JP6507495B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a resin composition containing a polycarbonate resin as a main component. More specifically, the present invention relates to a resin composition which is mainly composed of a polycarbonate resin whose raw material is biomass resource, and which is excellent in balance of transparency, heat resistance, low water absorption, surface hardness, low birefringence and impact resistance.

  In recent years, due to concerns about the exhaustion of petroleum resources and the problem of an increase in carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum and that carbon neutrality does not increase carbon dioxide even when burned However, in the field of polymers, biomass plastics produced from biomass resources are being actively developed.

  Since polylactic acid, a typical example of biomass plastic, has high transparency and excellent mechanical properties, its application development is spreading to dishes, packaging materials, general goods, etc., and its potential as an industrial material is also considered It has become. However, it can not be said that polylactic acid can be used widely as an industrial material from the viewpoints of heat resistance, hydrolysis resistance, impact resistance and the like.

  On the other hand, with the development of technology in the field of electronics and flat panel displays (FPDs), among industrial materials, the demand for optical materials such as plastic cell substrates, polarizing films, retardation films and transparent protective films is increasing. Among them, aromatic polycarbonate resins are being used as optical materials because they are excellent in heat resistance, transparency and the like.

  Under such background, in order to improve the rigidity of the aromatic polycarbonate resin and simultaneously improve all the transparency, moldability, transferability, etc., Patent Document 1 discloses biphenyl to 100 parts by mass of the aromatic polycarbonate resin. There is disclosed a resin composition comprising 0.01 to 40 parts by mass of a compound and / or a terphenyl compound.

In Patent Document 2, as a polycarbonate resin excellent in the balance of low birefringence, surface hardness, impact resistance, and heat resistance, an ether diol (isosorbide or the like) which can be produced from sugar using biomass resources as a raw material And polycarbonate resins polymerized from alicyclic dihydroxy compounds are disclosed.
Further, Patent Document 3 contains layered silicate which has been organically treated as a functionalization of a polycarbonate resin having isosorbide as a constitutional unit, and has excellent rigidity and thermal stability, and good surface hardness and transparency. Polycarbonate resin compositions are disclosed.

JP, 2000-239513, A JP, 2009-144018, A JP, 2011-1454, A

  In general, aromatic polycarbonate resins based on bisphenol-A are relatively flexible and therefore difficult to apply to applications requiring surface hardness. On the other hand, when attempting to improve the rigidity by the technique according to Patent Document 1, a large problem which has not been clarified, that is, the heat resistance of the aromatic polycarbonate resin is significantly impaired occurs. In addition, in general, an aromatic polycarbonate resin having bisphenol-A as a main component has a high photoelastic coefficient and is likely to cause birefringence due to stress. Therefore, it is considered difficult to balance the heat resistance, the low birefringence, and the surface hardness required for the optical material.

  On the other hand, the polycarbonate resins disclosed in Patent Document 2 and Patent Document 3 have high polarity compared to aromatic polycarbonate resins obtained from diols having a large amount of oxygen atoms derived from the structure of ether diol and having no ether moiety. . Therefore, it has a problem that it has high water absorption compared to aromatic polycarbonate resin, and the dimensional stability of the molded product is reduced due to water absorption, the heat resistance is reduced at the time of wet heat, and the birefringence is easily changed. Further, depending on the application of the optical material, further improvement in surface hardness is also required.

  That is, the object of the present invention is to obtain a polycarbonate resin composition excellent in the balance of heat resistance, low water absorption, surface hardness, transparency, low birefringence and impact resistance.

As a result of intensive studies conducted in view of the above problems, the present inventors have surprisingly found that a polycarbonate resin containing a structural unit derived from a specific ether diol is a main component and a specific amount of a specific aromatic compound is contained The polycarbonate resin composition thus obtained has almost no decrease in heat resistance as compared with the case where an aromatic polycarbonate resin is used, and further, the surface hardness and the low water absorption are improved, and the transparency and the low birefringence are obtained. The inventors have also found that they are excellent in impact resistance, and have completed the present invention.
That is, the present invention is as follows.

[1] A polycarbonate resin composition containing the following polycarbonate resin (A) as a main component and containing the following aromatic compound (B), and the total mass of the polycarbonate resin (A) and the aromatic compound (B) The polycarbonate resin composition characterized in that the proportion of the aromatic compound (B) occupied is 1% by mass or more and 8% by mass or less.
(A) Polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1) in part of the structure (B) at least one selected from the group consisting of a biphenyl compound, a terphenyl compound and a stilbene compound Species of aromatic compounds

[2] The glass transition temperature Tg (X) of the polycarbonate resin composition is single, and the glass transition temperature Tg (A) of the polycarbonate resin (A) and the Tg (X) are
0 ° C. ≦ Tg (A) −Tg (X) ≦ 30 ° C.
The polycarbonate resin composition according to the above [1], having the following relationship:
[3] The composition ratio of the structural unit derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate resin (A) is 30 mol% or more and 95 mol% or less. The polycarbonate resin composition as described in 2].
[4] The polycarbonate resin composition according to any one of the above [1] to [3], wherein the polycarbonate resin (A) further comprises a structural unit derived from 1,4-cyclohexanedimethanol .
[5] A sheet formed using the polycarbonate resin composition according to any one of [1] to [4].

  According to the present invention, a polycarbonate resin composition using biomass resources as a raw material which is excellent in the balance of heat resistance, low water absorption, surface hardness, transparency, low birefringence and impact resistance and is suitable for applications such as optical materials It is possible to get things.

  The embodiment of the present invention will be described in detail below, but the description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following unless the gist is exceeded. The present invention is not limited to the contents of the above, and can be appropriately modified and implemented.

[Polycarbonate resin (A)]
The polycarbonate resin composition of the present invention (hereinafter, also referred to as “the present composition”) is a polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following general formula (1) in part of the structure (A) is a main component. Here, the main component means that the content ratio of (A) is the largest in all the components constituting the composition, and usually more than 50% by mass, preferably 70% by mass or more, more preferably 90 It says that it is mass% or more.
By using the polycarbonate resin (A) as a main component, the present composition is excellent in the balance of heat resistance, low water absorption, transparency, surface hardness, low birefringence and impact resistance.

Examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide and isoidide which are in a stereoisomer relationship. One of these may be used alone, or two or more of these may be used in combination.
Since these dihydroxy compounds do not have a phenolic hydroxyl group, they are usually difficult to polymerize by the interfacial method, and the polycarbonate resin (A) according to the present invention is usually produced by transesterification using a diester of carbonic acid .

  Among these dihydroxy compounds, among others, isosorbide obtained by dehydration condensation of sorbitol which is abundant as a plant-derived resource and is produced from various starches which are easily available is easy to obtain and manufacture, light resistant The most preferable in view of the properties, optical properties, moldability, heat resistance and carbon neutrality.

  In addition, the dihydroxy compound which has a cyclic ether structure represented by the said General formula (1) which is represented by isosorbide tends to be gradually oxidized by oxygen. For this reason, in order to prevent decomposition by oxygen during storage or handling at the time of production, it is important that water is not mixed in, and that an oxygen scavenger be used or a nitrogen atmosphere be used. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin is produced using isosorbide containing these decomposition products, the polycarbonate resin to be obtained may be colored or the physical properties may be significantly degraded. It is also not preferable because it affects the polymerization reaction and a high molecular weight polymer can not be obtained. However, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, the obtained polycarbonate resin may be colored or the physical properties may be significantly deteriorated.

  Therefore, in the present invention, it is preferable to use the following specific stabilizer. As the stabilizer, it is preferable to use a stabilizer such as a reducing agent, an antacid agent, an antioxidant, an oxygen scavenger, a light stabilizer, a pH stabilizer, a thermal stabilizer, etc. In particular, the dihydroxy compound is denatured under acidic conditions It is preferable to contain a basic stabilizer because it is easy. Among these, sodium borohydride, lithium borohydride and the like can be mentioned as the reducing agent, and alkalis such as sodium hydroxide and the like can be mentioned as the antacid. However, the addition of the alkali metal salt is not preferable because the alkali metal can be a polymerization catalyst, and therefore, when the addition is excessive, the polymerization reaction can not be controlled.

  As a basic stabilizer, hydroxides, carbonates, phosphates, phosphites, hypophosphites of metals of Group 1 or 2 in the long period 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, Triethylmethyl ammonium hydroxide, triethyl benzyl ammonium hydroxide, triethyl phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, tributyl phenyl ammonium Basic ammonium compounds such as um hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl ammonium hydroxide, 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 And amine compounds such as aminoquinoline. Among them, sodium or potassium phosphates and phosphites are preferable in view of the effects and ease of distillation removal described later, and among these, disodium hydrogen phosphate and disodium hydrogen phosphite are preferable.

  The content of the basic stabilizer in the dihydroxy compound is not particularly limited, but from the viewpoint of balance between the expression of the effect of preventing the deterioration of the dihydroxy compound and the suppression of the modification of the dihydroxy compound, the dihydroxy compound is usually selected. The amount is 0.0001% to 1% by mass, preferably 0.001% to 0.1% by mass.

  In addition, when a dihydroxy compound containing such a basic stabilizer is used as a raw material for producing a polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, which makes it difficult to control the polymerization speed and quality, and also deteriorates the initial hue. The basic stabilizer is preferably removed by ion exchange resin, distillation or the like before using it as a raw material for producing a polycarbonate resin, since the light resistance of the composition obtained as a result may be deteriorated.

  In addition, in order to obtain a dihydroxy compound free of oxidative decomposition products generated during storage and handling during production, or to remove the above-mentioned basic stabilizer, distillation purification of the dihydroxy compound may be performed. preferable. 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, and to suppress denaturation by heat, 250 ° C. or less, preferably 200 ° C. or less, particularly 180 ° C. It is preferable to carry out on the conditions below ° C.

  By such distillation purification, the polycarbonate is obtained by setting the formic acid content in the dihydroxy compound represented by the general formula (1) to 20 mass ppm or less, preferably 10 mass ppm or less, particularly preferably 5 mass ppm or less It is possible to produce a polycarbonate resin excellent in color tone and thermal stability without impairing the polymerization reactivity during resin production. Measurement of the formic acid content is carried out using ion chromatography according to the following procedure. In the following procedures, isosorbide is exemplified as a representative dihydroxy compound.

Approximately 0.5 g of isosorbide is precisely weighed, taken into a 50 mL measuring flask, and made up to volume with pure water. A sodium formate aqueous solution is used as a standard sample, and a peak whose retention time matches the standard sample is defined as formic acid, and quantified from the peak area by an absolute calibration curve method.
The ion chromatograph uses a DX-500 type manufactured by Dionex, and an electrical conductivity detector is used as a detector. As a measurement column, AG-15 is used for a guard column made by Dionex, and AS-15 is used for a separation column. The measurement sample is injected into a 100 μL sample loop, and measurement is made using 10 mM NaOH as an eluent at a flow rate of 1.2 mL / min and a thermostat temperature of 35 ° C. A membrane suppressor is used as a suppressor, and a 12.5 mM H ₂ SO ₄ aqueous solution is used as a regenerating solution.

  Since the structure derived from the dihydroxy compound represented by the general formula (1) is rigid, it is hard and brittle if the structure derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate resin is too much There is a possibility that the formability or mechanical properties may be reduced. On the other hand, if the amount is too small, the heat resistance of the polycarbonate resin may be reduced. Therefore, in the production of a polycarbonate resin, by appropriately using other dihydroxy compounds together with the dihydroxy compound represented by the general formula (1), it is necessary to balance the heat resistance, the flexibility and the moldability of the polycarbonate resin. preferable.

  Structures derived from other dihydroxy compounds other than the structural unit (a) derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate resin (A) for imparting the flexibility of the polycarbonate resin (A), etc. When a unit is introduced, the polycarbonate resin (A) used in the present invention has a structural unit (a) derived from the dihydroxy compound represented by the general formula (1) with respect to all structural units derived from the dihydroxy compound In general, the content is preferably 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 40 mol% or more. Also, it is usually preferable to contain 95 mol% or less, more preferably 85 mol% or less, and particularly preferably 75 mol% or less.

  If the ratio of the structural unit (a) derived from the dihydroxy compound represented by the general formula (1) to the total structural units derived from the dihydroxy compound is 30 mol% or more, the present composition is excellent in heat resistance and surface hardness It is preferable because the On the other hand, if it is 95 mol% or less, the water absorption rate of the present composition becomes low, and deterioration due to heat decreases, which is preferable.

  As a structural unit (b) derived from other dihydroxy compounds other than the structural unit (a) derived from the dihydroxy compound represented by the said General formula (1) introduce | transduced into polycarbonate resin (A), an aliphatic dihydroxy compound And structural units derived from alicyclic dihydroxy compounds. Specific examples of the aliphatic dihydroxy compound and the alicyclic dihydroxy compound include the following.

<Aliphatic dihydroxy compounds>
As aliphatic dihydroxy compounds, for example, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-ethyl -1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

  In addition, the said exemplary compound is an example of the aliphatic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. One of these aliphatic dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.

  In the polycarbonate resin (A) used in the present invention, the molar ratio between the structural unit (a) derived from the dihydroxy compound represented by the general formula (1) and the structural unit (b) derived from the aliphatic dihydroxy compound is Although it can be selected at an arbitrary ratio, by adjusting the molar ratio, it is possible to balance rigidity and impact resistance and to design appropriate formability.

<Alicyclic dihydroxy compound>
Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5- or 6-membered ring structure, the heat resistance of the resulting polycarbonate resin (A) tends to be high. The six-membered ring structure may be fixed in a chair or cage shape by a covalent bond. The carbon number contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. An alicyclic dihydroxy compound having 70 or less carbon atoms is preferable because it is easy to synthesize and purify, and inexpensive and easy to obtain.

Specific examples of the alicyclic dihydroxy compound containing a 5- or 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
HOCH ₂ -R ₉ -CH ₂ OH (I)
HO-R ₁₀ -OH (II)
(However, in Formula (I) and Formula (II), R ₉ and R ₁₀ each independently represent a substituted or unsubstituted divalent group having a C 4 to C 20 cycloalkyl structure. )

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in the general formula (I), R ₉ is a group represented by the following general formula (Ia) (wherein, R ₁₁ is a hydrogen atom, or And various isomers represented by the substituted or unsubstituted C.sub.1-C.sub.12 alkyl group). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tetramethylcyclobutanediol and the like.

As tricyclodecane dimethanol which is an alicyclic dihydroxy compound represented by said general formula (I), and pentacyclopentadecane dimethanol, in General formula (I), R ₉ is the following general formula (Ib) , N represents 0 or 1.) includes various isomers represented by

As decalin dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I) or tricyclotetradecane dimethanol, in the general formula (I), R ₉ is the following general formula (Ic) (wherein m represents 0 or 1.) includes various isomers represented by). As such a thing, a 2, 6- decalin dimethanol, a 1, 5- decalin dimethanol, a 2, 3- decalin dimethanol etc. are mentioned specifically ,.

As the norbornanedimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), in the general formula (I), the various isomers which R ₉ is represented by the following general formula (Id) Include. As such a thing, a 2, 3- norbornane dimethanol, a 2, 5- norbornane dimethanol etc. are mentioned specifically ,.

The adamantane dimethanol is an alicyclic dihydroxy compound represented by formula (I), in formula (I), encompasses various isomers which R ₉ is represented by the following general formula (Ie). As such a thing, a 1, 3- adamantane dimethanol etc. are specifically mentioned.

Moreover, in General Formula (II), R ₁₀ is a group represented by the following General Formula (IIa) (wherein, R ₁₁ is a hydrogen atom, or And various isomers represented by the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol and the like.

As tricyclodecanediol which is an alicyclic dihydroxy compound represented by the said general formula (II), and pentacyclopentadecanediol, in General formula (II), R ₁₀ is the following general formula (IIb) (In the Formula, n And 0 represents 1 or 0.) includes various isomers represented by).

As decalin diol which is an alicyclic dihydroxy compound represented by the above general formula (II) or tricyclotetradecane diol, in the general formula (II), R ₁₀ is a group represented by the following general formula (IIc) (wherein m is It includes various isomers represented by 0 or 1.). As such a thing, a 2, 6- decalin diol, a 1, 5- decalin diol, a 2, 3- decalin diol etc. are mentioned specifically ,.

The norbornane diol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), includes various isomers where R ₁₀ is represented by the following general formula (IId). As such a thing, a 2, 3- norbornane diol, a 2, 5- norbornane diol etc. are mentioned specifically ,.

The adamantane diol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), includes various isomers where R ₁₀ is represented by the following general formula (IIe). As such a thing, a 1, 3- adamantanediol etc. are mentioned specifically ,.

  Among the specific examples of the above-mentioned alicyclic dihydroxy compounds, cyclohexanedimethanols, tricyclodecanedimethanols, adamantanediols and pentacyclopentadecanedimethanols are preferable, and they are easy to obtain and easy to handle. From the viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecanedimethanol, tetramethylcyclobutanediol are more preferable, and 1,4-cyclohexanedimethanol is particularly preferable. preferable.

  In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. One of these alicyclic dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.

  In the polycarbonate resin (A) used in the present invention, the molar ratio between the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound is selected at an arbitrary ratio. Although it is possible, by adjusting the molar ratio, the impact strength (for example, notched Charpy impact strength) may be improved, and it is possible to obtain the desired glass transition temperature of the polycarbonate resin.

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 90 ° C. to 160 ° C., more preferably 100 ° C. to 150 ° C., still more preferably 110 ° C. to 145 ° C., and 115 ° C. to 143 ° C. Particularly preferred. When the glass transition temperature of the polycarbonate resin (A) is 90 ° C. or more, the present composition is excellent in heat resistance. On the other hand, when the glass transition temperature of the polycarbonate resin (A) is 160 ° C. or less, the present resin composition is excellent in moldability and transparency.
Further, since the dihydroxy compound represented by the general formula (1) is generally easily thermally decomposed even in an inert atmosphere, the glass transition temperature may be set in the relevant range to eliminate the need to set the molten resin temperature excessively high. If possible, it is preferable because the possibility of causing significant thermal decomposition is small.

As a method of making the glass transition temperature of the polycarbonate resin (A) used in the present invention lower and achieving 160 ° C. or less, a structure derived from the dihydroxy compound represented by the general formula (1) in part of the structure Methods of reducing the ratio of units, selecting an alicyclic dihydroxy compound with low heat resistance, and reducing the ratio of structural units derived from an aromatic dihydroxy compound such as a bisphenol compound can be mentioned.
The glass transition temperature is a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC 220, manufactured by SII Nano Technology Inc.) in accordance with JIS-K7121 (2012). Refers to the extrapolated glass transition temperature to be measured.

  In the polycarbonate resin (A) used in the present invention, the molar ratio of the structural unit derived from the dihydroxy compound represented by the general formula (1) to the structural unit derived from the alicyclic dihydroxy compound is 95: 5 to 30. It is preferably 70, and more preferably 75:25 to 40:60. When the molar ratio is within the above range, coloring caused by thermal retention is unlikely to occur in the polycarbonate resin (A), and improvement in heat resistance can be achieved by increasing the molecular weight, improving the impact strength, and maintaining the glass transition temperature. It is preferable because

  In the polycarbonate resin (A) used in the present invention, a structural unit derived from the dihydroxy compound represented by the general formula (1), a structural unit derived from an aliphatic dihydroxy compound, as long as the effects of the present invention are not inhibited In addition to the structural units derived from the alicyclic dihydroxy compound, structural units derived from other dihydroxy compounds may be further included. As other dihydroxy compounds, dihydroxy compounds having a portion represented by the following general formula (3) in a part of the structure other than the dihydroxy compound represented by the above general formula (1), an aromatic dihydroxy compound, etc. Can be mentioned.

(However, the site represented by the general formula (3) unless a part of _-CH 2 -O-H.)

  Specific examples of the dihydroxy compound having a portion represented by the general formula (3) in a part of the structure other than the dihydroxy compound represented by the general formula (1) include diethylene glycol, triethylene glycol, tetra Oxyalkylene glycols such as ethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- ( -Hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2) And dihydroxy compounds such as, 2-dimethylpropoxy) phenyl) fluorene and the like, which have an aromatic group in the side chain and the ether group bonded to the aromatic group in the main chain is a moiety represented by the general formula (3) Be In addition, a part of heterocyclic groups such as compounds having a cyclic ether structure such as spiro glycol represented by compounds represented by the following general formula (4a) and compounds represented by the following general formula (4b) The dihydroxy compound which is a site | part represented by General formula (3) is mentioned.

  The "cyclic ether structure" of the above "compound having a cyclic ether structure" means a structure having an ether group in the cyclic structure and having a structure in which carbon constituting the cyclic chain is aliphatic carbon. . Among these, those having a plurality of ether groups are preferable, those having a plurality of cyclic ether structures are more preferable, and those having two cyclic ether structures are particularly preferable.

(In the above general formula (4a), R _{a to} R _d are each independently an alkyl group having 1 to 3 carbon atoms.)

  As the dihydroxy compound represented by the above general formula (4a), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (Conventional name: spiro glycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis ( 1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dioxane glycol and the like.

  Examples of aromatic dihydroxy compounds include bisphenol compounds (including substituted and unsubstituted ones). Specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1 1,1-Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) ) 3-Methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexene , 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bisphenol compounds having no substituent on an aromatic ring such as bis (4-hydroxyphenyl) cyclohexane; bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ) Having an aryl group as a substituent on an aromatic ring such as ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane and 2,2-bis (3-phenyl-4-hydroxyphenyl) propane Bisphenol compounds; bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methyl) Phenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-) Methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) Propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) ) Propane, 2,2-bis (4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-di) Methylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4 -Hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2- Bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ) Ethane, 2,2-bis (4-hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphene) ) Aromatics such as phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane and the like Bisphenol compounds having an alkyl group as a substituent on the ring; bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) A bisphenol compound in which a divalent group linking an aromatic ring such as -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane has an aryl group as a substituent; 4'-dihydroxydiphenyl ether, 3,3 ', 5,5'-tetramethyl-4, Bisphenol compounds in which an aromatic ring such as '-dihydroxydiphenyl ether is linked by an ether bond; 4,4'-dihydroxydiphenyl sulfone, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone, etc. Bisphenol compound in which aromatic ring is connected by sulfone bond; 4,4′-dihydroxydiphenyl sulfide, sulfide bond of aromatic ring such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide The bisphenol compound etc. which were connected by these, etc. are mentioned, Preferably 2,2-bis (4-hydroxyphenyl) propane (another name: bisphenol-A) is mentioned.

Generally, the dihydroxy compound represented by the above general formula (1) is inclined in the direction in which the polymerization reaction proceeds with polymerization as compared with aromatic dihydroxy compounds such as bisphenol-A, and heating or phenol removal is When it volatilizes, the polymerization reaction tends to be rapid, making it difficult to control the reaction.
For this reason, if a small amount of the aromatic dihydroxy compound is added at the final stage of the polymerization reaction, the polymerization end is blocked by the aromatic dihydroxy compound, and even if heating or phenol devolatization occurs, the polymerization reaction is rapid. You can expect an effect that you do not need to

  However, if the polycarbonate resin (A) contains a large amount of structural units derived from the aromatic dihydroxy compound, birefringence of the present composition increases, or heat resistance and surface hardness of the present composition decrease. Besides, there is a possibility that yellowing may occur due to ultraviolet absorption when the composition is used outdoors. Therefore, the structural unit derived from the aromatic dihydroxy compound may be contained in the minimum necessary range, but preferably not contained.

  The above-mentioned other dihydroxy compounds may be used alone or in combination of two or more.

<Carbon diester>
The polycarbonate resin (A) used in the present invention can be obtained by polycondensation by transesterification using a dihydroxy compound containing a dihydroxy compound represented by the above-mentioned general formula (1) and a carbonic diester as raw materials.

  As a carbonic acid diester to be used, what is normally represented by following General formula (5) is mentioned. One of these carbonic acid diesters may be used alone, or two or more thereof may be mixed and used.

However, in the above general formula (5), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group .

  Examples of the carbonic acid diester represented by the formula (5) include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. Is a diaryl carbonate such as diphenyl carbonate and diphenyl carbonate having a substituent, and among the diaryl carbonates, diphenyl carbonate is preferable.

  The carbonic acid diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or may deteriorate the hue of the obtained polycarbonate resin (A). Accordingly, it is preferable to use one purified by distillation or the like.

<Transesterification catalyst>
The polycarbonate resin (A) used in the present invention is obtained by transesterification between a dihydroxy compound containing a dihydroxy compound represented by the above general formula (1) and a carbonic acid diester as described above. More specifically, it is obtained by transesterification and removal of by-produced monohydroxy compounds etc. 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, may be simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the polycarbonate resin (A) used in the present invention has a light transmittance or a yellow index (in particular YI) May affect the value.

  As the catalyst to be used, those which can satisfy the light resistance of the polycarbonate resin (A) to be obtained, that is, the YI value described later can be made equal to or less than a predetermined value are preferable. For example, Group 1 or 2 in the long period periodic table And basic compounds such as metal compounds of basic groups (hereinafter simply referred to as “group 1” and “group 2”), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds and the like. Among these, preferably at least one of Group 1 metal compound and Group 2 metal compound is used.

  It is also possible to additionally use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound and the like together with at least one of the group 1 metal compound and the group 2 metal compound. It is particularly preferred to use at least one of Group 1 metal compounds and Group 2 metal compounds.

  In addition, at least one of the Group 1 metal compound and the Group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt, but is easily available. From the viewpoint of ease of handling, hydroxides, carbonates and acetates are preferred, and from the viewpoint of hue and polymerization activity, acetates are preferred.

  As Group 1 metal compounds, for example, sodium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium acetate, sodium stearate, sodium borohydride, sodium phenylated sodium, sodium benzoate, sodium benzoate, disodium hydrogen phosphate, phenyl phosphoric acid Sodium compounds such as disodium, sodium alcoholate or phenolate, and disodium salt of bisphenol A, potassium hydroxide, potassium hydrogen carbonate, potassium carbonate, potassium acetate, potassium stearate, potassium borohydride, potassium borohydride, potassium phenylborohydride , Potassium compounds such as potassium benzoate, dipotassium hydrogen phosphate, dipotassium phenylphosphate, alcoholates or phenolates of potassium, and dipotassium salt of bisphenol A, lithium hydroxide, Lithium hydrogen oxide, lithium carbonate, lithium acetate, lithium stearate, lithium borohydride, lithium phenylborohydride, lithium benzoate, lithium dihydrogenphosphate, lithium diphenylphosphate, alcoholates or phenolates of lithium, and bisphenol Lithium compounds such as the dilithium salt of A, cesium hydroxide, cesium hydrogen carbonate, cesium carbonate, cesium acetate, cesium stearate, cesium borohydride, cesium phenylborohydride, cesium benzoate, cesium benzoate, hydrogen cesium dibasic, phenyl Cesium phosphate such as cesium cesium phosphate, alcoholate or phenolate of cesium, and cesium salt of bisphenol A such as cesium salt can be mentioned. Among them, lithium compounds are preferred.

  Examples of Group 2 metal compounds include calcium compounds such as calcium hydroxide, calcium hydrogencarbonate, calcium carbonate, calcium acetate and calcium stearate, barium hydroxide, barium hydrogencarbonate, barium carbonate, barium acetate and barium stearate and the like Compounds, magnesium compounds such as magnesium hydroxide, magnesium hydrogen carbonate, magnesium carbonate, magnesium acetate and magnesium stearate, and strontium compounds such as strontium hydroxide, strontium hydrogen carbonate, strontium carbonate, strontium acetate and strontium stearate, etc. . Among them, magnesium compounds, calcium compounds and barium compounds are preferable, and from the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin, at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds is more preferable, and calcium is most preferable. It is a compound.

  As a basic boron compound, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl Sodium salt, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt and strontium salt etc. such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron etc. Be

  Examples of the basic phosphorus compound include triethyl phosphine, tri-n-propyl phosphine, triisopropyl phosphine, tri-n-butyl phosphine, triphenyl phosphine, tributyl phosphine and quaternary phosphonium salts.

  As the basic ammonium compound, for example, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethyl phenyl ammonium hydroxide, Triethylmethyl ammonium hydroxide, triethyl benzyl ammonium hydroxide, triethyl phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide Sid and butyl triphenyl ammonium hydroxide, and the like.

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

  The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, per mol of all the dihydroxy compounds used. Among them, when using at least one metal compound selected from the group consisting of lithium and a metal of long period periodic table group 2, particularly, at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound is used In this case, the amount of metal is preferably 0.1 to 20 μmol, more preferably 0.5 to 10 μmol, and particularly preferably 0.7 to 3 μmol, per mol of all dihydroxy compounds used.

  If the amount of the polymerization catalyst used is 0.1 μmol or more, the polymerization rate will be a certain level or more, and therefore, it is not necessary to raise the polymerization temperature when trying to obtain a polycarbonate resin having a desired molecular weight, The hue or light resistance of the resin may be deteriorated, or the unreacted raw material may be volatilized during polymerization to change the molar ratio of the dihydroxy compound containing the dihydroxy compound represented by the general formula (1) to the carbonic diester. It is preferable because the possibility of not reaching the molecular weight is small. On the other hand, it is preferable that the use amount of the polymerization catalyst is 300 μmol or less, since the possibility of deterioration of the color of the obtained polycarbonate resin and the light resistance of the polycarbonate resin is small. Moreover, it is preferable because the possibility of reaching a target molecular weight without sufficiently reducing the pressure in the polymerization reactor and the possibility of not sufficiently degassing the remaining monomer are small.

  In addition, Group 1 metals, in particular, lithium, sodium, potassium and cesium, if contained in a large amount in the polycarbonate resin, may adversely affect the hue, and the metal is not only from the catalyst used, but also the raw material or reactor May contaminate from Therefore, the total amount of these compounds in the polycarbonate resin is preferably 1 mass ppm or less, more preferably 0.8 mass ppm or less, and still more preferably 0.7 mass ppm or less in terms of metal amount. is there.

  The amount of metal in the polycarbonate resin can be measured using a method such as atomic emission, atomic absorption or inductively coupled plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing.

<Method of producing polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a transesterification of a dihydroxy compound containing a dihydroxy compound represented by the general formula (1) and a carbonic diester represented by the general formula (5) in the presence of a catalyst It can be obtained by polycondensation by reaction.
At this time, the raw material dihydroxy compound and the carbonic diester may be uniformly mixed before the transesterification reaction, or may be simultaneously introduced into the polymerization tank without being mixed, but it is preferable to uniformly mix.

  The mixing temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and the upper limit thereof is usually 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. or lower. is there. Among them, 100 ° C. or more and 120 ° C. or less are preferable. If the temperature of mixing is 80 ° C. or higher, the dissolution rate is increased, which is preferable because it is less likely to cause operation problems such as solidification due to insufficient solubility. In addition, if the mixing temperature is 250 ° C. or less, the possibility of thermal degradation of the dihydroxy compound is small, and the hue and light resistance of the obtained polycarbonate resin are favorable, which is preferable.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound represented by the above general formula (1), which is a raw material of the polycarbonate resin (A) used in the present invention, and the carbonic diester represented by the above general formula (5) The concentration is preferably 10% by volume or less, more preferably 0.0001% by volume to 10% by volume, still more preferably 0.0001% by volume to 5% by volume, particularly preferably 0.0001% by volume to 1% by volume It is preferable to carry out in the atmosphere from the viewpoint of preventing the hue deterioration.

  In order to obtain the polycarbonate resin (A) used in the present invention, the carbonic acid diester represented by the general formula (5) is used at a molar ratio of 0.900 to 1.200 with respect to all dihydroxy compounds used for the reaction. It is preferable to use, More preferably, it is a molar ratio of 0.995 to 0.999 or 1.001 to 1.115.

If the molar ratio is 0.900 or more, the increase in terminal hydroxyl groups of the produced polycarbonate resin (A) can be suppressed, and the thermal stability of the polymer is degraded, and the color during molding and the rate of transesterification are reduced. And so on, which is preferable because polycarbonate resins having a desired high molecular weight can be obtained.
Moreover, if the said molar ratio is 1.200 or less, possibility of the fall of the speed | rate of transesterification etc. is small, and since a desired high molecular weight polycarbonate resin is obtained, it is preferable. The decrease in transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue or light resistance of the resulting polycarbonate resin (A).

  Furthermore, if the molar ratio of carbonic diester to total dihydroxy compound to be used is 1.200 or less, these absorb the ultraviolet rays without increasing the amount of residual carbonic diester in the obtained polycarbonate resin (A) and polycarbonate resin It is preferable because the possibility of deteriorating the light resistance of (A), causing an odor during molding, and increasing the amount of deposits on the mold is small.

  If the molar ratio of carbonic diester to all the dihydroxy compounds used is 0.999 or less, or 1.001 or more, the polymerization rate does not become too fast and remains in the final polymerization tank until the polymerization is completed. It is particularly preferable because the monomer can be sufficiently degassed, and there is little risk of generation of an offensive odor during molding due to an increase in residual monomers in the resin, generation of air bubbles due to gas generation, pulsation in the molding machine, and the like.

Furthermore, when the raw material mixture is fed continuously to the polymerization tank by continuous polymerization, the fluctuation range of the molar ratio of carbonic diester to dihydroxy compound is preferably 0.07 or less, more preferably 0.05 or less, still more preferably 0. .03 or less.
If the fluctuation range is 0.07 or less, the width of the molecular weight obtained is not too wide because uniform polymerization proceeds, and a uniform polycarbonate resin having good moldability is obtained, and as a result, a uniform molded body It is preferable because

  In order to maintain high light resistance, the concentration of the carbonic diester represented by the general formula (5) remaining in the polycarbonate resin (A) used in the present invention is preferably 200 mass ppm or less, more preferably It is 100 mass ppm or less, more preferably 60 mass ppm or less, and particularly preferably 30 mass ppm or less. In practice, polycarbonate resin (A) may contain unreacted carbonic acid diester, and the lower limit of carbonic acid diester content is usually 1 mass ppm.

  In the present invention, the method of polycondensing the dihydroxy compound and the carbonic diester is carried out in multiple stages, usually using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be batch, continuous, or a combination of batch and continuous.

  At the initial stage of polymerization, it is preferable to obtain the prepolymer at relatively low temperature and low vacuum, and at the late stage of polymerization, it is preferable to raise the molecular weight to a predetermined value at relatively high temperature and high vacuum. Proper selection of the internal temperature and the pressure in the reaction system is important from the viewpoint of hue or light resistance.

  For example, if the temperature or pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will distill, causing the molar ratio of the dihydroxy compound to the carbonic acid diester to deviate, and the polymerization rate It is possible to cause a decrease or to fail to obtain a polymer having a predetermined molecular weight or end group. Furthermore, the polymer of uniform molecular weight may not be obtained, the composition ratio of the dihydroxy compound may not be as charged when the two or more dihydroxy compounds are copolymerized, and the polymer of uniform composition ratio is There is a possibility that it can not be obtained, and as a result, the formability and the physical properties of the molded product may be reduced, and the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to make the dihydroxy compound composition of the polymer uniform and to make the molecular weight of the resulting polymer constant, and in particular, the reaction at the initial stage of polymerization having many unreacted monomer components. The effect is great with The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used.

  In general, the temperature of the refrigerant introduced into the reflux condenser is preferably 45 to 180 ° C., more preferably 80 to 150 ° C., and particularly preferably 100 to 150 ° C. at the inlet of the reflux condenser. When the temperature of the refrigerant is too high, the amount of reflux is reduced, and the effect is reduced. Conversely, when the temperature is too low, the efficiency of distilling off the monohydroxy compound to be distilled off tends to decrease. As a refrigerant | coolant, warm water, steam, heat-medium oil etc. are mentioned, for example, Steam and heat-medium oil are preferable.

  In order to maintain the polymerization rate appropriately and to suppress the distillation of the monomer, in order not to impair the color, thermal stability or light resistance etc. of the final polycarbonate resin (A), the types of the above-mentioned catalysts And the choice of quantity is important.

  The polycarbonate resin (A) used in the present invention is preferably produced by multistage polymerization using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is the polymerization reaction In the early stage, it is important to suppress the volatilization of the monomer while maintaining the required polymerization rate because there are many monomers contained in the reaction liquid, and in the latter stage of the polymerization reaction, the equilibrium is shifted to the polymerization side It is important to distill off the by-produced monohydroxy compound sufficiently. Thus, 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 reactor used in the method of the present invention may be at least two or more, but from the viewpoint of production efficiency and the like, it is preferably three or more, more preferably three to five , Particularly preferably four.

  In the present invention, as long as there are two or more reactors, a plurality of reaction stages with different conditions may be further provided in the reactor, or the temperature and pressure may be changed continuously.

  In the present invention, the polymerization catalyst may be added to the raw material preparation tank and the raw material storage tank, or may be added directly to the polymerization tank, but from the viewpoint of supply stability and control of polymerization, it is supplied to the polymerization tank The catalyst supply line is installed in the middle of the raw material line prior to feeding, and is preferably supplied as an aqueous solution.

  If the temperature of the polymerization reaction is too low, it causes a decrease in productivity or an increase in the heat history to the product, and when it is too high, it may not only cause the volatilization of the monomer but also promote the decomposition or coloring of the polycarbonate resin.

  Specifically, the first stage reaction is preferably performed at 130 ° C. to 270 ° C., more preferably 150 ° C. to 240 ° C., still more preferably 180 ° C. to 230 ° C., as the maximum internal temperature of the polymerization reactor. Preferably generated under a pressure of 1 to 110 kPa, more preferably 5 to 70 kPa, still more preferably 10 to 30 kPa (absolute pressure), preferably 0.1 to 10 hours, more preferably 0.5 to 3 hours It carries out, distilling off a hydroxy compound out of the reaction system. Further, in the continuous polymerization equipment, a polymer having a uniform composition ratio and a uniform molecular weight can be obtained by making the temperature, pressure and time as constant as possible.

  In the reactions after the second stage, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the pressure of the reaction system (absolute ) Is preferably 1 kPa or less, and the maximum internal temperature is preferably 200 ° C. to 270 ° C., more preferably 220 ° C. to 260 ° C., preferably 0.1 to 10 hours, more preferably 1 to 6 hours , Particularly preferably for 0.5 to 3 hours. Further, in the continuous polymerization equipment, a polymer having a uniform composition ratio and a uniform molecular weight can be obtained by making the temperature, pressure and time as constant as possible.

  In particular, in order to suppress coloring or thermal deterioration of polycarbonate resin and obtain polycarbonate resin (A) having good hue or light resistance, it is preferable that the maximum internal temperature in all reaction stages is less than 260 ° C., particularly 220 It is preferable that it is -240 degreeC. In addition, in order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and to minimize the deterioration due to the heat history, it is possible to use a horizontal reactor excellent in plug flowability and interface renewal at the final stage of polymerization. preferable.

  When the polymerization temperature is increased and the polymerization time is increased to obtain a polycarbonate resin (A) having a predetermined molecular weight, the ultraviolet light transmittance tends to decrease and the YI value to increase.

  In order to obtain polycarbonate resin in a predetermined molecular weight range, the pressure and temperature are controlled to keep the agitation of the final polymerization tank constant, the agitation current value and the agitation torque be constant, and the current value of the gear pump after the polymerization tank is constant. It is desirable to

  From the viewpoint of effective utilization of resources, it is preferable that the by-produced monohydroxy compound be purified as necessary, and then reused as a raw material such as diphenyl carbonate or bisphenol-A.

  The polycarbonate resin (A) used in the present invention is usually solidified by cooling after polycondensation as described above, and is pelletized by a rotary cutter or the like.

  The method of pelletizing is not limited, for example, a method of extracting in the molten state from the final polymerization reactor, cooling and solidifying it in the form of a strand and pelletizing it, or uniaxially or in the molten state from the final polymerization reactor The resin was supplied to a twin-screw extruder, melted and extruded, and then solidified by cooling and pelletized, or it was extracted from the final polymerization reactor in the molten state, cooled and solidified in the form of strands and pelletized once After that, the resin is again supplied to a single-screw or twin-screw extruder, and after melt-extruding, it is cooled and solidified to pelletize it.

  At that time, in an extruder, the residual monomer is removed under reduced pressure, or a catalyst deactivator such as a phosphorus compound, a heat stabilizer, a neutralizer, an ultraviolet absorber, a mold release agent, and a color which are generally known. Additives, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers or flame retardants may be added and kneaded.

  The melt-kneading temperature in the extruder depends on the glass transition temperature or molecular weight of the polycarbonate resin, but is preferably 150 to 300 ° C., more preferably 200 to 270 ° C., still more preferably 230 to 260 ° C. is there. By setting the melt-kneading temperature to 150 ° C. or higher, the melt viscosity of the polycarbonate resin is reduced, the load on the extruder is reduced, and the productivity is improved. Further, by setting the melt-kneading temperature to 300 ° C. or less, it is possible to suppress the thermal deterioration of the polycarbonate resin and to prevent the reduction of the mechanical strength due to the reduction of the molecular weight and the generation of coloring or gas.

In the extruder, the vent pressure in the case of vacuum degassing is preferably 0.001 kPa to 5 kPa, more preferably 0.005 kPa to 3 kPa, and still more preferably 0.007 kPa to 2 kPa.
If the vent pressure is in the above-mentioned range, it is possible to sufficiently degas the remaining monomer and generated gas, and when extruding in the form of a strand, the strand may be cut, or the polymerization reaction or decomposition of the polycarbonate resin in the extruder. Is preferable because it is unlikely to progress.
A uniform resin can be obtained by making the amount of resin fed into the extruder, the number of revolutions of the extruder, the barrel temperature, and the vent pressure as constant as possible.
In addition, by keeping the temperature of the vent and the piping after the vent at 40 ° C. or higher, it is possible to maintain uniform vent pressure without solidifying the monomer to be distilled out in the vent and the piping after the vent.

  When manufacturing polycarbonate resin (A) used for this invention, in order to prevent mixing of a foreign material, it is preferable to install a filter. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of foreign matter removal of the filter is preferably 100 μm or less as the filtration accuracy of 99% removal. In particular, in the case of disfavoring the inclusion of a minute foreign substance for film applications etc., 40 μm or less is preferable, and 10 μm or less is more preferable.

  The extrusion of the polycarbonate resin (A) used in the present invention is preferably a clean room having a cleanliness higher than Class 7, more preferably Class 6, as defined in JIS B9920 (2002), in order to prevent contamination with foreign matter after extrusion. It is preferable to carry out in the inside.

Further, when the extruded polycarbonate resin (A) is cooled and chipped, it is preferable to use a cooling method such as air cooling or water cooling. As air used for air cooling, it is preferable to use air from which foreign matter in the air has been removed in advance with a hepa filter or the like to prevent reattachment of foreign matter in the air.
In the case of using water cooling, it is preferable to use water from which metal components in the water are removed with an ion exchange resin or the like and further from which foreign substances in the water have been removed by a filter. The pore size of the filter used is preferably 10 to 0.45 μm as a filtration accuracy of 99% removal.

  Further, by making the shape of the obtained pellet constant, polycarbonate resin pellets having good moldability can be obtained.

(Phosphorus compounds)
The polycarbonate resin (A) preferably contains a phosphorus-based compound in order to deactivate the polymerization catalyst and to suppress the coloration of the polycarbonate resin (A) at high temperatures. The phosphorus compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic phosphoric acid ester and aliphatic cyclic phosphorous acid ester. It is preferable to use Among the above, phosphorous acid, phosphonic acid and phosphonic acid ester are more excellent in the catalyst deactivation and color suppression effects, and phosphonic acid ester is particularly preferable.

  Examples of phosphonic acid include phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane- 1,1-diphosphonic acid, 4-methoxyphenyl phosphonic acid, nitrilotris (methylene phosphonic acid), propyl phosphonic acid anhydride etc. are mentioned.

  Examples of phosphonic acid esters include dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl benzyl phosphonate, diphenyl methyl phosphonate, ethyl phosphonate Diethyl, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl) phosphonate, 4-p-methylbenzylphosphonate diethyl, diethylphosphonoacetic acid, ethyl diethylphosphonoacetate, tert-butyl diethylphosphonoacetate, (4- Benzyl diethyl phosphonate, diethyl cyano phosphonate, diethyl cyano methyl phosphonate, diethyl 3,5-di-tert-butyl 4-hydroxybenzyl phosphonate, diethyl phosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl) phosphonate etc It can be mentioned.

  Examples of acidic phosphoric acid esters include dimethyl phosphate, diethyl diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, and phosphoric acid Examples thereof include diester of phosphate such as dioleyl, distearyl phosphate, diphenyl phosphate, dibenzyl phosphate or a mixture of diester and monoester, diethyl chlorophosphate, zinc stearyl phosphate and the like.

  Aliphatic cyclic phosphite is defined as a phosphite compound containing no aromatic group in the cyclic structure containing a phosphorus atom. For example, bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,6-tert-butylphenyl) pentaerythritol diphosphite, bis (nonyl) Phenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Examples thereof include a polymer type compound composed of a dihydroxy compound such as hydrogenated bisphenol A • pentaerythritol phosphite polymer and pentaerythritol diphosphite.

  One of these may be used alone, or two or more of them may be mixed and used in any combination and ratio.

  Content of the said phosphorus-type compound in polycarbonate resin (A) is 1 mass ppm or more and 8 mass ppm or less as content of the phosphorus atom in polycarbonate resin (A), 1.2 mass ppm or more, 7 mass ppm or less is preferable, and 1.5 mass ppm or more and 6 mass ppm or less are more preferable. If the content of the phosphorus-based compound is 1 mass ppm or more as the content of phosphorus atoms in the polycarbonate resin (A), the effects of catalyst deactivation and color suppression are sufficiently exhibited. On the other hand, if it is 8 mass ppm or less as content of the phosphorus atom in polycarbonate resin (A), there is little possibility that polycarbonate resin (A) may color.

  Since phosphorus trichloride is usually used as a starting material for the phosphorus-based compound, unreacted substances and chlorine-containing components derived from separated hydrochloric acid may remain, but the chlorine atoms contained in the phosphorus-based compound may be used. The amount is preferably 5% by mass or less. If the residual amount of chlorine atoms is 5% by mass or less, the metal part of the production facility to which the phosphorus compound is added is corroded or the thermal stability of the polycarbonate resin (A) is reduced, and the molecular weight due to coloring or thermal degradation There is little risk of promoting decline.

  It is preferable that the said phosphorus compound is added and knead | mixed to polycarbonate resin (A) using an extruder as above-mentioned. In particular, it is most effective that the polycarbonate resin (A) is supplied to the extruder as it is in a molten state after polymerization, and the phosphorus compound is immediately added to the resin. Furthermore, low-molecular weight components can be efficiently removed by degassing by vacuum venting with an extruder in a state where the catalyst is deactivated.

<Physical Properties of Polycarbonate Resin (A)>
The molecular weight of the polycarbonate resin (A) used in the present invention can be represented by a reduced viscosity, and the reduced viscosity of the polycarbonate resin (A) used in the present invention is usually 0.30 dL / g or more, preferably 0.35 dL / g The above is more preferable, and 1.20 dL / g or less is preferable, 1.00 dL / g or less is more preferable, and 0.80 dL / g or less is more preferable.

  If the reduced viscosity of the polycarbonate resin (A) used in the present invention is 0.30 dL / g or more, the impact resistance, surface hardness, and the like of the obtained present composition will be good. On the other hand, if the reduced viscosity is 1.20 dL / g or less, productivity or moldability can be maintained without the flowability of the polycarbonate resin (A) being lowered.

The range width of the reduced viscosity of the polycarbonate resin (A) used in the present invention is usually preferably 0.05 dL / g or less, more preferably 0.04 dL / g or less. If the range width of the reduced viscosity is 0.05 dL / g or less, it is preferable because the possibility of generating pulsation during extrusion molding, thickness variation and width variation of a molded product is small.
Here, the range width of the reduced viscosity of the polycarbonate resin (A) means, for example, continuously for 4 to 24 hours, or once every 1 to 8 hours for the polycarbonate resin (A) manufactured continuously. When the change over time of the reduced viscosity is examined by measuring the reduced viscosity, it corresponds to the difference between the maximum value and the minimum value.
As a method of producing a polycarbonate resin (A) having a small range width of reduced viscosity, the pressure and temperature are controlled to make the stirring of the final polymerization tank constant, the stirring current value and the stirring torque be constant, It is desirable to keep the current value of the gear pump constant.

  Furthermore, the lower limit of the concentration of the terminal group (referred to as “terminal phenyl group concentration”) represented by the following general formula (6) of the polycarbonate resin (A) used in the present invention is usually preferably 20 μeq / g, more preferably Is 40 μeq / g, particularly preferably 50 μeq / g, and the upper limit is preferably 160 μeq / g in general, more preferably 140 μeq / g, particularly preferably 100 μeq / g.

  If the concentration of the end group represented by the following general formula (6) of the polycarbonate resin (A) used in the present invention is 160 μeq / g or less, both the hue immediately after polymerization or during molding and the hue after exposure to ultraviolet light are good. It is preferable because Moreover, if it is 20 microeq / g or more, since it has sufficient thermal stability, it is preferable.

  In order to control the concentration of the end group represented by the general formula (6), in addition to controlling the molar ratio of the dihydroxy compound containing the dihydroxy compound represented by the above general formula (1), which is the raw material, to the carbonic diester, The type or amount of catalyst at the time of exchange reaction, the method of controlling the polymerization pressure or the polymerization temperature, and the like can be mentioned.

  When the polycarbonate resin (A) used in the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the above general formula (5), phenol and substituted phenol Although it is inevitable to leave the polycarbonate resin and remain in the polycarbonate resin, phenol and substituted phenols also have an aromatic ring, so they absorb ultraviolet rays and may cause deterioration of light resistance, as well as odor during molding May cause

  The polycarbonate resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of at least 2000 mass ppm after ordinary batch reaction, but in light resistance or odor reduction, or at the time of extrusion molding From the viewpoint of suppressing pulsation of the content of the aromatic monohydroxy compound of the polycarbonate resin (A) used in the present invention, preferably using a horizontal reactor excellent in degassing performance or an extruder with a vacuum vent, The content is preferably 1500 ppm by mass or less, more preferably 1000 ppm by mass or less, and particularly preferably 700 ppm by mass or less. However, it is difficult to completely remove the aromatic monohydroxy compound industrially, and the lower limit of the content of the aromatic monohydroxy compound of the polycarbonate resin (A) used in the present invention is usually 1 mass ppm. .

  Furthermore, the range width of the content of the aromatic monohydroxy compound of the polycarbonate resin (A) used in the present invention is preferably 500 mass ppm or less, particularly 400 mass ppm or less, particularly 300 mass ppm. If the range width of the content of the aromatic monohydroxy compound in the polycarbonate resin (A) is 500 mass ppm or less, there is little possibility that pulsation occurs in extrusion molding or uneven pressure fluctuation of the vent occurs. .

Here, the range width of the content of the aromatic monohydroxy compound of the polycarbonate resin (A) is, for example, continuously for 4 to 24 hours, or 1 to 8 for the polycarbonate resin (A) continuously produced. When the change over time in the content of the aromatic monohydroxy compound is examined by measuring the content of the aromatic monohydroxy compound at a frequency of once per hour, the value corresponding to the difference between the maximum value and the minimum value It is.
As a method of producing a polycarbonate resin (A) having a small range of the content range of the aromatic monohydroxy compound, the ratio of the dihydroxy compound to the carbonic acid diester charged is made constant, and the reflux temperature of the polymerization tank is made constant. The temperature and pressure of the polymerization tank may be kept constant, and in the operation in the depressurization system, some measures such as complete installation of a plurality of vacuum traps may be mentioned.

  These aromatic monohydroxy compounds may, of course, have substituents depending on the raw materials used, and may have, for example, an alkyl group having 5 or less carbon atoms.

When the number of moles of hydrogen atoms bonded to the aromatic ring of the polycarbonate resin (A) used in the present invention is (X) and the number of moles of hydrogen atoms bonded to other than aromatic rings is (Y), the polymer is bonded to the aromatic ring The ratio of the number of moles of hydrogen atoms to the number of moles of total hydrogen atoms is represented by X / (X + Y), but as described above, the light fastness can be affected by the aromatic ring having ultraviolet absorbing ability. In view of the property, X / (X + Y) is preferably 0.1 or less, more preferably 0.05 or less, still more preferably 0.02 or less, and particularly preferably 0.01 or less. X / (X + Y) can be quantified by ¹ H-NMR.

[Aromatic compound (B)]
It is important that the present composition contains at least one aromatic compound (B) selected from the group consisting of biphenyl compounds, terphenyl compounds and stilbene compounds. By containing the polycarbonate resin (A) and the aromatic compound (B), the composition surprisingly has almost no decrease in heat resistance as compared with the case where the aromatic polycarbonate resin is used, Moreover, the surface hardness and the low water absorption are improved, and the transparency and the low birefringence are also excellent.

  How the aromatic compound (B) acts on the polycarbonate resin (A) to exhibit the above effect, and why the heat resistance significantly reduced when the aromatic polycarbonate resin is used is polycarbonate resin (A It is not clear in detail as to whether or not it decreases when using), but it is attributable to the molecular structure of each of polycarbonate resin (A) and aromatic compound (B) which was not considered at all in the prior art. It is guessed that it is not due to the interaction.

Further, it is important to contain the aromatic compound (B) in the composition of 1% by mass or more and 8% by mass or less based on the total mass of the polycarbonate resin (A) and the aromatic compound (B). The content of the aromatic compound (B) is preferably 2% by mass or more, and more preferably 3% by mass. The content of the aromatic compound (B) is preferably 7% by mass or less, more preferably 6% by mass or less, and particularly preferably 5% by mass or less.
By containing the aromatic compound (B) in an amount of 1% by mass or more, the present composition is excellent in surface hardness and low water absorption. On the other hand, by containing the aromatic compound (B) in an amount of 8% by mass or less, the heat resistance, the transparency, and the low birefringence of the composition do not decrease.

  The biphenyl compound used in the present invention is a compound in which two benzene rings are linked by a single bond, and may have a substituent such as a halogen group, a hydroxyl group, an alkyl group, etc., among them having a substituent Preferred is biphenyl.

  The terphenyl compound used in the present invention is a compound in which three benzene rings are linked by a single bond, and examples thereof include an ortho terphenyl compound, a meta terphenyl compound and a paraterphenyl compound, and a halogen group, a hydroxyl group, an alkyl It may have a substituent such as a group. Among them, ortho terphenyl compounds or meta terphenyl compounds are preferable, and those having no substituent, that is, ortho terphenyl or meta terphenyl are more preferable.

  The stilbene compound used in the present invention is a compound in which two hydrogen atoms bonded to different carbon atoms in ethylene are substituted to a benzene ring, and a cis stilbene compound and trans by cis-trans isomerism of carbon-carbon double bond A stilbene compound is illustrated and may have a substituent such as a halogen group, a hydroxyl group or an alkyl group. Among them, trans stilbene compounds are preferable, and those having no substituent, that is, trans stilbene are more preferable.

[Other materials]
In the present composition, thermoplastic resins other than the polycarbonate resin (A) and thermosetting resins, thermal stabilizers other than the aromatic compound (B), and antioxidants, as long as the effects of the present invention are not impaired. Additives such as UV absorbers, light stabilizers, antibacterial and antifungal agents, antistatic agents, lubricants, pigments and dyes may be contained.

[This composition]
In the present composition, the proportion of the aromatic compound (B) in the total mass of the polycarbonate resin (A) and the polycarbonate resin (A) and the aromatic compound (B) is 1% by mass or more, 8 While being excellent in transparency and low birefringence by being not more than mass%, the heat resistance hardly decreases as described above.

  Specifically, the glass transition temperature Tg (X) of the present composition is preferably single. In the present invention, that the glass transition temperature Tg (X) of the mixture (X) is single means that the mixture (X) is heated at a heating rate of 10 ° C. under a nitrogen atmosphere according to JIS K 7121 (2012). The temperature was raised from 0 ° C. to 200 ° C./min and held at 200 ° C. for 1 minute, then cooled to 0 ° C. at a cooling rate of 10 ° C./min and raised again to 200 ° C. at a heating rate of 10 ° C./min It means that there is one glass transition point of the thermogram sometimes measured.

  Generally, a single glass transition temperature of the polymer blend composition means that the resins to be mixed are in a compatible state at the molecular level, which can be recognized as a compatible system. By the single glass transition temperature Tg (X) of the present composition, excellent transparency and low birefringence can be realized in the present composition.

In the composition, it is preferable that the glass transition temperature Tg (A) of the polycarbonate resin (A) and the Tg (X) have a relationship of 0 ° C. ≦ Tg (A) −Tg (X) ≦ 30 ° C. It is more preferable to have the relationship of 0 ° C. ≦ Tg (A) −Tg (X) ≦ 25 ° C., and it is particularly preferable to have the relationship of 0 ° C. ≦ Tg (A) −Tg (X) ≦ 20 ° C.
If the relationship between Tg (A) and Tg (X) has such a relation, it can be recognized that the present composition is a composition which hardly causes a decrease in heat resistance.

  That is, the glass transition temperature Tg (X) of the present composition is preferably 80 to 140 ° C., more preferably 90 to 130 ° C., and particularly preferably 100 to 125 ° C. If Tg (X) is 80 degreeC or more, since this composition has heat resistance, it is preferable. Moreover, if Tg (X) is 140 degrees C or less, since this composition is excellent in workability, it is preferable.

[Sheet]
Another subject matter of the present invention is a sheet formed using the present composition (hereinafter referred to as "the present sheet"). The sheet may be a single layer sheet or a multilayer sheet, and in the case of a multilayer sheet, it may have at least one layer comprising the present composition, among which at least one outermost layer of the sheet comprises the layer comprising the present composition If it has, it is preferable because the characteristics of the present composition of low water absorption and surface hardness are exhibited.

  Generally, "sheet" is thin according to the definition in JIS, and its thickness is small and flat according to length and width. Also, in general, a "film" is a thin flat product whose thickness is extremely small compared to the length and width, and the maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (JIS K 6900 (1994)). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish between the two in the present invention, in the present invention, a "film" is included even when it is called a "sheet".

The method for producing the sheet is not particularly limited, and conventionally known methods such as T-die casting method, roll forming method, press forming method, calendar method, inflation method and tubular method can be appropriately selected. When the T die casting method is mentioned as an example, the polycarbonate resin (A), the aromatic compound (B), and, if necessary, other resins and additives are melted by a single screw extruder, a twin screw extruder, etc. A non-oriented sheet can be produced by kneading, extruding into a sheet shape with a T die (die), quenching with a casting roll, and solidification.
The produced non-stretched sheet may be further stretched using a roll stretching method, a tenter stretching method, a tubular stretching method or the like.

  Although the thickness of the sheet is not particularly limited, for example, in consideration of processability and practicability, it is preferably 0.05 mm or more and 1.0 mm or less, and is 0.10 mm or more and 0.50 mm or less It is more preferable that When the thickness of the present sheet is 0.05 mm or more, the rigidity of a suitable sheet is developed, and the curl resistance is excellent. On the other hand, if the thickness of this sheet is 1.0 mm or less, since it is excellent in secondary processability, it can be used suitably for many uses.

The present composition is excellent in transparency, and in view of designability, visibility of contents, etc., the entire thickness of the single-layer main sheet at 0.10 mm is measured based on JIS K 7136 (2000). The haze value is preferably 5.0% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less. The lower limit of the total haze value is not particularly limited, and is preferably as small as possible.
In addition, the total light transmittance of the single-layer main sheet at a thickness of 0.10 mm is preferably 85% or more, more preferably 88% or more, which is measured based on JIS K 7136-1 (1997). Preferably, it is 90% or more.
If the total haze value and the total light transmittance are in the relevant range, the present composition is particularly excellent in transparency.

The composition is excellent in low birefringence, and the photoelastic coefficient of the single-layer sheet measured at a wavelength of 589 nm is preferably 30 × 10 ⁻¹² Pa ⁻¹ or less, and 25 × still more preferably 10 ^-12 Pa ^-1 or less, and particularly preferably 20 × ¹⁰ -12 ^{Pa -1} or less. The lower limit of the value of the photoelastic coefficient is not particularly limited, and is preferably as small as possible.
If the value of the photoelastic coefficient is in the range, the present composition is particularly excellent in low birefringence and has small optical distortion.

The present composition is excellent in low water absorption, and the value of the saturated water absorption of a single layer of this sheet is 0.8 mass% or less, which is measured based on method A of JIS K 7209 (2000). The content is preferably 0.7% by mass or less, particularly preferably 0.6% by mass or less. The lower limit of the saturated water absorption value is not particularly limited, and is preferably as small as possible.
By setting the value of the saturated water absorption to be in the above range, the present composition is particularly excellent in low water absorption, and the possibility of deterioration due to water becomes small.

The composition is excellent in surface hardness, and in microhardness measurement by indentation test, the microhardness defined by the test load applied to the indenter at a indentation depth of 10 μm of the single-layer main sheet is preferably 130 MPa or more The pressure is more preferably 140 MPa or more, and particularly preferably 150 MPa or more. The upper limit of the microhardness is not particularly limited, but is usually 200 MPa or less.
When the value of the microhardness is in the range, the present composition and the present sheet are particularly excellent in surface hardness and hardly scratched.

The composition is excellent in impact resistance, and in the high-speed impact test measured based on ASTM D3763, the breaking energy value of the single-layer main sheet is preferably 100 kgf · mm or more, 110 kgf · mm or more Is more preferable, and 120 kgf · mm or more is particularly preferable. The upper limit of the breaking energy value is not particularly limited, but is usually 200 kgf · mm or less.
When the value of the breaking energy is in the relevant range, the present composition and the present sheet are particularly excellent in impact resistance.

[Use]
The present composition can be utilized for the production of the present sheet as described above, but is not limited to this, and suitably used for the production of various press-formed articles, extrusion-formed articles, injection-formed articles, etc. Can.

  Moreover, since this sheet is a sheet excellent in balance of transparency, low water absorption, heat resistance, surface hardness, low birefringence and impact resistance, it can be used, for example, in construction materials, housing interior members, cars, railways, and aircrafts. Optical components such as interior and exterior members, display front plates, transparent sheets for surface protection, films for protecting polarizing plates, sheets for resin-coated metal plates, sheets for forming (vacuum / pressure forming, heat press forming etc.), shrink films It can be used as various packaging materials such as shrink tubes, members for home appliances, and members for OA equipment. In particular, it can be suitably used as an optical member such as a display front plate or a transparent sheet for surface protection.

  Although an example is shown below, the present invention is not restricted at all by these. In addition, the various measured values and evaluation about the raw material and test piece displayed in this specification were performed as follows.

[Evaluation method]
(1) Transparency (total haze value, total light transmittance)
Based on JIS K 7136 (2000) and JIS K 7136-1 (1997), the total haze value and total light transmittance of a 0.10 mm thick single layer sheet were measured, and the total haze value was 1.0% or less And those having a total light transmittance of 85% or more were accepted.

(2) Photoelastic coefficient Photoelastic coefficient was computed by measuring a phase difference in the state which applied the stress to the single layer sheet using Oji Scientific Instruments Co., Ltd. "KOBRA-WR." The thing whose photoelastic coefficient is 30 * 10 <^-12> Pa < ^{-1 >} or less was made into passing.

(3) Saturated water absorption rate Based on method A of JIS K 7209 (2000), after immersing the single layer sheet in water at 23 ° C., measure the amount of water absorption and pass the one having a saturated water absorption rate of 0.8 mass% or less And

(4) Heat resistance (glass transition temperature)
Using a differential scanning calorimeter ("Diamond DSC" manufactured by PerkinElmer, Inc.), in accordance with JIS K7121, raise 10 mg of the sample from 0 ° C to 200 ° C at a heating rate of 10 ° C / min, and at 200 ° C for 1 minute After holding, the temperature is lowered to 0 ° C. at a cooling rate of 10 ° C./min, and the glass transition temperature (Tg) (° C.) from the transition point of the thermogram measured when the temperature is raised again to 200 ° C. at a heating rate of 10 ° C./min. Asked for).

(5) Impact resistance (breaking energy)
Based on ASTM D3763, a hydro-shot high-speed impact test was conducted on a 0.10 mm-thick single-layer sheet under conditions of a striker speed of 3 m / s and a temperature of 23 ° C. Those with a breaking energy of 100 kgf · mm or more were considered to pass.

(6) Surface hardness (micro hardness)
An indentation test was performed on the single layer sheet. A test load applied to the indenter at a indentation depth of 10 μm of the test piece was rated as 130 MPa or more.

[Material used]
<Polycarbonate resin (A)>
(A) -1: A structural unit derived from isosorbide / a structural unit derived from 1,4-cyclohexanedimethanol = 70/30 mol% A polycarbonate resin ("DURABIO D7340R" manufactured by Mitsubishi Chemical Corporation)
(A) -2: polycarbonate resin composed of structural unit derived from isosorbide / structural unit derived from 1,4-cyclohexanedimethanol = 50/50 mol% ("DURABIO D5380R" manufactured by Mitsubishi Chemical Corporation)
(A) -3: aromatic polycarbonate resin composed of 100 mol% of structural unit derived from bisphenol-A ("Iupilon S3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.)

<Aromatic compound (B)>
(B) -1: Metaterphenyl (made by Tokyo Chemical Industry Co., Ltd.)
(B) -2: ortho terphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B) -3: biphenyl (made by Tokyo Chemical Industry Co., Ltd.)
(B) -4: Transstilbene (manufactured by Tokyo Chemical Industry Co., Ltd.)

Example 1
After dry blending (A) -1 and (B) -1 at a mixing mass ratio of 95: 5, the mixture is kneaded at 230 ° C. using a 25 mmφ co-directional twin screw extruder, and a T die (die) The sheet was extruded and then quenched with a casting roll at 100 ° C. to produce a non-stretched single-layer sheet having a thickness of 0.10 mm. Various evaluations were performed on the obtained sheet. The results are shown in Table 1.

(Example 2)
A sheet was prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -2 were dry blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Example 3)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -3 were dry-blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Example 4)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -4 were dry-blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Example 5)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -2 and (B) -1 were dry-blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Comparative example 1)
A sheet was prepared and evaluated in the same manner as in Example 1 using (A) -1 alone. The results are shown in Table 1.

(Comparative example 2)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -1 were dry-blended at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Comparative example 3)
A sheet was prepared and evaluated in the same manner as in Example 1 using (A) -2 alone. The results are shown in Table 1.

(Comparative example 4)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -2 and (B) -1 were dry-blended at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Comparative example 5)
The sheet was prepared and evaluated in the same manner as in Example 1 using (A) -3 alone. The results are shown in Table 1.

(Comparative example 6)
A sheet was produced and evaluated in the same manner as in Example 1 except that (A) -3 and (B) -1 were dry-blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

As is clear from Table 1, in the examples, all the properties of heat resistance, low water absorption, surface hardness, transparency, low birefringence and impact resistance exceeded the pass criteria and the balance of the respective properties was excellent. A polycarbonate resin composition was obtained.
On the other hand, as in Comparative Examples 1 and 3, when no specific aromatic compound was contained, low water absorption and surface hardness were poor.
On the other hand, as in Comparative Examples 2 and 4, when the specific aromatic compound is contained in the polycarbonate resin (A) beyond the specified range, the impact resistance, the transparency and the heat resistance are lowered. .
Also, as in Comparative Example 5, when only the aromatic polycarbonate resin is used, the low birefringence and the surface hardness are inferior. On the other hand, even when a specific aromatic compound is contained as in Comparative Example 6, the surface Hardness was hardly improved, heat resistance was considerably lowered, transparency was also lowered, and low birefringence was still inferior.

Claims (3)

It is a polycarbonate resin composition which has the following polycarbonate resin (A) as a main component, and contains the following aromatic compound (B), and the above-mentioned aroma accounts for the total mass of the polycarbonate resin (A) and the aromatic compound (B) A polycarbonate resin composition characterized in that the proportion of the group compound (B) is 1% by mass or more and 8% by mass or less.
(A) A structural unit derived from a dihydroxy compound represented by the following general formula (1) and a structural unit derived from 1,4-cyclohexanedimethanol are contained in part of the structure, and the above-mentioned general formula (1) is the molar ratio of the structural unit derived from a dihydroxy compound and structural units derived from the 1,4-cyclohexanedimethanol is 95: 5-30: 70 der Ru polycarbonate resin (B) biphenyl compounds, terphenyl compounds and At least one aromatic compound selected from the group consisting of stilbene compounds
The glass transition temperature Tg (X) of the polycarbonate resin composition is single, and the glass transition temperature Tg (A) of the polycarbonate resin (A) and the Tg (X) are:
0 ° C. ≦ Tg (A) −Tg (X) ≦ 30 ° C.
The polycarbonate resin composition according to claim 1, which has the following relationship: A sheet formed using the polycarbonate resin composition according to claim 1 or 2 .