JP6337739B2 - Polycarbonate resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded product thereof.

  In recent years, it has been described that isosorbide, which is a plant-derived monomer, is used as a polycarbonate resin using raw materials obtained from biomass resources, and a polycarbonate resin is obtained by transesterification with diphenyl carbonate (see Patent Document 1). Patent Document 2 describes a polycarbonate resin obtained by copolymerizing isosorbide and bisphenol A. Patent Document 3 describes that the rigidity of a polycarbonate resin is improved by copolymerizing isosorbide and an aliphatic diol. Patent Document 4 describes that a release agent and a heat stabilizer are added to a polycarbonate resin obtained by homopolymerizing isosorbide. Patent Document 5 describes that a polycarbonate resin obtained by polymerizing isosorbide contains at least one mold release agent selected from the group consisting of higher fatty acids and stearates.

British Patent 1,079,686 JP-A-56-055425 International Publication No. 2004/111106 Pamphlet JP 2008-274007 A JP 2011-105846 A

  By the way, the polycarbonate resin obtained by using isosorbide as a plant-derived monomer is insufficient in terms of heat resistance, transparency, and mechanical strength as compared with a conventional aromatic polycarbonate derived from petroleum raw materials. Moreover, there exists a problem that a mold release property is bad at the time of melt molding, it yellows and it is difficult to use as a transparent member or an optical member. In the prior art, attempts have been made to improve the releasability of polycarbonate resin obtained by homopolymerizing isosorbide, but it is insufficient. In the above-mentioned Patent Document 5, by using a specific compound as the release agent, the total light transmittance is high, the haze is low, the transparency is excellent, the strength is maintained, the appearance of the molded product is good, and the release is good. It is disclosed that the moldability is excellent.

However, in the region where the haze is lower, a new problem has been found that the color tone (plate YI) is insufficient with the release agent specifically described in Patent Document 5.
Accordingly, an object of the present invention is to provide a polycarbonate resin composition having at least a structural unit derived from a dihydroxy compound such as isosorbide and having a low color tone (plate YI) and excellent releasability while maintaining a low haze. Is to provide goods.

  As a result of studies by the present inventors, among the polycarbonate resins (A) containing the structural unit (a) derived from the dihydroxy compound represented by the formula (1), the polycarbonate resin (A) having a low haze is used. Discovered that a resin composition containing a phenolic antioxidant (B), a phosphite antioxidant (C) and a specific fatty acid ester compound (D) can achieve the above object, and completed the present invention. It came to do.

That is, the gist of the present invention is as follows.
(1) Polycarbonate resin (A) containing the structural unit (a) derived from the dihydroxy compound represented by the following formula (1), phenolic antioxidant (B), phosphite antioxidant (C) and fatty acid A resin composition containing an ester compound (D),
The haze value of the polycarbonate resin (A) measured under the following measurement conditions is 0.8 or less,
The fatty acid ester compound (D) is a fatty acid ester compound represented by the following formula (2),
A polycarbonate resin composition comprising 0.01 to 3% by weight of a fatty acid ester compound represented by the following formula (2) with respect to 100 parts by mass of a polycarbonate resin.

(In the above formula (2), one of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the other is a substituted or unsubstituted alkyl group or alkylene group having 10 or more carbon atoms. Represents.)

(Haze measurement conditions)
Pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.05 parts by weight, tris (2,4-di-tertbutylphenyl) per 100 parts by weight of polycarbonate resin ) The pellets of polycarbonate resin composition containing 0.1 parts by weight of phosphite were pre-dried at 80 ° C. for 4 hours. Next, the pellets of the dried polycarbonate resin composition were measured using a J75EII type injection molding machine manufactured by Nippon Steel Works under the molding conditions of a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, and a mold temperature of 60 ° C. of 60 mm × 60 mm × 3 mmt. Mold a flat plate.
Using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000, the haze of the flat plate shape | molded with the D65 light source is measured.

(2) The polycarbonate resin (A) is a copolymer polycarbonate resin containing a structural unit (b) derived from a dihydroxy compound other than the structural unit (a) derived from the dihydroxy compound represented by the formula (1). The polycarbonate resin composition according to (1), which is characterized. (3) Polycondensation of the polycarbonate resin is performed in the presence of a catalyst, and the catalyst is at least one metal compound selected from the group consisting of a metal of Group 2 of the long-period periodic table and lithium. The polycarbonate resin composition according to (1) or (2).
(4) A molded product obtained by molding the polycarbonate resin composition according to any one of (1) to (3).

  According to the present invention, a polycarbonate resin composition having excellent physical properties such as haze and yellow index value (YI) and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. And a molded article, a film, and a plate formed by molding this 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.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used for this invention is a polycarbonate resin characterized by including the structural unit (a) derived from the dihydroxy compound represented by following formula (1).

  Examples of the dihydroxy compound represented by the above formula (1) 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. Among them, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and manufacture, moldability, heat resistance, and impact resistance. Most preferable from the viewpoints of properties, surface hardness, and carbon neutral.

  Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is likely to be gradually 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 and handle under a nitrogen atmosphere. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. When isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, it may cause coloring of the obtained polycarbonate resin and polycarbonate resin composition, and may not only significantly deteriorate the physical properties but also polymerize. The reaction may be affected and a high molecular weight polymer may not be obtained.

  The polycarbonate resin (A) used in the present invention is a copolymer polycarbonate resin containing a structural unit (b) derived from a dihydroxy compound other than the structural unit (a) derived from the dihydroxy compound represented by the formula (1). It is preferable. Furthermore, at least one dihydroxy compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an ether group-containing dihydroxy compound other than the dihydroxy compound represented by formula (1) (hereinafter referred to as “other dihydroxy compounds”). It is more preferable from the viewpoint of impact resistance of the polycarbonate resin (A) that the copolymer polycarbonate resin contains the structural unit (b) derived from the aliphatic dihydroxy compound and the alicyclic compound. It is particularly preferred to contain any of the dihydroxy compounds.

  The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched aliphatic dihydroxy compound. For example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol and the like.

  Examples of alicyclic dihydroxy compounds include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, and 2,6-decalindi. Examples include methanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, and 1,3-adamantane dimethanol.

Examples of the ether group-containing dihydroxy compound include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 2000), poly-1,3-propylene glycol, and polytetramethylene glycol.
Considering the heat resistance of the polycarbonate resin (A), the other dihydroxy compound is preferably an alicyclic dihydroxy compound, and among the alicyclic dihydroxy compounds, cyclohexanedimethanol is preferable from the viewpoint of heat resistance and impact resistance. .

  The content ratio of the structural unit (b) derived from other dihydroxy compounds in the polycarbonate resin (A) used in the present invention is 10 mol% or more in the structural units derived from all dihydroxy compounds in the polycarbonate resin (A). Preferably, 20 mol% or more is more preferable, and 30 mol% or more is particularly preferable. Moreover, 50 mol% or less is preferable and 45 mol% or less is more preferable. If the structural unit (b) derived from the other dihydroxy compound in the polycarbonate resin (A) is too small, the impact resistance may be insufficient, and if it is too large, the heat resistance may be insufficient.

  The polycarbonate resin (A) used in the present invention can be produced by a generally used production method of a polycarbonate resin, and the production method is a solution polymerization method using phosgene, a melt in which a carbonic acid diester and a dihydroxy compound are reacted. Although any polymerization method may be used, a melt polymerization method in which a dihydroxy compound is reacted with a carbon dioxide diester having lower toxicity to the environment in the presence of a polymerization catalyst is preferable. In addition, as a polymerization catalyst (transesterification catalyst) in melt polymerization, a known alkali metal compound and / or alkaline earth metal compound is used. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound together with an alkali metal compound and / or an alkaline earth metal compound.

As the polymerization reaction, a known method can be used, and any method of a batch method, a continuous method, or a combination of a batch method and a continuous method may be used.
Moreover, when manufacturing the polycarbonate resin (A) used for this invention, in order to prevent mixing of a foreign material, it is desirable to install a filter. The filter installation position is preferably on the downstream side of the extruder, and the filter foreign matter removal size (opening) is usually preferably 100 μm or less as 99% removal filtration accuracy. In particular, in the case of disagreeing with the entry of minute foreign matters for film applications, 40 μm or less is preferable, and 10 μm or less is more preferable.

Extrusion of the polycarbonate resin (A) used in the present invention is preferably class 7 as defined in JIS B 9920 (2002), more preferably higher than class 6 in order to prevent foreign matter from being mixed after extrusion. It is desirable to carry out in a clean room.
Moreover, when cooling the extruded polycarbonate resin (A) to form chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

  The polycarbonate resin (A) used in the present invention is characterized in that the haze value measured under the following measurement conditions is 0.8 or less. In addition, about the upper limit of a haze value, since higher transparency is calculated | required, 0.6 or less is preferable and 0.4 or less is especially preferable. Further, the lower limit of the haze value is not particularly limited, but is usually 0.001 or more.

(Haze measurement conditions)
Pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.05 parts by weight, tris (2,4-di-tertbutylphenyl) per 100 parts by weight of polycarbonate resin ) The pellets of polycarbonate resin composition containing 0.1 parts by weight of phosphite were pre-dried at 80 ° C. for 4 hours. Next, the pellets of the dried polycarbonate resin composition were measured using a J75EII type injection molding machine manufactured by Nippon Steel Works under the molding conditions of a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, and a mold temperature of 60 ° C. of 60 mm × 60 mm × 3 mmt. Mold a flat plate.

Using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000, the haze of the flat plate shape | molded with the D65 light source is measured.
The molecular weight of the polycarbonate resin (A) used in the present invention can be represented by a reduced viscosity, and the reduced viscosity is usually preferably 0.30 dL / g or more, and more preferably 0.35 dL / g or more. The upper limit of the reduced viscosity is usually preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.

If the reduced viscosity of the polycarbonate resin (A) is too low, the toughness of the resin composition may be small. If the reduced viscosity is too large, the flow when molding electrical / electronic equipment parts and automotive interior / exterior parts There is a tendency that the productivity is lowered and the productivity and moldability are lowered. In addition, the molding temperature must be higher than appropriate, and the color tone may deteriorate.
The reduced viscosity of the polycarbonate resin is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL. .

  The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 90 ° C. or higher and 145 ° C. or lower, more preferably 100 ° C. or higher and 135 ° C. or lower, and particularly preferably 110 ° C. or higher and 125 ° C. or lower. If the glass transition temperature is less than 90 ° C, the heat resistance is insufficient, and if it is 145 ° C or more, the fluidity is insufficient at the time of molding, and the resin composition is not filled to the end of the product, or the strength at the weld part is reduced. There is.

  In the polycarbonate resin composition of the present invention, one type of polycarbonate resin (A) may be used alone, and the types of structural units derived from other dihydroxy compounds, copolymerization ratios, physical properties, and the like are different. Two or more may be mixed and used.

<Phenolic antioxidant (B)>
The polycarbonate resin composition of the present invention contains a phenolic antioxidant.
Examples of the phenol-based antioxidant include 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, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4, 4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro Examples include (5,5) undecane, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol and the like.

  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, pentaerythritol-tetrakis [3- (3,5-di-tert-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 pentaerythritol- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] A further preferred.

These compounds may use only 1 type and may use 2 or more types together.
When a phenolic antioxidant is added to the polycarbonate resin composition of the present invention, the amount added is usually preferably 0.001 part by mass or more, more preferably 0.001 part by mass relative to 100 parts by mass of the polycarbonate resin (A). 002 parts by mass or more, more preferably 0.005 parts by mass or more, usually 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

  If the amount of the phenolic antioxidant added is more than 5 parts by mass, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. On the other hand, when it is less than 0.001 part by mass, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

<Phosphite Antioxidant (C)>
The polycarbonate resin composition of the present invention contains a phosphite antioxidant.
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

Among these, trisnonylphenyl phosphite, 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 are preferred used.
These compounds may use only 1 type and may use 2 or more types together.

When the phosphite antioxidant is added to the polycarbonate resin composition of the present invention, the addition amount is usually preferably 0.001 parts by mass or more, more preferably 0, relative to 100 parts by mass of the polycarbonate resin (A). 0.002 parts by mass or more, more preferably 0.005 parts by mass or more, usually 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.
If the amount of the phosphite antioxidant added is more than 5 parts by mass, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. On the other hand, when it is less than 0.001 part by mass, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

<Fatty acid ester compound (D) represented by formula (2)>
The polycarbonate resin composition of the present invention contains 100 to 30000 ppm by weight of the fatty acid ester compound represented by the formula (2) with respect to 100 parts by mass of the polycarbonate resin.

(In the above formula (2), one of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the other is a substituted or unsubstituted alkyl group or alkylene group having 10 or more carbon atoms. Represents.)
As the alkyl group of the substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the lower limit value of the carbon number is 1 or more, and the upper limit value is 6 or less, 5 or less is preferable, and 4 or less is most preferable.

The substituted or unsubstituted alkyl group or alkylene group having 10 or more carbon atoms is characterized by a lower limit of 10 or more carbon atoms, characterized by 11 or more, more preferably 12 or more, Most preferred is 13 or less. The upper limit is preferably 30 or less, more preferably 28 or less, and most preferably 26 or less.
Specific examples of the fatty acid ester compound represented by the formula (2) include methyl stearate, ethyl stearate, propyl stearate, butyl stearate, isopropyl stearate, pentyl stearate, hexyl stearate, and methyl erucate. Ethyl erucate, propyl erucate, butyl erucate, pentyl erucate, hexyl erucate, butyl laurate, hexyl laurate, isopropyl palmitate, isopropyl myristate, stearyl caproate and the like.

In the polycarbonate resin composition of the present invention, the fatty acid ester compound (D) represented by the formula (2) is added to the fatty acid ester compound represented by the following formula (2) from 0.01 to 100 parts by mass of the polycarbonate resin. Contains 3% by weight. If the amount of the fatty acid ester compound represented by the formula (2) is too small, it is difficult to obtain a sufficient antistatic effect, and if it is too large, the haze deteriorates. Therefore, 0.05 weight% or more is preferable, 0.1 weight% or more is preferable, 0.15 weight% or more is more preferable, and 0.2 weight% or more is especially preferable. Moreover, 2.5 weight% or less is preferable, 2 weight% or less is preferable, 1.5 weight% or less is more preferable, and 1 weight% or less is especially preferable.

<Additives>
In the polycarbonate resin composition of the present invention, an antioxidant other than the above-described antioxidant, a light stabilizer, an ultraviolet absorber, and the above-described formula (2) within the range in which the scratch resistance and the original image sharpness can be maintained. A release agent other than the fatty acid ester compound represented by the formula, a colorant, a neutralizing agent, an antistatic agent, a lubricant, a lubricant, a plasticizer, a flame retardant, a filler, and the like can be added.

(Antioxidant)
As the antioxidant, a general antioxidant used for a resin can be used, but a sulfur-based antioxidant is preferable from the viewpoint of oxidation stability, thermal stability, jet blackness, and the like.

(Sulfur-based antioxidant)
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) ), Glycerol-3-stearylthiopropionate, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzui Imidazole, 1,1'-thiobis (2-naphthol), and the like.

Among these, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.
These compounds may use only 1 type and may use 2 or more types together.
When a sulfur antioxidant is added to the polycarbonate resin composition of the present invention, the amount added is usually preferably 0.001 part by mass or more, more preferably 0.002 with respect to 100 parts by mass of the polycarbonate resin (A). It is more than mass part, More preferably, it is 0.005 mass part or more, Usually, 5 mass part or less is preferable, More preferably, it is 3 mass part or less, More preferably, it is 2 mass part or less.

  If the amount of the sulfur-based antioxidant added is more than 5 parts by mass, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. On the other hand, when it is less than 0.001 part by mass, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

(Light stabilizer)
Examples of the light stabilizer include hindered amine light stabilizers, and the molecular weight is preferably 1000 or less, and more preferably 900 or less. When the molecular weight exceeds 1000, there is a possibility that sufficient weather resistance cannot be obtained when formed into a molded product. The molecular weight is preferably 300 or more, more preferably 400 or more. If the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated at the time of molding, and a molded product having an excellent surface appearance may not be obtained.

Furthermore, a compound having a piperidine structure is preferable. The piperidine structure defined here may be a saturated 6-membered amine structure, and includes a structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.
As the hindered amine light stabilizer, a compound having a plurality of piperidine structures is particularly preferable, and a compound in which the plurality of piperidine structures are linked by an ester structure is preferable.

  Such light stabilizers include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethylpiperidine-4-carboxylic acid) 1,2,3,4-butanetetrayl, 2,2, Condensate of 6,6-tetramethyl-pyridinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-pyridinol and methanol, 1,2,3, 4-Butanetetracarboxylic acid condensate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphene [Lu] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4, 4-hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane Tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-teto Methyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl) -1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6 , 6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane-diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro- A condensate with 1,3,5-triazine, Condensates of Haq dimethyl and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl piperidine.

When the light stabilizer is added to the polycarbonate resin composition of the present invention, the addition amount is usually 0.001 part by mass or more and 5 parts by mass or less, preferably 0 with respect to 100 parts by mass of the polycarbonate resin (A). 0.005 parts by mass or more and 3 parts by mass or less, more preferably 0.01 parts by mass or more and 1 part by mass or less.
When the added amount of the light stabilizer is more than 5 parts by mass, it tends to be colored, and even if a colorant is added, for example, it is difficult to obtain a jet black with depth and clarity. On the other hand, when it is less than 0.001 part by mass, there is a possibility that sufficient weather resistance may not be obtained when an automobile interior / exterior product is obtained.

(Coloring agent)
Examples of the colorant include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
Inorganic pigments include, for example, carbon black; oxides such as titanium oxide, zinc white, dial, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, etc. Pigments; and the like.

Examples of organic dyes such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensed polycycles such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone Dyes and pigments; anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl dyes; and the like.
These colorants may be used alone or in combination of two or more.

Among organic dyes such as the inorganic pigment, organic pigment and organic dye, inorganic pigments are preferable. By using an inorganic pigment as a colorant, sharpness and the like can be maintained for a long time even when the molded product is used outdoors.
When a colorant is added to the polycarbonate resin composition of the present invention, the addition amount is usually 0.05 parts by mass or more and 5 parts by mass or less, preferably 0. 05 parts by mass or more and 3 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less.
If the added amount of the colorant is less than 0.05 parts by mass, it is difficult to obtain a molded article with sharpness. On the other hand, when the amount is more than 5 parts by mass, the surface roughness of the molded product increases, and it is difficult to obtain an original molded product with sharpness.

(filler)
In the polycarbonate resin composition of the present invention, glass fiber, glass milled fiber, glass flake, glass beads, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate can be used as long as the design can be maintained. Calcium silicate such as talc, mica, wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, titanic acid Potassium fibers, inorganic fillers such as these whiskers, and powdery organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, and pulp powder; crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin, etc. Balun and spherical organic fillers: carbon fiber, synthetic fiber, natural fiber It can be added fibrous organic fillers such as.

<Production method of polycarbonate resin composition>
The polycarbonate resin composition of the present invention is produced by mixing the above components simultaneously in a predetermined ratio or in an arbitrary order by a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. can do.

<Molded product>
When molding a molded article using the polycarbonate resin composition of the present invention, any molding method can be used, but injection molding, injection compression, and injection press molding are preferably used. The runner used at that time can use not only a normal cold runner system but also a hot runner system. Also, insert molding, in-mold coating molding, two-color molding, sandwich molding, and the like are possible. Furthermore, in order to obtain a design property, it is also possible to use heat insulating mold forming and rapid heating / cooling mold forming.

  Since the film, plate, or injection-molded product obtained from the resin composition of the present invention is excellent in transparency, heat resistance, and impact resistance, the use of the resin composition of the present invention is not particularly limited. However, for example, building materials, interior parts, transparent films, films for resin-coated metal plates, films for molding (vacuum and pressure forming, hot press molding, etc.), colored plates, transparent plates, shrink films, shrink labels, shrink tubes, It can be used for automobile interior materials, home appliance housings, various parts, OA equipment parts and other injection molded products.

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

(1) Preparation method of test piece The pellet of the polycarbonate resin composition was dried at 90 ° C. for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 230 ° C., a mold temperature of 60 ° C., and a molding cycle of 45 seconds. (Width 60 mm × length 60 mm × thickness 3 mm) was molded.

(2) Haze measurement In accordance with JIS K7105 (1981), the haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used for the injection-molded plate obtained in (1), and the test piece was tested with a D65 light source. Haze was measured. In addition, 10% or less of haze was set as the pass.

(3) Hue measurement The injection-molded plate obtained in (2) is based on JIS K7105 (1981), using a spectral color difference meter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.), and by the C light source transmission method. The yellow index (YI) value of the test piece was measured. The smaller the YI value, the better the quality without yellowness, and 30 or less was accepted.

(4) Releasability The pellets of the polycarbonate resin composition were dried at 90 ° C. for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. A total of 10 shots (width 100 mm × length 100 mm × thickness 3 mm) were molded, and the releasability was evaluated according to the following criteria.
○: No occurrence of mold releasability in any molded product.
(Triangle | delta): The mold release defect is recognized by some molded articles.
X: Removability defects are recognized in all molded products.
Moreover, the symbol of the compound used by the following example and the comparative example is as follows.

<Raw material of polycarbonate resin (A)>
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
<Phenolic antioxidant>
IRGANOX 1010: Irganox 1010 (manufactured by BASF Japan)
<Phosphite antioxidant>
AS2112: ADK STAB 2112 (made by ADEKA)

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, 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) ~ 0.001 vol%).

  Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.
After the contents thus oligomerized are once restored to atmospheric pressure, they are 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 set to 133 Pa or less over 20 minutes. When the predetermined stirring power was reached, the pressure was restored, the contents were extracted in the form of strands, and pelletized (polycarbonate resin 1) with a rotary cutter.

  Next, two pellets of the obtained polycarbonate resin 1 and butyl stearate as a release agent, and Irganox 1010 and ADK STAB 2112 as antioxidants were used so as to have the composition shown in Table 1 below. Using a twin-screw extruder (LABOTEX30HSS) manufactured by Nippon Steel Works, which has a vent port, it is extruded in a strand shape so that the resin temperature at the exit of the extruder is 250 ° C., cooled and solidified with water, and then rotated with a rotary cutter. Pelletized. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The evaluation results of the obtained pellet-like polycarbonate resin composition according to the above method are shown in Table 1 described later.

[Example 2]
Except that methyl erucate was used in place of butyl stearate as a release agent and the composition shown in Table 1 below was used, the same procedure as in Example 1 was carried out to produce and evaluate the polycarbonate resin composition. The results are shown in Table 1.
[Comparative Example 1]
A polycarbonate resin composition was produced and evaluated in the same manner as in Example 1 except that the release agent was not used and the composition shown in Table 1 below was used. The results are shown in Table 1. .

[Comparative Example 2]
The same procedure as in Example 1 was conducted except that stearic acid was used as a mold release agent and the addition amount was changed so that the composition shown in Table 1 below was obtained, and a polycarbonate resin composition was produced and evaluated. Are shown in Table 1.
[Comparative Example 3]
Using stearyl alcohol as a mold release agent, the same procedure as in Example 1 was carried out except that the amount added was changed to the composition shown in Table 1 below. Are shown in Table 1.

[Comparative Example 4]
Using stearyl stearate as a mold release agent, except that the amount added was changed to the composition shown in Table 1 below, the same procedure as in Example 1 was conducted to produce and evaluate a polycarbonate resin composition. The results are shown in Table 1.
[Comparative Example 5]
Using stearic acid monoglyceride as a mold release agent, except that the amount added was changed to the composition shown in Table 1 below, the same procedure as in Example 1 was conducted to produce and evaluate a polycarbonate resin composition. The results are shown in Table 1.

As is clear from Table 1, the polycarbonate resin composition of the present invention exhibited a low haze and a low YI compared to the polycarbonate resin composition of the comparative example. Therefore, the polycarbonate resin molded product of the present invention has good transparency and color tone such as haze and yellow index value (YI), and is suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. I can see that

  According to the present invention, a polycarbonate resin composition having excellent physical properties such as haze and yellow index value (YI) and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. In addition, a molded product, a film, and a plate obtained by molding the same can be obtained, and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like.

Claims (4)

Polycarbonate resin (A) containing the structural unit (a) derived from the dihydroxy compound represented by the following formula (1), phenolic antioxidant (B), phosphite antioxidant (C) and fatty acid ester compound ( D) a resin composition comprising:
The haze value of the polycarbonate resin (A) measured under the following measurement conditions is 0.8 or less,
The fatty acid ester compound (D) is a fatty acid ester compound represented by the following formula (2),
A polycarbonate resin composition comprising 0.01 to 3% by weight of a fatty acid ester compound represented by the following formula (2) with respect to 100 parts by mass of a polycarbonate resin.

(In the above formula (2), one of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the other is a substituted or unsubstituted alkyl group or alkylene group having 10 or more carbon atoms. Represents.)
(Haze measurement conditions)
Pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.05 parts by weight, tris (2,4-di-tertbutylphenyl) per 100 parts by weight of polycarbonate resin ) The pellets of polycarbonate resin composition containing 0.1 parts by weight of phosphite were pre-dried at 80 ° C. for 4 hours. Next, the pellets of the dried polycarbonate resin composition were measured using a J75EII type injection molding machine manufactured by Nippon Steel Works under the molding conditions of a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, and a mold temperature of 60 ° C. of 60 mm × 60 mm × 3 mmt. Mold a flat plate.
Using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000, the haze of the flat plate shape | molded with the D65 light source is measured.   The polycarbonate resin (A) is a copolymer polycarbonate resin containing a structural unit (b) derived from a dihydroxy compound other than the structural unit (a) derived from the dihydroxy compound represented by the formula (1). The polycarbonate resin composition according to claim 1.   The polycondensation of the polycarbonate resin is performed in the presence of a catalyst, and the catalyst is at least one metal compound selected from the group consisting of metals of Group 2 of the long-period periodic table and lithium. 3. The polycarbonate resin composition according to 1 or 2.   The molded article formed by shape | molding the polycarbonate resin composition of any one of Claims 1-3.