JP6188272B2 - Polycarbonate resin composition and molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin composition excellent in flame retardancy, light resistance, hue, heat resistance, thermal stability, mechanical strength, and the like, and a molded product thereof.

Polycarbonate resins are generally composed of bisphenols as monomer components, taking advantage of transparency, heat resistance, mechanical strength, etc., and electrical / electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles It is widely used as so-called engineering plastics in the fields of optical recording media and lenses.
However, conventional polycarbonate resins are limited in use outdoors or in the vicinity of lighting devices, because their hue, transparency, and mechanical strength deteriorate when used in places exposed to ultraviolet rays or visible light for a long time. .

  In order to solve such problems, a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a benzoxazine ultraviolet absorber to a polycarbonate resin is widely known (for example, Non-Patent Document 1). However, when such an ultraviolet absorber is added, although the hue after UV irradiation is improved, the hue, heat resistance, and transparency of the resin are deteriorated in the first place. There were problems such as contamination of the mold.

  Since the bisphenol compound used in the conventional polycarbonate resin has a benzene ring structure, it absorbs a large amount of ultraviolet rays. This causes a deterioration in the light resistance of the polycarbonate resin. Therefore, an aliphatic dihydroxy compound having no benzene ring structure in the molecular skeleton. If a cyclic dihydroxy compound monomer unit having an ether bond in the molecule, such as a compound, an alicyclic dihydroxy compound, or isosorbide, is used, it is expected that light resistance is improved in principle. 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 1 to 6). .

  However, cyclic dihydroxy compounds having an ether bond in the molecule, such as the above aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and isosorbide, do not have phenolic hydroxyl groups, and thus are widely known as methods for producing polycarbonate resins using bisphenol A as a raw material. It is difficult to polymerize by the conventional interface method, and it is usually produced by a method called a transesterification method or a melting method. In this method, the dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified at a high temperature of 200 ° C. or higher in the presence of a basic catalyst, and the polymerization proceeds by removing by-product phenol and the like out of the system, A polycarbonate resin is obtained. However, a polycarbonate resin obtained using a monomer having no phenolic hydroxyl group as described above is inferior in thermal stability to a polycarbonate resin obtained using a monomer having a phenolic hydroxyl group such as bisphenol A. In addition, there is a problem that coloring occurs during polymerization or molding that is exposed to high temperatures, and as a result, ultraviolet light and visible light are absorbed, resulting in deterioration of light resistance. Among these, when a monomer having an ether bond in the molecule, such as isosorbide, is used, the hue is remarkably deteriorated, and it is difficult to solve the improvement in brightness. Furthermore, when it is used as various molded products, it is melt-molded at a high temperature. At that time, a material having good thermal stability and excellent moldability and mold release properties has been demanded.

In addition, a method using a flame retardant for improving the flame retardancy of a polycarbonate resin is known. However, generally, when the hue of the polycarbonate resin before mixing the flame retardant is poor, there is a problem that the hue after mixing the flame retardant is further deteriorated.

International Publication No. 04/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897 JP 2006-28441 A JP 2008-24919 A JP 2009-91404 A JP 2009-91417 A

Polycarbonate resin handbook (issued by Seiichi Honma, published by Nikkan Kogyo Shimbun, August 28, 1992)

  An object of the present invention is to eliminate the above-mentioned conventional problems and to provide a polycarbonate resin composition excellent in flame retardancy, light resistance, transparency, hue, heat resistance, thermal stability, mechanical strength, moldability, and the like. It is to provide a molded article.

As a result of intensive studies to solve the above problems, the present inventors have determined that a polycarbonate resin and a specific amount containing at least a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in the molecule And a polycarbonate resin composition containing a specific amount of a specific metal as a catalyst for the polycarbonate resin, not only has excellent light resistance but also excellent flame resistance. The present invention has been found by having properties such as property, hue, heat resistance, thermal stability and mechanical strength.
That is, the gist of the present invention resides in the following [1] to [9].

[1] A polycarbonate resin composition comprising a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure, and a flame retardant, the polycarbonate resin 100 parts by weight with respect to 100 parts by weight, containing at least one metal selected from the group consisting of lithium and a metal of Group 2 of the long-period periodic table, containing 0.01 to 30 parts by weight of a flame retardant A polycarbonate resin composition, which is contained as a catalyst for a polycarbonate resin, and the amount of metal contained as the catalyst is 20 ppm by weight or less in total with respect to the entire polycarbonate resin composition.

(However, the site represented by the above formula (1) unless a portion constituting a _-CH 2 -O-H.)

[2] In [1], the flame retardant includes at least one selected from a phosphorus-containing compound flame retardant, a halogen-containing compound flame retardant, a sulfonic acid metal salt flame retardant, and a silicon-containing compound flame retardant. The polycarbonate resin composition as described.

[3] The polycarbonate resin composition according to [1] or [2], wherein the dihydroxy compound having a part represented by the formula (1) in a part of the structure is a dihydroxy compound represented by the following formula (2): object.

[4] Any one of [1] to [3], wherein the polycarbonate resin includes a structural unit derived from at least one compound selected from the group consisting of a chain aliphatic dihydroxy compound and an alicyclic dihydroxy compound. The polycarbonate resin composition described in 1.

[5] The polycarbonate resin is obtained by polycondensation of a dihydroxy compound having a site represented by the formula (1) in a part of the structure with a carbonic acid diester represented by the following formula (3). ] To the polycarbonate resin composition according to any one of [4].

(In the above formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. And A ¹ and A ² may be the same or different.)

[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 lithium compound and a metal of Group 2 of the long-period periodic table, And the polycarbonate resin composition as described in [5] whose total amount of these metal compounds is 20.0 micromol or less as a metal amount with respect to 1 mol of used dihydroxy compounds.

[7] The catalyst is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds, and the total content of sodium, potassium and cesium in the polycarbonate resin is 1 ppm by weight as the metal amount The polycarbonate resin composition according to [6], which is as follows.

[8] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [7].

[9] The polycarbonate resin molded product according to [8], which is molded by an injection molding method.

  According to the present invention, not only has excellent flame resistance, but also excellent light resistance, hue, heat resistance, thermal stability, mechanical strength, etc., and injection molding of electrical / electronic parts, automotive parts, etc. We can provide polycarbonate resins that can be applied to a wide range of fields such as fields, films, sheets, bottles, containers, etc., and provide polycarbonate resins that are particularly suitable for applications exposed to light including ultraviolet rays such as outdoors and lighting parts. It becomes possible to do.

  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. In the present specification, “to” is used as an expression including numerical values or physical quantities before and after.

1. Polycarbonate resin composition
The polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure, and a flame retardant. And containing at least 0.01 part by weight and not more than 30 parts by weight of a flame retardant with respect to 100 parts by weight of the polycarbonate resin, and at least selected from the group consisting of lithium and a metal of Group 2 of the long-period periodic table One type of metal is contained as a catalyst for the polycarbonate resin, and the amount of the metal contained as the catalyst is 20 ppm by weight or less in total with respect to the entire polycarbonate resin composition.

(However, the site represented by the above formula (1) unless a portion constituting a _-CH 2 -O-H.)

  Details of the polycarbonate resin, the flame retardant, and the blending amount thereof in the polycarbonate resin composition of the present invention will be described later. The polycarbonate resin composition of the present invention is made of a group consisting of lithium and a metal of Group 2 of the long-period periodic table. The polycarbonate resin containing at least one structural unit derived from the dihydroxy compound having the site represented by the above formula (1) as the at least one selected metal (hereinafter sometimes referred to as “polycarbonate resin used in the present invention”). In addition, it contains a total of 20 ppm by weight or less of the metals contained therein, that is, lithium and metals of Group 2 of the long-period type periodic table. The total content of lithium and long-period group 2 metal in the polycarbonate resin composition is preferably small in order to make the polycarbonate resin composition excellent in light resistance, more preferably It is 10 weight ppm or less, More preferably, it is 5 weight ppm or less.

However, in the polycarbonate resin composition of the present invention, the lithium and the metal of Group 2 of the long-period periodic table are derived from the catalyst preferably used for the production of the polycarbonate resin and are contained in the polycarbonate resin composition. Since it is difficult to industrially remove the metals contained in the system, the total content thereof is usually 0.01 ppm by weight or more, preferably 0.05 as the amount of metal relative to the polycarbonate resin composition. It is at least ppm by weight, more preferably at least 0.1 ppm by weight. The long-period periodic table group 2 metal contained in the polycarbonate resin composition of the present invention refers to beryllium, magnesium, calcium, strontium, barium, and among these long-period periodic table group 2 metals, The polycarbonate resin composition preferably contains magnesium or calcium, and more preferably contains calcium.

  Further, the polycarbonate resin composition of the present invention may also contain a metal selected from sodium, potassium and cesium, but the total content of sodium, potassium and cesium in the polycarbonate resin composition is the whole of the polycarbonate resin composition. It is preferable that it is 1 weight ppm or less as a metal amount with respect to this. Sodium, potassium and cesium may be mixed not only from the catalyst used in the production of the raw material polycarbonate resin, but also from raw materials such as dihydroxy compounds and reaction equipment, so these compounds are also produced when the polycarbonate resin composition is produced. The total amount of is more preferably 0.8 ppm by weight or less, and still more preferably 0.7 ppm by weight or less as the amount of metal. When the total content of sodium, potassium, and cesium is within the above range, there is an effect that the light resistance of the polycarbonate resin composition is excellent.

  The amount of metal in the polycarbonate resin composition can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin by a method such as wet ashing, atomic emission, atomic absorption, Inductively Coupled Plasma ( ICP) and other methods can be used.

The polycarbonate resin composition of the present invention has an initial yellow index (YI) value based on ASTM D1925-70 measured by reflected light as a molded body (thickness 3 mm) from the viewpoint of light resistance, and YI ₁ , In an environment of 63 ° C. and relative humidity of 50%, the yellow index (YI) value after irradiation for 100 hours at an irradiance of 1.5 kW / m ² with a wavelength of 300 nm to 400 nm using a metal halide lamp is defined as YI ₂ In this case, | YI ₁ −YI ₂ | ≦ 7.0 or less is preferable, the above value is preferably 6.0 or less, and more preferably 5.0 or less. In addition, the irradiation process using the metal halide lamp in this invention means the metal halide lamp irradiation test in the Example mentioned later.

  From the viewpoint of light resistance, the polycarbonate resin composition of the present invention is formed into a molded body (thickness 3 mm), and the haze value before and after irradiation with a metal halide lamp is measured by the method described in Examples below. The difference obtained by subtracting the value before irradiation from the value of is preferably 18 or less, more preferably 15 or less, and even more preferably 11 or less.

  In order to reduce the difference in the absolute value and the haze value of the YI value before and after irradiation with the metal halide lamp described above, that is, to make the polycarbonate resin composition excellent in light resistance, for example, the polycarbonate resin used in the present invention Appropriately select the type and amount of the catalyst used in the production, select the temperature and time during polymerization of the polycarbonate resin as appropriate, reduce the amount of residual phenol, residual diphenyl carbonate, dihydroxy, etc. It can be produced by reducing the amount of a substance having absorption in the ultraviolet region as a raw material monomer such as a compound or reducing the amount of a substance having absorption in the ultraviolet region contained as an impurity in the raw material. In particular, the type and amount of the catalyst, the temperature and time during the polymerization are important, and in particular, adopting the conditions that are preferable in the description of the polycarbonate resin described later, as described above, the lithium in the entire polycarbonate resin composition and It is preferable that a long-period type periodic table group 2 metal is contained in a specific amount or less.

  The polycarbonate resin composition of the present invention preferably contains 60 ppm by weight or less of carbonic acid diester represented by the following formula (3) from the viewpoint of hue. Since the carbonic acid diester represented by the following formula (3) is mainly derived from the raw material of the polycarbonate resin, the details will be described in the description of the polycarbonate resin.

(In the above formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. And A ¹ and A ² may be the same or different.)

  Moreover, the polycarbonate resin composition of the present invention preferably contains an aromatic monohydroxy compound in an amount of 700 ppm by weight or less, and 500 ppm by weight or less based on the entire polycarbonate resin composition from the viewpoint of light resistance and odor reduction. More preferably, it is particularly preferably 300 ppm by weight or less. The aromatic monohydroxy compound is derived from what is mainly contained in the raw material polycarbonate resin and is contained in the polycarbonate resin composition. The aromatic monohydroxy compound is described in detail in the description of the polycarbonate resin below. Describe. However, the aromatic monohydroxy compound contained in the polycarbonate resin composition is used in a sense excluding those which can be contained in the polycarbonate resin composition as an “antioxidant”.

2. Polycarbonate resin The polycarbonate resin blended in the polycarbonate resin composition of the present invention and the production method thereof will be described in detail below.

<Raw material>
(Dihydroxy compound)
The polycarbonate resin contained in the polycarbonate resin composition of the present invention may be referred to as a dihydroxy compound having a site represented by the following formula (1) in a part of the structure (hereinafter referred to as “dihydroxy compound used in the present invention”). ) At least. That is, the dihydroxy compound used in the present invention refers to a compound containing at least two hydroxyl groups and a site represented by the following formula (1).

(However, the site represented by the above formula (1) unless a portion constituting a _-CH 2 -O-H.)

The dihydroxy compound used in the present invention is not particularly limited as long as it has a site represented by the above formula (1) in a part of its structure. Specifically, diethylene glycol, triethylene glycol, Oxyalkylene glycols such as tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-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- ( -Hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 , 5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2, 2-dimethylpropoxy) phenyl) fluorene, etc., a compound having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, a dihydroxy compound represented by the following formula (2), the following formula ( Examples thereof include compounds having a cyclic ether structure such as a dihydroxy compound represented by 4) and a dihydroxy compound represented by the following formula (5). From the viewpoint of availability, handling, reactivity during polymerization, and hue of the resulting polycarbonate resin, diethylene glycol and triethylene glycol are preferred, and from the viewpoint of heat resistance, a compound having a cyclic ether structure is preferred, and the structure From the viewpoint of physical stability, a dihydroxy compound having two cyclic ether structures such as a dihydroxy compound represented by the following formula (2) and a dihydroxy compound represented by the following formula (4) is more preferred. Anhydrosugar alcohols typified by dihydroxy compounds represented by) are particularly preferred. These dihydroxy compounds may be used alone or in combination of two or more depending on the required performance of the obtained polycarbonate resin.

  Examples of the dihydroxy compound represented by the above formula (2) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.

  Of these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the polycarbonate resin, and among them, it is abundant as a plant-derived resource and is produced from various easily available starches. Isosorbide obtained by dehydrating and condensing sorbitol is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and 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 used in the present invention (hereinafter sometimes referred to as “other dihydroxy compound”), and other dihydroxy compounds. Examples thereof include aliphatic dihydroxy compounds such as chain aliphatic dihydroxy compounds and alicyclic dihydroxy compounds, and aromatic bisphenols. Among these, aliphatic dihydroxy compounds are preferable, and alicyclic dihydroxy compounds are more preferable.

The chain aliphatic dihydroxy compound is a compound having a hydrocarbon skeleton having a chain structure and two hydroxyl groups, and does not include a compound having an oxygen atom such as an ether group except for the hydroxyl group. The chain aliphatic dihydroxy compound includes a straight chain aliphatic dihydroxy compound and a branched aliphatic dihydroxy compound. Examples of the linear chain aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,5-heptanediol, 1,10-decanediol, 1,12-dodecanediol and the like. Examples of the branched aliphatic dihydroxy compound include neopentyl glycol and hexylene glycol.

The alicyclic dihydroxy compound is a compound having a hydrocarbon skeleton having a cyclic structure and two hydroxyl groups, and the hydroxyl group may be directly bonded to the cyclic structure or via a substituent such as an alkylene group. And may be bonded to a ring structure. The cyclic structure may be monocyclic or polycyclic. As a suitable thing of an alicyclic dihydroxy compound, the alicyclic dihydroxy compound which has the 5-membered ring structure mentioned below, and the alicyclic dihydroxy compound which has a 6-membered ring structure are mentioned. Since the rigidity of the polycarbonate resin obtained by using the alicyclic dihydroxy compound which has a 5-membered ring structure and the alicyclic dihydroxy compound which has a 6-membered ring structure can be improved as an alicyclic dihydroxy compound, it is preferable. The carbon number of the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. The greater the number of carbons, the higher the heat resistance of the resulting polycarbonate resin. However, the smaller the number of carbons, the easier the purification and the easy procurement of raw materials.

  Examples of alicyclic dihydroxy compounds having a five-membered ring structure include tricyclodecanediols, pentacyclopentadecanediols, cyclopentanediols such as 1,3-cyclopentanediol, and 1,3-cyclopentanedimethanol. Cyclopentanedimethanols, 2,6-decalindiol, 1,5-decalindiol, decalindiols such as 2,3-decalindiol, 1,5-decalindimethanol, 2,6-decalindimethanol, 2, Examples include decalin dimethanols such as 3-decalin dimethanol, tricyclodecane diols, tricyclodecane dimethanols, and pentacyclopentadecane dimethanols.

Examples of alicyclic dihydroxy compounds having a 6-membered ring structure include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. Cyclohexenediols such as 4-cyclohexene-1,2-diol, 2,3-norbornanediol,
Norbornanediols such as 1,5-norbornanediol, 1,3-adamantanediol, adamantanediols such as 2,2-adamantanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanols such as cyclohexanedimethanol, cyclohexenediols such as 4-cyclohexene-1,2diol, norbornanedimethanols such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, 1,3- Examples include adamantane dimethanol such as adamantane dimethanol and 2,2-adamantane dimethanol.

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 (4-hydride) Xylphenyl) 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 the other dihydroxy compounds listed above, from the viewpoint of light resistance of the polycarbonate resin, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, a group consisting of a chain aliphatic dihydroxy compound and an alicyclic dihydroxy compound. It is preferable to use at least one compound selected from the above, and as the chain aliphatic dihydroxy compound, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are particularly preferable. As the dihydroxy compound, 1,4-cyclohexanedimethanol and tricyclodecane dimethanol are particularly preferable.

  By using these other dihydroxy compounds, it is possible to obtain effects such as improvement in flexibility of polycarbonate resin, improvement in heat resistance, improvement in moldability, but structural units derived from other dihydroxy compounds. If the content ratio is too large, mechanical properties and heat resistance may be lowered. Therefore, the ratio of the structural unit derived from the dihydroxy compound used in the present invention to the structural unit derived from all dihydroxy compounds is 20 It is preferably at least mol%, more preferably at least 30 mol%, particularly preferably at least 50 mol%.

The dihydroxy compound used in 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 used in the invention is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include Group 1 or Group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the Long Periodic Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylan Basic ammonium compounds such as nium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferred, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferred because of their effects and ease of distillation removal described below.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound used for this invention of these basic stabilizers, if there is too little, there exists a possibility that the effect which prevents the quality change of the dihydroxy compound used for this invention may not be acquired, and too much. Since it may cause modification of the dihydroxy compound used in the present invention, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound used in the present invention. It is.

  Further, when the dihydroxy compound used in the present invention containing these basic stabilizers is used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In order to deteriorate the initial hue and consequently deteriorate the light resistance of the 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 the polycarbonate resin.

  When the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle 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 raw material for producing a polycarbonate resin, the resulting polycarbonate resin may be colored.

  In order to obtain the dihydroxy compound used in the present invention which does not contain the above oxidative decomposition product, and in order to remove the aforementioned 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 thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the formic acid content in the dihydroxy compound used in the present invention is preferably 20 ppm by weight or less, more preferably 10 ppm by weight or less, and particularly preferably 5 ppm by weight or less. When a dihydroxy compound containing a dihydroxy compound used in is used as a polycarbonate resin production raw material, it is possible to produce a polycarbonate resin 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 dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester as raw materials. As a carbonic acid diester used, what is normally represented by following formula (3) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

(In the above formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. And A ¹ and A ² may be the same or different.)

  Examples of the carbonic acid diester represented by the above formula (3) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonate and substituted difel carbonate, particularly preferably diphenyl carbonate. Here, the “substitution” with respect to the above formula (3) means that it is substituted with a substituent having a molecular weight of 200 or less. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

<Transesterification reaction catalyst>
The polycarbonate resin used in the present invention is produced by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention with a carbonic acid diester as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

  The transesterification reaction catalyst (hereinafter sometimes simply referred to as catalyst or polymerization catalyst) that can be used in the production of the polycarbonate resin used in the present invention can affect the light transmittance at a wavelength of 350 nm and the yellow index value. Accordingly, the catalyst that can be used in the present invention is preferably one that can satisfy light resistance, that is, the light transmittance at a wavelength of 350 nm described above and a yellow index that can be set to a predetermined value. A compound containing at least one metal selected from the group consisting of metals belonging to Table 2 is essential in the production of the polycarbonate resin used in the present invention.

  Along with a compound containing at least one metal selected from the group consisting of lithium and long-period periodic table group 2 metals used as a catalyst, a long-period periodic table group 1 metal other than lithium It is also possible to use a basic compound such as a compound containing a hydrogen atom, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound, but from lithium and a metal of Group 2 of the long-period periodic table It is particularly preferred to use only compounds containing at least one metal of the group.

  In addition, as a form of a compound containing a metal of Group 1 of the long-period periodic table or a compound of Group 2 of the long-period periodic table, a salt such as a hydroxide, carbonate, carboxylate or phenol salt is usually used. However, from the viewpoint of easy availability and ease of handling, hydroxides, carbonates, and acetates are preferable, and acetates are preferable from the viewpoint of hue and polymerization activity.

Examples of the lithium compound used as the catalyst include lithium hydroxide, lithium hydrogen carbonate,
Lithium carbonate, lithium acetate, lithium stearate, lithium borohydride, lithium phenyl borohydride, lithium benzoate, dilithium hydrogen phosphate, dilithium phenyl phosphate, lithium alcoholate or phenolate, dilithium salt of bisphenol A Etc.

  Examples of the compound containing a metal belonging to Group 2 of the long-period type periodic table used as a catalyst include calcium compounds such as calcium hydroxide, calcium bicarbonate, calcium carbonate, calcium acetate, and calcium stearate, barium hydroxide, and hydrogen carbonate. Barium compounds such as barium, barium carbonate, barium acetate and barium stearate, magnesium compounds such as magnesium hydroxide, magnesium bicarbonate, magnesium carbonate, magnesium acetate and magnesium stearate, strontium hydroxide, strontium bicarbonate, strontium carbonate and acetic acid Examples include strontium compounds such as strontium and strontium stearate. Among them, magnesium compounds, calcium compounds and barium compounds are preferable, and the polymerization activity and the polycarbonate obtained. From the viewpoint of the hue of over preparative resin, at least one metal compound is more preferably selected from the group consisting of magnesium compound and calcium compound, most preferably a calcium compound.

  Examples of the compound containing a long-period group 1 metal other than lithium that can be used as a catalyst include sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, sodium stearate, sodium borohydride, and phenylation. Sodium compounds such as sodium boron, sodium benzoate, disodium hydrogen phosphate, disodium phenyl phosphate, sodium alcoholate or phenolate, disodium salt of bisphenol A, potassium hydroxide, potassium bicarbonate, potassium carbonate, acetic acid Potassium, potassium stearate, potassium borohydride, potassium phenyl borohydride, potassium benzoate, dipotassium hydrogen phosphate, dipotassium phenyl phosphate, potassium alcoholate or phenolate, bisphenol A Potassium compounds such as potassium salts, cesium hydroxide, cesium bicarbonate, cesium carbonate, cesium acetate, cesium stearate, cesium borohydride, cesium phenyl borohydride, cesium benzoate, 2 cesium hydrogen phosphate, 2 cesium phenyl phosphate Cesium compounds such as alcoholate or phenolate of cesium, dicesium salt of bisphenol A, and the like.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples thereof include sodium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron, potassium 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, Tri-BR> G tilmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltri Phenylammonium hydride Roxide, butyltriphenylammonium hydroxide, etc. are mentioned.

  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.

  In order to make the polycarbonate resin composition of the present invention particularly excellent in transparency, hue and light resistance, the catalyst is a compound containing at least one metal selected from the group consisting of magnesium compounds and calcium compounds. Is preferred.

  The amount of the polymerization catalyst used is usually 0.1 μmol to 300.0 μmol, preferably 0.5 μmol to 100.0 μmol, based on 1 mol of all dihydroxy compounds used. Among them, lithium and metals of Group 2 of the long-period type periodic table are used. When using at least one metal compound selected from the group consisting of, in particular, when using at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds, the amount of metal per 1 mol of all dihydroxy compounds used Usually, 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. Further, the upper limit is usually 20.0 μmol, preferably 10.0 μmol, more preferably 3.0 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst 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 hue and light resistance of the obtained polycarbonate resin are deteriorated. In addition, the unreacted raw material may volatilize during the polymerization and the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention to the carbonic acid diester may collapse, and the desired molecular weight may not be reached. On the other hand, when there is too much usage-amount of a polymerization catalyst, the hue of the polycarbonate resin obtained will be deteriorated and the light resistance of a polycarbonate resin may deteriorate.

  Moreover, in the polycarbonate resin used in the present invention, metals of Group 1 of the long-period periodic table, especially sodium, potassium and cesium, may be mixed not only from the catalyst used, but also from the raw materials and the reactor, When these metals are contained in a large amount in the polycarbonate resin, the hue may be adversely affected. Therefore, the metal may be mixed not only from the catalyst used but also from the raw materials and the reactor. The total amount of these compounds is preferably small, and the metal amount is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, more preferably 0.7 ppm by weight or less.

  The amount of metal in the polycarbonate resin can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin by a method such as wet ashing, atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) It can measure using the method of these. In the present invention, all the metals in the polycarbonate resin can be regarded as remaining in the polycarbonate resin composition unless an operation for removing a metal such as a catalyst is performed.

<Manufacturing method>
The polycarbonate resin used in the present invention is obtained by polycondensation of a dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester by a transesterification reaction. The raw material dihydroxy compound and the carbonic acid diester are converted before the transesterification reaction. It is preferable to mix uniformly.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 95 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. The hue of the polycarbonate resin thus obtained may deteriorate, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the polycarbonate resin used in the present invention, and the carbonic acid diester is an oxygen concentration of 10% by volume or less, further 0.0001% by volume to 10% by volume, and in particular, 0. It is preferable from the viewpoint of preventing hue deterioration to be performed in an atmosphere of 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%.

  In order to obtain the resin of the present invention, the carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably to the total dihydroxy compound including the dihydroxy compound used in the present invention used in the reaction. Is a molar ratio of 0.95 to 1.10. When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring occurs at the time of molding, the rate of transesterification reaction is decreased, and the desired high molecular weight. The body may not be obtained.

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

Furthermore, when the molar ratio of the carbonic acid diester is increased with respect to all the dihydroxy compounds including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin increases, and these absorb the ultraviolet rays to absorb the polycarbonate resin. May deteriorate the light resistance of the glass. The concentration of the carbonic acid diester represented by the formula (3) remaining in the polycarbonate resin used in the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly 30 wt. ppm or less is preferred. Actually, the polycarbonate resin may contain unreacted carbonic acid diester, and the lower limit of the 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. May be incurred.

Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components.
The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler. Preferably, it is 80 degreeC-150 degreeC, Most preferably, it is 100 degreeC-130 degreeC. If the temperature of the refrigerant is too high, the amount of reflux decreases and the effect is reduced. On the other hand, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. 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, but not to impair the hue, thermal stability, light resistance, etc. of the final polycarbonate resin, Selection is important.

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

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

  Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C., and the pressure is absolute, as the maximum internal temperature of the polymerization reactor. The pressure is 110 kPa to 10 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 1 kPa, the reaction time is 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours, and the generated monohydroxy compound is removed from the reaction system. It is carried out while distilling off.

  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. to 270 ° C., preferably 220 ° C. to 250 ° C., usually 0.1 hours to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0. Perform for 5 to 3 hours.

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

In order to obtain a polycarbonate resin having a predetermined molecular weight, if the polymerization temperature is increased and the polymerization time is too long, the ultraviolet transmittance decreases and the YI value tends to increase.

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 from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

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

  The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity may be lowered. When the temperature is higher than 300 ° C., the polycarbonate resin is severely deteriorated by heat, and there is a fear that mechanical strength is reduced 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 foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

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 to 0.45 μm as 99% removal filtration accuracy.

<Physical properties>
The molecular weight of the polycarbonate resin used in the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, usually 1 .20 dL / g or less, more preferably 1.00 dL / g or less, and still 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 may be small. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease. The reduced viscosity was prepared by using methylene chloride as a solvent, and the polycarbonate concentration was precisely adjusted to 0.6 g / dL, and the temperature was 20.0 ° C. ± 0.1 ° C.
Measure with an Ubbelohde viscometer.

  Furthermore, the lower limit of the concentration of the terminal group represented by the following formula (6) of the polycarbonate resin used in the present invention (in this specification, sometimes referred to as “terminal phenyl group concentration”) is usually 20 μeq / g, preferably Is 40 μeq / g, particularly preferably 50 μeq / g, and the upper limit is usually 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, even if the hue at the time of polymerization or at the time of molding is good, the hue after UV exposure may be deteriorated. Stability may be reduced.

  In order to control the concentration of the terminal group represented by the above formula (6), in addition to controlling the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as a raw material and the carbonic acid diester, Examples thereof include a method of controlling the type and amount, the polymerization pressure and the polymerization temperature.

  When the polycarbonate resin used in the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the formula (3), the phenol resin and the substituted phenol are by-produced, 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 removed. It is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less using a horizontal reactor having excellent volatility or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight. These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

Further, when the number of moles of hydrogen atoms bonded to the aromatic ring of 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, the number of moles of hydrogen atoms bonded to the aromatic ring The ratio of the total number of hydrogen atoms to the number of moles is represented by X / (X + Y). However, as described above, since the aromatic ring having the ability to absorb ultraviolet rays may affect the light resistance, X / (X + Y) is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. X / (X + Y) can be quantified by ¹ H-NMR.

  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 50% or more, more preferably 60% or more, particularly preferably. 70% or more. When the light transmittance at the wavelength is less than 50%, the absorption increases and the light resistance may deteriorate.

  The polycarbonate resin used in the present invention preferably has a light transmittance of 30% or more at a wavelength of 320 nm of a molded body (thickness 3 mm flat plate) molded from the polycarbonate resin, 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.

3. Flame Retardant The polycarbonate resin composition of the present invention contains 0.01 to 30 parts by weight of a flame retardant with respect to 100 parts by weight of the polycarbonate resin.

The amount of the flame retardant used is selected in accordance with the type of flame retardant and the degree of flame retardant within the above predetermined range, but is preferably 0.05 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. More preferably, it is 0.1 parts by weight or more, while it is 25 parts by weight or less, preferably 20 parts by weight or less. If the amount of the flame retardant used is too small, the flame retardancy of the polycarbonate resin composition will be insufficient, and if it is too large, the hue and transparency of the polycarbonate resin composition may be deteriorated.

  Examples of the flame retardant include a phosphorus-containing compound flame retardant, a halogen-containing compound flame retardant, a sulfonic acid metal salt flame retardant, a silicon-containing compound flame retardant, and the like in this embodiment. At least one selected can be used. These may be used alone or in combination of two or more. As the flame retardant used in the polycarbonate resin composition of the present invention, it is preferable to use one or more members selected from the group consisting of a phosphorus-containing compound flame retardant, a halogen-containing compound flame retardant, and a sulfonic acid metal salt flame retardant.

  Examples of the phosphorus-containing compound flame retardant include phosphate ester compounds, phosphazene compounds, red phosphorus, coated red phosphorus, polyphosphate compounds, and the like. The amount of the phosphorus-containing compound-based flame retardant is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the blending amount is too small, sufficient flame retardancy is difficult to obtain, and if it is too large, the heat resistance tends to decrease.

  Examples of the halogen-containing compound flame retardant include tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromoallyl ether, Examples thereof include tetrabromobisphenol A carbonate oligomer, ethylenebistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, and hexabromocyclododecane.

  The compounding amount of the halogen-containing compound flame retardant is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the blending amount of the halogen-containing compound-based flame retardant is excessively small, sufficient flame retardancy is difficult to obtain, and if it is excessively large, the mechanical strength is lowered, and the flame retardant may cause discoloration due to bleeding.

  Examples of the sulfonic acid metal salt-based flame retardant include an aliphatic sulfonic acid metal salt, an aromatic sulfonic acid metal salt, a perfluoroalkane-sulfonic acid metal salt, and the like. Preferred metals for these metal salts are alkali metals such as lithium, sodium, potassium, rubidium and cesium, strontium, barium, beryllium and magnesium.

Among the sulfonic acid metal salt flame retardants, aromatic sulfonesulfonic acid metal salts, perfluoroalkane-sulfonic acid metal salts, and the like are preferable from the viewpoints of flame retardancy and thermal stability. The aromatic sulfonesulfonic acid metal salt is preferably an aromatic sulfonesulfonic acid alkali metal salt or an aromatic sulfonesulfonic acid alkaline earth metal salt. These may be polymers. Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, and 4,4′-dibromodiphenyl-sulfone-3-sulfone. Sodium salt of acid, potassium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfone, disodium salt of diphenylsulfone-3,3′-disulfonic acid, dipotassium salt of diphenylsulfone-3,3′-disulfonic acid Etc.

  The perfluoroalkane-sulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkane-sulfonic acid, a strontium salt of perfluoroalkane-sulfonic acid, a barium salt of perfluoroalkane-sulfonic acid, or the like. Furthermore, a sulfonic acid alkali metal salt having a C 4-8 perfluoroalkane group, a sulfonic acid strontium salt having a C 4-8 perfluoroalkane group, and a sulfone having a C 4-8 perfluoroalkane group An acid barium salt or the like is more preferable.

  Specific examples of the perfluoroalkane-sulfonic acid metal salt include, for example, perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, Examples include perfluorooctane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonate.

  The blending amount of the sulfonic acid metal salt flame retardant is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the blending amount of the sulfonic acid metal salt flame retardant is excessively small, sufficient flame retardancy is difficult to obtain, and if it is excessively large, the thermal stability tends to be lowered.

  Examples of the silicon-containing compound flame retardant include silicone varnish, a silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain having a branched structure. And a silicone compound having an aromatic group in the organic functional group contained therein, a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of the silica powder, and an organopolysiloxane-polycarbonate copolymer Etc. Of these, silicone varnish is preferred.

As the silicone varnish, for example, mainly composed of a bifunctional unit [R ⁰ ₂ SiO] and a trifunctional unit [R ⁰ SiO _1.5 ], a monofunctional unit [R ⁰ ₃ SiO _0.5 ] and / or A relatively low molecular weight solution-like silicone resin that may contain tetrafunctional units [SiO ₂ ] may be mentioned. Here, R ⁰ is a C 1-12 hydrocarbon group or a C 1-12 hydrocarbon group substituted with one or more substituents. Examples of the substituent include an epoxy group, an amino group, a hydroxyl group, and a vinyl group. By changing the type of R ^0, the compatibility with the matrix resin can be improved.

  Examples of the silicone varnish include a solventless silicone varnish and a silicone varnish containing a solvent. In the present embodiment, a silicone varnish containing no solvent is preferable. The silicone varnish can be produced, for example, by hydrolysis of alkylalkoxysilanes such as alkyltrialkoxysilanes, dialkyldialkoxysilanes, trialkylalkoxysilanes, and tetraalkoxysilanes. The molecular structure (crosslinking degree) and molecular weight can be controlled by adjusting the molar ratio of these raw materials, the hydrolysis rate, and the like. Furthermore, although alkoxysilane remains depending on the production conditions, if it remains in the composition, the hydrolysis resistance of the polycarbonate resin may be lowered.

  The viscosity of the silicone varnish is preferably 300 centistokes or less, more preferably 250 centistokes or less, and still more preferably 200 centistokes or less. If the viscosity of the silicone varnish is excessively large, flame retardancy may be insufficient.

  The compounding amount of the silicon-containing compound flame retardant is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the compounding amount of the silicon-containing compound flame retardant is excessively small, sufficient flame retardancy is difficult to obtain, and if it is excessively large, the heat resistance tends to decrease.

  In this embodiment, in order to achieve higher flame retardancy, it is preferable to use polytetrafluoroethylene for preventing dripping. Anti-dripping polytetrafluoroethylene tends to disperse easily in the polymer and bind the polymers together to produce a fibrous material. Examples of commercially available products for preventing dripping include Teflon (registered trademark) 6J, Teflon (registered trademark) 30J (Mitsui / Dupont Fluorochemical Co., Ltd.), Polyflon F201L (Daikin Chemical Industry Co., Ltd.), and the like.

  The amount of polytetrafluoroethylene for preventing dripping is preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin. When the blending amount of polytetrafluoroethylene for dripping prevention is excessively small, the effect of preventing melt dripping at the time of combustion is insufficient, and when it is excessively large, the appearance of the molded product tends to deteriorate.

  In this Embodiment, the addition time of the flame retardant mix | blended with polycarbonate resin and the addition method are not specifically limited. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin melted during mixing of the polycarbonate resin and other compounding agents regardless of the polymerization method. A case where it is blended and kneaded with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As an addition method, a method of directly mixing or kneading an inorganic filler with a polycarbonate resin; a high-concentration master batch prepared using a small amount of a polycarbonate resin or other resin and a flame retardant can also be added.

4). Antioxidant The polycarbonate resin composition of the present invention preferably further contains an antioxidant. In the case of using an antioxidant, it is usually 0.0001 part by weight or more and 1 part by weight or less, preferably 0.0002 part by weight or more and 0.1 part by weight or less, based on 100 parts by weight of the polycarbonate resin. Preferably they are 0.001 weight part or more and 0.01 weight part or less. When the content of the antioxidant is usually 0.0001 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin, the coloring suppression effect at the time of molding tends to be good, but the content of the antioxidant is 100% by weight of the polycarbonate resin. If the amount exceeds 1 part by weight with respect to parts by weight, the amount of deposits on the mold during injection molding increases or the amount of deposits on the roll increases when forming a film by extrusion molding. The surface appearance may be impaired.

  The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphate antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphate oxidations. An inhibitor is more preferred.

Examples of the phenol-based 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-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3- ert- butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-spiro (5,5) compounds such 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.

  Examples of the phosphate antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl 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) pentaeri Li 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 preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  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.

5. Release Agent The polycarbonate resin composition of the present invention preferably contains a release agent. Although it does not specifically limit as a mold release agent, A higher fatty acid, a stearic acid ester, etc. are mentioned, Preferably it is a higher fatty acid.

  As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. As such a saturated fatty acid, myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like are more preferable. Of these, palmitic acid and stearic acid are more preferable, and stearic acid is particularly preferable.

  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. Examples of partial esters or total esters of monohydric or polyhydric alcohols and stearic acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, pentaerythritol monostearate, pentaerythritol. Tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like are more preferable. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferable, and stearic acid monoglyceride and stearyl stearate are particularly preferable.

  One of these release agents may be used alone, or two or more thereof may be mixed and used. When a release agent is used, the amount is usually 0.0001 to 2 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. Preferably they are 0.1 weight part-0.5 weight part. If the release agent content is excessively large, mold deposits may increase at the time of molding. If a large amount of molding is performed, it may require labor to maintain the molding machine. When the molding agent content is 0.0001 parts by weight or more with respect to 100 parts by weight, which may cause poor appearance, the molded product will be easily released from the mold during molding. There is an advantage that it is easy to do.

  In the present embodiment, the addition timing and addition method of the release agent are not particularly limited. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin melted during mixing of the polycarbonate resin and other compounding agents regardless of the polymerization method. A case where it is blended and kneaded with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As an addition method, a release agent may be directly mixed or kneaded with a polycarbonate resin; a high-concentration master batch prepared using a release agent with a small amount of a polycarbonate resin or other resin may be added.

6). Other components In the polycarbonate resin composition of the present invention, a filler, an acidic compound, an ultraviolet absorption aid, a bluing agent, a heat stabilizer, a light stabilizer, an antistatic agent, etc. are appropriately added within a range not impairing the object of the present invention. It is possible to mix. However, the components listed below are representative examples of those that can be used, and do not preclude blending the present invention with components other than those listed below.

  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 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin. The blending amount of the filler is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and still more preferably 35 parts by weight or less. Although the reinforcing effect of the polycarbonate resin composition can be obtained by blending the filler, the appearance tends to be deteriorated when blending more than 100 parts by weight.

  Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, silica, alumina, titanium oxide, gypsum, gypsum whisker, barium sulfate, talc, mica, wollastonite and other calcium silicates; carbon black Graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker and the like. Among these, glass fiber filler, glass powder filler, glass flake filler; various whiskers, mica and talc are preferable. More preferably, glass fiber, glass flake, glass milled fiber, wollastonite, mica and talc are mentioned. Particularly preferred is at least one selected from glass fiber and talc. Although the inorganic filler mentioned above can also be used only by 1 type, it can also be used in combination of 2 or more type.

  Among inorganic fillers, any glass fiber or glass milled fiber may be used as long as it is used in thermoplastic resins. In particular, alkali-free glass (E glass) is preferable. The diameter of glass fiber becomes like this. Preferably they are 6 micrometers-20 micrometers, More preferably, they are 9 micrometers-14 micrometers. If the diameter of the glass fiber is too small, the reinforcing effect tends to be insufficient. On the other hand, if it is excessively large, the product appearance is liable to be adversely affected.

  The glass fiber is preferably chopped strands cut to a length of 1 mm to 6 mm; preferably glass milled fibers that are commercially available after being pulverized to a length of 0.01 mm to 0.5 mm. You may use these individually or in mixture of both.

  The glass fiber used in the present invention is made of an acrylic resin or urethane to improve surface treatment with a silane coupling agent such as aminosilane or epoxysilane, or to improve handling properties, in order to improve adhesion to the polycarbonate resin. It may be used after being subjected to a focusing treatment with a resin or the like.

  Any glass beads can be used as long as they are used in thermoplastic resins. Among these, alkali-free glass (E glass) is preferable. The shape of the glass beads is preferably spherical with a particle size of 10 μm to 50 μm.

  As glass flakes, scaly glass flakes can be mentioned. The maximum diameter of the glass flake after blending the polycarbonate resin is generally 1000 μm or less, preferably 1 μm to 500 μm, and the aspect ratio (the ratio of the maximum diameter to the thickness) is 5 or more, preferably 10 or more, Preferably it is 30 or more.

  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: Fibrous organic fillers such as carbon fibers, synthetic fibers, and natural fibers can be used.

The carbon fiber is not particularly limited. For example, the carbon fiber is produced by firing using acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, lignin, etc. as a raw material, and has flame resistance, carbon, graphite, etc. There are various types. The average of the aspect ratio (fiber length / fiber diameter) of the carbon fibers is preferably 10 or more, more preferably 50 or more. If the average aspect ratio is too small, the conductivity, strength, and rigidity of the polycarbonate resin composition tend to be reduced. The diameter of the carbon fiber is 3 μm to 15 μm, and any shape such as a chopped strand, a roving strand, or a milled fiber can be used to adjust the aspect ratio. Carbon fiber can be used 1 type or in mixture of 2 or more types.

  As long as the properties of the polycarbonate resin composition of the present invention are not impaired, the carbon fiber may be subjected to surface treatment such as epoxy treatment, urethane treatment, oxidation treatment, etc., in order to increase the affinity with the polycarbonate resin.

  The polycarbonate resin composition of the present invention may further contain an acidic compound. When an acidic compound is used, the compounding amount of the acidic compound is 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight based on 100 parts by weight of the polycarbonate resin. Part to 0.01 part by weight, more preferably 0.0002 part to 0.001 part by weight. When the compounding amount of the acidic compound is 0.00001 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin, it is possible to suppress coloration when the residence time of the polycarbonate resin composition in the injection molding machine becomes long during injection molding. Although it is preferable at a point, when the compounding quantity of an acidic compound is more than 0.1 weight part with respect to 100 weight part of polycarbonate resin, the hydrolysis resistance of a polycarbonate resin composition may fall.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.

  These acidic compounds can be added in the manufacturing process of a polycarbonate resin composition as a compound which neutralizes the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate resin mentioned above.

  The polycarbonate resin composition of the present invention can be blended with an ultraviolet absorber as long as the object of the present invention is not impaired. The blending amount of the UV absorber can be appropriately selected according to the type of the UV absorber, but in the present invention, the UV absorber is 0 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. is there.

  Here, the ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability. Examples of the compound having ultraviolet absorbing ability include organic compounds and inorganic compounds. Of these, organic compounds are preferred because they are easy to ensure affinity with the polycarbonate resin and are easily dispersed uniformly.

The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Also. Usually, it is 600 or less, preferably 450 or less, more preferably 400 or less. If the molecular weight is too small, there is a possibility of causing a decrease in UV resistance performance after long-term use. When the molecular weight is excessively large, there is a possibility that the transparency of the resin composition is lowered after long-term use.

  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 may be used alone or in combination of two or more. The brominated aromatic triazine mentioned as “halogen-containing compound flame retardant” is a triazine compound, but is not regarded as an ultraviolet absorber in this specification.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl-3- (3- (2H-benzotriazol-2-yl ) -5-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of hydroxybenzophenone compounds include 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like.

  Examples of the malonic acid ester compounds include 2- (1-arylalkylidene) malonic acid esters, tetraethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, and the like.

  Examples of the triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy, Tinuvin 1577FF) and the like.

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.

  Examples of the oxalic acid anilide compound include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

  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. 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.

As a specific bluing agent, for example, the general name Solvent Violet 13
[CA. No (color index No) 60725], generic name Solvent Violet 31 [CA. No 68210], common name Solvent Violet 33 [CA. No. 60725], generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No. 68210], general name Solvent Blue 97 [manufactured by Bayer "Macrolex Violet RR"], general name Solvent Blue 45 [CA. No. 61110] is a typical example. These bluing agents may be used alone or in combination of two or more. These bluing agents are usually blended at a ratio of 0.1 × 10 ⁻⁵ to 2 × 10 ⁻⁴ parts by weight with respect to 100 parts by weight of the polycarbonate resin.

Moreover, a system light stabilizer can be mix | blended in order to further improve the light resistance of the polycarbonate resin composition and polycarbonate resin molded product of the present invention. Examples of such a light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [[ 6- (1,1,3
, 3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2, 6,6-tetramethyl-4-piperidyl) imino]], N, N′-bis (3-aminopropyl)
Ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidylamino) -6-chloro-1,3,5-triazine condensate, dibutylamine 1,3,5-triazine, N, N′-bis (2,2,6,6) -tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6- And a polycondensate of tetramethyl-4-piperidyl) butylamine. Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

  The blending amount of the light stabilizer can be blended at a ratio of 0 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin used in the present invention. It is preferable to mix | blend in the ratio of 5 weight part or less, and it is more preferable to mix | blend in the ratio of 0.01 weight part or more and 0.2 weight part or less. By blending the light stabilizer in such a range, the molded product obtained by molding the polycarbonate resin composition of the present invention without causing bleeding of the light stabilizer on the surface of the polycarbonate resin composition and deterioration of mechanical properties of various molded products. Light resistance can be improved.

  Furthermore, the polycarbonate resin composition of the present invention can contain an antistatic agent within a range that does not impair the object of the present invention.

  In the present embodiment, the addition timing and the addition method of components such as a filler, an acidic compound, an ultraviolet absorption aid, a bluing agent, a heat stabilizer, a light stabilizer, and an antistatic agent to be blended in the polycarbonate resin composition are particularly It is not limited. For example, when the polycarbonate resin is produced by the transesterification method, the addition time is as follows: at the end of the polymerization reaction; A state in which the product is melted; for example, when blending and kneading with a polycarbonate resin composition in a solid state such as pellets or powder using an extruder or the like. As an addition method, various components can be directly mixed or kneaded with a polycarbonate resin; a high-concentration masterbatch prepared using a small amount of a polycarbonate resin composition or other resin and various components can also be added.

In addition, the polycarbonate resin composition of the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS resin, AS and other synthetic resins, polylactic acid, polybutylene It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as succinate and rubber.

7). Polycarbonate resin molded product In the present embodiment, a polycarbonate resin molded product is obtained by molding the above-described polycarbonate resin composition. Molding of the polycarbonate resin composition is performed by directly mixing the polycarbonate resin and, if necessary, other raw materials such as resins and additives, and feeding them into an extruder or an injection molding machine. A method of melt-mixing using a shaft extruder, extruding into a strand shape to produce pellets, and then charging the pellets into an extruder or injection molding machine to form can be mentioned. The molding method of the polycarbonate resin molded product is not particularly limited, but the injection molding method is preferable from the viewpoint of the degree of freedom of the molded product shape.

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 addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used. In the following, the physical properties or characteristics of the polycarbonate resin and the polycarbonate resin composition were evaluated by the following methods.

1) Measurement of oxygen concentration
The oxygen concentration in the polymerization reaction apparatus was measured using an oxygen meter (manufactured by AMI: 1000RS).

2) Measurement of reduced viscosity
A polycarbonate resin sample was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd., and the relative viscosity η _rel is obtained from the following equation from the passage time t _{0 of the} solvent and the passage time t of the solution. It was.
η _rel = t / t ₀
And specific viscosity (eta) _sp was calculated _| required from the following formula from relative viscosity (eta) _rel .
η _sp = (η−η ₀ ) / η ₀ = η _rel −1
The reduced viscosity η _sp / c was determined by dividing the specific viscosity η _sp by the concentration c (g / dL). The higher this value, the higher the molecular weight.

3) Measurement of structural unit ratio derived from each dihydroxy compound in polycarbonate resin and concentration of terminal phenyl group The ratio of each dihydroxy compound structural unit in polycarbonate resin was measured by weighing 30 mg of polycarbonate resin and dissolved in about 0.7 mL of deuterated chloroform. The solution was put into an NMR tube having an inner diameter of 5 mm, and a ¹ H NMR spectrum was measured at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. The structural unit ratio derived from each dihydroxy compound was determined from the signal intensity ratio based on the structural unit derived from each dihydroxy compound.
The terminal phenyl group concentration was determined from the signal intensity ratio based on the internal standard and the terminal phenyl group by measuring ¹ H-NMR in the same manner as described above using 1,1,2,2-tetrabromoethane as the internal standard.

4) Measurement of metal concentration in polycarbonate resin and metal content in polycarbonate resin composition Polycarbonate resin pellets in a microwave decomposition container manufactured by PerkinElmer Co., Ltd.
. 5 g was precisely weighed, 2 mL of 97% sulfuric acid was added, sealed and microwave heated at 230 ° C. for 10 minutes. After cooling to room temperature, 1.5 mL of 68% nitric acid is added, sealed and microwave heated at 150 ° C. for 10 minutes, cooled again to room temperature, added with 2.5 mL of 68% nitric acid, and sealed again. And microwaved at 230 ° C. for 10 minutes to completely decompose the contents. After cooling to room temperature, the liquid obtained above was diluted with pure water and quantified with ICP-MS manufactured by ThermoQuest.
Based on the metal concentration in the polycarbonate resin determined by the above measurement, the metal content relative to the entire polycarbonate resin composition was calculated. In the calculation method, first, the weight part of calcium relative to the polycarbonate resin is obtained from the molecular weight of each raw material, the formula weight of the catalyst, and the molar ratio between each raw material and the catalyst, and then the weight part (weight ppm) relative to the entire polycarbonate resin composition. Asked.

5) Measurement of content of aromatic monohydroxy compound in polycarbonate resin, content of carbonic acid diester represented by the above formula (3) After dissolving 1.25 g of polycarbonate resin sample in 7 ml of methylene chloride to make a solution, the total amount is 25 ml. Acetone was added so that a reprecipitation treatment was performed. Next, the treatment liquid was filtered through a 0.2 μm disk filter and quantified by liquid chromatography.

6) Ratio of moles X of hydrogen atoms bonded to the aromatic ring to moles X + Y of all hydrogen atoms (where Y is the number of moles of hydrogen atoms bonded to other than the aromatic ring)
The spectrum of only deuterated chloroform to which tetramethylsilane (TMS) has been added and mixed in advance as an internal standard substance is measured, and the signal ratio of residual hydrogen atoms contained in TMS and deuterated chloroform is determined. Next, 30 mg of polycarbonate resin was weighed and dissolved in about 0.7 mL of the deuterated chloroform. This was put into an NMR tube having an inner diameter of 5 mm, and a ¹ H NMR spectrum was measured at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. From the integrated value of the signal appearing at 6.5 ppm to 8.0 ppm in the obtained NMR chart, the integrated value of the residual H signal contained in deuterated chloroform (the integrated value of the TMS signal and the previously calculated TMS and The value obtained by subtracting (determined from the ratio to the residual hydrogen atoms contained in chloroform) is x. On the other hand, when the integral value of the signal appearing at 0.5 ppm to 6.5 ppm is y, x / (x + y) = X / (X + Y), and thus this was obtained.

7) Measurement of light transmittance at wavelengths of 350 nm and 320 nm Polycarbonate resin pellets were dried at 110 ° C. for 10 hours in a nitrogen atmosphere. Next, the dried polycarbonate resin pellets are supplied to an injection molding machine (J75EII type, manufactured by Nippon Steel Co., Ltd.), and an injection molded piece (width 60 mm × length 60 mm) under the conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds. × Thickness 3 mm) was molded, and the light transmittance in the thickness direction was measured using an ultraviolet-visible spectrophotometer (U2900 manufactured by Hitachi High-Technologies Corporation), and the average value was calculated and evaluated.

8) Flame retardancy Dried pellets of polycarbonate resin composition were compliant with the UL94 standard on a J75EII type injection molding machine manufactured by Nippon Steel Co., Ltd. under conditions of a cylinder temperature of 230 ° C, a molding cycle of 45 seconds, and a mold temperature of 60 ° C. A 1.5 mmt combustion test piece was molded. The obtained test piece was subjected to a UL94 standard vertical combustion test.

9) Method for evaluating initial hue of polycarbonate resin composition The pellets of the polycarbonate resin composition were dried at 110 ° C for 10 hours in a nitrogen atmosphere. Next, the pellets of the dried polycarbonate resin composition were supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and injection molded pieces (width 60 mm × length) under the conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds. The yellow index (initial YI) value in the transmitted light with respect to the square surface of the injection-molded pieces obtained in the 10th to 20th shots is repeated using a color tester (Konica Minolta). The average value was calculated using CM-3700d). The smaller the YI value, the better the quality without yellowness.

10) Metal halide lamp irradiation test Using a metal ring weather meter M6T manufactured by Suga Test Instruments Co., Ltd., a horizontal metal ring lamp as a light source, quartz as an inner filter, and quartz A # 500 filter is attached as an outer filter in the surroundings, the irradiance is set to 1.5 kw / m ² at a wavelength of 300 nm to 400 nm, and the 20th shot flat plate (width 60 mm × length) obtained in 6) above. A square surface of 60 mm × thickness 3 mm) was irradiated for 100 hours. The YI value after irradiation was measured in the same manner as in 8) above.

The abbreviations of the compounds used in the description of the following examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Nippon Rika Co., Ltd., SKY C
HDM)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
(Flame retardants)
PX-200: Aromatic condensed phosphate ester (Daihachi Chemical Industry Co., Ltd.)
SR-245: Brominated aromatic triazine (Daiichi Kogyo Seiyaku Co., Ltd.)
KSS: Potassium diphenylsulfonate (manufactured by Sun Chemical Co., Ltd.)
(Antioxidant)
Irganox (registered trademark) 1010: pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF Japan Ltd.)
Irgaphos (registered trademark) 168: Tris (2,4-di-tertbutylphenyl) phosphite (manufactured by BASF Japan Ltd.)
(Release agent)
NAA-180: Stearic acid (manufactured by NOF Corporation)

[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 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.69 / 0.31 / 1.00 / 1.3 × 10 ⁻⁶ , and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol. % To 0.001% by volume). 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 to maintain this temperature, and at the same time, pressure reduction was started, 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 content thus oligomerized is once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled 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 228 ° C. and the pressure was 133 Pa or less over 20 minutes, and when the predetermined stirring power was reached, the pressure was restored, and a molten polycarbonate resin was obtained from the outlet of the polymerization reactor.

  Further, the melted polycarbonate resin is continuously supplied to a twin-screw extruder provided with 3 vents and water injection equipment, and “Irganox (registered trademark) 1010” and “Irgaphos (registered trademark) 168” as antioxidants, “NAA-180” as a release agent was continuously added to 100 parts by weight of the polycarbonate resin so as to have the ratio shown in Table 1, and each vent part provided in the twin screw extruder. After low-molecular weight substances such as phenol were devolatilized under reduced pressure, pelletization was performed with a pelletizer to obtain a pellet-like polycarbonate resin.

  Feed the obtained pellet-shaped polycarbonate resin and “PX-200” as a flame retardant to a twin screw extruder equipped with a vent facility so as to have a predetermined ratio shown in Table 1 with respect to 100 parts by weight of the polycarbonate resin. Thus, a polycarbonate resin composition was obtained. Various physical properties and the like were evaluated by the evaluation methods described above. The obtained results are shown in Table-1.

[Examples 2 and 3]
The same procedure as in Example 1 was performed except that the amount and type of the flame retardant added in Example 1 were changed.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the flame retardant of Example 1 was not added.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that cesium carbonate was used instead of calcium acetate monohydrate.

  In addition, about the aromatic monohydroxy compound content of the said Example and comparative example, most was substantially phenol.

[Evaluation of results]
As shown in Table 1, Comparative Example 2 was inferior in flame retardancy as compared with Examples 1 to 5, and had a large difference in YI values before and after the metal halide lamp irradiation treatment, and was also inferior in light resistance. Moreover, although the comparative example 1 showed the value equivalent to Examples 1-5 in the difference of the YI value before and behind a metal halide lamp irradiation process, it was inferior in flame retardance.

  The polycarbonate resin composition of the present invention is excellent in flame retardancy, light resistance, hue, heat resistance, moldability, mechanical strength, etc., such as injection molding fields such as electrical / electronic parts and automotive parts, films, sheets, etc. It is possible to provide materials in a wide range of fields such as extrusion.

Claims (11)

A polycarbonate resin composition comprising a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound represented by the following formula (2), and a flame retardant,
The polycarbonate resin contains 1 ppm by weight to 700 ppm by weight of phenol,
The light transmittance at a wavelength of 350 nm of a molded body (3 mm thick flat plate) molded from polycarbonate resin is 70 % or more,
Containing 0.01 to 30 parts by weight of a flame retardant with respect to 100 parts by weight of the polycarbonate resin;
And it contains at least one metal selected from the group consisting of metals of Group 2 of the long-period periodic table as a catalyst for the polycarbonate resin,
Moreover Ri der 20 ppm by weight or less in total amount of metal contained in the for the entire polycarbonate resin composition as a catalyst,
The sodium polycarbonate resin, the total content of potassium and cesium, polycarbonate resin composition, wherein the 1 ppm by weight or less der Rukoto metal amount.

When the number of moles of hydrogen atoms bonded to the aromatic ring of the polycarbonate resin is X and the number of moles of hydrogen atoms bonded to other than the aromatic ring is Y, the number of moles of all hydrogen atoms in the number of moles of hydrogen atoms bonded to the aromatic ring. The polycarbonate resin composition according to claim 1 , wherein the ratio to (X / (X + Y)) is 0.1 or less. The flame retardant includes at least one selected from a phosphorus-containing compound-based flame retardant, a halogen-containing compound-based flame retardant, a sulfonic acid metal salt-based flame retardant, and a silicon-containing compound-based flame retardant.
Or the polycarbonate resin composition of 2. Furthermore, the polycarbonate resin composition of any one of Claim 1 to 3 which contains antioxidant 0.001 weight part or more and 1 weight part or less with respect to 100 weight part of polycarbonate resin. The polycarbonate resin composition according to any one of claims 1 to 4 , wherein the polycarbonate resin includes a structural unit derived from a dihydroxy compound other than the dihydroxy compound represented by the formula (2). The polycarbonate resin according to any one of claims 1 to 5 , wherein the polycarbonate resin contains a structural unit derived from at least one compound selected from the group consisting of a chain aliphatic dihydroxy compound and an alicyclic dihydroxy compound. Composition. The polycarbonate resin, the dihydroxy compound having a moiety represented by the formula in a part of the structure (1), obtained by polycondensation of the carbonic acid diester represented by the following formula (3), of claims 1-6 The polycarbonate resin composition according to any one of the above.

(In the above formula (3), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. And A ¹ and A ² may be the same or different.) 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 The polycarbonate resin composition according to claim 7 , wherein the total amount is 20.0 μmol or less as a metal amount per 1 mol of the dihydroxy compound used. Wherein said catalyst is Ru least one metal compound der selected from the group consisting of magnesium compound and calcium compound, a polycarbonate resin composition according to claim 8. A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 9 . The polycarbonate resin molded product according to claim 10 , which is molded by an injection molding method.