JP2013213100A - Polycarbonate resin composition, method of producing the same, and polycarbonate resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in heat resistance, color, translucency, and mechanical strength and suitable for recycling; and a molded product of the polycarbonate resin composition.SOLUTION: A polycarbonate resin composition is produced by mixing a polycarbonate resin (A) and a polycarbonate resin (B) together. The polycarbonate resin (A) is obtained by molding a polycarbonate resin, which is prepared using a compound including lithium and at least one metal selected from the group consisting of metals belonging to Group 2 of the long form periodic table as a catalyst, includes a structural unit derived from a dihydroxy compound having a site represented by formula (1), and includes the metal used as the catalyst at a content of ≤20 wt.ppm. (The moiety represented by formula (1) excludes a part of -CH-O-H).

Description

  The present invention relates to a polycarbonate resin composition, a method for producing the same, and the polycarbonate resin molded article. More specifically, the present invention relates to a polycarbonate resin composition using a recycled polycarbonate resin, a method for producing the same, and a polycarbonate resin molded product obtained by molding the polycarbonate resin composition.

  In recent years, studies have been made on obtaining polycarbonate resin by transesterification with diphenyl carbonate using plant-derived monomers such as isosorbide as a polycarbonate resin using raw materials obtained from biomass resources. However, the polycarbonate resin obtained using plant-derived monomers is insufficient in terms of heat resistance, transparency, and mechanical strength, although the concern for environmental impact is further reduced as compared with conventional aromatic polycarbonate derived from petroleum raw materials. There is a problem that it is yellowed during melt molding and is difficult to use as a transparent member or an optical member. Conventional polycarbonate resin can suppress yellowing to some extent, but is not a material with excellent recyclability.

  On the other hand, as materials having excellent recyclability, Patent Documents 1 and 2 describe a polycarbonate resin composition in which a polycarbonate resin and a recycled polycarbonate resin are mixed.

JP 2001-026719 A JP 2001-310993 A

  However, according to the study of the present inventors, the recycled polycarbonate resin compositions described in Patent Documents 1 and 2 are still insufficient in various physical properties such as color tone, transparency, and light resistance. There is a demand for a polycarbonate resin composition using a recycled polycarbonate resin and having more excellent physical properties.

  An object of the present invention is to provide a polycarbonate resin composition having a good heat resistance, color tone, transparency and mechanical strength using a recycled polycarbonate resin containing a structural unit derived from a dihydroxy compound such as isosorbide, and a molded product thereof. There is to do.

  As a result of intensive studies to solve the above problems, the present inventors have used a polycarbonate resin composition containing both a polycarbonate resin that has not been molded and a recycled polycarbonate resin that has been molded. As a polycarbonate resin, it is found that the transparency, hue, etc. of the polycarbonate resin composition can be greatly improved by specifying the type of metal compound catalyst having a specific structural unit and used at the time of production. Reached. That is, the gist of the present invention resides in the following [1] to [7].

[1] A dihydroxy compound having a moiety represented by the following formula (1), produced using as a catalyst a compound containing at least one metal selected from the group consisting of lithium and Group 2 of the long-period periodic table A polycarbonate resin (A) obtained by molding a polycarbonate resin containing a structural unit derived from the above and having a metal content of 20 ppm by weight or less used as a catalyst thereof, and a polycarbonate resin (B) A polycarbonate resin composition comprising:

（但し、上記式（１）で表される部位が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。）
［２］ 前記ポリカーボネート樹脂（Ａ）と前記ポリカーボネート樹脂（Ｂ）との混合比が重量比で［ポリカーボネート樹脂（Ａ）］：［ポリカーボネート樹脂（Ｂ）］＝１０：９０〜９０：１０である前記［１］に記載のポリカーボネート樹脂組成物。
［３］ 前記ポリカーボネート樹脂（Ａ）と前記ポリカーボネート樹脂（Ｂ）とが前記式（１）で表される部位を有するジヒドロキシ化合物に由来する構造単位として、同じ種類のジヒドロキシ化合物に由来する構造単位をそれぞれ１０モル％以上含むものである、前記［１］又は［２］に記載のポリカーボネート樹脂組成物。
［４］ 前記ポリカーボネート樹脂（Ｂ）が、リチウム及び長周期型周期表における２族からなる群より選ばれた少なくとも１種の金属を含む化合物を触媒として用いて製造され、前記式（１）で表される部位を有するジヒドロキシ化合物に由来する構造単位を含むポリカーネート樹脂である、前記［１］乃至［３］のいずれかに記載のポリカーボネート樹脂組成物。
［５］ 前記［１］乃至［４］のいずれかに記載のポリカーボネート樹脂組成物を成形してなる、ポリカーボネート樹脂成形品。
［６］ ポリカーボネート樹脂組成物を射出成形又は押出成形してなる、前記［５］に記載のポリカーボネート樹脂成形品。
［７］ リチウム及び長周期型周期表における２族からなる群より選ばれた少なくとも１種の金属を含む化合物を触媒として用いて製造され、下記式（１）で表される部位を有するジヒドロキシ化合物に由来する構成単位を含み、かつその触媒として用いられた金属の含有量が２０重量ｐｐｍ以下であるポリカーネート樹脂を、成形を経て得られたポリカーボネート樹脂（Ａ）と、ポリカーボネート樹脂（Ｂ）とを混合する工程を含むポリカーボネート樹脂組成物の製造方法。

（但し、上記式（１）で表される部位が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above formula (1) unless it is part of -CH ₂ -O-H.)
[2] The mixing ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is [polycarbonate resin (A)]: [polycarbonate resin (B)] = 10:90 to 90:10 by weight ratio. The polycarbonate resin composition according to [1].
[3] As the structural unit derived from the dihydroxy compound having the site represented by the formula (1), the structural unit derived from the same kind of dihydroxy compound is used as the polycarbonate resin (A) and the polycarbonate resin (B). The polycarbonate resin composition according to the above [1] or [2], each containing 10 mol% or more.
[4] The polycarbonate resin (B) is produced by using, as a catalyst, a compound containing lithium and at least one metal selected from the group consisting of Group 2 in the long-period periodic table. The polycarbonate resin composition according to any one of the above [1] to [3], which is a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a represented site.
[5] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [4].
[6] The polycarbonate resin molded article according to [5], which is formed by injection molding or extrusion molding a polycarbonate resin composition.
[7] A dihydroxy compound having a moiety represented by the following formula (1), produced using as a catalyst a compound containing at least one metal selected from the group consisting of lithium and Group 2 of the long-period periodic table A polycarbonate resin (A) obtained by molding a polycarbonate resin containing a structural unit derived from the above and having a metal content of 20 ppm by weight or less used as a catalyst thereof, and a polycarbonate resin (B) The manufacturing method of the polycarbonate resin composition including the process of mixing.

(However, the site represented by the above formula (1) unless it is part of -CH ₂ -O-H.)

  The polycarbonate resin (A) of the present invention is excellent in hue and transparency as compared with the conventional polycarbonate resin, and has good hue and transparency even after being molded. By mixing with (B), a polycarbonate resin composition having good recyclability can be provided.

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

<Polycarbonate resin composition>
The polycarbonate resin composition of the present invention is produced using a compound containing lithium and at least one metal selected from the group consisting of two groups in the long-period periodic table as a catalyst, and is represented by the following formula (1). A polycarbonate resin (A) obtained by molding a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a moiety and having a metal content used as a catalyst of 20 ppm by weight or less, and a polycarbonate It is characterized by being mixed with resin (B).

（但し、上記式（１）で表される部位が−ＣＨ₂−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above formula (1) unless it is part of -CH ₂ -O-H.)

  As described above, the polycarbonate resin composition of the present invention contains the polycarbonate resin (A) and the polycarbonate resin (B) as essential components. Hereinafter, the polycarbonate resin (A) and the polycarbonate resin (B) of the present invention will be described.

[Polycarbonate resin (A)]
In the present invention, the “polycarbonate resin (A)” is produced by using, as a catalyst, a compound containing at least one metal selected from the group consisting of lithium and Group 2 in the long-period periodic table. And a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a site represented by the formula (II) and having a metal content of 20 ppm by weight or less used as the catalyst in the resin, and further molding at least once. It refers to what was obtained through the process.
In the present invention, the “polycarbonate resin (A)” is used as a concept including not only the polycarbonate resin itself but also a composition containing components other than the polycarbonate resin. However, even when the polycarbonate resin (A) is a composition, it is necessary to satisfy the above-mentioned condition of “having undergone molding”.

  In the present invention, “obtained through molding” does not mean a material that has undergone a pelletization process using an extruder or the like, and includes, for example, various molding methods such as injection molding, extrusion molding, and blow molding. This means something that has undergone molding.

In the present invention, the polycarbonate resin (A) before molding, which has not been molded with respect to the polycarbonate resin (A), is referred to as “polycarbonate resin (A ₀ )”. In the present invention, when only the polycarbonate resin component in the polycarbonate resin (A ₀ ) is explicitly shown, it may be expressed as “polycarbonate resin (a)”.

  As described above, the polycarbonate resin (A) used in the present invention is produced by using, as a catalyst, a compound containing lithium and at least one metal selected from the group consisting of two groups in the long-period periodic table. And the content of the metal used as the catalyst in the resin is 20 ppm by weight or less. The content of the metal used as the catalyst is preferably 15 ppm or less, on the other hand, preferably 1 pp or more, more preferably 0.1 ppm or more. When the content of the catalyst is too large, that is, when the amount of catalyst used at the time of production is too large, the catalyst itself remains in the resin, which may deteriorate the color tone and transparency of the resin. On the other hand, when the content of the metal used as the catalyst is equal to or higher than the upper limit, it is possible to advance the transesterification reaction quickly when producing the polycarbonate resin (a), and to reduce the heat history of the resin. And even if it recycles, these outstanding resin can be obtained so that a color tone, transparency, etc. are not impaired.

  Usually, when a product such as a polycarbonate resin is manufactured by an injection molding method or the like, a sprue, a runner, or a non-standard molded product (hereinafter, these molded products may be referred to as “collected molded products”). Will occur. In addition, with the recent reduction in size and weight of various products, the parts used (molded products) are also being reduced in size, and resins (compositions) having excellent moldability are often used for these parts. These parts (molded products) are small and have a lot of foil. In the case of such a small part (molded product), especially when the weight ratio of the sprue or runner part to the weight of one part is large, and the collected molded product such as the sprue or runner is discarded. Since the commercialization rate of the resin composition is lowered, the resin composition is recycled without being discarded. In the present invention, polycarbonate resin (A) is used as a resin or resin composition that is once recycled after being molded in the present invention, and polycarbonate resin (B) described later is used as the other resin, resulting in excellent recyclability. It can be used as a polycarbonate resin composition. That is, the polycarbonate resin composition of the present invention is a polycarbonate resin obtained by blending (mixing) a polycarbonate resin (A) that is a recycled resin from a recovered molded product and a polycarbonate resin (B) that is a so-called virgin resin that has not been molded. The polycarbonate resin (A), which is a composition and is a recycled resin, is reused.

<Raw material of polycarbonate resin (a)>
(Dihydroxy compound)
The polycarbonate resin (a) is a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure (hereinafter sometimes referred to as “dihydroxy compound used in the present invention”). Including at least. That is, the dihydroxy compound used in the present invention refers to a compound containing at least two hydroxyl groups and a structural moiety represented by the following formula (1).

（但し、上記式（１）で表される部位が−ＣＨ₂−Ｏ−Ｈを構成する部位である場合を除く。）

(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 3) and a dihydroxy compound represented by the following formula (4). 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 (3) 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 (a) 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”). Examples of the dihydroxy compound 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 linear aliphatic dihydroxy compound and a branched aliphatic dihydroxy compound. Examples of the linear aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, Examples include 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. , Cyclohexene diols such as 4-cyclohexene-1,2-diol, norbornane diols such as 2,3-norbornane diol, 2,5-norbornane diol, 1,3-adamantane diol, 2,2-adamantane diol, etc. Adamantanediols, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanols such as 1,4-cyclohexanedimethanol, cyclohexenediols such as 4-cyclohexene-1,2diol, - norbornane methanol, 2,5-norbornane methanol, etc. norbornanedimethanol such, 1,3-adamantane dimethanol, etc. adamantane dimethanol such as 2,2-adamantane dimethanol and the like.

  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, hypophosphorous acid in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as um 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 preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

  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 polycarbonate resin production raw material, the resulting polycarbonate resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. In some cases, a high molecular weight polymer cannot be obtained.

  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 dihydroxy compound used in the present invention is made to have a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. When a dihydroxy compound containing is used as a polycarbonate resin production raw material, a polycarbonate resin excellent in hue and thermal stability can be produced without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin (a) can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester as raw materials.

  As a carbonic acid diester used, what is normally represented by following formula (5) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

（上記式（５）において、Ａ¹、Ａ²は、置換又は無置換の炭素数１〜１８の脂肪族又は置換又は無置換の芳香族基であり、Ａ¹とＡ²は同一であっても異なっていてもよい。）
上記式（５）で表される炭酸ジエステルとしては、例えば、ジフェニルカーボネート、ジトリルカーボネート等の置換ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネート及びジ−ｔ−ブチルカーボネート等が例示されるが、好ましくはジフェニルカーボネート、置換ジフェニルカーボネートであり、特に好ましくはジフェニルカーボネートである。なお、炭酸ジエステルは、塩化物イオンなどの不純物を含む場合があり、重合反応を阻害したり、得られるポリカーボネート樹脂の色相を悪化させたりする場合があるため、必要に応じて、蒸留などにより精製したものを使用することが好ましい。

(In the above formula (5), A ¹ and A ² are substituted or unsubstituted C 1-18 aliphatic or substituted or unsubstituted aromatic groups, and A ¹ and A ² are the same. May be different.)
Examples of the carbonic acid diester represented by the above formula (5) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

<Transesterification reaction catalyst used for production of polycarbonate resin (a)>
The polycarbonate resin (a) is produced by subjecting a dihydroxy compound containing a dihydroxy compound used in the present invention and a carbonic acid diester to an ester exchange reaction 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 (a) is particularly suitable for the light transmittance at a wavelength of 350 nm and the yellow index value. May have an impact.

  Accordingly, in the present invention, lithium and a group 2 metal compound in the long-period periodic table (hereinafter referred to as “lithium compound” and “group 2 metal compound”, respectively) may be mentioned. Preferably a Group 2 metal compound is used.

  In addition, lithium compounds and / or Group 2 metal compounds are usually used in the form of hydroxides or salts such as carbonates, carboxylates and phenol salts, but are easily available and easy to handle. From the viewpoints of hue and polymerization activity, acetates are preferred.

  Examples of lithium compounds that can be used as a catalyst include lithium hydroxide, lithium hydrogen carbonate, lithium carbonate, lithium acetate, lithium stearate, lithium borohydride, lithium phenyl borohydride, lithium benzoate, dilithium hydrogen phosphate, and phenyl. Examples thereof include dilithium phosphate, lithium alcoholate, phenolate, and dilithium salt of bisphenol A.

  Examples of the Group 2 metal compound that can be used as a catalyst include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, carbonate Barium, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc., among which magnesium compounds, calcium compounds and barium compounds are preferred. And at least one metal selected from the group consisting of magnesium compounds and calcium compounds from the viewpoint of polymerization activity and hue of the polycarbonate resin obtained. More preferably compounds, most preferably a calcium compound.

  Along with the lithium compound and / or the group 2 metal compound used as a catalyst, a group 1 metal compound in the long-period type periodic table other than lithium (hereinafter simply referred to as “group 1 metal compound other than lithium”). It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound, but only a lithium compound and / or a Group 2 metal compound may be used. It is particularly preferred to use it. The following are examples of catalysts that can be used supplementarily.

  Group 1 metal compounds other than lithium include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, acetic acid. Cesium, sodium stearate, potassium stearate, cesium stearate, sodium borohydride, potassium borohydride, cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, benzoic acid Potassium, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dicesium phenyl phosphate, sodium Collate, potassium alcoholate, cesium alcoholate, sodium phenolate, potassium phenolate, cesium phenolate, disodium salt of bisphenol A, dipotassium salt of bisphenol A, dicesium salt of bisphenol A, etc. It is done.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl. Examples thereof include sodium salts such as boron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron, potassium salts, lithium 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, quaternary phosphonium salt, and the like.

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

  The amount of the polymerization catalyst used is usually 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol per 1 mol of all dihydroxy compounds used, and among them, at least one metal selected from the group consisting of magnesium compounds and calcium compounds. When a compound is used, the amount of metal is usually 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more, per 1 mol of all dihydroxy compounds used. Further, the upper limit is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst is too small, the polymerization rate 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.

  In addition, Group 1 metals other than lithium, especially sodium, potassium and cesium, especially lithium, sodium, potassium and cesium may have a bad influence on the hue when contained in polycarbonate resin. The total amount of these compounds in the polycarbonate resin is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, as the amount of metal. More preferably, it is 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 of the metal in the polycarbonate resin, particularly the metal used as the catalyst, can be regarded as remaining in the polycarbonate resin (a) and then in the polycarbonate resin composition of the present invention.

<Production method of polycarbonate resin (a)>
The polycarbonate resin (a) is obtained by polycondensation of a dihydroxy compound containing a 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, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often 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 (a), and the carbonic acid diester is an oxygen concentration of 10% by volume or less, further 0.0001% by volume to 10% by volume. It is preferable to carry out in an atmosphere of 0001 volume% to 5 volume%, particularly 0.0001 volume% to 1 volume% from the viewpoint of preventing hue deterioration.

  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 during molding, the rate of transesterification reaction is reduced, 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 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 remaining in the polycarbonate resin (a) is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. Actually, 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. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components.

  The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C.

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

  As described above, the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency and the like, three or more, preferably 3 to 5, particularly preferably 4 are used. One.

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

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

  If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized but also decomposition and coloring of the polycarbonate resin may be promoted.

  Specifically, the first stage reaction is carried out at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor, preferably 110 to 1 kPa, Is carried out at a pressure of 70 to 5 kPa, more preferably 30 to 10 kPa (absolute pressure) for 0.1 to 10 hours, preferably 0.5 to 3 hours, while distilling off the generated monohydroxy compound out of the reaction system. Is done.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 210 to 270 ° C., preferably 220 to 250 ° C., usually 0.1 to 10 hours, preferably 1 to 6 hours, particularly preferably 0.5 to 3 hours React with.

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

  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 (a) is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.

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

  At that time, in the extruder, the residual monomer under reduced pressure devolatilization, as will be described later, thermal stabilizer, neutralizer, UV absorber, mold release agent, colorant, antistatic agent, lubricant, lubricant, 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 (a), but is usually 150 to 300 ° C, preferably 200 to 270 ° C, and more preferably 230 to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin (a) is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When producing the polycarbonate resin (a), it is desirable to install a filter in order to prevent foreign matter 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.

  The extrusion of the polycarbonate resin (a) is preferably carried out in a clean room having a higher degree of cleanliness than class 7, as defined in JIS B9920 (2002), and more preferably, in order to prevent foreign matter from being mixed after extrusion. It is desirable.

  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 0.45 to 10 μm as 99% removal filtration accuracy.

<Physical properties of polycarbonate resin (a)>
The molecular weight of the polycarbonate resin (a) 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. The upper limit is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.

  If the reduced viscosity of the polycarbonate resin (a) 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 is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., precisely prepared at a polycarbonate concentration of 0.6 g / dL using methylene chloride as a solvent.

  Further, the lower limit of the concentration of the terminal group represented by the following formula (6) of the polycarbonate resin (a) is usually 20 μeq / g, preferably 40 μeq / g, particularly preferably 50 μeq / g, and the upper limit is usually 160 μeq / g. g, preferably 140 μeq / g, particularly preferably 100 μeq / g.

  If the concentration of the end group represented by the above formula (6) is too high, even if the hue at the time of polymerization or 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 formula (6), in addition to controlling the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the 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 a polycarbonate resin (a) is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the formula (5), phenol and substituted phenol are by-produced in the polycarbonate resin. However, phenol and substituted phenols also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, and may also cause odor during molding. is there. 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 H bonded to the aromatic ring of the polycarbonate resin (a) is (M) and the number of moles of H bonded to other than the aromatic ring is (N), the number of moles of H bonded to the aromatic ring The ratio of the total H to the number of moles is expressed by M / (M + N). However, since the aromatic ring having the ability to absorb ultraviolet rays may affect the light resistance as described above, M / ( M + N) is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. M / (M + N) can be quantified by 1H-NMR.

<Components other than polycarbonate resin (a) of polycarbonate resin (A ₀ )>
Comprising the structural unit represented by the formula (1) produced using a compound containing at least one metal selected from the group consisting of lithium of the present invention and Group 2 of the long-period periodic table as a catalyst; In addition, the polycarbonate resin (A ₀ ) having a metal content of 20 ppm by weight or less used as the catalyst in the resin has an antioxidant, a release agent, an acid, and the like within the range not impairing the object of the present invention. Components other than the polycarbonate resin (a) such as a compound and a filler can be blended and contained. Components other than the polycarbonate resin (a) that can be blended in the polycarbonate resin and the amount of use thereof are described below.

The polycarbonate resin (A ₀ ) of the present invention preferably contains an antioxidant. When an antioxidant is used, it is usually 0.0001 part by weight or more and 1 part by weight or less, preferably 0.0001 part by weight or more and 0.1 part by weight or less, with respect to 100 parts by weight of the polycarbonate resin (a). And more preferably 0.0002 parts by weight or more and 0.01 parts by weight or less. When the content of the antioxidant is usually 0.0001 part by weight or more with respect to 100 parts by weight of the polycarbonate resin (a), the coloring suppression effect at the time of molding tends to be good, but the content of the antioxidant is When the amount exceeds 1 part by weight with respect to 100 parts by weight of the polycarbonate resin, the amount of deposits on the mold during injection molding increases, or the number of deposits on the roll increases when forming a film by extrusion molding. The surface appearance of the product may be damaged.

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

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

  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.

The polycarbonate resin (A ₀ ) 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 using a mold release agent, the compounding quantity is 0.0001 weight part-2 weight part normally with respect to 100 weight part of polycarbonate resin (a), Preferably it is 0.01 weight part-1 weight part. More preferably 0.1 to 0.5 parts by weight. If the release agent content is excessively large, the amount of deposits on the mold may increase during 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 of the polycarbonate resin (a), the molded product may be easily released from the mold during molding. There is an advantage that a molded product is easy to obtain.

  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 solid polycarbonate resin 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.

The polycarbonate resin (A ₀ ) 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, based on 100 parts by weight of the polycarbonate resin (a). It is 0.0001 parts by weight or more and 0.01 parts by weight or less, and more preferably 0.0002 parts by weight or more and 0.001 parts by weight or less. 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 (a), when the residence time in the injection molding machine of the polycarbonate resin composition becomes long when injection molding is performed. Although it is preferable at the point of coloring suppression, when the compounding quantity of an acidic compound is more than 0.1 weight part with respect to 100 weight part of polycarbonate resin (a), 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.

A filler can be blended in the polycarbonate resin (A ₀ ) 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 (a). 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, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, wollastonite and the like. Calcium silicate: 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 are glass fiber and mica. 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 for 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 powdered organic fillers such as wood powder, bamboo powder, coconut starch, krk powder, and pulp powder; balun-like and spherical shapes such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin, and the like. Organic fillers: Fibrous organic fillers such as carbon fibers, synthetic fibers, and natural fibers can be used.

  The carbon fiber is not particularly limited, and is produced by firing using, for example, acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, lignin or the like as a raw material, such as flame resistance, carbonaceous, and graphite. 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 chopped strand, roving strand, milled fiber, etc. 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 (A ₀ ) of the present invention are not impaired, the carbon fiber is subjected to surface treatment such as epoxy treatment, urethane treatment, oxidation treatment, etc. in order to increase the affinity with the polycarbonate resin (a). May be.

In the present embodiment, the addition timing and addition method of the filler to be blended with the polycarbonate resin (A ₀ ) are not particularly limited. As the addition time, for example, when the polycarbonate resin (a) is produced by the transesterification method, at the end of the polymerization reaction; and, regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin and other compounding agents Melted state: When blending and kneading 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 masterbatch prepared using a small amount of a polycarbonate resin or other resin and an inorganic filler can also be added.

A flame retardant can be blended in the polycarbonate resin (A ₀ ) of the present invention as long as the object of the present invention is not impaired. The blending amount of the flame retardant can be appropriately selected according to the kind of the flame retardant and the degree of flame retardancy. In the present invention, the flame retardant is 0 part by weight with respect to 100 parts by weight of the polycarbonate resin (a). -30 parts by weight.

  Examples of the flame retardant include phosphorus-containing compound flame retardants, halogen-containing compound flame retardants, sulfonic acid metal salt flame retardants, and silicon-containing compound flame retardants. In the present embodiment, at least one selected from these groups can be used. These can be used alone or in combination of two or more.

  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 compounding quantity of a phosphorus containing compound type flame retardant is 0 weight part-20 weight part with respect to 100 weight part of polycarbonate resin (a). If the amount 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 quantity of a halogen-containing compound type flame retardant is 0 weight part-20 weight part with respect to 100 weight part of polycarbonate resin (a). If the blending amount of the halogen-containing compound-based flame retardant 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 examples of the metal of these metal salts include metals of Group 1 of the periodic table and metals of Group 2 of the periodic table. Specifically, alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as calcium, strontium and 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, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid And the dipotassium salt of diphenylsulfone-3,3′-disulfonic acid.

  The perfluoroalkane-sulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkane-sulfonic acid, an alkaline earth metal 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 alkaline earth metal salt having a C 4-8 perfluoroalkane group, and the like are 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 compounding quantity of a sulfonic-acid metal salt type flame retardant is 0-5 weight part with respect to 100 weight part of polycarbonate resin (a). If the amount of the sulfonic acid metal salt flame retardant 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 ² SiO] and a trifunctional unit [R ³ SiO _1.5 ], a monofunctional unit [R ¹ SiO _0.5 ] and / or a tetrafunctional unit [SiO ₂ ], a relatively low molecular weight solution-like silicone resin. Here, R is a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms 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 types of R ^{1 to} R ³ , 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 quantity of a silicon containing compound type flame retardant is 0-10 weight part with respect to 100 weight part of polycarbonate resin (a). When the compounding amount of the silicon-containing compound flame retardant is excessively large, the heat resistance tends to be lowered.

  In order to achieve higher flame retardancy, the combined use of polytetrafluoroethylene for preventing dripping is preferable. 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 6J, Teflon 30J (Mitsui DuPont Fluorochemical Co., Ltd .; registered trademark), Polyflon F201L (Daikin Chemical Industry Co., Ltd.), and the like.

  The amount of polytetrafluoroethylene for preventing dripping is 0 to 2.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin (a). 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 the present embodiment, the addition timing and addition method of the flame retardant compounded in the polycarbonate resin (A ₀ ) are not particularly limited. As the addition time, for example, when the polycarbonate resin (a) is produced by the transesterification method, at the end of the polymerization reaction; and, regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin and other compounding agents Melted state: When blending and kneading with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As an addition method, a filler can be directly mixed or kneaded with a polycarbonate resin; it can also be added as a high-concentration master batch prepared using a small amount of a polycarbonate resin or other resin and the filler.

The polycarbonate resin (A ₀ ) 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 ultraviolet absorber can be appropriately selected according to the type of the ultraviolet absorber, but in the present invention, the ultraviolet absorber is 0 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (a). Part.

  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. Among these, an organic compound is preferable because it is easy to ensure affinity with the polycarbonate resin (a) and is 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.

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

  Examples of the malonic ester compounds include 2- (1-arylalkylidene) malonic 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 compounds include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

In the polycarbonate resin (A ₀ ) of the present invention, a bluing agent can be blended in order to counteract the yellowness 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] and the like are given as representative examples. These bluing agents may be used alone or in combination of two or more. These blueing agents are usually blended at a ratio of 0.1 × 10 ⁻⁵ to 2 × 10 ⁻⁴ parts by weight when the polycarbonate resin is 100 parts by weight.

The polycarbonate resin (A ₀ ) of the present invention can contain a light stabilizer as long as the object of the present invention is not impaired. The content of the stabilizer is usually 0 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (a). In addition, the polycarbonate resin composition of the present invention can contain an antistatic agent as long as the object of the present invention is not impaired.

The polycarbonate resin (A ₀ ) of the present invention is produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, extruder or the like. Can do. Furthermore, nucleating agents, impact modifiers, foaming agents, dyes and the like that are usually used in the resin composition may be included within the range not impairing the object of the present invention.

Polycarbonate resin (A ₀ ) is, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS resin, AS, or other synthetic resin, 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.

As described above, the polycarbonate resin (A) of the present invention is obtained through molding. Specifically, the polycarbonate resin (A) is molded by various molding methods such as injection molding and extrusion molding. It is the obtained molded product and sprue, runner or non-standard molded product (collected molded product) produced as a by-product during molding. In addition, trimming residues (end materials) at the time of packaging such as films and sheets are also targeted.
These recovered molded products are usually melted and kneaded by an extruder after pulverization, pelletized by cutting, and mixed with the polycarbonate resin (B) described later to obtain the polycarbonate resin composition of the present invention.

<Polycarbonate resin (B)>
The polycarbonate resin (B) contained in the polycarbonate resin composition of the present invention is a polycarbonate resin different from the polycarbonate resin (A), and usually by a transesterification reaction using a dihydroxy compound containing a dihydroxy compound and a carbonic acid diester as raw materials. It is obtained by polycondensation. Since the polycarbonate resin (B) has good compatibility with the polycarbonate resin (A), the polycarbonate resin (A) can be recycled and used in combination to obtain the polycarbonate resin composition of the present invention. .

The polycarbonate resin (B) is not particularly limited as long as it is a polycarbonate obtained using a dihydroxy compound and a carbonic acid diester as raw materials. As a dihydroxy compound used as a raw material, a chain aliphatic dihydroxy compound, an alicyclic dihydroxy compound, an aromatic bisphenol, and the like are used in addition to the dihydroxy compound having the structural unit represented by the formula (1). be able to. Among these, from the viewpoint of further improving the compatibility with the polycarbonate resin (A), the polycarbonate resin (B) has the structural unit represented by the above formula (1) as in the polycarbonate resin (A). It is desirable to include it.
Further, as the structural unit derived from the formula (1), the polycarbonate resin (A) and the polycarbonate resin (B) each have a structural unit derived from the same kind of dihydroxy compound in an amount of 10 mol% or more, preferably 25 mol%. It is desirable to include the above.

Furthermore, in order to make the polycarbonate composition of the present invention particularly excellent in transparency, the polycarbonate resin (B) contains at least one metal selected from the group consisting of lithium and two groups in the long-period type periodic table. Particularly preferred is a polycarbonate resin obtained by using a compound as a catalyst. That is, as the polycarbonate resin (B), a polycarbonate resin (A ₀ ) can be preferably used.

  The polycarbonate resin (B) is a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer, a compatibilizer, a difficult agent, if necessary. Additives such as a flame retardant can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder or the like.

  The polycarbonate resin (B) of the present invention is, for example, a synthetic resin such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, 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.

<Polycarbonate resin composition>
The polycarbonate resin composition of the present invention contains the polycarbonate resin (A) and the polycarbonate resin (B) as essential components.
The blend ratio of the polycarbonate resin (A) and the polycarbonate resin (B) in the polycarbonate resin composition is [polycarbonate resin (A)]: [polycarbonate resin (B)] = 10:90 to 90:10 by weight ratio. Preferably, [polycarbonate resin (A)]: [polycarbonate resin (B)] = 10:90 to 80:20, more preferably [polycarbonate resin (A)]: [polycarbonate resin (B)] = 10: 90 to 70:30 is particularly preferable. Since the polycarbonate resin (A) of the present invention is once molded, from the viewpoint of improving the physical properties of the polycarbonate resin of the present invention, the proportion of the polycarbonate resin (A) is small, and the polycarbonate resin (B) A higher proportion is preferred.

  In addition, the polycarbonate resin of this invention can mix | blend components other than polycarbonate resin (A) and polycarbonate resin (B) suitably in the range which does not impair the objective of this invention.

<Production method of polycarbonate resin composition>
In the present invention, the method of mixing the polycarbonate resin (A) and the polycarbonate resin (B) is not particularly limited as long as it can be uniformly mixed, and a conventional compound technique can be used.

The polycarbonate resin (A) is obtained by pulverizing a recovered molded product such as a sprue or a runner with a pulverizer or the like, or further melting, extruding, pelletizing, mixing with the polycarbonate resin (B) with a mixer, etc. It can be kneaded by heating and melting and pelletized again.
If there is a concern about deterioration of hue or physical properties due to thermal history, polycarbonate resin (A) and polycarbonate resin obtained by pulverizing recovered molded products such as sprue and runner with a pulverizer etc. (B) After the pellets are mixed and dried with a mixer or the like, they are put into a hopper of a molding machine and directly injection-molded to obtain a resin material. However, since the shape of the pellet and the pulverized product are different, this is not the case when a measurement defect occurs during molding.

  Specifically, the polycarbonate resin composition of the present invention is prepared by weighing a predetermined amount of a raw material resin (pulverized product and / or pellet) composed of the polycarbonate resin (A) and the polycarbonate resin (B) and, if necessary, a resin additive. It can be obtained by a method of mixing with various mixers such as a blender, mixer, tumbler, etc., melting, kneading, extruding with an extruder or the like, cutting with a pelletizer or mill, and pelletizing, granulating or powdering. In the case of pelletizing by melt-kneading, it is desirable to supply the pulverized product from the side feed port of the extruder for the purpose of avoiding thermal decomposition, deterioration, and alteration as much as possible. The extruder that can be used at this time may be either a single screw extruder or a twin screw extruder provided with a vent port.

  The particle size of the pulverized product of the polycarbonate resin (A) is preferably 0.1 to 20 mm, more preferably 0.5 to 10 mm, and still more preferably 1 to 5 mm. If the particle size is too small or too large, it will be difficult to mix with the pellets of the polycarbonate resin (B), there is a possibility that poor measurement due to poor feed to the molding machine, and appearance defects such as silver may occur. There is also.

  When a film or sheet is used as the polycarbonate resin (A), the thickness is preferably 0.1 to 20 mm, more preferably 0.5 to 10 mm, even more preferably by cutting, cutting, or the like. By setting the thickness to 1 to 5 mm, it can be easily molded.

  The polycarbonate resin (A) is preferably dried before mixing with the polycarbonate resin (B). Further, drying is not particularly limited as long as it is a condition for drying the resin, but it is preferably performed in a nitrogen atmosphere. The drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C. Furthermore, the drying time is preferably 5 to 15 hours, more preferably 7 to 13 hours. This drying step may be performed before or after the step of pulverizing or cutting the polycarbonate resin (A).

<Polycarbonate resin molded product>
The polycarbonate resin composition of the present invention can be produced as a polycarbonate resin molded article by a molding method conventionally known as a molding method of a thermoplastic resin composition, such as an injection molding method, an extrusion molding method, or a compression molding method. it can. Among these molding methods, the injection molding method is particularly preferable from the viewpoint of the degree of freedom of molding.

  The polycarbonate resin composition of the present invention can be suitably applied to various applications by using the above-described polycarbonate resin molded product. For example, injection molding field such as electrical / electronic parts and automotive parts, film and sheet fields, bottle and container fields that require heat resistance, and lens applications such as camera lenses, viewfinder lenses, CCD and CMOS lenses To a wide range of fields such as retardation film, diffusion sheet, polarizing film, and other films, sheets, optical disks, optical materials, optical components, dyes, charge transfer agents, etc. Materials can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is changed. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value 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.

<Evaluation of physical properties and characteristics of polycarbonate resin composition>
In the following, the physical properties and characteristics of the polycarbonate resin and the resin composition were evaluated by the following methods.

(1) Evaluation Method of Initial Hue of Polycarbonate Resin Composition Pellets (or pulverized products) of the polycarbonate resin composition were dried at 110 ° C. for 10 hours in a nitrogen atmosphere. Next, the dried pellets (or pulverized product) of the polycarbonate resin composition are supplied to an injection molding machine (J75EII type, manufactured by Nippon Steel Works), and injection molded pieces (with a resin temperature of 220 ° C. and a molding cycle of 23 seconds) Repeat the operation to form (width 60mm x length 60mm x thickness 3mm) and color the yellow index (initial YI) value in the transmitted light in the thickness direction of the injection molded pieces obtained in the 11th to 15th shots Measurement was performed using a tester (CM-3700d manufactured by Konica Minolta), and an average value was calculated. The smaller the YI value, the better the quality without yellowness.

(2) Measurement of total light transmittance of polycarbonate resin composition and measurement of haze Injection molded piece (width 60 mm x length 60 mm) molded by Nippon Denshoku Industries Co., Ltd. haze meter NDH2000 and D65 light source as described in 1) above. × Thickness 3 mm) Total light transmittance and haze were measured.

(3) Measurement of light transmittance at a wavelength of 350 nm The light transmittance in the thickness direction of the injection-molded piece (width 60 mm × length 60 mm × thickness 3 mm, 10th shot to 20th shot) obtained in 1) above, Measurement was performed using an ultraviolet-visible spectrophotometer (U2900 manufactured by Hitachi High-Technologies Corporation), and the average value was calculated and evaluated.

(4) Measurement of metal concentration in polycarbonate resin Approximately 0.5 g of the injection-molded piece obtained in 1) above was precisely weighed, and 2 mL of 97% sulfuric acid was added to a microwave decomposition vessel manufactured by PerkinElmer, and sealed. Then, microwave heating was performed 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 the metal concentration was measured by ICP-MS manufactured by ThermoQuest.

<Manufacture of polycarbonate resin>
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 (New Nippon Rika Co., Ltd., SKY CHDM)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

[Antioxidant]
Irganox 1010: Pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (BASF Japan Ltd .; Irganox (registered trademark) 1010)
Irgaphos 168: Tris (2,4-di-tertbutylphenyl) phosphite (manufactured by BASF Japan; Irgaphos (registered trademark) 168)
[Release agent]
S-100A: Glycerol monostearate (Riken Vitamin Co., Ltd .; Riquemar (registered trademark) S-100A)

[Production Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB, CHDM, DPC having a chloride ion concentration of 10 ppb or less by distillation purification, and calcium acetate monohydrate are in a molar ratio. In ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ and sufficiently purged with nitrogen (oxygen concentration 0.0005) Volume% to 0.001 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 control was performed to maintain this temperature when the internal temperature reached 215 ° C. At the same time, pressure reduction was started, and 215 ° C was reached. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  The contents thus oligomerized are once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set to 230 ° C. 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 molten polycarbonate resin is continuously supplied to a twin-screw extruder equipped with 3 vents and water injection equipment, and 0.3 parts by weight of S100A is used as a release agent, and Irganox 1010 is used as an antioxidant. Part by weight and Irgafos 168 are continuously added and 0.05 parts by weight are continuously added, and low molecular weight substances such as phenol are devolatilized under reduced pressure at each vent part provided in the twin screw extruder, and then pelletized by a pelletizer. Polycarbonate resin pellets were obtained (referred to as “PC resin A”). The obtained polycarbonate resin was evaluated for various physical properties by the evaluation methods described above. The obtained results are shown in Table-1. That is, the PC resin A corresponds to the polycarbonate resin (A ₀ ) in the present invention, and also corresponds to the polycarbonate resin (B).
The Ca content in the PC resin A was 0.28 ppm by weight.

[Production Example 2]
Resin pellets produced in the same manner as “PC resin A” (Ca content: 0.28 ppm by weight) were dried at 110 ° C. for 10 hours in a nitrogen atmosphere. Next, the dried polycarbonate resin pellets were supplied to an injection molding machine (J75EII type, manufactured by Nippon Steel Co., Ltd.), injection-molded under the conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds, and a test piece (width 60 mm × 60 mm long x 3 mm thick). The sprue and runner generated at this time were pulverized by a pulverizer GSL180 / 180 manufactured by ZERMA to obtain a polycarbonate resin (referred to as “PC resin B”). That is, the PC resin B corresponds to the polycarbonate resin (A) in the present invention.

[Production Example 3]
A cesium carbonate was used instead of calcium acetate monohydrate, and the others were carried out in the same manner as in Production Example 1 to obtain a pellet of a polycarbonate resin composition (referred to as “PC resin C”). About the obtained polycarbonate resin, various physical properties etc. were evaluated by the evaluation method of the said description. The obtained results are shown in Table-1.

[Production Example 4]
The same procedure as in Production Example 2 was carried out except that polycarbonate resin pellets produced in the same manner as in “PC resin C” were used, and a polycarbonate resin composition sprue and runner were pulverized (“PC resin D” ”.) That is, the PC resin D is not a polycarbonate resin (A) in the present invention although it has undergone molding.

<Manufacture of polycarbonate resin composition>
[Example 1]
"PC resin A" and "PC resin B" were weighed and tumbled and mixed at a weight ratio of 50:50, and the obtained polycarbonate resin composition was evaluated for various physical properties by the evaluation method described above. . The obtained results are shown in Table-2.

[Example 2]
“PC resin A” and “PC resin B” were weighed in a weight ratio of 50:50, and further, 0.15 parts by weight of Riquemar (registered trademark) S-100A as a release agent and Irga as an antioxidant. Addition of 0.05 parts by weight of Knox (registered trademark) 1010 and 0.025 parts by weight of Irgaphos (registered trademark) 168 and tumbler mixing, and the resulting polycarbonate resin composition is fed with a twin gas extruder while supplying nitrogen gas Supplied to. After devolatilization under reduced pressure at each vent portion provided in the twin screw extruder, the resin temperature at the die head portion was adjusted to 265 ° C., and pelletized by a pelletizer. Various physical properties of the obtained polycarbonate resin composition were evaluated. The obtained results are shown in Table-2.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that “PC resin C” was used instead of “PC resin A” and “PC resin D” was used instead of “PC resin B”. Various physical properties of the obtained polycarbonate resin composition were evaluated. The obtained results are shown in Table-2.

  As shown in Tables 1 and 2, the polycarbonate resin compositions of Examples 1 and 2 have higher light transmittance at a wavelength of 350 nm, lower YI value, and lower haze than those of Comparative Example 1. It was. That is, it was shown that the polycarbonate resin compositions of Examples 1 and 2 do not absorb ultraviolet rays as compared with Comparative Example 1, and thus are less likely to be colored by ultraviolet rays, and are excellent in color tone. .

  The polycarbonate resin composition of the present invention is excellent in transparency, hue, heat resistance, thermal stability, and mechanical strength, and is an injection molding field such as electric / electronic parts and automotive parts, film and sheet fields, In the field of bottles and containers that require heat resistance, as well as lens applications such as camera lenses, viewfinder lenses, CCD and CMOS lenses, retardation films used in liquid crystals and plasma displays, diffusion sheets, polarizing films, etc. It is possible to provide materials in a wide range of fields such as binder applications for fixing films, sheets, optical disks, optical materials, optical components, dyes, charge transfer agents, and the like.

Claims (7)

Produced using as a catalyst a compound containing at least one metal selected from the group consisting of lithium and two groups in the long-period periodic table, and derived from a dihydroxy compound having a site represented by the following formula (1) A polycarbonate resin (A) obtained by molding a polycarbonate resin containing a structural unit and having a metal content of 20 ppm by weight or less as a catalyst is mixed with a polycarbonate resin (B). A polycarbonate resin composition characterized by comprising:

(However, the site represented by the above formula (1) unless it is part of _-CH 2 -O-H.)   The mixing ratio of the polycarbonate resin (A) and the polycarbonate resin (B) is [polycarbonate resin (A)]: [polycarbonate resin (B)] = 10:90 to 90:10 by weight ratio. The polycarbonate resin composition as described.   As the structural unit derived from the dihydroxy compound having the site represented by the formula (1), the polycarbonate resin (A) and the polycarbonate resin (B) each have 10 mol of a structural unit derived from the same type of dihydroxy compound. % Or more of the polycarbonate resin composition according to claim 1 or 2.   The polycarbonate resin (B) is produced by using a compound containing lithium and at least one metal selected from the group consisting of two groups in the long-period periodic table as a catalyst, and represented by the formula (1). The polycarbonate resin composition according to any one of claims 1 to 3, which is a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a moiety.   A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4.   The polycarbonate resin molded article according to claim 5, wherein the polycarbonate resin composition is formed by injection molding or extrusion molding. Produced using as a catalyst a compound containing at least one metal selected from the group consisting of lithium and two groups in the long-period periodic table, and derived from a dihydroxy compound having a site represented by the following formula (1) A polycarbonate resin (A) obtained by molding a polycarbonate resin containing a structural unit and having a metal content of 20 ppm by weight or less as a catalyst is mixed with a polycarbonate resin (B). The manufacturing method of the polycarbonate resin composition characterized by including a process.

(However, the site represented by the above formula (1) unless it is part of _-CH 2 -O-H.)