JP7643022B2 - Polycarbonate resin and polycarbonate resin composition - Google Patents

Description

The present invention relates to a polycarbonate resin excellent in color, thermal stability and flexibility, and a polycarbonate resin composition excellent in mechanical strength and heat resistance.

Polycarbonate resins are generally made of bisphenols as monomer components, and are used in a wide range of applications, including electrical and electronic components, automotive parts, optical recording media, and other applications, taking advantage of their superior properties such as transparency, heat resistance, and mechanical strength.
It is widely used as a so-called engineering plastic in the optical field such as lenses. On the other hand, due to concerns about global warming caused by the depletion of petroleum resources and the increase in carbon dioxide emissions, there is a demand for the development of plastics made from carbon-neutral plant-derived monomers. In this situation, polycarbonate resins produced using isosorbide (hereinafter sometimes referred to as "ISB"), a plant-derived raw material, have been developed in recent years and have begun to be used for automobile parts, optical applications, and glass replacement applications (see, for example, Patent Documents 1 and 2).

Polycarbonate resins obtained from ISB not only have excellent optical properties, but also have extremely excellent weather resistance and surface hardness compared to conventional aromatic polycarbonate resins. On the other hand, further improvement in mechanical properties such as tensile elongation or impact resistance at parts where stress is concentrated is required. In response to this problem, for example, Patent Document 3 discloses a method for improving impact resistance by adding an elastomer to a polycarbonate resin.

International Publication No. 2004/111106 International Publication No. 2007/148604 JP 2017-88774 A

As disclosed in Patent Document 3, by blending an elastomer with a polycarbonate resin, excellent improvement in impact resistance can be expected, but in many cases, the materials used as impact improvers are derived from petroleum and other mainly exhaustible resources. In recent years, as the use of non-exhaustible resources is increasingly expected, society is demanding resins that have a higher biomass content and excellent practical properties.

An object of the present invention is to provide a polycarbonate resin which is excellent in hue, thermal stability and flexibility, and a polycarbonate resin composition which uses the same and which has excellent impact resistance and heat resistance.

As a result of intensive research aimed at solving the above problems, the present inventors have found a polycarbonate resin that has excellent flexibility, color, and thermal stability by using a compound produced from a plant-derived raw material. Furthermore, by using the polycarbonate resin as an impact resistance improver, they have found a polycarbonate resin composition that has a high biomass content and is excellent in impact resistance and heat resistance. That is, the gist of the present invention is as follows.

[1] A polycarbonate resin containing at least a structural unit represented by formula (1) and a structural unit represented by formula (2), the structural unit represented by formula (1) being contained in an amount of 10% by weight or more and 7% by weight or less.
0% by weight or less of a structural unit represented by the formula (2), and 30% by weight or more and 80% by weight or less of a structural unit represented by the formula (2).

(In formula (2), n is 2 or more.)
[2] The average value of n in the structural unit represented by the formula (2) is 3 or more and 45 or less, [
1] The polycarbonate resin according to 1).
[3] The polycarbonate resin according to [1] or [2], which has a number average molecular weight of 15,000 or more and 50,000 or less as calculated by ¹ H-NMR analysis.
[4] A polycarbonate resin composition comprising the polycarbonate resin according to any one of [1] to [3] (first polycarbonate resin) and a polycarbonate resin (second polycarbonate resin) having at least a structural unit represented by the formula (1) and a structure different from that of the first polycarbonate resin,
The second polycarbonate resin contains 40% by weight or more of the structural unit represented by the formula (1),
Contains 90% by weight or less,
The weight ratio of the first polycarbonate resin to the second polycarbonate resin is 1/99.
The polycarbonate resin composition has a viscosity of 100:1 or less.
[5] The polycarbonate resin composition according to [4], wherein the second polycarbonate resin has a glass transition temperature of 90° C. or higher and 200° C. or lower.
[6] The polycarbonate resin composition according to [4] or [5], wherein the second polycarbonate resin contains a structural unit derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound.
[7] An acrylic resin containing 50% by weight or more of a structural unit represented by the following formula (3) in an amount of 0.
The polycarbonate resin composition according to any one of [4] to [6], containing 01% by weight or more and 10% by weight or less of a tertiary amine.

(In formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. ^{R 2} is an aryl group which may have a substituent or an aralkyl group which may have a substituent.)
[8] The polycarbonate resin composition according to any one of [4] to [7], further comprising 0.1% by weight or more and 10% by weight or less of polytrimethylene ether glycol having a number average molecular weight of 300 or more and 10,000 or less.
[9] A method for producing the polycarbonate resin according to any one of [1] to [3], comprising a step of polycondensing a dihydroxy compound forming a structural unit represented by formula (1), a dihydroxy compound forming a structural unit represented by formula (2), and a carbonate diester as monomer raw materials by transesterification,
In the step, the dihydroxy compound forming the structural unit represented by the formula (2) is polytrimethylene ether glycol, and the number average molecular weight of the polytrimethylene ether glycol is 200 or more and 2,500 or less.

The polycarbonate resin of the present invention is excellent in hue, thermal stability, and flexibility. In addition, the polycarbonate resin composition of the present invention is excellent in mechanical strength and heat resistance. By using such a polycarbonate resin or polycarbonate resin composition, it is possible to obtain a high-quality molded product. The polycarbonate resin or polycarbonate resin composition of the present invention can also be made into a resin having a high biomass ratio, and the widespread use of resin materials having a high biomass ratio can contribute to the realization of a sustainable society.

The present invention will be described in detail below, but the present invention is not limited to the following description and can be modified in any manner without departing from the gist of the present invention.

In this specification, when "~" is used to express a numerical value or a physical property value,
It will be used including the values before and after it.

In this specification, the term "repeated structural unit" refers to a structural unit in which the same structure appears repeatedly in a resin, and each of the structural units is linked to form the resin. For example, in the case of a polycarbonate resin, the carbonyl group is also referred to as the repeating structural unit. In addition, the term "structural unit" refers to a partial structure that constitutes a resin, and a specific partial structure contained in the repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerizable reactive group present at the end of a polymer and a linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is the linking group, and a partial structure sandwiched between adjacent carbonyl groups is referred to as a structural unit. In this specification, the weight ratio of each structural unit in a polycarbonate resin is calculated by assuming the total weight of all structural units and linking groups to be 100% by weight.

[Polycarbonate resin]
A first aspect of the present invention is a polycarbonate resin containing at least a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), the polycarbonate resin containing 10% by weight or more and 70% by weight or less of the structural unit represented by the formula (1) and 30% by weight or less of the structural unit represented by the formula (2).
The polycarbonate resin contains 80% by weight or more and 80% by weight or less.
The structural unit represented by the formula (1) may be referred to as a “structural unit (1)”, and the structural unit represented by the formula (2) may be referred to as a “structural unit (2)”. In the second embodiment described later, the polycarbonate resin may be referred to as a “first polycarbonate resin”.

式（２）中、ｎは２以上である。

In formula (2), n is 2 or more.

The dihydroxy compound forming the structural unit (1) includes isosorbide (ISB), isomannide, and isoidet, which are stereoisomers. These may be used alone or in combination of two or more. Among them, isosorbide obtained by dehydration condensation of sorbitol produced from various starches, which are abundant and easily available as a plant-derived resource, is most preferred in terms of availability, ease of production, and properties of the resulting molded product (e.g., heat resistance, impact resistance, surface hardness, carbon neutrality). Also, it is preferable to use isosorbide from the viewpoint of carbon neutrality.

The weight ratio of the structural unit (1) in the polycarbonate resin of the present invention is 10% by weight or more, and 70% by weight or more.
% by weight or less, and the lower limit is more preferably 15% by weight or more, even more preferably 20% by weight or more, and particularly preferably 25% by weight or more. The upper limit is more preferably 60% by weight or less, even more preferably 55% by weight or less, and particularly preferably 50% by weight or less. Within the above range, the solidification temperature of the resulting polycarbonate resin can be made to be room temperature or higher, and when the polycarbonate resin is made into pellets and handled, fusion of the pellets can be prevented. In addition, the structural unit (1
) forms a hard segment, enabling the polymer molecular chain to exhibit high tensile strength.

As the dihydroxy compound forming the structural unit (2), polytrimethylene ether glycol (PO3G) is used. PO3G is a 1,3-
It is preferable to use PO3G with a biomass content of 100%, which is synthesized by condensing propanediol. Whether isosorbide or PO3G is produced from a plant-derived resource can be confirmed, for example, by measuring the concentration of radioactive carbon ( ^14C ).

The number average molecular weight of PO3G is preferably 200 or more and 2500 or less. The lower limit is more preferably 300 or more, further preferably 400 or more, and particularly preferably 450 or more. The upper limit is 200
More preferably 0 or less, even more preferably 1,500 or less, particularly preferably 1,200 or less,
The number average molecular weight of PO3G and the average polymerization degree of the structural unit (2) in the polycarbonate resin (the average value of n) are preferably 2 or more and 45 or less. The lower limit is more preferably 5 or more, even more preferably 6 or more, and particularly preferably 7 or more. The upper limit is more preferably 35 or less, even more preferably 25 or less, and particularly preferably 20 or less.
When the average degree of polymerization of is within the above range, the transparency of the copolymer polycarbonate containing the structural unit (1) and the structural unit (2) is improved. In addition, the polymer molecular chain containing the structural unit (2) forms a soft segment, which exhibits high tensile elongation and excellent impact resistance. Furthermore, when the polycarbonate resin of the present invention is used as a modifier and blended with other resins, the impact resistance of the resin composition can be improved. The number average molecular weight of PO3G is calculated from the analysis of the hydroxyl value described later.

The weight ratio of the structural unit (2) in the polycarbonate resin of the present invention is 30% by weight or more, and 80% by weight or more.
% by weight or less, and the lower limit is more preferably 35% by weight or more, further preferably 40% by weight or more, and particularly preferably 42% by weight or more. The upper limit is more preferably 78% by weight or less, further preferably 75% by weight or less, and particularly preferably 70% by weight or less. Within the above range, the structural unit (
Polymer molecular chains containing 2) form soft segments, which exhibit high tensile elongation and excellent impact resistance. Furthermore, when the polycarbonate resin of the present invention is used as a modifier and blended with other resins, the impact resistance of the resin composition can be improved.

The properties of PO3G are explained by comparing it with similar compounds such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene ether glycol (PTMG). PEG has good compatibility with the structural unit (1),
A copolymerized polycarbonate resin of the structural unit (1) and PEG is a resin with relatively high transparency. However, because the compatibility is too high, no phase separation form is formed to express elastomeric properties, and the performance such as tensile elongation is inferior to PO3G. In addition, PEG is easily colored during the polymerization reaction, and the hue is inferior. PO3G has a moderate compatibility with the structural unit (1), and therefore forms a form in which the phase consisting of the PO3G structural unit is uniformly dispersed in microns, and thus expresses excellent flexibility and impact resistance. As for PPG, a transparent and flexible resin can be obtained like PO3G, but PPG has a disadvantage of having a relatively low thermal decomposition temperature and is inferior in thermal stability. PTMG is not easily compatible with the structural unit (1), and therefore a transparent resin cannot be obtained. In addition, it causes non-uniform phase separation, and therefore the flexibility and impact resistance modification effect are inferior. In addition, the thermal stability is also inferior.

The polycarbonate resin of the present invention may contain structural units other than the structural unit (1) and the structural unit (2). Hereinafter, structural units other than the structural unit (1) and the structural unit (2) may be referred to as "other structural units". Examples of compounds forming other structural units include aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, ether-containing dihydroxy compounds, acetal-containing dihydroxy compounds, aromatic-containing dihydroxy compounds, and diester compounds. Note that polycarbonate resins partially incorporating structural units derived from diester compounds are referred to as polyester carbonate resins. In this specification, polycarbonate resins include polyester carbonate resins.

Examples of the aliphatic dihydroxy compound include the following dihydroxy compounds: ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4
linear aliphatic dihydroxy compounds such as 1,5-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; and branched aliphatic dihydroxy compounds such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

Examples of the alicyclic dihydroxy compound include the following dihydroxy compounds: 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4
-Cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2
dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by dihydroxy compounds derived from terpene compounds such as 1,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and limonene; dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. Examples of the oxyalkylene glycol that can be used include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of acetal-containing dihydroxy compounds include spiroglycol (also known as 3,
9-Bis(1,1-dimethyl-2-hydroxyethyl-2,4,8,10-tetraoxaspiro[5,5]undecane) and dioxane glycol (also known as 2-(1,1-dimethyl-2-hydroxyethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane)
etc. can be used.

As the aromatic dihydroxy compound, for example, the following dihydroxy compounds can be used: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2
,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1
-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(
2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-
1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihyd aromatic bisphenol compounds such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone; dihydroxy compounds having an ether group bonded to an aromatic group such as 9,9-bis(4-
(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(
4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(
4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-
bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene,
9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6
dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene, and the like;

Examples of the diester compound include the following dicarboxylic acids: aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid;
Alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. These dicarboxylic acid components can be used as raw materials for polyester carbonate resins as dicarboxylic acids themselves, but depending on the production method, dicarboxylic acid esters such as methyl esters and phenyl esters, and dicarboxylic acid derivatives such as dicarboxylic acid halides can also be used as raw materials.

When other structural units are introduced into the polycarbonate resin of the present invention, the content of the other structural units is relatively small, and it is preferable to use the other structural units for the purpose of adjusting the heat resistance, refractive index, and compatibility with other resins, or for the purpose of improving the transparency of the polycarbonate resin of the present invention (improving the compatibility of the structural unit (1) and the structural unit (2)). Among the above-mentioned other structural units, from the viewpoint of adjusting various physical properties such as mechanical properties, heat resistance, and refractive index without impairing weather resistance, aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and aromatic-containing dihydroxy compounds are preferred. Since the structural unit (2) has a structure with a relatively low refractive index, the refractive index of the resulting polycarbonate resin can be adjusted to be higher by copolymerizing an aromatic-containing dihydroxy compound with a high refractive index. When the polycarbonate resin of the present invention is blended with other resins and used as a resin composition, the transparency of the resulting resin composition can be improved by matching the refractive index with the other resin. From the viewpoint of improving heat resistance and hardness, aromatic-containing dihydroxy compounds, alicyclic dihydroxy compounds, acetal-containing dihydroxy compounds, and diester compounds are preferred. Among the above dihydroxy compounds, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, spiroglycol, and 2,2-bis(4-hydroxyphenyl)propane are particularly useful.

When the polycarbonate resin of the present invention contains other structural units, the content ratio of the other structural units in the polycarbonate resin of the present invention is preferably 1% by weight or more, more preferably 2% by weight or more, and is preferably 20% by weight or less, more preferably 10% by weight or less.
Within the above range, other desired properties can be imparted without impairing the resin properties obtained from the structural units (1) and (2).

By using aromatic dihydroxy compounds or diester compounds such as bisphenol compounds as copolymerization components, the heat resistance of polycarbonate resins can be improved in some cases, but on the other hand, when the polycarbonate resin contains a large amount of aromatic structures, the weather resistance tends to decrease. In addition, since there is a large difference in the polymerization reactivity between bisphenol compounds or diester compounds and dihydroxy compounds forming structural units (1) or structural units (2), the bisphenol compounds or diester compounds remain in the terminal groups, making it difficult to obtain a polycarbonate resin with a high molecular weight, and mechanical properties such as impact resistance tend to decrease. If the reaction temperature is raised to a high level in order to promote the reaction, the structural unit (1) is thermally decomposed, and the resulting polycarbonate resin tends to become colored. For these reasons, the content ratio of structural units derived from aromatic dihydroxy compounds or diester compounds is preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

[Method for producing first polycarbonate resin]
The first polycarbonate resin can be synthesized by a process of polycondensation through an ester exchange reaction using as raw materials at least a dihydroxy compound forming a structural unit represented by the formula (1), a dihydroxy compound forming a structural unit represented by the formula (2), and a carbonate diester.
More specifically, it can be obtained by removing from the system the monohydroxy compound and the like which are by-produced in the transesterification reaction in addition to the polycondensation.

In this step, the dihydroxy compound forming the structural unit (1) and the dihydroxy compound forming the structural unit (2) are the same as those described above. In particular, it is preferable that the dihydroxy compound forming the structural unit (2) is polytrimethylene ether glycol, and the number average molecular weight of the polytrimethylene ether glycol is 200 to 2500. The lower limit is more preferably 300 or more, even more preferably 400 or more, and particularly preferably 450 or more. The upper limit is more preferably 2000 or less, even more preferably 1500 or less, and particularly preferably 120
It is particularly preferably 0 or less, and most preferably 1100 or less.
The transparency of the copolymer polycarbonate containing the structural unit (2) is improved. In addition, the polymer molecular chain containing the structural unit (2) forms a soft segment, which exhibits high tensile elongation, and when the polycarbonate resin of the present invention is used as a modifier and blended with other resins, the impact resistance of the resin composition can be improved. The number average molecular weight of PO3G is calculated from the analysis of the hydroxyl value described later.

The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst is referred to as a "polymerization catalyst"). The type of polymerization catalyst determines the reaction rate of the transesterification reaction,
And it can have a significant effect on the quality of the resulting polycarbonate resin.

The polymerization catalyst is used to improve the transparency, color tone, heat resistance, weather resistance, and other properties of the resulting polycarbonate resin.
There is no particular limitation as long as it can satisfy the requirements for the above and mechanical properties.
Metal compounds of Group I or Group II (hereinafter simply referred to as "Group 1" and "Group 2") in the long form periodic table, as well as basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used, and among these, Group 1 metal compounds and/or Group 2 metal compounds are preferred.

Examples of Group 1 metal compounds include the following compounds: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborate, potassium phenylborate, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate,
Lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium salt, dipotassium salt, dilithium salt and dicesium salt of bisphenol A, etc. As the Group 1 metal compound, from the viewpoints of polymerization activity and color tone of the obtained polycarbonate resin, lithium compounds are preferred.

Examples of Group 2 metal compounds include the following compounds: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. As the Group 2 metal compound, magnesium compounds, calcium compounds, or barium compounds are preferred, and from the viewpoints of polymerization activity and color tone of the resulting polycarbonate resin, magnesium compounds and/or calcium compounds are more preferred, and calcium compounds are most preferred.

Although it is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the Group 1 metal compound and/or the Group 2 metal compound, it is more preferable to use only the Group 1 metal compound and/or the Group 2 metal compound, and from the viewpoint of the color tone of the resulting polycarbonate resin, it is most preferable to use only the Group 2 metal compound.

The amount of the polymerization catalyst used was 1 μm per 1 mol of the total dihydroxy compound used in the reaction.
The amount of the polymerization catalyst used is preferably 30 μmol or more per mol of the total dihydroxy compounds used in the reaction.
It is preferably 0 μmol or less, more preferably 200 μmol or less, and particularly preferably 100 μmol or less.

By adjusting the amount of the polymerization catalyst used within the above-mentioned range, the polymerization rate can be increased, and therefore it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and therefore deterioration in the color tone of the polycarbonate resin can be suppressed.
In addition, since it is possible to prevent the unreacted raw materials from volatilizing during the polymerization, which would cause the molar ratio of the dihydroxy compound and the carbonic acid diester to be lost, it is possible to more reliably obtain a resin having a desired molecular weight and copolymerization ratio. Furthermore, since it is possible to suppress the occurrence of side reactions, it is possible to further prevent the color tone of the polycarbonate resin from deteriorating or the coloring during molding.

Considering the adverse effects of sodium, potassium, and cesium among the group 1 metals on the color tone of polycarbonate resin, and the adverse effects of iron on the color tone of polycarbonate resin, the total content of sodium, potassium, cesium, and iron in polycarbonate resin is 1 ppm by weight or less.
m or less. In this case, the deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be further improved. From the same viewpoint, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is more preferably 0.5 weight ppm or less. These metals may be mixed not only from the catalyst used, but also from the raw materials or reaction equipment. Regardless of the source, the total amount of the compounds of these metals in the polycarbonate resin is preferably within the above-mentioned range as the total content of sodium, potassium, cesium, and iron.

The method of polycondensing a dihydroxy compound and a carbonic acid diester is carried out in multiple stages using multiple reactors in the presence of the above-mentioned catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise manner and a continuous manner, but it is preferable to adopt a continuous manner, which is excellent in productivity and can obtain a polycarbonate resin with less heat history.

From the viewpoint of controlling the polymerization rate and the quality of the obtained polycarbonate resin, it is important to appropriately select the jacket temperature, the internal temperature, and the pressure in the reaction system according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction, and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stage of the reaction.
In this case, the distillation of unreacted monomers is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester can be easily adjusted to a desired ratio. As a result, the decrease in the polymerization rate can be suppressed. In addition, it becomes possible to more reliably obtain a polymer having a desired molecular weight and terminal group.

By adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and prevent the increase in the heat history of the product. Furthermore, it is possible to further prevent the volatilization of the monomer and the decomposition and coloration of the polycarbonate resin. Specifically, the following conditions can be adopted as the reaction conditions in the first stage reaction. That is, the maximum temperature inside the polymerization reactor is usually 16
The temperature is set within the range of 0 to 230° C., preferably 170 to 220° C., and more preferably 180 to 210° C. The pressure in the polymerization reactor (hereinafter, pressure refers to absolute pressure) is usually set within the range of 1 to 11
The pressure is set in the range of 0 kPa, preferably 5 to 50 kPa, and more preferably 7 to 30 kPa. The reaction time is set in the range of usually 0.1 to 10 hours, and preferably 1 to 5 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound outside the reaction system.

From the second stage onwards, the pressure in the reaction system is gradually lowered from the pressure in the first stage, and the monohydroxy compounds that are subsequently generated are removed from the reaction system, and the pressure (absolute pressure) of the reaction system is finally reduced to 1.
The maximum internal temperature of the polymerization reactor is usually 200 to 300 kPa.
The reaction temperature is set to 260° C., preferably 210 to 240° C., and particularly preferably 215 to 230° C. The reaction time is set to usually 0.1 to 10 hours, preferably 0.5 to 5 hours, and particularly preferably 1 to 3 hours.

When it is confirmed that the specified melt viscosity (molecular weight) has been reached using the stirring power as an indicator, the polymerization reaction is stopped by introducing nitrogen into the reactor to return the pressure to normal pressure or by withdrawing the molten resin from the reactor. The molten resin is discharged from the die head in the form of strands,
The resin is cooled and solidified, and then pelletized using a rotary cutter or the like. If necessary, extrusion devolatilization, extrusion kneading, and extrusion filtration processes may be added before pelletization. In these processes, additives are mixed into the resin, low molecular weight components are devolatilized using a vacuum vent, and foreign matter is removed using a polymer filter. In the examples described below, some resins do not solidify at room temperature. In such cases, the molten resin after the polymerization reaction is extracted in a lump state, and the resin is cut into pellets for use in molding and evaluation.

[Additives]
In the range not impairing the effects of the present invention, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers,
Examples of the additives include fillers and other filling agents, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity imparting agents, crosslinking agents, crosslinking assistants, metal deactivators, molecular weight regulators, antibacterial agents, antifungal materials, fluorescent brightening agents, and light diffusing agents such as organic diffusing agents and inorganic diffusing agents. These additives can be used within the range that does not impair the effects of the present invention.

When the first polycarbonate resin is used as a modifier and blended with other resins, it is preferable to add an acidic compound that deactivates (neutralizes) the polymerization catalyst and an antioxidant from the viewpoint of improving stability during melt processing, since the first polycarbonate resin is mixed by melt extrusion kneading. As the acidic compound, phosphonic acid and phosphonic acid ester are particularly preferable. It is preferable to add the acidic compound in an amount that is 0.5 to 3 times the mol of the polymerization catalyst metal in the resin.

[Characteristics of the first polycarbonate resin]
Biomass Degree In the present invention, the biomass degree of the first polycarbonate resin is defined as the weight ratio of structural units synthesized from plant-derived resources to all structural units constituting the polycarbonate resin. The biomass degree of the first polycarbonate resin is preferably 80% by weight or more. It is particularly preferably 85% by weight or more. In the examples described later, ISB, PO3G,
1,3-PDO is synthesized from plant-derived resources, and other PEG and PP are
Since G, PTMG, CHDM, and DPC are synthesized from fossil resources, the biomass degree of the polycarbonate resin synthesized using these is the sum of the weight ratios of the structural units derived from ISB, the structural units derived from PO3G, and the structural units derived from 1,3-PDO.

Transparency The first polycarbonate resin may be transparent or opaque, but is preferably transparent from the viewpoint of expanding the range of applications to which it can be applied. Regarding the evaluation of transparency, since the solidification temperature of the polycarbonate resin of the present invention is below room temperature and it may be difficult to mold it into a certain shape, whether the obtained resin pellet is transparent or opaque is evaluated by visual inspection.

The hue of the first polycarbonate resin can be evaluated by the YI of the pellets described later.
The absolute value of YI of the pellets is preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less.

・Flexibility (tensile elongation, tensile modulus)
The flexibility of the first polycarbonate resin can be evaluated by the tensile elongation and tensile modulus described later, and the tensile elongation of the first polycarbonate resin is preferably 300% or more, more preferably 350% or more, even more preferably 400% or more, and particularly preferably 450% or more.
The tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less, and more preferably 50 MPa or less.
When the above range is satisfied, the composition can be suitably used in applications where toughness is required, or as an impact modifier for other resins.

Thermal Stability The thermal stability of the first polycarbonate resin can be evaluated by the 5% weight loss temperature described later. The 5% weight loss temperature of the first polycarbonate resin is preferably 330° C. or higher.
C. or higher, more preferably 350.degree. C. or higher, particularly preferably 350.degree. C. or higher. Within this range, deterioration of properties due to thermal decomposition during melt processing can be sufficiently suppressed.

Number Average Molecular Weight The number average molecular weight of the first polycarbonate resin is preferably 15,000 or more and 50,000 or less. The lower limit is more preferably 20,000 or more, even more preferably 25,000 or more, and is preferably 300 or less.
00 or more is particularly preferred. The upper limit is more preferably 48,000 or less, and particularly preferably 45,000 or less. Within the above range, high tensile elongation, excellent flexibility, and impact resistance are obtained, and when blended with other resins, a phase separation form suitable for expressing impact resistance is easily formed. In addition, stickiness of the resin surface is suppressed, and when used in the form of pellets, fusion between pellets can be prevented. The number average molecular weight of the first polycarbonate resin is calculated by ¹ H-NMR analysis described later.

[Uses of the first polycarbonate resin]
The polycarbonate resin of the present invention is excellent in transparency, thermal stability, flexibility, etc., and is therefore useful in a wide range of applications, including vibration-proofing materials, vibration-damping materials, cushioning materials, soundproofing materials, sound-absorbing materials, footwear applications, sealing materials, various grips, medical devices, adhesives, viscosity modifiers added to oils and lubricants, agricultural films, 3D
It can be used as a modeling material for printers, a resin modifier, etc. Among them, it is preferable to use it by kneading with other resins as a modifier for improving impact resistance and flexibility.

[Polycarbonate resin composition]
A second aspect of the present invention is a resin composition containing a first polycarbonate resin and a polycarbonate resin (hereinafter sometimes referred to as a second polycarbonate resin) that contains at least a structural unit represented by formula (1) above and has a structure different from that of the first polycarbonate resin, wherein the second polycarbonate resin contains 40% by weight or more and 90% by weight or less of the structural unit represented by formula (1), and the weight ratio of the first polycarbonate resin to the second polycarbonate resin is 1/99 to 99/1.
In the polycarbonate resin composition of the present invention, the weight ratio of the first polycarbonate resin to the second polycarbonate resin is preferably 2/98 to 90/10, more preferably 3/97 to 80/10.
Within the above range, various physical properties such as heat resistance, impact resistance, and transparency can be balanced at a high level.
The first polycarbonate resin and the second polycarbonate resin each contain the structural unit (1):
However, the resin structures are different from one another. Specifically, for example, the content of the structural unit (1) constituting each resin, the copolymerization components, the molecular weight, etc. are different.

[Second polycarbonate]
The content of the structural unit (1) in the second polycarbonate resin is 40% by weight or more and 90% by weight or less.
The lower limit is preferably 45% by weight or more, and more preferably 50% by weight or more.
The upper limit is more preferably 80% by weight or less, and particularly preferably 75% by weight or less.

The second polycarbonate resin may contain structural units derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound, or other structural units, and the content is preferably 1% by weight or more and 70% by weight or less. The lower limit is more preferably 5% by weight or more, and particularly preferably 10% by weight or more. The upper limit is more preferably 60% by weight or less, even more preferably 50% by weight or less, and particularly preferably 40% by weight or less.

In particular, since aliphatic dihydroxy compounds and alicyclic dihydroxy compounds have flexible molecular skeletons, it is preferable that the content of structural units derived from these compounds is within the above range, since heat resistance and fluidity suitable for melt processing can be obtained and mechanical properties such as tensile elongation and impact resistance can be improved. Dihydroxy compounds preferably used as the aliphatic dihydroxy compound and the alicyclic dihydroxy compound are the same as those in the first polycarbonate resin, and among them, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferably used because they have an excellent balance between heat resistance and mechanical properties.

The second polycarbonate resin may contain structural units other than the structural units derived from the aliphatic dihydroxy compound and the alicyclic dihydroxy compound. As in the first embodiment, examples of the compounds forming the other structural units include ether-containing dihydroxy compounds, acetal-containing dihydroxy compounds, dihydroxy compounds containing an aromatic structure, and diester compounds.

The second polycarbonate resin may contain a structural unit represented by structural unit (2). The content is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less. Within the above range, the first polycarbonate resin and the second polycarbonate resin undergo appropriate phase separation, and high impact resistance can be exhibited.

[Characteristics of the second polycarbonate resin]
Biomass Degree The biomass degree in the second polycarbonate resin is preferably 40% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more.

Glass Transition Temperature The glass transition temperature of the second polycarbonate resin is preferably 90° C. or higher and 200° C. or lower.
The lower limit is more preferably 100° C. or more, even more preferably 110° C. or more, and particularly preferably 120° C. or more. The upper limit is more preferably 180° C. or less, even more preferably 160° C. or less, and particularly preferably 150° C. or less.
A temperature of 0° C. or less is particularly preferred. Within the above range, the second polycarbonate resin can be used in a wide range of applications, can be easily melt-processed, and can easily achieve mechanical properties such as tensile elongation and impact resistance. The glass transition temperature of the second polycarbonate resin is measured by a differential scanning calorimeter described below. The glass transition temperature of the second polycarbonate resin can be appropriately adjusted, for example, by changing the type of structural unit constituting the resin, the copolymerization ratio, etc.

Number Average Molecular Weight The number average molecular weight of the second polycarbonate resin is preferably 8,000 or more and 30,000 or less. The lower limit is more preferably 8,500 or more, and particularly preferably 9,000 or more. The upper limit is 2,500.
The number average molecular weight of the second polycarbonate resin is more preferably 0 or less, and particularly preferably 20,000 or less. Within this range, the balance between mechanical properties such as impact resistance and fluidity during melt molding is excellent. The number average molecular weight of the second polycarbonate resin is calculated by ¹ H-NMR analysis described later.

[Method for producing second polycarbonate resin]
The second polycarbonate resin can be synthesized by a step of polycondensing monomer raw materials containing at least a dihydroxy compound and a carbonic acid diester that form the structural unit represented by (1) above through an ester exchange reaction.
The monomer raw material may contain, for example, an aliphatic dihydroxy compound or an alicyclic dihydroxy compound. The dihydroxy compounds preferably used as the aliphatic dihydroxy compound or the alicyclic dihydroxy compound are the same as those in the first polycarbonate resin,
Among these, it is particularly preferable to use 1,4-cyclohexanedimethanol and tricyclodecanedimethanol, since they have an excellent balance between heat resistance and mechanical properties.

[Additives for the polycarbonate resin composition of the present invention]
The polycarbonate resin composition of the present invention may contain other components such as additives in addition to the first polycarbonate resin and the second polycarbonate resin. In addition, within a range that does not impair the effects of the present invention, for example, one of synthetic resins such as polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, amorphous polyolefin, acrylic resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and acrylonitrile-styrene copolymer (AS resin); elastomers such as acrylic rubber and butadiene rubber; biodegradable resins such as polylactic acid and polybutylene succinate;
Alternatively, two or more of them may be kneaded with the above-mentioned polycarbonate resin. In other words, the polycarbonate resin composition may be a polymer alloy.

By using a relatively small amount of a compound compatible with the first polycarbonate resin as another component, the properties of the polycarbonate resin composition can be further improved. Among them, as the compound compatible with the first polycarbonate resin, an acrylic resin containing 50% by weight or more of a structural unit represented by the following formula (3) is preferable. The structural unit represented by the formula (3) may be referred to as "structural unit (3)".

式（３）中、Ｒ^１は水素原子、置換基を有していてもよい炭素数１～１０のアルキル基
である。Ｒ^２は置換基を有していてもよいアリール基、置換基を有していてもよいアラル
キル基である。

In formula (3), ^R1 is a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, ^{and R2} is an optionally substituted aryl group or an optionally substituted aralkyl group.

The present inventors have found that, in one embodiment, the acrylic resin is compatible with the first polycarbonate resin and incompatible with the second polycarbonate resin. To achieve such a state, R ¹ in the formula (3) is preferably a hydrogen atom or a methyl group,
^R2 is preferably a phenyl group or a benzyl group. That is, the vinyl compound forming the structural unit (3) is preferably phenyl acrylate, phenyl methacrylate, benzyl acrylate, or benzyl methacrylate. Among these, phenyl acrylate and
Phenyl methacrylate is preferred, and particularly phenyl acrylate.

The acrylic resin may be a homopolymer substantially free of structural units other than the structural unit (3), or may be a copolymerized acrylic resin containing structural units other than the structural unit (3). From the viewpoint of compatibility between the acrylic resin of the present invention and the first polycarbonate resin, the content of the structural unit (3) in the acrylic resin is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.

Examples of vinyl compounds that form structural units other than the structural unit (3) include methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, acrylonitrile, styrene, α-methylstyrene, and butadiene. Among these, from the viewpoint of improving thermal stability and mechanical properties, methyl acrylate and n-butyl acrylate are preferred. Since structural units other than the structural unit (3) are not compatible with the first polycarbonate resin, it is preferable that the content of these structural units is relatively small, and the content in the acrylic resin is preferably 10% by weight or less, and particularly preferably 5% by weight or less.

In the resin composition of the present invention, the acrylic resin is dissolved in the phase consisting of the first polycarbonate resin and plays a role in adjusting the refractive index. The first polycarbonate resin and the second polycarbonate resin are not completely compatible, so when they are mixed together, phase separation occurs. The first polycarbonate resin and the second polycarbonate resin usually have different refractive indices, so the resin composition does not become completely transparent. Here, since the refractive index of the first polycarbonate resin is usually lower than that of the second polycarbonate resin, by mixing the acrylic resin, which has a higher refractive index than the first and second polycarbonate resins, at an appropriate blending ratio, the refractive indexes of the two phases can be matched, and the transparency of the resin composition can be improved. In order not to impair the original characteristics of the first polycarbonate resin, it is preferable that the amount of the acrylic resin added is relatively small. In order to obtain the effect of increasing the refractive index even with a small amount, the refractive index of the acrylic resin is preferably 1.54 or more and 1.65 or less. The lower limit is more preferably 1.55 or more, and particularly preferably 1.56 or more. The upper limit is more preferably 1.63 or less, and particularly preferably 1.60 or less. When the refractive index is within the above range, the amount of the acrylic resin added can be kept small.

The polycarbonate resin composition of the present invention may contain polytrimethylene ether glycol. As can be easily imagined, PO3G is easily compatible with the first polycarbonate resin. In particular, since it dissolves in the phase consisting of the structural unit (2) in the first polycarbonate resin, the glass transition temperature of the soft segment is lowered, and the impact resistance can be further improved.

The number average molecular weight of PO3G is preferably 300 or more and 10,000 or less. The lower limit is more preferably 500 or more, even more preferably 1,000 or more, and particularly preferably 2,000 or more. The upper limit is more preferably 8,000 or less, and particularly preferably 5,000 or less. Within the above range, the first
It is possible to obtain compatibility with polycarbonate resins, and also to suppress bleeding out during melt processing and after forming into a molded product.

As other components, it is also preferable to include elastomers such as acrylic rubber and butadiene rubber. Of these, from the viewpoint of excellent impact resistance and transparency of the resin composition, it is preferable to include acrylic rubber, and more preferable to include acrylic rubber having a core-shell structure. Of these, alkyl acrylate-alkyl methacrylate-styrene copolymer is particularly preferable.

[Method of producing resin composition]
The resin composition can be produced, for example, by a method of mechanically melt-kneading each of the above-mentioned components constituting the resin composition. As the melt-kneader, for example, a single-screw extruder, a twin-screw extruder, a Brabender, a Banbury mixer, a kneader blender, a roll mill, etc. can be used. When kneading, each component may be kneaded at once, or a multi-stage division kneading method in which an arbitrary component is kneaded and then the remaining components are added and kneaded may be used. Among them, a method in which each component is continuously charged using a twin-screw extruder equipped with a vacuum vent and a resin composition is continuously obtained is preferable from the viewpoint of productivity and quality uniformity. The lower limit of the kneading temperature is usually 150° C. or more, preferably 180° C. or more, and more preferably 200° C. or more. The upper limit of the kneading temperature is usually 2
80° C. or less, preferably 260° C. or less, more preferably 250° C. or less, and particularly preferably 2
The temperature is not higher than 40° C. When the temperature is in this range, the productivity (the processing speed of kneading) can be increased while suppressing thermal deterioration caused by heating in the kneader or heat generation due to shear.

[Characteristics of polycarbonate resin composition]
Biomass Degree The resin composition of the present invention preferably has a biomass degree of 50% by weight or more. More preferably, the biomass degree is 55% by weight or more, even more preferably, 60% by weight or more, and particularly preferably, 65% by weight or more. In order to obtain a high biomass degree, it is preferable to use a structural unit (1) produced from a plant-derived raw material.
It is necessary to optimize the blending so as to obtain the desired physical properties while containing as much of the structural unit (2) as possible.

Impact strength The resin composition of the present invention has an Izod impact value of 15 kJ/ ^m2 as measured by the method described below.
It is preferable that the impact strength is 20 kJ/ ^m2 or more, more preferably 30 kJ/ ^m2 or more. If the impact strength is within the above range, the material has a sufficiently high impact resistance strength, and can be used for applications such as automobile interior parts that require high impact resistance properties, and for molded products having fitting parts that are prone to breakage due to stress concentration.

Heat Resistance The resin composition of the present invention has a deflection temperature under load of 90° C. or more, as measured by the method described below.
The lower limit is preferably 50° C. or lower. The lower limit is more preferably 92° C. or higher, and particularly preferably 95° C. or higher.
The upper limit is more preferably 140° C. or less, and particularly preferably 135° C. or less.
It has practical heat resistance, and also has excellent mechanical properties such as impact resistance and melt processability.

Transparency When the resin composition of the present invention is applied to an application requiring transparency, the haze value measured by the method described below is preferably 40% or less. In this case, 20% or less is more preferable, 10% or less is even more preferable, 5% or less is particularly preferable, and 1% or less is most preferable. If it is within the above range, it can be used as a coloring material that develops sharp colors by blending a colorant into the resin, or can be applied to a member requiring transparency.

[Method of manufacturing molded products]
The polycarbonate resin and polycarbonate resin composition of the present invention can be molded, for example, by injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.),
It can be processed into various molded products by molding methods such as extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The shape of the molded product is not particularly limited, and examples thereof include sheets, films, plates, particles, lumps, fibers, rods, porous bodies, and foams, and are preferably sheets, films, and plates. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include roll method, tenter method, and tubular method. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, which are usually used industrially, can also be performed.

[Use]
The applications of the molded articles are not particularly limited, but since the polycarbonate resin and polycarbonate resin composition of the present invention are excellent in weather resistance and optical properties in addition to mechanical properties, they are suitably used for interior and exterior components of automobiles, building materials used outdoors (lighting covers, carports, highway soundproofing walls, etc.), display front panels, housings for electric and electronic devices, etc.

The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[Measurement method]
Various physical properties were measured according to the following methods.

Number average molecular weight of polytrimethylene ether glycol (PO3G) The hydroxyl value of polytrimethylene ether glycol was measured by a method using an acetylation reagent in accordance with JIS K1557-1. The number average molecular weight was calculated from the hydroxyl value using the following formula. The number average molecular weights of PEG, PPG, and PTMG used in the examples described below were also measured in the same manner.
Number average molecular weight=1/(hydroxyl value/1000/56.11/2)
Unit of hydroxyl value: mg-KOH/g-polymer
56.11: Molecular weight of calcium hydroxide (KOH)

Number average molecular weight of polycarbonate resin Approximately 15 mg of a polycarbonate resin sample was weighed out and dissolved in approximately 0.7 mL of deuterated chloroform, which was then placed in an NMR tube with an inner diameter of 5 mm, and the ¹ H-NMR spectrum was measured. The number average molecular weight was calculated from the intensity ratio of the signal based on the structural unit derived from each dihydroxy compound constituting the polycarbonate resin and the signal of each terminal group. The equipment and conditions used were as follows.
Equipment: JNM-ECZ400S (manufactured by JEOL Ltd.)
Measurement temperature: 30°C
Relaxation time: 6 seconds Accumulation count: 64 times

For example, ¹ H-NMR analysis of a copolymer polycarbonate of ISB and PO3G500 is carried out as follows.
[Range for calculating integral value]
(a): 5.4-4.4 ppm: all derived from ISB repeating structural units (proton number: 4, molecular weight: 172.14)
(b): 2.2-1.5 ppm: all derived from PO3G500 repeating structural units (number of protons:
17.63, molecular weight: 539.99)
(c): 4.4 ppm: derived from ISB hydroxyl end group (proton number: 1)
(d): 2.6 ppm: derived from ISB hydroxyl end group (proton number: 1)
(e): 7.4 ppm: derived from DPC end groups (proton number: 2, molecular weight: 93.10)
Although double bond terminals may be generated from ISB and PO3G by thermal decomposition, the amount was negligibly small in the examples described below. Similarly, the amount of hydroxyl terminal groups of PO3G was below the lower limit of quantification.
[Calculation of the value equivalent to the number of moles of each structure]
Total ISB repeating structural units (a'): (a) integral value/4
Total PO3G500 repeating structural units (b'): (b) integral value/17.63
ISB hydroxy end group (c'): (c) integral value + (d) integral value DPC end group (e'): (e) integral value/2
[Calculation of Number Average Molecular Weight]
(a'×172.14+b'×539.99+e'×93.10)/{(c'+e')/
2}

Pellet color The color of the polycarbonate resin pellets was measured by reflected light using a spectrophotometer CM-5 (manufactured by Konica Minolta) in accordance with ASTM D1925.
0 mm, SCE was selected. A petri dish calibration glass CM-A212 was fitted into the measurement section, and a zero calibration box CM-A124 was placed over it to perform zero calibration, followed by white calibration using the built-in white calibration plate. Pellets were packed into a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm to a depth of about 40 mm, and the YI value was measured. The closer the YI value is to 0, the less coloring such as yellowing and the better the hue.

・TG-DTA
As an index of the thermal stability of polycarbonate resin, the 5% weight loss temperature was measured by thermogravimetric differential thermal analysis (TG-DTA).
About 10 mg of a sample was placed in an aluminum pan using a 100 mL/min nitrogen flow rate and heated from 30° C. to 5° C. at a rate of 10° C./min under a nitrogen atmosphere.
The temperature was raised to 100° C. The temperature at which the weight of the sample was reduced by 5% from the weight at the time the sample temperature was 100° C. was defined as the 5% weight loss temperature. A higher 5% weight loss temperature indicates better thermal stability.

Tensile test Approximately 5 g of resin pellets were placed on a SUS spacer 14 cm long, 14 cm wide, and 0.1 mm thick, with Teflon (registered trademark) sheets laid above and below the sample, preheated at 150 to 170°C for 3 minutes, pressurized at 7 MPa for 5 minutes, removed together with the spacer, and cooled to produce a film. A rectangular sample 10 mm wide and 100 mm long was cut out from the obtained film, and tested using a tabletop precision universal testing machine AUTOGRAPH AGS-X (manufactured by Shimadzu Corporation).
A tensile test was performed with an initial chuck distance of 50 mm and a tensile speed of 50 mm/min, and the tensile elongation (elongation at break) and tensile modulus were measured.
It represents excellent flexibility.

Glass transition temperature: The glass transition temperature was measured using a differential scanning calorimeter DSC6220 (manufactured by SII NanoTechnology Inc.). Approximately 10 mg of the resin was placed in an aluminum pan manufactured by the same company, sealed, and then cooled to 50 ml.
Measurement was started at 200° C. under a nitrogen gas flow of 1 L/min, and cooled to 30° C. at a rate of 20° C./min. The sample was held at 30° C. for 3 minutes, and then heated again to 200° C. at a rate of 20° C./min. DS during heating
From the C data, the extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum. This was used as the glass transition temperature.

Refractive index: A rectangular test piece 40 mm long and 8 mm wide was cut out from the film prepared by the above-mentioned heat pressing method to prepare a measurement sample. The refractive index nD was measured using a multi-wavelength Abbe refractometer DR-M4/1550 manufactured by Atago Co., Ltd., using a 589 nm (D line) interference filter. The measurement was performed at 20°C using monobromonaphthalene as the interface liquid.

Izod impact strength: According to ASTM D256, a 3.2 mm thick notched test piece was used at 23°C.
The Izod impact strength (unit: kJ/m ² ) was measured at 100° C. The test pieces were prepared as follows. The resin pellets were vacuum dried at 90° C. for 5 hours or more, and then injected into a small injection molding machine C.
An Izod test specimen was prepared using Mobile-0813 (manufactured by Shinko Selvic Co., Ltd.).
The test piece was cut using a cutter and a notch with a tip radius of 0.25 mm was made.
The larger the impact strength value, the more excellent the impact resistance.

・Head deflection temperature (HDT)
The resin pellets were vacuum-dried at 90° C. for 5 hours or more, and then an ISO test piece for mechanical properties was obtained using an injection molding machine EC-75 (manufactured by Toshiba Machine Co., Ltd.).
A rectangular test piece having a length of 0 mm, width of 10 mm, and thickness of 4 mm was cut out. The deflection temperature under load of the rectangular test piece was then determined using a heat deformation tester (manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7191-1, using the flatwise method and a bending stress of 1.8 MPa. The higher the deflection temperature under load, the more excellent the heat resistance.

Haze: Using the above-mentioned injection molding machine EC-75, a plate molded product with a width of 60 mm, length of 60 mm, and thickness of 3 mm was obtained. The haze of the plate molded product was measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) under a D65 light source in accordance with JIS K7136. The lower the haze, the more excellent the transparency.

(Raw materials used)
The abbreviations and manufacturers of the compounds used in the following Examples and Production Examples are as follows.

[Dihydroxy Compounds]
・ISB: Isosorbide (manufactured by Rocket Fleuret)
PO3G500: Polytrimethylene ether glycol, measured number average molecular weight 514 (
ALLESSA, product name: VELVETOL)
PO3G650: Polytrimethylene ether glycol, measured number average molecular weight 715 (
(Manufactured by ALLESSA)
PO3G1000: Polytrimethylene ether glycol, measured number average molecular weight 104
3 (manufactured by ALLESSA)
PO3G2700: Polytrimethylene ether glycol, measured number average molecular weight 262
8 (manufactured by ALLESSA)
PEG600: Polyethylene glycol, measured number average molecular weight 581 (manufactured by Sanyo Chemical Industries, Ltd.)
PPG600: Polypropylene glycol, measured number average molecular weight: 597 (manufactured by Sanyo Chemical Industries, Ltd.)
PTMG650: Polytetramethylene glycol, measured number average molecular weight 653 (manufactured by Mitsubishi Chemical Corporation)
CHDM: 1,4-cyclohexanedimethanol (SK Chemical Co., Ltd.)
1,3-PDO: 1,3-propanediol (manufactured by DuPont)
BPA: 2,2-bis(4-hydroxyphenyl)propane (manufactured by Mitsubishi Chemical Corporation)

[Carbonate diester]
DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)
[Catalyst deactivator]
- Phosphonic acid (Tokyo Chemical Industry Co., Ltd.)
[Heat stabilizer (antioxidant)]
Irganox 1010: Pentaerythritol-tetrakis(3-(3,5-di-t
tert-Butyl-4-hydroxyphenyl)propionate (manufactured by BASF)
AS2112: Tris(2,4-di-tert-butylphenyl)phosphite (AD
(Manufactured by EKA)

[Acrylic resin]
PPhMA: Phenyl methacrylate/methyl acrylate=99/1% by weight copolymer. Synthesized according to the method described in JP-A-2010-116501.
[Impact resistance modifier]
Acrylic core-shell rubber: butyl acrylate, methyl methacrylate, styrene copolymer (core: butyl acrylate, shell: methyl methacrylate, styrene)

(Example 1-1) PC1-1
Polymerization was carried out using a batch polymerization apparatus consisting of two vertical stirring reactors equipped with stirring blades and reflux condensers. ISB 46.69 parts by weight (0.320 mol), PO3G500 42.
83 parts by weight (0.083 mol), DPC 86.30 parts by weight (0.403 mol), and 2.13×10 ⁻³ parts by weight (1.21×10 ⁻⁵ m
The inside of the reactor was replaced with nitrogen under reduced pressure, and then heated with a heat medium. When the inside temperature reached 100°C, stirring was started. After 40 minutes from the start of the temperature increase, the inside temperature reached 210°C, and while controlling to maintain this temperature, pressure reduction was started. After reaching 210°C, the inside temperature was increased by 90%.
The pressure was adjusted to 13.3 kPa in 0 minutes. Phenol vapor by-produced during the polymerization reaction was introduced into a reflux condenser at 110°C, a small amount of monomer components contained in the phenol vapor were returned to the reactor, and the uncondensed phenol vapor was introduced into a condenser at 45°C and collected. Nitrogen was introduced into the first reactor to restore the pressure to atmospheric pressure, and the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Next, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was adjusted to 220°C and the pressure to 20 kPa in 40 minutes. Thereafter, the polymerization was allowed to proceed while further reducing the pressure until a predetermined stirring power was reached. When the predetermined power was reached, nitrogen was introduced into the reactor to restore the pressure, and the produced polycarbonate was extruded into water, and the strands were cut to obtain pellets. This resin is called "PC1-1". The ratio of structural units derived from each monomer was ISB/PO3
The ratio of G500/DPC was 46.1/42.7/11.3% by weight. The results of the above-mentioned various evaluations are shown in Table 1. The obtained resin was transparent, had a good color, and exhibited high tensile elongation.

(Example 1-2) PC1-2
The raw materials were 29.71 parts by weight (0.203 mol) of ISB and 6 parts by weight of PO3G500.
1.87 parts by weight (0.120 mol), DPC 69.34 parts by weight (0.324 mol)
The same procedure as in Example 1-1 was repeated, except that the amount of calcium acetate monohydrate was 2.28×10 ⁻³ parts by weight (1.29×10 ⁻⁵ mol).

(Example 1-3) PC1-3
The raw materials were ISB 46.69 parts by weight (0.320 mol), PO3G650 4
3.42 parts by weight (0.061 mol), DPC 81.45 parts by weight (0.380 mol)
The same procedure as in Example 1-1 was repeated, except that the amount of calcium acetate monohydrate was 2.01×10 ⁻³ parts by weight (1.14×10 ⁻⁵ mol).

(Example 1-4) PC1-4
The raw materials were 25.47 parts by weight (0.174 mol) of ISB and 1000 parts by weight of PO3G.
68.30 parts by weight (0.065 mol), DPC 51.36 parts by weight (0.240 mol)
), and calcium acetate monohydrate were 2.11×10 ⁻³ parts by weight (1.20×10 ⁻⁵ mol), but the same procedure was followed as in Example 1-1.

(Example 1-5) PC1-5
The raw materials were 33.96 parts by weight (0.232 mol) of ISB and 8.47 parts by weight of CHDM.
Part by weight (0.059 mol), PO3G1000 48.79 part by weight (0.047 mol
), DPC 72.35 parts by weight (0.338 mol), calcium acetate monohydrate 1.79
The same procedure as in Example 1-1 was carried out except that the amount of the fluorine-containing compound was changed to 1.01×10 ⁻³ parts by weight (1.01×10 ⁻⁵ mol).

(Example 1-6) PC1-6
The raw materials were 32.26 parts by weight (0.221 mol) of ISB and 10.77 parts by weight of BPA.
Part by weight (0.047 mol), PO3G1000 48.79 part by weight (0.047 mol
), DPC 68.06 parts by weight (0.318 mol), calcium acetate monohydrate 2.77
The same procedure as in Example 1-1 was repeated except that the amount of the copolymer was changed to 1.57×10 ⁻³ parts by weight (1.57×10 ⁻⁵ mol) and the final polymerization temperature was changed to 230° C.

(Comparative Example 1-1)
The raw materials were 46.69 parts by weight (0.320 mol) of ISB and 43 parts by weight of PEG 600.
．． 07 parts by weight (0.074 mol), DPC 84.32 parts by weight (0.394 mol),
The same procedure as in Example 1-1 was repeated except that calcium acetate monohydrate was used in an amount of 2.08×10 ⁻³ parts by weight (1.18×10 ⁻⁵ mol).

(Comparative Example 1-2)
The raw materials were ISB 46.70 parts by weight (0.320 mol), PPG 600 43
．． 12 parts by weight (0.074 mol), DPC 83.93 parts by weight (0.394 mol),
The same procedure as in Example 1-1 was repeated except that calcium acetate monohydrate was used in an amount of 2.07×10 ⁻³ parts by weight (1.18×10 ⁻⁵ mol).

(Comparative Example 1-3)
The raw materials were 46.69 parts by weight (0.320 mol) of ISB and 4
3.28 parts by weight (0.066 mol), DPC 82.65 parts by weight (0.386 mol)
The same procedure as in Example 1-1 was repeated, except that the amount of calcium acetate monohydrate was 6.80×10 ⁻³ parts by weight (3.86×10 ⁻⁵ mol).

(Comparative Example 1-4) PC2-6
This was carried out by the method shown in Production Example 6 below.

(Comparative Example 1-5) PC2-3
This was carried out by the method shown in Production Example 3 described below.

(Production Example 1) PC2-1
A continuous polymerization system consisting of three vertical stirring reactors, one horizontal stirring reactor, and a twin-screw extruder was used to polymerize polycarbonate resin. ISB and DPC were melted in tanks, respectively, and the polymerization rates were 42.5 kg/hr for ISB and 63.2 kg/hr for DPC (ISB/DPC molar ratio).
PC=1.000/1.015) to the first vertical stirred reactor. At the same time, an aqueous solution of calcium acetate monohydrate, which is a polymerization catalyst, was continuously fed to the first vertical stirred reactor at a flow rate of 1 mol
The internal temperature, internal pressure, and residence time of each reactor were respectively: First vertical stirring reactor: 19
0°C, 25 kPa, 120 minutes, second vertical stirred reactor: 195°C, 10 kPa, 90 minutes, third vertical stirred reactor: 205°C, 4 kPa, 45 minutes, fourth horizontal stirred reactor: 220°C, 0.
The number average molecular weight of the resulting polycarbonate resin was 8.
The internal pressure of the fourth horizontal stirred reactor was finely adjusted so that the internal pressure was within the range of 0.000 to 9,000. The polycarbonate resin discharged from the fourth horizontal stirred reactor was fed in a molten state to a vented twin-screw extruder TEX30α (manufactured by Japan Steel Works, Ltd.). The extruder had three vacuum vent ports, where residual low molecular weight components in the resin were removed by volatilization, and phosphonic acid was added as a catalyst deactivator just before the first vent in an amount of 0.64 ppm by weight based on the polycarbonate resin.
m was added, and 1000 ppm by weight and 500 ppm by weight of Irganox 1010 and AS2112 were added to the polycarbonate resin before the third vent. The polycarbonate resin that passed through the extruder was passed through an Ultipleats candle filter (manufactured by PALL) with a mesh size of 10 μm while still in a molten state to filter out foreign matter. The polycarbonate resin was then extruded from the die in the form of strands, cooled with water, solidified, and cut with a rotary cutter to pelletize. The pelletized polycarbonate resin thus obtained is referred to as "PC2-1". The results of the various evaluations described above are shown in Table 2.

(Production Example 2) PC2-2
In addition to the raw materials used in Production Example 1, CHDM was also melted in a tank. The raw materials were charged at ISB 38.3 kg/hr, CHDM 4.19 kg/hr, DPC 62.9 kg/hr,
The same procedure as in Production Example 1 was repeated except that the flow rates were changed to 1000 ml/hr (ISB/CHDM/DPC molar ratio = 0.900/0.100/1.010).

(Production Example 3) PC2-3
The raw materials were fed at 29.8 kg/hr for ISB, 12.6 kg/hr for CHDM, and 12.6 kg/hr for DPC.
62.9 kg/hr (molar ratio ISB/CHDM/DPC = 0.700/0.300/
The same procedure as in Production Example 2 was repeated except that the flow rate was changed to 1.008).

(Production Example 4) PC2-4
The raw materials were fed at 21.3 kg/hr for ISB, 21.1 kg/hr for CHDM, and 21.1 kg/hr for DPC.
62.9 kg/hr (molar ratio ISB/CHDM/DPC = 0.500/0.500/
The same procedure as in Production Example 2 was repeated except that the flow rate was changed to 1.005).

(Production Example 5) PC2-5
Using the reaction equipment used in Example 1-1, the raw materials were charged in the following amounts: 70.89 parts by weight of ISB (
0.485 mol), 1,3-PDO 12.6.30 parts by weight (0.162 mol), D
PC 138.54 parts by weight (0.647 mol), calcium acetate monohydrate 5.70 x 1
The same procedure as in Example 1-1 was repeated except that the amount was 0 ^{to 4} parts by weight (3.23×10 ⁻⁶ mol).

(Production Example 6) PC2-6
The raw materials were ISB 70.47 parts by weight (0.482 mol), PO3G500 1
6.18 parts by weight (0.031 mol), DPC 110.58 parts by weight (0.516 mol)
), and calcium acetate monohydrate were 9.05×10 ⁻⁴ parts by weight (5.14×10 ⁻⁶ mol), but the same procedure was followed as in Example 1-1.

(Production Example 7) PC2-7
The raw materials were ISB 75.56 parts by weight (0.517 mol), PO3G500 1
0.47 parts by weight (0.020 mol), DPC 115.70 parts by weight (0.540 mol
), and calcium acetate monohydrate 2.84×10 ⁻⁴ parts by weight (1.61×10 ⁻⁶ mol) were used, and the same procedure was followed as in Example 1-1.

(Example 2-1)
50 parts by weight of pellets of polycarbonate resin PC1-1 obtained in Example 1-1 and 950 parts by weight of pellets of polycarbonate resin PC2-3 obtained in Production Example 3 were blended, and then extrusion kneading was performed using a twin-screw extruder TEX30HSS (manufactured by Japan Steel Works, Ltd.) equipped with a vacuum vent at a cylinder temperature of 240°C and an extrusion rate of 12 kg/hr to obtain pellets of a polycarbonate resin composition. The obtained polycarbonate resin composition was subjected to the various evaluations described above. The results are shown in Table 3.

(Examples 2-2 to 2-15)
The same procedure as in Example 2-1 was carried out except that the composition was changed to that shown in Table 3.

(Comparative Example 2-1 to Comparative Example 2-8)
The polycarbonate resins obtained in Production Examples 1 to 7 were subjected to the various evaluations described above.

Claims (9)

A polycarbonate resin containing at least a structural unit represented by formula (1) and a structural unit represented by formula (2), the polycarbonate resin containing 10% by weight or more and 70% by weight or less of the structural unit represented by formula (1) and 30% by weight or more and 80% by weight or less of the structural unit represented by formula (2).

(In formula (2), the average value of n is 3 or more and 45 or less .) The polycarbonate resin according to claim 1, wherein the structural unit represented by the formula (2) has a number average molecular weight of 200 or more and 2,500 or less. 3. The polycarbonate resin according to claim 1, which has a number average molecular weight of 15,000 or more and 50,000 or less as calculated by ¹ H-NMR analysis. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 3 (a first polycarbonate resin) and a polycarbonate resin (a second polycarbonate resin) which contains at least a structural unit represented by the formula (1) and has a structure different from that of the first polycarbonate resin,
The second polycarbonate resin contains 40% by weight or more and 90% by weight or less of the structural unit represented by the formula (1),
A polycarbonate resin composition in which the weight ratio of the first polycarbonate resin to the second polycarbonate resin is 1/99 to 99/1. The polycarbonate resin composition according to claim 4, wherein the glass transition temperature of the second polycarbonate resin is 90°C or higher and 200°C or lower. The polycarbonate resin composition according to claim 4 or 5, wherein the second polycarbonate resin contains structural units derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound. 7. The polycarbonate resin composition according to claim 4, comprising 0.01% by weight or more and 10% by weight or less of an acrylic resin containing 50% by weight or more of a structural unit represented by the following formula (3):

(In formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. ^{R 2} is an aryl group which may have a substituent or an aralkyl group which may have a substituent.) The polycarbonate resin composition according to any one of claims 4 to 7, further comprising 0.1% by weight or more and 10% by weight or less of polytrimethylene ether glycol having a number average molecular weight of 300 or more and 10,000 or less. A method for producing the polycarbonate resin according to any one of claims 1 to 3, comprising a step of polycondensing a monomer raw material containing at least a dihydroxy compound forming a structural unit represented by formula (1), a dihydroxy compound forming a structural unit represented by formula (2), and a carbonate diester by transesterification,
In the step, the dihydroxy compound forming the structural unit represented by the formula (2) is polytrimethylene ether glycol, and the number average molecular weight of the polytrimethylene ether glycol is 200 or more and 2,500 or less.