Patent Application
20220389159
The present invention relates to a novel polycarbonate resin.
It is known that polyethylene glycol, poly(2-methyl) ethylene glycol or the like is blended in a thermoplastic resin such as a polycarbonate resin. Patent Document 1 describes a γ-ray irradiation-resistant polycarbonate resin containing this, and Patent Document 2 describes a thermoplastic resin composition having excellent antistatic properties and surface appearance that is blended in PMMA, etc.
Further, Patent Document 3 proposes to improve the transmittance and color phase by blending a polyalkylene glycol composed of a linear alkyl group. By blending a polytetramethylene ether glycol, the transmittance and the degree of yellowness (yellow index: YI) are improved.
Moreover, Patent Document 4 describes a method for producing a polycarbonate copolymer, wherein a diol obtained by diesterification of polyalkylene glycol is used as a raw material (comonomer). However, in this polycarbonate copolymer, a diester diol of polyalkylene glycol is unstable, and for this reason, impact resistance is insufficient and the color phase and heat discoloration resistance are unsatisfactory.
For molding optical components, high barrel temperatures and high-speed injection are required. With this, there is a problem that the amount of gas generated at the time of molding increases and mold contamination tends to progress. For this reason, resins to be used for molding optical components are required not only to have excellent optical properties, but also to cause less mold contamination due to the generation of gas at the time of injection molding at high temperatures and to have excellent impact resistance.
The present invention was made in consideration of the above-described actual circumstances, and the purpose thereof is to provide a polycarbonate resin, wherein the amount of gas generated is small.
The present inventor diligently made researches in order to solve the above-described problem and found that the generation of gas at the time of molding can be suppressed by a specific polycarbonate resin, and thus the present invention was achieved.
Specifically, the present invention relates to a polycarbonate resin described below.
<1> A polycarbonate resin comprising a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (4):
wherein in general formula (1):
R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms and an aralkyl group having 7 to 17 carbon atoms, and each of the alkyl group, the aryl group, the alkenyl group, the alkoxy group and the aralkyl group may have a substituent; and
X represents —O—, —S—, —SO—, —SO2—, —CO—, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by general formula (2) or general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms:
wherein in general formula (2):
R9 and R10 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and an alkenyl group having 2 to 15 carbon atoms;
each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group of R9 and R10 may have a substituent;
R9 and R10 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and each of the carbocyclic ring and the heterocyclic ring may have a substituent; and
n represents an integer of 0 to 20,
wherein in general formula (3):
R11 and R12 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and an alkenyl group having 2 to 15 carbon atoms, and each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group may have a substituent; and
R11 and R12 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and each of the carbocyclic ring and the heterocyclic ring may have a substituent,
wherein in general formula (4): Rz and Rx each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 3 to 10; and p represents an integer of 5 to 600.
<2> The polycarbonate resin according to item <1>, wherein the mass ratio between the structural unit (A) and the structural unit (B) (A/B) is 1/99 to 50/50.
<3> A polycarbonate resin comprising only a structural unit (B) represented by general formula (4):
wherein: Rz and Rx each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 3 to 10; and p represents an integer of 5 to 600.
<4> The polycarbonate resin according to any one of items <1> to <3>, wherein the concentration of a terminal hydroxyl group in the polycarbonate resin is 1 ppm to 3000 ppm.
<5> The polycarbonate resin according to any one of items <1> to <4>, wherein i in general formula (4) is an integer of 3 or 4.
<6> The polycarbonate resin according to any one of items <1> to <5>, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin is 1,000 to 60,000.
<7> The polycarbonate resin according to any one of items <1> to <6>, wherein the glass transition temperature (Tg) of the polycarbonate resin is −100 to 140° C.
When using the polycarbonate resin of the present invention, the amount of gas generated is small, and the polycarbonate resin has the effect of widening the range of resin design according to various applications.
Hereinafter, the present invention will be described in detail by way of embodiments, examples, etc.
In this specification, “-” is used to mean that numerical values described at the both sides of “-” are included as the lower limit and the upper limit, unless otherwise specified.
The first embodiment of the present invention is a polycarbonate resin containing a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (4).
In general formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms), an alkenyl group having 2 to 7 carbon atoms (preferably 2 to 5 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably 1 to 4 carbon atoms) and an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 11 carbon atoms), and are preferably selected from the group consisting of a hydrogen atom, a phenyl group and a methyl group. More preferably, all of R1 to R8 represent a hydrogen atom, or alternatively, R1 or R3, and R6 or R8 represent a phenyl group and the others represent a hydrogen atom.
Note that each of the alkyl group, the aryl group, the alkenyl group, the alkoxy group and the aralkyl group may have a substituent, and preferred examples of the substituent include a phenyl group.
In general formula (1), X represents —O—, —S—, —SO—, —SO2—, —CO—, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by general formula (2) or general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms. Preferably, X represents a divalent group represented by general formula (2) or a divalent group represented by general formula (3).
In general formula (2), R9 and R10 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 10 carbon atoms) and an alkenyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms), and are preferably selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group and a phenyl group. More preferably, both R9 and R10 represent a methyl group.
Each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group of R9 and R10 may have a substituent.
R9 and R10 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 5 to 15 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 5 to 10 carbon atoms), and each of the carbocyclic ring and the heterocyclic ring may have a substituent. Preferred examples of the substituent include a cyclohexyl group, an adamantyl group, a cyclododecane group and a norbornane group.
In general formula (2), n represents an integer of 0 to 20, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2.
In general formula (3), R11 and R12 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 3 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 11 carbon atoms) and an alkenyl group having 2 to 15 carbon atoms, and are preferably selected from the group consisting of a hydrogen atom and a phenyl group. More preferably, both R11 and R12 represent a hydrogen atom.
Note that each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group may have a substituent, and preferred examples of the substituent include a phenyl group.
R11 and R12 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and each of the carbocyclic ring and the heterocyclic ring may have a substituent.
Preferred examples of a monomer constituting the structural unit (A) represented by general formula (1) include poly-n-propylene glycol and polytetramethylene ether glycol, and poly-n-propylene glycol is more preferred.
In general formula (4), Rz and Rx each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represent a hydrogen atom, a methyl group or an ethyl group. More preferably, both Rz and Rx represent a hydrogen atom.
In general formula (4), i represents an integer of 3 to 10, preferably an integer of 3 to 6, and more preferably 3 or 4.
In general formula (4), p represents an integer of 5 to 600, preferably an integer of 5 to 550, and more preferably an integer of 5 to 500.
Preferred examples of a monomer constituting the structural unit (B) represented by general formula (4) include bisphenol A, bisphenol S, 4,4′-oxydiphenol, 4,4′-biphenol and 4,4′-thiodiphenol, and bisphenol A and bisphenol S are more preferred. In particular, when employing bisphenol A, a polycarbonate resin having a small YI value and excellent heat resistance is obtained, and it is preferred from the viewpoint of marketability. Bisphenol S is also preferred from the viewpoint of heat resistance.
In the polycarbonate resin of the present invention, the mass ratio between the structural unit (A) and the structural unit (B) (A/B) is preferably 1/99 to 50/50, more preferably 5/95 to 50/50, even more preferably 5/95 to 40/60, still more preferably 5/95 to 35/65, and particularly preferably 10/90 to 30/70.
The polycarbonate resin of the present invention is preferably a polycarbonate resin which includes a carbonate bond derived from bisphenol A and a carbonate bond derived from poly-n-propylene glycol that may have a substituent.
Regarding the mass ratio between bisphenol A and poly-n-propylene glycol that constitute the polycarbonate resin based on the total (100% by mass) thereof, it is preferred that bisphenol A is 5-50% by mass and poly-n-propylene glycol is 50-95% by mass, it is more preferred that bisphenol A is 5-40% by mass and poly-n-propylene glycol is 60-95% by mass, and it is even more preferred that bisphenol A is 5-35% by mass and poly-n-propylene glycol is 65-95% by mass. When the amount of poly-n-propylene glycol is less than 50% by mass, the color phase of the polycarbonate resin is deteriorated, and when it is more than 95% by mass, a white turbidity tends to be yielded.
The polycarbonate resin of the present invention is preferably represented by general formula (5) below, and specifically, it is preferably a polycarbonate resin composed of a polycarbonate unit derived from bisphenol A and a polycarbonate unit derived from poly-n-propylene glycol.
In general formula (5), Ra, Rb and Rc each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably represent a hydrogen atom, a methyl group or an ethyl group. m represents an integer of 1 to 3000, and more preferably an integer of 1 to 2500. n represents an integer of 5 to 600, and more preferably an integer of 5 to 550. l represents an integer of 1 to 3000, and more preferably an integer of 1 to 2500.
The polycarbonate resin of the present invention can be produced by a commonly-used production method such as an interfacial polymerization method and a melt polymerization method, and for example, it can be produced by a method of reacting at least bisphenol A, poly-n-propylene glycol and a carbonate precursor such as phosgene and diphenyl carbonate.
As the poly-n-propylene glycol that may have a substituent, various types of poly-n-propylene glycols can be used, and preferred examples thereof include a poly-n-propylene glycol represented by general formula (6) below, wherein a methylene group may have a substituent.
In general formula (6), Ra, Rb and Rc each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably represent a hydrogen atom, a methyl group or an ethyl group. n represents an integer of 6 to 600, and more preferably an integer of 6 to 550.
As the poly-n-propylene glycol, (2-methyl)-n-propylene glycol (in general formula (6), Rb is a methyl group), (2-ethyl)-n-propylene glycol (in general formula (6), Rb is an ethyl group) and n-propylene glycol (all of Ra, Rb and Rc are a hydrogen atom) are more preferred, and among them, n-propylene glycol (all of Ra, Rb and Rc are a hydrogen atom) (i.e., trimethylene glycol) is even more preferred.
The poly-n-propylene glycol represented by general formula (6) may be a homopolymer composed of one type of Ra, Rb and Rc or a copolymer composed of different Ras, Rbs and Rcs.
Examples of commercially-available products of the poly-n-propylene glycol represented by general formula (6) include “VELVETOL” (trade name) manufactured by Allessa, which is a commercially-available product of a poly-n-propylene glycol, wherein all of Ra, Rb and Rc in general formula (6) are a hydrogen atom, i.e., polytrimethylene glycol.
The poly-n-propylene glycol represented by general formula (6) may be a copolymer with a linear polyalkylene glycol such as polyethylene glycol, polytetramethylene glycol, polypentamethylene glycol and polyhexamethylene glycol, but preferred is a homopolymer composed of polytrimethylene glycol because transparency of molded products obtained is improved in this case.
The poly-n-propylene glycol may contain a polyalkylene glycol copolymer, which has, in addition to an n-propylene ether unit (P1) represented by general formula (7) below, a branched alkylene ether unit (P2) selected from among units represented by general formulae (8-1) to (8-4) below.
In general formula (7), Ra, Rb and Rc are the same as those in general formula (6).
In general formulae (8-1) to (8-4), R1 to R10 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in each of general formulae (8-1) to (8-4), at least one of R1 to R10 represents an alkyl group having 1 to 3 carbon atoms.
Regarding branched alkylene ether units represented by general formulae (8-1) to (8-4), either a homopolymer composed of a branched alkylene ether unit having any one of structures of general formulae (8-1) to (8-4) or a copolymer composed of a branched alkylene ether unit having a plurality of structures may be employed.
Regarding the n-propylene ether unit represented by general formula (7), when it is described as a glycol, it is an n-propylene glycol, and in addition to the n-propylene glycol, at least one of ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc. may be mixed, but the n-propylene glycol alone is preferred. More preferred is the n-propylene glycol, wherein all of Ra, Rb and Rc are a hydrogen atom (i.e., trimethylene glycol) alone.
Trimethylene glycol is industrially produced by a method in which ethylene oxide is hydroformylated to obtain 3-hydroxypropionaldehyde, which is then hydrogenated, or a method in which acrolein is hydrated to obtain 3-hydroxypropionaldehyde, which is then hydrogenated with an Ni catalyst. Recently, a bio method is also employed, and according to this, glycerin, glucose, starch or the like is reduced using microorganisms to produce trimethylene glycol.
Regarding the branched alkylene ether unit represented by general formula (8-1) above, when it is described as a glycol, examples thereof include (2-methyl) ethylene glycol, (2-ethyl) ethylene glycol and (2,2-dimethyl) ethylene glycol, and these substances may be mixed. Preferred are (2-methyl) ethylene glycol and (2-ethyl) ethylene glycol.
Regarding the branched alkylene ether unit represented by general formula (8-2) above, when it is described as a glycol, examples thereof include (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol, (3-ethyl) triethylene glycol, (2,2-dimethyl) trimethylene glycol, (2,2-methylethyl) trimethylene glycol, (2,2-diethyl) trimethylene glycol (i.e., neopentyl glycol), (3,3-dimethyl) trimethylene glycol, (3,3-methylethyl) trimethylene glycol and (3,3-diethyl) trimethylene glycol, and these substances may be mixed.
Regarding the branched alkylene ether unit represented by general formula (8-3) above, when it is described as a glycol, examples thereof include (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol, (4-ethyl) tetramethylene glycol, (3,3-dimethyl) tetramethylene glycol, (3,3-methylethyl) tetramethylene glycol, (3,3-diethyl) tetramethylene glycol, (4,4-dimethyl) tetramethylene glycol, (4,4-methylethyl) tetramethylene glycol and (4,4-diethyl) tetramethylene glycol, and these substances may be mixed. Preferred is (3-methyl) tetramethylene glycol.
Regarding the branched alkylene ether unit represented by general formula (8-4) above, when it is described as a glycol, examples thereof include (3-methyl) pentamethylene glycol, (4-methyl) pentamethylene glycol, (5-methyl) pentamethylene glycol, (3-ethyl) pentamethylene glycol, (4-ethyl) pentamethylene glycol, (5-ethyl) pentamethylene glycol, (3,3-dimethyl) pentamethylene glycol, (3,3-methylethyl) pentamethylene glycol, (3,3-diethyl) pentamethylene glycol, (4,4-dimethyl) pentamethylene glycol, (4,4-methylethyl) pentamethylene glycol, (4,4-diethyl) pentamethylene glycol, (5,5-dimethyl) pentamethylene glycol, (5,5-methylethyl) pentamethylene glycol and (5,5-diethyl) pentamethylene glycol, and these substances may be mixed.
Thus, regarding the units represented by general formulae (8-1) to (8-4) constituting the branched alkylene ether units, glycols are described as examples for the sake of convenience, but the units are not limited to these glycols, and alkylene oxides thereof and polyether-forming derivatives thereof may also be employed.
Regarding preferred examples of a poly-n-propylene glycol copolymer, a copolymer composed of the n-propylene ether unit and the unit represented by general formula (8-2) is preferred, and in particular, a copolymer composed of a trimethylene ether unit and a 3-methyltrimethylene ether unit is more preferred.
The poly-n-propylene glycol copolymer may be a random copolymer or a block copolymer.
In the poly-n-propylene glycol copolymer, the copolymerization ratio between the n-propylene ether unit (P1) represented by general formula (7) and the branched alkylene ether units (P2) represented by general formulae (8-1) to (8-4) ((P1)/(P2), molar ratio) is preferably 95/5 to 5/95, more preferably 93/7 to 40/60, and even more preferably 90/10 to 65/35, and it is more preferably rich with the n-propylene ether unit (P1).
Note that the molar fraction is measured using a 1H-NMR measurement apparatus and deuterated chloroform as a solvent.
Among the above-described examples, a particularly preferred poly-n-propylene glycol is a homopolymer of an n-propylene glycol not having a substituent, i.e., trimethylene glycol.
In the structure of the poly-n-propylene glycol, a structure derived from a polyol such as 1,4-butanediol, glycerol, sorbitol, benzenediol, bisphenol A, cyclohexanediol and spiroglycol may be included. By adding these polyols at the time of the polymerization of polyalkylene glycol, organic groups thereof can be imparted to the main chain. Particularly preferred examples thereof include glycerol, sorbitol and bisphenol A.
Preferred examples of the poly-n-propylene glycol containing an organic group in its structure include:
The weight average molecular weight (Mw) of the poly-n-propylene glycol is preferably 600-8,000, and it is more preferably 800 or more, and even more preferably 1,000 or more, and it is more preferably 6,000 or less, even more preferably 5,000 or less, and particularly preferably 4,000 or less. When the weight average molecular weight is more than the above-described upper limit, compatibility tends to be reduced. When the weight average molecular weight is lower than the above-described lower limit, impact resistance of the polycarbonate resin may be reduced.
Note that the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight measured using gel permeation chromatography (GPC) with THF as a developing solvent.
Specifically, it is a value obtained as a polystyrene equivalent molecular weight (weight average molecular weight) using a high-speed GPC apparatus “HLC-8320” manufactured by Tosoh Corporation as GPC, columns: HZ-M (4.6 mm×150 mm)×3 manufactured by Tosoh Corporation (connected in series), and an eluant: chloroform.
Among monomers as raw materials of the polycarbonate resin, examples of the carbonate precursor to be used include a carbonyl halide and a carbonate ester. As the carbonate precursor, one material may be used solely, or two or more types of materials may be used in any combination at any ratio.
Specific examples of the carbonyl halide include phosgene; and a haloformate such as a bischloroformate form of a dihydroxy compound and a monochloroformate form of a dihydroxy compound.
Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and a carbonate form of a dihydroxy compound such as a biscarbonate form of a dihydroxy compound, a monocarbonate form of a dihydroxy compound and a cyclic carbonate.
As the polycarbonate resin of the present invention, a bisphenol A-poly-n-propylene glycol copolymerized polycarbonate represented by general formula (9) below is particularly preferred.
In general formula (9), m, n and l are the same as those in general formula (5).
The second embodiment of the present invention is a polycarbonate resin containing only a structural unit (B) represented by general formula (4):
In general formula (4), Rz, Rx, i and p are the same as those in the above-described first embodiment.
The method for producing the polycarbonate resin of the present invention is not particularly limited, and any publicly-known method can be employed. Examples of the method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method for a cyclic carbonate compound and a solid phase transesterification method for a prepolymer. Among them, a melt transesterification method and an interfacial polymerization method are preferred, and more preferred is a melt transesterification method.
The polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin of the present invention is preferably 1,000-60,000, and more preferably 5,000-40,000. The lower limit is even more preferably 6,000 or more, and particularly preferably 7,000 or more, and the upper limit is even more preferably 37,000 or less, and particularly preferably 35,000 or less. When the weight average molecular weight (Mw) is more than the above-described upper limit, compatibility tends to be reduced. When the weight average molecular weight is lower than the above-described lower limit, a gas tends to be generated at the time of molding.
The weight average molecular weight (Mw) of the polycarbonate resin of the present invention can be adjusted by selection of Mw of a polyalkylene glycol that is one of raw materials of a comonomer diol, adjustment of the ratio of the carbonate precursor, addition of a terminator, adjustment of the temperature or pressure at the time of polymerization, or the like. For example, in the melt transesterification method, Mw can be increased by adjusting the monomer raw material ratio so that the reaction ratio between diphenyl carbonate that is a carbonate precursor monomer and a diol monomer becomes close to 1, keeping a high polymerization temperature so that a by-product phenol can be easily removed from the polymerization system, reducing the pressure as low as possible, actively carrying out interface renewal by means of stirring, etc.
Note that the weight average molecular weight (Mw) of the polycarbonate resin of the present invention is a polystyrene equivalent molecular weight measured using GPC with chloroform as a developing solvent.
Specifically, it is a value obtained as a polystyrene equivalent molecular weight (weight average molecular weight) using a high-speed GPC apparatus “HLC-8320” manufactured by Tosoh Corporation as GPC, columns: HZ-M (4.6 mm×150 mm)×3 manufactured by Tosoh Corporation (connected in series), and an eluant: chloroform, at a measurement temperature: 25° C.
The concentration of a terminal hydroxyl group in the polycarbonate resin of the present invention is preferably 1 ppm to 3000 ppm from the viewpoint of maintaining hydrolysis resistance, and it is more preferably 1-1000 ppm, and particularly preferably 1-500 ppm. In the present invention, as the method for measuring the concentration of the terminal hydroxyl group, the method described in the Examples below can be used.
The glass transition temperature (Tg) of the polycarbonate resin of the present invention is preferably −100 to 140° C. from the viewpoint of ease of handling, and it is more preferably −70 to 120° C., and particularly preferably −70 to 110° C. In the present invention, as the method for measuring the glass transition temperature, the method described in the Examples below can be used.
The polycarbonate resin of the present invention may contain additives other than those described above, for example, an antioxidant, a mold release agent, an ultraviolet absorber, a fluorescent brightener, a pigment, a dye, another polymer other than the polycarbonate resin, a flame retardant, an impact resistance improver, an antistatic agent, a plasticizer, a compatibilizer, etc. These additives may be blended solely, or two or more of them may be blended.
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the below-described examples.
It was obtained by dissolving 0.05 g of a resin sample in 1 ml of deuterated chloroform (containing 0.05 w/v % TMS) and carrying out the 1H-NMR measurement at 23° C. Specifically, the concentration of the terminal hydroxyl group (OH concentration) was calculated from the integration ratio between a peak related to the hydroxyl group and other peaks included in the resin skeleton.
Apparatus: 500 MHz nuclear magnetic resonance apparatus AVANCE III HD manufactured by BRUKER
Using GPC with chloroform as a developing solvent, a calibration curve was produced using a standard polystyrene having an already-known molecular weight (molecular weight distribution=1) (“PStQuick MP-M” manufactured by Tosoh Corporation). The elution time and molecular weight value of each peak were plotted based on the measured standard polystyrene, and three-dimensional approximation was conducted to obtain a calibration curve. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained as polystyrene equivalent values using the below-described calculation formula.
Mw=Σ(Wi×Mi)÷Σ(Wi) [Calculation formula]
In this regard, “i” represents the “i”th dividing point when dividing the molecular weight M, “Wi” represents the “i”th weight, and “Mi” represents the “i”th molecular weight. The molecular weight M represents the value of the molecular weight of polystyrene at the corresponding elution time in the calibration curve.
Apparatus: HLC-8320GPC manufactured by Tosoh Corporation
Guard column: TSKguardcolumn SuperMPHZ-M×1
Analysis column: TSKgel SuperMultiporeHZ-M×3
Solvent: HPLC grade chloroform
Injection amount: 10 VL
Sample concentration: 0.2 w/v % HPLC grade chloroform solution
Flow rate of solvent: 0.35 ml/min
Measurement temperature: 40° C.
The measurement was carried out using an apparatus for simultaneous thermogravimetry/differential thermal analysis (TG/TDA) (product name “TGDTA7300” manufactured by Hitachi High-Tech Science Corporation).
5 mg of a sample was precisely weighed in a platinum pan (Pt open type sample container, cylindrical container having a diameter of 5.2 mm and a height of 5.0 mm) to prepare a measurement sample.
The measurement was carried out under nitrogen atmosphere (flow rate of nitrogen: 250 ml/min). For a reference cell, 5.52 mg of α-alumina was used as a reference substance. Further, the measurement sample was heated to measure the weight thereof as described later. Assuming that the whole decreased weight corresponds to the gasified sample, the amount of gas generated (%) “120° C.→350° C.” was calculated as described below.
Amount of gas generated (%) “120° C.→350° C.”=(weight at 350° C.-weight at 120° C.)/weight at 120° C.×100
The amount of gas generated (%) “120° C.→320° C.” was calculated as described below.
Amount of gas generated (%) “120° C.→320° C.”=(weight at 320° C.-weight at 120° C.)/weight at 120° C.×100
In this regard, the weight at 350° C. means a weight obtained when the temperature of the measurement sample was elevated from 120° C. at a rate of 10° C./min to reach 350° C. The weight at 120° C. means a weight obtained after the temperature of the measurement sample was elevated from room temperature to 120° C. at a rate of 10° C./min and then kept at 120° C. for 2 hours. The weight at 320° C. means a weight obtained when the temperature of the measurement sample was elevated from 120° C. at a rate of 10° C./min to reach 320° C.
The measurement was carried out using a differential scanning calorimeter (DSC) (product name “DSC-7000” manufactured by Hitachi High-Tech Science Corporation).
7 to 12 mg of a test piece was precisely weighed in a sample container for AI autosampler (RDC aluminum pan, cylindrical container having a diameter of 6.8 mm and a height of 2.5 mm), and the upper portion of the sample container was sealed using a cover for AI autosampler, thereby preparing a measurement sample.
The measurement was carried out under nitrogen atmosphere (flow rate of nitrogen: 50 ml/min). For a reference cell, 10.0 mg of alumina was used as a reference substance. Further, the temperature of the measurement sample was adjusted to −70° C. and then elevated to 200° C. at a rate of 10° C./min. After that, cooling was carried out at a rate of 10° C./min to decrease the temperature to −70° C. After that, the temperature was elevated again to 200° C. at a rate of 10° C./min, and the measurement was carried out.
The measurement was carried out using a spectroscopic colorimeter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, 12 g of a resin sample was dissolved in 60 mL of dichloromethane, and the measurement was carried out using a quartz cell having an optical path length of 6 cm. As a blank, dichloromethane was used.
As raw materials, a poly-n-propylene glycol Velvetol H500 (Mw: 1700) manufactured by ALLESSA in an amount equivalent to 85% by mass, bisphenol A (hereinafter referred to as BPA) in an amount equivalent to 15% by mass, and diphenyl carbonate (hereinafter referred to as DPC) at a molar ratio relative to diol of 1.16 were put into a polymerization apparatus equipped with a three-necked flask. Further, as a catalyst, an aqueous solution of Cs2CO3 was added thereto in an amount of 11 μmol (as Cs) per 1 mol of diol.
Drying in the system was carried out for 1 hour, and then the pressure in the polymerization apparatus was recovered using nitrogen. The polymerization was initiated at the point when the polymerization apparatus in which the pressure was recovered was immersed in an oil bath, and the polymerization was carried out according to the temperature elevation/pressure reduction program shown in Table 1. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 1 was 70 ppm.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 2 was 240 ppm, and the concentration of OH in the polycarbonate resin obtained in Example 3 was 1100 ppm.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 2. Physical properties of the obtained polycarbonate resin are shown in Table 5.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 3. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 5 was 2200 ppm.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 4. Physical properties of the obtained polycarbonate resin are shown in Table 5.
The reaction was performed in a manner similar to that in Example 4, except that the raw materials were changed to those shown in Table 5. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Comparative Example was 850 ppm.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 6. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 7. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 8. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 9. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 10. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 11. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 12. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 13. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 14. Physical properties of the obtained polycarbonate resin are shown in Table 17.
The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 15. Physical properties of the obtained polycarbonate resin are shown in Table 17.
When using the polycarbonate resin of the present invention, the amount of gas generated is very small, and therefore it can be suitably utilized for various molded products.
In general, a polycarbonate resin has a high Tg, and for this reason, at the time of melt molding, it is required to be heated to a high temperature (180° C. or higher) and melted. For reduction of the cost for molding, molding at lower temperatures has been desired. Further, as a material for various industrial products, a polycarbonate having a low Tg has been desired. For example, though Tg of a widely-known bisphenol A-type polycarbonate resin is generally about 150° C., a material having a Tg lower than that has been desired. In the present invention, the copolymerized polycarbonate of polytetramethylene glycol and bisphenol A, and in particular, the copolymerized polycarbonate of poly-n-propylene glycol and bisphenol A have a low Tg and can be widely and usefully used as materials for industrial products.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-173685 | Sep 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/033013 | 9/1/2020 | WO |
