

[0049] <9> The resin composition as described in <8> above, wherein:

[0050] The above-mentioned polycarbonate resin also contains structural unit (a) shown in the following general formula (A) (wherein, the above-mentioned structural unit (a) does not include structural unit (b) shown in the above-mentioned general formula (A-1)).

[0051]

[0052] (In formula (A), R1 to R8 independently represent hydrogen, fluorine, chlorine, bromine, iodine, and alkyl groups with 1 to 7 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkenyl groups with 2 to 7 carbon atoms, alkoxy groups with 1 to 7 carbon atoms, or aralkyl groups with 7 to 17 carbon atoms, which may have substituents. X represents -O-, -S-, -SO-, -SO2-, -CO-, or any divalent group represented by any of the formulas (2) to (4) below.)

[0053]

[0054] (In equations (2) to (4), R9 and R 10 Each can independently represent hydrogen, halogen, and alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 17 carbon atoms, or alkenyl groups having 2 to 15 carbon atoms, or

[0055] R9 and R 10 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms;

[0056] c represents an integer from 0 to 20;

[0057] R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 5 carbon atoms, aryl with 6 to 12 carbon atoms, aralkyl with 7 to 17 carbon atoms, or alkenyl with 2 to 15 carbon atoms, or

[0058] R 11 and R 12 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms;

[0059] R 13 ~R 22 Each can be independently represented by either hydrogen or an alkyl group having 1 to 3 carbon atoms.

[0060] <10> The resin composition as described in <8> or <9> above, wherein:

[0061] The above general formula (A) includes one or more of the formulas (B) to (H) below.

[0062]

[0063] <11> The resin composition as described in <9> or <10> above, wherein:

[0064] The content ratio of the above structural unit (b) to the above structural unit (a) [(b) / (a)] is 50 / 50 to 100 / 0 in molar ratio.

[0065] <12> The resin composition as described in any one of <8> to <11> above, wherein:

[0066] The mass ratio of the above-mentioned polycarbonate resin to the above-mentioned hydroxyl compound (polycarbonate resin / hydroxyl compound) is 1 / 99 to 50 / 50.

[0067] <13> The resin composition as described in any one of <8> to <12> above, wherein:

[0068] The boiling point of the above-mentioned hydroxyl compounds is above 50°C.

[0069] <14> The resin composition as described in any one of <8> to <13> above, wherein:

[0070] The aforementioned hydroxyl compound is selected from one or more 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.

[0071] <15> The resin composition as described in any one of <8> to <14> above, wherein:

[0072] The above resin composition is a resin solution.

[0073] <16> A printing ink comprising any one of the resin compositions described in <1> to <15> above.

[0074] <17> A resin solution for a 3D printer, comprising the resin composition described in any one of <1> to <15> above.

[0075] <18> A conductive paste comprising the resin composition described in any one of <1> to <15> above.

[0076] <19> A coating solution comprising any one of the resin compositions described in <1> to <15> above.

[0077] <20> A film formed from the resin composition described in any one of <1> to <15> above.

[0078] Invention Effects

[0079] According to a preferred embodiment of the resin composition of the present invention, since a glycol-based solvent is used as a weak solvent, it is possible to form a coating surface that is difficult to penetrate substrates such as polycarbonate (hereinafter sometimes referred to as "PC") sheets during coating, exhibiting low penetration, precision, and high strength. Furthermore, since glycol-based solvents generally have lower toxicity and odor, they are effective in terms of the working environment for applications such as screen printing coatings and optical components, and are suitable as resin compositions for various inks, coatings, conductive pastes, and 3D printers. Moreover, according to another preferred embodiment of the resin composition of the present invention, since it can provide a higher concentration of polycarbonate resin solution, it is excellent for use in technical fields requiring high concentrations. Detailed Implementation

[0080] 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 in any way without departing from the spirit of the present invention.

[0081] [Resin Composition of the First Embodiment]

[0082] The resin composition of the first embodiment of the present invention comprises: a solvent represented by the above general formula (1); and a polycarbonate resin containing a structural unit (a) represented by the following general formula (A) (wherein, the polycarbonate resin does not include polycarbonate homopolymers composed only of structural units represented by the following formula (i)).

[0083]

[0084] As shown in Comparative Example 1 described later, the polycarbonate homopolymer obtained by using only 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes referred to as "BPA") as the diol component is insoluble in the diol solvents used in this invention, and therefore the resin cannot be used. However, as shown in Example 8 described later, even when BPA is used as the diol component, the copolymer can be used when other diol components specified in this invention are used together to prepare the polycarbonate copolymer.

[0085]

[0086] In general formula (A),

[0087] R1 to R8 represent hydrogen, fluorine, chlorine, bromine, and iodine, respectively, and can be alkyl with 1 to 7 carbon atoms, aryl with 6 to 12 carbon atoms, alkenyl with 2 to 7 carbon atoms, alkoxy with 1 to 7 carbon atoms, or aralkyl with 7 to 17 carbon atoms, respectively.

[0088] It should be noted that, in this specification, when referred to as "may have substituents", the substituents may include "fluorine atom, chlorine atom, bromine atom, iodine atom, alkyl with 1 to 7 carbon atoms, aryl with 6 to 12 carbon atoms, alkenyl with 2 to 7 carbon atoms, alkoxy with 1 to 5 carbon atoms, aralkyl with 7 to 17 carbon atoms" and so on (the same applies below).

[0089] X represents a divalent group represented by -O-, -S-, -SO-, -SO2-, -CO-, or any of the following formulas (2) to (4).

[0090]

[0091] R9 and R 10 Each of the following can independently represent hydrogen, halogen, and alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 17 carbon atoms, or alkenyl groups having 2 to 15 carbon atoms, or R9 and R 10 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms.

[0092] C represents integers from 0 to 20.

[0093] R 11 and R 12 Each of the following can independently represent hydrogen, halogen, alkyl (with 1-20 carbon atoms), alkoxy (with 1-5 carbon atoms), aryl (with 6-12 carbon atoms), aralkyl (with 7-17 carbon atoms), or alkenyl (with 2-15 carbon atoms), or R. 11 and R 12 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms.

[0094] R 13 ~R 22 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0095] In the first embodiment of the present invention, the structural unit (a) shown in the above general formula (A) preferably includes one or more structural units selected from the structural units shown in formulas (B) to (G) below.

[0096]

[0097] <Polycarbonate resin>

[0098] The polycarbonate resin used in the resin composition of the first embodiment of the present invention can be manufactured by reacting a bisphenol that can derive the structural unit (a) shown in the above general formula (A) with a carbonate to form a compound. Therefore, it can be manufactured using known methods used in manufacturing polycarbonate resins derived from bisphenol A, such as the direct reaction of bisphenol with phosgene (phosgene method) or the transesterification reaction of bisphenol with diaryl carbonate (transesterification method).

[0099] The bisphenols of the raw material monomers of the polycarbonate resin used in the resin composition of the first embodiment of the present invention are represented by the following general formula (A').

[0100]

[0101] (In the formula, R1~R4, R5~R8 and X are the same as in general formula (A).)

[0102] Specific examples of monomers represented by the above general formula (A') include 4,4'-biphenyldiol, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(2-hydroxyphenyl) sulfone, bis(4-hydroxy-3-methylphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) ketone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl) ketone, and others. 2,2-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane 1,1-Bis(4-hydroxyphenyl)cyclohexane, 1,1-Bis(4-hydroxyphenyl)cycloundecane, 1,1-Bis(4-hydroxyphenyl)cyclododecane, 2,2-Bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-Bis(4-hydroxyphenyl)cyclohexane, 9,9-Bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-Bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-Bis(4-hydroxyphenyl)fluorene, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, [Hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,4-phenylenebis(1-methylethylene)]bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc. Two or more of these can also be used in combination.

[0103] Among these, 2,2-bis(4-hydroxyphenyl)propane (BPC), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP), 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (TMC) and 2,2-bis(4-hydroxyphenyl)-4-methylpentane (MIBK) are particularly preferred.

[0104] In the phosgene process, the monomers represented by the above general formula (A') are typically reacted with phosgene in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as pyridine, sodium hydroxide, and potassium hydroxide; examples of solvents include dichloromethane and chloroform. Furthermore, to promote the polycondensation reaction, catalysts such as tertiary amines like triethylamine or quaternary ammonium salts like benzyltriethylammonium chloride are preferably added. In addition, to adjust the degree of polymerization, monofunctional compounds such as phenol, p-tert-butylphenol, p-isopropylphenylphenol, p-hydroxyphenylethanol, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, and long-chain alkyl-substituted phenols are preferably added as molecular weight regulators. Furthermore, antioxidants such as sodium sulfite and dithionite, and branching agents such as phloroglucinol and indomethacin bisphenol may be added in small amounts as desired. The reaction is typically suitably set within the range of 0–150°C, preferably 5–40°C. The reaction time varies depending on the reaction temperature, typically ranging from 0.5 minutes to 10 hours, preferably from 1 minute to 2 hours. Furthermore, it is preferable to maintain the pH of the reaction system above 10 during the reaction.

[0105] On the other hand, in the transesterification method, the monomer shown in the above general formula (A') is mixed with a diaryl carbonate and reacted under reduced pressure at high temperature. Examples of diaryl carbonates include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthalene carbonate. Two or more of these compounds may also be used together. The reaction is usually carried out at a temperature in the range of 150–350°C, preferably 200–300°C. Furthermore, the reduced pressure is preferably below 1 mmHg, and the phenols generated from the diaryl carbonate through the transesterification reaction are distilled off the system. The reaction time varies depending on the reaction temperature and reduced pressure, and is typically about 1–24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. In addition, molecular weight regulators, antioxidants, and branching agents may be added as desired.

[0106] The polycarbonate resin used in the resin composition of the first embodiment of the present invention preferably maintains a good balance of solvent solubility, coatability, peelability, scratch resistance, and impact resistance, which are required for use as a coating film forming resin. By setting the lower limit of the intrinsic viscosity of the resin to a value above a specified value, scratch resistance and impact resistance can be improved; by setting the upper limit of the intrinsic viscosity to a value below a specified value, the decrease in solvent solubility and the increase in solution viscosity can be suppressed, thus maintaining coatability. The intrinsic viscosity (η) of the polycarbonate resin is preferably in the range of 0.3 to 2.0 dl / g, more preferably in the range of 0.35 to 1.5 dl / g. On the other hand, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably in the range of 10,000 to 80,000, more preferably in the range of 15,000 to 50,000. The intrinsic viscosity (η) and viscosity-average molecular weight (Mv) of the polycarbonate resin can be measured by the method described in the examples described later.

[0107] In the resin composition of the first embodiment of the present invention, the mass ratio (solvent / polycarbonate resin) of the solvent to the polycarbonate resin is preferably 99.99 / 0.01 to 50 / 50, more preferably 99 / 1 to 60 / 40, and particularly preferably 95 / 5 to 70 / 30. When the amount of solvent and polycarbonate resin used in the present invention is within the above range, a good balance between solvent solubility and coatability is achieved, which improves workability and appearance.

[0108] <Diol-based organic solvents>

[0109] The resin composition of the first embodiment of the present invention is a solution obtained by dissolving the above-mentioned polycarbonate resin in a solvent (diol-based organic solvent) of the following general formula (1), which is generally referred to as a transparent coating. The resin composition of the first embodiment of the present invention can be further dissolved or dispersed with desired dyes and / or pigments to prepare a colored coating composition.

[0110]

[0111] In general formula (1),

[0112] R a The group represents hydrogen, and may have substituents, specifically an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an acyl group with 2 to 20 carbon atoms. R is preferred. a It represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.

[0113] R bThis indicates that the substituents can be alkyl (1-20 carbon atoms), aryl (6-20 carbon atoms), alkenyl (2-20 carbon atoms), aralkyl (7-20 carbon atoms), or acyl (2-20 carbon atoms). R is preferred. b It represents an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an acyl group with 2 to 6 carbon atoms.

[0114] R c ~R f Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R is preferred. c ~R f It indicates hydrogen or methyl.

[0115] n represents an integer from 1 to 10, preferably an integer from 1 to 4, and more preferably 2 or 3.

[0116] The solvent represented by the above general formula (1) used in this invention is preferably derived from ethylene glycol (R). c ~R f (all hydrogen) or propylene glycol (R) c ~R f (Either of which is methyl).

[0117] Furthermore, in this invention, the solvent represented by the above general formula (1) preferably contains one or more selected from glycol ether solvents, glycol ester solvents and glycol dimethyl ether solvents.

[0118] Specific examples of the aforementioned glycol ether solvents include, preferably, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, diethylene glycol tert-butyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol n-propyl ether, triethylene glycol n-butyl ether (butyltri-diol), triethylene glycol tert-butyl ether, triethylene glycol monohexyl ether, and triethylene glycol monophenyl ether. Among these, triethylene glycol n-butyl ether (butyltri-diol) is more preferably listed. Two or more of these can be used in combination.

[0119] Specific examples of the aforementioned glycol ester solvents include, preferably, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether propionate. Among these, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate) and diethylene glycol monoethyl ether acetate (ethyl carbitol acetate) are more preferred. Two or more of these can be used in combination.

[0120] Specific examples of the aforementioned glycol dimethyl ether solvents include, for instance, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethyl glycol dimethyl ether, methyl ethyl diethylene glycol dimethyl ether, butyl diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Among these, tetraethylene glycol dimethyl ether is more preferred. Two or more of these solvents can be used in combination.

[0121] It should be noted that glycol dimethyl ether refers to a solvent classified as a glycol ether, characterized by the ether bonding of an alkyl group to a diol (a compound with two OH groups). For example, triethylene glycol dimethyl ether has a structure formed by methylating two hydroxyl groups of triethylene glycol, represented by the following structural formula.

[0122]

[0123] The solvent represented by the above general formula (1) used in this invention preferably has a boiling point of 140°C or higher, more preferably 140 to 300°C.

[0124] [Resin Composition of the Second Embodiment]

[0125] The resin composition of the second embodiment of the present invention comprises: a polycarbonate resin containing a structural unit (b) of the following general formula (A-1); and a hydroxyl compound, wherein the hydroxyl compound is represented by the above general formula (1a) or the above general formula (1b).

[0126]

[0127] The inventors of this invention believe that, in order to dissolve the polymer in a solvent and obtain a higher concentration of polycarbonate resin solution, it is preferable that the polymer used has a structure with small interactions between the polymer chains and has sites that interact with the solvent, as a necessary condition. Furthermore, it is believed that, as shown below, the presence of F (fluorine) atoms in the polymer chains increases the distance between the polymer chains due to electron repulsion, and bisphenol AF-based polycarbonate resins as shown below are of particular interest.

[0128]

[0129] It is further argued that, as a necessary condition for the solvent used, a structure having a site that interacts with the polymer is preferable. It is also believed that, as shown below, since hydroxyl groups (OH) are present in the solvent, they form hydrogen bonds with the F (fluorine) atoms in the polymer, thereby increasing the affinity between the polymer and the solvent.

[0130]

[0131] On the other hand, as shown below, intramolecular hydrogen bonds are ineffective in isopropanol and ethanol, while the interactions resulting from intermolecular hydrogen bonds in the solvent are significant. In other words, it is assumed that stronger intermolecular bonds in the solvent lead to poorer solubility of the polycarbonate resin.

[0132] Example: Isopropanol

[0133] The inventors of this invention ultimately concluded that solvents with low intermolecular interactions due to the formation of intramolecular hydrogen bonds caused by the effects of adjacent functional groups such as ether oxygen are preferred. This is believed to improve compatibility with polycarbonate resins.

[0134]

[0135] 1-Methoxy-2-propanol (also known as propylene glycol monomethyl ether)

[0136] The polycarbonate resin used in the resin composition of the second embodiment of the present invention also preferably contains structural unit (a) shown in the following general formula (A) (wherein, the structural unit (a) does not include the structural unit (b) shown in the above general formula (A-1)).

[0137]

[0138] Here, the meaning of the structural unit (a) shown in the above general formula (A) is the same as that described in the resin composition of the first embodiment of the present invention.

[0139] In the second embodiment of the present invention, the structural unit (a) shown in the above general formula (A) preferably includes one or more structural units selected from the structural units shown in formulas (B) to (H) below.

[0140]

[0141] In the resin composition of the second embodiment of the present invention, the content ratio of the above-mentioned structural unit (b) to the above-mentioned structural unit (a) [(b) / (a)] is preferably 50 / 50 to 100 / 0 in molar ratio, and more preferably 60 / 40 to 100 / 0.

[0142] The polycarbonate resin used in the resin composition of the second embodiment of the present invention preferably maintains a good balance of solvent solubility, coatability, peelability, scratch resistance, and impact resistance, which are essential for coating film formation. By setting the lower limit of the intrinsic viscosity of the resin to a value above a specified value, scratch resistance and impact resistance can be improved; by setting the upper limit of the intrinsic viscosity to a value below a specified value, the decrease in solvent solubility and the increase in solution viscosity can be suppressed, thus maintaining coatability. The intrinsic viscosity (η) of the polycarbonate resin is preferably in the range of 0.3 to 2.0 dl / g, more preferably in the range of 0.35 to 1.5 dl / g. On the other hand, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably in the range of 10,000 to 80,000, more preferably in the range of 15,000 to 50,000. The intrinsic viscosity (η) and viscosity-average molecular weight (Mv) of the polycarbonate resin can be measured by the method described in the examples described later.

[0143] In the resin composition of the second embodiment of the present invention, the mass ratio of the polycarbonate resin to the hydroxyl compound (polycarbonate resin / hydroxyl compound) is preferably 1 / 99 to 50 / 50, more preferably 5 / 95 to 50 / 50, even more preferably 5 / 95 to 30 / 70, and particularly preferably 7 / 93 to 13 / 87. When the mass ratio of polycarbonate resin exceeds 50% by mass, the viscosity is sometimes too high, and when it is less than 1% by mass, it is sometimes too thin to be practically usable.

[0144] <Hydroxy compounds>

[0145] The resin composition of the second embodiment of the present invention is a solution obtained by dissolving the above-mentioned polycarbonate resin in a hydroxyl compound (organic solvent) represented by the following general formula (1a) or the following general formula (1b), which is generally referred to as a transparent coating. The resin composition of the second embodiment of the present invention can be further dissolved or dispersed to prepare a colored coating composition.

[0146]

[0147] In general formula (1a),

[0148] R a This indicates that the substituent may be an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an acyl group with 2 to 20 carbon atoms. R is preferred. a It represents an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an acyl group with 2 to 6 carbon atoms.

[0149] R b ~R eEach of the following can be independently represented: either hydrogen or an alkyl group having 1 to 10 carbon atoms. R is preferred. b ~R e It indicates hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen or methyl.

[0150] n represents an integer from 1 to 10, preferably an integer from 1 to 4, and more preferably 2 or 3.

[0151]

[0152] In general formula (1b), R k The alkyl group having a hydroxyl group and may have a branched chain with 3 to 20 carbon atoms is indicated, preferably an alkyl group having a hydroxyl group and may have a branched chain with 3 to 10 carbon atoms.

[0153] Specific examples of hydroxyl compounds used in the second embodiment of the present invention include, but not limited to, butyl carbitol, ethyl carbitol, butyl cellosolve, 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-methoxy-2-butanol, 2-hydroxyethyl methacrylate (also known as (2-hydroxyethyl) methacrylate), diacetone alcohol, etc. One of these compounds may be used alone, or two or more may be used in combination.

[0154] Among these, preferred hydroxyl compounds include ethyl carbitol, butyl cellosolve, 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), 2-hydroxyethyl methacrylate (also known as (2-hydroxyethyl) methacrylate), and diacetone alcohol. More preferred hydroxyl compounds include ethyl carbitol, 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), 2-hydroxyethyl methacrylate (also known as (2-hydroxyethyl) methacrylate), and diacetone alcohol.

[0155] The following shows the structural formulas of representative hydroxyl compounds preferred for use in this invention, but are not limited thereto.

[0156]

[0157] The boiling point of the hydroxyl compound used in the second embodiment of the present invention is preferably 50°C or higher, and more preferably 50 to 250°C.

[0158] <Any Additives>

[0159] When using the resin composition of the first or second embodiment of the present invention, pigments or dyes, coloring particles, or light-interfering particles can be added to improve the color effect. Examples of pigments or dyes include organic pigments such as azo pigments and phthalocyanine pigments, specifically examples of red 104, red 106, red 201, red 202, red 204, red 215, red 220, orange 203, orange 204, blue 1, blue 404, yellow 205, yellow 401, and yellow 405. Furthermore, white, pearlescent, and metallic colors can also be used. To express a shimmering effect, mica titanium, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silicon dioxide, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, and nickel can be used. Light-interfering particles refer to particles that improve the color effect through the reflection or scattering of light; examples include glass beads, tiny seashells, and mica. They can be added to the resin composition in the range of 0.0001 to 10.0% by mass, as desired.

[0160] Rust inhibitors, antioxidants, dispersants, UV absorbers, defoamers, or leveling agents can also be added as needed.

[0161] The viscosity of the resin composition according to the first embodiment of the present invention can be arbitrarily set according to the desired application, preferably in the range of 20 to 200,000 mPa·s, more preferably in the range of 50 to 20,000 mPa·s. The viscosity of the resin composition according to the second embodiment of the present invention can be arbitrarily set according to the desired application, preferably in the range of 5 to 200,000 mPa·s, more preferably in the range of 10 to 20,000 mPa·s, even more preferably in the range of 10 to 5,000 mPa·s, further preferably in the range of 10 to 1,000 mPa·s, and particularly preferably in the range of 10 to 100 mPa·s. As a method for measuring viscosity, for example, a vibration viscometer (CJV5000) manufactured by A&D Corporation can be used to measure the viscosity at a measurement temperature of 25°C.

[0162] The coating thickness after applying and drying the resin composition of the first or second embodiment of the present invention is preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 120 μm, and particularly preferably in the range of 10 to 60 μm. A coating thickness of 1 μm or more ensures surface protective strength, and a thickness of 200 μm or less suppresses peeling caused by coating shrinkage, which is therefore preferable.

[0163] Other embodiments of the present invention include printing inks, 3D printer resin solutions, conductive pastes, and coating solutions comprising the resin composition of the first or second embodiment of the present invention described above. Another embodiment of the present invention is a film formed from the resin composition of the first or second embodiment of the present invention described above. The resin composition of the first embodiment of the present invention has low toxicity and excellent stability (no corrosion) and uniformity on the substrate during coating, and is therefore particularly excellent in the above-described applications.

[0164] Example

[0165] The following examples and comparative examples illustrate the invention in detail, but the invention is not limited to these examples.

[0166] (Synthesis example 1)

[0167] Dissolve 102.4 g (0.4 mol) of 2,2-bis(4-hydroxy-3-methylphenyl-)propane (hereinafter referred to as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.) and 0.1 g of dithionite in 1100 ml of 5 w / w sodium hydroxide aqueous solution.

[0168] Add 500ml of dichloromethane, and while stirring, add 0.5g of benzyltriethylammonium chloride (hereinafter referred to as "TEBAC"), then maintain at 15°C, and then blow in 60g of phosgene after 60 minutes.

[0169] After the phosgene blowing is completed, 1.5g of p-tert-butylphenol (hereinafter referred to as "PTBP": manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) as a molecular weight regulator is added, and the mixture is stirred vigorously to emulsify the reaction solution. After emulsification, 0.4ml of triethylamine is added, and the mixture is stirred at 20-25°C for about 1 hour to polymerize it.

[0170] After polymerization, the reaction solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid and repeatedly washed with water until the conductivity of the initial solution (aqueous phase) reached below 10 μS / cm. The obtained polymer solution was added dropwise to warm water maintained at 45°C, and the solvent was evaporated to obtain a white powdery precipitate. The precipitate was filtered and dried at 105°C for 24 hours to obtain polymer powder.

[0171] The intrinsic viscosity of a 0.5 g / dL solution of the polymer in dichloromethane at 20°C is 0.65 dL / g. Analysis of the obtained polymer by infrared absorption spectroscopy shows that the viscosity at 1770 cm⁻¹ is... －1 Absorption from the carbonyl group was confirmed at a nearby location, at 1240 cm⁻¹. －1Absorption from ether bonds was confirmed at a nearby location, confirming it as a polycarbonate resin with carbonate bonds (hereinafter referred to as "PC-1").

[0172] (Synthesis example 2)

[0173] Instead of BPC, 54 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter referred to as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) and 58 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter referred to as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.) were used, PTBP was changed to 2.0 g, and TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-2") with an intrinsic viscosity of 0.49 dl / g.

[0174] (Synthesis example 3)

[0175] The BPC was changed to 60.4g, the PTBP was changed to 1.8g, and 40.1g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "BPA": manufactured by Mitsubishi Chemical Corporation) was used. TEBAC was not used. Otherwise, the polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-3") with an intrinsic viscosity of 0.58dl / g.

[0176] (Synthesis Example 4)

[0177] Instead of BPC, 108g of MIBK was used, and instead of PTBP, 4.3g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (hereinafter referred to as "BTAZ": manufactured by Otsuka Chemical Co., Ltd.) was used. TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-4") with an intrinsic viscosity of 0.54dl / g.

[0178] (Synthesis Example 5)

[0179] The BPC was changed to 60.4g, and 40.1g of BPA and 1.92g of p-hydroxyphenylethanol (hereinafter referred to as "PHEP": manufactured by Otsuka Chemical Co., Ltd.) were used. PTBP was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-5") with an intrinsic viscosity of 0.72dl / g.

[0180] (Synthesis Example 6)

[0181] Instead of BPC, 107.2g of BPZ was used, PTBP was changed to 2.0g, and TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-6") with an intrinsic viscosity of 0.44dl / g.

[0182] (Synthesis Example 7)

[0183] Instead of BPC, 116.0 g of BPAP was used, PTBP was changed to 2.0 g, and TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-7") with an intrinsic viscosity of 0.43 dl / g.

[0184] (Synthesis Example 8)

[0185] Instead of BPC, 124.0 g of 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter referred to as "TMC": manufactured by Sanko Co., Ltd.) was used, PTBP was changed to 1.62 g, and TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-8") with an intrinsic viscosity of 0.48 dl / g.

[0186] (Synthesis Example 9)

[0187] Instead of BPC, 91.2g of BPA was used, PTBP was changed to 2.0g, and TEBAC was not used. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (hereinafter referred to as "PC-9") with an intrinsic viscosity of 0.49dl / g.

[0188] [Examples 1-13, Comparative Examples 1-3]

[0189] Five g of each polycarbonate (PC) resin obtained in the above synthesis examples 1 to 9 and 45 g of solvent were added to a mayonnaise bottle in the combination shown in Table 1 below, and stirred with a shaker to prepare a resin composition.

[0190] The resin compositions of Examples 1-13 and Comparative Examples 1-3 obtained in this way were subjected to the tests and physical property measurements shown below. The results are shown in Table 1 below.

[0191] <Solvent Solubility Test>

[0192] When preparing the resin composition, i.e., when adding 5g of polycarbonate resin and 45g of solvent as shown in Table 1 below to a mayonnaise bottle and stirring with a shaker, the time from the start of stirring until the resin is completely dissolved visually is measured (dissolution time).

[0193] Dissolution time less than 3 hours: "A".

[0194] Dissolution time is more than 3 hours but less than 48 hours: "B".

[0195] Dissolution time is 48 hours or more: "C".

[0196] Insoluble: "D".

[0197] <Viscosity of the resin composition>

[0198] The viscosity of the resin composition was measured at 25°C using a vibration viscometer (CJV5000) manufactured by A&D Corporation.

[0199] <PC Coating Evaluation>

[0200] (Coating preparation)

[0201] Prepare a PC sheet (NF-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.), and apply the resin composition prepared above onto the PC sheet using a 60μm thick gap coater. After coating, dry the sheet at 120°C for 1 minute using a box-type warm air dryer to form a coating film.

[0202] (Slipability during coating formation)

[0203] The evaluation will be conducted as described below.

[0204] During coating formation, there is no jamming between the coating machine and the PC sheet, allowing for uniform coating formation: "〇".

[0205] During coating formation, there is a jam between the coating machine and the PC sheet, resulting in an uneven coating: "×".

[0206] (Penetration into the substrate)

[0207] After coating the resin composition, the coating is dried at 120°C for 1 minute using a box-type warm air dryer, and then the resulting coating is visually evaluated.

[0208] There was no penetration at the interface between the PC sheet and the coating: "0".

[0209] A slight infiltration is visible: "△".

[0210] Significant penetration, messy interface: "×".

[0211] <PC Substrate Etching Test>

[0212] Cut a PC sheet (NF-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) into 1cm x 1cm squares, place them in a 9cc glass bottle, and then add the resin composition prepared above to completely submerge the PC sheet. Let it stand in this state, and visually check the condition of the PC sheet after 24 hours.

[0213] Keep the original shape: "A".

[0214] The swelling of the PC sheet is visible: "B".

[0215] The shape of the PC sheet collapsed and partially dissolved in the solution: "C".

[0216] <Determination of intrinsic viscosity (η) and viscosity-average molecular weight (Mv) of polycarbonate resin>

[0217] Regarding the intrinsic viscosity [η] dL / g of the polycarbonate resins obtained in Synthetic Examples 1 to 9, it was determined using an Uberloud capillary viscometer at 20°C for a dichloromethane solution of 0.5 g / dL polycarbonate resin, and calculated using the Herkins constant of 0.45 by the following mathematical formula (I).

[0218] η = 1.23 × 10 －4 ×Mv 0.83 (I)

[0219] [Table 1]

[0220]

[0221] ECA: Ethyl carbitol acetate

[0222] BCsA: Butyl cellolytic acetate

[0223] TGM: Tetraethylene glycol dimethyl ether

[0224] BTG: Butyltri-diol

[0225] PGMEA: Propylene glycol monomethyl ether acetate; DMAc: N,N-dimethylacetamide (non-diol solvent)

[0226]

[0227] Although N,N-dimethylacetamide (a non-diol solvent) used in Comparative Example 2 showed good solubility for polycarbonate resin, its solution viscosity was significantly low, resulting in poor sliding properties during coating formation and excessive penetration after coating formation. Furthermore, the resin composition of Comparative Example 2 showed penetration into the PC substrate. The isophorone (a non-diol solvent) used in Comparative Example 3 not only took longer to dissolve the polycarbonate resin, but its resin composition also showed penetration into the PC substrate.

[0228] (Synthesis Example 10)

[0229] Dissolve 90.0 g (0.34 mol) of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter referred to as "BPAF": manufactured by Central Glass Co., Ltd.) and 0.5 g of dithionite in 750 ml of 6.3 w / w sodium hydroxide aqueous solution.

[0230] Add 300 ml of dichloromethane, and while stirring, add 0.1 g of benzyltriethylammonium chloride (hereinafter referred to as "TEBAC"), and then maintain the temperature at 15-25°C. After 30 minutes, blow in 42.4 g of phosgene.

[0231] After the phosgene blowing is completed, 1.34g of p-tert-butylphenol (hereinafter referred to as "PTBP": manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.) as a molecular weight regulator is added, and the mixture is stirred vigorously to emulsify the reaction solution. After emulsification, 0.5ml of triethylamine is added, and the mixture is stirred at 20-30°C for about 1 hour to polymerize it.

[0232] After polymerization, the reaction solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid and repeatedly washed with water until the conductivity of the initial solution (aqueous phase) reached below 10 μS / cm. The resulting polymer solution was transferred to an aluminum pan, and the solvent was evaporated off on a heating plate. The resulting solid was then dried at 120°C for 24 hours to obtain the polymer solid.

[0233] The intrinsic viscosity of a 0.5 g / dL solution of the polymer in dichloromethane at 20°C is 0.33 dl / g, and the viscosity-average molecular weight (Mv) is 15300. Analysis of the obtained polymer by infrared absorption spectroscopy shows that at 1770 cm⁻¹... －1 Absorption from the carbonyl group was confirmed at a nearby location, at 1240 cm⁻¹. －1 Absorption from ether bonds was confirmed at a nearby location, confirming that it is a polycarbonate resin with carbonate bonds (hereinafter referred to as "PC-10").

[0234] (Synthesis Example 11)

[0235] Using 63.0 g of BPAF and 18.0 g of 1,1-bis(4-hydroxyphenyl)propane (hereinafter referred to as "BPA": manufactured by Mitsubishi Chemical Co., Ltd.), and replacing PTBP with 0.92 g of p-hydroxyphenylethanol (hereinafter referred to as "PHEP": manufactured by Otsuka Chemical Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 27000, hereinafter referred to as "PC-11").

[0236] (Synthesis Example 12)

[0237] Using 54.0 g of BPAF and 28.7 g of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter referred to as "BPZ": manufactured by Taoka Chemical Industry Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 17600, hereinafter referred to as "PC-12").

[0238] (Synthesis Example 13)

[0239] Using 54.0 g of BPAF and 31.1 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter referred to as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 19400, hereinafter referred to as "PC-13").

[0240] (Synthesis Example 14)

[0241] Using 54.0 g of BPAF and 40.1 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter referred to as "TMC": manufactured by Honshu Chemical Industry Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 17300, hereinafter referred to as "PC-14").

[0242] (Synthesis Example 15)

[0243] Using 45.0 g of BPAF and 34.3 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 17300, hereinafter referred to as "PC-15").

[0244] (Synthesis Example 16)

[0245] Using 63.0 g of BPAF and 30.4 g of 9,9-bis(-4-hydroxy-3-methylphenyl)fluorene (hereinafter referred to as "BCFL": manufactured by Honshu Chemical Industry Co., Ltd.), the same polymerization was carried out as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 15800, hereinafter referred to as "PC-16").

[0246] (Synthesis Example 17)

[0247] Using 91.2 g of BPA, changing PTBP to 2.00 g, and omitting TEBAC, the polymerization was carried out in the same manner as in Synthesis Example 10 to obtain polycarbonate resin (Mv: 21000, hereinafter referred to as "PC-17").

[0248] For the above synthetic examples 10-17, the weights of the monomers and chain terminators used as raw materials, the copolymerization ratio (mol%), and the viscosity-average molecular weight (Mv) of the resulting polycarbonate resins are shown in Table 2.

[0249] [Table 2]

[0250] Table 2

[0251]

[0252] [Examples 14-1 to 20-4, Comparative Examples 4-1 to 11-5]

[0253] 4.0 g of PC-10 obtained as a polycarbonate resin in Synthesis Example 10 and 36.0 g of ethyl carbitol as a hydroxyl compound were added to a mayonnaise bottle and stirred with a shaker for 24 hours to obtain a resin solution.

[0254] Using the polycarbonate resin and hydroxyl compound shown in Table 3, the resin solutions of other examples and comparative examples were obtained by operating in the same manner as in Example 14-1.

[0255] The resin solutions of Examples 4-1 to 20-4 and Comparative Examples 4-1 to 11-5 obtained in this way were subjected to the following solubility test. The results are shown in Table 3. For the resin solutions obtained in Examples 14-2, 15-2, 16-2, 17-2, 18-2, 19-2, and 20-2, the viscosity and transmittance measured by the following method are shown in Table 3. Similarly, the viscosity and transmittance of the resin solution obtained in Comparative Example 11-2 were attempted to be measured, but due to the presence of undissolved resin, it could not be evaluated as a resin solution.

[0256] <Determination of intrinsic viscosity (η) and viscosity-average molecular weight (Mv) of polycarbonate resin>

[0257] The intrinsic viscosity [η] dL / g of the obtained polycarbonate resin was determined using an Uberloud capillary viscometer at 20°C on a dichloromethane solution of 0.5 g / dL polycarbonate resin, and calculated using the Herkins constant of 0.45 by the following mathematical formula (I).

[0258] η = 1.23 × 10 －4 ×Mv 0.83 (I)

[0259] <Glass transition temperature>

[0260] The glass transition temperature of the obtained polycarbonate resin was determined using a differential scanning calorimeter (DSC).

[0261] Measuring instrument: Differential scanning calorimeter (DSC) DSC-50 manufactured by Shimadzu Corporation.

[0262] Heating rate: 10℃ / minute.

[0263] Airflow environment: Nitrogen 20ml / min.

[0264] Sample pretreatment: Heating to 300℃ to melt.

[0265] <Solubility of Resin Solution>

[0266] Visually inspect the appearance of the obtained resin solution and judge it according to the following indicators.

[0267] Transparent with no resin residue: "〇".

[0268] A small amount of undissolved resin is present: "△".

[0269] The resin did not dissolve at all: "×".

[0270] <Viscosity of resin solution>

[0271] The viscosity of the obtained resin solution was measured using a vibratory viscometer.

[0272] Measuring device: CJV5000 vibration viscometer manufactured by A&D Corporation.

[0273] Measurement temperature: 25℃.

[0274] <Transmittance of Resin Solution>

[0275] The transmittance of the obtained resin solution was determined using a spectrophotometer.

[0276] Measuring instrument: UV-1280 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation.

[0277] Container: 1cm quartz container.

[0278] Measurement wavelength: 800nm.

[0279] Measurement procedure: In photometric mode, after zero-point calibration at 800 nm using propylene glycol monomethyl ether (PGM), the transmittance of the resin solution was measured.

[0280] [Table 3]

[0281]

[0282] [Table 4]

[0283]

[0284] Industrial availability

[0285] The resin composition of the first embodiment of the present invention is a resin composition obtained by dissolving a specific polycarbonate resin with high solubility in a specific glycol solvent. It has low toxicity, moderate viscosity, and minimal corrosion to the substrate, making it suitable as a coating or ink, or a conductive paste. Furthermore, the resin composition of the second embodiment of the present invention can provide a higher concentration of polycarbonate resin solution, thus making it suitable for applications requiring high concentrations, such as coatings or inks, or conductive pastes.

Claims

1. A resin composition, characterized in that, Include: The solvent represented by the general formula (1) below; and a polycarbonate resin containing a structural unit (a) represented by the general formula (A) below, wherein the polycarbonate resin does not include polycarbonate homopolymers composed solely of structural units represented by the formula (i) below. The mass ratio of the solvent to the polycarbonate resin, expressed as solvent / polycarbonate resin, is 99.99 / 0.01 to 50 / 50. In formula (1), R a represents hydrogen, an alkyl group having 1 to 20 carbon atoms with or without a substituent, an aryl group having 6 to 20 carbon atoms with or without a substituent, 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; R b The terms refer to alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or acyl groups having 2 to 20 carbon atoms, with or without substituents. R c ~R f Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; n is 2 or 3 In formula (A), R1 to R8 independently represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl groups with or without substituents, having 1 to 7 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkenyl groups with 2 to 7 carbon atoms, alkoxy groups with 1 to 7 carbon atoms, or aralkyl groups with 7 to 17 carbon atoms, respectively; X represents -O-, -S-, -SO-, -SO2-, -CO-, or any divalent group represented by any of the formulas (2) to (4) below. In equations (2) to (4), R9 and R 10 Each of the following can independently represent hydrogen, halogen, alkyl groups with or without substituents, having 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 17 carbon atoms, or alkenyl groups with 2 to 15 carbon atoms, or R9 and R 10 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms; c represents an integer from 0 to 20; R 11 and R 12 Each of the following can be independently represented as hydrogen, halogen, alkyl group with or without substituents, having 1 to 20 carbon atoms, alkoxy group with 1 to 5 carbon atoms, aryl group with 6 to 12 carbon atoms, aralkyl group with 7 to 17 carbon atoms, or alkenyl group with 2 to 15 carbon atoms, or R 11 and R 12 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms; R 13 ~R 22 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The general formula (A) includes one or more of the following formulas (E) and (G). 。 2. The resin composition according to claim 1, characterized in that: The solvent has a boiling point of 140°C or higher.

3. The resin composition according to claim 1 or 2, characterized in that: In the general formula (1), R a R represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. b R 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. c ~R f This indicates hydrogen or methyl, where n is 2 or 3.

4. The resin composition according to claim 1 or 2, characterized in that: The solvent represented by the general formula (1) contains one or more solvents selected from glycol ether solvents, glycol ester solvents and glycol dimethyl ether solvents.

5. A resin composition, characterized in that: The resin composition comprises: a polycarbonate resin containing structural unit (b) of the following general formula (A-1); and a hydroxyl compound, The hydroxyl compound is represented by the following general formula (1a) or the following general formula (1b). The mass ratio of the polycarbonate resin to the hydroxyl compound is expressed as polycarbonate resin / hydroxyl compound and ranges from 1 / 99 to 50 / 50. In equation (1a), R a It indicates 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, with or without substituents. R b ~R e Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; n represents an integer from 1 to 10. In equation (1b), R k This refers to an alkyl group having 3 to 20 carbon atoms, with or without a branched chain, and containing a hydroxyl group. The polycarbonate resin further comprises a structural unit (a) represented by the following general formula (A), wherein the structural unit (a) does not include the structural unit (b) represented by the general formula (A-1). In formula (A), R1 to R8 independently represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl groups with or without substituents, having 1 to 7 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkenyl groups with 2 to 7 carbon atoms, alkoxy groups with 1 to 7 carbon atoms, or aralkyl groups with 7 to 17 carbon atoms, respectively; X represents -O-, -S-, -SO-, -SO2-, -CO-, or any divalent group represented by any of the formulas (2) to (4) below. In equations (2) to (4), R9 and R 10 Each of the following can independently represent hydrogen, halogen, alkyl groups with or without substituents, having 1 to 20 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 17 carbon atoms, or alkenyl groups with 2 to 15 carbon atoms, or R9 and R 10 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms; c represents an integer from 0 to 20; R 11 and R 12 Each of the following can be independently represented as hydrogen, halogen, alkyl group with or without substituents, having 1 to 20 carbon atoms, alkoxy group with 1 to 5 carbon atoms, aryl group with 6 to 12 carbon atoms, aralkyl group with 7 to 17 carbon atoms, or alkenyl group with 2 to 15 carbon atoms, or R 11 and R 12 They combine to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms; R 13 ~R 22 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The general formula (A) includes one or more formulas selected from (E) to (G) below. 。 6. The resin composition according to claim 5, characterized in that: The content ratio (b) / (a) of the structural unit (b) to the structural unit (a) is 50 / 50 to 100 / 0 in molar ratio.

7. The resin composition according to claim 5 or 6, characterized in that: The boiling point of the hydroxyl compound is above 50°C.

8. The resin composition according to claim 5 or 6, characterized in that: The hydroxyl compound is selected from one or more 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.

9. The resin composition according to claim 5 or 6, characterized in that: The resin composition is a resin solution.

10. A printing ink, characterized in that: A resin composition comprising any one of claims 1 to 9.

11. A resin solution for a 3D printer, characterized in that: A resin composition comprising any one of claims 1 to 9.

12. A conductive paste, characterized in that: A resin composition comprising any one of claims 1 to 9.

13. A coating solution, characterized in that: A resin composition comprising any one of claims 1 to 9.

14. A film formed from the resin composition according to any one of claims 1 to 9.

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