JP2009144013A - Civil engineering and construction material component comprising polycarbonate - Google Patents

Abstract

【選択図】 なし[PROBLEMS] To provide material parts having characteristics suitable for the field of civil engineering and architecture while improving the environment and resource conservation as much as possible.
A civil engineering and building material part comprising a polycarbonate containing a structural unit derived from a dihydroxy compound represented by the following general formula (1).

[Selection figure] None

Description

  The present invention consists of a polycarbonate polymer containing isosorbide which is a biomass resource, and has a glass transition temperature, high surface hardness, little discoloration due to ultraviolet rays, and good mechanical strength, such as sheets, plates and films. It is about.

  Plastic sheets are used in various applications because of their low specific gravity and easy processing such as cutting and cutting. Especially in the case of transparent sheets for civil engineering and building materials, as concrete examples of lighting and sound insulation fields, arcade ceiling sheets and plates, sound insulation walls such as roads, facility roofing materials, signs, and in the housing equipment field, carport sheets and Corrugated sheets, terrace sheets, signboards, and housing interior materials. Conventionally, polyvinyl chloride, polyacrylate, and polycarbonate have been used for these applications. Here, since the polyvinyl chloride resin may generate dioxins at the time of waste incineration, it is not preferable for the environment, and its use has decreased recently.

On the other hand, in these applications, since the size of the sheet is large, dimensional stability against changes in the operating environment temperature is required, and in an amorphous resin, the glass transition temperature (T _g ) of the resin is high. For example, if the temperature is 80 ° C. or higher, more preferably 100 ° C. or higher, the dimensional change is suppressed in a considerable temperature range, so that the heat resistance of the sheet, for example, the glass transition temperature (T _g ) Is an important factor. From this point, since the glass transition temperature of the polyacrylic resin is 80 to 90 ° C., there are restrictions on the application to be applied. Since the glass transition temperature of the polycarbonate resin is 130 to 150 ° C., it can be applied to most fields of civil engineering and building materials from the viewpoint of heat resistance.

  Furthermore, it is desirable that the sheet has ultraviolet (UV) resistance and high surface hardness, good tensile strength, high optical transparency and good impact strength. Polyacrylic resin has less discoloration due to ultraviolet rays, high surface hardness, and good transparency, but is slightly inferior in mechanical strength, and also has a problem that flame retardancy does not reach the self-extinguishing class There is. On the other hand, polycarbonate is excellent in mechanical strength and self-extinguishing, but has a problem that it has a large color change due to ultraviolet rays and a low surface hardness. Low surface hardness is important in civil engineering and building materials applications, as the surface of the sheet is scraped by flying sand, etc. during use, leading to reduced transparency and, in severe cases, reduced mechanical strength. It is a characteristic.

  By the way, polyvinyl chloride, polyacrylate and polycarbonate are generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the depletion of petroleum resources, and there is a demand for providing civil engineering and building materials from plastic using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. Development of civil engineering and building material parts such as sheets, plates, and films made of plastic is required.

  Conventionally, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1). However, the polycarbonate obtained is brown and is not satisfactory. Further, as a copolymerized polycarbonate of isosorbide and another dihydroxy compound, a polycarbonate copolymerized with bisphenol A has been proposed (for example, see Patent Document 2), and further, by copolymerizing isosorbide and an aliphatic diol. Attempts have been made to improve the rigidity of homopolycarbonate composed of isosorbide (see, for example, Patent Document 3).

  On the other hand, many polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, have been proposed (for example, Patent Documents 4 and 5). The molecular weight of these polycarbonates is as low as about 4000 at most. Therefore, many of them have a low glass transition temperature.

In this way, polycarbonates using isosorbide have been proposed, but these documents disclose only the glass transition temperature and the basic mechanical properties for the above-mentioned civil engineering and building material parts. However, it does not disclose characteristics such as surface hardness that are important to the above.
GB1079686 Publication JP-A-56-55425 WO 2004/111106 gazette JP-A-6-145336 Japanese Patent Publication No. 63-12896

  As described above, polyvinyl chloride, polyacrylate, and polycarbonate, which are currently widely used in civil engineering and building material applications, have some problems in the properties for the applications, and in the construction of a better future society. Also have problems from the viewpoint of environmental and oil resource conservation. This was done for the purpose of improving the environment and resource conservation as much as possible, and at the same time providing material parts with characteristics suitable for civil engineering and construction.

  In view of the above-mentioned problems, the present inventors have found that these properties are civil engineering architecture because polycarbonates made from plant-derived monomers, such as isosorbide, have high surface hardness, low weather discoloration, and self-extinguishing properties. It was found that the material parts are good in important characteristics, and the present invention has been completed. Furthermore, it has been found that a polycarbonate copolymer obtained by copolymerizing an alicyclic dihydroxy compound has a good balance between glass transition temperature and impact resistance and can be applied to a wide range of civil engineering and building material parts.

That is, the gist of the present invention resides in the following [1] to [6].
[1] A civil engineering and building material part comprising a polycarbonate containing a structural unit derived from a dihydroxy compound represented by the following general formula (1).

[2] The civil engineering and building material part according to [1], wherein the polycarbonate has a glass transition temperature of 80 ° C. or higher.
[3] The civil engineering and building material part according to [1] or [2], wherein the polycarbonate further includes a structural unit derived from an alicyclic dihydroxy compound.
[4] The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate is 100: 0 to 30:70. The civil engineering and building material part according to [3], which is in a range of
[5] The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate is 90:10 to 40:60. The civil engineering and building material part according to [3], which is in a range of
[6] The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate is 85:15 to 45:55. The civil engineering and building material part according to [3], which is in a range of

  Bisphenol A type polycarbonate resins and acrylic resins have advantages and disadvantages in characteristics such as surface hardness, weather resistance, flammability, glass transition temperature, and impact resistance, and also have problems in environmental and petroleum resource conservation. However, civil engineering and building material parts made of polycarbonate of the present invention using plant-derived monomers have good environmental and petroleum resource conservation, high surface altitude, small weather discoloration, self-extinguishing, Good balance between glass transition temperature and impact strength, so in daylighting and sound insulation fields, such as arcade ceiling sheets and plates, road insulation walls, facility roofing materials, signs, and housing equipment, carport seats and corrugated sheets It can be used for terrace seats, signboards, and home interior materials.

  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. It is not limited to the contents.

  The polycarbonate of the present invention is characterized in that it contains a structural unit derived from a dihydroxy compound represented by the following general formula (1), and a part of the dihydroxy compound is replaced with another type of dihydroxy compound such as a fatty acid. It may be a copolymer substituted with a structural unit derived from an aromatic or aromatic dihydroxy compound, or a copolymerized structural unit such as polyalkylene glycol.

  In the present invention, examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide, and isoidet, which are related to stereoisomers. These may be used alone or in combination of two kinds. A combination of the above may also be used.

  Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and manufacture, optical properties, moldability From the viewpoint of

  Since isosorbide is gradually oxidized by oxygen, in order to prevent decomposition due to oxygen during storage and handling during production, do not mix moisture, use an oxygen scavenger, or use a nitrogen atmosphere. It is important to set it down. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate is produced using isosorbide containing these decomposition products, the resulting polycarbonate is colored or causes a significant deterioration in physical properties. In addition, the polymerization reaction may be affected, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate, or physical properties may be significantly deteriorated. As the stabilizer, a reducing agent or an antacid is used. Among them, examples of the reducing agent include sodium borohydride and lithium borohydride. Examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt also serves as a polymerization catalyst, and if it is excessively added, the polymerization reaction may not be controlled.

In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Moreover, also when the stabilizer is mix | blended in order to prevent the oxidation and decomposition | disassembly of isosorbide, you may distill isosorbide as needed. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. After the atmosphere is an inert gas atmosphere such as argon or nitrogen, distillation is performed under reduced pressure.
By performing such distillation of isosorbide, in the present invention, it is preferable to use a high purity isosorbide having a formic acid content of less than 20 ppm, more preferably 10 ppm or less, particularly 5 ppm or less.

  On the other hand, the dihydroxy compound of a copolymerization structural unit suitable for use in the present invention may be any of linear aliphatic, cycloaliphatic, and aromatic dihydroxy compounds. Examples of linear aliphatic dihydroxy compounds include butanediol-1,4, pentanediol-1,5, neopentyl glycol, hexanediol-1,6, heptanediol-1,7, octanediol-1,8,2- Examples include ethylhexanediol-1,6,2,2,4-trimethylhexanediol-1,6, decanediol-1,10, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and the like.

  Examples of the cycloaliphatic (alicyclic) dihydroxy compound that can be used in the present invention include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1, Hexanediols such as 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol And norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol and the like. Of these, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,2-cyclohexanedimethanol are preferred.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned.

  Further, the polyalkylene glycol as the copolymerization unit preferably contains 2 to 40 carbonsyl groups having 2 to 4 carbon atoms per molecule, and examples thereof include polyethylene glycol and polypropylene glycol.

  The hydroxy compound which is these copolymerization structural units may be used individually by 1 type, and may mix and use 2 or more types. Use of a linear aliphatic dihydroxy compound or polyalkylene glycol as a copolymerization component is not preferable because the glass transition temperature is drastically lowered, and the use as a civil engineering / building material part is restricted. When an aromatic dihydroxy compound is used as a copolymerization component, the reactivity is significantly different from that of the dihydroxy compound represented by the general formula (1), and transparency and the like deteriorate. In general, it is difficult to obtain a polycarbonate resin having a single dihydroxy compound represented by the general formula (1) having a high molecular weight. On the other hand, when a cycloaliphatic (sometimes referred to as alicyclic) dihydroxy compound is used as a copolymerization component, the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy as shown below. Good balance of reactivity with compounds, relatively high molecular weight, relatively low glass transition temperature, less than linear aliphatic dihydroxy compounds, sufficiently high surface hardness and mechanical strength This is desirable.

  As described above, a polycarbonate obtained by copolymerizing a structural unit derived from the dihydroxy compound represented by the general formula (1) and a structural unit derived from the alicyclic dihydroxy compound, which is a preferred polycarbonate in the present invention, has not yet been reported. The details thereof will be described below, but the copolymers with other dihydroxy compounds are basically similar, and can be produced with reference to the above-mentioned patent documents.

  About the content rate of the structural unit derived from the dihydroxy compound represented by General formula (1), and the structural unit derived from an alicyclic dihydroxy compound, it can select in arbitrary ratios. However, when a differential scanning calorimetry (DSC) is performed, a single glass transition temperature is given. The polycarbonate copolymer of the present invention is a dihydroxy compound represented by the general formula (1) and an alicyclic dihydroxy compound. The glass transition temperature can be obtained as a polymer having an arbitrary glass transition temperature from about 45 ° C. to about 155 ° C. depending on the application.

  Therefore, for civil engineering and building material applications of the present invention, by setting the glass transition temperature to 80 ° C. or higher, heat resistance (usable temperature) of 70 ° C. or higher can be ensured, and therefore, represented by the general formula (1). It is necessary to appropriately select the ratio between the structural unit derived from the dihydroxy compound and the structural unit derived from the alicyclic dihydroxy compound. The ratio is preferably 100: 0 to 30:70 (mol%), particularly 90:10 to 40:60 (mol%), more preferably 85:15 to 45:55 (mol%). If the number of structural units derived from the dihydroxy compound represented by the general formula (1) is larger than the above range and the number of structural units derived from the alicyclic dihydroxy compound is small, coloring tends to occur. Conversely, the structural formula is represented by the general formula (1). When the number of structural units derived from the dihydroxy compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight is difficult to increase and the glass transition temperature tends to decrease.

  The degree of polymerization of the polycarbonate of the present invention is precisely adjusted to a polycarbonate concentration of 1.00 g / dl using a 1: 1 mixed solution of phenol and 1,1,2,2, -tetrachloroethane as a solvent. The reduced viscosity (hereinafter simply referred to as “reduced viscosity of polycarbonate”) measured at a temperature of 20.0 ° C. ± 0.1 ° C. is 0.40 dl / g or more, particularly 0.40 dl / g or more. The degree of polymerization is preferably 0 dl / g or less. When the reduced viscosity of this polycarbonate is extremely low, the mechanical strength when molded into civil engineering and building materials is weak. Further, when the reduced viscosity of the polycarbonate is increased, the fluidity at the time of molding is lowered, the cycle characteristics are lowered, the distortion of the molded product is increased, and it tends to be easily deformed by heat. Therefore, the reduced viscosity of the polycarbonate of the present invention is preferably in the range of 0.40 dl / g to 2.0 dl / g, particularly 0.45 dl / g to 1.5 dl / g.

  The polycarbonate of the present invention can be produced by a generally used polymerization method, and the polymerization method may be either a solution polymerization method using phosgene or a melt polymerization method in which it reacts with a carbonic acid diester. In the presence, a melt polymerization method in which a dihydroxy compound is reacted with a diester carbonate that is less toxic to the environment is preferred.

  Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (2).

(In General formula (2), A and A 'are the C1-C18 aliphatic groups which may have a substituent, or the aromatic group which may have a substituent, A and A ′ may be the same or different.)

  Examples of the carbonic acid diester represented by the general formula (2) include diphenyl carbonate, substituted diphenyl carbonate represented by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Particularly preferred are diphenyl carbonate and substituted diphenyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more.

  The carbonic acid diester is preferably used in a molar ratio of 0.96 to 1.10, more preferably 0.98 to 1.04, relative to the dihydroxy compound. When this molar ratio is less than 0.96, the terminal OH groups of the produced polycarbonate are increased and the thermal stability of the polymer is deteriorated. On the other hand, when the molar ratio is higher than 1.10. The rate of the exchange reaction is reduced, making it difficult to produce a polycarbonate copolymer having a desired molecular weight, as well as increasing the amount of residual carbonic acid diester in the produced polycarbonate. This is not preferable because it causes odor of the molded product.

  Moreover, as a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only metal compounds and / or alkaline earth metal compounds.

  Examples of the alkali metal compound used as the polymerization catalyst 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 phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid Cium, 2 sodium hydrogen phosphate, 2 potassium hydrogen 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, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

  Examples of the alkaline earth 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, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

  These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more.

  Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethyl Sodium salt such as phenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, potassium salt, lithium Examples thereof include salts, calcium salts, barium salts, magnesium salts, and strontium salts.

  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 and the like.
These basic compounds may be used alone or in combination of two or more.

  When the alkali metal compound and / or alkaline earth metal compound is used, the polymerization catalyst is used in an amount of metal with respect to 1 mol in total of the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy compound. As a conversion amount, it is normally used within the range of 0.1 to 100 μmol, preferably within the range of 0.5 to 50 μmol, and more preferably within the range of 1 to 25 μmol. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the hue of the resulting polycarbonate deteriorates, By-products are generated and fluidity is lowered and gel is generated more frequently, making it difficult to produce polycarbonate having the target quality.

  In the production of the polycarbonate of the present invention, the dihydroxy compound such as the dihydroxy compound represented by the general formula (I) may be supplied as a solid, or heated and supplied in a molten state. Alternatively, it may be supplied as an aqueous solution. When these raw material dihydroxy compounds are supplied in a molten state or in an aqueous solution, there is an advantage that they can be easily measured and transported when industrially produced.

  In the present invention, the method of reacting the dihydroxy compound represented by the general formula (I) or the copolymer component with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in two or more multistage processes. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C, preferably 150 to 200 ° C for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onward, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure of the first stage, and at the same time, the phenol generated at the same time is removed from the reaction system. Is 200 Pa or less and a polycondensation reaction is performed under the temperature range of 210-280 degreeC.

  In the pressure reduction in this polycondensation reaction, it is important to control the balance between temperature and pressure in the reaction system. In particular, if either one of the temperature and the pressure is changed too quickly, unreacted monomers are distilled out, the molar ratio of the dihydroxy compound and the carbonic acid diester may be changed, and the degree of polymerization may be lowered. For example, when isosorbide and 1,4-cyclohexanedimethanol are used as the dihydroxy compound, 1,4-cyclohexanedimethanol is used when the molar ratio of 1,4-cyclohexanedimethanol to the total dihydroxy compound is 50 mol% or more. Since methanol easily distills out as a monomer, the reaction is carried out under a reduced pressure of about 13 kPa while the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour, and further up to about 6.67 kPa. When the temperature is increased at a temperature increase rate of 40 ° C. or less per hour under the pressure of, and finally the polycondensation reaction is performed at a temperature of 200 to 250 ° C. at a pressure of 200 Pa or less, the degree of polymerization is sufficiently increased. Since the obtained polycarbonate is obtained, it is preferable.

  In addition, when the molar ratio of 1,4-cyclohexanedimethanol is less than 50 mol% with respect to all dihydroxy compounds, particularly when the molar ratio is 30 mol% or less, 1,4-cyclohexanedimethanol Compared with the case where the molar ratio is 50 mol% or more, the viscosity rises rapidly. For example, the temperature is increased at a rate of 40 ° C. or less per hour until the pressure in the reaction system is reduced to about 13 kPa. And the reaction is carried out at a pressure of up to about 6.67 kPa while increasing the temperature at a rate of temperature rise of 40 ° C. or more, preferably at a rate of temperature rise of 50 ° C. or more per hour. When a polycondensation reaction is finally performed at a temperature of 220 to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate having a sufficiently high degree of polymerization is obtained, which is preferable.

  The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  When the polycarbonate of the present invention is produced by a melt polymerization method, a phosphoric acid compound or a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound components. When the addition amount of the phosphorus compound is less than the above lower limit, the effect of preventing coloring is small, and when it is more than the above upper limit, haze is increased, or on the contrary, the coloring is promoted or the heat resistance is lowered.

  When adding a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound component. It is preferable to do. If the amount of the phosphite compound is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, it may cause haze to increase, or conversely promote coloring or reduce heat resistance. Sometimes.

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, It is preferable to set it as 0.0001 mol% or more and 0.005 mol% or less, More preferably, it is 0.0003 mol% or more and 0.003 mol% or less. If the amount added is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, haze may be increased, or conversely, coloring may be promoted or heat resistance may be lowered.

  The polycarbonate of the present invention thus produced can be blended with a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate , Diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate (co) polymer, and further blending a phosphorous acid compound by the blending method described later, the haze at the time of polymerization More heat stabilizers can be blended while avoiding the rise, coloring, and heat resistance reduction, and the hue can be prevented from deteriorating.

  The blending amount of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.2 part by weight when polycarbonate is 100 parts by weight. Part is more preferred.

  The polycarbonate of the present invention can be blended with an antioxidant generally known for the purpose of antioxidant.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, One type or two or more types such as 4,8,10-tetraoxaspiro (5,5) undecane may be mentioned.

  The blending amount of these antioxidants is preferably 0.0001 to 0.5 parts by weight when the polycarbonate is 100 parts by weight.

  In addition, the polycarbonate of the present invention has a mold release within a range that does not impair the object of the present invention in order to further improve the release from the cooling roll during sheet molding or the mold release during injection molding. It is also possible to mix an agent.

  Such release agents include higher fatty acid esters of mono- or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like.

  Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

  As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

  One of these release agents may be used alone, or two or more thereof may be mixed and used.

  The compounding amount of the release agent is preferably 0.01 to 5 parts by weight when the polycarbonate is 100 parts by weight.

  Further, the polycarbonate of the present invention is significantly less discolored by ultraviolet rays than the current polycarbonate resin, but for the purpose of further improvement, an ultraviolet absorber and a light stabilizer are blended within a range that does not impair the purpose of the present invention. be able to.

  Examples of such ultraviolet absorbers and light stabilizers include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one), and the like.

These ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more.
Such a blending amount is preferably 0.01 to 2 parts by weight when the polycarbonate is 100 parts by weight.

  In addition, a blueing agent can be blended with the polycarbonate of the present invention in order to counteract the yellowness of civil engineering and building material parts based on polymers and ultraviolet absorbers. Any bluing agent can be used without any problem as long as it is used for the current polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available.

  Specific examples of the bluing agent include, for example, the general name Solvent Violet 13 [CA.No (Color Index No) 60725], the general name Solvent Violet et31 [CA.No 68210, the general name Solvent Violet 33 [CA.No 60725; Typical examples are Solvent Blue 94 [CA.No 61500], generic name Solvent Violet 36 [CA.No 68210], generic name Solvent Blue 97 ["Macrolex Violet RR" manufactured by Bayer, Inc.] and generic name Solvent Blue 45 [CA.No 61110]. As mentioned.

These bluing agents may be used individually by 1 type, and may use 2 or more types together. These blueing agents are usually blended at a ratio of 0.1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ parts by weight when polycarbonate is 100 parts by weight.

  The composition of the polycarbonate of the present invention and the above-mentioned various additives is, for example, a method of mixing with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc., or each of the above components For example, there is a solution blending method in which it is mixed in a state of being dissolved in a common good solvent such as methylene chloride, but this is not particularly limited, and any method can be used as long as it is a commonly used polymer blending method. It may be used.

  The polycarbonate of the present invention thus obtained or the polycarbonate composition obtained by adding various additives to the polycarbonate as it is or after being once pelletized by a melt extruder, injection molding method, extrusion molding method, compression molding method, etc. It can be made into a civil engineering and building material molding by a generally known method.

  In order to increase the miscibility of the polycarbonate of the present invention and obtain stable physical properties, it is preferable to use a single screw extruder or a twin screw extruder in the melt extrusion. A method using a single screw extruder or a twin screw extruder does not use a solvent or the like, has a small environmental load, and can be preferably used from the viewpoint of productivity. Polycarbonate for civil engineering and building material use of the present invention (in the case of the extruder, the melt kneading temperature of the extruder is usually 200 to 300 ° C., preferably 220 to 260 ° C. If the melt kneading temperature is lower than 200 ° C., the polycarbonate The melt viscosity is high and the load on the extruder is increased, resulting in a decrease in productivity.If the temperature is higher than 300 ° C., the polycarbonate is likely to be deteriorated, and the color of the polycarbonate is yellowed or the molecular weight is reduced. May deteriorate.

  When using an extruder, it is desirable to install a filter in order to prevent polycarbonate from being burned and foreign matters from being mixed during extrusion. The size (opening) of the filter for removing foreign substances depends on the required optical accuracy, but is preferably 100 μm or less. In particular, in the case of dislike mixing foreign substances, it is preferably 40 μm or less, more preferably 10 μm or less. Furthermore, it is desirable to carry out the extrusion of the polycarbonate in a clean room in order to prevent foreign matter from being mixed after the extrusion.

  Further, when cooling the extruded polycarbonate into 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. There are various sizes (openings) of filters to be used, but those having a filter of 10 to 0.45 μm are preferable.

  The polycarbonate of the present invention is not limited to the above, and various known additives such as ultraviolet absorbers, weather resistance imparting agents, impact resistance improvers, flame retardants, flame retardants are within the scope of the present invention. Auxiliaries, hydrolysis inhibitors, antistatic agents, foaming agents, dyes and pigments may be contained. In addition, for example, a civil engineering construction of a polymer alloy kneaded with a synthetic resin such as aromatic polycarbonate, aromatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, or a biodegradable resin such as polylactic acid or polybutylene succinate. It can also be used as a material for material parts.

  The civil engineering and building material parts using the polycarbonate of the present invention can be usually formed in the same manner as the molding method of bisphenol A type polycarbonate resin. In extrusion molding of a sheet or the like, for example, the die temperature can be set to 230 to 280 ° C and the cooling roll temperature can be set to 80 to 120 ° C. In the case of injection molding, the mold temperature is preferably 30 to 120 ° C., and the resin temperature is preferably 220 to 290 ° C.

  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. In the following, the physical properties and characteristics of polycarbonate were evaluated by the following methods.

(1) Reduced viscosity
Using an Ubbelohde viscometer, a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 was used as a solvent, the concentration was precisely adjusted to 1.00 g / dl, and a temperature of 20. Measurement was performed at 0 ° C. ± 0.1 ° C. The higher this number, the greater the molecular weight.

(2) Glass transition temperature (Tg)
Using a differential scanning calorimeter ("DSC822" manufactured by METTLER) with a sample of about 10mg, heated at a rate of temperature increase of 10 ° C / min, measured according to JIS K 7121 (1987). The extrapolated glass transition start temperature Tg, which is the temperature at the intersection of the straight line obtained by extending the line to the high temperature side and the broken line drawn at the point where the slope of the step change portion of the glass transition is maximized, was determined. .

(3) Impact strength
Test using Custom Scientific's minimax injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm The piece was injection-molded, and a notch with a depth of 1.2 mm was provided with a notching machine to obtain a test piece.
About this test piece, the Izod impact strength with a notch at 23 degreeC was measured using the custom scientific minimax Izod impact tester "CS-183TI type". The larger this value, the greater the impact strength and the more difficult it is to break.

(4) Scratch hardness (pencil method) test Using a custom scientific mini-max injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm and a width of 6 .2mm, 0.8mm thick test piece is injection molded, and the pencil hardness is in the range of 6B to 6H in accordance with JIS K5600-5-4, using a scratch hardness (pencil method) tester manufactured by Co-Tech. Measured with 6B indicates that the surface hardness is low, and 6H indicates that the surface hardness is high.

(5) Flammability test Using Custom Scientific's minimax injection molding machine "CS-183MMX", temperature of 240-300 ° C, length 31.5mm, width 6.2mm, thickness A test piece having a thickness of 0.8 mm was injection-molded and measured according to a UL-94 standard horizontal flammability test (HB). However, the combustion state was confirmed by a method in which a test flame was applied to one end of the test piece for 30 seconds and removed. If the fire is extinguished without spreading over the entire specimen, it is judged as a self-extinguishing material.

(6) Weather resistance discoloration test Using a custom scientific mini-max injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., injection-molded length 31.5 mm, width 6. A test specimen with a thickness of 2 mm and a thickness of 0.8 mm was installed on the inclined surface of 45 degrees south in Yokkaichi, Yokkaichi City, Mie Prefecture, and the weather discoloration test was conducted from mid-January to mid-October 2006. Carried out. For the test pieces before and after the test, a color difference ΔE was measured using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller ΔE, the smaller the discoloration.

(7) Quantification of formic acid Isosorbide was diluted 100 times with pure water and measured with a DX-500 model manufactured by Ion Chromatograph Dionex.
In addition, the formic acid content of isosorbide used in Examples 1 to 5 was 5 ppm.

[Example 1]
13.4-cyclohexanedimethanol (Eastman, hereinafter abbreviated as “1,4-CHDM”) with respect to 27.7 parts by weight (0.516 mol) of isosorbide (Rocket Fleure) 0 parts by weight (0.221 mol), diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol), and cesium carbonate (Wako Pure Chemical Industries, Ltd.) as a catalyst Manufactured) 2.21 × 10 ⁻⁴ parts by weight (1.84 × 10 ⁻⁶ mol) was put into a reaction vessel, and the heating bath temperature was 150 ° C. as the first step of the reaction under a nitrogen atmosphere. The raw material was dissolved with stirring as necessary (about 15 minutes).
Subsequently, the pressure was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while the heating bath temperature was increased to 190 ° C. over 1 hour.

  After maintaining the entire reaction vessel at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is set to 6.67 kPa, the heating bath temperature is increased to 230 ° C. in 15 minutes, and the generated phenol is removed. It was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was allowed to reach 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was extruded into water to obtain polycarbonate pellets. With respect to the obtained polycarbonate, reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, flammability, and weather resistance discoloration (ΔE) were evaluated by the above-described evaluation methods. The obtained results are shown in Table 1.

[Example 2]
In Example 1, 19.7 parts by weight (0.363 mol) of isosorbide, 21.6 parts by weight of 1,4-CHDM (0.404 mol), 58.8 parts by weight of DPC (0.741 mol), and carbonic acid as a catalyst. It implemented similarly except having changed into cesium 2.19 * 10 <^-4> weight part (1.82 * 10 <^-6> mol). The obtained results are shown in Table 1.

[Example 3]
In Example 1, 25.8 parts by weight (0.480 moles), 58.6 parts by weight (0.734 moles) DPC, and 15.7 parts by weight (0.288 moles) isosorbide, and The same procedure was performed except that the catalyst was changed to 2.18 × 10 ⁻⁴ parts by weight (1.80 × 10 ⁻⁶ mol) of cesium carbonate. The obtained results are shown in Table 1.

[Example 4]
In Example 1, 35.9 parts by weight (0.674 moles) of isosorbide, 4.4 parts by weight of 1,4-CHDM (0.083 moles), 59.7 parts by weight of DPC (0.764 moles), carbonic acid as a catalyst. It implemented similarly except having changed to cesium 2.22 * 10 <^-4> weight part (1.87 * 10 <^-6> mol). The obtained results are shown in Table 1.

[Example 5]
In Example 1, 59.9 parts by weight of DPC (0.592 mol, cesium carbonate 2.23 × 10 ⁻⁴ parts by weight (1.45 as a catalyst) with respect to 40.1 parts by weight (0.581 mol) of isosorbide. This was carried out in the same manner except that × 10 ⁻⁶ mol) was changed to Table 1. The results obtained are shown in Table 1.

[Comparative Example 1]
With respect to bisphenol A type polycarbonate resin (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics), reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, flammability, and weather resistance discoloration (ΔE) were evaluated by the above-described evaluation methods. . The obtained results are shown in Table 1.

[Comparative Example 2]
For the polyacrylic resin (Acrypet MF manufactured by Mitsubishi Rayon Co., Ltd.), the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, flammability, and weathering discoloration (ΔE) were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.

Table 1 shows the following.
1) Polycarbonate resin is a self-extinguishing material having properties such that the glass transition temperature and impact strength are too sufficient as materials for civil engineering and building material parts. However, the pencil hardness is as low as B, and weather discoloration is a big problem. On the other hand, the acrylic resin has a sufficient pencil hardness of 2H and little discoloration, but the glass transition temperature and impact resistance are the lower limit values and are easily combustible.
2) Polycarbonate copolymers having a mixing ratio of isosorbide of Examples 1 and 2 and 1,4-CHDM of 68/32 and 47/53 have sufficient glass transition temperature and impact strength for civil engineering and building materials, Pencil hardness and weather resistance discoloration are characteristics close to acrylic resin, and flammability, which was a major drawback of acrylic resin, has also been improved to a self-extinguishing class. It is a very good characteristic for civil engineering and building materials.
3) In Example 3 in which the blending ratio of isosorbide and 1,4-CHDM is 37/63, the glass transition temperature is close to that of an acrylic resin, but the impact resistance is further improved compared to the polycarbonate resin. On the other hand, Examples 4 and 5 having a blending ratio of 89/11 and 100/0 have a glass transition temperature close to that of a polycarbonate resin, but have an impact resistance close to that of an acrylic resin. Weather resistance discoloration is excellent, and it is necessary to select a field among civil engineering and building materials, but the characteristics that have been a significant limitation when using polycarbonate resin and acrylic resin have been improved, increasing the possibility of use It is something to be made.

  Civil engineering building material parts made of polycarbonate of the present invention using plant-derived monomers have good environmental and petroleum resource conservation, high surface altitude, low weather discoloration resistance, self-extinguishing properties, glass transition A good balance between temperature and impact strength, so in the lighting and sound insulation fields, such as arcade ceiling sheets / plates, sound insulation walls such as roads, facility roofing materials, signs, and housing equipment fields, carport seats, corrugated plates and terraces It can be used for seats, signboards, house interior materials, etc.

Claims (6)

Civil engineering and building material parts made of polycarbonate containing structural units derived from dihydroxy compounds represented by the following general formula (1).

  The civil engineering / building material part according to claim 1, wherein the polycarbonate has a glass transition temperature of 80 ° C. or higher.   The civil engineering and building material part according to claim 1 or 2, wherein the polycarbonate further contains a structural unit derived from an alicyclic dihydroxy compound.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate and the structural unit derived from the alicyclic dihydroxy compound is in the range of 100: 0 to 30:70. The civil engineering and building material part according to claim 3, wherein the part is a civil engineering and building material part.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate and the structural unit derived from the alicyclic dihydroxy compound is in the range of 90:10 to 40:60. The civil engineering and building material part according to claim 3, wherein the part is a civil engineering and building material part.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate is in the range of 85:15 to 45:55. The civil engineering and building material part according to claim 3, wherein the part is a civil engineering and building material part.