JP2009120707A - Polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin material having improved high flowability, transparency and durability. <P>SOLUTION: A resin composition comprises 100 pts.wt. of a polycarbonate-based resin (component A) comprising a polycarbonate-polyorganosiloxane copolymer (component A1) containing polyorganosiloxane units having a number-average polymerization degree of 10 to 60 or comprising the component A1 and a polycarbonate except the component A1, wherein the content of the polyorganosiloxane units is 0.1 to 20 wt.%per 100 wt.%of the component A, and 0.1 to 20 pts.wt. of a polycarbonate oligomer (component B) having an average polymerization degree of 3 to 15. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition having improved high fluidity, transparency and durability. More specifically, the present invention relates to a resin composition having such characteristics improved by combining a specific polyorganosiloxane-polycarbonate copolymer and a polycarbonate oligomer, and a particularly thin portion formed from such a resin composition. It relates to a molded product.

  Polycarbonate resins are used in many applications such as mechanical parts, automobile parts, and electric / electronic parts because of their excellent properties such as mechanical strength and transparency. In recent years, each resin member has become thinner due to the progress of miniaturization (including thinning) and lightening of portable information terminals represented by mobile phones, smartphones, and mobile personal computers (see, for example, Patent Document 1). . Therefore, the resin material forming such a member is required to have practical durability in a thin-walled molded product while having high fluidity corresponding to thin-walled molding. Further, some parts constituting a portable information terminal use a transparent hard resin as a button member of a key. In such a member, a transparent polycarbonate resin is used from the viewpoints of transparency, mechanical strength, and durability. As described above, due to the tendency to reduce the thickness, such a member needs to have a strength that can withstand repeated pressure when a button is pressed while maintaining a good transparency. Thus, a polycarbonate resin material having improved high fluidity, transparency, and durability may be required.

  Regarding a button member of a portable information terminal formed from a polycarbonate-based resin composition, for a key of a portable information terminal obtained by blending an oligomeric phosphate ester with a polycarbonate resin having a viscosity average molecular weight of 16,000 to 22,000. The resin composition (refer patent document 2) and the resin composition which consists of a polycarbonate resin and a styrene- acrylonitrile copolymer (AS) resin (The weight average molecular weight of the resin of an Example is about 78,000) were formed. Key molded product for portable information terminals (see Patent Document 3), Key molded product for portable information terminals formed by molding a polycarbonate resin having an acetone soluble content of 2% by weight or less and a ductile brittle transition temperature of 15 ° C. or less (see Patent Document 4) ), And a polycarbonate resin comprising a polycarbonate resin, a phosphazene compound, a heat stabilizer and a release agent Molded from the composition portable information terminal keys moldings (see Patent Document 5) are known. Furthermore, a key molded article for a portable information terminal comprising a polyorganosiloxane-polycarbonate copolymer and a release agent is also known (see Patent Document 6).

  On the other hand, it is known that a polycarbonate oligomer is blended with a polycarbonate-based material to maintain transparency and improve flow characteristics (see Patent Documents 7 and 8). Furthermore, a resin composition obtained by mixing a polyorganosiloxane-polycarbonate copolymer, a polycarbonate resin, a polycarbonate oligomer, and an organically treated montmorillonite with a Banbury mixer and then extruding is known (see Patent Document 9). . However, the compounding effect of the polycarbonate oligomer in such a resin composition is only a slight improvement in the low temperature impact value.

JP 2007-048602 A JP 2004-346112 A JP-A-2005-044130 JP 2006092951 A JP 2007-045909 A Japanese Patent Laid-Open No. 11-045139 JP 2006-188594 A JP 61-123658 A Special table 2007-514854 gazette

  In contrast to the current situation in which polycarbonate resin materials with improved high flow, transparency and durability are required as described above, the above prior art is mainly aimed at improving moldability, and durability in use. It could not be said that this was fully considered. An object of the present invention is to improve a point that has not been sufficiently considered in the prior art, and to provide a polycarbonate resin material having improved high fluidity, transparency, and durability. As a result of intensive studies, the present inventors have found that the above object can be achieved by combining a polycarbonate copolymer containing a specific polyorganosiloxane structure and a polycarbonate oligomer. It was. Although the polycarbonate oligomer is known to have an effect mainly on a general-purpose bisphenol A type polycarbonate resin, a polycarbonate resin containing a polycarbonate-organosiloxane copolymer can also provide good transparency and the polycarbonate oligomer. It was surprising that the excellent durability of the resin was not greatly reduced. Based on this finding, we have completed the present invention.

  The object of the present invention is (1) a polycarbonate-polyorganosiloxane copolymer (A1 component) containing a polyorganosiloxane unit of the following general formula (α1), or a polycarbonate other than the A1 component and the A1 component A polycarbonate oligomer (B) having an average polymerization degree of 3 to 15 parts by weight per 100 parts by weight of a polycarbonate-based resin (component A) having a polyorganosiloxane unit content of 0.1 to 20% by weight in 100% by weight of component A Component) Achieved by a polycarbonate resin composition containing 0.1 to 20 parts by weight.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は炭素数１〜６のアルキル基またはフェニル基を示し、同一でも異なっていてもよく、Ｒ_５は脂肪族または芳香族化合物からの二価の有機残基を示し、ｎはカッコ内の単位の繰り返し数を示し、その数平均値が１０〜６０であり、カッコ内の構成単位は２種以上の混合物であってもよい。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different, and R ₅ represents a group derived from an aliphatic or aromatic compound. And n represents the number of repeating units in parentheses, the number average value of which is 10 to 60, and the constituent units in parentheses may be a mixture of two or more.)

The component A polycarbonate-based resin is excellent in transparency and durability. The B component is excellent in compatibility with the A component, and in this respect, it is considered that transparency and good durability are maintained.
The composition ratio of the A component and the B component is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 9 parts by weight with respect to 100 parts by weight of the A component. .

  One preferred embodiment of the present invention is (2) a structural unit represented by the following general formula (i) having the structural unit represented by the following general formula (α2) as the general formula (α1) of the A1 component. It is a polycarbonate resin composition of the said structure (1) which is a polycarbonate polyorganosiloxane copolymer which has this.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４、並びにｎは上記一般式（α１）と同じであり、Ｒ_１１およびＲ_１２は、炭素数２〜６のアルキレン基を表し、これらは同一でも異なっていてもよく、Ｙは、ベンゼン環に結合したＲ_１１またはＲ_１２、および酸素原子（Ｏ）とは、異なる位に置換した水素原子またはアルコキシ基を表す。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ , and n are the same as those in the general formula (α1), R ₁₁ and R ₁₂ represent an alkylene group having 2 to 6 carbon atoms, Y may be the same or different, and Y represents R ₁₁ or R ₁₂ bonded to the benzene ring and a hydrogen atom or an alkoxy group substituted at a different position from the oxygen atom (O).

（Ａは下記式（ｉ−１）〜（ｉ−３）および（ｉ−５）からなる群より選択される少なくとも１種の二価の有機残基、単結合、または下記式（ｉ−４）のいずれかの結合を表し、ｓおよびｔはそれぞれ独立して０または１〜４の整数であり、Ｒ_１３およびＲ_１４はそれぞれ独立して、ハロゲン原子、または炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基、および炭素数７〜２０のアラルキルオキシ基からなる群より選択される有機残基を表す。）

(A is at least one divalent organic residue selected from the group consisting of the following formulas (i-1) to (i-3) and (i-5), a single bond, or the following formula (i-4 ) And s and t are each independently 0 or an integer of 1 to 4, and R ₁₃ and R ₁₄ are each independently a halogen atom or an alkyl group having 1 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon number It represents an organic residue selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms.)

（式（ｉ−１）中、Ｒ_１５、Ｒ_１６、Ｒ_１７およびＲ_１８はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表す。）

(In formula (i-1), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（ｉ−２）中、Ｒ_１９およびＲ_２０はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表す。）

(In formula (i-2), R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms.)

（上記式（ｉ−３）において、ｕは４〜１１の整数を表し、かかる複数のＲ_２１およびＲ_２２はそれぞれ独立して水素原子、ハロゲン原子、および炭素数１〜３のアルキル基から選択される基を表す。）

(In the above formula (i-3), u represents an integer of 4 to 11, and the plurality of R ₂₁ and R ₂₂ are each independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. Represents a group to be

（式（ｉ−５）中、Ｒ_２３およびＲ_２４はそれぞれ独立して、水素原子、ハロゲン原子、および炭素数１〜１０の炭化水素基から選択される基を表す。）

(In formula (i-5), R ₂₃ and R ₂₄ each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms.)

  The α2 is excellent in hydrolysis resistance, and a resin composition having better durability can be obtained.

  One of the preferred embodiments of the present invention is (3) the polycarbonate resin composition having the above constitutions (1) to (2), wherein the component A has a viscosity average molecular weight in the range of 16,000 to 25,000. is there. When the viscosity average molecular weight (M) of the component A is less than 10,000, it is difficult to obtain practical mechanical strength in many fields, and when it exceeds 50,000, the resin composition has a high melt viscosity, and generally has a high molding. Since the processing temperature is required, the viscosity average molecular weight of the component A is suitably in the range of 10,000 to 50,000. Further, in the thin-walled molded article as described above, the viscosity average molecular weight of the component A is 16,000 to 25,000, more preferably 17,000 to 21,000.

  Moreover, one of the suitable aspects of this invention is the polycarbonate resin composition of the said structure (3) whose viscosity average molecular weight of the (4) said A1 component is the range of 16,000-25,000. The viscosity average molecular weight of the A component of the present invention in the above configuration (3) may be adjusted by mixing the A1 component outside this range and a polycarbonate other than the A1 component. Therefore, for example, an A component having a viscosity average molecular weight of 20,000 can be obtained by mixing an A1 component having a viscosity average molecular weight of 100,000 with another polycarbonate resin having a viscosity average molecular weight of 15,000. However, since mixing of components having greatly different viscosity average molecular weights generally tends to cause a decrease in transparency, the A1 component is also preferably in the range of the viscosity average molecular weight of the preferred A component. Therefore, according to the configuration (4), a polycarbonate resin composition having more excellent transparency is provided.

  One preferred embodiment of the present invention is that (5) the A component has a polyorganosiloxane unit content of 1 to 20% by weight in 100% by weight of the A1 component, It is a polycarbonate resin composition of said structure (1)-(4) whose polyorganosiloxane unit content is 0.5-5 weight%. The polyorganosiloxane unit content contained in 100% by weight of the A1 component is not particularly limited, but if it is too high, the transparency of the resin composition tends to be lowered, so the range of 0.1 to 40% by weight. Is appropriate. The content is preferably 1 to 20% by weight, more preferably 2 to 12% by weight, and still more preferably 3 to 10% by weight. Below the lower limit of the preferable range, the adjustment range of the polyorganosiloxane concentration in the component A is limited, resulting in inferior production efficiency. When the upper limit of the preferable range is exceeded, the transparency is stably exhibited. In this respect, production efficiency is inferior. Further, the polyorganosiloxane unit content in 100% by weight of component A is 0.1 to 20% by weight, preferably 0.5 to 5% by weight, more preferably 1.5 to 4.5% by weight. More preferably, it is in the range of 2 to 4% by weight. The said structure (5) is a structure which makes the polyorganosiloxane unit content in 100 weight% of A component into this more suitable range using A1 component which has this suitable polyorganosiloxane unit content. Thereby, a polycarbonate resin composition excellent in both transparency and durability is provided.

  One of the preferred embodiments of the present invention is (6) a polycarbonate resin composition having the above constitutions (1) to (5), wherein n in the general formula (α1) is in the range of 16 to 50. When n indicating the degree of polymerization of such a polyorganosiloxane is less than 10, sufficient durability cannot be imparted to the resin composition, whereas when it exceeds 60, transparency is inferior. This is because fine dispersion is required in terms of transparency, and it is advantageous that the layers are separated to some extent in terms of durability. Such n is more preferably in the range of 16-50, and even more preferably in the range of 20-40. According to this configuration (5), both better transparency and durability can be achieved.

  One of the preferred embodiments of the present invention is (7) the polycarbonate resin composition according to any one of the above constitutions (1) to (6), wherein the component B is an oligomer comprising a constitutional unit represented by the following general formula (β1).

（式（β１）中、Ａ、ｓ、ｔ、Ｒ_１３およびＲ_１４は、いずれも上記式（ｉ）と同一の基、原子、または数値を表す。）

(In the formula (β1), A, s, t, R ₁₃ and R ₁₄ all represent the same group, atom or numerical value as in the above formula (i).)

  Oligomers composed of such structural units are excellent in thermal stability and are more suitable for thin wall molding that requires high temperature molding. A more preferred embodiment is (8) the polycarbonate resin composition having the constitution (7), wherein the component B is an oligomer represented by the following general formula (β2).

（式（β２）中、Ａ、ｓ、ｔ、Ｒ_１３およびＲ_１４は、いずれも上記式（ｉ）と同一の基、原子、または数値を表し、Ｚは水素原子、水素原子の一部がフッ素原子で置換されていてもよい炭素数１〜９の直鎖または分岐のアルキル基あるいはフェニル基置換アルキル基、炭素数１０〜５０の長鎖アルキル基、珪素原子数４〜４０のポリオルガノシロキサン鎖、若しくは−Ｘ−Ｃ_ｍＨ_２ｍ＋１を表し、ここでＸは、−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−であり、かかるＲは単結合または炭素数１〜１０の二価の脂肪族炭化水素基を表し、ｍは１０〜５０の整数を表す。）

(In the formula (β2), A, s, t, R ₁₃ and R ₁₄ all represent the same group, atom or numerical value as in the above formula (i), and Z is a hydrogen atom or a part of the hydrogen atom. C1-C9 linear or branched alkyl group or phenyl group-substituted alkyl group optionally substituted with a fluorine atom, C10-50 long-chain alkyl group, polyorganosiloxane having 4-40 silicon atoms A chain, or —X—C _m H _{2m + 1} , where X is —R—O—, —R—CO—O— or —R—O—CO—, where R is a single bond or carbon number 1-10 divalent aliphatic hydrocarbon groups are represented, m represents an integer of 10-50.)

  By having such a terminal structure, better thermal stability is obtained, and a resin material suitable for high temperature molding is provided. Furthermore, the injection molded article can obtain good durability due to such thermal stability.

One of the preferred embodiments of the present invention is (9) a polycarbonate resin composition having the above-mentioned constitutions (1) to (8), wherein a haze having a thickness of 2 mm measured by JIS K7105 is 0.3 to 20%. According to still another aspect, a transparent resin molded product obtained by injection-molding the polycarbonate resin composition having the configuration (10), and one of the preferred aspects of the aspect is (11) the injection molding This is a transparent resin molded product having the above-described configuration (10), wherein the product is mainly composed of a portion having a thickness of 0.05 to 0.5 mm. Here, the transparent resin molded product refers to a molded product having a haze of 0.1 to 20%, preferably 0.2 to 4%, more preferably 0.2 to 2%.
The details of the present invention will be further described below.

(A1 component: polycarbonate-polyorganosiloxane copolymer)
The A1 component of the present invention contains a polyorganosiloxane unit of the general formula (α1) as described above. Specific examples of R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (α1) include methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, pentyl group, heptyl group, and A phenyl group etc. are illustrated suitably, and especially a methyl group is preferable. R ₅ represents a divalent organic residue from an aliphatic or aromatic compound. When —Si—R ₅ — has a bond of —Si—O—, R ₅ can include various alicyclic diol residues and divalent phenol residues. As such alicyclic diol and dihydric phenol, those similar to the polycarbonate described later can be used. In —Si—R ₅ —, when having a bond of —Si—C—, R ₅ is an o-allylphenol residue, a p-hydroxystyrene residue, a 4-allyl-2-methoxyphenol residue, and an iso Propenylphenol residues and the like are suitably exemplified, and o-allylphenol residues are particularly preferable. That is, as described above, the A1 component preferably has the structural unit represented by the general formula (α2) as the general formula (α1), but the R ₁₁ and R ₁₂ are ethane-1,2-diyl group, propane-1 , 3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-2,3-diyl group, etc., among which ethane-1,2-diyl group and propane- A 1,3-diyl group is preferred, and a propane-1,3-diyl group is particularly preferred.

In the polycarbonate-polyorganosiloxane copolymer in the A1 component, the polycarbonate unit copolymerized with the polyorganosiloxane unit is not particularly limited. That is, it can have various carbonate units obtained by reacting a dihydric phenol and / or an aliphatic and / or alicyclic bifunctional alcohol with a carbonate precursor. Preferred are carbonate units derived from dihydric phenols. In particular, as described above, the structural unit represented by the general formula (i) is preferable. On the other hand, alicyclic diols are more preferred as the difunctional alcohols for deriving the structural units of polycarbonate, such as cyclohexanedimethanol, cyclohexanediol, tricyclo (5.2.1.0 ^2,6 ) decanedimethanol, Norbornane dimethanol, decalin-2,6-dimethanol, spiroglycol, 1,4; 3,6-dianhydro-D-glucitol, 1,4; 36-dianhydro-D-mannitol, and 1,4; Examples include 6-dianhydro-L-iditol.

Specific examples of the general formula (i) will be described based on specific examples of the dihydroxy compound from which the structural unit is derived.
Examples of the compound when A in Formula (i) is a single bond include 4,4′-biphenol and 4,4′-bis (2,6-dimethyl) diphenol.

  Examples of the compound when A is the formula (i-1) include α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropyl. Examples include benzene (usually referred to as “bisphenol M”) and α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene.

  Examples of the compound when A is the formula (i-2) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. .

  As the compound when A is the formula (i-3), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane Etc.

  As the compound when A is any one of the formulas (i-4), 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4, 4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide and And bis (3,5-dimethyl-4-hydroxyphenyl) sulfone.

  As the compound when A is any one of the formula (i-5), 1,1-bis (4-hydroxyphenyl) methane, 2,4′-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, Bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-2-phenyl) -1-phenylethane, 1,1-bis (4- Hydroxy-2-chlorophenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (usually “bisph Nord A "), 2,2-bis (4-hydroxy-3-methylphenyl) propane (usually referred to as" bisphenol C "), 2,2-bis (3-phenyl-4-hydroxy) Phenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-) Isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5 -Dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 2,2-bis (4-hydroxyphenyl) -1 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) ) Butane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (3- Examples thereof include methyl-4-hydroxyphenyl) decane and 1,1-bis (2,3-dimethyl-4-hydroxyphenyl) decane.

  Furthermore, as the dihydric phenol from which the structural unit other than formula (i) is derived, 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms, 3- (4 -Hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3 , 3 ′, 3′-tetramethylspiroindane, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- (4-hydroxyphenyl) -3- [1 -(4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione, Fine ethylene glycol bis (4-hydroxyphenyl) ether, and the like.

  Among the above dihydric phenols, bisphenol M in formula (i-1), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene in formula (i-2), 1, in formula (i-3), 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, formula ( 3,4'-Dimethyl-4,4'-dihydroxydiphenyl sulfide is preferred for i-4), and bisphenol A, bisphenol C, and 1,1-bis (4-hydroxyphenyl) decane are preferred for formula (i-5). . Of these, bisphenol A, which has excellent strength and good durability, is most preferred.

  The polycarbonate-polyorganosiloxane copolymer can be produced by various known methods. A more suitable method is a method in which a polyorganosiloxane capped at both ends with a group having a phenolic hydroxyl group is reacted with a carbonate oligomer. Other methods include reacting with a carbonate precursor in the presence of a polyorganosiloxane capped at both ends with a group having a phenolic hydroxyl group and a dihydric phenol or aliphatic diol, and a chlorine atom at the end. Examples include a method of reacting a polyorganosiloxane having a carbonic acid oligomer with a carbonate oligomer. In this reaction, the same conditions as those for normal polymerization of polycarbonate can be used, and the polymerization conditions for polycarbonate will be described later. That is, in the A1 component, the production conditions, the end terminator, the branching agent component, and the like can be the same as those of polycarbonate other than the A1 component described later.

  The polycarbonate-polyorganosiloxane copolymer does not bind to the polycarbonate, and the free polyorganosiloxane or polyorganosiloxane used as a raw material for the polymer binds to the carbonate unit or the carbonate unit of the end stopper. However, it contains components which are insufficient (hereinafter referred to as “free polyorganosiloxane etc.”). The amount of such free polyorganosiloxane can be calculated by extraction with n-hexane.

  Free polyorganosiloxane tends to aggregate and cause a decrease in the transparency of the resin composition. Therefore, in the A1 component of the present invention, the content ratio of the free polyorganosiloxane and the like, that is, the ratio of the n-hexane extract amount is 10% by weight or less with respect to the polyorganosiloxane component contained in the A1 component. , Preferably 3% by weight or less, more preferably 2% by weight or less. On the other hand, the lower limit of the content is about 0.1% by weight. The n-hexane extraction amount is calculated by subjecting the weighed copolymer sample to Soxhlet extraction treatment with special grade n-hexane. Such Soxhlet extraction treatment is carried out for 3 hours at an average cycle of about 20 times / hour, and is calculated by removing n-hexane from the solution after treatment. In order to reduce free polyorganosiloxane and the like, the feed ratio of raw materials and polymerization accelerator, emulsification state, temperature, and stirring conditions are adjusted so that the monomers in the reaction system sufficiently react.

(Polycarbonate)
The A component of the present invention may be the A1 component alone or a mixture of the A1 component and a polycarbonate other than the A1 component. As the polycarbonate other than the A1 component, a known polycarbonate obtained by reacting a dihydric phenol and / or an aliphatic and / or alicyclic difunctional alcohol with a carbonate precursor can be used. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. As described above, the polycarbonate of component A may also be a branched polycarbonate obtained by polymerizing a trifunctional component in addition to dihydric phenol or alcohol, and also aliphatic dicarboxylic acid or aromatic dicarboxylic acid, and vinyl-based monomer. A copolymer polycarbonate obtained by copolymerizing the body may also be used.

  Among the polycarbonates other than the A1 component, those having the structural unit represented by the above formula (i) are preferable. Such specific examples and preferred embodiments thereof are also as described above, and bisphenol A is particularly preferred. Other details of the polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing. Specific examples of the bifunctional alcohol for deriving the structural unit of the polycarbonate are the same as those in the A1 component.

Polycarbonate can contain a branched component, and the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate is 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene. -2,2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4 -Hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4 Preferred examples include trisphenol such as-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol. Is done. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferred. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1 mol%, more preferably 0.07 to 0 in a total of 100 mol% with respect to structural units from other divalent components. 0.7 mol%, particularly preferably 0.1 to 0.4 mol%. The branched structural unit may be derived not from a polyfunctional aromatic compound but also from a polyfunctional aromatic compound such as a side reaction during a melt transesterification reaction. . The ratio of such a branched structure can be calculated by ¹ H-NMR measurement. As described above, the branched component may be contained in the A1 component.

  Polycarbonate includes polyester carbonate copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. You may contain the unit induced | guided | derived from this dicarboxylic acid in A1 component.

  The viscosity average molecular weights of the A component and the A1 component are as described above, but the polycarbonate may be obtained by mixing those outside the range. In particular, a polycarbonate having a viscosity average molecular weight exceeding 50,000 can increase the melt tension of the resin composition and improve the moldability based on such properties. The upper limit is appropriately 300,000. Such a high molecular weight polycarbonate can be mixed at a ratio of 20% by weight in the component A as a guide and adjusted so as to satisfy a predetermined molecular weight range, thereby improving molding processability.

  In the polycarbonate polymerization reaction, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is preferably used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are preferably used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can also be used. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used.

  The polycarbonate organic solvent solution obtained by the interfacial polycondensation method is usually washed with water. This washing step is preferably performed with water having an electric conductivity of 10 μS / cm or less, such as ion-exchanged water, and more preferably 1 μS / cm or less. The organic solvent solution and water are mixed and stirred, and then allowed to stand. Alternatively, the organic solvent solution phase and the aqueous phase are separated using a centrifuge or the like, and the organic solvent solution phase is removed repeatedly to remove water-soluble impurities. By washing with high-purity water, water-soluble impurities are efficiently removed, and the hue of the obtained polycarbonate is improved. The organic solvent solution of polycarbonate described above is also preferably subjected to acid cleaning or alkali cleaning in order to remove impurities such as a catalyst.

The organic solvent solution is preferably removed from foreign substances that are insoluble impurities. As a method for removing the foreign matter, a method of filtering or a method of treating with a centrifuge is preferably employed.
The organic solvent solution that has been washed with water is then subjected to an operation of removing the solvent to obtain a polycarbonate resin powder.

  As a method (granulation process) for obtaining a polycarbonate resin granule, since operation and post-treatment are simple, stirring is performed in a granulation apparatus in which polycarbonate granule and hot water (about 65 to 90 ° C.) are present. However, a method of producing a slurry by continuously supplying an organic solvent solution of polycarbonate and evaporating the solvent is used. As the granulator, a mixer such as a stirring tank or a kneader is used. The produced slurry is continuously discharged from the upper or lower part of the granulator. The discharged slurry can then be subjected to hot water treatment. In the hydrothermal treatment step, the slurry is supplied to a hydrothermal treatment container containing hot water at 90 to 100 ° C., or after being supplied, the water temperature is changed to 90 to 100 ° C. by blowing steam or the like. The organic solvent contained is removed.

  The slurry discharged in the granulation step or the slurry after the hot water treatment is preferably filtered, centrifuged, etc. to remove water and organic solvent, and then dried to give polycarbonate resin granules (powder or flakes) Can be obtained. The dryer may be a conduction heating method or a hot air heating method, and the polycarbonate resin particles may be allowed to stand, be transferred, or stirred. Among these, a grooved or cylindrical dryer in which the polycarbonate resin particles are stirred by a conductive heating method is preferable, and a grooved dryer is particularly preferable. The drying temperature is preferably in the range of 130 ° C to 150 ° C.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases it is in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the reaction system is reduced to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable. The molten polycarbonate resin obtained by the melt transesterification method can be pelletized by a melt extruder. This pellet is used for molding.

  The mixing of the A1 component with other polycarbonates can be performed by the methods represented by the following (i) to (iv), but is not limited thereto. That is, (i) applying the technique disclosed in Japanese Patent Application Laid-Open No. 05-306336, an emulsion for synthesizing a polycarbonate-polyorganosiloxane copolymer and an emulsion for synthesizing another polycarbonate (Ii) Polycarbonate-polyorganosiloxane co-polymerization, a method of recovering the A-component polycarbonate resin from the combined emulsion by maintaining the emulsified state in the same reactor and mixing and allowing to stand to advance the polymerization. A method of mixing a solution of a coalescence with a solution of another polycarbonate and recovering the polycarbonate-based resin of component A from the mixed solution, (iii) A powder of a polycarbonate-polyorganosiloxane copolymer and a powder of another polycarbonate A method of mixing and integrating the granules and then mixing with the component B, and (iv) polycarbonate-poly Granular material Lugano copolymer, granular material of other polycarbonates, and methods such as mixing the granular material of the B component is supplied to the extruder, and the like.

  Thus, it is preferable that the polycarbonate-type resin of A component manufactured is 0.1-100 ppm of Cl amount, and 0.1-30 eq / ton of OH terminal amount. The amount of Cl in the polycarbonate resin is measured by a combustion method. After the sample is weighed, it is burned in a mixed gas stream of argon and oxygen, and is determined by the amount of electrification transfer of the silver electrode. An example of the measuring apparatus is TOX-2100H manufactured by Mitsubishi Chemical Corporation. Such OH terminal amount can be calculated by NMR method, IR method, and titration method. By satisfying such characteristics, it becomes possible to obtain a molding material and a molded article having excellent thermal stability and little discoloration. The resin composition of the present invention is a thin wall molded at high temperature and under a high pressure load. More suitable for molded products.

The viscosity average molecular weight of the polycarbonate of component A and component A1 is first determined using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. Ask
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component)
The B component of the present invention is a polycarbonate oligomer having an average degree of polymerization of 3 to 15 as described above. Such a polycarbonate is composed of the same structural unit as the above-mentioned polycarbonate. That is, the component B polycarbonate oligomer is obtained by reacting one or more dihydric phenols and / or one or more aliphatic and / or alicyclic bifunctional alcohols with a carbonate precursor. Here, the structure of the polycarbonate oligomer may be any of linear, branched (including highly branched), and cyclic forms. From the viewpoint of productivity and production stability, a straight chain is excellent and preferred.
As the bifunctional alcohol in the B component polycarbonate oligomer, an alicyclic diol is more preferable, and a preferred specific example thereof is the same as the above-described A component (A1 component).

  Furthermore, as described above, a preferable component B of the present invention is an oligomer composed of the structural unit represented by the general formula (β1). More preferably, the component B is an oligomer represented by the general formula (β2). In this general formula, the preferred embodiment of the dihydric phenol from which the repeating unit is derived is the same as in the case of the polycarbonate described above. Of these, bisphenol A is preferred. Specific examples of monofunctional phenols for deriving molecular chain ends in the general formula (β2) include, for example, phenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, decylphenol, dodecylphenol, tetradecyl. Phenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol, hydroxydecyl benzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, hydroxybenzoic acid Docosyl and triacontyl hydroxybenzoate are mentioned. The shorter the chain length at the molecular chain end, the better the transparency, and the longer the chain length, the better the fluidity. In consideration of these, the structure at the end of the molecular chain can be selected. However, in view of transparency, thermal stability, and durability, alkyl-substituted phenols having 1 to 9 carbon atoms are preferable, and p-tert- Butylphenol is preferred.

  Polycarbonate oligomer production methods are widely known to those skilled in the art, for example, reaction of a dihydric phenol compound with phosgene using an interfacial polycondensation method, bischloroformate and dihydric phenol or fat derived from dihydric phenol. And polycondensation reaction with aliphatic diol (including alicyclic diol) and melt polycondensation reaction between diaryl carbonate and dihydric phenol or aliphatic diol (including alicyclic diol) in the presence of a polymerization catalyst. .

  The average polymerization degree of B component is 3-15, Preferably it is 3-12, More preferably, it is 4-10. Such an average degree of polymerization can be calculated by combining GPC measurement and NMR measurement, and such points are well known to those skilled in the art.

(C component: mold release agent)
A release agent can be blended in the polycarbonate resin composition of the present invention as needed, and it is preferable to blend. This is because in the thin-wall molding, the molding temperature is high and high-pressure filling is performed, so that the molded product is likely to be in close contact with the mold and mold release defects are likely to occur. Such a defective mold release is not preferable in many cases because it tends to become a starting point of cracks due to its residual stress in terms of durability in addition to cracks during molding.

  Known release agents can be used as the release agent of the present invention. For example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound (represented by polyfluoroalkyl ether) Fluorinated oil), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferred from the viewpoint of availability, releasability, and transparency of the resin composition. Such a release agent is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, and still more preferably 0.03 to 0.3 part by weight based on 100 parts by weight of the polycarbonate resin of component A. 2 parts by weight, particularly preferably 0.07 to 0.15 parts by weight. When the addition amount is less than the lower limit of the above range, the release property is not sufficiently improved. When the addition amount exceeds the upper limit, the thermal stability of the resin composition is deteriorated and the molding stability is deteriorated. Furthermore, depending on the type of the release agent, there may be a problem that a solvent crack is caused in the molded product due to the release agent deposited on the mold.

  Among the above, fatty acid ester (C-1 component) is mentioned as a preferable release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, And saturated aliphatic carboxylic acids such as docosanoic acid (behenic acid) and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid it can. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. Such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats and oils (such as palm oil). Of other carboxylic acid components. Therefore, also in manufacture of the C-1 component of this invention, it manufactures from this natural fats and oils and consists of the form of the mixture containing another carboxylic acid component. The acid value in the fatty acid ester is preferably 20 or less (can take substantially 0). However, in the case of all esters (full esters), it is preferable to contain at least free fatty acids in order to improve releasability. In this respect, the acid value in the full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The fatty acid ester of the present invention may be either a partial ester or a full ester. In the present invention, a partial ester is more preferable in terms of good releasability and durability. Of these, glycerin monoester is preferred. Glycerin monoester is mainly composed of monoester of glycerin and fatty acid. Suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid, lauric acid, oleic acid, and linoleic acid. And unsaturated fatty acids such as sorbic acid, and those having glycerin monoesters of stearic acid, behenic acid, and palmitic acid as main components are particularly preferred. Such fatty acids are synthesized from natural fatty acids and become a mixture as described above. The glycerin monoester can be used in combination with other release agents, particularly fatty acid full esters, but even when used in combination, it is preferable that the glycerin monoester is the main component. That is, it is preferably 60% by weight or more in 100% by weight of the release agent.

  In addition, partial esters are often inferior to full esters in terms of thermal stability. In order to improve the thermal stability of such a partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by an ordinary method and then purifying it by molecular distillation or the like.

  Specifically, after removing gas components and low-boiling substances with a spray nozzle type degassing apparatus, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a falling film distillation apparatus. For example, a high molecular weight fatty acid ester is distilled off using a centrifugal molecular distillation apparatus at a distillation temperature of 160 to 230 ° C. and a vacuum of 0.01 to 0.2 Torr. The sodium metal can be removed as a distillation residue. By subjecting the resulting distillate to repeated molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to prevent the contamination of the sodium metal component from the external environment by thoroughly washing the inside of the molecular distillation apparatus by an appropriate method in advance and improving airtightness. Such a fatty acid ester is available from a specialist (for example, Riken Vitamin Co., Ltd.).

(Other additives)
The polycarbonate resin composition of this invention can contain the various additives normally mix | blended with polycarbonate resin other than the said A component-C component.

(I) Phosphorus stabilizer It is preferable that the polycarbonate resin composition of the present invention further contains various phosphorous stabilizers mainly for the purpose of improving the thermal stability during the molding process. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. In addition, such phosphorus stabilizers include tertiary phosphines.

  Specific examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) 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, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 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) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, 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-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

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

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(Ii) Hindered phenol stabilizer The polycarbonate resin composition of the present invention includes a hindered phenol stabilizer mainly for the purpose of improving heat stability, heat aging resistance, and ultraviolet resistance during molding. Can be further blended. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). ) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- ( N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ′ -Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2 , 6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2, 2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert- Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thio Ethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di -Tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di- tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The amount of (i) phosphorus stabilizer and (ii) hindered phenol antioxidant is 0.0001 to 1 part by weight, preferably 0.001 to 100 parts by weight of polycarbonate resin (component A). 0.1 parts by weight, more preferably 0.005 to 0.1 parts by weight. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

  In the polycarbonate resin composition of the present invention, an antioxidant other than the hindered phenol antioxidant can be used in order to further stabilize the hue at the time of heat treatment of the molded product. Examples of such other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the A-component polycarbonate resin.

(Iii) Ultraviolet Absorber Specifically, the ultraviolet absorber of the present invention is, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone in the benzophenone series. 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4 -Methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-so Diasulfoxybenzophenone, bis (5-benzoy 4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred from the viewpoint of ultraviolet absorbing ability, and cyclic iminoesters and cyanoacrylates are preferred from the viewpoint of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part with respect to 100 weight part of polycarbonate-type resin (A component), Preferably it is 0.03-2 weight part, More preferably, it is 0.02-1 weight part, More preferably, it is 0.05-0.5 weight part.

(Iv) Light Stabilizer The polycarbonate resin composition of the present invention comprises bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4). -Piperidyl) sebacate, 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] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4 A hindered amine light stabilizer represented by-(2,2,6,6-tetramethyl) piperidinyl] siloxane and the like can also be included.

  The above light stabilizers may be used alone or in a mixture of two or more. The amount of the light stabilizer used is preferably from 0.0005 to 3 parts by weight, more preferably from 0.01 to 2 parts by weight, and even more preferably from 0.02 to 1 part by weight based on 100 parts by weight of the polycarbonate resin (component A). preferable.

(V) Blueing agent The polycarbonate resin composition of the present invention preferably further comprises 0.05 to 3.0 ppm (weight ratio) of a blueing agent in the resin composition. In the resin composition of the present invention, the use of a bluing agent is very effective for further reducing the yellowness and imparting a natural transparency to the molded product. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By adding the bluing agent, the polycarbonate resin composition of the present invention can obtain a better hue. If the amount of the bluing agent is less than 0.05 ppm, the effect of improving the hue may be insufficient. On the other hand, if it exceeds 3.0 ppm, the light transmittance decreases, which is not appropriate. A more preferable amount of bluing agent is in the range of 0.2 to 2.0 ppm in the resin composition. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polysynthrene Blue RLS manufactured by Clariant.

(Vi) Fluorescent Dye Since the polycarbonate resin composition of the present invention has good transparency, it further includes a fluorescent brightening agent to give higher light transmittance and natural transparency, and to increase fluorescence. By including a white agent or other fluorescent dyes that emit light, it is possible to impart a design effect utilizing the light emission color.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin. Among them, a coumarin fluorescent dye, that is, a fluorescent dye composed of a coumarin derivative is preferable from the viewpoint of maintaining good characteristics even in combination with the component B of the present invention. The compounding amount of the fluorescent dye (including the fluorescent brightening agent) is 0.0001 to 3 parts by weight, preferably 0.0005 to 1 part by weight, more preferably 0.005 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). The amount is 0005 to 0.5 parts by weight, more preferably 0.001 to 0.5 parts by weight, and particularly preferably 0.001 to 0.1 parts by weight. Within such a range, better UV resistance and hue, thermal stability and light transmittance are compatible.

(Vii) Antistatic agent The polycarbonate resin composition of the present invention may require antistatic performance (for example, to prevent adhesion of dust during printing). In such a case, it is preferable to include an antistatic agent. . Examples of the antistatic agent include (i) an organic sulfonic acid phosphonium salt such as an aryl sulfonic acid phosphonium salt represented by (i) dodecylbenzenesulfonic acid phosphonium salt, and an alkyl sulfonic acid phosphonium salt, and a tetrafluoroboric acid phosphonium salt. Examples thereof include phosphonium borate salts. The phosphonium salt has an appropriate composition ratio of 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and 1.5 to 3 parts by weight. A range of parts is more preferred.

  Examples of the antistatic agent include (ii) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Organic sulfonate alkali (earth) metal salts of Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The organic sulfonate alkali (earth) metal salt has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and 0.005 to 0.005. 2 parts by weight is more preferred. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (iii) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The composition ratio of the ammonium salt is 0.05 parts by weight or less per 100 parts by weight of the component A. Examples of the antistatic agent include (iv) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less per 100 parts by weight of component A.

(Viii) Hydrolysis improver In the polycarbonate resin composition of the present invention, various hydrolysis improvers are blended for the purpose of improving the hydrolysis resistance of the component A as long as the object of the present invention is not impaired. You can also. Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include an alicyclic epoxy compound represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and a silicon atom-containing epoxy represented by 3-glycidylpropoxy-triethoxysilane. The compound is preferably exemplified. The content of the hydrolysis improver is preferably in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of component A.

(Ix) Compound having heat ray absorbing ability In the polycarbonate resin composition of the present invention, a compound having heat ray absorbing ability in an amount that does not impair the object of the present invention can be used. Examples of the compound include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. Examples of carbon fillers include carbon black, graphite (including both natural and artificial, and whiskers), carbon fibers (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon. Black and graphite. These can be used alone or in combination of two or more. The phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, with respect to 100 parts by weight of the polycarbonate resin (component A). 0.07 part by weight is more preferable. The metal oxide near-infrared absorber, metal boride-based near infrared absorber and carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention, and in the range of 0.5 to 100 ppm. Is more preferable.

(X) Other dyes / pigments In the polycarbonate resin composition of the present invention, various dyes / pigments can be used in addition to the bluing agent and the fluorescent dye as long as the effects of the invention are exhibited. In particular, a dye is preferable because it does not impair the transparency. On the other hand, a deeper color or a metallic pigment can be blended to obtain a better metallic color.

  As dyes, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. The amount of these dyes used is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, per 100 parts by weight of the polycarbonate resin of component A.

  In the polycarbonate resin composition of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of the flame retardant include brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, sulfonate salt Organic acid metal salts other than these, silicone flame retardants, and the like can be used, and one or more of them can be used. Each of these flame retardants can be blended in a known amount relative to the polycarbonate resin.

  In the polycarbonate resin composition of the present invention, other resins and elastomers other than the component B can be used in a small proportion without impairing the object of the present invention. The resin is not particularly limited, but from the viewpoint of transparency when blended with a polycarbonate resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cyclohexanedimethanol (CHDM) copolymerized polyethylene terephthalate, polyarylate, polysulfone, polyphenylene ether An epoxy resin, a phenoxy resin, and the like are preferably exemplified. Such other resin is preferably in the range of 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of component A.

  Further, the polycarbonate resin composition of the present invention includes various inorganic fillers, flow modifiers (other than component B), antibacterial agents, photocatalytic antifouling agents, light diffusing agents, white pigments for high light reflection, and photochromic agents. Etc. can be blended.

(Haze value)
The polycarbonate resin composition of the present invention is preferably a smooth plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm, and having a haze measured by JIS K7105 of 0.3 to 3 μm. It is preferable to satisfy 20%, more preferably 0.3 to 5%, and still more preferably 0.3 to 3%. The haze value is measured using a haze meter. Such a smooth flat plate is obtained by subjecting the pellets to predetermined drying, and then injection-molding the pellets into a cavity constituted by a mold surface having an arithmetic average roughness (Ra) of 0.03 μm. The arithmetic average roughness (Ra) of the mold surface can be measured using a surface roughness meter.

(About the manufacturing method of a resin composition)
In producing the polycarbonate resin composition of the present invention, the production method is not particularly limited. However, the polycarbonate resin composition of the present invention is preferably produced by melt-kneading each component.

  Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, and an extruder. Among them, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin screw extruder is more preferable. In such a twin screw extruder, a more preferred embodiment is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw that has a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 45, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  Furthermore, as an extruder, what has a vent which can deaerate the water | moisture content in a raw material and the volatile gas generate | occur | produced from melt-kneading resin can be used preferably. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Furthermore, the feeding method of the component B and other additives (simply referred to as “additive” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified. (I) A method of supplying the additive into the extruder independently of the polycarbonate resin. (Ii) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. In any method, the polycarbonate-polyorganosiloxane copolymer of the A1 component and the other polycarbonate in the polycarbonate resin may be an integral mixture or may be independent solids.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to an extruder. Another method is a method in which a master agent containing a high concentration of additives is prepared, and the master agent is separately or further premixed with the remaining polycarbonate resin or the like and then supplied to the extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer, but a high-speed stirring type mixer such as a super mixer is preferable. Still another premixing method is, for example, a method in which a polycarbonate resin and additives are uniformly dispersed in a solvent and then the solvent is removed. Further, as the third method, (iii) a method in which an additive and a polycarbonate resin are previously melt-kneaded to form a master pellet.

  The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and 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, and still more preferably 2.5 to 3.5 mm.

(About a molded article made of the resin composition of the present invention)
The polycarbonate resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The polycarbonate resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. Furthermore, it can be formed as a heat-shrinkable tube or an optical functional film by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  Thereby, a molded article having excellent transparency and durability and comprising a thin-walled polycarbonate resin composition is provided. Furthermore, various surface treatments can be performed on the molded article made of the polycarbonate resin composition of the present invention. Surface treatment here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Hard coat is a particularly preferred and required surface treatment.

  Since the polycarbonate resin composition of the present invention has improved fluidity, transparency, and durability, it can be used for parts that could not be used conventionally by taking advantage of such characteristics. Among them, it is suitable for the use of thin-walled injection-molded products, and is particularly suitable for applications requiring transparency and receiving repeated external forces. Specific examples of thin-walled injection molded products include various housing molded products such as battery housings, lens barrels, memory cards, speaker cones, disk cartridges, surface light emitters, mechanical parts for micromachines, hinged molded products or hinge molded products, Illustrative examples include translucent and light guiding buttons and touch panel components. Therefore, the industrial effect that it produces is exceptional.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method. The following raw materials were used as raw materials.

(I) Evaluation of polycarbonate resin composition (i) Transparency of molded product: An injection molding machine (Sumitomo Heavy Industries, Ltd.) using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm. SG-150U) manufactured under the conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C., a width of 50 mm, a length of 90 mm and a thickness of 3 mm (length 20 mm) and 2 mm (length) from the gate side in a molding cycle of 50 seconds. A three-stage plate having a length of 45 mm) and 1 mm (length 25 mm) was molded. The total light transmittance and haze of the molded plate having a thickness of 2.0 mm of the three-stage plate were measured according to ASTM D1003. Haze is the turbidity of the molded product. The lower the value, the less turbidity.
(Ii) Fluidity: Using a Sumitomo Heavy Industries, Ltd. SG-150U molding machine, the flow length was evaluated with an Archimedes spiral flow mold (channel thickness 2 mm, channel width 8 mm). The conditions were a cylinder temperature of 290 ° C., a mold temperature of 70 ° C., and an injection pressure of 100 MPa.
(Iii) Fatigue characteristics: Using the so-called """shaped""test piece shown in FIG. 1, the difference in the number of times to break in the fatigue test in each sample was observed (breaking means that the test piece bears the test load) It means the state of disappearing and does not mean that the test piece is cut in two). The average value of the three test pieces was defined as the number of breaks. The test was performed under the conditions of a temperature of 23 ° C., a relative humidity of 50%, a sine wave with a frequency of 1 Hz, and a maximum load of 6.86 N (7 kgf). A fatigue testing machine (Shimadzu servo pulsar EHF-FD1-10LA type manufactured by Shimadzu Corporation) was used as a test apparatus. The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds.

(Examples 1-5 and Comparative Examples 1-3)
A resin composition having the blending ratio shown in Table 1 was prepared as follows. The description will be made according to the symbols in the following table. The ingredients listed in Table 1 were all weighed into a polyethylene bag, and the bag was shaken to create a uniform premix. This preliminary mixture was supplied to the first inlet of the last part of the vent type twin screw extruder (Japan Steel Works TEX-30XSST) having a screw diameter of 30 mm. Extrusion is performed using a vacuum pump at a cylinder temperature of 230 ° C. to 280 ° C. (raise almost uniformly from the barrel of the screw to the die), a screw rotation speed of 180 rpm, and a discharge rate of 15 kg per hour. It was. The extruded strand was cooled in a water bath, then cut with a pelletizer and pelletized. The obtained pellets were dried at 120 ° C. for 6 hours using a hot air circulating dryer, and then the above test specimens were prepared.
The raw materials used in Table 1 are as follows.

(A component)
(A1 component)
PC-PDMS-1: The viscosity average molecular weight produced by the following production method was 20,300, the polydimethylsiloxane component content with an average polymerization degree of 25 was 4% by weight, and the n-hexane extraction ratio was 1.2% by weight. A polycarbonate-polyorganosiloxane copolymer having a molecular weight distribution Mw / Mn of 2.4.
PC-PDMS-2: Viscosity average molecular weight produced by the following production method is 20,000, polydimethylsiloxane component content having an average polymerization degree of 38 is 4% by weight, and n-hexane extraction ratio is 1.7% by weight. A polycarbonate-polyorganosiloxane copolymer having a molecular weight distribution Mw / Mn of 2.4.
PC-PDMS-3: Viscosity average molecular weight produced by the following production method was 16,000, polydimethylsiloxane component content with an average polymerization degree of 25 was 4% by weight, and n-hexane extraction ratio was 1.3% by weight. A polycarbonate-polyorganosiloxane copolymer having a molecular weight distribution Mw / Mn of 2.4.
PC-PDMS-4 (for comparison): Viscosity average molecular weight produced by the following production method is 20,000, polydimethylsiloxane component content of average polymerization degree 67 is 3.9% by weight, and n-hexane extraction ratio is A polycarbonate-polyorganosiloxane copolymer having 2.2% by weight and a molecular weight distribution Mw / Mn of 2.4.

  Production of the A1 component used above was performed as follows. In this description, “parts” indicates parts by weight.

(Method for producing PC-PDMS-1): A reactor equipped with a thermometer and a stirrer was charged with 3310 parts of ion-exchanged water and 650 parts of a 48.5% by weight aqueous sodium hydroxide solution, and 1.2 parts of hydrosulfite was added thereto. Subsequently, after 596 parts of bisphenol A was dissolved, 2230 parts of methylene chloride was added and 312 parts of phosgene was blown in at 40 ° C. for about 40 minutes while stirring vigorously. After completion of the phosgene blowing, the temperature of the reaction solution was raised to 28 ° C., and both ends were capped with 16 parts of p-tert-butylphenol, 173 parts of 48.5% by weight sodium hydroxide aqueous solution, and o-allylphenol. After adding 31 parts of polydimethylsiloxane (X-22-1875 manufactured by Shin-Etsu Chemical Co., Ltd.) having an average polymerization degree of 25 containing a phenolic hydroxyl group to the emulsified state, the mixture was vigorously stirred again. Under such stirring, 0.9 part of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 1 hour at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. The methylene chloride was evaporated while stirring to obtain a copolymer powder. The copolymer had a viscosity average molecular weight of 20,300 and a polydimethylsiloxane component content of 3.95% by weight. This content was calculated based on the measurement of ¹ H-NMR. The obtained copolymer was subjected to Soxhlet extraction with n-hexane (special grade manufactured by Wako Pure Chemical Industries, Ltd.) for 3 hours at a cycle of 20 times / hour, and the n-hexane extraction ratio was calculated. This ratio was 1.2% by weight in 100% by weight of polydimethylsiloxane contained in the copolymer. The molecular weight distribution Mw / Mn calculated by GPC measurement was 2.4.

  (Production method of PC-PDMS-2): In the production method of PC-1, both ends are capped with o-allylphenol as polydimethylsiloxane, and an average degree of polymerization of 38 containing phenolic hydroxyl groups at both ends. A copolymer powder was obtained in the same manner as in PC-1 except that 31 parts of polydimethylsiloxane (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane component content of 4% by weight, an n-hexane extraction ratio of 1.7% by weight, and a molecular weight distribution Mw / Mn of 2.4. It was.

  (Production method of PC-PDMS-3): A copolymer powder was obtained in the same manner as in the production method of PC-1 except that 24 parts of p-tert-butylphenol was used. The copolymer had a viscosity average molecular weight of 16,000, a polydimethylsiloxane component content of 4% by weight, an n-hexane extraction ratio of 1.3% by weight, and a molecular weight distribution Mw / Mn of 2.4. It was.

  (Manufacturing method of PC-PDMS-4): In the manufacturing method of said PC-1, as polydimethylsiloxane, both ends are capped with o-allylphenol, and the average degree of polymerization 67 containing phenolic hydroxyl groups at both ends A copolymer powder was obtained in the same manner as the method for producing PC-1, except that 31 parts of polydimethylsiloxane (X-22-1822 manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The copolymer has a viscosity average molecular weight of 20,000, a polydimethylsiloxane component content of 3.9% by weight, an n-hexane extraction ratio of 2.2% by weight, and a molecular weight distribution Mw / Mn of 2.4. Met.

(Polycarbonate other than A1 component)
PC-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 (Panlite L-1225WX manufactured by Teijin Chemicals Ltd.)
PC-2: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 16,000 (Panlite CM-1000 manufactured by Teijin Chemicals Ltd.)

(B component)
B-1: A polycarbonate oligomer having an average degree of polymerization of about 7 and a number average molecular weight of 2,400 produced by the following production method.

  Manufacture of B-1 component was performed as follows. In this description, “parts” indicates parts by weight.

  (Production method of B-1): A thermometer and a reactor equipped with a stirrer were charged with 3310 parts of ion-exchanged water and 650 parts of a 48.5 wt% aqueous sodium hydroxide solution, followed by 1.2 parts of hydrosulfite. After dissolving 596 parts of bisphenol A, 2230 parts of methylene chloride was added and 325 parts of phosgene was blown into the reaction at 17 ° C. with vigorous stirring for about 40 minutes. After completion of the phosgene blowing, the temperature of the reaction solution was raised to 28 ° C., and 173 parts of a 48.5% by weight aqueous sodium hydroxide solution and 118 parts of p-tert-butylphenol dissolved in 955 parts of methylene chloride were added. Then, the mixture was vigorously stirred again. Under such stirring, 1.8 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 1 hour at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, so that the conductivity of the aqueous phase was almost the same as that of ion-exchanged water. Methylene chloride was evaporated from the methylene chloride solution to obtain a polycarbonate oligomer. From the end group analysis by NMR, the number average molecular weight was 2,400.

(C component: mold release agent)
C-1: Glycerol monostearate with a sodium metal content of 0.2 ppm (manufactured by Riken Vitamin Co., Ltd.)
C-2: Glycerol monostearate having a sodium metal content of 9.8 ppm (manufactured by Riken Vitamin Co., Ltd.)

  In addition, said sodium metal content is measured by the method as described in WO2006 / 025587 pamphlet. Moreover, this stearic acid shows that it is a main component and is a mixture which uses vegetable oil as a raw material.

(Other ingredients)
ST-P1: Phosphonite heat stabilizer (manufactured by Clariant: Sandstub P-EPQ (trade name))
ST-P2: Phosphite-based heat stabilizer (Ciba Specialty Chemicals: Irgafos 168)
ST-H1: Phenolic antioxidant (Irganox 1076 (trade name) manufactured by Ciba Specialty Chemicals)
UVA: 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) (manufactured by Takemoto Yushi Co., Ltd .: CEi-P)
BLM: A blueing agent master obtained by uniformly mixing a blueing agent (manufactured by Bayer Co., Ltd .: Macrolex Violet B) with the above PC-2 and a super mixer so as to be 0.1% by weight.

From the comparison between Examples and Comparative Examples in Table 1, it can be seen that the polycarbonate resin composition of the present invention is excellent in durability represented by transparency, fluidity and fatigue characteristics.
Further, the pellets obtained in the above Examples 1 to 4 were manufactured using Sumitomo Heavy Industries, Ltd. SG260M-HP, cylinder temperature 320 ° C., mold temperature 80 ° C., firing speed 50 mm / sec, and molding. A test piece for UL94 combustion test having a thickness of 0.4 mm was formed under a cycle of 70 seconds. In any case, a transparent molded product free from short shots, defective mold release and residual strain was obtained. All the haze values were 0.3 to 0.4.

  Since the polycarbonate resin composition of the present invention is excellent in transparency and fluidity, in addition to the applications described above, a small lens and lens unit, an optical card substrate, a display cover, and various housings that require visual effects. It is applicable to a wide range of fields such as bodies, game machines and their circuit protection covers, sensor covers, and medical equipment. In addition, the above-mentioned button molded product can be applied to a button molded product having a structure in which the sheet-shaped member and the button part are integrally formed by injection molding, which is bonded to the sheet-shaped member after being cut from the sprue. become. In such a case, the thickness of the sheet-like member is generally 50 to 200 μm, and can be applied to an injection molded product having such a very thin portion.

It is a front view of what is called a U-shaped test piece used in order to evaluate fatigue property. The thickness of the test piece is 3 mm. A jig of a testing machine is passed through the hole portion indicated by reference numeral 4 and a test is performed by applying a predetermined load in the vertical direction indicated by reference numeral 3.

Explanation of symbols

1 U-shaped test piece main body 2 Broken line 3 indicating the coupling position of the U-shaped portion and the arc portion 3 Direction of load imposed on the test piece on the fatigue test character 4 Jig mounting hole (3 mm diameter circle)
5 The central angle (60 °) indicating the position of the jig mounting hole, and 6 the target axis of the test piece centered on the intersection of 7 (upper and lower symmetry in the figure)
7 Intersection of broken line 2 and axis of symmetry 8 Angle of the U-shaped part (90 °)
9 R surface of the inner part of the U-shaped part (R1.5: radius 1.5mm)
10 R surface of the outer part of the U-shaped part (R10: radius 10mm)
11 Width of the U-shaped part (10mm)

Claims (11)

It consists of a polycarbonate-polyorganosiloxane copolymer (A1 component) containing a polyorganosiloxane unit of the following general formula (α1), or a polycarbonate other than the A1 component and the A1 component, and the polyorganosiloxane unit content is 0.1 to 20 parts by weight of polycarbonate oligomer (component B) having an average degree of polymerization of 3 to 15 with respect to 100 parts by weight of polycarbonate resin (component A) of 0.1 to 20% by weight in 100 parts by weight of component A A polycarbonate resin composition.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different, and R ₅ represents a group derived from an aliphatic or aromatic compound. And n represents the number of repeating units in parentheses, the number average value of which is 10 to 60, and the constituent units in parentheses may be a mixture of two or more.) A polycarbonate-polyorganosiloxane copolymer having a structural unit represented by the following general formula (α2) as the general formula (α1) of the A1 component and having a structural unit represented by the following general formula (i): 2. The polycarbonate resin composition according to 1.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ , and n are the same as those in the general formula (α1), R ₁₁ and R ₁₂ represent an alkylene group having 2 to 6 carbon atoms, Y may be the same or different, and Y represents R ₁₁ or R ₁₂ bonded to the benzene ring and a hydrogen atom or an alkoxy group substituted at a different position from the oxygen atom (O).

(A is at least one divalent organic residue selected from the group consisting of the following formulas (i-1) to (i-3) and (i-5), a single bond, or the following formula (i-4 ) And s and t are each independently 0 or an integer of 1 to 4, and R ₁₃ and R ₁₄ are each independently a halogen atom or an alkyl group having 1 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon number It represents an organic residue selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms.)

(In formula (i-1), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In formula (i-2), R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms.)

(In the above formula (i-3), u represents an integer of 4 to 11, and the plurality of R ₂₁ and R ₂₂ are each independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. Represents a group to be

(In formula (i-5), R ₂₃ and R ₂₄ each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms.)   The polycarbonate resin composition according to claim 1, wherein the component A has a viscosity average molecular weight in the range of 16,000 to 25,000.   The polycarbonate resin composition according to claim 3, wherein the A1 component has a viscosity average molecular weight in the range of 16,000 to 25,000.   The A component has a polyorganosiloxane unit content of 1 to 20% by weight in 100% by weight of the A1 component, and a polyorganosiloxane unit content in 100% by weight of the A component of 0.5 to 5% by weight. The polycarbonate resin composition according to any one of claims 1 to 4.   N in the said general formula ((alpha) 1) is the range of 16-50, The polycarbonate resin composition of any one of Claims 1-5. The said B component is an oligomer which consists of a structural unit of the following general formula ((beta) 1), The polycarbonate resin composition of any one of Claims 1-6.

(In the formula (β1), A, s, t, R ₁₃ and R ₁₄ all represent the same group, atom or numerical value as in the above formula (i).) The polycarbonate resin composition according to claim 7, wherein the component B is an oligomer represented by the following general formula (β2).

(In the formula (β2), A, s, t, R ₁₃ and R ₁₄ all represent the same group, atom or numerical value as in the above formula (i), and Z is a hydrogen atom or a part of the hydrogen atom. C1-C9 linear or branched alkyl group or phenyl group-substituted alkyl group optionally substituted with a fluorine atom, C10-50 long-chain alkyl group, polyorganosiloxane having 4-40 silicon atoms A chain, or —X—C _m H _{2m + 1} , where X is —R—O—, —R—CO—O— or —R—O—CO—, where R is a single bond or carbon number 1-10 divalent aliphatic hydrocarbon groups are represented, m represents an integer of 10-50.)   The polycarbonate resin composition according to any one of claims 1 to 8, wherein a haze having a thickness of 2 mm measured by JIS K7105 is 0.3 to 20%.   A transparent resin molded product obtained by injection molding the polycarbonate resin composition of claim 9.   The transparent resin molded product according to claim 10, wherein the injection molded product is mainly composed of a portion having a thickness of 0.05 to 0.5 mm.

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