Patent Application
20240124648
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.
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).
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.
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.
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 follows.
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.
Hereinafter, the present invention will be described in detail by illustrating embodiments, examples, and the like, but the present invention is not limited to the embodiments, examples, or the like illustrated below and may be modified as desired within the scope not departing from the gist of the present invention.
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),
Herein, examples of a “substituent” implied by the phrase “optionally substituted” include “a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C1-C7 alkyl group, a C6-C12 aryl group, a C2-C7 alkenyl group, a C1-C5 alkoxy group, a C7-C17 aralkyl group” and the like (the same applies hereinafter.)
X represents —O—, —S—, —SO—, —SO2—, —CO—, or a divalent group represented by any of Formulae (2)-(4) below.
In Formulae (2)-(4),
In the first embodiment of the present invention, the structural unit (a) represented by General formula (A) above preferably includes one or more selected from the group consisting of structural units represented by Formulae (B)-(G) below.
The polycarbonate resin used in the resin composition of the first embodiment can be produced by reacting a bisphenol that generates the structural unit (a) represented by General formula (A) above with a carbonate ester-forming compound. Thus, the polycarbonate resin can be produced by employing a known method for producing a bisphenol A-derived polycarbonate resin, such as direct reaction between a bisphenol and phosgene (phosgene method) or transesterification reaction between a bisphenol and a bisaryl carbonate (transesterification method).
The bisphenol used as a raw material monomer of the polycarbonate resin used in the resin composition of the first embodiment of the present invention is a bisphenol represented by General formula (A′) below.
Specifically, examples of the monomer represented by General formula (A′) above 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′-dihydroxydiphenylsulfone, 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)-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-t-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)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]polydimethylsiloxane, 4,4′-[1,4-phenylene bis(1-methylethylidene)]bisphenol, 4,4′-[1,3-phenylene bis(1-methylethylidene)]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, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane. It is also possible to use two or more kinds of them in combination.
Among them, 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.
According to the phosgene method, in general, a monomer represented by General formula (A′) above is reacted with phosgene in the presence of an acid-binding agent and a solvent. For example, a pyridine, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or the like may be used as the acid-binding agent while methylene chloride, chloroform, or the like may be used as the solvent. In addition, in order to accelerate the condensation polymerization reaction, it is preferable to add a catalyst, for example, a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride. Furthermore, for adjusting the degree of polymerization, a monofunctional compound such as phenol, p-t-butylphenol, p-cumylphenol, p-hydroxyphenethyl alcohol, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole or a long-chain alkyl-substituted phenol is preferably added as a molecular weight regulator. Moreover, an antioxidant such as sodium sulfite or hydrosulfite, and a branching agent such as phloroglucin or isatin bisphenol may also be added in small amounts if desired. The reaction temperature is usually in the range of 0-150° C., preferably 5-40° C. While the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. The pH of the reaction system is desirably kept at 10 or higher during the reaction.
Alternatively, according to the transesterification method, a monomer represented by General formula (A′) above is mixed with a bisaryl carbonate and reacted at high temperature under reduced pressure. Examples of the bisaryl carbonate include bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. It is also possible to use two or more kinds of these compounds in combination. The reaction is usually carried out at a temperature in the range of 150-350° C., preferably 200-300° C., and the final degree of pressure reduction is preferably 1 mmHg or lower to distill phenols derived from the bisaryl carbonate generated by the transesterification reaction away from the system. While the reaction time depends on the reaction temperature and the degree of pressure reduction, it is usually about 1-24 hours. The reaction is preferably performed under an inert gas atmosphere such as nitrogen or argon. In addition, if desired, a molecular weight regulator, antioxidant, and branching agent may be added to perform the reaction.
The polycarbonate resin used in the resin composition of the first embodiment of the present invention preferably retains solvent solubility, coating property, peelability, scratch resistance, impact resistance, and the like that are required as a coating film-forming resin in a good balance. By setting the lower limit of the intrinsic viscosity of the resin equal to or higher than a predetermined value, scratch resistance and anti-impact strength can be enhanced, and by setting the upper limit of the intrinsic viscosity equal to or lower than a predetermined value, the decrease in solvent solubility and the increase in solution viscosity can be suppressed, thereby maintaining the coating property. The intrinsic viscosity (η) of the polycarbonate resin is preferably in the range of 0.3-2.0 dl/g, and still more preferably in the range of 0.35-1.5 dl/g. Meanwhile, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably in the range of 10,000-80,000, and still more preferably in the range of 15,000-50,000. The intrinsic viscosity (i) and viscosity-average molecular weight (Mv) of the polycarbonate resin can be measured by the methods described in the example below.
The mass ratio of the above solvent to the above polycarbonate resin in the resin composition of the first embodiment of the present invention (solvent/polycarbonate resin) is preferably 99.99/0.01 to 50/50, more preferably 99/1 to 60/40, and still more preferably 95/5 to 70/30. As long as the amounts of the solvent and polycarbonate resin used in the present invention are within such a range, solvent solubility and coating property will be well balanced, and workability and appearance will be improved.
The resin composition of the first embodiment of the present invention is a solution of the above-mentioned polycarbonate resin dissolved in a solvent represented by General formula (1) below (glycol-based organic solvent). In this state, the solution is a paint generally called a clear color. The resin composition of the first embodiment of the present invention can also be made into a colored paint composition by further dissolving or dispersing a desired dye and/or pigment.
(In General formula (1),
The solvent represented by General formula (1) above used in the present invention is preferably a solvent derived from ethylene glycol (all of Rc-Rf are hydrogen) or propylene glycol (any one of Rc-Rf is a methyl group.)
Moreover, according to the present invention, the solvent represented by General formula (1) above preferably comprises one or more selected from the group consisting of glycol ether-based solvents, glycol ester-based solvents, and glyme-based solvents.
Specific examples of the aforementioned glycol ether-based solvent preferably include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-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 mono-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 mono-n-butyl ether (butyl triglycol), triethylene glycol mono-tert-butyl ether, triethylene glycol monohexyl ether, and triethylene glycol monophenyl ether. More preferred examples among them include triethylene glycol mono-n-butyl ether (butyl triglycol). It is also possible to use two or more kinds of them in combination.
Specific examples of the aforementioned glycol ester-based solvent include 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. More preferred examples among them include ethylene glycol monobutyl ether acetate (butyl cellosolve acetate) and diethylene glycol monoethyl ether acetate (ethyl carbitol acetate). It is also possible to use two or more kinds of them in combination.
Specific examples of the aforementioned glyme-based solvents include monoglyme, diglyme, triglyme, tetraglyme, ethylglyme, methyl ethyl diglyme, butyl diglyme, and dipropylene glycol dimethyl ether. More preferred examples among them include tetraglyme. It is also possible to use two or more kinds of them in combination.
Glymes are one type of solvents classified as glycol ethers, and are characterized by an ether bond of an alkyl group to a diol (which has two OH groups). For example, a triglyme has a structure in which two hydroxy groups of triethylene glycol are methylated, and is represented by the following structural formula.
The solvent represented by General formula (1) above used in the present invention preferably has a boiling point of 140° C. or higher, more preferably 140-300° C.
A resin composition of a second embodiment of the present invention is 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) above.
The present inventors considered that, in order to dissolve a polymer in a solvent to obtain a more concentrated polycarbonate resin solution, the polymer used should have a structure in which the interaction between polymer chains is small and which has a moiety that interacts with the solvent, and they considered that the presence of F (fluorine) atoms in the polymer chain increases the distance between polymer chains due to electron repulsion and therefore focused on the following bisphenol AF-based polycarbonate resin shown below.
Next, as a requirement for the solvent to be used, the present inventors considered that the solvent should have a structure with a moiety that interacts with the polymer. As shown below, the presence of a hydroxyl group (OH) in the solvent allows hydrogen bond with the F (fluorine) atom in the polymer, which enhances the affinity between the polymer and the solvent.
On the other hand, as shown below, intramolecular hydrogen bond does not work with isopropyl alcohol or ethanol, and interaction due to hydrogen bonds between solvent molecules is large. In other words, the solubility of a polycarbonate resin was considered to be poor due to the strong bonding between the solvent molecules.
Consequently, the present inventors concluded that a solvent, such as ether oxygen, which forms intramolecular hydrogen bonds due to the effect of neighboring functional groups and thus has small interactions between solvent molecules as shown below is preferred. This is thought to improve the compatibility with a polycarbonate resin.
The polycarbonate resin used in the resin composition of the second embodiment of the present invention preferably 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.)
Here, the structural unit (a) represented by General formula (A) above is synonymous with that described for the resin composition of the first embodiment of the present invention.
In the second embodiment of the present invention, the structural unit (a) represented by General formula (A) above preferably includes one or more selected from the group consisting of structural units represented by Formulae (B)-(H) below.
In the resin composition of the second embodiment of the present invention, the content ratio of the structural unit (b) to the structural unit (a) [(b)/(a)] is preferably 50/50 to 100/0, and more preferably 60/40 to 100/0 in mole ratio.
The polycarbonate resin used in the resin composition of the second embodiment of the present invention preferably retains solvent solubility, coating property, peelability, scratch resistance, impact resistance, and the like that are required as a coating film-forming resin in a good balance. By setting the lower limit of the intrinsic viscosity of the resin equal to or higher than a predetermined value, scratch resistance and anti-impact strength can be enhanced, and by setting the upper limit of the intrinsic viscosity equal to or lower than a predetermined value, the decrease in solvent solubility and the increase in solution viscosity can be suppressed, thereby maintaining the coating property. The intrinsic viscosity (1) of the polycarbonate resin is preferably in the range of 0.3-2.0 dl/g, and still more preferably in the range of 0.35-1.5 dl/g. Meanwhile, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably in the range of 10,000-80,000, and still more preferably in the range of 15,000-50,000. The intrinsic viscosity (η) and viscosity-average molecular weight (Mv) of the polycarbonate resin can be measured by the methods described in the example below.
In the resin composition of the second embodiment of the present invention, the mass ratio of the polycarbonate resin to the hydroxy compound (polycarbonate resin/hydroxy compound) is preferably 1/99 to 50/50, more preferably 5/95 to 50/50, still more preferably 5/95 to 30/70, and particularly preferably 7/93 to 13/87. If the mass ratio of the polycarbonate resin exceeds 50% by mass, the viscosity may become too high, while if it is less than 1% by mass, it may be too thin for practical use.
The resin composition of the second embodiment of the present invention is a solution of the above-mentioned polycarbonate resin dissolved in a hydroxy compound represented by General formula (1a) or General formula (1b) below (organic solvent). In this state, the solution is a paint generally called a clear color. The resin composition of the second embodiment of the present invention can also be made into a colored paint composition by further dissolving or dispersing a desired dye and/or pigment.
In General formula (1a),
In General formula (1b), Rk represents an optionally branched C3-C20 alkyl group with a hydroxyl group, and preferably an optionally branched C3-C10 alkyl group with a hydroxyl group.
Specific examples of the hydroxy compound used in the second embodiment of the present invention include, but are 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 methacrylic acid (2-hydroxyethyl)), and diacetone alcohol. One of these compounds can be used alone or two or more of them may be used in combination.
Examples of more preferred hydroxy compound among them include ethyl carbitol, butyl cellosolve, 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), 2-hydroxyethyl methacrylate (also known as methacrylic acid (2-hydroxyethyl)), and diacetone alcohol, and examples of still more preferred hydroxy compound include ethyl carbitol, 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), 2-hydroxyethyl methacrylate (also known as methacrylic acid (2-hydroxyethyl)), and diacetone alcohol.
Structural formulae of representative hydroxy compounds that can favorably, but not exclusively, be used in the present invention are shown below.
The hydroxy compound used in the second embodiment of the present invention preferably has a boiling point of 50° C. or higher, more preferably 50-250° C.
If the resin composition of the first or second embodiment of the present invention is to be used by way of application, a pigment, a dye, colored particles, or light-interfering particles can be added to enhance the color effect. Examples of the pigment and dye include organic pigments such as azo pigments and phthalocyanine pigments, specifically, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 215, Red No. 220, Orange No. 203, Orange No. 204, Blue No. 1, Blue No. 404, Yellow No. 205, Yellow No. 401, and Yellow No. 405. In addition, mica titanium, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, nickel, or the like can be used to produce white color, pearl color, metallic color, or lamé appearance. Particles with light interference properties are particles that enhance color effects by reflecting and scattering light, and examples thereof include glass beads, microscopic shells, and mica. These should be added as desired in the range of 0.0001-10.0% by mass in the resin composition.
If necessary, an anti-rust agent, antioxidant, dispersant, UV absorber, defoaming agent, or leveling agent may further be added.
While the viscosity of the resin composition of the first embodiment of the present invention can be set freely according to the desired application, it is preferably in the range of 20-200,000 mPa·s, and more preferably in the range of 50-20,000 mPa·s. While the viscosity of the resin composition of the second embodiment of the present invention can be set freely according to the desired application, it is preferably in the range of 5-200,000 mPa·s, more preferably in the range of 10-20,000 mPa·s, still more preferably in the range of 10-5,000 mPa·s, yet still more preferably in the range of 10-1,000 mPa·s, and particularly preferably in the range of 10-100 mPa·s. The viscosity can be measured, for example, at a measurement temperature of 25° C. using a vibro viscometer (CJV5000) manufactured by A&D Company, Limited.
The thickness of the coating film after the application and drying of the resin composition of the first or second embodiment of the present invention is preferably in the range of 1-200 μM, more preferably in the range of 5-120 μm, and particularly preferably in the range of 10-60 μm. A coating film thickness of 1 μm or more ensures the surface protection strength as a coating film, and a coating film thickness of 200 μm or less is preferred to suppress peeling caused by shrinkage of the coating film.
Other embodiments of the present invention are a printing ink, resin solution for 3D printers, electroconductive paste, and coating solution, all of which contain the aforementioned resin composition of the first or second embodiment of the present invention. Yet another embodiment of the present invention is a film formed of the aforementioned resin composition of the first or second embodiment of the present invention. The resin composition of the first embodiment of the present invention is particularly suitable for the above-mentioned applications because of its low toxicity, excellent stability (no penetration) and uniformity on a base material when applied.
Hereinafter, examples of the present invention will be described along with comparative examples to illustrate the present invention in detail, but the present invention is not limited to these examples.
In 1100 ml of a 5 w/w % aqueous sodium hydroxide solution, 102.4 g (0.4 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as “BPC”: manufactured by Honshu Chemical Industry Co., Ltd.) and 0.1 g of hydrosulfite were dissolved.
To this, 500 ml of methylene chloride was added and, while keep stirring, 0.5 g of benzyltriethylammonium chloride (hereinafter abbreviated as “TEBAC”) was added. Then, while keeping the temperature at 15° C., 60 g of phosgene was blown therein over 60 minutes.
After the phosgene blowing, 1.5 g of p-t-butylphenol (hereinafter abbreviated as “PTBP”: manufactured by Dainippon Ink and Chemicals, Incorporated) was added as a molecular weight regulator and the mixture was thoroughly stirred to emulsify the reaction solution. After the emulsification, 0.4 ml of triethylamine was added, and the mixture was stirred at 20-25° C. for about 1 hour to allow polymerization.
After the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly rinsed with water until the conductivity of the former liquid (aqueous phase) became 10 μS/cm or less. The resulting polymer solution was dropped into warm water kept at 45° C. to remove the solvent by evaporation to obtain white powdery precipitate. The resulting precipitate was filtered and dried at 105° C. for 24 hours to obtain polymer powder.
A solution of this polymer in methylene chloride as a solvent at a concentration of 0.5 g/dl had an intrinsic viscosity of 0.65 dl/g at 20° C. The obtained polymer was analyzed by infrared absorption spectroscopy, and absorption due to a carbonyl group at around 1,770 cm−1 and absorption due to an ether bond at around 1,240 cm−1 were observed, confirming that it was a polycarbonate resin with a carbonate bond (hereinafter, referred to as “PC-1”.)
Polymerization was carried out in the same manner as in Example 1 except that 54 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as “MIBK”: manufactured by Honshu Chemical Industry Co., Ltd.) and 58 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as “BPAP”: manufactured by Honshu Chemical Industry Co., Ltd.) were used instead of BPC, the amount of PTBP was changed to 2.0 g, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.49 dl/g (hereinafter abbreviated as “PC-2”.)
Polymerization was carried out in the same manner as in Example 1 except that the amounts of BPC and PTBP were changed to 60.4 g and 1.8 g, respectively, 40.1 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as “BPA”: manufactured by Mitsubishi Chemical Corporation) was used at the same time, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.58 dl/g (hereinafter abbreviated as “PC-3”.)
Polymerization was carried out in the same manner as in Example 1 except that 108 g of MIBK was used instead of BPC, 4.3 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (hereinafter abbreviated as “BTAZ”: manufactured by Otsuka Chemical Co. Ltd.) was used instead of PTBP, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.54 dl/g (hereinafter abbreviated as “PC-4”.)
Polymerization was carried out in the same manner as in Example 1 except that the amount of BPC was changed to 60.4 g, 40.1 g of BPA and 1.92 g of p-hydroxyphenethyl alcohol (hereinafter abbreviated as “PHEP” manufactured by Otsuka Chemical Co. Ltd.) were used at the same time, and PTBP was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.72 dl/g (hereinafter abbreviated as “PC-5”.)
Polymerization was carried out in the same manner as in Example 1 except that 107.2 g of BPZ was used instead of BPC, the amount of PTBP was changed to 2.0 g, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.44 dl/g (hereinafter abbreviated as “PC-6”.)
Polymerization was carried out in the same manner as in Example 1 except that 116.0 g of BPAP was used instead of BPC, the amount of PTBP was changed to 2.0 g, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.43 dl/g (hereinafter abbreviated as “PC-7”.)
Polymerization was carried out in the same manner as in Example 1 except that 124.0 g of 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as “TMC”: manufactured by Sanko Co., Ltd.) was used instead of BPC, the amount of PTBP was changed to 1.62 g, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.48 dl/g (hereinafter abbreviated as “PC-8”.)
Polymerization was carried out in the same manner as in Example 1 except that 91.2 g of BPA was used instead of BPC, the amount of PTBP was changed to 2.0 g, and TEBAC was not used, thereby obtaining a polycarbonate resin with an intrinsic viscosity of 0.49 dl/g (hereinafter abbreviated as “PC-9”.)
5 g of each polycarbonate (PC) resin obtained in Synthesis examples 1 through 9 described above and 45 g of solvent were placed in a mayonnaise bottle in the combination shown in Table 1 below and stirred in a shaker to produce a resin composition.
The resin compositions of Examples 1 through 13 and Comparative examples 1 through 3 obtained in this way were subjected to the following tests and physical property measurements. The results are shown in Table 1 below.
When preparing the resin composition, that is, when 5 g of polycarbonate resin and 45 g of solvent listed in Table 1 below were placed in a mayonnaise bottle and stirred in a shaker, the time that took from the start of stirring until the resin was visually completely dissolved (dissolving time) was measured.
The viscosity of the resin composition was measured at 25° C. using a vibro viscometer (CJV5000) manufactured by A&D Company, Limited.
A PC sheet (NF-2000 manufactured by Mitsubishi Engineering-Plastics Corporation) was acquired, and the resin composition prepared above was applied to this PC sheet using a 60 μm-thick gap coater. After the application, drying was performed in a box-type hot-air dryer at 120° C. for 1 minute to form a coating film.
Evaluation was carried out as follows.
After application of the resin composition, drying was performed in a box-type hot-air dryer at 120° C. for 1 minute to visually evaluate the resulting coating film.
PC sheet (NF-2000 manufactured by Mitsubishi Engineering-Plastics Corporation) was cut into a 1 cm×1 cm square piece and placed in a 9 cc vial, to which the resin composition prepared above was further added so that the PC piece was completely immersed into it. The PC piece was left in place to visually inspect its state after 24 hours.
The viscosity of a 0.5 grams/deciliter methylene chloride solution of the polycarbonate resin obtained in each of Synthesis examples 1 through 9 was measured at 20° C. with a Ubbelohde capillary viscometer to calculate the intrinsic viscosity [η] (deciliter/gram) of said polycarbonate resin by Formula (I) below using Huggins' constant of 0.45.
η=1.23×10−4×Mv0.83 (I)
Although N,N-dimethylacetamide (non-glycol-based solvent) used in Comparative example 2 showed good solubility of the polycarbonate resin, the viscosity of the solution was remarkably low, smoothness during the formation of the coating film was poor, and there were many bleeds after the film formation. In addition, the resin composition of Comparative example 2 resulted in biting into the PC base material. Isophorone (non-glycol-based solvent) used in Comparative example 3 took longer to dissolve the polycarbonate resin, and the resin composition thereof resulted in biting into the PC base material.
In 750 ml of a 6.3 w/w % aqueous sodium hydroxide solution, 90.0 g (0.34 mol) of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter abbreviated as “BPAF”: manufactured by Central Glass Co., Ltd.) and 0.5 g of hydrosulfite were dissolved.
To this, 300 ml of methylene chloride was added and, while keep stirring, 0.1 g of benzyltriethylammonium chloride (hereinafter abbreviated as “TEBAC”) was added. Then, while keeping the temperature at 15-25° C., 42.4 g of phosgene was blown therein over 30 minutes.
After the phosgene blowing, 1.34 g of p-t-butylphenol (hereinafter abbreviated as “PTBP”: manufactured by Dainippon Ink and Chemicals, Incorporated) was added as a molecular weight regulator and the mixture was thoroughly stirred to emulsify the reaction solution. After the emulsification, 0.5 ml of triethylamine was added, and the mixture was stirred at 20-30° C. for about 1 hour to allow polymerization.
After the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly rinsed with water until the conductivity of the former liquid (aqueous phase) became 10 μS/cm or less. The resulting polymer solution was transferred onto an aluminum plate to remove the solvent by evaporation on a hot plate, and the resulting solid was further dried at 120° C. for 24 hours to obtain a polymer solid.
A solution of this polymer in methylene chloride as a solvent at a concentration of 0.5 g/dl had an intrinsic viscosity of 0.33 dl/g at 20° C. and a viscosity-average molecular weight (Mv) of 15,300. The obtained polymer was analyzed by infrared absorption spectroscopy, and absorption due to a carbonyl group at around 1,770 cm−1 and absorption due to an ether bond at around 1,240 cm−1 were observed, confirming that it was a polycarbonate resin with a carbonate bond (hereinafter abbreviated as “PC-10”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 63.0 g, 18.0 g of 1,1-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as “BPA”: manufactured by Mitsubishi Chemical Corporation) was used at the same time, and PTBP was replaced by 0.92 g of p-hydroxyphenethyl alcohol (hereinafter abbreviated as “PHEP”: manufactured by Otsuka Chemical Co. Ltd.), thereby obtaining a polycarbonate resin (Mv: 27,000, hereinafter abbreviated as “PC-11”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 54.0 g, and 28.7 g of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as “BPZ”: manufactured by Taoka Chemical Co., Ltd.) was used at the same time, thereby obtaining a polycarbonate resin (Mv: 17,600, hereinafter abbreviated as “PC-12”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 54.0 g, and 31.1 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as “BPAP” manufactured by Honshu Chemical Industry Co., Ltd.) was used at the same time, thereby obtaining a polycarbonate resin (Mv: 19,400, hereinafter abbreviated as “PC-13”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 54.0 g, and 40.1 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter abbreviated as “TMC”: manufactured by Honshu Chemical Industry Co., Ltd.) was used at the same time, thereby obtaining a polycarbonate resin (Mv: 17,300, hereinafter abbreviated as “PC-14”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 45.0 g, and 34.3 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as “BPC”: manufactured by Honshu Chemical Industry Co., Ltd.) was used at the same time, thereby obtaining a polycarbonate resin (Mv: 17,300, hereinafter abbreviated as “PC-15”.)
Polymerization was carried out in the same manner as in Synthesis example 10 except that the amount of BPAF was changed to 63.0 g, and 30.4 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as “BCFL”: manufactured by Honshu Chemical Industry Co., Ltd.) was used at the same time, thereby obtaining a polycarbonate resin (Mv: 15,800, hereinafter abbreviated as “PC-16”.)
Polymerization was carried out in the same manner as in Example 10 except that 91.2 g of BPA was used, the amount of PTBP was changed to 2.00 g, and TEBAC was not used, thereby obtaining a polycarbonate resin (Mv: 21,000, hereinafter abbreviated as “PC-17”.)
For each of Synthetic examples 10 through 17 described above, the weights of the raw material monomers and terminator, copolymer ratio (mol %), and viscosity-average molecular weight (Mv) of the resulting polycarbonate resin are shown in Table 2.
4.0 g of PC-10 obtained in Synthesis example 10 as a polycarbonate resin and 36.0 g of ethyl carbitol as a hydroxy compound were placed in a mayonnaise bottle and stirred in a shaker for 24 hours to obtain a resin solution.
Resin solutions of other examples and comparative examples were obtained in the same manner as in Example 14-1, using the polycarbonate resins and hydroxy compounds shown in Table 3.
The thus-obtained resin solutions of Examples 14-1 through 20-4 and Comparative examples 4-1 through 11-5 were subjected to the solubility test described below. The results are shown in Table 3. The viscosities and transmittances of the resin solutions obtained in Examples 14-2, 15-2, 16-2, 17-2, 18-2, 19-2, and 20-2 measured by the following methods are shown in Table 3. Similarly, the present inventors attempted to measure the viscosity and transmittance of the resin solution obtained in Comparative example 11-2, but it could not be evaluated as a resin solution due to the presence of undissolved resin.
The viscosity of a 0.5 grams/deciliter methylene chloride solution of each of the obtained polycarbonate resin was measured at 20° C. with a Ubbelohde capillary viscometer to calculate the intrinsic viscosity [η] (deciliter/gram) of said polycarbonate resin by Formula (I) below using Huggins' constant of 0.45.
η=1.23×10−4×Mv0.83 (I)
The glass transition temperatures of the resulting polycarbonate resins were determined using a differential scanning calorimeter (DSC).
Appearances of the obtained resin solutions were visually inspected and judged according to the following indices.
The viscosities of the obtained resin solutions were measured using a vibro viscometer.
The transmittances of the obtained resin solutions were measured using a spectrophotometer.
The resin composition of the first embodiment of the present invention is a resin composition obtained by dissolving a specific highly soluble polycarbonate resin in a specific glycol-based solvent, which is suitable as a paint, ink, or electroconductive paste because of its low toxicity, moderate viscosity, and low penetration into the base material. In addition, since the resin composition of the second embodiment of the present invention can provide a more concentrated polycarbonate resin solution, it is suitable for applications requiring a highly concentrated polycarbonate resin solution, such as a paint, ink, and electroconductive paste.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-023321 | Feb 2021 | JP | national |
| 2021-155162 | Sep 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/005260 | 2/10/2022 | WO |
