JP2011241277A - Copolycarbonate - Google Patents

Abstract

Disclosed is a polycarbonate that is easy to mold, has excellent mechanical strength and transparency, and has a high degree of planting.
A copolymerized polycarbonate comprising a sugar-derived alcohol and a polydiol, wherein the structure derived from the sugar-derived alcohol is greater than 90 mol% with respect to the total amount of the repeating structure portion other than the carbonate bond portion. Polycarbonate.
[Selection figure] None

Description

  The present invention relates to a polycarbonate copolymer containing a high proportion of structural units that can be derived from a carbohydrate such as starch, which is a biomass resource, and excellent in transparency, mechanical strength, and surface hardness.

  Polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate using raw materials obtained from biomass resources such as plants. In addition, since global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, the development of polycarbonate using carbon-neutral plant-derived monomers as raw materials is required even after disposal after use. Yes. It has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (for example, see Patent Document 1).

  Polycarbonate obtained from isosorbide is known to have excellent optical properties such as low optical distortion, but on the other hand, due to its rigid structure, the glass transition temperature and melt viscosity become very high, and molding processing Is difficult, and the mechanical strength is low, and it has been proposed to improve by copolymerization with various dihydroxy compounds (see, for example, Patent Documents 2 and 3). However, dihydroxy compounds, which are copolymer monomers, are generally produced from petroleum-derived raw materials, and by copolymerizing them, the proportion of plant-derived raw materials in the polymer decreases, and the degree of planting decreases. End up. In order to improve mechanical strength, there is a method of using a long-chain dihydroxy compound having a flexible structure as a copolymerization component. For example, in polycarbonate, a material is modified using polysiloxane as a copolymerization component. (For example, see Patent Document 4). However, when copolymerizing with such a high-molecular-weight dihydroxy compound, polymers having different structures are generally incompatible and have different refractive indexes, so that there is a problem that the transparency of the obtained polycarbonate is lowered. It was.

British Patent No. 1079686 International Publication No. 04/111106 Pamphlet JP 2008-024919 A Special table 2006-518803 gazette

  In spite of the demand for the development of a polycarbonate having both a high degree of plantation and excellent transparency and mechanical strength as described above, such a polycarbonate has not been reported. An object of the present invention is to provide a polycarbonate which solves the above-mentioned conventional problems, can be easily molded, has excellent mechanical strength and transparency, and has a high degree of planting.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has achieved excellent mechanical strength while maintaining a high degree of plantation, while a copolymer polycarbonate comprising a dihydroxy compound containing a sugar-derived alcohol and a polydiol is maintained. And the present invention has been found.
That is, the gist of the present invention resides in the following [1] to [9].
[1]
A copolymeric polycarbonate comprising a sugar-derived alcohol and a polydiol, wherein the structure derived from the sugar-derived alcohol is greater than 90 mol% with respect to the total amount of the repeating structure portion other than the carbonate bond portion.
[2]
Copolycarbonate as described in [1] whose glass transition temperature is 60 degreeC or more.
[3]
The copolymer polycarbonate according to [1] or [2], wherein the haze is 10.0% or less.
[4]
The copolymeric polycarbonate according to any one of [1] to [3], which has a tensile elongation of 10% or more.
[5]
The copolymeric polycarbonate according to any one of [1] to [4], wherein the pencil hardness is F or more.
[6]
The copolymeric polycarbonate according to any one of [1] to [5], wherein the melt viscosity at 240 ° C. at a shear rate of 1000 sec ⁻¹ is 800 Pa · s or less.
[7]
The copolymer polycarbonate according to any one of [1] to [6], wherein the sugar-derived alcohol is a compound represented by the following formula (1).

[8]
The copolymer polycarbonate according to any one of [1] to [7], wherein the polydiol is a polydiol represented by the following formula (2).

(In Formula (2), n is 2-120. R is H or a methyl group.)
[9]
The copolymer polycarbonate according to any one of [1] to [8], obtained by melt polycondensation of the sugar-derived alcohol, the polydiol, and a carbonic acid diester represented by the following formula (3): .

(In Formula (3), A ¹ and A ² are each independently an aliphatic group having 1 to 18 carbon atoms which may have a substituted or unsubstituted substituent, or a substituted or unsubstituted group. A substituted aromatic group having 6 to 18 carbon atoms may be an aromatic group, and A ¹ and A ² may be the same or different.

  The polycarbonate copolymer of the present invention is excellent in transparency and mechanical strength, and can widely adjust the glass transition temperature depending on the application. In addition, it has characteristics such as low optical distortion, high surface hardness, and excellent solvent resistance, so it must be flexible film, sheet field, heat resistant bottle, container field, and camera lens. , Lens applications such as finder lenses, CCD and CMOS lenses, retardation films used for liquid crystal and plasma displays, films such as diffusion sheets and polarizing films, sheets, optical disks, optical materials, optical components, dyes, charge transfer It is possible to provide materials in a wide range of fields such as binder applications for fixing agents.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. The present invention is not limited to the contents described above, and can be implemented with appropriate modifications.
The copolymeric polycarbonate of the present invention comprises a sugar-derived alcohol and a polydiol, and the sugar-derived alcohol-derived structure occupies a proportion of more than 90 mol% with respect to the total amount of the repeating structure other than the carbonate bond portion. It is.

[Copolymer polycarbonate]
<Sugar-derived alcohol>
As the sugar-derived alcohol in the present invention, any alcohol can be used as long as it produces a copolymer polycarbonate with a polydiol, and it may be a sugar itself, or a product obtained by reducing aldose or ketose. Those obtained by intramolecular dehydration cyclization may also be used. In addition, the use of alcohols derived from a plurality of sugars is not hindered. As the alcohol derived from sugar, an alcohol derived from a divalent sugar is usually used to form a copolymer polycarbonate, but it may be an alcohol derived from a sugar having a trivalent or higher hydroxyl group.

  Among these, from the viewpoints of optical properties, mechanical properties, and heat resistance of the obtained polycarbonate, an anhydrous sugar alcohol represented by a dihydroxy compound represented by the following formula (1) is preferable.

Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide, and isoidet having a stereoisomeric relationship, and these may be used alone or in combination of two or more. Also good.
Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various easily available starches, which are abundant as plant-derived resources, is easy to obtain and manufacture, and is light-resistant. From the viewpoint of optical properties, moldability, heat resistance, and carbon neutrality, it is most preferable.

  The anhydrous sugar alcohol represented by the above formula (1) may contain a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer, and a heat stabilizer. It is preferable that an anhydrous sugar alcohol contains a basic stabilizer because it is easily altered under acidic conditions. Basic stabilizers include Group 1 or Group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the Long Periodic Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylan Basic ammonium compounds such as nium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine Pyrrolidine, piperidine, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diisopropylethanolamine, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole , Imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and other amine compounds, di- (tert-butyl) amine, 4-hydroxy-2,2,6,6-tetramethylpiperidine and other hindered amine compounds Is mentioned. Among the stabilizers, amine compounds are preferable from the viewpoint of stabilizing effect, and morpholine and diisopropylethanolamine are particularly preferable.

  The content of these basic stabilizers in the saccharide-derived alcohol of the present invention is not particularly limited, but the saccharide-derived alcohol of the present invention is accelerated in the acidic state, and therefore the present invention containing the above-mentioned stabilizer. It is preferable to add a stabilizer so that the pH of the aqueous solution of the alcohol derived from the sugar is 7 to 8. If the amount is too small, there is a possibility that the effect of preventing the alteration of the alcohol derived from the sugar of the present invention may not be obtained. If the amount is too large, the sugar-derived alcohol of the present invention may be modified. Usually, it is 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the sugar-derived alcohol of the present invention.

In addition, when the sugar-derived alcohol of the present invention containing these basic stabilizers is used as a raw material for producing polycarbonate, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In order to deteriorate the resin hue, it is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for producing polycarbonate.
In order to obtain the sugar-derived alcohol of the present invention that does not contain the above oxidative decomposition product, and in order to remove the aforementioned basic stabilizer, it is preferable to perform distillation purification. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.
By such distillation purification, when the dihydroxy compound containing the sugar-derived alcohol of the present invention is used as a polycarbonate production raw material, it is possible to produce a polycarbonate having excellent hue and thermal stability without impairing polymerization reactivity. It becomes.

<Polydiol>
As the polydiol according to the copolymer polycarbonate of the present invention, any one can be used as long as it produces a copolymer polycarbonate with a sugar-derived alcohol, and has a linear structure. Also, it may have a cyclic structure, may have a branched structure, or may have a hetero atom other than oxygen in the hydroxyl group in the molecule. In addition, the use of multiple types of polydiols is not hindered.
In order to increase the transparency of the copolymerized polycarbonate of the present invention, it is preferable to select a polydiol used for copolymerization that is highly compatible with sugar-derived alcohols. The compatibility of the two components is represented by a solubility parameter (SP value), a χ parameter, and the like, and the molecular weight of the polydiol also affects the compatibility.

  The higher the molecular weight of the polydiol, the more flexible and mechanical strength can be imparted to the copolymer polycarbonate, but if the molecular weight is too large, transparency may not be obtained, so the number average molecular weight of the polydiol used is preferably 100 to 20000, more preferably 100 to 5000, particularly preferably 200 to 2000. Specific examples of the polydiol used in the present invention include polyalkylene diol, polyether diol, polycarbonate diol, polyester diol, and polysiloxane. Polydiols having reactivity with hydroxyl groups affect the polymerization reaction and may adversely affect the color of the polymer or the desired mechanical properties may not be obtained. Among the above polydiols, polyalkylene diols and polyether diols Polysiloxanes are preferred, and polyether diols having good compatibility with sugar-derived alcohols are particularly preferred. Especially, the polyoxyalkylene glycol represented by following formula (4) is used suitably.

M in Formula (4) is 1-4, n is 2-120, R represents a methyl group or a hydrogen atom. Among them, m is preferably 2 to 4, and 2 is particularly preferable. Further, n is preferably 2 to 100, more preferably 2 to 80. More specific examples of the polyoxyalkylene glycol represented by the formula (4) include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol.
In particular, polyoxyalkylene glycol represented by the following formula (2), that is, polyethylene glycol or polypropylene glycol is preferably used.

N in Formula (2) is 2-120, and R represents a methyl group or a hydrogen atom.
If the content of polydiol is too large, the heat resistance is lowered, so the ratio of the structural unit of polydiol to the structural unit derived from all dihydroxy compounds is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly 5 mol. % Or less is preferable. <Other dihydroxy compounds>
The copolymeric polycarbonate of the present invention may contain a structural unit derived from a dihydroxy compound other than the sugar-derived alcohol and polydiol (hereinafter sometimes referred to as “other dihydroxy compounds”) according to the present invention. . Other dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptane Diols, aliphatic dihydroxy compounds such as 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedi Methanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol, 1,4-cyclohexanediol, 2 Alicyclic dihydroxy compounds such as 2-bis (4-hydroxycyclohexyl) propane, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2-bis (4-hydroxyphenyl) propane [= Bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-) 3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2, , 2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4 ′ -Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Aromatic bisphenols, 9,9-bis (4- (2-hydroxyethoxy Phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 1,3-bis ( Bis (hydroxyalkoxy) aryls such as 2-hydroxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) sulfone, and the like. These other dihydroxy compounds do not prevent the use of multiple species.

<Terminal structure>
The copolymeric polycarbonate of the present invention may have a terminal structure other than the structure selected from the sugar-derived alcohol and polydiol according to the present invention and the structure derived from those structures. As this terminal structure, any structure generally known as a terminal structure of polycarbonate can be adopted.

<Copolymerization ratio>
In the copolymeric polycarbonate of the present invention, the alcohol-derived structure derived from the sugar is larger than 90 mol% with respect to the total amount of the repeating structure portion other than the carbonate bond portion.
The molar ratio of the sugar-derived alcohol-derived structure in the present invention is a repeating structure part other than the carbonate bond part of the copolymer polycarbonate, that is, the sugar-derived alcohol-derived structure excluding the carbonate structure and the terminal structure from the copolymer polycarbonate, polydiol It is defined by the molar ratio of the sugar-derived alcohol-derived structure to the total amount of the derived structure and other dihydroxy compound-derived structures.
More specifically, it is the molar ratio of alcohol derived from sugar to the total amount of divalent or higher-valent alcohol components used in the production of the copolymer polycarbonate, and in the copolymer polycarbonate, it is determined by ¹ H-NMR or ¹³ C-NMR. Measured.

<Molecular weight>
The molecular weight of the polycarbonate of the present invention can be represented by a reduced viscosity. The reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, and the upper limit of the reduced viscosity is 1.20 dL / g. Hereinafter, 1.00 dL / g or less is more preferable, and 0.80 dL / g or less is still more preferable.

If the reduced viscosity of the polycarbonate is too low, the mechanical strength of the molded product may be low. If it is too high, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.
The reduced viscosity is measured by using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., precisely adjusting the polycarbonate concentration to 0.6 g / dL using methylene chloride as a solvent.
Furthermore, the lower limit of the concentration of the terminal group represented by the following formula (6) in the polycarbonate of the present invention is usually 20 μeq / g, preferably 40 μeq / g, particularly preferably 50 μeq / g, and the upper limit is usually 160 μeq / g. g, preferably 140 μeq / g, particularly preferably 100 μeq / g.

If the concentration of the terminal group represented by the following formula (5) is too high, the amount of the residual monohydroxy compound and the residual carbonic acid ester increases, and if it is too low, the thermal stability may be lowered.
In order to control the concentration of the terminal group represented by the following formula (5), when producing the polycarbonate of the present invention, the dihydroxy compound containing the alcohol of the present invention, which is the raw material, and the polydiol, and the formula described later are used. In addition to controlling the molar ratio of the carbonic acid diester represented by (3), a method for controlling the type and amount of the catalyst during the transesterification reaction, the polymerization pressure and the polymerization temperature, and the like can be mentioned.

<Glass transition temperature>
The copolymeric polycarbonate of the present invention preferably has a glass transition temperature of 50 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher, from the viewpoints of heat resistance and moldability. . The glass transition temperature in this invention is measured based on the method prescribed | regulated to JISK7121. More specifically, the measurement is performed using a differential scanning calorimeter (DSI 6220, manufactured by SII Nanotechnology). As measurement conditions, about 10 mg of a polycarbonate sample is put in an aluminum pan manufactured by the same company, and sealed at 50 mL / min. Under a nitrogen stream, the temperature is raised from room temperature to 250 ° C. at a rate of temperature rise of 20 ° C./min. In this state, the temperature can be maintained at 0 ° C. for 3 minutes, and the temperature can be increased again to 200 ° C. at a rate of 20 ° C./min. This temperature can be the glass transition temperature.
The glass transition temperature of the copolymeric polycarbonate of the present invention can be adjusted by the copolymerization composition of sugar-derived alcohol, polydiol, and other dihydroxy compounds.

<Haze>
In order to use the copolymeric polycarbonate of the present invention as a transparent material or an optical material, the haze is preferably 10.0% or less, more preferably 5.0% or less, particularly 3.0%. The following is preferred. As described above, the haze in the present invention is particularly affected by the molecular structure and molecular weight of the polydiol, and thus can be adjusted to these preferred ranges by appropriately adjusting them.
The haze of the copolymer polycarbonate of the present invention is measured in accordance with JIS K7361-1 of a molded product having a thickness of 3 mm molded from polycarbonate, and can be measured with a haze meter. Specifically, a plate molded product having a thickness of 3 mm can be molded and measured using a Nippon Denshoku Industries Co., Ltd. haze meter (1001DP).

<Tensile elongation>
The tensile elongation of the copolymeric polycarbonate of the present invention is preferably 10% or more, more preferably 15% or more, and particularly preferably 20% or more from the viewpoint of moldability and durability of the molded product.
The tensile elongation of the copolymeric polycarbonate of the present invention can be improved by increasing the copolymerization ratio of the polydiol, but the copolymerization ratio is adjusted in consideration of the balance between the heat resistance and mechanical properties of the copolymeric polycarbonate. Further, since the tensile elongation increases as the molecular weight of the copolymer polycarbonate increases, it is preferable to increase the molecular weight within a range that does not impair the moldability by the polymerization reaction.
The tensile elongation of the copolymeric polycarbonate of the present invention is measured according to ISO 527. Specifically, a 1A type test piece is molded and measured under conditions of a temperature of 23 ° C., a relative humidity of 50%, and a tensile speed of 50 mm / min.

<Pencil hardness>
The pencil hardness of the copolymerized polycarbonate of the present invention is preferably F or higher, more preferably H or higher, and particularly preferably 2H or higher because it relates to the surface scratch resistance of the molded product.
The pencil hardness of the copolymerized polycarbonate of the present invention is particularly affected by the copolymerization ratio of the sugar-derived alcohol of the present invention. The higher the sugar-derived alcohol content, the higher the pencil hardness. However, the copolymerization ratio of the sugar-derived alcohol is preferably adjusted in consideration of balance with mechanical properties and moldability.
The pencil hardness of the copolymer polycarbonate of the present invention is measured by the method described in JIS K5600-5-4. Specifically, a plate molded product having a thickness of 3 mm is prepared and measured using a pencil scratch coating film hardness tester manufactured by Toyo Seiki Co., Ltd.

<Melt viscosity>
The melt viscosity of the copolymeric polycarbonate of the present invention is preferably 800 Pa · s or less, more preferably 700 or less, particularly preferably 600 or less, at 240 ° C. at a shear rate of 1000 sec ⁻¹ . If the melt viscosity is too high, silver is likely to occur during molding, and appearance defects of the molded product are likely to occur. Further, if the molding temperature is increased for improving the moldability, it causes coloring, which is not preferable.
Since the melt viscosity of the copolymeric polycarbonate of the present invention depends on the molecular weight, it is important to control the polymerization reaction so that an appropriate molecular weight can be obtained.
The melt viscosity of the copolymerized polycarbonate of the present invention is measured using a capillograph. More specifically, for example, the melt viscosity at 240 ° C. at a shear rate of 1000 sec ⁻¹ is measured using a capillograph (Toyo Seiki Co., Ltd. capillary viscometer, nozzle diameter 1 mm × length 10 mm).

[Method for producing copolymer polycarbonate]
The copolymeric polycarbonate of the present invention can be obtained by polycondensation by a transesterification reaction using the aforementioned sugar-derived alcohol, polydiol, and carbonic acid diester as raw materials.
<Carbonated diester>
As a carbonic acid diester used, what is normally represented by following formula (3) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In Formula (3), A ¹ and A ² are each independently an aliphatic group having 1 to 18 carbon atoms which may have a substituted or unsubstituted substituent, or a substituted or unsubstituted group. The aromatic group which may have a substituent having 6 to 18 carbon atoms, and A ¹ and A ² may be the same or different.)

  Examples of the carbonic acid diester represented by the above formula (3) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate, and are purified by distillation as necessary. It is preferable to use one.

<Transesterification reaction catalyst>
As described above, the polycarbonate of the present invention is produced by subjecting the dihydroxy compound containing the sugar-derived alcohol of the present invention and the polydiol and the carbonic acid diester represented by the above formula (3) to an ester exchange reaction. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.
The transesterification reaction catalyst (hereinafter simply referred to as a catalyst or a polymerization catalyst) that can be used in the production of the polycarbonate of the present invention can affect the reaction rate and the color tone of the polycarbonate.

(Catalyst type)
The catalyst used is not limited as long as it can satisfy the transparency, hue, heat resistance, thermal stability, and mechanical strength of the produced polycarbonate, but is not limited to Group 1 or Group 2 in the long-period periodic table. (Hereinafter, simply referred to as “Group 1” and “Group 2”) include basic compounds such as metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include 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 borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate 2 potassium potassium phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, lithium compounds are preferable.

  Examples of the Group 2 metal compound include 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, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, among which magnesium compounds, calcium compounds, and barium compounds are preferably used, and polymerization activity From the viewpoint of the hue of the polycarbonate obtained, magnesium compounds and / or calcium compounds are more preferably used, particularly preferably calcium compounds Used.

  Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

  Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine and the like.

(amount to use)
The amount of the polymerization catalyst used is usually 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used in the polymerization. Among them, from the group consisting of lithium and two groups in the long-period type periodic table When a compound containing at least one selected metal is used, particularly when a magnesium compound and / or a calcium compound is used, the amount of metal is usually 0.1 μmol or more, preferably 0, per 1 mol of the total dihydroxy compound. .5 μmol or more, particularly preferably 0.7 μmol or more. Further, the upper limit is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst is too small, the polymerization rate will slow down. As a result, when trying to obtain a polycarbonate having a desired molecular weight, the polymerization temperature has to be increased, and the hue of the obtained polycarbonate is deteriorated or unreacted. May be volatilized during the polymerization and the molar ratio of the dihydroxy compound containing the sugar-derived alcohol and polydiol of the present invention to the carbonic acid diester represented by the above formula (2) may collapse, and may not reach the desired molecular weight. . On the other hand, when the amount of the polymerization catalyst used is too large, there is a possibility that the hue of the obtained polycarbonate is deteriorated or the resin is colored during the molding process.

In addition, Group 1 metals, especially sodium, potassium, and cesium, especially lithium, sodium, potassium, and cesium, may have an adverse effect on the hue when they are contained in a large amount in polycarbonate. However, the total amount of these in the polycarbonate is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, more preferably 0.7 wt. ppm or less.
The amount of metal in the polycarbonate can be measured using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP) after recovering the metal in the polycarbonate by a method such as wet ashing.

<Monomer storage method>
In the case of having an ether structure such as isosorbide or polyoxyalkylene glycol, which is a raw material of the polycarbonate of the present invention, it is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage and production, do not mix moisture. Also, it is important to use an oxygen scavenger or the like or handle under a nitrogen atmosphere. When the above compounds are oxidized, decomposition products such as formic acid may be generated. For example, the use of raw materials containing these decomposition products may lead to coloration of the resulting polycarbonate, and may not only significantly deteriorate the physical properties, but also affect the polymerization reaction, resulting in a high molecular weight. In some cases, coalescence cannot be obtained.

<Method for preparing raw materials>
The polycarbonate of the present invention can be obtained by polycondensation of the dihydroxy compound containing the sugar-derived alcohol of the present invention and the carbonic acid diester of the above formula (3) by a transesterification reaction. The raw material dihydroxy compound and carbonic acid diester are: It is preferable to mix uniformly before the transesterification reaction.
The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be deteriorated by heat, and the polymerization reactivity may be lowered or the hue of the resulting polycarbonate may be deteriorated.

  The operation of mixing the sugar-derived alcohol of the present invention, which is a raw material of the polycarbonate of the present invention, and the dihydroxy compound containing polydiol and the carbonic acid diester represented by the above formula (3), is performed at an oxygen concentration of 10 vol% or less, and further It is preferable from the viewpoint of preventing the deterioration of the hue to be performed in an atmosphere of 0001 vol% to 10 vol%, particularly 0.0001 vol% to 5 vol%, and particularly 0.0001 vol% to 1 vol%.

In order to obtain the resin of the present invention, the carbonic acid diester represented by the formula (3) is 0.90 to 1.20 with respect to the dihydroxy compound containing the sugar-derived alcohol and polydiol of the present invention used in the reaction. The molar ratio is preferably 0.95 to 1.10.
When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate is increased, the thermal stability of the polymer is deteriorated, coloring occurs during molding, the rate of transesterification reaction is decreased, and the desired high molecular weight product. May not be obtained.

Moreover, when this molar ratio becomes large, the rate of transesterification may decrease, or it may be difficult to produce a polycarbonate having a desired molecular weight. The decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction and may deteriorate the hue of the resulting polycarbonate.
Moreover, when the molar ratio of the carbonic acid diester represented by the formula (3) is increased with respect to the dihydroxy compound containing the sugar-derived alcohol and the polydiol of the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate is increased. This may be a cause of odor during molding and may increase the amount of deposits on the mold. The concentration of the carbonic acid diester remaining in the polycarbonate of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. Actually, polycarbonate may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

Furthermore, when using the substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the formula (3) to produce the polycarbonate of the present invention, phenol and substituted phenol are by-produced, Although it cannot be avoided, phenol and substituted phenol may cause odor during molding. Polycarbonate contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but it has excellent devolatilization performance from the viewpoint of odor reduction. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor or an extruder equipped with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.
These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

<Reactor>
In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important for stable reaction and from the viewpoint of hue. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group may not be obtained.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler. Preferably, it is 80 degreeC-150 degreeC, Most preferably, it is 100 degreeC-130 degreeC. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer while maintaining the hue and thermal stability of the final polycarbonate, it is important to select the type and amount of the catalyst described above. is there.
The polycarbonate of the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is that in the initial stage of the polymerization reaction, Therefore, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate. This is because it is important to sufficiently distill off the hydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

As described above, the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency and the like, three or more, preferably 3 to 5, particularly preferably 4 are used. One.
In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

In the present invention, the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.
If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If the temperature is too high, not only the monomer is volatilized but also decomposition and coloring of the polycarbonate may be promoted.

<Reaction conditions>
Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor. The monohydroxy compound generated is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours. Carried out while distilling.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 200 ° C. to 270 ° C., preferably 210 ° C. to 250 ° C., usually 0.1 hour to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0.5 hour. Perform for ~ 3 hours.

  In particular, in order to suppress polycarbonate coloring and thermal deterioration and obtain a polycarbonate having a good hue, the maximum internal temperature in all reaction stages is preferably less than 250 ° C, particularly 210 ° C to 240 ° C. In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

In order to obtain a polycarbonate having a predetermined molecular weight, if the polymerization temperature is increased and the polymerization time is excessively long, the hue and thermal stability of the obtained polycarbonate tend to deteriorate.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
As described above, the polycarbonate of the present invention is usually cooled and solidified after being polycondensed and pelletized with a rotary cutter or the like.

<Pelletization>
The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

(Extruder)
At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When producing the polycarbonate of the present invention, it is desirable to install a filter in order to prevent contamination by foreign substances. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

The extrusion of the polycarbonate of the present invention is preferably carried out in a clean room having a higher degree of cleanliness than Class 7, more preferably Class 6 as defined in JIS B 9920 (2002), in order to prevent foreign matter from being mixed after extrusion. Is desirable.
Further, when the extruded polycarbonate is cooled to form chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

[Molding method]
The polycarbonate of the present invention can be formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method.
In addition, the polycarbonate of the present invention may be used as necessary before performing various moldings, such as a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer. Additives such as additives, compatibilizers, flame retardants, and the like can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder, and the like.
The polycarbonate of the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, synthetic resin such as ABS, AS, and MBS, polylactic acid, and polybutylene succinate. It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as rubber and rubber.

  According to the present invention, a polycarbonate excellent in transparency, hue, heat resistance, thermal stability, and mechanical strength can be provided while maintaining a high degree of planting.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
<Abbreviation>
The abbreviations of the compounds used in the description of the following examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB PS)
PEG-400: Polyethylene glycol, number average molecular weight 400 (manufactured by Sanyo Chemical Industries)
PEG-1000: Polyethylene glycol, number average molecular weight 1000 (manufactured by Sanyo Chemical Industries)
PTMG-1000: polytetramethylene glycol, number average molecular weight 1000 (Mitsubishi Chemical Corporation)
PPG-1000: Polypropylene glycol, number average molecular weight 1000 (manufactured by Sanyo Chemical Co., Ltd.)
PDMS-1000: polydimethylsiloxane, number average molecular weight 1000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd.)
DEG: Diethylene glycol (Mitsubishi Chemical Corporation)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

<Physical properties>
In the following examples, the physical properties and characteristics of polycarbonate were evaluated by the following methods.
(1) Measurement of oxygen concentration An oxygen meter (manufactured by AMI: 1000RS) was used for measurement.
(2) Reduced viscosity A methylene chloride was used as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd., and obtained the relative viscosity ηrel from the following equation from the solvent passage time t ₀ and the solution passage time t

ηrel = t / t ₀
From the relative viscosity, the specific viscosity ηsp was determined from the following formula.

ηsp = (η−η ₀ ) / η ₀ = ηrel−1
The reduced viscosity ηsp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(3) Monomer unit ratio in polycarbonate 30 mg of polycarbonate was weighed and dissolved in about 0.7 mL of deuterated chloroform. This was put into an NMR tube having an inner diameter of 5 mm, a ¹ H-NMR spectrum was measured at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL, and determined from a signal intensity ratio based on each unit.

(4) Glass transition temperature (Tg) of polycarbonate
The glass transition temperature of polycarbonate was measured using a differential scanning calorimeter (DSC 6220 manufactured by SII Nanotechnology). About 10 mg of a polycarbonate sample was put in an aluminum pan manufactured by the same company and sealed, and the temperature was raised from room temperature to 250 ° C. at a heating rate of 20 ° C./min under a nitrogen stream of 50 mL / min. After maintaining the temperature for 3 minutes, it was cooled to 0 ° C. at a rate of 20 ° C./min. The temperature was maintained at 0 ° C. for 3 minutes, and the temperature was increased again to 200 ° C. at a rate of 20 ° C./min. From the DSC data obtained at the second temperature increase, the extrapolated glass transition start temperature was adopted.

(5) Haze The polycarbonate pellets are dried at 110 ° C. for 10 hours in a nitrogen atmosphere. Next, the dried polycarbonate pellets are supplied to an injection molding machine (J75EII type, manufactured by Nippon Steel), and a test piece having a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C., width 60 mm × length 60 mm × thickness 3 mm. Was measured using a Nippon Denshoku Industries Co., Ltd. haze meter (1001DP).

(6) Tensile elongation Measured according to ISO 527. A 1A type test piece was molded by the above-described injection molding and measured under the conditions of a temperature of 23 ° C., a relative humidity of 50%, and a tensile speed of 50 mm / min.
(7) Melt viscosity Using a Capillograph manufactured by Toyo Seiki Co., Ltd., the melt viscosity at a temperature of 240 ° C. and a shear rate of 1000 sec ⁻¹ was measured using a die having a diameter of 1 mm × length of 10 mm.

(8) Pencil hardness Using the same test piece as the above haze measurement, the pencil hardness is measured by the method described in JIS K5600-5-4 using a pencil scratch coating film hardness tester manufactured by Toyo Seiki Co., Ltd. did.
(9) Photoelastic coefficient C
It measured using the apparatus which combined the birefringence measuring apparatus which consists of a He-Ne laser, a polarizer, a compensation board, an analyzer, and a photodetector, and a vibration type viscoelasticity measuring apparatus (DVE-3 by Rheology). (For details, see Journal of Japanese Society of Rheology, Vol. 19, p. 93-97 (1991).)
A polycarbonate sample (4.0 g), which was vacuum-dried at 80 ° C. for 5 hours, was heated in a hot press at a hot press temperature of 250 ° C. using a spacer having a width of 8 cm, a length of 8 cm and a thickness of 0.5 mm, and a pressure of 20 MPa. After pressurizing for 1 minute under the above conditions, the entire spacer was taken out, and the water tube cooled press was pressurized and cooled at a pressure of 20 MPa for 3 minutes to produce a sheet. A sample having a width of 5 mm and a length of 20 mm was cut out from the sheet, fixed to a viscoelasticity measuring apparatus, and the storage elastic modulus E ′ was measured at a room temperature of 25 ° C. at a frequency of 96 Hz. At the same time, the emitted laser light is passed through the polarizer, sample, compensator, and analyzer in this order, picked up by a photodetector (photodiode), and passed through a lock-in amplifier with respect to the amplitude and distortion of the waveform of angular frequency ω or 2ω. The phase difference was determined, and the strain optical coefficient O ′ was determined. At this time, the directions of the polarizer and the analyzer were orthogonal to each other, and each was adjusted so as to form an angle of π / 4 with respect to the extending direction of the sample.

The photoelastic coefficient C was obtained from the following equation using the storage elastic modulus E ′ and the strain optical coefficient O ′.
C = O '/ E'

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB, PEG # 400, DPC having a chloride ion concentration of 10 ppb or less by distillation purification, and calcium acetate monohydrate were added. In a molar ratio, ISB / PEG # 1000 / DPC / calcium acetate monohydrate = 0.99 / 0.01 / 1.00 / 8.0 × 10 ⁻⁷ , and sufficiently purged with nitrogen ( Oxygen concentration 0.0005-0.001 vol%). Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C. 40 minutes after starting the temperature rise, the internal temperature is set to 210 ° C., and when the internal temperature reaches 210 ° C., control is performed so that this temperature is maintained. At the same time, pressure reduction is started, and 90 minutes after the temperature reaches 210 ° C. The pressure was maintained at 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 30 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser at 100 ° C., and a monomer component contained in a small amount in the phenol vapor is returned to the polymerization reactor, and the non-condensed phenol vapor is led to a condenser at 45 ° C. And recovered.

  The content thus oligomerized is once restored to atmospheric pressure and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled at 100 ° C. The internal temperature was 230 ° C. and the pressure was 200 Pa in 50 minutes. Thereafter, the pressure was reduced to 133 Pa or less over 20 minutes, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and pelletized with a rotary cutter.

  The reduced viscosity of the obtained polycarbonate copolymer was 0.421 dL / g, the glass transition temperature was 137 ° C., and the transparency was good. Subsequently, various test samples were molded by the method described above, and mechanical properties, haze, and photoelastic coefficient were measured. These results are shown in Table 1.

[Example 2]
ISB, PPG # 1000, DPC and calcium acetate monohydrate in a molar ratio of ISB / PPG # 400 / DPC / calcium acetate monohydrate = 0.99 / 0.01 / 1.00 / 2.0 × The same procedure as in Example 1 was performed except that 10 ^-6 was charged.
The obtained polycarbonate copolymer was cloudy and a transparent molded product could not be obtained.

[Example 3]
ISB, PTMG # 1000, DPC and calcium acetate monohydrate in a molar ratio of ISB / PTMG # 1000 / DPC / calcium acetate monohydrate = 0.99 / 0.01 / 1.00 / 2.0 × The same procedure as in Example 1 was performed except that 10 ^-6 was charged.
The obtained polycarbonate copolymer was cloudy and a transparent molded product could not be obtained.

[Example 4]
ISB, PDMS # 550, DPC and calcium acetate monohydrate in terms of molar ratio ISB / PTMG # 1000 / DPC / calcium acetate monohydrate = 0.99 / 0.01 / 1.00 / 3.0 × The same procedure as in Example 1 was performed except that 10 ^-6 was charged.
The obtained polycarbonate copolymer was cloudy and a transparent molded product could not be obtained.

[Example 5]
ISB, PEG # 400, DPC and calcium acetate monohydrate in a molar ratio of ISB / PEG # 1000 / DPC / calcium acetate monohydrate = 0.97 / 0.03 / 1.00 / 8.00 × The same procedure as in Example 1 was performed except that ^10-7 was charged.
The obtained polycarbonate copolymer had good transparency, and the haze was lower than that of Example 1.

[Example 6] ISB / PEG # 400, DPC and calcium acetate monohydrate in a molar ratio of ISB / PEG # 1000 / DPC / calcium acetate monohydrate = 0.93 / 0.07 / 1.00 This was carried out in the same manner as in Example 1 except that it was charged to /8.00×10 ⁻⁷ .
The obtained polycarbonate copolymer had good transparency, and the haze was lower than that of Example 1.

[Comparative Example 1]
ISB, DPC and calcium acetate monohydrate were charged in a molar ratio of ISB / DPC / calcium acetate monohydrate = 1.00 / 1.00 / 8.00 × 10 ⁻⁷ , and final polymerization temperature Was carried out in the same manner as in Example 1 except that the temperature was changed to 240 ° C.
The polycarbonate copolymer obtained had a reduced viscosity of 0.389 dl / g and a glass transition temperature of 159 ° C., and a transparent resin was obtained. However, the tensile test showed only a low tensile elongation.

[Comparative Example 2]
ISB, DPC and calcium acetate monohydrate were charged in a molar ratio of ISB / DPC / calcium acetate monohydrate = 1.00 / 1.00 / 1.00 × 10 ⁻⁶ , and final polymerization temperature Was carried out in the same manner as in Example 1 except that the temperature was changed to 250 ° C.
The polycarbonate copolymer obtained had a reduced viscosity of 0.475 dl / g and a glass transition temperature of 161 ° C., and a transparent resin was obtained.
Since the melt viscosity was very high, the moldability during injection molding was poor, silver was generated in the molded product, and haze was deteriorated. In the tensile test, sufficient tensile elongation was obtained.

[Comparative Example 3]
ISB, CHDM, DPC and calcium acetate monohydrate in a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.90 / 0.10 / 1.00 / 1.0 × 10 ⁻⁶ The same procedure as in Example 1 was performed, except that charging was performed.
The reduced viscosity of the obtained polycarbonate copolymer was 0.460 dl / g, and the glass transition temperature was 143 ° C.
A resin with good transparency was obtained, but the tensile test showed only low tensile elongation.

[Comparative Example 4]
ISB, CHDM, DPC and calcium acetate monohydrate in a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.0 × 10 ⁻⁶ The same procedure as in Example 1 was performed, except that charging was performed.
The reduced viscosity of the obtained polycarbonate copolymer was 0.480 dl / g, and the glass transition temperature was 122 ° C. Transparency was good. These results are shown in Table 1. The haze was low and the tensile elongation was excellent, but the pencil hardness decreased and the photoelastic coefficient increased.

  The above results are comprehensively evaluated from various evaluations and are shown in Table 1 below. The glass transition temperature (Tg), haze, tensile elongation, melt viscosity, pencil hardness and photoelastic coefficient are comprehensively taken into consideration, and those with few defects are comprehensively excellent. Somewhat inferior ones were indicated by Δ, and one inferior ones by ×.

  Compared to a polycarbonate composed only of sugar-derived alcohol, the polycarbonate of the present invention has a large tensile elongation, a low haze and excellent transparency, a sufficient pencil hardness and a high surface hardness, and at the same time a glass transition temperature. From the viewpoint that the molding process is low and good, it is excellent overall. Polycarbonates composed only of sugar-derived alcohols have low tensile elongation and low values, or those with large tensile elongation have only a poor moldability due to their extremely high melt viscosity.

  Also, compared with a copolymer polycarbonate using a low molecular weight dihydroxy compound as a copolymerization component, the tensile elongation is large and the pencil hardness is high, so that it is excellent overall. In the case of a copolymer polycarbonate using a low molecular weight dihydroxy compound as a copolymerization component, the pencil elongation is F and the surface hardness is inferior when the tensile elongation is low and the tensile elongation is large. .

  Furthermore, the copolymeric polycarbonate of the present invention has a higher degree of planting than using a low molecular weight dihydroxy compound as a copolymerization component, and at the same time is excellent in mechanical properties and surface hardness. Further, it is possible to obtain a material having high transparency and low optical distortion.

The polycarbonate copolymer of the invention has high pencil hardness, high surface hardness, and can be suitably used for film applications and structural material applications such as housings that dislike surface scratches.
The polycarbonate copolymer of the present invention is suitable for films that require flexibility, sheet fields, bottles that require heat resistance, container fields, and various structural materials that require impact strength. In addition, since optical distortion is small, lens lenses such as camera lenses, finder lenses, CCD and CMOS lenses, retardation films used for liquid crystals and plasma displays, films such as diffusion sheets and polarizing films, sheets and optical disks It is suitable for use in applications such as a binder for fixing a film, a sheet, an optical material, an optical component, a dye, a charge transfer agent and the like.

Claims (9)

  A copolymeric polycarbonate comprising a sugar-derived alcohol and a polydiol, wherein the structure derived from the sugar-derived alcohol is greater than 90 mol% with respect to the total amount of the repeating structure portion other than the carbonate bond portion.   The copolymer polycarbonate of Claim 1 whose glass transition temperature is 60 degreeC or more.   The copolymer polycarbonate according to claim 1 or 2, wherein the haze is 10.0% or less.   The copolymeric polycarbonate according to any one of claims 1 to 3, wherein the tensile elongation is 10% or more.   The copolycarbonate according to any one of claims 1 to 4, wherein the pencil hardness is F or more. The copolymer polycarbonate according to any one of claims 1 to 5, wherein a melt viscosity at 240 ° C at a shear rate of 1000 sec ^-1 is 800 Pa · s or less. The copolymeric polycarbonate according to any one of claims 1 to 6, wherein the sugar-derived alcohol is a compound represented by the following formula (1).

The copolymer polycarbonate according to any one of claims 1 to 7, wherein the polydiol is a polydiol represented by the following formula (2).

(In Formula (2), n is 2-120. R is H or a methyl group.) The copolymer polycarbonate according to any one of claims 1 to 8, obtained by melt polycondensation of the sugar-derived alcohol, the polydiol, and a carbonic acid diester represented by the following formula (3). .

(In Formula (3), A ¹ and A ² are each independently an aliphatic group having 1 to 18 carbon atoms which may have a substituted or unsubstituted substituent, or a substituted or unsubstituted group. A substituted aromatic group having 6 to 18 carbon atoms may be an aromatic group, and A ¹ and A ² may be the same or different.