JP2020139115A - Polycarbonate resin composition and molded article thereof - Google Patents

Abstract

To provide a polycarbonate resin composition excellent in impact resistance, light-shielding properties, heat resistance, and dry heat resistance.SOLUTION: The polycarbonate resin composition of the present disclosure contains: a polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit; and an impact resistance modifier (B). The impact resistance modifier (B) is contained in an amount of 1-20 pts.mass based on 100 pts.mass of the polycarbonate resin (A) and is an epoxy group-containing polyethylene.SELECTED DRAWING: None

Description

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

Polycarbonate resins are typically polymers in which aromatic or aliphatic diol compounds are linked with carbonic acid esters. Among them, the polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (sometimes referred to as bisphenol A) has excellent transparency, heat resistance, and mechanical properties such as impact resistance. Due to its properties, it is used in many fields.

Generally, polycarbonate resin is produced using raw materials obtained from petroleum resources. However, in recent years, there is concern about the depletion of petroleum resources, and polycarbonate resins using ether diols produced from sugars of biogenic substances have been studied.

For example, Patent Document 1 proposes a homopolycarbonate resin having a melting point of 203 ° C., which is produced by using a melt transesterification method. Patent Document 2 proposes a polycarbonate resin having a glass transition temperature of 170 ° C. or higher, which is produced by using a tin catalyst. Patent Document 3 proposes a copolymerized polycarbonate of isosorbide and a linear aliphatic diol. Patent Document 4 proposes a decorative sheet including a polycarbonate resin layer containing a plant-derived ether diol residue.

Patent Documents 5 to 7 disclose compositions in which various impact modifying components are added to an isosorbide polycarbonate resin for the purpose of improving impact resistance. Further, as for the polycarbonate resin composition described in Patent Document 8, a composition having improved dry heat resistance is disclosed.

UK Patent Application Publication No. 1079686 International Publication No. 2007/013463 International Publication No. 2004/1110106 International Publication No. 2011/021720 International Publication No. 2012/0083344 International Publication No. 2014/021475 Japanese Unexamined Patent Publication No. 2012-214692 JP-A-2018-30908

For example, when considering the development of a polycarbonate resin prepared using plant-derived isosorbide for industrial use, it is necessary to improve the impact resistance. For example, the ISO 179 notched Charpy impact strength of an isosorbide homopolycarbonate resin having a specific viscosity of 0.33 is about 6 kJ / m ² . This value is inadequate for industrial applications and needs further improvement.

In general, the impact resistance largely depends on the molecular weight that contributes to the specific viscosity of the resin and the like. Therefore, when trying to improve the impact resistance, it is necessary to increase the molecular weight of the resin. The isosorbide polycarbonate resin described in Patent Documents 1 and 2 has a problem that when the molecular weight is increased, the melt viscosity of the resin becomes too high and molding becomes difficult. The polycarbonate resin described in Patent Document 3 also has, for example, a notched Charpy impact strength of a polycarbonate resin having a reduced viscosity of about 0.9, which corresponds to Example 6, according to ISO179, which is about 7 kJ / m ² , which is further applied to industrial applications. Needs improvement.

Patent Documents 5 to 7 disclose isosorbide polycarbonate resin compositions having improved impact resistance, but do not disclose a description regarding dry heat resistance, which is an important test item in an actual environment. According to the studies by the present inventors, it has been found that the impact-resistant modifiers used in the polycarbonate resin compositions described in Patent Documents 5 to 7 are inferior in dry heat resistance.

Further, as for the polycarbonate resin composition described in Patent Document 8, a composition having improved dry heat resistance is shown. On the other hand, since it has high transparency, it has poor light-shielding property, which may cause a problem when it is used for actual light-shielding applications. For example, it has been found that it is not suitable for use as a glass substitute member such as privacy glass for automobiles and smoked glass used for windows and the like. Therefore, a polycarbonate resin composition having excellent impact resistance, light shielding property, heat resistance, and dry heat resistance has been desired.

Therefore, an object of the present disclosure is to provide a polycarbonate resin composition having excellent impact resistance, light shielding property, heat resistance, and dry heat resistance.

〈態様２〉
前記ポリカーボネート樹脂（Ａ）が、ジオールに由来する全構造単位１００モル％に対して前記式１で表される構造単位を３０モル％以上含む、態様１に記載の組成物。
〈態様３〉
前記耐衝撃改質剤（Ｂ）が、エチレン−グリシジル（メタ）アクリレート共重合体である、態様１又は２に記載の組成物。
〈態様４〉
前記ポリカーボネート樹脂（Ａ）が、前記式１以外のジオール化合物に由来する構造単位をさらに含む、態様１〜３のいずれかに記載の組成物。
〈態様５〉
１．８ＭＰａ条件下の荷重たわみ温度が、９０℃以上である、態様１〜４のいずれかに記載の組成物。
〈態様６〉
厚み２ｍｍの成形板にて測定した全光線透過率が、３０％以下である、態様１〜５のいずれかに記載の組成物。
〈態様７〉
厚み２ｍｍの成形板にて測定したヘイズが、５０％以上である、態様１〜６のいずれかに記載の組成物。
〈態様８〉
態様１〜７のいずれかに記載の組成物を用いて成形された、ポリカーボネート樹脂成形品。 <Aspect 1>
It contains a polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit, and an impact resistance modifier (B).
The impact-resistant modifier (B) is contained in a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and is an epoxy group-containing polyethylene. :

<Aspect 2>
The composition according to aspect 1, wherein the polycarbonate resin (A) contains 30 mol% or more of the structural units represented by the formula 1 with respect to 100 mol% of all structural units derived from the diol.
<Aspect 3>
The composition according to aspect 1 or 2, wherein the impact-resistant modifier (B) is an ethylene-glycidyl (meth) acrylate copolymer.
<Aspect 4>
The composition according to any one of aspects 1 to 3, wherein the polycarbonate resin (A) further contains a structural unit derived from a diol compound other than the formula 1.
<Aspect 5>
The composition according to any one of aspects 1 to 4, wherein the deflection temperature under load under 1.8 MPa conditions is 90 ° C. or higher.
<Aspect 6>
The composition according to any one of aspects 1 to 5, wherein the total light transmittance measured on a molded plate having a thickness of 2 mm is 30% or less.
<Aspect 7>
The composition according to any one of aspects 1 to 6, wherein the haze measured on a molded plate having a thickness of 2 mm is 50% or more.
<Aspect 8>
A polycarbonate resin molded product molded using the composition according to any one of aspects 1 to 7.

According to the present disclosure, it is possible to provide a polycarbonate resin composition having excellent impact resistance, light shielding property, heat resistance, and dry heat resistance.

Further, the polycarbonate resin composition of the present disclosure having the above-mentioned performance includes, for example, various kinds of members for films or sheets, members for interior or exterior of electric or electronic devices, members for interior or exterior of various vehicles such as automobiles, bottles and the like. It can be widely used for various purposes such as container or packaging member, building interior or exterior member.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist of the invention.

The polycarbonate resin composition of one embodiment of the present disclosure contains the polycarbonate resin (A) containing the structural unit represented by the following formula 1 as a repeating unit and the impact resistance modifier (B), and the impact resistance modification Polycarbonate resin composition in which the pledge agent (B) is contained in a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A) and is an epoxy group-containing polyethylene:

The polycarbonate resin composition of the present disclosure is excellent in impact resistance, light shielding property, heat resistance, and dry heat resistance. Although not limited by the principle, the principle of action of the polycarbonate resin composition of the present disclosure is considered to be as follows.

The polycarbonate resin composition of the present disclosure contains a specific polycarbonate resin and a specific impact-resistant modifier in a specific ratio. It is considered that the structure of the impact-resistant modifier contributes to the improvement of impact resistance without adversely affecting the heat resistance and dry-heat resistance of the specific polycarbonate resin itself. In addition, neither the polycarbonate resin nor the impact-resistant modifier contains unsaturated bonds in the structure. Therefore, it is presumed that the change in hue is reduced or prevented because the formation of substances that cause coloring is suppressed under heating conditions.

Furthermore, it has been found that the formulation of this specific impact-resistant modifier also contributes to light-shielding properties. In general, the decrease in total light transmittance and the increase in haze value due to the blending of the impact resistance modifier are often caused by the decrease in dispersibility between the polycarbonate resin and the impact resistance modifier. In this case, as the dispersibility of the impact-resistant modifier decreases, other performances such as heat resistance, dry heat resistance, and impact resistance generally decrease. However, the specific impact-resistant modifier of the present disclosure unexpectedly improves the light-shielding property in addition to the impact resistance without adversely affecting the heat resistance and dry heat resistance of the specific polycarbonate resin itself. It was found to get. We believe that this is a predominant action and effect that has not been known so far, which accompanies the selection of a specific polycarbonate resin and a specific impact resistance modifier.

<< Polycarbonate resin composition >>
From the viewpoint of impact resistance and light-shielding property, the polycarbonate resin composition of the present disclosure contains 1 part by mass or more of the impact resistance modifier (B) described later with respect to 100 parts by mass of the polycarbonate resin (A) described later. It is preferable to mix by mass or more, 3 parts by mass or more, or 5 parts by mass or more. The upper limit of the blending amount of the impact-resistant modifier (B) is not particularly limited, but for example, from the viewpoint of appearance performance such as in-plane unevenness of the molded product, it is resistant to 100 parts by mass of the polycarbonate resin (A). It is preferable to blend the impact modifier (B) in an amount of 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less.

The polycarbonate resin composition of the present disclosure is excellent in various performances as shown below.

<Impact resistance>
The polycarbonate resin composition of the present disclosure has excellent impact resistance. For example, the molded product obtained from the polycarbonate resin composition, in Charpy impact strength test described below, 10 kJ / ^{m 2} or more, 15 kJ / ^{m 2} or more, 20 kJ / ^{m 2} or more, or to achieve a 25 kJ / ^{m 2} or more it can. No particular limitation is imposed on the upper limit values, for example, 100 kJ / ^{m 2} or less, it is possible to define 90 kJ / ^{m 2} or less, or 80 kJ / ^{m 2} or less and.

<Shielding performance>
(Total light transmittance)
The polycarbonate resin composition of the present disclosure has excellent shielding properties. For example, when a sheet having a thickness of 2 mm obtained from a polycarbonate resin composition is used, the total light transmittance of the sheet is 30% or less, 20% or less, 10% or less, 5% or less, or 1% or less. be able to. The lower limit is not particularly limited, but may be specified as, for example, 0% or more, more than 0%, or 0.1% or more. Here, in the present disclosure, the "total light transmittance" indicates the level of transparency, and means the ratio of transmitted light to incident light by the method E308 of ASTM-D1003-61.

(Haze)
The light-shielding property can be specified not only by the total light transmittance but also by the haze. For example, when a sheet having a thickness of 2 mm obtained from a polycarbonate resin composition is used, the haze in the sheet can be 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more. .. This upper limit is not particularly limited, but may be specified as, for example, 100% or less, less than 100%, or 99% or less. Here, in the present disclosure, "haze" indicates the level of transparency, and the ratio (%) of transmitted light deviating from the incident luminous flux due to forward scatter when passing through the test piece according to ASTM-D1003-61. ) Means.

<Heat-resistant>
The polycarbonate resin composition of the present disclosure has excellent heat resistance. The heat resistance is intended to cause less deformation of the molded product under high temperature, and can be evaluated by, for example, a deflection temperature test under load described later. The molded product obtained from the polycarbonate resin composition can achieve 90 ° C. or higher, 95 ° C. or higher, or 100 ° C. or higher in such a deflection temperature test under load. The upper limit is not particularly limited, but may be specified as, for example, 130 ° C. or lower, 120 ° C. or lower, or 110 ° C. or lower.

<Dry heat resistance>
The polycarbonate resin composition of the present disclosure is excellent in dry heat resistance. The dry heat resistance is intended to mean that when the molded product is left at a high temperature for a long period of time, there is little change in hue or deterioration of the molded product. For example, a molded product obtained from a polycarbonate resin composition can achieve a yellowing degree (ΔYI) of 10 or less, 8 or less, or 5 or less in a dry heat resistance test described later. The lower limit is not particularly limited, but may be specified as, for example, 0.1 or more, 0.5 or more, or 1 or more.

<Polycarbonate resin (A)>
The polycarbonate resin (A) of the present disclosure contains a structural unit represented by the following formula 1 as a repeating unit:

(Structural unit represented by Equation 1)
The ratio of the structural units represented by the formula 1 is not particularly limited, but from the viewpoint of substitution from petroleum resources, heat resistance, impact resistance, etc., for example, 100 mol% of all structural units derived from diol. On the other hand, it can be 30 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more, and particularly preferably 50 mol% or more. The upper limit of the structural unit is not particularly limited, but may be specified as, for example, 100 mol% or less, 90 mol% or less, or 80 mol% or less. Here, the molar ratio of structural units in the polycarbonate resin can be measured and calculated using, for example, proton NMR of JNM-AL400 manufactured by JEOL Ltd.

The structural unit of the formula 1 can include the structural unit represented by the following formulas 1-1 to 1-3, which are related to stereoisomers:

These structural units are derived from carbohydrate-derived ether diols. Such an ether diol is, for example, a substance obtained from natural biomass or the like, and is one of the substances called renewable resources.

The structural units represented by the formulas 1-1 to 1-3 are derived from substances called isosorbide, isomannide, and isoidide, respectively. For example, isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can also be obtained by the same reaction except for the starting material.

Among isosorbide, isomannide, and isosorbide, isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is preferable. A polycarbonate resin containing a structural unit derived from isosorbide as a repeating unit is relatively easy to manufacture and has excellent heat resistance.

(Structural unit other than Equation 1)
The polycarbonate resin (A) may contain as a repeating unit other structural units derived from various diol compounds other than the structural unit represented by the formula 1. The diol compound (diol monomer) may be any of an aliphatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound, and for example, a diol compound as described in Patent Documents 3 and 4 and a diol compound. Examples thereof include oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol. These may be used alone or in combination of two or more. Representative diol compounds are illustrated below, but are not limited thereto.

Examples of the aliphatic diol compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1.9-nonanediol. , 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl -1,3-Propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, 2- Ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. Can be mentioned.

Examples of the alicyclic diol compound include cyclohexanedimethanol, tricyclodecanedimethanol, adamantandiol, pentacyclopentadecanedimethanol, and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4. , 8,10-Tetraoxaspiro [5.5] undecane, 2,2,4,4-tetramethylcyclobutanediol, 1,1'-spirobiindane-6,6'-diol, decalin-2,6-dimethanol , Norbornane dimethanol, cyclopentane-1,3-dimethanol and the like.

Examples of the aromatic dihydroxy compound include α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis ( 4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane (Bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF), biphenol, 1,1-bis (4-hydroxyphenyl) Decane, bis (2-hydroxyethoxy) naphthalene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -1,8-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy)- 3-Methylphenyl) -1,8-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -1,8-diphenylfluorene, 9,9-bis (4-( 2-Hydroxyethoxy) -1-naphthyl) -1,8-diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -1,8-diphenylfluorene, 9,9-bis (4-Hydroxyphenyl) -1,8-diphenylfluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -1,8-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenyl) Phenyl) -1,8-diphenylfluorene, 9,9-bis (4-hydroxy-1-naphthyl) -1,8-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -1,8 −Diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,7-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -2 , 7-Diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -2,7-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1) −naphthyl) -2,7-diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -2,7-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -2,7-Diphenylfluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -2,7-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -2,7 -Diphenylfluorene, 9,9-bis (4-hydroxy-1-naphthyl) -2,7-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -2,7-diphenylfluorene, 9, 9-bis (4- (2-hydroxyethoxy) phenyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1-naphthyl) -3, 6-Diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -3,6-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -3,6-diphenylfluorene , 9,9-bis (4-hydroxy-3-methylphenyl) -3,6-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -3,6-diphenylfluorene, 9,9 -Bis (4-hydroxy-1-naphthyl) -3,6-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -3,6-diphenylfluorene, 9,9-bis (4-( 2-Hydroxyethoxy) phenyl) -4,5-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -4,5-diphenylfluorene, 9,9-bis (4) -(2-Hydroxyethoxy) -3-phenylphenyl) -4,5-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1-naphthyl) -4,5-diphenylfluorene, 9, 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -4,5-diphenylfluorene, 9,9-bis ( 4-Hydroxy-3-methylphenyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxy- 1-naphthyl) -4,5-diphenylfluorene, 9,9-bis ( 6-Hydroxy-2-naphthyl) -4,5-diphenylfluorene, 2,2'-bis (2-hydroxyethoxy) -3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis ( 2-Hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthyl, 2,2 '-Bis (2-hydroxyethoxy) -3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -6,6'-dimethyl-1,1'-binaphthyl , 2,2'-bis (2-hydroxyethoxy) -7,7'-dimethyl-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene and the like.

The proportion of structural units derived from diol compounds other than formula 1 is 70 mol% or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less with respect to 100 mol% of all structural units derived from diols. Can be. The lower limit of the structural unit is not particularly limited, but may be specified as, for example, more than 0%, 10 mol% or more, or 20 mol% or more.

(Manufacturing method of polycarbonate resin (A))
The method for producing the polycarbonate resin (A) is not particularly limited, and a known production method for a normal polycarbonate resin can be adopted. For example, it can be produced by a method of reacting a diol component with a carbonic acid precursor such as a carbonic acid diester. Hereinafter, some embodiments of the method for producing the polycarbonate resin (A) will be described.

The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method in which a predetermined proportion of the diol component is stirred with the carbonic acid diester while heating in an inert gas atmosphere to distill off the produced alcohol or phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by reducing the pressure from the initial stage and distilling off the produced alcohols or phenols. Further, if necessary, a terminal terminator, an antioxidant or the like may be used.

The carbonic acid diester used in the transesterification reaction is not particularly limited, and examples thereof include esters such as an aryl group or an aralkyl group having 6 to 12 carbon atoms which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable.

The amount of carbonic acid diester used, particularly diphenyl carbonate, is preferably in the range of 0.97 to 1.10 mol, preferably in the range of 1.00 to 1.06 mol, based on 1 mol of the total dihydroxy compound. Is more preferable.

Further, in the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate. Examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, metal compounds and the like. These compounds can be used alone or in combination of two or more. Among them, compounds of alkali metals or alkaline earth metals such as organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides and quaternary ammonium hydroxides are preferably used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, and acetate. Lithium, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate , Disodium hydrogen phosphate, disodium phenylphosphate, disodium salt of bisphenol A, dipotassium salt, dicesium salt, dilithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt and the like.

Examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, and strontium diacetate. Examples thereof include barium diacetate and barium stearate.

Examples of the nitrogen-containing compound include alkyl and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide, and quaternary ammonium hydroxide. Kind. Examples thereof include tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Examples thereof include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate and tetraphenylammonium tetraphenylborate.

Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like.

The amount of the polymerization catalyst used is preferably 1 × ^10-9 to 1 × 10 ⁻² equivalents, more preferably 1 × ^10-8 to 1 × 10 ⁻⁵ equivalents, particularly 1 × 10 ⁻⁹ to 1 × 10 ⁻² equivalents, relative to 1 mol of the diol component. It is preferably 1 × 10 ^-7 to 1 × 10 ^-3 equivalents.

It is also possible to add a catalyst deactivating agent in the latter stage of the reaction. The catalyst deactivating agent to be used is not particularly limited, but a known catalyst deactivating agent is effectively used. Of these, ammonium salts of sulfonic acids, phosphonium salts of sulfonic acids, and esters of sulfonic acids are preferable. These can be used alone or in combination of two or more.

Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

Examples of the ester of sulfonic acid include methyl benzenesulfonic acid, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonic acid, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, and paratoluene. Butyl sulfonate, octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Of these, the tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is most preferably used.

The amount of these catalyst deactivators used is 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from the alkali metal compound and the alkaline earth metal compound is used. The ratio is preferably 0.5 to 10 mol, and particularly preferably 0.8 to 5 mol.

The polycarbonate resin (A) of the present disclosure thus obtained can have the following properties.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin (A) of the present disclosure is preferably in the range of 0.2 to 1.5 from the viewpoint of molding processability, strength of the obtained molded product, and the like. It is more preferably in the range of 25 to 1.2, further preferably in the range of 0.3 to 1.0, and particularly preferably in the range of 0.3 to 0.5.

The specific viscosity can be obtained from the solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer from the following formula 2.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ … Equation 2
Here, t ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall.

More specifically, the polycarbonate resin is dissolved in methylene chloride having a weight of 20 to 30 times that of the polycarbonate resin, and the methylene chloride-soluble component is collected through Celite filtration, and then sufficiently dried to remove methylene chloride to remove methylene chloride-soluble. Obtain a solid polycarbonate resin from the minutes. The specific viscosity at 20 ° C. is determined from a solution of 0.7 g of the obtained solid in 100 ml of methylene chloride using an Ostwald viscometer.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin (A) of the present disclosure is preferably in the range of 100 to 160 ° C., preferably in the range of 110 to 150 ° C. from the viewpoint of heat resistance stability and moldability. Is more preferable, and the range of 120 to 140 ° C. is particularly preferable.

The glass transition temperature (Tg) can be measured at a heating rate of 20 ° C./min using, for example, a 2910 type DSC measuring device manufactured by TA Instruments Japan Co., Ltd.

(5% weight loss temperature: Td)
The 5% weight loss temperature (Td) of the polycarbonate resin (A) of the present disclosure is preferably 280 ° C. or higher, or 300 ° C. or higher, from the viewpoint of the decomposition resistance of the resin during molding. It is preferably 400 ° C. or lower, 390 ° C. or lower, or 380 ° C. or lower. The 5% weight loss temperature can be measured by, for example, a TGA measuring device (model TGA2950) manufactured by TA Instruments.

(Melting viscosity)
The polycarbonate resin (A) of the present disclosure has a melt viscosity measured by a capillary leometer at 240 ° C. in the range of 0.01 × 10 ^{3 to} 1.10 × 10 ³ Pa · s under the condition of a share rate of 6080 sec ^-1. It is preferably in the range of 0.05 × 10 ^{3 to} 1.0 × 10 ³ Pa · s, more preferably in the range of 0.1 × 10 ^{3 to} 0.8 × 10 ³ Pa · s. It is more preferable to have. When the melt viscosity is in such a range, the fluidity is good, so that secondary processing such as injection molding can be performed at a low temperature, and deterioration due to heat of the resin such as deterioration of hue and degree of polymerization can be reduced. Since it can be prevented, the defect rate at the time of molding can be reduced, and a molded product having sufficient mechanical strength can be obtained.

<Impact resistant modifier (B)>
The polycarbonate resin composition of the present disclosure contains an impact-resistant modifier (B). The impact-resistant modifier (B) is not particularly limited as long as it is an epoxy group-containing polyethylene, that is, polyethylene having an epoxy group, and may be, for example, a copolymer of ethylene and a compound having an epoxy group. However, polyethylene may be graft-modified with a compound having an epoxy group.

As the compound having an epoxy group used for producing the epoxy group-containing polyethylene, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity. Therefore, as the impact-resistant modifier (B), an ethylene-glycidyl (meth) acrylate copolymer is particularly preferably used. Here, in the present disclosure, (meth) acrylate means acrylate or methacrylate.

The content of the epoxy group in the epoxy group-containing polyethylene is preferably 1% by mass or more, 2% by mass or more, or 3% by mass or more from the viewpoint of impact resistance, light shielding property, etc., and also contains an epoxy group. From the viewpoint of ease of production of polyethylene, it is preferably 20% by mass or less, 15% by mass or less, or 10% by mass.

The epoxy group-containing polyethylene may contain a copolymerization component having an ethylenic double bond in addition to ethylene. Examples of such a copolymerization component include alkyl (meth) acrylate, acrylonitrile, α-olefin, conjugated diene and the like. Among these, from the viewpoint of good polymerization reactivity as a raw material monomer for epoxy group-containing polyethylene, methyl (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, vinyl acetate, styrene, butadiene, acrylonitrile, and At least one selected from the group consisting of propylene is preferable, and methyl acrylate and / or vinyl acetate is more preferable.

The impact-resistant modifier (B) of the present disclosure can be obtained as a commercially available product. Examples of commercially available products include "BONDFAST" manufactured by Sumitomo Chemical Co., Ltd., which is an ethylene-glycidyl methacrylate (GMA) copolymer, and "LOTADER" manufactured by Arkema.

Only one type of epoxy group-containing polyethylene may be used, or, for example, two or more types having different ethylene unit contents, copolymerization components, physical properties, etc. may be used in combination.

The average particle size of the impact-resistant modifier (B) is not particularly limited, but is preferably 10 nm or more, 15 nm or more, or 20 nm or more, and 1000 nm, for example, from the viewpoint of impact resistance, light-shielding property, and the like. Hereinafter, it is preferably 900 nm or less, or 800 nm or less. Here, the average particle size of the impact-resistant modifier (B) can be measured by, for example, a dynamic light scattering method.

<Arbitrary ingredient>
The polycarbonate resin composition of the present disclosure can optionally be, for example, a heat stabilizer, a mold release agent, an ultraviolet absorber, a light stabilizer, a brewing agent, a dye, a fluorescent dye, a filler, a pigment, a polycarbonate plasticizer, a flame retardant. , Additives such as lubricants, antibacterial agents, surfactants, antistatic agents, and other resin components other than the polycarbonate resin (A) can be appropriately contained. These optional components may be used alone or in combination of two or more. Some of these additives are described in more detail below.

The method for mixing the polycarbonate resin (A) and various optional components is not particularly limited, and any commonly used polymer blending method may be used. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like, or each optional component is dissolved in a common good solvent such as methylene chloride. Examples thereof include a solution blending method in which the mixture is mixed in a state.

The polycarbonate resin composition of the present disclosure can exhibit light-shielding properties by using the polycarbonate resin (A) and the impact-resistant modifier (B) in combination. Therefore, the polycarbonate resin composition of the present disclosure is a conventional light-shielding polycarbonate resin containing an inorganic pigment because it is not necessary to mix the inorganic pigment, which has been conventionally blended to impart light-shielding properties, into the composition. It can also be lighter than the material. When the inorganic pigment is blended in the polycarbonate resin composition of the present disclosure, the blending amount of the inorganic pigment is 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less per 100 parts by mass of the polycarbonate resin (A). It can be 10 parts by mass or less, or 5 parts by mass or less.

Further, the impact-resistant modifier used in the polycarbonate resin compositions described in Patent Documents 5 to 7 is composed of a rubber or an elastomer containing an acrylic component, a butadiene component, a styrene component and the like, and is composed of the present inventor. According to these studies, it was found that such an impact-resistant modifier reduces the dry-heat resistance performance. Therefore, from the viewpoint of dry heat resistance, the polycarbonate resin composition of the present disclosure is composed of a shock-resistant modifier composed of rubber or elastomer, particularly rubber or elastomer containing an acrylic component, a butadiene component, a styrene component and the like. It is preferable that the impact-resistant modifier is not contained, and when the impact-resistant modifier is blended, 40 parts by mass or less, 30 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the polycarbonate resin (A). It is preferably 10 parts by mass or less, or 5 parts by mass or less.

(Heat stabilizer)
The polycarbonate resin (A) preferably contains a heat stabilizer in order to suppress a decrease in molecular weight and deterioration of hue during various moldings such as extrusion. In particular, since the ether diol residue of the structural unit represented by the above formula 1 is deteriorated by heat and oxygen and easily colored, it is preferable to contain a phosphorus-based heat stabilizer as the heat stabilizer. Further, as a phosphorus-based heat stabilizer, it is more preferable to blend a pentaerythritol-type phosphite compound or a phosphite compound that reacts with divalent phenols and has a cyclic structure.

Examples of the pentaerythritol-type phosphyte compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-). 4-Mentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol Diphosphite, dicyclohexerythritol pentaerythritol diphosphite and the like, and more preferably, distearyl pentaerythritol diphosfite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosfite can be mentioned. ..

Examples of the phosphite compound that reacts with divalent phenols and has a cyclic structure include 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phos. Fight, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phos Fight, 2,2'-methylene-bis- (4,6-di-t-butylphenyl) octylphosphite, 6-tert-butyl-4- [3-[(2,4,8,10) -tetra Examples thereof include -tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] propyl] -2-methylphenol.

Examples of other phosphorus-based heat stabilizers include various phosphite compounds, phosphate compounds, phosphonite compounds, and phosphonate compounds other than the above.

Examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, and diisopropyl. Monophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris (diethylphenyl) phos Fight, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, and Tris (2,6-di) -Tart-butylphenyl) phosphite and the like.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate and dioctyl. Examples thereof include phosphate and diisopropyl phosphate, with preference given to triphenyl phosphate and trimethyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-. Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenedi Phenylonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite , Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, Bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, Bis (2,6) −Di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl) Examples thereof include phenyl) -3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable. 2,4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferable. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the above alkyl group is substituted by 2 or more.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like.

The above phosphorus-based heat stabilizer can be used alone or in combination of two or more, but at least an effective amount of a pentaerythritol-type phosphite compound or a phosphite compound having a cyclic structure that reacts with dihydric phenols is blended. It is preferable to do so.

The blending amount of the phosphorus-based heat stabilizer is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, and further preferably 1 part by mass, per 100 parts by mass of the polycarbonate resin (A). It is 0.01 to 0.3 parts by mass.

A hindered phenol-based heat stabilizer is added in combination with a phosphorus-based heat stabilizer as a heat stabilizer for the purpose of suppressing a decrease in molecular weight and deterioration of hue during molding such as extrusion of the polycarbonate resin (A). You can also do it.

The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function, and is, for example, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-. Butylphenyl) propionate, tetrakis {methylene-3- (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate} methane, distearyl (4-hydroxy-3-methyl-5-t-butylbenzyl) ) Malonate, triethireglycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,3) 5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3) , 5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis {(octylthio) methyl} -o -Cresol, Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2 (4', 8', 12'-trimethyltridecyl ) Chroman-6-ol, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri- Examples thereof include p-cresol.

Among them, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate}, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a'-(mesitylen-2,4,6-triyl) tri-p -Cresol, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} and the like are preferable.

These hindered phenolic heat stabilizers may be used alone or in combination of two or more.

The blending amount of the hindered phenol-based heat stabilizer is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, and further, per 100 parts by mass of the polycarbonate resin (A). It is preferably 0.01 to 0.3 parts by mass.

(Release agent)
In order to further improve the mold release property from the mold during melt molding, the polycarbonate resin (A) can be blended with a mold release agent within a range that does not impair the object of the present invention.

Examples of the release agent include higher fatty acid esters of monovalent or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic acid anhydride groups, and silicones. Examples include oil and organopolysiloxane.

As the higher fatty acid ester, for example, a partial ester or a total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of the partial ester or total ester of the monovalent or polyvalent alcohol and the saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.

Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenic behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

These release agents may be used alone or in combination of two or more. The amount of the release agent to be blended is preferably 0.01 to 5 parts by mass when the polycarbonate resin (A) is 100 parts by mass.

(UV absorber, light stabilizer)
The polycarbonate resin composition of the present invention may contain an ultraviolet absorber and a light stabilizer as long as the object of the present invention is not impaired. The ultraviolet absorber and the light stabilizer may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl). Examples thereof include benzophenone-based ultraviolet absorbers typified by methane. Examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole. , 2- (2'-Hydroxy-3', 5'-bis (α, α'-dimethylbenzyl) phenylbenzotriazole, 2,2' methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol Examples thereof include benzotriazole-based ultraviolet absorbers typified by the condensate of 2- (4,6-diphenyl-1,3,5-triazine-2-yl) as the ultraviolet absorber. Hydroxyphenyltriazine compounds such as -5-hexyloxyphenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol Can be mentioned.

Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and tetrakis. (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,3,4-diyl) 2,6,6-Tetramethylpiperidyl) imino] Hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, Polymethylpropyl 3-oxy- [4- (2,2,6,6) -Tetramethyl) piperidinyl] A hindered amine-based light stabilizer typified by siloxane can be mentioned. Such a light stabilizer can exhibit better performance in terms of weather resistance and the like when used in combination with the above-mentioned ultraviolet absorber and various antioxidants.

The blending amount of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 2 parts by mass when the polycarbonate resin (A) is 100 parts by mass.

(Bluing agent)
A brewing agent can be added to the composition of the present disclosure in order to counteract the yellowness of the molded product caused by the polycarbonate resin or the ultraviolet absorber. The brewing agent is not particularly limited as long as it is used for a polycarbonate resin. In general, anthraquinone dyes are preferable because they are easily available.

Specific examples of the brewing agent include the generic name Solvent Violet 13 (CA. No. (color index No.) 60725), the generic name Solvent Violet 31 (CA. No. 68210), and the generic name Solvent Violet 33 (CA. No.). 60725), generic name Solvent Blue94 (CA.No.61500), generic name Solvent Violet36 (CA.No.68210), generic name Solvent Blue97 (Bayer's "Macrolex Violet RR") and generic name Solvent Blue45 (CA. No. 61110) is a typical example.

These brewing agents may be used alone or in combination of two or more. These brewing agents are usually blended in a proportion of 0.1 × 10 ^-4 to 2 × 10 ^-4 parts by mass when the polycarbonate resin (A) is 100 parts by mass.

(Fluorescent dye, dye)
The compositions of the present disclosure may contain fluorescent dyes and other dyes as long as the object of the present invention is not impaired.

The fluorescent dye is not particularly limited as long as it can be used for a thermoplastic resin, and examples thereof include xanthene-based, thiazole-based, thiazine-based, perylene-based, coumarin-based, and diaminostilbene-based fluorescent dyes. In particular, perylene-based and coumarin-based fluorescent dyes are preferable. Such fluorescent dyes are commercially available and can be easily obtained, for example, as Lumogen Color manufactured by BASF, Fluoresent manufactured by Arimoto Chemical Industry, and Macrolex manufactured by Baycr.

When the polycarbonate resin (A) is 100 parts by mass, the fluorescent dye is preferably blended in a proportion of 0.001 to 5 parts by mass in consideration of fluorescence and discoloration resistance, and is preferably 0.01 to 2 parts by mass. It is more preferable to mix in a proportion of parts.

(filler)
The composition of the present disclosure may contain a filler as long as the object of the present invention is not impaired. Examples of such fillers include inorganic fillers and organic fillers. The shape of the filler may be any shape such as a particle shape, a fibrous shape, and a plate shape. Further, the filler may be used alone or in combination of two or more.

Examples of the inorganic filler include glass fiber, glass milled fiber, glass flakes, glass beads, silica particles, alumina particles, titanium oxide particles, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate particles, talc, mica and wax. Calcium silicate such as lastnite; carbon fiber, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide particles, silicon carbide fiber, silicon nitride particles, silicon nitride fiber, brass fiber, stainless fiber and potassium titanate. Examples include fibers and these whiskers. Among these, glass fibrous fillers, glass powder fillers, glass flake fillers; various whiskers, mica or talc are preferred. More preferably, it is glass fiber, glass flakes, glass milled fiber, wallastnite, mica or talc, and particularly preferably glass fiber and / or talc.

As the glass fiber or the glass milled fiber, any one used for the thermoplastic resin can be used, but a glass fiber made of non-alkali glass (E glass) is particularly preferable.

The diameter of the glass fiber is preferably 6 μm to 20 μm, and more preferably 9 μm to 14 μm in consideration of the reinforcing effect and the balance of the appearance of the molded product.

Further, as the glass fiber, chopped strands cut to a length of 1 mm to 6 mm, glass milled fiber crushed to a length of 0.01 mm to 0.5 mm, and the like can also be preferably used.

The glass fiber is a surface treatment with a silane coupling agent such as aminosilane or epoxysilane in order to improve the adhesion with the polycarbonate resin (A), or an acrylic resin or urethane resin in order to improve handleability. It may be focused by such as.

The glass beads may be any glass beads as long as they are used for the thermoplastic resin. Of these, those composed of non-alkali glass (E glass) are preferable. As the glass beads, spherical beads having an average particle size of 10 μm to 50 μm are preferable.

Examples of the glass flakes include scaly glass flakes. The maximum diameter of the glass flakes after blending with the polycarbonate resin composition is preferably 1000 μm or less, and more preferably 1 μm to 500 μm. The aspect ratio (ratio of maximum diameter to thickness) of the glass flakes is preferably 5 or more, 10 or more, or 30 or more. The upper limit of the aspect ratio is not particularly limited, and can be, for example, 10,000 or less, preferably 200 or less. The aspect ratio of such glass flakes is a value in the resin composition.

The carbon fiber is not particularly limited, and is produced by firing using, for example, acrylic fiber, petroleum or carbon-based special pitch, cellulosic fiber, lignin, or the like as a raw material, and is of flame resistance, carbon, or graphite. Various things can be mentioned.

Considering the conductivity, strength, rigidity, etc. of the polycarbonate resin composition, the diameter of the carbon fibers is preferably 3 μm to 15 μm, and the average value of the aspect ratio (fiber length / fiber diameter) of the carbon fibers is It is preferably 10 or more, 30 or more, or 50 or more. The upper limit of the aspect ratio is not particularly limited, and can be, for example, 10,000 or less, preferably 200 or less. The aspect ratio of such carbon fibers is a value in the resin composition.

As long as the characteristics of the polycarbonate resin composition of the present disclosure are not impaired, the carbon fibers may be subjected to surface treatment such as epoxy treatment, urethane treatment or oxidation treatment in order to improve the affinity with the polycarbonate resin. May be given.

Examples of the organic filler include powdered organic fillers such as wood powder, bamboo powder, coconut starch, curk powder and pulp powder; balun-like and spherical particles such as crosslinked polyester, polystyrene, styrene / acrylic copolymer and urea resin. Organic fillers; Examples include fibrous organic fillers such as synthetic fibers and natural fibers.

The amount of the filler is preferably 1 part by mass or more, 2 parts by mass or more, or 5 parts by mass or more per 100 parts by mass of the polycarbonate resin in consideration of the reinforcing effect and the balance of the appearance of the molded product. , 100 parts by mass or less, 70 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less.

<Manufacturing method of polycarbonate resin composition>
The method for producing the polycarbonate resin composition of the present disclosure is not particularly limited. For example, the polycarbonate resin (A), the impact-resistant modifier (B), and optional components (hereinafter, these may be collectively referred to as “each component”) are premixed, and then melt-kneaded and pelletized. Can be manufactured in the form of polycarbonate.

Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the premixing, granulation can also be performed by an extrusion granulator, a briquetting machine, or the like.

After premixing, the mixture is melt-kneaded with a melt-kneader typified by a bent twin-screw extruder, and pelletized with a device such as a pelletizer. Examples of the melt kneader include a Banbury mixer, a kneading roll, a constant heat stirring vessel, and the like, but a vent type twin-screw extruder is preferable. In addition, a method of independently supplying each component to a melt kneader typified by a twin-screw extruder can also be adopted without premixing each component. The cylinder temperature at the time of melt-kneading is preferably 180 to 270 ° C., more preferably 190 to 260 ° C., and further preferably 200 to 250 ° C. in consideration of thermal decomposition of the polycarbonate resin and the like.

The polycarbonate resin composition of the present disclosure is preferably produced by melt-kneading each component using an extruder. As the extruder, a twin-screw extruder is particularly suitable, and one having a vent capable of degassing water in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. It is preferable that the vent is equipped with a vacuum pump for efficiently discharging the generated water and volatile gas to the outside of the extruder.

It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the polycarbonate resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (for example, a disc filter) and the like.

The method for supplying the impact-resistant modifier (B) and the optional component (hereinafter, these may be collectively referred to as “additive”) to the extruder is not particularly limited, but the following (i) to (i) to Method (iv) is typically exemplified:
(I) A method of supplying an additive into an extruder independently of the polycarbonate resin (A).
(Ii) A method in which the resin powder of the polycarbonate resin (A) and the additive are premixed using a mixer such as a super mixer and then supplied to the extruder.
(Iii) A method in which an additive and a polycarbonate resin (A) are melt-kneaded in advance to form a master pellet.
(Iv) As another premixing method, a method in which the polycarbonate resin (A) and the additive are uniformly dispersed in a solvent, and then the solvent is removed.

The polycarbonate resin composition extruded from the extruder can be directly cut and pelletized, or the strands can be cut with a pelletizer and pelletized after forming the strands. When it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder.

Further, in the production of pellets, the methods already proposed for polycarbonate resins for optical discs and cyclic polyolefin resins for optics are used to narrow the shape distribution of pellets, reduce miscuts, and occur during transportation or transportation. It is preferable to appropriately reduce the amount of fine powder and the number of bubbles (vacuum bubbles) generated inside the strands and pellets. With these formulations, it is possible to increase the cycle of molding and reduce the occurrence rate of defects such as silver.

The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, still more preferably 2.5 to 3.5 mm.

<Molding>
The polycarbonate resin composition of the present disclosure is excellent in impact resistance, light shielding property, heat resistance, and dry heat resistance. Therefore, the molded product formed by using the polycarbonate resin composition having such performance includes, for example, interior or exterior members of electric or electronic devices, interior or exterior members of various vehicles such as automobiles, bottles and the like. It can be widely used for various purposes such as various container or packaging members, building interior or exterior members. Specifically, the molded product can be used, for example, as a substitute for flat or curved glass such as smoked glass or privacy glass, or as a smoked film or privacy film used by adhering to glass or the like.

The shape of the molded product is not particularly limited, and various shapes such as a planar shape such as a film, a sheet, or a plate, a curved surface shape, and a three-dimensional shape can be adopted.

<Manufacturing method of molded products>
The molded product obtained from the polycarbonate resin composition of the present disclosure can be produced by a known method such as injection molding or extrusion molding.

When formed by injection molding, the cylinder temperature is preferably in the range of 180 to 270 ° C., more preferably in the range of 190 to 260 ° C., in order to suppress coloring and decrease in molecular weight due to decomposition of the polymer. preferable. The mold temperature can be in the range of 40 to 140 ° C., but is preferably in the range of 40 to 120 ° C., preferably 40 to 100 ° C., from the viewpoint of shortening the molding cycle and the melt residence time of the resin. More preferably, it is in the range.

The injection molding can be performed not only by a normal cold runner type molding method but also by a hot runner type molding method. In injection molding, not limited to the usual injection molding method, injection compression molding, injection press molding, gas assisted injection molding, foam molding, insert molding, in-mold coating molding, heat insulating mold molding, rapid molding, depending on the purpose as appropriate. Injection molding methods such as heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding can also be used. Here, the foam molding also includes foam molding by injecting a supercritical fluid.

Further, the polycarbonate resin composition of the present disclosure can be extruded into, for example, an extruded product having a tube shape or various irregular shapes, or an extruded product such as a sheet or a film. In the molding of the sheet and the film, for example, an inflation method, a calendar method, a casting method and the like can also be used. It can also be molded as a heat shrink tube by a specific stretching operation. Further, a molded product can be obtained by using a rotary molding method, a blow molding method, or the like.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited thereto.

<< Examples 1 and 2 and Comparative Examples 1 to 8 >>
The polycarbonate resin obtained by the methods shown in Synthesis Examples 1 and 2 below and the composition containing the resin were evaluated as follows, and the results are shown in Tables 1 and 2. Here, the numerical values of the polycarbonate resin and the impact resistance modifier in Table 2 are all parts by mass.

<Evaluation of polycarbonate resin>
(Specific viscosity (η _sp ))
The pellets obtained in each synthesis example were dissolved in methylene chloride, the concentration of the polycarbonate resin was about 0.7 g / dL, and the temperature was 20 ° C. Was used to determine the specific viscosity (η _sp ) from Equation 3 below:
_{η sp = t / t o -1} ... Equation 3
Here, t is the flow time of the sample solution, t _o is the flow time of the solvent alone.

(Melting viscosity)
It was obtained as a result of measurement using a capillary rheometer (capillograph model 1D) manufactured by Toyo Seiki Co., Ltd. under the conditions of a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 240 ° C. The melt viscosity at 6080 sec ^-1 was read based on the Shear Rate / Viscosity curve.

(Glass transition temperature (Tg))
Using a DSC measuring device (model DSC2910) manufactured by TA Instruments, about 10 mg of pellets obtained in each synthetic example was heated at a heating rate of 20 ° C./min to measure the glass transition temperature.

(5% weight loss temperature)
Using a TGA measuring device (model TGA2950) manufactured by TA Instruments, about 10 mg of pellets obtained in each synthetic example was heated at a heating rate of 20 ° C./min, and a 5% weight loss temperature was measured.

<Evaluation of polycarbonate resin>
(Charpy impact strength (impact resistance))
The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C. for 12 hours, and then tested using JSWJ-75EIII manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 240 ° C. and a mold temperature of 90 ° C. The piece was molded. Using the obtained test piece, a notched Charpy impact test was performed in accordance with ISO179, and the Charpy impact strength was measured.

(Deflection temperature under load (heat resistance))
The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C. for 12 hours, and then tested using JSWJ-75EIII manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 240 ° C. and a mold temperature of 90 ° C. The piece was molded. With respect to the obtained test piece, the deflection temperature under load under a high load (1.8 MPa) was measured according to ISO75.

(Total light transmittance)
After drying the pellets of the polycarbonate resin composition obtained in each example at 80 to 110 ° C. for 12 hours, a molding temperature of 240 ° C. and gold were used using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.). Width 50 mm, length 90 mm, thickness 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm) from the gate side at a mold temperature of 80 ° C. and a molding cycle of 50 seconds. A three-stage plate having an arithmetic average roughness (Ra) of 0.03 μm was formed. The total light transmittance of the three-stage plate at a thickness of 2.0 mm was measured using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to ISO13468.

(Haze)
After drying the pellets of the polycarbonate resin composition obtained in each example at 80 to 110 ° C. for 12 hours, a molding temperature of 240 ° C. and gold were used using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.). Mold temperature 80 ° C., molding cycle 50 seconds, width 50 mm, length 90 mm, thickness 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm) from the gate side A three-stage plate having an arithmetic average roughness (Ra) of 0.03 μm was formed. The haze at a thickness of 2.0 mm of the three-stage plate was measured using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to ISO17482.

(Dry heat resistance test)
After drying the pellets of the polycarbonate resin composition obtained in each example at 80 to 110 ° C. for 12 hours, a molding temperature of 240 ° C. and gold were used using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.). Mold temperature 80 ° C., molding cycle 50 seconds, width 50 mm, length 90 mm, thickness 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm) from the gate side A three-stage plate having an arithmetic average roughness (Ra) of 0.03 μm was formed. A molded plate is prepared by cutting out a 2 mm portion of the three-stage plate to a size of 50 mm × 45 mm, and the molded plate is placed in a vacuum oven manufactured by Tokyo Rika Kikai Co., Ltd. under the condition that no decompression operation is performed at 110 ° C. It was allowed to stand in VOS-301SD for 300 hours.

The yellowing degree (ΔYI) of the molded plate before and after the static treatment was measured with a C light source using a colorimetric color difference meter CE-7000 manufactured by Macbeth Co., Ltd. in accordance with JIS K7136 (2000). In this evaluation, it is shown that the smaller the value of ΔYI, the smaller the change in color tone when used in a high temperature drying environment for a long period of time, and the better the dry heat resistance.

(Appearance evaluation of molded products)
After drying the pellets of the polycarbonate resin composition obtained in each example at 80 to 110 ° C. for 12 hours, a molding temperature of 240 ° C. and gold were used using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.). Mold temperature 80 ° C., molding cycle 50 seconds, width 50 mm, length 90 mm, thickness 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm) from the gate side A three-stage plate having an arithmetic average roughness (Ra) of 0.03 μm was formed. The appearance of the three-stage plate was visually observed. A product having a uniform appearance without molding unevenness was evaluated as “◯”, and a product having an appearance unevenness was evaluated as “x”.

<Synthesis of polycarbonate resin>
(Synthesis Example 1: Production of Copolymerized Polycarbonate Resin (PC-1))
Isosorbide (hereinafter abbreviated as ISS) 441.29 parts by mass, 1,9-nonanediol (hereinafter abbreviated as ND) 65.99 parts by mass, diphenyl carbonate (hereinafter abbreviated as DPC) 749.77 parts by mass, and catalyst As a result, 3.0 × ^10-2 parts by mass of tetramethylammonium hydroxide and 2.0 × 10 ^-3 parts by mass of sodium hydroxide were mixed and heated to 170 ° C. in a nitrogen atmosphere to melt them.

After melting, the transesterification reaction step was started. After the start of decompression, the pressure was reduced while adjusting the final decompression degree to 13.4 kPa over 70 minutes, and the decompression degree was maintained after reaching 13.4 kPa. At the same time as the start of depressurization, the temperature was raised at a rate of 10 ° C./hour until the final resin temperature reached 190 ° C. After reaching 190 ° C., the mixture was kept at a reduced pressure of 13.4 kPa and a resin temperature of 190 ° C. for 10 minutes until 80% of phenol was distilled off from the theoretical amount.

After distilling off 80%, the temperature was raised at a rate of 0.5 ° C./min so that the final resin temperature was 220 ° C. Further, in parallel with the temperature rise, the pressure was reduced over 60 minutes so that the final degree of pressure reduction was 3 kPa.

Subsequently, the temperature was raised at a rate of 1 ° C./min so that the final resin temperature was 240 ° C. Further, in parallel with the temperature rise, the pressure was reduced over 20 minutes until the final degree of pressure reduction reached 134 Pa. The reaction is terminated when the predetermined stirring power value is reached, dodecylbenzenesulfonate tetrabutylphosphonium salt in an amount twice the amount of the catalyst is added to inactivate the catalyst, and then nitrogen pressurization is performed from the bottom of the reaction vessel. , Polycarbonate resin was discharged and cut with a pelletizer while cooling in a water tank to obtain pellets. The evaluation results of the pellets are shown in Table 1.

(Synthesis Example 2: Production of Copolymerized Polycarbonate Resin (PC-2))
Pellets were obtained in the same manner as in Synthesis Example 1 except that ISS375.74 parts, 1,6-hexanediol (hereinafter abbreviated as HD) 101.23 parts, and DPC749.70 parts were used. The evaluation results of the pellets are shown in Table 1.

(Example 1)
The polycarbonate resin (A-1) and the impact-resistant modifier (B-1) are weighed and uniformly mixed at the ratios shown in Table 2 below, and the obtained mixture is charged into an extruder. Pellets of the polycarbonate resin composition were prepared. Each physical property was evaluated using pellets dried at 90 ° C. for 12 hours, and the results are shown in Table 2.

Here, as the extruder, a vent type twin-screw extruder having a diameter of 15 mmφ (KZW15-25MG manufactured by Technobel Co., Ltd.) was used. The extrusion conditions were a discharge rate of 8.4 kg / hour, a screw rotation speed of 250 rpm, a vent vacuum degree of 3 kPa, and an extrusion temperature of 240 ° C. from the first supply port to the die portion.

(Example 2 and Comparative Examples 1 to 8)
The same operation as in Example 1 was carried out except that the polycarbonate resin and the impact resistance modifier were used in the ratios shown in Table 2. The evaluation results are shown in Table 2. The polycarbonate resin and impact-resistant modifier corresponding to each symbol shown in Table 2 are shown below.

(Component A: Polycarbonate resin)
A-1 is a pellet of the copolymerized polycarbonate resin (PC-1) produced in Synthesis Example 1.

A-2 is a pellet of the copolymerized polycarbonate resin (PC-2) produced in Synthesis Example 2.

(B component: impact resistance modifier)
B-1 is an impact-resistant modifier composed of an ethylene-glycidyl methacrylate-methyl acrylate copolymer (“BONDFAST ™ 7M” manufactured by Sumitomo Chemical Co., Ltd.). The content of the glycidyl methacrylate unit of the copolymer is 3% by mass, and the content of the methyl acrylate unit is 27% by mass.

B-2 is an impact-resistant modifier composed of a core-shell rubber polymer having a core made of butadiene and butyl acrylate and a shell made of methyl methacrylate.

B-3 is an impact resistant modifier composed of a core-shell rubber polymer having a core made of butyl acrylate and a shell made of methyl methacrylate.

<result>
As can be seen from the results in Table 2, the polycarbonate resin compositions of Examples 1 and 2 containing a specific amount of a specific polycarbonate resin and a specific impact-resistant modifier have impact resistance, light-shielding property, molded product appearance, and heat resistance. , Excellent results were shown in all the evaluation items of dry heat resistance.

From the present results, it can be seen that according to the polycarbonate resin composition of the present disclosure, a polycarbonate resin composition having improved impact resistance and dry heat resistance and a molded product thereof can be obtained while maintaining heat resistance.

Further, the polycarbonate resin composition of the present disclosure is lighter than glass, has high impact resistance, and is also excellent in light-shielding property. Therefore, it is used as an alternative to glass, for example, automobiles and the like. It can be seen that it is particularly suitable for use in applications that require impact resistance but low total light transmittance, such as privacy glass or smoked glass for window building materials. Alternatively, for example, it can be seen that it is also suitable for applications such as smoke films used by applying it to window glass and the like.

Since the polycarbonate resin composition of the present disclosure is excellent in impact resistance, light shielding property, heat resistance, and dry heat resistance, a molded product formed by using the polycarbonate resin composition having such performance is, for example, a film. Alternatively, various members such as seat members, interior or exterior members of electric or electronic devices, interior or exterior members of various vehicles such as automobiles, various containers or packaging members such as bottles, interior or exterior members of buildings, etc. It can be widely used for various purposes.

Claims (8)

It contains a polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit, and an impact resistance modifier (B).
The impact-resistant modifier (B) is contained in a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and is an epoxy group-containing polyethylene. :

The composition according to claim 1, wherein the polycarbonate resin (A) contains 30 mol% or more of the structural units represented by the formula 1 with respect to 100 mol% of all structural units derived from the diol. The composition according to claim 1 or 2, wherein the impact-resistant modifier (B) is an ethylene-glycidyl (meth) acrylate copolymer. The composition according to any one of claims 1 to 3, wherein the polycarbonate resin (A) further contains a structural unit derived from a diol compound other than the formula 1. The composition according to any one of claims 1 to 4, wherein the deflection temperature under load under 1.8 MPa conditions is 90 ° C. or higher. The composition according to any one of claims 1 to 5, wherein the total light transmittance measured on a molded plate having a thickness of 2 mm is 30% or less. The composition according to any one of claims 1 to 6, wherein the haze measured on a molded plate having a thickness of 2 mm is 50% or more. A polycarbonate resin molded product molded by using the composition according to any one of claims 1 to 7.