JP2013203932A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which has designability (metallic appearance, sharpness, deep colorability, and the like) and simultaneously has light resistance, impact resistance and stay stability, and to provide a polycarbonate resin molded article using the polycarbonate resin composition.SOLUTION: A polycarbonate resin composition comprises a polycarbonate resin containing structure units originated from a dihydroxy compound having a cyclic ether structure, and a pigment comprising metal particles surface-treated with a surface-treating agent, wherein the metal particles comprise at least one metal selected from the group consisting of aluminum, gold, silver, copper, nickel, titanium, magnesium and stainless steel, or an alloy.

Description

  The present invention relates to a polycarbonate resin composition having a design property (metallic tone, sharpness, and deep coloring) and simultaneously having light resistance, impact resistance, and retention stability, and a molded product thereof.

  A resin material having a metallic tone used in home appliances and toys is manufactured by kneading plate-like metal powder into a resin. For example, silver color is given by mixing aluminum powder with resin (for example, refer to patent documents 1).

  In recent years, a molded product obtained by molding a resin composition has been made thinner, denser, and larger, and demands for improving various physical properties of the molded product are increasing. In particular, in the case of electrical / electronic / OA equipment casings, interior / exterior parts for automobiles, and other exterior parts related to daily life, in order to bring out a high-class feeling, design properties (deep coloring, clearness, It has been required to have both flame retardancy and heat retention stability.

  However, as demands such as application expansion, color tone selectivity, and high durability have increased in recent years, the degree of freedom to select a wider variety of metallic designs has been demanded.

  A polycarbonate resin is also a resin composition containing polycarbonate resin (A), metallic pigment (B) and other colorant (C) as essential components, which is obtained by injection molding the resin composition. There has been disclosed a metallic polycarbonate resin composition excellent in appearance in which the light transmittance of the product is in a specific range, and a molded product comprising the same (for example, see Patent Document 2).

  On the other hand, since the bisphenol compound used in the conventional polycarbonate resin has a benzene ring structure, the ultraviolet absorption is large, and this tends to affect the light resistance of the polycarbonate resin. For this reason, if a cyclic dihydroxy compound monomer unit having an ether bond in the molecule, such as an aliphatic dihydroxy compound that does not have a benzene ring structure in the molecular skeleton, an alicyclic hydrocarbon dihydroxy compound, or isosorbide, is used in principle. It is expected that the light resistance will be improved. Among them, a polycarbonate resin using isosorbide obtained from biomass resources as a monomer is excellent in heat resistance and mechanical strength, so that many studies have been made in recent years (for example, Patent Documents 3 to 7). .

JP-A-8-41284 JP 2010-006861 A International Publication No. 04/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897 JP 2006-28441 A JP 2008-24919 A JP 2009-74029 A

Conventionally, these technologies have been able to satisfy the requirements for specific applications. However, with the recent increase in requirements such as expansion of applications, higher design, and higher durability, there is a wider variety of metallic tone. The degree of freedom to select a design has been demanded.
In addition, according to the study of the present inventor, the conventional polycarbonate resin composition has a wide range of glitter design, light resistance, impact resistance, color developability, and inferior retention stability. Was found.

  Therefore, an object of the present invention is a polycarbonate resin composition having design properties (metallic tone, sharpness, deep coloring, etc.), and simultaneously having light resistance, impact resistance, and residence stability, and molding thereof. Is to provide goods.

As a result of intensive studies to solve the above problems, the present inventor has obtained a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure, and aluminum, gold, silver, copper, nickel, titanium, magnesium. And a polycarbonate resin composition comprising a pigment using particles of at least one metal or alloy selected from the group consisting of stainless steel, exhibiting a wide metallic design, less discoloration before and after the light resistance test, and good light resistance At the same time, the present inventors have found that a resin composition and a molded product having impact resistance and residence stability are provided, and have reached the present invention.
That is, the gist of the present invention resides in the following [1] to [19].

[1] A polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure, and a pigment made of metal particles surface-treated with a surface treatment agent, the metal particles being aluminum, gold, silver, copper A polycarbonate resin composition comprising at least one metal or alloy selected from the group consisting of nickel, titanium, magnesium and stainless steel.

[2] The polycarbonate resin composition according to [1], wherein the dihydroxy compound is a dihydroxy compound having a structure represented by the following formula (1).

[3] The polycarbonate resin composition according to [1] or [2], wherein the polycarbonate resin includes a structural unit derived from an aliphatic hydrocarbon dihydroxy compound.

[4] The polycarbonate resin composition according to [3], wherein the aliphatic hydroxy dihydroxy compound is cyclohexanedimethanol.

[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the polycarbonate resin is obtained by polycondensation of a dihydroxy compound containing a dihydroxy compound having a cyclic ether structure and a carbonic acid diester. object.

[6] The polycondensation is performed in the presence of a catalyst, and the catalyst is at least one metal compound selected from the group consisting of a metal of Group 2 of the long-period periodic table and lithium, and these metal compounds The total amount of is a polycarbonate resin composition according to [5], wherein the metal amount is 20 μmol or less per 1 mol of the dihydroxy compound including the dihydroxy compound having the cyclic ether structure.

[7] The polycarbonate resin composition according to [6], wherein the content of the metal derived from the catalyst is 20 ppm by weight or less with respect to the polycarbonate resin composition.

[8] The polycarbonate resin composition according to any one of [1] to [7], wherein a ratio of a volume average particle diameter to an average thickness of the metal particles is 2 to 300.

[9] The polycarbonate resin composition according to any one of [1] to [8], wherein the volume average particle size of the metal particles is less than 20 μm.

[10] The polycarbonate resin composition according to any one of [1] to [9], wherein the average thickness of the metal particles is 0.1 to 1.5 μm.

[11] Any of [1] to [10], wherein the surface treatment agent is at least one compound selected from the group consisting of wax, modified polyolefin, metal soap, silane coupling agent, and titanate coupling agent. A polycarbonate resin composition according to any one of the above.

[12] The polycarbonate resin composition according to any one of [1] to [11], wherein the pigment is blended in the composition as a master batch of a thermoplastic resin different from the polycarbonate resin.

[13] The polycarbonate resin composition according to any one of [1] to [12], wherein the metal particles are metal particles containing aluminum.

[14] The polycarbonate resin composition according to any one of [1] to [13], which contains 0.01 to 50 parts by weight of the pigment in terms of metal with respect to 100 parts by weight of the polycarbonate resin.

[15] The polycarbonate resin composition according to any one of [1] to [14], wherein the 3 mm-thick injection molded product molded from the polycarbonate resin composition has a total light transmittance of 3.0% or less.

[16] The polycarbonate resin composition according to any one of [1] to [15], which contains 0.0001 to 3 parts by weight of an antioxidant with respect to 100 parts by weight of the polycarbonate resin.

[17] The polycarbonate resin composition according to any one of [1] to [16], which contains 0.001 to 2 parts by weight of a release agent with respect to 100 parts by weight of the polycarbonate resin.

[18] A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [17].

[19] The polycarbonate resin molded product according to [18], wherein the polycarbonate resin molded product is molded by an injection molding method.

According to the present invention, there is provided a polycarbonate resin composition and a molded article that have design properties (metallic tone, sharpness, deep coloring), and at the same time have light resistance, impact resistance, color development, and retention stability. Provided.
The polycarbonate resin composition of the present invention having such features can be used for molded products in a wide range of fields that can give a product a high-class feeling and profound feeling, and can be used for housings of electrical / electronic / OA equipment. Application to body, interior / exterior parts for automobiles, other exterior parts for daily life can be expected.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention includes a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure (hereinafter sometimes referred to as “polycarbonate resin of the present invention”), aluminum, gold, silver, and copper. A pigment obtained by surface-treating metal particles made of at least one metal or alloy selected from the group consisting of nickel, titanium, magnesium and stainless steel with a surface treatment agent (hereinafter sometimes referred to as “metal pigment”). It is characterized by including.

[Metal pigment]
[Metal particles]
The metal pigment used in the present invention is obtained by surface-treating metal particles made of at least one metal or alloy selected from the group consisting of aluminum, gold, silver, copper, nickel, titanium, magnesium and stainless steel with a surface treatment agent. Is. The metal or alloy constituting the metal particles of the metal pigment can be appropriately selected and used depending on the desired design properties (metallic tone, sharpness, deep colorability), and can be used alone. It is also possible to use a mixture of two or more. For example, in order to develop a silver metallic base color, the metal particles preferably contain aluminum. Moreover, in order to color the metal particles themselves, metal particles coated with a different metal may be used. The metal particles used in the present invention may be alloy particles containing one or more of the above metals as a main component.

  Here, the particle diameter of the metal particles used in the present invention is arbitrary, and may be appropriately selected and determined according to the use of the polycarbonate resin composition containing the metal pigment. Therefore, the volume average particle diameter of the metal particles is preferably 40 μm or more, and more preferably 60 μm or more. On the other hand, from the viewpoint of suppressing the occurrence of gel, unevenness and weld lines in the molded product, the volume average particle size of the metal particles is preferably less than 300 μm, and more preferably less than 100 μm.

  Further, from the viewpoint of increasing fluidity during injection molding, the volume average particle size of the metal particles is preferably 1 μm or more, and more preferably 3 μm or more. On the other hand, from the viewpoint of making the metal particles inconspicuous and improving the concealing property, the volume average particle size of the metal particles is preferably less than 40 μm, and more preferably less than 20 μm.

  Furthermore, in order to bring out the metallic feel of the resin molded product and to suppress quality defects such as the occurrence of weld lines and the difference in brightness between the left and right, the metal particles having a volume average particle size of 40 μm or more and the volume average particle size are You may use together with the metal particle less than 40 micrometers. In this case, from the viewpoint of the difference in brightness between the right and left bordered by the weld line, the mass ratio of the metal particles having a volume average particle size of 40 μm or more and the metal particles having a volume average particle size of less than 40 μm contained in the polycarbonate resin composition is It is preferably within the range of 2: 1 to 1: 5. In the present invention, the volume average particle diameter can be determined by calculating the volume average particle diameter from, for example, a particle size distribution measured using a laser diffraction particle size distribution measuring apparatus.

  The average thickness of the metal particles used in the present invention can be appropriately set depending on the desired powder particle shape and the like, but is usually 0.05 to 25 μm. If the average thickness of the metal particles is set within this range, it becomes possible to impart excellent design properties (metallic tone, sharpness, deep colorability), etc. to the molded product with a smaller amount of particles. . Further, from the viewpoint of increasing fluidity during injection molding, the average thickness of the metal particles is more preferably 0.1 to 1.5 μm. The average thickness of the metal particles can be determined by observing an arbitrary cross section of the injection molded body with a scanning electron microscope, measuring the thickness of 20 particles, and calculating the average.

  The particle size of the metal particles refers to the length of the portion where the distance between these plates is the largest when the metal particles are sandwiched between two parallel plates, and the thickness of the metal particles is The length of the portion where this interval is the shortest.

  The shape of the metal particles used in the present invention is not particularly limited, and a scaly shape, a spherical shape, an indefinite shape, and the like can be appropriately selected and used. From the viewpoint of developing a high metallic feeling, the metal particles are scaly. The ratio of the volume average particle diameter to the average thickness (volume average particle diameter / average thickness) of the scaly metal particles is preferably 2 to 300, and more preferably 5 to 150.

<Surface treatment>
In the present invention, the metallic pigment is as uniform as possible in the polycarbonate resin composition from the viewpoint of imparting design properties (metallic tone, sharpness, deep colorability) to the resin molded product and exhibiting high concealing properties. Therefore, the metal particles are preferably surface-treated with at least one compound selected from the group consisting of wax, modified polyolefin, metal soap, silane coupling agent, and titanate coupling agent. Used after surface treatment with an agent.

  Examples of the wax as the surface treatment agent include plant waxes, mineral waxes, and synthetic waxes. Specifically, as the plant-based wax, rice wax, montanic acid wax, montanic acid ester wax, partially saponified wax and the like, as mineral wax, petroleum wax and the like, as synthetic wax, Examples thereof include polyethylene wax, polypropylene wax, oxidized polyethylene wax, and amide wax.

  Examples of the modified polyolefin include maleic anhydride-modified propylene polymer and its chloride, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer and its chloride, anhydrous Maleic acid-modified ethylene-propylene-butene copolymer and its chloride, acrylic acid-modified propylene polymer and its chloride, acrylic acid-modified ethylene-propylene copolymer and its chloride, acrylic acid-modified propylene-butene copolymer Examples thereof include a coalescence and a chloride thereof.

  Examples of the metal soap include barium laurate, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, zinc oleate, and 12-hydroxy magnesium stearate.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- ( N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane Vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane and the like, and partial hydrolysis condensates of the above silane coupling agents can also be used.

  Examples of the titanate coupling agent include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2 -2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.

Among these, as the surface treating agent, synthetic wax, maleic anhydride-modified polyolefin, γ-mercaptopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane are preferable, and polyethylene wax is particularly preferable.
A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The surface treatment amount with the surface treatment agent may be appropriately set according to desired design properties (metallic tone, sharpness, deep colorability), etc., but usually the surface treatment is performed on 100 parts by weight of the metal particles. The amount of the surface treatment agent used in the coating is preferably 0.5 to 100 parts by weight, more preferably 5 to 50 parts by weight.

  The surface treatment method using such a surface treatment agent is not particularly limited, and can be obtained, for example, by directly mixing the above-described metal particles and the surface treatment agent using a known apparatus such as a mixer or a blender. . At this time, mixing may be performed while appropriately heating as necessary. It is possible to adjust the volume average particle diameter of the metal particles by milling simultaneously with the surface treatment. Furthermore, a solvent such as mineral spirit or toluene can be added and mixed, and it can be used in a wet state (paste) with these solvents.

<Blending amount>
In the polycarbonate resin composition of the present invention, the content of the metal pigment is preferably 0.01 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin of the present invention, as the content of metal particles. The amount is more preferably 0.05 parts by weight or more and 10 parts by weight or less, and particularly preferably 0.1 parts by weight or more and 5 parts by weight or less. If the content of the metal pigment is too small, the design properties (metallic tone, vividness, deep coloring) due to the metal pigment will be difficult to develop. May be a problem. The content in terms of metal particles of the metal pigment in the polycarbonate resin composition of the present invention can be measured from the polycarbonate resin composition by various conventionally known methods. For example, it can be measured by a method such as an ashing method.

<Master batch>
In the present invention, the metal pigment blended in the polycarbonate resin composition is masterbatched with a thermoplastic resin and contained in the composition, so that the metal pigment is contained in the polycarbonate resin composition of the present invention. It is preferable from the viewpoint that it can be uniformly dispersed.

  The thermoplastic resin preferably has high dispersibility with respect to the polycarbonate resin used in the polycarbonate resin composition of the present invention from the viewpoint of high strength of the polycarbonate resin composition and reduction of foreign matters. The resin is preferably a low-density amorphous resin, and examples thereof include linear low-density polyethylene (LLDPE).

  In the present invention, the content of the metal pigment in the master batch is preferably 5 to 90% by weight, more preferably 40 to 80% by weight in terms of metal particles in the metal pigment. When the content of the metal pigment in the master batch is larger than the above range, in the step of producing the polycarbonate resin composition of the present invention, the metal pigment tends to be difficult to uniformly disperse. A large amount of thermoplastic resin derived from the masterbatch is mixed in the product, and the physical properties such as surface hardness and heat resistance of the polycarbonate resin composition of the present invention may be lowered.

From the viewpoint of uniformly dispersing the metal pigment in the master batch, the metal pigment is preferably surface-treated by the above-described method.
In addition, it is preferable that the weight ratio of the surface treatment agent of the thermoplastic resin and the metal pigment in the masterbatch is set to 10: 1 to 5: 1.

  Various additives used in the present invention can be blended in the master batch simultaneously with the metal pigment. For example, the colorant is preferably added to the masterbatch from the viewpoint of suppressing the occurrence of uneven color and weld lines in the polycarbonate resin composition of the present invention.

  As a method for masterbatch of the metal pigment, a known method may be used. For example, the metal particles, the surface treatment agent, the thermoplastic resin, and necessary additives as raw materials are supplied to a twin screw extruder. There are methods such as kneading while heating, extruding in a molten state from an extruder, cutting with a pelletizer after cooling, and pellets. When the metal particles are in the form of a paste containing a solvent, it is possible to form a master batch by providing a vent port in the extruder and degassing and removing the volatile solvent.

[Polycarbonate resin]
The polycarbonate resin used in the polycarbonate resin composition of the present invention contains a structural unit derived from a dihydroxy compound having a cyclic ether structure (hereinafter sometimes referred to as “the dihydroxy compound of the present invention”).

  The polycarbonate resin can be obtained, for example, by polycondensing a dihydroxy compound having a cyclic ether structure and a carbonic acid diester in the presence of a catalyst.

<Dihydroxy compound>
Examples of the dihydroxy compound of the present invention include dihydroxy compounds having a cyclic ether structure represented by the following formulas (1), (2) and (3).
Among these dihydroxy compounds, from the viewpoint of enhancing heat resistance, compounds having an anhydrous sugar alcohol structure represented by the following formula (1), and spiroglycol represented by the following formulas (2) and (3) Compounds having a structure are preferable, and among them, those having a plurality of ring structures represented by the following formula (1) and the following formula (2) are particularly preferable.

  These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin and polycarbonate resin composition to be obtained.

  As the dihydroxy compound of the present invention, a dihydroxy compound having a structure represented by the above formula (1) is preferable, and examples of the dihydroxy compound include isosorbide, isomannide, and isoidet, which have a stereoisomeric relationship. May be used individually by 1 type, and may be used in combination of 2 or more type. Among these, in particular, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and produce, moldability, Most preferable in terms of heat resistance, impact resistance, surface hardness, flame retardancy, and heat retention stability carbon neutral.

The polycarbonate resin used in the present invention may contain a structural unit derived from a dihydroxy compound other than the dihydroxy compound of the present invention (hereinafter sometimes referred to as “other dihydroxy compound”).
As other dihydroxy compounds, dihydroxy compounds having a site represented by the following formula (5) in a part of the structure can be used.

  Here, the other dihydroxy compound having a site represented by the above formula (5) as part of the structure does not include those having a cyclic ether structure. More specifically, oxyalkylene glycols and compounds having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain are exemplified.

  Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, and tetraethylene glycol.

  Examples of compounds having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxy) Ethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis ( -(2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene and the like.

  Among these other dihydroxy compounds, diethylene glycol and triethylene are available from the viewpoint of easy availability, ease of handling, high reactivity during polymerization, and the hue of the resulting polycarbonate resin and polycarbonate resin composition. Glycol is preferred.

  Furthermore, an aliphatic hydrocarbon dihydroxy compound having 2 to 20 carbon atoms can also be used as another dihydroxy compound. Here, straight chain aliphatic hydrocarbons, branched aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and hydrocarbons having a plurality thereof are included in the aliphatic hydrocarbons. Preferably, a linear or cyclic aliphatic hydrocarbon dihydroxy compound having 2 to 20 carbon atoms is used, more preferably a linear or cyclic aliphatic hydrocarbon dihydroxy compound having 2 to 12 carbon atoms, and still more preferably. Is a dihydroxy compound of a linear or cyclic aliphatic hydrocarbon having 2 to 8 carbon atoms.

Specific examples of the linear aliphatic hydrocarbon dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propane-sdiol, 1,4-butanediol, 1,3-butanediol, 1, Examples include dihydroxy compounds such as 2-butanediol, 1,5-heptanediol, and 1,6-hexanediol.
Specific examples of the alicyclic hydrocarbon dihydroxy compound include cyclohexane dimethanols such as 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, and 1,4-cyclohexane dimethanol; tricyclodecane dimethanol, Pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3- Examples thereof include adamantane dimethanol.

  Furthermore, other dihydroxy compounds include aromatic bisphenols. Specific examples of aromatic bisphenols include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5) -Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis ( -Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3, 3'-dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy -2-methylphenyl) fluorene and the like.

  Among these other dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of light resistance of the obtained polycarbonate resin and polycarbonate resin composition. In particular, as other dihydroxy compounds, among aliphatic hydrocarbon dihydroxy compounds, straight-chain aliphatic hydrocarbon dihydroxy compounds include 1,3-propanediol, 1,4-butanediol, and 1,6-hexane. Diols are preferred, and 1,4-cyclohexanedimethanol and tricyclodecane dimethanol are preferred as dihydroxy compounds of alicyclic hydrocarbons.

  By using these other dihydroxy compounds, it is possible to obtain effects such as improved flexibility, improved heat resistance, and improved moldability of the polycarbonate resin and the polycarbonate resin composition. When the content ratio of the derived structural unit is too large, the mechanical properties and the heat resistance may be lowered. Therefore, the structural unit of the present invention with respect to the structural unit derived from all dihydroxy compounds contained in the polycarbonate resin of the present invention. The proportion of the structural unit derived from the dihydroxy compound is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 55 mol% or more. Preferably, it is 95 mol% or less, more preferably 90 mol% or less, and even more preferable. 80 mol% or less, still more preferably 70 mol% or less, particularly preferably not more than 50 mol%.

  In the case of using an aliphatic hydrocarbon dihydroxy compound among other dihydroxy compounds, the structural unit derived from the aliphatic hydrocarbon dihydroxy compound relative to the structural unit derived from all the dihydroxy compounds contained in the polycarbonate resin of the present invention. Is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 40 mol% or more, preferably 60 mol% or less, more preferably Is 55 mol% or less, particularly preferably 53 mol% or less.

  In addition, from the viewpoint of increasing the compatibility between the polycarbonate resin composition of the present invention and other resins, particularly from the viewpoint of increasing the compatibility with other polycarbonate resins, the entire structure derived from the dihydroxy compound of the polycarbonate resin of the present invention. It is preferable that a unit consists only of a structural unit derived from the dihydroxy compound of the present invention and a structural unit derived from an aliphatic hydrocarbon dihydroxy compound. In this case, the ratio of the structural unit derived from the dihydroxy compound of the present invention to the structural unit derived from the aliphatic hydroxy dihydroxy compound is 40 to 90 mol% of the structural unit derived from the dihydroxy compound of the present invention in a molar ratio. On the other hand, it is preferable that it is 60-10 mol% of structural units derived from the dihydroxy compound of an aliphatic hydrocarbon.

  The dihydroxy compound used in the polycarbonate resin of the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound of the invention is easily altered under acidic conditions, it preferably contains a basic stabilizer.

  As the basic stabilizer, a metal hydroxide of Group 1 or Group 2 in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) (hereinafter sometimes simply referred to as long-period periodic table). , Carbonates, phosphates, phosphites, hypophosphites, borates, fatty acid salts, basic ammonium compounds, and amine compounds.

  Basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethyl Ammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, Tilt Li phenyl 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 2-dimethyl. Examples include amine compounds such as aminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

  Of these, sodium or potassium phosphates and phosphites are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

  The content of these basic stabilizers in the dihydroxy compound of the present invention is not particularly limited. However, if the amount is too small, the effect of preventing the alteration of the dihydroxy compound of the present invention may not be obtained. Since this may lead to modification of the dihydroxy compound of the invention, it is usually 0.0001% by weight or more, preferably 0.001% by weight or more, usually 1% by weight or less, preferably 0% with respect to the dihydroxy compound of the invention. .1% by weight or less.

  Further, when the dihydroxy compound of the present invention containing these basic stabilizers is used as a raw material for the production of polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, which makes it difficult to control the polymerization rate and quality, as well as the initial stage. In order to affect the hue and affect the light resistance of the resulting molded product, it is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for producing polycarbonate resin.

  When the dihydroxy compound of the present invention has a cyclic ether structure such as isosorbide, it is likely to be gradually oxidized by oxygen. It is important to use an oxygen agent or the like or handle it under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a polycarbonate resin production raw material, it may cause coloring of the obtained polycarbonate resin and polycarbonate resin composition, and may not only significantly deteriorate physical properties. In some cases, the polymerization reaction is affected, and a high molecular weight polymer cannot be obtained.

  In order to obtain the dihydroxy compound of the present invention which does not contain the above oxidative decomposition product, and in order to remove the above basic stabilizer, it is preferable to carry out distillation purification. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress heat denaturation, it is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably. Is performed under conditions of 180 ° C. or less.

  By such purification by distillation, the dihydroxy compound of the present invention is contained by adjusting the formic acid content in the dihydroxy compound of the present invention to 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound is used as a raw material for producing a polycarbonate resin, it becomes possible to produce a polycarbonate resin and a polycarbonate resin composition excellent in hue and thermal stability without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

<Carbonated diester>
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials.

  As a carbonic acid diester used, what is normally represented by following formula (4) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In the formula (4), A ¹ and A ² each independently represent a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. )

A preferable example of A ¹ and A ² is a substituted or unsubstituted aromatic hydrocarbon group, and a more preferable example is an unsubstituted aromatic hydrocarbon group. In addition, examples of the substituent of the aliphatic hydrocarbon group include an ester group, an ether group, a carboxylic acid, an amide group, and a halogen. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group such as a methyl group and an ethyl group. Is mentioned.

  Examples of the carbonic acid diester represented by the above formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. Are preferably diphenyl carbonate and substituted diphenyl carbonate, and particularly preferably diphenyl carbonate.

  Carbonic acid diesters may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or affect the hue of the resulting polycarbonate resin and polycarbonate resin composition. Therefore, it is preferable to use a product purified by distillation or the like, if necessary.

<Transesterification reaction catalyst>
The production method of the polycarbonate resin used in the present invention is not particularly limited. As a typical example, a dihydroxy compound containing the dihydroxy compound of the present invention having a cyclic ether structure and a carbonic acid represented by the above formula (4) are used. A method for producing a polycarbonate resin by transesterification with a diester is mentioned. More specifically, there may be mentioned a method in which polycondensation is performed by transesterification in the presence of a transesterification reaction catalyst, and a monohydroxy compound or the like by-produced during the transesterification reaction is removed from the system.

  The catalyst used is not limited as long as it can satisfy the light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength of the produced polycarbonate resin and polycarbonate resin composition. Metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amines of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” and “Group 2”) in the periodic table And basic compounds such as compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used. These may be used alone or in combination of two or more.

  It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  The group 1 metal compound is a compound containing a group 1 metal such as lithium, potassium, and cesium. More specifically, as a Group 1 metal compound, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, carbonate Potassium, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride Cesium borohydride, sodium borohydride, potassium borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, phosphorus 2 sodium hydrogen, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, Examples thereof include lithium, cesium alcoholate, phenolate, bisphenol A disodium salt, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, lithium compounds are preferred.

  The group 2 metal compound is a compound containing a group 2 metal such as magnesium, calcium, strontium, and barium. More specifically, as a Group 2 metal compound, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, carbonate Barium, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc., among which magnesium compounds, calcium compounds and barium compounds are preferred. From the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin and polycarbonate resin composition, magnesium compounds and / or calcium compounds are more preferred. , Most preferably a calcium compound.

  Examples of basic boric acid compounds include tetramethyl boric acid, tetraethyl boric acid, tetrapropyl boric acid, tetrabutyl boric acid, trimethylethyl boric acid, trimethylbenzyl boric acid, trimethylphenyl boric acid, triethylmethyl boric acid, and triethyl. Sodium salts such as benzylboric acid, triethylphenylboric acid, tributylbenzylboric acid, tributylphenylboric acid, tetraphenylboric acid, benzyltriphenylboric acid, methyltriphenylboric acid, butyltriphenylboric acid, potassium salts, lithium Examples thereof include salts, calcium salts, barium salts, magnesium salts, and strontium salts.

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

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

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

  The amount of the polymerization catalyst used is usually 0.1 μmol or more, preferably 0.5 μmol or more, usually 300 μmol or less, preferably 100 μmol or less, per 1 mol of all dihydroxy compounds used in the polymerization. Among them, when using a compound containing at least one metal selected from the group consisting of lithium and group 2 metals in the long-period periodic table as a polymerization catalyst, particularly when using a magnesium compound and / or a calcium compound, The amount in terms of metal is usually 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more, per 1 mol of the total dihydroxy compound. The upper limit thereof is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the polymerization catalyst used is too small, the polymerization rate is slowed down. As a result, when trying to obtain a polycarbonate resin having a desired molecular weight, the polymerization temperature has to be increased, and the obtained polycarbonate resin and polycarbonate resin composition are obtained. It affects the hue and light resistance of the product, or the unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound of the present invention and the carbonic acid diester represented by the above formula (4) collapses. The desired molecular weight may not be reached. On the other hand, when the amount of the polymerization catalyst used is too large, the hue of the resulting polycarbonate resin and the polycarbonate resin composition is affected, which may affect the light resistance of the polycarbonate resin and the polycarbonate resin composition.

<Production method of polycarbonate resin>
Hereinafter, the method for producing the polycarbonate resin of the present invention will be described in detail.
The polycarbonate resin of the present invention is obtained, for example, by polycondensation of a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester represented by the above formula (4) by a transesterification reaction. It is preferable that the carbonic acid diester is uniformly mixed before the transesterification reaction.

  The mixing temperature is usually 80 ° C or higher, preferably 90 ° C or higher, more preferably 100 ° C or higher, and the upper limit is usually 250 ° C or lower, preferably 200 ° C or lower, more preferably 150 ° C or lower, particularly preferably 120 ° C. It is as follows. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, and the operation may be affected by solidification or the like. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a change in the hue of the polycarbonate resin and the polycarbonate resin composition, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound of the present invention, which is a raw material of the polycarbonate resin used in the present invention, and the carbonic acid diester represented by the formula (4) has an oxygen concentration of usually 0.0001% by volume or more. Usually, it is preferably performed in an atmosphere of 10% by volume or less, preferably 5% by volume or less, more preferably 1% by volume or less from the viewpoint of influence on hue.

In order to obtain the polycarbonate resin of the present invention, the carbonic acid diester represented by the formula (4) is usually 0.90 or more, preferably 0.95 or more with respect to the dihydroxy compound containing the dihydroxy compound of the present invention. It is preferably used in a molar ratio, and usually used in a molar ratio of 1.20 or less, preferably 1.10 or less.
When this molar ratio decreases, the terminal hydroxyl group of the produced polycarbonate resin increases, which affects the thermal stability of the polymer, causing coloration during molding, reducing the rate of transesterification, It may be difficult to obtain a molecular weight body.

  Moreover, when this molar ratio becomes large, the rate of transesterification may decrease, or it may be difficult to produce a polycarbonate having a desired molecular weight. The decrease in the transesterification reaction rate increases the thermal history during the polymerization reaction and may affect the hue and light resistance of the resulting polycarbonate resin and polycarbonate resin composition.

  Furthermore, when the molar ratio of the carbonic acid diester represented by the formula (4) is increased with respect to the dihydroxy compound containing the dihydroxy compound of the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin is increased. Absorption of ultraviolet rays may affect the light resistance of the polycarbonate resin and the polycarbonate resin composition. In addition, the concentration of the carbonic acid diester remaining in the polycarbonate resin composition of the present invention is usually 200 ppm by weight or less, preferably 100 ppm by weight or less. Of these, 30 ppm by weight or less is preferable. Actually, the polycarbonate resin composition may contain an unreacted carbonic acid diester, and the lower limit of the carbonic acid diester concentration is usually 1 ppm by weight.

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

  In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, 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 suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 ° C. or more at the inlet of the reflux condenser. Preferably it is 80 degreeC or more, More preferably, it is 100 degreeC or more, Usually, 180 degreeC or less, More preferably, it is 150 degreeC or less, Most preferably, it is 130 degreeC or less. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the final polycarbonate resin and polycarbonate resin composition, the above-mentioned catalyst It is important to select the type and amount.

  The polycarbonate resin used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is the initial stage of the polymerization reaction. In order to shift the equilibrium to the polymerization side in the later stage of the polymerization reaction, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate because there are many monomers contained in the reaction solution. This is because it is important to sufficiently distill off the by-produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

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

  In the present invention, the polymerization catalyst can be mixed in the raw material preparation tank, the raw material storage tank, or can be directly mixed in the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.

  If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If the temperature is too high, not only the monomer is volatilized, but also the decomposition and coloring of the polycarbonate resin and the polycarbonate resin composition are promoted. there is a possibility.

  Specifically, the reaction in the first stage is usually 140 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and usually 270 ° C. or lower, as the maximum internal temperature of the polymerization reactor. 240 ° C. or less, more preferably 230 ° C. or less, usually 1 kPa or more, preferably 5 kPa or more, more preferably 10 kPa or more, usually 110 kPa or less, preferably 70 kPa or less, more preferably 30 kPa or less (absolute pressure). The reaction is usually performed for 0.1 hour or longer, preferably 0.5 hour or longer, usually 10 hours or shorter, preferably 3 hours or shorter, while distilling off the generated monohydroxy compound to the outside of the reaction system.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. The maximum internal temperature is usually 210 ° C. or higher, preferably 220 ° C. or higher, usually 270 ° C. or lower, preferably 250 ° C. or lower, usually 0.1 hours or longer, preferably 0.5 hours. Above, more preferably 1 hour or more, usually 10 hours or less, preferably 6 hours or less, more preferably 3 hours or less.

  In order to obtain a polycarbonate resin and a polycarbonate resin composition having good hue and light resistance, it is preferable that the maximum internal temperature in all reaction steps is less than 250 ° C, particularly 225 ° C to 245 ° C. In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

  The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.

The polycarbonate resin used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.
The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand and pelletized, or uniaxial or biaxial extrusion in the molten state from the final polymerization reactor. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Or after supplying resin to a twin-screw extruder, melt-extruding, cooling and solidifying and pelletizing, etc. are mentioned.

  At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, and the like can be mixed and kneaded.

  The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 150 ° C or higher, preferably 200 ° C or higher, more preferably 230 ° C or higher, and usually 300 ° C or lower, preferably It is 270 degrees C or less, More preferably, it is 260 degrees C or less. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the melt-kneading temperature is higher than 300 ° C., the polycarbonate is severely thermally deteriorated, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

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

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

<Physical properties of polycarbonate resin>
The molecular weight of the polycarbonate resin of the present invention obtained by the above-described method for producing a polycarbonate resin can be represented by a reduced viscosity. The reduced viscosity of the polycarbonate resin used in the present invention is usually 0.30 dL / g or more, and 35 dL / g or more is preferable, while it is usually 1.20 dL / g or less, preferably 1.00 dL / g or less, and more preferably 0.80 dL / g or less. If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product obtained may be small. If it is too high, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.
The reduced viscosity of the polycarbonate resin is measured using a Ubbelohde viscosity tube at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent, adjusting the polycarbonate resin concentration to 0.6 g / dL precisely. .

  The polycarbonate resin used in the present invention is preferably excellent in transparency of the polycarbonate resin itself in order to increase the light reflectance of the polycarbonate resin composition of the present invention, so that the polycarbonate resin composition is excellent in light resistance. The polycarbonate resin itself preferably has excellent light resistance. Coloring by sunlight or artificial lighting is considered to be due to absorption of light of a specific wavelength by the polycarbonate resin.

  From the above viewpoint, the polycarbonate resin used in the present invention preferably has a light transmittance at a wavelength of 350 nm of a molded product (thickness 3 mm) molded from the polycarbonate resin of 60% or more, more preferably 65% or more. Especially preferably, it is 70% or more. When the light transmittance at the wavelength is less than 60%, the absorption increases and the light resistance may deteriorate.

  Further, in the polycarbonate resin used in the present invention, the light transmittance at a wavelength of 320 nm of a molded body (thickness 3 mm) molded from the polycarbonate resin is preferably 30% or more, more preferably 40% or more, 50 % Or more is particularly preferable. When the light transmittance at the wavelength is less than 30%, the light resistance tends to deteriorate.

Further, the polycarbonate resin used in the present invention is a radiation (wavelength: 300 nm to 400 nm) of a molded body (thickness: 3 mm) molded from the polycarbonate resin in an environment of 63 ° C. and a relative humidity of 50% using a metal halide lamp. It is preferable that the yellow index (YI) value based on ASTM D 1925-70 measured by transmitted light after irradiation treatment at an illuminance of 1.5 kW / m ² for 100 hours is 12 or less, and this value is more preferably 10 Hereinafter, it is particularly preferably 8 or less.

The irradiation treatment using the metal halide lamp in the present invention will be described later, but with a specific device, a specific filter or the like is used to mainly emit light having a wavelength of 300 nm to 400 nm (light having a wavelength other than this wavelength range). This means irradiating the sample for 100 hours with an irradiance of 1.5 kW / m ² .

  Further, the polycarbonate resin used in the present invention is a yellow index value obtained by measuring a molded body (thickness 3 mm) molded from the polycarbonate resin with transmitted light without performing irradiation treatment with the metal halide lamp as described above. (Hereinafter referred to as the initial yellow index value, “initial YI value”) is usually 10 or less, preferably 7 or less, particularly preferably 5 or less, and the yellow index value before and after irradiation with the metal halide lamp. The absolute value of the difference is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When the initial YI value of the polycarbonate resin exceeds 10, the light resistance tends to deteriorate.

  Further, the polycarbonate resin used in the present invention usually has an L * value defined by the International Commission on Illumination (CIE), which is obtained by measuring a molded body (thickness 3 mm) molded from the polycarbonate resin with transmitted light, and is 96.3. The above is preferably 96.6 or more, and preferably 96.8 or more. When the L * value is less than 96.3, the light resistance tends to deteriorate.

  Furthermore, the lower limit of the concentration of the terminal group represented by the following formula (6) in the polycarbonate resin used in the present invention is usually 20 μeq / g, preferably 40 μeq / g, particularly preferably 50 μeq / g, and the upper limit is Usually, it is 160 μeq / g, preferably 140 μeq / g, particularly preferably 100 μeq / g. If the concentration of the end group represented by the following formula (6) is too high, the hue after exposure to ultraviolet rays may be deteriorated even if the hue immediately after polymerization or molding is good. There is a risk that the thermal stability will decrease. In order to control the concentration of the terminal group represented by the following formula (6), the dihydroxy compound containing the dihydroxy compound of the present invention as a raw material and the carbonic acid diester represented by the formula (4) are used during the production of the polycarbonate resin. In addition to controlling the molar ratio, a method for controlling the type and amount of the catalyst during the transesterification reaction, the polymerization pressure and the polymerization temperature, and the like can be mentioned.

  Further, in the production of the polycarbonate resin, when a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate is used as the carbonic acid diester represented by the formula (4), phenol and substituted phenol are by-produced during the reaction, and the polycarbonate resin. Although it is unavoidable that it remains in the interior, phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, as well as causing odor during molding. There is. The polycarbonate resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is devolatilized. Using a horizontal reactor excellent in performance or an extruder with a vacuum vent, the content of these aromatic monohydroxy compounds in the polycarbonate resin is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, particularly 300 It is preferable to make it weight ppm or less. However, it is difficult to remove the aromatic monohydroxy compound completely industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin is usually 1 ppm by weight. These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

Further, when the number of moles of hydrogen atoms bonded to the aromatic ring in the polycarbonate resin used in the present invention is (X) and the number of moles of hydrogen atoms bonded to other than the aromatic ring is (Y), hydrogen bonded to the aromatic ring The ratio of the number of moles of atoms to the number of moles of all hydrogen atoms is represented by X / (X + Y). However, as described above, there is a possibility that the aromatic ring having the ability to absorb ultraviolet rays affects the light resistance. Therefore, X / (X + Y) is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.02 or less, and particularly preferably 0.01 or less. X / (X + Y) can be quantified by ¹ H-NMR.

  The glass transition temperature of the polycarbonate resin used in the present invention is preferably 75 ° C. or higher and 105 ° C. or lower, more preferably 80 ° C. or higher and 105 ° C. or lower, and 85 ° C. or higher and 105 ° C. or lower. Is more preferable. By using a polycarbonate resin having a glass transition temperature within such a range, a molded product having excellent heat resistance can be provided.

[Production Method of Polycarbonate Resin Composition]
The polycarbonate resin composition of the present invention contains the above-described polycarbonate resin of the present invention and a metal pigment.

  The polycarbonate resin of the present invention may be added to a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer before performing various moldings as necessary. Additives such as additives, compatibilizers, and flame retardants can also be added and mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder, or the like.

  The other component which can be mix | blended with the polycarbonate resin composition of this invention below is mentioned. However, the components listed below are representative examples of what can be blended in the polycarbonate resin composition of the present invention, and do not prevent blending of components other than those listed below in the polycarbonate resin composition of the present invention.

There are no particular limitations on the timing and method of addition of the various components blended in the polycarbonate resin composition of the present invention. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; regardless of the polymerization method, the polycarbonate resin is melted in the middle of kneading the polycarbonate resin with another compounding agent. Using an extruder or the like and blending and kneading with a solid polycarbonate resin such as pellets or powder. Examples of the addition method include a method in which an additive is directly mixed or kneaded with a polycarbonate resin; a method in which the additive is added as a high-concentration master batch prepared using a small amount of a polycarbonate resin or other resin and the additive, and the like.
In addition, for the metal pigment, preferably, the above-described master batch containing the metal pigment may be added in the same manner as the addition timing and addition method of the above-mentioned various additives. Is preferably kneaded by heating in an extruder after mixing with polycarbonate resin pellets.

<Antioxidant>
The polycarbonate resin composition of the present invention can be blended with an antioxidant as long as the object of the present invention is not impaired, and contains 0.0001 part by weight or more of the antioxidant with respect to 100 parts by weight of the polycarbonate resin. The content is preferably 0.001 part by weight or more, and more preferably 0.01 part by weight or more. On the other hand, the content is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, and still more preferably 1 part by weight or less.

  If the content of the antioxidant in the polycarbonate resin composition is excessively small, the coloring suppression effect during molding may be insufficient. Also, if the content of the antioxidant is excessively large, the amount of deposits on the mold during injection molding increases or the number of deposits on the roll increases when forming a film by extrusion. May affect the surface appearance of the product

  The antioxidant is at least one selected from the group consisting of phosphite antioxidants, phenolic antioxidants and sulfur antioxidants from the viewpoint of oxidation stability, thermal stability, sharpness, and the like. It is preferable that there is a phenolic antioxidant and / or a phosphite antioxidant. Moreover, 1 type of these antioxidants may be used independently, and 2 or more types may be mixed and used for them.

(Phosphite antioxidant)
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

  Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used. These compounds can be used alone or in combination of two or more.

  Here, the content of the phosphite antioxidant is usually 0.0001 parts by weight or more, preferably 0.0002 parts by weight or more, usually 1 part by weight or less, preferably 0, relative to 100 parts by weight of the polycarbonate resin. .1 part by weight or less, more preferably 0.01 part by weight or less. If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be affected.

(Phenolic antioxidant)
Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-bull-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} And compounds such as -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred.

  Here, the content of the phenolic antioxidant is usually 0.0001 parts by weight or more, preferably 0.0002 parts by weight or more, and usually 1 part by weight or less, preferably 0.000 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. 1 part by weight or less, more preferably 0.01 part by weight or less. If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be affected.

(Sulfur-based antioxidant)
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. . Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

  Here, the content of the sulfur-based antioxidant is usually 0.0001 parts by weight or more, preferably 0.0002 parts by weight or more, usually 1 part by weight or less, preferably 0.000 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. 1 part by weight or less, more preferably 0.01 part by weight or less. If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

  The polycarbonate resin composition of the present invention may contain a phosphite-based antioxidant and a sulfur-based antioxidant alone, but by including both, it is possible to exert a great effect on coloring suppression during molding. It is more preferable because it has

<Release agent>
A release agent can be blended with the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. In the polycarbonate resin composition of the present invention, the release agent is preferably contained in an amount of 0.001 part by weight or more, more preferably 0.005 part by weight or more, relative to 100 parts by weight of the polycarbonate resin. More preferably, it is contained by weight or more. On the other hand, the content is preferably 2 parts by weight or less, more preferably 1 part by weight, and even more preferably 0.5 parts by weight or less.

  If the content of the release agent is within this range, there is an advantage that the molded product is easy to release from the mold during molding, and the molded product is easy to obtain, but if the content of the release agent is too small The molded product is difficult to release from the mold, causing a problem in workability. On the other hand, if the content of the release agent is excessively large, deposits on the mold may increase during molding, and if molding is carried out in large quantities, it may require labor to clean the mold. The product may cause poor appearance.

  Although it does not specifically limit as a mold release agent, A stearic acid ester, a higher fatty acid, etc. are mentioned, From a mold release property and transparency viewpoint, a stearic acid ester is more preferable as a mold release agent.

  As the stearic acid ester, a partial or total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid is preferable. Such partial esters or total esters of monohydric or polyhydric alcohols and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, ethylene glycol distearate, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferable, and ethylene glycol distearate and stearic acid monoglyceride are particularly preferable.

As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable, and an unsubstituted saturated fatty acid having 10 to 30 carbon atoms is more preferable. Examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid. Further, saturated fatty acids having 16 to 18 carbon atoms are more preferable, and examples of such saturated fatty acids include palmitic acid and stearic acid, and stearic acid is particularly preferable.
One of these release agents may be used alone, or two or more thereof may be mixed and used.

<Colorant>
In the polycarbonate resin composition of the present invention, when a colored molded product is desired, a colorant can be blended within a range that does not impair the object of the present invention. In this case, the polycarbonate resin composition of the present invention preferably contains 0.00001 part by weight or more and 3 parts by weight or less of the colorant with respect to 100 parts by weight of the polycarbonate resin. If the type of the colorant is too large or the amount of the colorant is too large, the effect of light reflection or scattering by the colorant increases, and the clarity of the polycarbonate resin composition may be reduced. That is, in order to improve the sharpness of the polycarbonate resin composition, it is preferable that the kind and amount of the colorant used are small. In order to obtain high definition, the content of the colorant (as a total amount when two or more colorants are used) is 0.001 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin. More preferably, it is 0.005 parts by weight or more, particularly preferably 0.01 parts by weight or more, more preferably 3 parts by weight or less, still more preferably 2 parts by weight or less, particularly preferably 1 part by weight. Or less.

  The colorant is not particularly limited as long as it can color the polycarbonate resin composition, but dyes and pigments that cause deterioration of the polycarbonate resin during molding and do not cause problems such as a decrease in molecular weight can be preferably used. Examples include inorganic pigments, organic pigments, and dyes.

  Examples of inorganic pigments include carbon black, titanium oxide, zinc white, petal, iron oxide pigment, ultramarine, cobalt blue, chromium oxide, titanium yellow, zinc-iron brown, spinel green, lead collate pigment, cadmium Examples thereof include pigments, copper-chromium black, and copper-iron black.

  Examples of organic pigments include azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, and perylene pigments. , Anthraquinone pigment, perinone pigment, dioxazine violet and the like.

  Examples of dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, azine dyes Oxazine dye, thiazine dye, sulfur dye, aminoketone / oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine dye, pyrazolone dye, perinone dye, quinophthalone dye and the like.

<Light resistance stabilizer>
The polycarbonate resin composition of the present invention can be blended with a light-resistant stabilizer as long as the object of the present invention is not impaired. The light-resistant stabilizer is added in an amount of 0.0001 parts by weight or more and 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It is preferable to contain a part or less.
The light-resistant stabilizer used in the present invention is preferably an ultraviolet absorber and a hindered amine light stabilizer. These may be used alone, but it is more preferable to use an ultraviolet absorber and a hindered amine light stabilizer in combination because the light resistance is further improved.

(UV absorber)
The polycarbonate resin composition of the present invention preferably contains 0.005 parts by weight or more and 5 parts by weight or less of an ultraviolet absorber with respect to 100 parts by weight of the polycarbonate resin in order to suppress photobleaching of the colorant. The content of the ultraviolet absorber is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. On the other hand, it is preferably 3 parts by weight or less, and more preferably 1 part by weight or less. If the content of the ultraviolet absorber is too small, the effect of improving the weather resistance due to the inclusion of the ultraviolet absorber is lowered, and if it is too large, there is a risk of appearance failure due to bleeding out of the ultraviolet absorber.

Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, and the like. . Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferably used.
These ultraviolet absorbers may be used alone or in combination of two or more.

(Hindered amine light stabilizer)
The content of the hindered amine light stabilizer in the polycarbonate resin of the present invention is usually 0.005 parts by weight or more and 3 parts by weight or less, preferably 0.01 parts by weight or more, relative to 100 parts by weight of the polycarbonate resin. More preferably 0.05 parts by weight or more, on the other hand, preferably 2 parts by weight or less, more preferably 1 part by weight or less.

In the present invention, it is more preferable to use an ultraviolet absorber and a hindered amine light stabilizer in combination because the light resistance is further improved. In this case, the usage amount of the ultraviolet absorber can be reduced according to the usage amount of the hindered amine light stabilizer.
These may be used alone or in combination of two or more.

<Other optional components>
In the polycarbonate resin composition of the present invention, in addition to the above-mentioned components, a bluing agent, a fluorescent whitening agent, a filler, an antistatic agent, a flame retardant, as long as the object of the present invention is not impaired. Additives such as: an acidic compound as a thermal degradation inhibitor; and resin components other than the polycarbonate resin used in the present invention, impact resistance improvers, and the like can be appropriately contained. These may be used alone or in combination.

(Bluing agent)
In the polycarbonate resin composition of the present invention, a bluing agent can be blended in order to counteract the yellowishness of the lens based on the polymer or the ultraviolet absorber. These bluing agents may be used alone or in combination of two or more. These bluing agents are usually blended at a ratio of 1 × 10 ⁻⁶ to 1 × 10 ⁻² wt% with respect to the entire polycarbonate resin composition.

  As the bluing agent, any conventional bluing agent can be used as long as it is used for polycarbonate resin. In general, anthraquinone dyes are preferred because they are readily available.

(Fluorescent brightener)
In the polycarbonate resin composition of the present invention, for the purpose of obtaining a good hue and enhancing light reflectance and light resistance, it contains any conventionally known fluorescent whitening agent within a range not impairing the effects of the present invention. Can do. The fluorescent whitening agent used in the present invention is a pigment or dye added to a molded product to make the molded product appear brighter, and is an additive that removes the yellowishness of the molded product and increases the brightness. The brightening agent removes yellow light, whereas the fluorescent whitening agent absorbs ultraviolet rays and changes its energy into a blue-violet light in the visible region and emits it.

  In this invention, it is preferable to contain 1-1000 weight ppm of said fluorescent whitening agents in a polycarbonate resin composition. Even if it exceeds the upper limit of the above content, not only the whitening effect can be expected to be commensurate with the increase in content, but also the heat stability and appearance may be deteriorated.

  Examples of fluorescent brighteners include coumarin, naphthotriazolyl stilbene, benzoxazole, benzimidazole, and diaminostilbene-disulfonate. Fluorescent brighteners include benzoxazole, coumarin, and naphthotriazolyl. Examples include rustylben-based, benzimidazole-based, and diaminostilbene-disulfonate-based fluorescent whitening agents. In the resin composition of this invention, these may be used individually by 1 type and may be used in mixture of 2 or more types.

(filler)
A filler can be blended in the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Examples of the filler that can be blended in the polycarbonate resin composition of the present invention include inorganic fillers and organic fillers.

  The blending amount of the filler is 0% by weight or more and 60% by weight or less with respect to the entire polycarbonate resin composition. The blending amount of the filler is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 35% by weight or less. The reinforcing effect of the polycarbonate resin composition can be obtained by blending the filler, but if the blending amount of the filler is excessively large, the appearance of the obtained molded product tends to deteriorate.

  Examples of the inorganic filler include glass, silica, alumina, gypsum, carbon black, silicon carbide, silicon nitride, and carbon, but glass fiber, gypsum whisker, carbon fiber, silicon carbide fiber, silicon nitride fiber, various whiskers, and the like. It is more preferable to use a fibrous inorganic filler such as glass flakes, talc, graphite, etc., because the shape effect is exhibited. Although the said inorganic filler can also be used only by 1 type, it can also be used in combination of 2 or more type. These inorganic fillers are used in order to improve adhesion with the polycarbonate resin of the present invention, surface treatment with a silane coupling agent such as aminosilane, epoxy silane, etc. It may be used after being surface-treated with a resin.

  Examples of organic fillers include powdery organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, and pulp powder; balun-like and spherical shapes such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, and urea resin. Organic fillers: Examples include fibrous organic fillers such as synthetic fibers and natural fibers. These organic fillers may be subjected to a surface treatment such as an epoxy treatment, a urethane treatment, or an oxidation treatment in order to increase the affinity with the polycarbonate resin.

(Antistatic agent)
The polycarbonate resin composition of the present invention can contain an antistatic agent as long as the object of the present invention is not impaired. When an antistatic agent is blended in the polycarbonate resin composition of the present invention, the content of the antistatic agent is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. When the content of the antistatic agent is less than the above lower limit, an antistatic effect cannot be obtained, and when it is more than the above upper limit, hydrolysis resistance and thermal stability may be deteriorated, which is not preferable.

Specific examples of the antistatic agent include sulfonates having an alkyl group, an alkylbenzene group, a polyoxyalkylene group, and the like, anionic systems such as phosphates, quaternary ammonium salts, and cation systems typified by imidazoline, Examples include amphoteric systems such as betaine, fatty acid ester compounds, sulfonic acid ester compounds, phosphate ester compounds, hydroxyalkylamine compounds, alkylamine compounds, and polyoxyalkylene compounds. From the viewpoint of maintaining hydrolyzability, an anionic or nonionic system having a polyoxyethylene chain in the molecular structure is preferable, and a nonionic system having a polyoxyethylene chain in the molecular structure is preferable. Further preferred.
One of these antistatic agents may be used alone, or two or more thereof may be mixed and used.

(Flame retardants)
Moreover, the polycarbonate resin composition of the present invention can contain a flame retardant.
In this case, the blending amount of the flame retardant is selected according to the type of the flame retardant and the required flame retardance, but the flame retardant is usually 0.01 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. Preferably it is 0.02 weight part or more, and is 30 weight part or less normally, Preferably it is the range of 25 weight part or less. By blending a flame retardant, a polycarbonate resin composition having excellent flame retardancy can be obtained.

  Examples of the flame retardant include phosphorus-containing compound flame retardants, halogen-containing compound flame retardants, sulfonic acid metal salt flame retardants, and silicon-containing compound flame retardants. As the flame retardant, at least one selected from these groups can be used. Two or more of these may be used in combination.

(Other resins)
In the polycarbonate resin composition of the present invention, a resin other than the polycarbonate resin (hereinafter sometimes simply referred to as “other resin”) is used for the purpose of further improving and adjusting the molding processability and various physical properties. You can also.

  When using other resin, it is preferable to set it as 0 to 30 weight% with respect to the whole polycarbonate resin composition used by this invention as the compounding quantity.

  Specific examples of other resins include resins such as polyester resins, polyethers, polyamides, polyolefins, polymethylmethacrylates, and rubber-like modified resins such as core-shell type, graft type or linear random and block copolymers. Examples include quality agents. Among them, in order to maintain high color developability and sharpness, a resin having perfect compatibility with the polycarbonate resin of the present invention is preferable, and various polycarbonate resins not containing a structural unit derived from a dihydroxy compound having a cyclic ether structure. Is preferred. Among the various polycarbonate resins, those having a refractive index close to that of the polycarbonate resin of the present invention are particularly preferable.

[Physical properties of polycarbonate resin composition]
In the polycarbonate resin composition of the present invention, the total light transmittance of an injection-molded product having a thickness of 3 mm is preferably 3.0% or less. If the light transmittance exceeds 3.0%, it is difficult to obtain a deep metallic appearance because the molded product can be seen through, which is not preferable because it is inferior in design. The light transmittance is preferably as small as possible, and the lower limit is preferably 0.0. In addition, the said light transmittance is measured based on JISK7105 as described in an Example.

  The polycarbonate resin composition of the present invention includes a compound containing at least one metal selected from the group consisting of lithium and metals of Group 2 of the long-period periodic table. The total content of these metals in the polycarbonate resin composition is 20 ppm by weight or less, preferably 15 ppm by weight or less, in terms of metal, from the viewpoint of enhancing the light resistance and color tone of the polycarbonate resin composition. Preferably it is 12 weight ppm or less. On the other hand, since the metal is derived from the catalyst used for the polycondensation of the polycarbonate resin of the present invention and contained in the polycarbonate resin, the content of the metal is usually 0.1 ppm by weight or more.

  In addition, the long-period periodic table group 2 metal contained in the polycarbonate resin composition of the present invention refers to beryllium, magnesium, calcium, strontium, and barium. Among these long-period periodic table group 2 metals, the polycarbonate resin composition preferably contains magnesium or calcium, and more preferably contains calcium.

  In addition, long-period type periodic table Group 1 metals, particularly lithium, sodium, potassium, cesium, especially sodium, potassium, cesium, may affect the hue when contained in a large amount in the polycarbonate resin composition, Since the metal may be mixed not only from the catalyst used but also from the raw materials and the reaction apparatus, the total content of these metals in the polycarbonate resin composition is usually 1% by weight or less as a metal conversion amount, Preferably it is 0.8 weight% or less, More preferably, it is 0.7 weight% or less.

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

  The polycarbonate resin composition contains an aromatic monohydroxy compound derived from the raw material or the polycondensation reaction product, and the content of the compound is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less. In particular, it is preferably 300 ppm by weight or less. However, it is difficult to remove the aromatic monohydroxy compound completely industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin composition is usually 1 ppm by weight.

  In the polycarbonate resin composition of the present invention, the content of the carbonic acid diester represented by the formula (4) is preferably 60 ppm by weight or less, more preferably 30 ppm by weight or less, from the viewpoint of hue. The carbonic acid diester represented by the formula (4) is mainly derived from the raw material of the polycarbonate resin, and the lower limit of the content is usually 1 ppm by weight.

[Polycarbonate resin molded product]
The polycarbonate resin molded product of the present invention can be obtained by molding the above-described polycarbonate resin composition of the present invention.

  The method for producing a resin molded product from the polycarbonate resin composition of the present invention is not particularly limited, and is a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an ultra-high speed injection molding method. , Injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding An IMC (in-mold coating molding) molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method, and the like can be employed. Moreover, the shaping | molding method using a hot runner system can also be selected. Among these, the injection molding method is preferable from the viewpoint of the degree of freedom of the shape of the molded product.

  As a molding method of the polycarbonate resin molded product of the present invention, a polycarbonate resin, a metal pigment, and, if necessary, other raw materials such as other resins and additives are directly mixed to obtain a polycarbonate resin composition, which is an extruder or injection molding. A method of molding by putting into a machine, or the raw material is melt-mixed using a twin-screw extruder, extruded into a strand shape to produce pellets, and then the pellets are fed into an extruder or injection molding machine A method of molding can be mentioned.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, the physical properties or characteristics of the polycarbonate resin composition and the molded product were evaluated by the following methods.

1) Evaluation method of total light transmittance After drying the polycarbonate resin composition pellets at 110 ° C. for 4 hours or more in a nitrogen atmosphere, the cylinder temperature was 270 ° C. using an M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho. Under the conditions of a mold temperature of 80 ° C. and a molding cycle of 55 seconds, an ASTM test piece and a flat molded product (90 mm × 50 mm × 3 mm thickness) were prepared. Based on JIS K7105, the obtained injection-molded piece was measured for total light transmittance with a D65 light source using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The greater the total light transmittance, the better the transparency.

2) Spectral colorimetry method According to JIS K7105, the flat plate-shaped molded product was measured using a spectral color difference meter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.), C / 2 light source reflection method (2 ° field of view), L ^* , The a ^* and b ^* values were measured.

3) Light resistance test Using a metering weather meter M6T manufactured by Suga Test Instruments Co., Ltd., with a black panel temperature of 63 ° C and a relative humidity of 50%, a horizontal metalling lamp as the light source, quartz as the inner filter, and lamp A filter of # 500 is attached as an outer filter around the surface, and the irradiance is set to 1.5 kw / m ² at a wavelength of 300 nm to 400 nm. A time irradiation process was performed, and the color difference was determined using the L ^* , a ^* , and b ^* values measured by the spectral colorimetry method before and after the irradiation process. The values before irradiation are L ₀ ^* , a ₀ ^* , b ₀ ^* , the values after irradiation are L ^* , a ^* , b ^*, and ΔL ^* , Δa ^* , Δb ^* , and color difference ΔE _ab ^* are expressed by the following equations. Asked. It means that it is excellent in light resistance, so that the value of (DELTA) _Eab ^* is small.
ΔL ^* = | L ^* −L ₀ ^* |
Δa ^* = | a ^* −a ₀ ^* |
Δb ^* = | b ^* −b ₀ ^* |
ΔE _ab ^* = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2

Moreover, the symbol of the compound used by the following example and the comparative example is as follows.
<Polycarbonate resin raw material>
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
<Polycarbonate resin>
M7022J: Polycarbonate resin (Novalex M7022J, manufactured by Mitsubishi Chemical Corporation)

<Antioxidant>
2112: Phosphite antioxidant (Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by ADEKA, Adekastab 2112)
AO-60: Phenolic antioxidant (pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by ADEKA, ADK STAB AO-60)
<Release agent>
S-100A: stearic acid monoglyceride (manufactured by Riken Vitamin Co., Ltd., S-100A)

<Metal pigment>
NME005N1: Master batch containing 70% by weight of metal pigment composed of surface-treated aluminum particles (manufactured by Toyo Aluminum Co., Ltd., METAX NEO NME005N1, volume average particle size of aluminum particles: 5 μm, average thickness: 0.2 μm, scaly, polyethylene Wax surface treated product, LLDPE used as masterbatch resin)
NME070N6: masterbatch containing 70% by weight of metal pigment made of surface-treated aluminum particles (manufactured by Toyo Aluminum Co., Ltd., METAX NEO NME070N6, volume average particle diameter of aluminum particles: 70 μm, average thickness: 0.5 μm, scaly, polyethylene Wax surface treated product, LLDPE used as masterbatch resin)

[Production Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 weight ppb or less by distillation purification, The mixture was charged so that the ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ and sufficiently purged with nitrogen (oxygen concentration 0. 0005 to 0.001 vol%). Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  The contents thus oligomerized are once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set to 230 ° C. over 20 minutes, the pressure was 133 Pa or less, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and pelletized with a rotary cutter. This polycarbonate resin is referred to as “ISB-PC”.

[Example 1]
Two polycarbonate resin pellets obtained in Production Example 1, S-100A as a release agent, Adeka Stub AO-60 and Adeka Stub 2112 as antioxidants, and 2 NME005N1 as metal pigments so as to have the composition shown in Table 1. Using a twin-screw extruder (TEX30HSS-32) manufactured by Nippon Steel Works, which has two vent ports, it is extruded in a strand shape so that the resin temperature at the outlet is 250 ° C., cooled and solidified with water, and then a rotary cutter And pelletized. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The obtained pellets of the polycarbonate resin composition were dried at 90 ° C. for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. (Width 60 mm × length 60 mm × thickness 3 mm) was molded and evaluated by the above method. The results are shown in Table 1.

[Example 2]
In Example 1, it evaluated similarly to Example 1 except having changed the metal pigment into NME070N6, and the result was shown in Table 1.

[Comparative Example 1]
Nippon Steel, which has two vent openings, polycarbonate resin M7022J, S-100A as a release agent, Adekastab AO-60 and Adekastab 2112 as antioxidants, and NME070N6 as a metal pigment so as to have the composition shown in Table 1. Using a twin screw extruder (TEX30HSS-32) manufactured by Tosho Co., Ltd., it was extruded in a strand shape so that the resin temperature at the outlet was 280 ° C., cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The pellets of the obtained polycarbonate resin composition were dried at 120 ° C. for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds. (Width 60 mm × length 60 mm × thickness 3 mm) was molded and evaluated by the above method. The results are shown in Table 1.

From Table 1, it can be seen that the polycarbonate resin composition of the present invention has a low total light transmittance and a low ΔE _ab by a light resistance test.
In addition, since the injection-molded plates obtained in Examples 1 and 2 have low total light transmittance, the aluminum pigment is uniformly dispersed in the polycarbonate resin composition, and this shows a good metallic design. It is also estimated that ΔE _ab is low, which indicates that the light resistance is good. Furthermore, it was confirmed that the polycarbonate resin compositions of Examples 1 and 2 have good moldability and good scratch resistance.

  The polycarbonate resin composition of the present invention not only has a wide range of design properties (metallic tone, vividness, deep colorability), but also has light resistance, good moldability, and scratch resistance. Because it is good, it can be used in a wide range of fields such as injection molding fields such as electrical and electronic parts, office automation equipment, toys, stationery, automotive interior and exterior parts, and other exterior parts for daily life, and extrusion fields such as films and sheets. Materials can be provided.

Claims (19)

  A polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure, and a pigment made of metal particles surface-treated with a surface treatment agent, the metal particles comprising aluminum, gold, silver, copper, nickel, A polycarbonate resin composition comprising at least one metal or alloy selected from the group consisting of titanium, magnesium and stainless steel. The polycarbonate resin composition according to claim 1, wherein the dihydroxy compound is a dihydroxy compound having a structure represented by the following formula (1).

  The polycarbonate resin composition of Claim 1 or 2 in which a polycarbonate resin contains the structural unit derived from the dihydroxy compound of an aliphatic hydrocarbon.   The polycarbonate resin composition according to claim 3, wherein the aliphatic hydroxy dihydroxy compound is cyclohexanedimethanol.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polycarbonate resin is obtained by polycondensation of a dihydroxy compound containing a dihydroxy compound having a cyclic ether structure and a carbonic acid diester.   The polycondensation is performed in the presence of a catalyst, and the catalyst is at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table and lithium, and the total amount of these metal compounds The polycarbonate resin composition according to claim 5, wherein the metal amount is 20 μmol or less per 1 mol of the dihydroxy compound containing the dihydroxy compound having the cyclic ether structure.   The polycarbonate resin composition according to claim 6, wherein the content of the metal derived from the catalyst is 20 ppm by weight or less based on the polycarbonate resin composition.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein a ratio of a volume average particle diameter to an average thickness of the metal particles is 2 to 300.   The polycarbonate resin composition according to claim 1, wherein the metal particles have a volume average particle size of less than 20 μm.   The polycarbonate resin composition according to claim 1, wherein the average thickness of the metal particles is 0.1 to 1.5 μm.   The said surface treating agent is at least 1 sort (s) of compounds chosen from the group which consists of a wax, modified polyolefin, a metal soap, a silane coupling agent, and a titanate coupling agent. Polycarbonate resin composition.   The polycarbonate resin composition according to any one of claims 1 to 11, wherein the pigment is blended in the composition as a master batch of a thermoplastic resin different from the polycarbonate resin.   The polycarbonate resin composition according to any one of claims 1 to 12, wherein the metal particles are metal particles containing aluminum.   The polycarbonate resin composition according to any one of claims 1 to 13, wherein the pigment is contained in an amount of 0.01 to 50 parts by weight in terms of metal particles with respect to 100 parts by weight of the polycarbonate resin.   The polycarbonate resin composition according to any one of claims 1 to 14, wherein a total light transmittance of an injection molded article having a thickness of 3 mm molded from the polycarbonate resin composition is 3.0% or less.   The polycarbonate resin composition according to any one of claims 1 to 15, comprising 0.0001 parts by weight or more and 3 parts by weight or less of an antioxidant with respect to 100 parts by weight of the polycarbonate resin.   The polycarbonate resin composition according to any one of claims 1 to 16, comprising a release agent in an amount of 0.001 part by weight to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.   A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 17.   The polycarbonate resin molded product according to claim 18, wherein the polycarbonate resin molded product is molded by an injection molding method.