CN101434750B - Polycarbonate resin composition - Google Patents

Abstract

An object of the present invention is to provide a polycarbonate resin material having improved fluidity, transparency and durability. The present invention provides a resin composition, which contains a polycarbonate resin (A component) and a polycarbonate oligomer (B component), relative to 100 parts by weight of A component, B component is 0.1 to 20 parts by weight, wherein , A component is composed of a polycarbonate-polyorganosiloxane copolymer (A1 component) containing a polyorganosiloxane unit with a number average degree of polymerization of 10 to 60, or is composed of the A1 component and a polycarbonate other than the A1 component. It is composed of ester, and the polyorganosiloxane unit content in 100% by weight of component A is 0.1-20% by weight; the average degree of polymerization of component B is 3-15.

Description

polycarbonate resin composition

technical field

The present invention relates to a polycarbonate resin composition having improved fluidity, transparency and durability. More specifically, the present invention relates to a resin composition having the above-mentioned properties improved by combining a specific polyorganosiloxane-polycarbonate copolymer and a polycarbonate oligomer, and a thin film formed from the above-mentioned resin composition. Wall moldings.

Background technique

Polycarbonate resins can be used in various applications such as mechanical parts, automobile parts, electric and electronic parts, etc., due to their excellent characteristics of mechanical strength and transparency. In recent years, various resin components have become thinner due to the miniaturization (including thinning) and weight reduction of portable information terminals represented by mobile phones, smart phones, and mobile computers (for example, refer to Patent Document 1). Therefore, a resin material forming such a part requires high fluidity in order to form a thin wall, and on the other hand, requires practical durability of a thin-wall molded product. Furthermore, among the components constituting the portable information terminal, a transparent hard resin may be used for a button component of a key. In such parts, transparent polycarbonate resin is used from the viewpoint of transparency, mechanical strength and durability. Due to the above-mentioned thinning trend, it is required for such components to maintain good transparency while taking into account thin walls and repeated compression strength during button input. Therefore, such polycarbonate resin materials with improved fluidity, transparency and durability are often required.

As a button part material for a portable information terminal formed from a polycarbonate resin composition, it has been proposed to use a polycarbonate resin with a viscosity average molecular weight of 16,000 to 22,000 to add an oligomer-type phosphate ester to a key for a portable information terminal. Resin composition (see Patent Document 2). In addition, a key molded product for a portable information terminal formed of a resin composition composed of polycarbonate resin and styrene-acrylonitrile copolymer (AS) resin (the weight average molecular weight of the resin of the embodiment is about 78,000) has been proposed (see patent Document 3). There is also proposed a key molded product for a portable information terminal molded using 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). Also, a key molded product for a portable information terminal molded from a polycarbonate resin composition composed of a polycarbonate resin, a phosphazene compound, a heat stabilizer, and a mold release agent has been proposed (see Patent Document 5). Furthermore, as a known document, there is a healthy molded product for a portable information terminal composed of a polyorganosiloxane-polycarbonate copolymer and a mold release agent (see Patent Document 6).

On the other hand, techniques for maintaining transparency and improving flow characteristics by blending polycarbonate oligomers into polycarbonate-based materials are disclosed (see Patent Documents 7 and 8). In addition, it is also disclosed that polyorganosiloxane-polycarbonate copolymer, polycarbonate resin, polycarbonate oligomer, and organically treated montmorillonite (montmorillonite) are mixed using a Banbury mixer. A resin composition obtained by extrusion (see Patent Document 9). However, the compounding effect of the polycarbonate oligomer in this resin composition is limited to a slight increase in the low-temperature impact value.

(Patent Document 1) JP Unexamined Publication No. 2007-048602

(Patent Document 2) JP Unexamined Publication No. 2004-346112

(Patent Document 3) JP Unexamined Publication No. 2005-044130

(Patent Document 4) JP Unexamined Publication No. 2006-092951

(Patent Document 5) JP Unexamined Publication No. 2007-045909

(Patent Document 6) JP Unexamined Patent Publication No. 11-045139

(Patent Document 7) JP Unexamined Publication No. 2006-188594

(Patent Document 8) JP Unexamined Patent Publication No. 61-123658

(Patent Document 9) JP Special Publication No. 2007-514854

Contents of the invention

As mentioned above, in order to obtain the current state of the polycarbonate resin material with improved fluidity, transparency and durability, the above-mentioned prior art mainly aims at the improvement of formability, but does not fully consider the durability at the time of use. . An object of the present invention is to provide a polycarbonate resin material having improved fluidity, transparency and durability which have not been sufficiently considered in the prior art. In order to achieve such purpose, the present inventors etc. have been through meticulous and continuous research, and as a result, it has been found that by combining polycarbonate copolymers and polycarbonate oligomers containing specific polyorganosiloxane structures, the above-mentioned Purpose. Polycarbonate oligomers are known to be effective mainly on general-purpose bisphenol A-type polycarbonate resins, but they can also give good results to polycarbonate resins containing polycarbonate-polyorganosiloxane copolymers. It was also surprisingly found that the excellent durability of the polycarbonate resin was not greatly reduced. Based on the above findings, we have accomplished the present invention.

The object of the present invention described above is accomplished as follows.

(1) A resin composition comprising a polycarbonate resin (component A) and a polycarbonate oligomer (component B), wherein the component B is 0.1 to 20 parts by weight based on 100 parts by weight of the component A, wherein, Component A consists of a polycarbonate-polyorganosiloxane copolymer (component A1) containing a polyorganosiloxane unit represented by the following general formula (α1), or consists of the component A1 and a polycarbonate other than the component A1. It is composed of ester, and the polyorganosiloxane unit content in 100% by weight of component A is 0.1-20% by weight; the average degree of polymerization of component B is 3-15.

(wherein, R ₁ , R ₂ , R ₃ and R ₄ represent alkyl or phenyl groups with 1 to 6 carbon atoms, the same or different; R ₅ represents a divalent organic residue derived from aliphatic or aromatic compounds ; n represents the repeating number of the units in the brackets, and the average value of the repeating numbers is 10 to 60; the structural units in the brackets are mixtures of more than two kinds or not.)

The polycarbonate resin which is A component is excellent in transparency and durability. Since the compatibility of component B and component A is excellent, transparency and favorable durability can be maintained from this point.

The composition ratio of A component and this B component is 0.1-20 weight part with respect to 100 weight part of A component, Preferably it is 1-15 weight part, More preferably, it is 2-9 weight part.

One of the suitable embodiments of the present invention is (2) a resin composition, which is the resin composition of the above-mentioned (1), wherein the polycarbonate-polyorganosiloxane copolymer as the above-mentioned A1 component has It is a structural unit of the following general formula (α2) which is general formula (α1) and has a structural unit represented by the following general formula (i).

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ and n are the same as the above general formula (α1); R ₁₁ and R ₁₂ represent alkylene groups with 2 to 6 carbon atoms, and these groups are the same or different; Y represents a hydrogen atom or an alkoxy group substituted at different positions of R ₁₁ , R ₁₂ and oxygen atom (O) combined with the benzene ring.)

(A represents 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) Any bond selected; s and t are independently 0 or an integer of 1 to 4; _R13 and _R14 independently represent a halogen atom or an alkyl group with 1 to 10 carbon atoms, carbon Alkoxy group with 1 to 10 atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, aryl group with 6 to 10 carbon atoms, aryl group with 7 to 20 carbon atoms An organic residue selected from the group consisting of an aralkyl group, 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 represent 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 independently represent a group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. group selected from the group.)

(In the formula, in (i-5), R ₂₃ and R ₂₄ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group with 1 to 10 carbon atoms.)

The above-mentioned α2 can provide a resin composition having excellent hydrolysis resistance and further excellent durability.

One of suitable embodiment of this invention (3) Resin composition which is the resin composition of said (1)-(2) whose viscosity average molecular weight of the said A component is the range of 16,000-25,000. When the viscosity-average molecular weight (M) of component A is less than 10,000, it is difficult to obtain practical mechanical strength in many fields. If it exceeds 50,000, the melt viscosity of the resin composition is high, and a high molding processing temperature is generally required. The average molecular weight is suitably in the range of 10,000 to 50,000. Furthermore, the viscosity-average molecular weight of the component A is 16,000 to 25,000, more preferably 17,000 to 21,000 in parts requiring durability in the thin-walled molded product described above.

Moreover, (4) the resin composition which is one of suitable embodiment of this invention which is the resin composition of said (3) whose viscosity average molecular weight of the said A1 component is the range of 16,000-25,000. The viscosity average molecular weight of the A component of this invention in said (3) can also be prepared by mixing the A1 component outside this range, and the polycarbonate other than A1 component. Therefore, for example, component A having a viscosity average molecular weight of 20,000 can be obtained by mixing component A1 having a viscosity average molecular weight of 100,000 and another polycarbonate resin having a viscosity average molecular weight of 15,000. However, mixing of components with a large difference in viscosity average molecular weight generally tends to cause a decrease in transparency, so it is preferable that the A1 component is also within the range of the viscosity average molecular weight of the above-mentioned A component. Therefore, according to this (4), a resin composition more excellent in transparency can be provided.

One of the preferred embodiments of the present invention is (5) a resin composition, which is the resin composition of the above-mentioned (1) to (4), wherein the above-mentioned A component, 100% by weight of the polyorganic acid contained in the A1 component The unit content of siloxane is 1 to 20% by weight, and the unit content of polyorganosiloxane in 100% by weight of component A is 0.5 to 5% by weight. The unit content of polyorganosiloxane contained in 100% by weight of component A1 is not particularly limited, but if it is too high, the transparency of the resin composition tends to decrease, so it is suitable to be in the range of 0.1 to 40% by weight. . 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. When it is lower than the lower limit of the appropriate range, the adjustment range of the polyorganosiloxane concentration in component A is limited, and the production efficiency deteriorates, but when the upper limit of the appropriate range is exceeded, the transparency cannot be stably exhibited, thus lead to poor productivity. In addition, the unit content of polyorganosiloxane 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, and most preferably 2 to 4% by weight. weight percent range. The above (5) is constituted by controlling the unit content of the polyorganosiloxane contained in 100% by weight of the component A to the more suitable range using the A1 component having the appropriate polyorganosiloxane unit content. Thereby, the resin composition compatible with transparency and durability can be provided.

One of the preferred embodiments of the present invention is (6) a resin composition, which is the resin composition of (1) to (5) above, wherein n in the above general formula (α1) is 16 to 50 scope. When n indicating the degree of polymerization of the polyorganosiloxane is less than 10, sufficient durability cannot be imparted to the resin composition, and on the other hand, when it exceeds 60, transparency will deteriorate. From the viewpoint of transparency, microdispersion is required, and from the viewpoint of durability, it is advantageous to have a certain degree of layer separation. More suitably, this n is 16-50, and it is the range of 20-40 more suitably. According to this (6), better transparency and durability can be achieved at the same time.

As one of the preferred embodiments of the present invention, (7) a resin composition, which is the resin composition of the above-mentioned (1) to (6), wherein the above-mentioned B component is represented by the following general formula (β1): An oligomer formed of structural units.

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

Oligomers formed from the above structural units have excellent thermal stability and are suitable for thin-wall molding that requires high-temperature molding. In particular, a more suitable embodiment is (8) a resin composition which is the resin composition in (7) above, wherein the B component 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 the above-mentioned formula (i); Z is a hydrogen atom, a part of the hydrogen atom is substituted by a fluorine atom or not Straight-chain or branched-chain alkyl groups or phenyl-substituted alkyl groups with 1-9 carbon atoms substituted by fluorine atoms, long-chain alkyl groups with 10-50 carbon atoms, polysiloxane with 4-40 silicon atoms Alkane chain, or -XC _m H _2m+1 , wherein, X is -R—O—,—R—CO—O—or—R—O—CO—, the R represents a single bond or the number of carbon atoms is 1～ 10 binary aliphatic hydrocarbon group; m represents an integer of 10 to 50, r represents an integer of 1 to 5, and p represents an integer of 3 to 15.)

By having this terminal structure, better thermal stability can be obtained, and a resin material suitable for high-temperature molding can be provided. And, due to the better thermal stability, injection molded products can obtain good durability.

One of the suitable embodiments of the present invention, (9) a resin composition, which is the resin composition of the above-mentioned (1) to (8), the haze value of 2 mm thickness measured by JIS K7105 is 0.3 to 20% . According to another aspect, (10) a transparent resin molded article obtained by injection molding a resin composition. One of the preferred embodiments is (11) a transparent resin molded article, which is the transparent resin molded article of (10) above, wherein the wall thickness of the injection molded article is mainly formed by a portion of 0.05 to 0.5 mm. Here, the transparent resin molded article has a haze value of 0.1 to 20%, preferably 0.2 to 4%, more preferably 0.2 to 2%.

Description of drawings

Fig. 1 is a front view of a so-called "<"-shaped test piece used for fatigue evaluation. In addition, the thickness of the test piece was 3 mm. The part of the hole indicated by the symbol 4 passes through the jig of the testing machine, and the test is carried out by applying a specified load in the vertical direction indicated by the symbol 3.

Reference signs:

1: The body of the "<" shaped test piece

2: A dotted line indicating the joint position of the "<" shape part and the arc part

3: The direction in which the test piece is loaded on the fatigue test body

4: Hole for fixture installation (circle with a diameter of 3mm)

5: Indicates the central angle (60°) of the position of the hole for fixture installation, which takes the intersection point of symbol 7 as the center

6: The axis of symmetry of the test piece (upper and lower symmetry on the picture)

7: Intersection of the dotted line of symbol 2 and the axis of symmetry 6

8: Angle of "<" shaped part (90°)

9: R surface of the inner part of the "<" shaped part (R1.5: radius 1.5mm)

10: R surface of the outer part of the "<" shaped part (R10: radius 10mm)

11: Width of "<" shaped part (10mm)

Detailed ways

Hereinafter, the present invention is described in more detail

(A1 component: polycarbonate-polyorganosiloxane copolymer)

As mentioned above, component A1 of this invention contains the polyorganosiloxane unit represented by general formula (α1). Specific examples of R ₁ , R ₂ , R ₃ and R ₄ in the general formula (α1) preferably include methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, heptyl, group, phenyl group, etc., particularly preferred is methyl group. R5 represents a divalent organic residue derived from an aliphatic or aromatic compound. In —Si—R ₅ —, when a —Si—O— bond is contained, examples of R ₅ include various alicyclic diol residues and divalent phenol residues. As the alicyclic diol and divalent phenol, the same polycarbonate as described below can be used. In —Si—R ₅ , when there is a —Si—C—bond, R ₅ preferably includes o-allylphenol residues, p-hydroxystyrene residues, 4-allyl-2-methoxy An allylphenol residue, an isopropenylphenol residue, and the like, and an ortho-allylphenol residue is particularly preferable. That is, as described above, it is preferable that the A1 component has a structural unit represented by the general formula (α2) as the general formula (α1). The R ₁₁ and R ₁₂ can include ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl and butane-1,4-diyl 2, 3-diyl and the like, among which, ethane-1,2-diyl and propane-1,3-diyl are preferable, and propane-1,3-diyl is particularly preferable.

In the polycarbonate-polyorganosiloxane copolymer of component A1, the polycarbonate unit to be copolymerized with the polyorganosiloxane unit is not particularly limited. That is, it may have various carbonate units obtained by reacting divalent phenol and/or aliphatic and/or alicyclic bifunctional alcohol with a carbonate precursor. Preferred are carbonate units derived from divalent phenols. Particularly preferred are the structural units represented by the general formula (i) as described above. On the other hand, the difunctional alcohol as the structural unit of the derived polycarbonate is more preferably an alicyclic diol, for example, cyclohexanedimethanol, cyclohexanediol, tricyclic (5.2. 1.0 ^2.6 ) Decane dimethanol, norbornane dimethanol, decahydronaphthalene-2,6-dimethanol, spiroethylene glycol, 1,4; 3,6-dianhydro-D-glucitol, 1,4 ; 3,6-dianhydro-D-mannitol and 1,4; 3,6-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 in which A in the formula (i) is a single bond include 4,4'-biphenol, 4,4'-bis(2,6-dimethyl)diphenol, and the like.

As a compound when A is formula (i-1), α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl) - m-diisopropylbenzene (commonly known as "bisphenol M") and α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, etc.

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

When A is a compound of formula (i-3), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5 —Trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane And 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, etc.

As a compound when A is any one of formula (i-4), 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, Phenyl ether, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenyl Base sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide and bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, etc.

When A is any one of the compounds in formula (i-5), 1,1-bis(4-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(2 -Hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyl-5-nitrophenyl)methane, bis(4-hydroxyl-2,6-dimethyl-3-methoxy phenyl)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 (commonly known as "bisphenol A"), 2,2-bis(4-hydroxy-3-methylphenyl)propane (commonly known as "bisphenol C"), 2,2-bis(3-phenyl Base-4-hydroxyphenyl)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-hydroxybenzene base) 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-methyl-4-hydroxyphenyl)decane and 1,1-bis(2,3-dimethyl-4 -Hydroxyphenyl) decane, etc.

Furthermore, as dihydric phenols derived from structural units other than formula (i), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms are preferable. Phenol, 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethylindan- 5-alcohol, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiroindane, 1-methyl-1,3-bis(4-hydroxyphenyl)-3-iso Propylcyclohexane, 1-methyl-2-(4-hydroxyphenyl)-3-[1-(4-hydroxyphenyl)isopropyl]cyclohexane, 1,6-bis(4-hydroxy Phenyl)-1,6-hexanedione and ethylene glycol bis(4-hydroxyphenyl) ether, etc.

Among the above-mentioned dihydric phenols, preferred in formula (i-1) is bisphenol M; preferred in formula (i-2) is 9,9-bis(4-hydroxyl-3-methylphenyl)fluorene; Preferred in formula (i-3) are 1,1-bis(4-hydroxyl phenyl) cyclohexane, 1,1-bis(4-hydroxyl-3-methylphenyl) cyclohexane, 1,1 - bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; preferred in formula (i-4) is 3,3'-dimethyl-4,4'-dihydroxy di phenylsulfide; and preferred in formula (i-5) are bisphenol A, bisphenol C and 1,1-bis(4-hydroxyphenyl)decane. Among them, bisphenol A is most preferable because it is excellent in strength and has good durability.

The polycarbonate-polyorganosiloxane copolymer can be produced by various known methods. A more preferable method is a method of reacting a polyorganosiloxane whose both ends are capped with a group having a phenolic hydroxyl group, and a carbonate oligomer. As another method, a method of reacting a polyorganosiloxane whose both ends are blocked by a group having a phenolic hydroxyl group and a dihydric phenol or an aliphatic diol coexists with a carbonate precursor, and A method of reacting a polyorganosiloxane having a chlorine atom at a terminal with a carbonate oligomer, and the like. In addition, in this reaction, the same conditions as those for normal polycarbonate polymerization can be used, and the polymerization conditions for polycarbonate will be described later. That is, in the A1 component, the production conditions, the components of the terminal stopper and the chain branching agent, and the like can be similarly used for polycarbonates other than the A1 component described later.

In addition, the polycarbonate-polyorganosiloxane copolymer contains a lot of free polyorganosiloxane used as a polymer raw material that is not bonded to polycarbonate or even in polyorganosiloxane A carbonate unit or a carbonate unit of a terminal stopper is bonded to an alkane, but these are not sufficient components (hereinafter referred to as "free polyorganosiloxane, etc."). The amount of free polyorganosiloxane and the like can be calculated by extraction treatment with n-hexane.

Aggregation of free polyorganosiloxane and the like tends to cause a reduction 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 extraction amount, is 10% by weight relative to the polyorganosiloxane component contained in the A1 component. or less, preferably 3% by weight or less, more preferably 2% by weight or less. On the other hand, from a practical point of view, the lower limit of the content ratio is about 0.1% by weight. In addition, the calculation of the n-hexane extraction amount is calculated by subjecting a weighed copolymer sample to Soxhlet extraction treatment with extra-grade n-hexane. This Soxhlet extraction treatment was performed for 3 hours at an average cycle of about 20 times/hour, and n-hexane was removed from the treated solution to calculate. In order to reduce free polyorganosiloxane, etc., it is necessary to adjust the addition ratio of raw materials or polymerization accelerators, emulsification state, temperature and stirring conditions, so that the monomers in the reaction system can fully react.

(polycarbonate)

Component A in the present invention may be composed of component A1 alone, or may be a mixture of component A1 and a polycarbonate other than component A1. As the polycarbonate other than the component A1, a known polycarbonate obtained by reacting a dihydric phenol and/or an aliphatic and/or alicyclic bifunctional 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. When the interfacial polycondensation method is used, a monohydric phenolic terminal stopper is usually used. As mentioned above, the polycarbonate of component A may also be a branched polycarbonate that is added to a dihydric phenol or alcohol to polymerize a trifunctional component. Furthermore, it may be a copolycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, and a vinyl monomer.

Among the polycarbonates other than the component A1, a polycarbonate having a structural unit represented by the above formula (i) is preferable. The specific examples and preferred embodiments are also as described above, and bisphenol A is particularly preferred. Other details about polycarbonates are described in WO03/080728 pamphlet, JP Patent Application Publication No. 6-172508, JP Patent Application Publication No. 8-27370, JP Patent Application Publication No. 2001-55435 and JP Patent Application Publication No. 2001-55435. Publication No. 2002-117580, etc. Moreover, the specific example of the difunctional alcohol which derives the structural unit of polycarbonate is the same as that of A1 component.

The polycarbonate may contain a branched chain component, and examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate include 4,6-dimethyl-2,4,6-tris(4-hydroxyl Diphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl) Benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis( 2-hydroxyl-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethyl Triphenols such as benzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferable. The structural unit derived from the polyfunctional aromatic compound is preferably 0.03 to 1 mol%, more preferably 0.07 to 0.7 mol%, in a total of 100 mol% of structural units derived from other divalent components, and particularly Preferably it is 0.1 to 0.4 mol%. In addition, the branched structural unit may be derived not only from a polyfunctional aromatic compound, but may also be derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. In addition, the ratio to the branched chain structure can be calculated by ¹ H-NMR measurement. As mentioned above, you may contain a branched chain component in A1 component.

Polycarbonates include polyester carbonates obtained by copolymerizing aromatic or aliphatic (including alicyclic) difunctional carboxylic acids. The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include, for example, sebacic acid (sebacic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosadioic acid. Alicyclic diacids such as chain saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Units derived from this dicarboxylic acid may also be contained in component A1.

The viscosity average molecular weights of A component and A1 component are as above-mentioned, however, polycarbonate may be obtained by mixing the polycarbonate outside the range. In particular, polycarbonate having a viscosity-average molecular weight exceeding 50,000 can increase the melt tension of the resin composition and improve molding processability based on this characteristic. The upper limit thereof is preferably 300,000. The high-molecular-weight polycarbonate can be mixed in a target ratio of 20% by weight in the component A, and adjusted to satisfy a predetermined molecular weight range, thereby improving molding processability.

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

In addition, in this polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as the terminal stopper. As the monofunctional phenols, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used.

The organic solvent solution of polycarbonate obtained by the interfacial polycondensation method is usually washed with water. In this water washing step, it is preferable to use water having a conductivity of 10 μS/cm or less, more preferably 1 μS/cm or less, such as ion-exchanged water. In the water washing process, after mixing and stirring the above-mentioned organic solvent solution and water, let stand or use a centrifuge to separate the organic solvent solution phase and the water phase, take out the organic solvent solution phase, and repeat the above operation, thereby removing the aqueous solution. sexual impurities. By washing with high-purity water, water-soluble impurities can be effectively removed, and the hue of the obtained polycarbonate can be improved. In addition, in order to remove impurities such as catalysts, acid washing or alkali washing may also be preferably performed on the above-mentioned organic solvent solution of polycarbonate.

In addition, it is preferable to remove foreign matter which is an insoluble impurity with respect to the said organic solvent solution. As the method of removing foreign matter, it is preferable to employ a method of filtering or a method of treating with a centrifuge.

The above-mentioned organic solvent solution washed with water is then subjected to an operation for removing the solvent to obtain polycarbonate resin particles.

As a method of obtaining polycarbonate resin powder (granulation process), in view of the simplicity of operation or post-processing, a granulation device in which polycarbonate powder and warm water (about 65 to 90°C) exist is used. In this method, an organic solvent solution of polycarbonate is continuously supplied while stirring, and the solvent is evaporated to produce a slurry. As the granulation device, a mixer such as a stirring tank or a kneader can be used. The generated slurry is continuously discharged from the upper or lower part of the granulation device. Next, hot water treatment may be performed on the discharged slurry. The hot water treatment process is to supply the slurry into a hot water treatment container with hot water at 90-100°C or after supplying it, and then adjust the water temperature to 90-100°C by blowing steam or the like to remove the slurry contained in the slurry. in organic solvents.

For the slurry discharged in the granulation process or the amount of slurry after hot water treatment, water and organic solvents can be preferably removed by filtration, centrifugation, etc., and then dried to obtain polycarbonate resin powders (powder or flakes) ). As a dryer, either conduction heating or hot air heating can be used, and the polycarbonate resin powder can be left standing, transferred or stirred. Among them, a tank-type or cylinder dryer in which the polycarbonate resin powder is stirred by conduction heating is preferred, and a tank-type dryer is particularly preferred. The drying temperature is preferably in the range of 130°C to 150°C.

The melt transesterification reaction is usually the transesterification reaction of a dihydric phenol and a carbonate. In the presence of an inert gas, the dihydric phenol and carbonate are mixed while heating, and the resulting alcohol or phenol is distilled off. . The reaction temperature varies depending on the boiling point of alcohol or phenol to be produced, but is almost always in the range of 120 to 350°C. In the later 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 produced alcohol or phenol. The reaction time is usually about 1 to 4 hours.

As the above-mentioned carbonate esters, esters such as aryl groups, aralkyl groups, or alkyl groups with 1 to 4 carbon atoms having or not having substituents, among which dicarbonate is preferred. phenyl esters. The molten polycarbonate obtained by the melt transesterification method can be pelletized using a melt extruder. The pellets can be provided for molding.

The mixing of component A1 and other polycarbonates can be performed by methods represented by the following (i) to (iv), but is not limited thereto. Right now,

(i) Using the technology disclosed in JP Patent Publication No. 05-306336, the emulsion for synthesizing polycarbonate-polyorganosiloxane copolymer and the emulsion for synthesizing other polycarbonates are placed in the same reaction tank Mixing under the condition that both of them are maintained in an emulsified state, allowing it to stand still to promote polymerization, and recovering the polycarbonate resin as the A component from the integrated emulsion;

(ii) A method of mixing a polycarbonate-polyorganosiloxane copolymer solution with another polycarbonate solution, and recovering a polycarbonate resin as component A from the mixed solution;

(iii) A method of mixing component B after mixing and integrating polycarbonate-polyorganosiloxane copolymer powders and other polycarbonate powders; and

(iv) A method in which the powder or grain of polycarbonate-polyorganosiloxane copolymer, other polycarbonate powder or grain, and the powder or grain of component B are supplied to an extruder or the like and mixed.

The polycarbonate resin of component A thus produced preferably has a C1 amount of 0.1 to 100 ppm and an OH terminal amount of 1 to 30 eq/ton. The amount of C1 in this polycarbonate resin can be measured by a combustion method. After the sample was weighed, it was burnt in a mixed flow of argon and oxygen, and the charge transfer amount of the silver electrode was measured. As a measuring device, TOX-2100H manufactured by Mitsubishi Chemical Corporation is mentioned. In addition, the OH terminal amount can be calculated by NMR method, IR method and titration method. By satisfying these characteristics, a molding material and a molded article having excellent thermal stability and little discoloration can be obtained. Therefore, the resin composition of the present invention is more suitable for thin-walled molded articles molded under high temperature and high pressure load.

The viscosity average molecular weight of the polycarbonate of component A and component A1 was calculated|required by the following method. That is, first, from a solution obtained by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C., the specific viscosity (η _sp ) calculated by the following formula was obtained using an Ostwald viscometer,

Specific viscosity (η _sp )=(tt ₀ )/t ₀

[ _t0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]

Calculate the viscosity-average molecular weight (M) from the obtained specific viscosity (η _sp ) with the following mathematical 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

In addition, in the resin composition of this invention, the calculation of the viscosity average molecular weight is performed by the following method. That is, the composition is mixed with methylene chloride 20 to 30 times its weight to dissolve the soluble components in the composition. The soluble fraction was obtained by filtration through celite. Then, the solvent in the resulting solution was removed. The solid after removal of the solvent was sufficiently dried to obtain a solid dissolved in a dichloromethane component. From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity at 20° C. was determined in the same manner as above, and the viscosity average molecular weight (M) was determined from the specific viscosity in the same manner as above.

(B component)

As mentioned above, component B in this invention is a polycarbonate oligomer whose average degree of polymerization is 3-15. This polycarbonate is composed of the same structural units as the above-mentioned polycarbonate. That is, the polycarbonate oligomer of component B is obtained by reacting one or more dihydric phenols and/or one or more aliphatic and/or alicyclic difunctional alcohols with a carbonate precursor. Here, the structure of the polycarbonate oligomer may be any of linear, branched (including highly branched) and cyclic. From the standpoint of productivity and production stability, a linear form is preferable.

The difunctional alcohol in the polycarbonate oligomer of the B component is preferably an alicyclic diol, and its preferred specific examples are also the same as those of the above-mentioned A component (A1 component).

In addition, as described above, in the present invention, component B is preferably an oligomer composed of structural units represented by the above-mentioned general formula (β1). Component B is more preferably an oligomer represented by the above general formula (β2). In the general formula, the preferred form of the dihydric phenol inducing the repeating unit is the same as in the case of the above-mentioned polycarbonate. Among them, bisphenol A is preferable. In addition, specific examples of monofunctional phenols that induce molecular chain ends in the above general formula (β2) include phenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, decylphenol, Dialkylphenol, Myristylphenol, Hexadecylphenol, Octadecylphenol, Eicosylphenol, Docosylphenol, Triaconylphenol, Decyl Hydroxybenzoate, Hydroxybenzoin lauryl hydroxybenzoate, myristyl hydroxybenzoate, cetyl hydroxybenzoate, eicosyl hydroxybenzoate, behenyl hydroxybenzoate and tridecyl hydroxybenzoate. The shorter the chain length at the end of the molecular chain, the better the transparency, and the longer the chain length, the better the fluidity. Referring to this, the structure at the end of the molecular chain can be selected. In consideration of transparency, thermal stability, and durability, alkyl-substituted phenols having 1 to 9 carbon atoms are preferable, and p-tert-butylphenol is particularly preferable.

The manufacture method of polycarbonate oligomer has been well known by those skilled in the art, for example, adopts the reaction of dihydric phenol compound and phosgene by interfacial polycondensation method, dichloroformate and dihydric phenol induced from dihydric phenol Or the polycondensation reaction of aliphatic diols (including alicyclic diols) and the melt polycondensation reaction of diaryl carbonate and dihydric phenol or aliphatic diols (including alicyclic diols) under the conditions 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. The average degree of polymerization can be calculated by combining GPC measurement, NMR measurement, etc., and this method is well known to those skilled in the art.

(Component C: release agent)

In the resin composition of the present invention, a mold release agent may also be blended if necessary, and such a form is preferably used. This is because in thin-wall molding, since the molding temperature is high and the molding is filled under high pressure, the molded product tends to adhere to the metal mold, and mold release failure is likely to occur. In addition to causing cracks during molding, this poor mold release is not preferable in many cases because the residual stress tends to be the starting point of cracks in terms of durability.

A well-known mold release agent can be used as a mold release agent of this invention. Examples include fatty acid esters, polyolefin waxes (polyethylene waxes, 1-alkene polymers, etc., polyolefin waxes modified by compounds containing functional groups such as acid modification can also be used), Silicon compounds, fluorine compounds (fluorine oil represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. Among them, fatty acid esters are preferred from the viewpoints of easy availability, mold release properties, and transparency of the resin composition. The release agent is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, still more preferably 0.03 to 0.2 part by weight, and particularly preferably 0.07 to 0.15 parts by weight relative to 100 parts by weight of the polycarbonate resin as component A. parts by weight. When the amount added is less than the lower limit of the above range, the effect of improving mold releasability is insufficient, and when it exceeds the upper limit, the thermal stability of the resin composition deteriorates and molding stability deteriorates. Furthermore, depending on the type of the mold release agent, solvent cracks may occur in the molded product due to the mold release agent deposited on the mold.

Among the above, fatty acid ester (component C-1) is mentioned as a preferable mold release agent. The fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, the carbon number of this alcohol is the range of 3-32, More preferably, it is the range of 5-30. Examples of the monohydric alcohol include dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, eicosyl alcohol, tetracyl alcohol, hexadecanyl alcohol, and triacyl alcohol. wait. Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Among the fatty acid esters of the present invention, polyhydric alcohols are more preferred.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid ( Stearic acid), nonadecanoic acid, eicosanic acid and behenic acid (behenic acid) and other saturated aliphatic carboxylic acids and palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, Unsaturated aliphatic carboxylic acids such as eicosapentaenoic acid and cetenoic acid. Among the above, the aliphatic carboxylic acid having 14 to 20 carbon atoms is preferable as the aliphatic carboxylic acid. Among them, saturated aliphatic carboxylic acids are preferred. Since the aliphatic carboxylic acids are usually produced from natural oils such as animal fats (tallow, lard, etc.) or vegetable fats (palm oil, etc.), these aliphatic carboxylic acids usually contain different carbon atoms. Mixtures of other carboxylic acid components. Therefore, in the production of the C-1 component of the present invention, it is also produced from these natural oils and fats, and it is a mixture system containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (may be substantially 0). However, in the case of a full ester (full ester), it is preferable to contain many free fatty acids in order to improve mold releasability. From this point of view, the acid value in the full ester is preferably in the range of 3-15. In addition, the iodine value of the fatty acid ester is preferably 10 or less (may be substantially 0). These properties can be obtained by the methods specified in JIS K 0070.

The fatty acid ester of the present invention may be either a partial ester or a full ester, but a partial ester is preferred in view of excellent mold release properties and durability. Among them, monoglycerides are preferable. The main components of monoglycerides are monoesters of glycerin and fatty acids. Examples of preferred fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, octadecanoic acid, and lauric acid, or oleic acid, Unsaturated fatty acids such as linoleic acid and sorbic acid are particularly preferably fatty acids containing monoglycerides of stearic acid, behenic acid, and palmitic acid as main components. In addition, this fatty acid is synthesize|combined from natural fatty acid, and it is a mixture as mentioned above. Monoglycerides may be used in combination with other mold release agents, especially fatty acid full esters, but even when used in combination, it is preferable to use monoglycerides as 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 mostly less thermally stable than full esters. In order to increase the thermal stability of the partial ester, it is preferred that the partial ester contains less than 20 ppm, more preferably less than 5 ppm, even more preferably less than 1 ppm sodium metal. Fatty acid partial esters having a sodium metal content of less than 1 ppm are produced by producing fatty acid partial esters by a usual method and then refining them by molecular distillation or the like.

Specifically, there is a method in which, after removing gas and low-boiling substances by a nozzle-type degasser, they are removed using a falling-film distillation device at a distillation temperature of 120-150°C and a vacuum degree of 0.01-0.03kPa. Polyhydric alcohol components such as glycerin, and further, using a centrifugal molecular distillation device, under the conditions of a distillation temperature of 160-230°C and a vacuum degree of 0.01-0.2 Torr, a method of obtaining high-purity fatty acid partial esters as a fraction, etc., sodium Metals can be removed as distillation bottoms. By repeatedly distilling the obtained fraction, the purity can be further improved, and fatty acid partial esters with less sodium metal content can be obtained. In addition, it is also important to sufficiently wash the interior of the molecular distillation apparatus by an appropriate method in advance, and to prevent the mixing of sodium metal components from the external environment by improving airtightness and the like. This fatty acid ester is available from a specialized company (for example, Riken Vitamin Co., Ltd.).

(about other additives)

The resin composition of the present invention may contain various additives that are usually blended in polycarbonate resins in addition to the above-mentioned components A to C.

(i) Phosphorus stabilizer

In the resin composition of the present invention, various phosphorus-based stabilizers are preferably blended for the main purpose of improving thermal stability during molding. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters of these acids, and the like. Furthermore, the phosphorus stabilizer includes tertiary phosphine.

As a specific phosphite (phosphite) compound, for example, triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctyl Alkyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylene bis(4,6-di-tert-butylphenyl) octyl phosphite, tri(diethylbenzene base) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearoyl 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, phenyl bisphenol A pentaerythritol diphosphite Phosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like.

Furthermore, as another phosphite compound, the phosphite compound which reacts with dihydric phenols and has a cyclic structure can be used. For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylene Bis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butyl phenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl Base-4-methylphenyl) phosphite, etc.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, Diphenyl mono-o-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., preferably triphenyl phosphate and trimethyl phosphate.

As the phosphonite compound (phosphonite), tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl) Butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Four (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, four (2,6-di-tert-butylphenyl)-4,3'-biphenylene Phenyl 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 base)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butyl phenyl)-3-phenyl-phenylphosphonite, etc. Among them, preferred tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, more preferably tetrakis(2,4 -di-tert-butylphenyl)-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. The phosphonite compound can be used in combination with the above-mentioned phosphite compound having two or more aryl group substitutions in the alkyl group, and this method is preferably used.

Examples of the phosphonate compound (phosphonate) include dimethyl phenylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate.

Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethane Base phosphine, diphenyl octyl phosphine, triphenyl phosphine, tri-p-tolyl phosphine, trinaphthyl phosphine and diphenyl benzyl phosphine, etc. A particularly preferred tertiary phosphine is triphenylphosphine.

The above-mentioned phosphorus stabilizers may be used alone or in combination of two or more. Among the above-mentioned phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. Particularly preferred are three (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite and bis( 2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Moreover, it is also preferable to use these together with a phosphoric acid ester compound.

(ii) Hindered phenolic stabilizers

For the main purpose of improving the thermal stability, thermal aging resistance and ultraviolet resistance during molding, the resin composition of the present invention can also be blended with hindered phenolic stabilizers. Examples of the hindered phenolic stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-ditertiary Butylphenyl) propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2, 6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 2,2'- Methylbis(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'-dimethylenebis(6-α-methyl benzyl-p-cresol), 2,2'-ethylene-bis(4,6-di-tert-butylphenol), 2,2'-butylene-bis(4-methyl-6-tert-butyl phenol), 4,4'-butylene-bis(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]undeca Alkane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thio Bis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6- Di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodivinyl-bis[3-(3,5-di-tert-butyl Base-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3 , 5-triazine, N, N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide), 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, 1,3,5-tris Methyl-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) base) isocyanurate, 1,3,5-tri-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate ester, tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc. These are readily available. The aforementioned hindered phenolic stabilizers may be used alone or in combination of two or more.

The content of the (i) phosphorus stabilizer and (ii) hindered phenol stabilizer is 0.0001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, or more, based on 100 parts by weight of the polycarbonate resin (component A). Preferably it is 0.005-0.1 weight part. When the content of the stabilizer is too less than the above range, it is difficult to obtain a good stabilizing effect, and when it is too much, the physical properties of the composition will be reduced.

In order to further stabilize the hue of the molded article during heat treatment, other stabilizers may be used in the resin composition of the present invention in addition to the aforementioned hindered phenol stabilizers. Examples of other stabilizers include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. wait. The usage-amount of these other stabilizers is preferably 0.001-0.05 weight part with respect to 100 weight part of the polycarbonate resin which is A component.

(iii) UV absorbers

Specific examples of the ultraviolet absorber include benzophenones, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methyl Oxygen-5-sulfoxy trihydrogen compound benzophenone (2-hidrokishi-4-metokish-5-sulhokishitrihidridereittobenzophenone), 2,2'-dihydroxy-4-methoxydiphenone Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4,4'-dimethoxy-5-sodium sulphonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4- n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

Specific examples of benzotriazoles as ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl) Benzotriazole, 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-chlorobenzo Triazole, 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-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl -6-benzotriazole phenyl), 2,2'-p-phenylene bis(1,3-benzoxazin-4-one), 2-[2-hydroxyl-3-(3,4, 5,6-tetrahydrophthalamidemethyl)-5-methylphenyl]benzotriazole, 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H- A copolymer of benzotriazole and a vinyl monomer that can be copolymerized with the monomer or 2-(2'-hydroxyl-5-acryloyloxyethylphenyl)-2H-benzotriazole and a copolymer that can be mixed with the monomer Copolymers of vinyl monomers, such as copolymers of monomers, polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, and the like.

As the hydroxyphenyl triazines of the ultraviolet absorber, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-tri Azin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol and 2-(4 , 6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol and the like. Further, among the above-mentioned exemplary compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc. The phenyl group becomes 2,4-dimethylphenyl compound.

As cyclic imino esters of ultraviolet absorbers, specifically, 2,2'-p-phenylene bis(3,1-benzoxazin-4-one), 2,2'-( 4,4'-diphenylene)bis(3,1-benzoxazin 4-one) and 2,2'-(2,6-naphthyl)bis(3,1-benzoxazin 4- ketones) etc.

In addition, as cyanoacrylates of ultraviolet absorbers, specific examples include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2, 2-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]methylpropane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) Oxygen] benzene, etc.

Furthermore, the above-mentioned ultraviolet absorber may also be obtained by adopting a monomer compound structure that can undergo radical polymerization, and combining the ultraviolet absorbing monomer and/or photostable monomer with an alkyl (meth)acrylate or the like. A polymeric ultraviolet absorber obtained by copolymerizing a body. Examples of the above-mentioned ultraviolet absorber monomer include preferably (meth)acrylic acid esters containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imidate skeleton, and cyanoacrylic acid ester substituents. Compounds with an ester backbone.

Among the above, benzotriazoles and hydroxyphenyl triazines are preferably used in consideration of ultraviolet absorbing ability, and cyclic imide esters and cyano groups are preferably used in consideration of heat resistance and hue (transparency). Acrylics. The above ultraviolet absorbers may be used alone or in combination of two or more.

The compounding amount of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 1 part by weight, and even more preferably 0.05 to 1 part by weight relative to 100 parts by weight of the polycarbonate resin (component A). 0.5 parts by weight.

(iv) light stabilizer

In addition, the resin combination of the present invention may also contain bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl Base-4-piperidinyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, poly{[6-(1,1,3,3 -tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidinyl)imino]hexamethylene[ (2,2,6,6-tetramethylpiperidinyl)imino]}, and polymethylpropyl-3-oxo-[4-(2,2,6,6-tetramethyl)piperidine Hindered amine light stabilizers represented by base] siloxane and the like.

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

(v) Bluing agent

The composition of the present invention further preferably contains 0.05 to 3.0 ppm (weight ratio) of a bluing agent in the resin composition. In the resin composition of the present invention, it is very effective to use a bluing agent in order to further reduce yellowness and impart a natural sense of transparency to molded articles. The bluing agent mentioned here refers to a coloring agent that exhibits blue or purple by absorbing orange or yellow light, and is particularly preferably a dye. By adding a bluing agent, the polycarbonate resin composition of the present invention can obtain a better hue. When the amount of the bluing agent is less than 0.05 ppm, the effect of improving the hue may not be sufficient. On the other hand, when the amount of the bluing agent exceeds 3.0 ppm, the transmittance of light decreases, which is not preferable. A more preferable amount of the bluing agent is in the range of 0.2 to 2.0 ppm in the resin composition. As a representative example of the bluing agent, Bayer (Bayer) company's Makulu Lux times red (Macrorex Biolet) B, Maku Lux Blue (Macrorex Blue) RR, and Clariant's Polysins Blue (Polysins レンブル—) RLS and so on.

(vi) Fluorescent dyes

Since the resin composition of the present invention has good transparency, by further containing a fluorescent whitening agent, higher light transmittance and a natural sense of transparency can be imparted, and by containing a fluorescent whitening agent or other luminous fluorescence dye, thereby giving an appearance effect that effectively utilizes the luminous color.

Fluorescent dyes (including fluorescent whitening agents) used in the present invention include, for example, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, and thioindigo-based fluorescent dyes. , Xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazide-based fluorescent dyes, and diaminostilbene-based fluorescent dyes, etc. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less deteriorated during molding processing of polycarbonate resins, are preferable. Among them, coumarin-based fluorescent dyes, that is, fluorescent dyes composed of coumarin derivatives are preferred because they can maintain good characteristics even in combination with the B component of the present invention. The compounding quantity of fluorescent dye (including fluorescent whitening agent) is 0.0001-3 weight part with respect to 100 weight part of polycarbonate resin (A component), Preferably it is 0.0005-1 weight part, More preferably, it is 0.0005-0.5 weight part , more preferably 0.001 to 0.5 parts by weight, particularly preferably 0.001 to 0.1 parts by weight. Within this range, better ultraviolet resistance, hue, thermal stability, and light transmittance can be achieved at the same time.

(vii) Antistatic agent

The resin composition of the present invention may be required to have antistatic properties (for example, to prevent adhesion of dust during printing, etc.), and in this case it is preferable to contain an antistatic agent. As the antistatic agent, for example (i) organic sulfonic acid phosphonium salts such as (i) arylsulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, alkylsulfonic acid phosphonium salts, and tetrafluorophosphonium salts such as Phosphonium borate salts such as borate phosphonium salts. The composition ratio of the phosphonium salt is 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1.5 to 3 parts by weight, based on 100 parts by weight of component A.

Examples of antistatic agents include (ii) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, barium organic sulfonate Other organic sulfonic acid alkali (alkaline earth) metal salts. Specific examples thereof include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The composition ratio of organic sulfonic acid alkali (alkaline earth) metal salt is 0.5 weight part or less with respect to 100 weight part of A component, Preferably it is 0.001-0.3 weight part, More preferably, it is 0.005-0.2 weight part. Particularly preferred are alkali metal salts such as potassium, cesium, and rubidium.

Examples of the antistatic agent include (iii) organic sulfonate ammonium salts such as alkylsulfonate ammonium salts and arylsulfonate ammonium salts. It is preferable that the composition ratio of this ammonium salt is 0.05 weight part or less with respect to 100 weight part of A components. As an antistatic agent, the polymer which contains a poly(oxyalkylene) glycol component as its structural component, such as (iv) polyether ester amide, is mentioned, for example. It is preferable that this polymer is 5 weight part or less with respect to 100 weight part of A components.

(viii) Hydrolysis improver

In order to improve the hydrolysis resistance of A component, various hydrolysis modifiers can be added to the resin composition of this invention within the range which does not impair the objective of this invention. As this compound, an epoxy compound, an oxetane, a silane compound, a phosphonic acid compound, etc. are mentioned. Particularly preferred are epoxy compounds and oxetane compounds. As the epoxy compound, alicyclic epoxy compounds represented by 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate, and 3-glycidyl Propoxy-triethoxysilane is an epoxy compound containing a silicon atom. It is preferable that content of these hydrolysis improvers is the range of 0.01-1 weight part with respect to 100 weight part of A components.

(ix) Compounds with heat absorption energy

For the resin composition of the present invention, a compound having heat-absorbing energy can be used within the range not impairing the object of the present invention. As the compound, preferable examples include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, and ruthenium oxide, and metals such as lanthanum boride, cerium boride, and tungsten boride. Various metal compounds and carbon fillers having excellent near-infrared absorption performance such as boride-based near-infrared absorbers. As the carbon filler, carbon black, graphite (including any of natural graphite and artificial graphite, and further including whiskers), carbon fiber (including carbon fiber according to the vapor phase growth method), carbon nanotube and fullerene (fullerene) can be mentioned. ) etc., preferably carbon black and graphite. These may 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, and still more preferably 0.001 to 0.07 parts by weight, based on 100 parts by weight of the polycarbonate resin (component A). The metal oxide-based near-infrared absorber, the metal boride-based near-infrared absorber, and the carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably 0.5 to 100 ppm (weight ratio) in the resin composition of the present invention. range.

(x) Other dyes and/or pigments

In the resin composition of the present invention, various dyes and/or pigments other than the above-mentioned bluing agent and fluorescent dye can be used within the range in which the effects of the invention are exhibited. In particular, it is preferable to use a dye from the viewpoint of less damage to transparency. On the other hand, it is also possible to obtain good metallic colors by blending deep colors or metallic pigments.

Examples of dyes include perylene-based dyes, coumarin-based dyes, thioindigo-based dyes, anthraquinone-based dyes, thioxanthone-based dyes, ferrocyanides such as Prussian blue (cyanine), and perinones. quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes and phthalocyanine dyes, etc. The usage-amount of these dyes is preferably 0.0001-1 weight part with respect to 100 weight part of polycarbonate resins which are A component, More preferably, it is 0.0005-0.5 weight part.

A flame retardant can also be used in the resin composition of this invention within the range which does not impair the object of this invention. Examples of flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, Compounds, phosphazene oligomer compounds, phosphonic acid amide compounds, metal salts of organic acids other than sulfonates, silicon-based flame retardants, etc., and one or more of these can be used. These flame retardants can be compounded in known compounding amounts with respect to the polycarbonate resin, respectively.

In the resin composition of the present invention, within the range that does not impair the object of the present invention, a small amount of other resins or elastomers other than the B component can also be used. Although there is no particular limitation on the resin, considering the polymer The transparency after the carbonate resin is compounded preferably includes polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and cyclohexanedimethanol (CHDM ) copolymerized polyethylene terephthalate, polyarylate, polysulfone, polyphenylene ether, epoxy resin, and phenoxy resin, etc. This other resin is 0.5-15 weight part with respect to 100 weight part of A components, Preferably it is 1-10 weight part.

Furthermore, in the resin composition of the present invention, various inorganic fillers, flow modifiers (substances other than component B), antibacterial agents, photocatalytic antifouling agents, light diffusing agents, white Pigments and photochromic agents, etc.

(haze value)

In the resin composition of the present invention, the haze value measured by JIS K7105 is 0.3 to 20%, preferably It is 0.3 to 5%, more preferably 0.3 to 3%. The haze value is measured by a nephelometer. The smooth flat plate was obtained by injection molding the pellets in a cavity formed of a mold surface having an arithmetic mean roughness (Ra) of 0.03 μm after drying the pellets as prescribed. The arithmetic mean roughness (Ra) of the mold surface can be measured using a surface roughness meter.

(About the production method of the resin composition)

When producing the resin composition of the present invention, there is no particular limitation on its production method. However, the polycarbonate resin composition of the present invention is preferably produced by melt-kneading various components.

Specific methods for the above melt-kneading include Banbury mixers, kneading rolls, extruders, and the like. Among these, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is more preferable. A more preferable embodiment in this twin-screw extruder is as follows. That is, as the shape of the screw, single-flight, double-flight, and three-flight flight-type screws can be used, and it is particularly preferable to use a double-flight screw that has a wide range of application in terms of the ability to transport molten resin and the ability to shear and knead. screw. The ratio (L/D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20-45, more preferably 28-42. The larger the L/D value, the easier it is to achieve a uniform dispersion state, but if it is too large, the resin is likely to be decomposed due to thermal aging. The screw must have one or more kneading zones, preferably 1 to 3, wherein the kneading zone is composed of a kneading disc section (or a kneading section equivalent thereto) for improving kneading performance.

Furthermore, as the extruder, it is preferable to use an extruder having an exhaust port capable of removing moisture in the raw material or volatile gas generated by melting and kneading the resin. It is preferable to provide a vacuum pump for efficiently exhausting generated moisture or volatile gas to the outside of the extruder from the exhaust port. In addition, a filter for removing impurities and the like mixed in the extruded raw material is provided in the area before the die part of the extruder, whereby impurities can also be removed from the resin composition. As this filter screen, a metal screen, a screen changer, a sintered metal plate (disc filter, etc.), etc. are mentioned.

Furthermore, the method of supplying the B component and other additives (in the following examples, simply referred to as "additives") to the extruder is not particularly limited, but the following methods can be enumerated as its representative example: (i) A method in which the additive and the polycarbonate resin are supplied to the extruder independently; (ii) a method in which the additive and the polycarbonate resin powder are premixed in advance using a mixer such as a super mixer, and then supplied to the extruder. In addition, in any method, the polycarbonate-polyorganosiloxane copolymer of the A1 component in the polycarbonate resin and other polycarbonates may be either an integrated compound or independent solids. .

One of the above methods (ii) is a method of pre-mixing all required raw materials and then supplying them to an extruder. Other methods are to prepare a high-concentration main agent (master) that is mixed with additives, and then pre-mix the main agent alone or with the remaining polycarbonate resin, and then supply it to the extruder. method. In addition, the main ingredient can be selected from a powder form and any shape obtained by compressing and granulating the powder. In addition, as other premixing methods, for example, Nauta mixer, V-type mixer, Henschel mixer, chemical power plant, extrusion mixer, etc., but high-speed stirring type such as super mixer are preferred. mixer. Furthermore, as another premixing method, the method of removing this solvent after preparing a solution by uniformly dispersing a polycarbonate resin and an additive in a solvent is mentioned, for example. In addition, as the third method, (iii) the method of melt-kneading the additive and the polycarbonate resin in advance to prepare master pellets (master pellets)

The resin extruded by the twin-screw extruder may be directly cut and pelletized, or after being formed into strands, the strands may be cut and pelletized by a pelletizer. In addition, when it is necessary to reduce the influence of the outside such as dust, it is preferable to clean the ambient air around the extruder. In addition, the particle shape obtained may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. Preferably, the diameter of the cylinder is 1-5 mm, more preferably 1.5-4 mm, even more preferably 2-3.3 mm. On the other hand, the length of the column is preferably 1 to 30 mm, more preferably 2 to 5 mm, even more preferably 2.5 to 3.5 mm.

(About the molded article formed from the resin composition of the present invention)

The resin composition of the present invention obtained as described above is usually subjected to injection molding of the pellets produced as described above to produce various finished products. In this injection molding, not only ordinary molding methods can be used, but also injection compression molding, injection pressure molding, gas-assisted injection molding, foam molding (including molding by supercritical fluid injection), and insert molding can be appropriately used according to the purpose. , In-Mold Coating (In-Mold Coating) molding, heat insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding and other injection molding methods to obtain molded products. The advantages of these various forming methods are well known. In addition, molding can choose any one of the cold runner method and the hot runner method.

In addition, the resin composition of the present invention can also be utilized in the form of various extrusion-molded products, sheets, and films by extrusion molding. In addition, blow molding, calendering, casting, and the like can also be used for sheet or film molding. Furthermore, by performing a specific stretching operation, it can also be molded into a heat-shrinkable tube or a photofunctional film. In addition, the polycarbonate resin composition of the present invention can also be produced as a molded article by rotational molding, blow molding, or the like.

Thereby, a thin-walled molded article made of a resin composition having excellent transparency and durability can be provided. Furthermore, various surface treatments can be performed on the molded article formed from the resin composition of the present invention. The surface treatment mentioned here refers to vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-melt plating, etc.), painting, coating, printing, etc. on resin molded products. For the treatment of forming a new coating on the surface layer, the method generally used for polycarbonate resin can be used. Specific examples of the surface treatment include various surface treatments such as hard coat, water-repellent/oleophobic coat, ultraviolet-absorbing coat, infrared-absorbing coat, and metal coat (vapor deposition). Among them, a hard coat layer is particularly preferable and a necessary surface treatment.

The inventors of the present invention consider that the best embodiment of the present invention is an embodiment in which the preferred ranges of the above-mentioned requirements are gathered, and representative examples thereof are described in the following examples, for example. Of course, the present invention is not limited by these embodiments.

Example

The following examples illustrate the present invention. But the present invention is not limited thereto. In addition, the measurement of various characteristics in an Example was performed by the following method; The raw material used the raw material mentioned below.

(1) Evaluation of polycarbonate resin composition

(i) Transparency of molded product: Using a metal mold with a cavity surface having an arithmetic average roughness (Ra) of 0.03 μm, through an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.), Under the conditions of cylinder temperature of 290°C and metal mold temperature of 80°C, the molding width is 50mm, length is 90mm, and thickness is 3mm (length: 20mm), 2mm (length: 45mm), and thickness from the gate side. 1mm (length 25mm) three-section plate. The total light transmittance and Haze in the molded plate where the thickness of the three-stage plate is 2.0 mm were measured according to the standard of ASTM D1003. Haze indicates the haze of the molded product, and the lower the value, the smaller the haze.

(ii) Fluidity: using an SG-150U molding machine manufactured by Sumitomo Heavy Industries, Ltd., the flow length was evaluated with an Archimedes type spiral flow die (flow path thickness: 2 mm, flow path width: 8 mm). The conditions are: cylinder body temperature 290°C, metal mold temperature 70°C, injection pressure 100MPa.

(iii) Fatigue characteristics: Use the so-called "<"-shaped test piece shown in Figure 1 to observe the difference in the number of times that each test piece reaches rupture in the fatigue test (the said rupture refers to the point where the test piece cannot bear the test load. state, does not mean that the test piece is cut into two parts). The average value of the three test pieces was taken as the number of ruptures. The test was carried out under the conditions of a temperature of 23° C., a relative humidity of 50%, a sine wave with a frequency of vibration of 1 Hz, and a maximum load of 6.86 N (7 kgf). A fatigue testing machine (Shimadzu SA-BOPPALSA-EHF-FDI-10LA type, manufactured by Shimadzu Corporation) was used as the test device. The test piece was molded with an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 290°C and a mold temperature of 80°C with a molding cycle of 50 seconds.

Examples 1-5 and Comparative Examples 1-3

Resin compositions having the compounding ratios described in Table 1 were produced by the following method. In addition, descriptions are made according to the symbols in the table below. The entire amount of the components described in Table 1 was weighed into a polyethylene bag, and mixed by shaking to prepare a uniform premix. This premix was supplied to the first inlet at the rear end of a vented twin-screw extruder (TEX-30XSST, manufactured by Nippon Steel Works, Ltd.) with a screw diameter of 30 mm. Extrusion is carried out under the following conditions: use a vacuum pump, and under a vacuum of 3kPa, the cylinder temperature is 230-280°C (uniform rise between the barrel and the mold at the root of the screw), the screw speed is 180rpm, and the speed per hour The extrusion amount was 15 kg. After cooling the extruded strands in a water bath, they were cut with a pelletizer to pelletize them. The obtained pellets were dried at 120° C. for 6 hours with a hot-air circulation dryer, and then test pieces for the above-mentioned tests were prepared respectively.

The used raw materials described in Table 1 are as follows.

(A component)

(A1 ingredient)

PC-PDMS-1: Polydimethylsiloxane with a viscosity-average molecular weight of 20,300 and an average degree of polymerization of 25 produced by the following production method has a content of 4% by weight, an extraction ratio of n-hexane of 1.2% by weight, and a molecular weight distribution of ( Mw/Mn) is a polycarbonate-polyorganosiloxane copolymer of 2.4.

PC-PDMS-2: The content of polydimethylsiloxane with a viscosity average molecular weight of 20,000 and an average degree of polymerization of 38 produced by the following production method is 4% by weight, the extraction ratio of n-hexane is 1.7% by weight, and the molecular weight distribution ( Mw/Mn) is a polycarbonate-polyorganosiloxane copolymer of 2.4.

PC-PDMS-3: The content of polydimethylsiloxane with a viscosity average molecular weight of 16,000 and an average degree of polymerization of 25 produced by the following production method is 4% by weight, the extraction ratio of n-hexane is 1.3% by weight, and the molecular weight distribution ( Mw/Mn) is a polycarbonate-polyorganosiloxane copolymer of 2.4.

PC-PDMS-4 (for comparison): The content of polydimethylsiloxane with a viscosity average molecular weight of 20,000 and an average degree of polymerization of 67 produced by the following production method is 3.9% by weight, and the extraction ratio of n-hexane is 2.2 A polycarbonate-polyorganosiloxane copolymer having a weight % and a molecular weight distribution (Mw/Mn) of 2.4.

The above-mentioned production using the A1 component was carried out by the following method. In addition, "part" in this description means a weight part.

(Manufacturing method of PC-PDMS-1): Add 3,310 parts of ion-exchanged water and 650 parts of 48.5% by weight of sodium hydroxide aqueous solution into a reactor with a thermometer and a stirrer to dissolve 1.2 parts of bisulfite Next, 596 parts of bisphenol A were dissolved, and then, 2,230 parts of methylene chloride was added, and 312 parts of phosgene was blown in at 20° C. for about 40 minutes while vigorously stirring, to perform a reaction. After blowing into phosgene, the temperature of the reaction solution was raised to 28°C, 16 parts of p-tert-butylphenol, 173 parts of 48.5% by weight aqueous sodium hydroxide solution were added and both ends were sealed with o-allylphenol. 31 parts of polydimethylsiloxane (X-22-1875, manufactured by Shin-Etsu Chemical Co., Ltd.) having a phenolic hydroxyl group with an average degree of polymerization of 25 was brought into an emulsified state, followed by vigorous stirring again. Under this stirring, 0.9 parts of triethylamine was added to the reaction liquid at 26°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction, separate the organic phase, dilute it with dichloromethane, wash it with water, make hydrochloric acid for acidic washing, and when the conductivity of the water phase is almost the same as that of ion-exchanged water, add it to a kneader filled with warm water, and evaporate the dichloride while stirring. Chloromethane to obtain the powder of the copolymer. The viscosity-average molecular weight of this copolymer was 20,300, and the polydimethylsiloxane component content was 3.95% by weight. This content can be calculated from 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.) at a cycle of 20 times/hour for 3 hours, and the n-hexane extraction ratio was calculated. This ratio is 1.2% by weight in 100% by weight of polydimethylsiloxane contained in the copolymer. In addition, the molecular weight distribution (Mw/Mn) calculated by GPC measurement was 2.4.

(Manufacturing method of PC-PDMS-2): In the above-mentioned manufacturing method of PC-1, as polydimethylsiloxane, both ends are sealed with o-allyl phenol, and phenolic hydroxyl groups are added at both ends. Except for 31 parts of polydimethylsiloxane (X-22-1821, manufactured by Shin-Etsu Chemical Co., Ltd.) with an average degree of polymerization of 38, the powder of the copolymer can be obtained in the same manner as PC-1. The copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane component content of 4% by weight, a n-hexane extraction ratio of 1.7% by weight and a molecular weight distribution (Mw/Mn) of 2.4.

(Manufacturing method of PC-PDMS-3): Except adding 24 parts of p-tert-butylphenol, the powder of the copolymer was obtained similarly to the manufacturing method of PC-1. The copolymer had a viscosity average molecular weight of 16,000, a polydimethylsiloxane component content of 4% by weight, a n-hexane extraction ratio of 1.3% by weight and a molecular weight distribution (Mw/Mn) of 2.4.

(Manufacturing method of PC-PDMS-4): In the above-mentioned manufacturing method of PC-1, as polydimethylsiloxane, both ends are sealed with o-allyl phenol, and phenolic hydroxyl groups are added at both ends. In addition to 31 parts of polydimethylsiloxane (X-22-1822, manufactured by Shin-Etsu Chemical Co., Ltd.) with an average degree of polymerization of 67, other copolymer powders can be obtained in the same manner as PC-1. The copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane component content of 3.9% by weight, a n-hexane extraction ratio of 2.2% by weight and a molecular weight distribution (Mw/Mn) of 2.4.

(polycarbonate other than A1 component)

PC-1: Linear aromatic polycarbonate resin powder with a viscosity average molecular weight of 19,700 (Panlite L-1225WX, manufactured by Teijin Chemicals Co., Ltd.)

PC-2: Linear aromatic polycarbonate resin powder with a viscosity average molecular weight of 16,000 (Panlite CM-1000, manufactured by Teijin Chemicals Co., 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.

The manufacture of the B-1 component was carried out according to the following method. In addition, "part" in this description means a weight part.

(Manufacturing method of B-1): Put 3,310 parts of ion-exchanged water and 650 parts of 48.5% by weight aqueous sodium hydroxide solution into a reactor equipped with a thermometer and a stirrer to dissolve hydrogen sulfite 1.2 parts of salt, and then 596 parts of bisphenol A were dissolved, then 2,230 parts of dichloromethane was added, and 325 parts of phosgene was blown in at 17° C. for about 40 minutes while vigorously stirring to react. After the blowing of phosgene was completed, the temperature of the reaction liquid was raised to 28° C., and 173 parts of 48.5% by weight aqueous sodium hydroxide solution and 118 parts of p-tert-butylphenol dissolved in 955 parts of methylene chloride were added to make emulsified state. Stir vigorously again. Under this stirring, 1.8 parts of triethylamine was added to the reaction solution at 26°C, and stirring was continued for 1 hour at a temperature of 26-31°C to complete the reaction. After the reaction, the organic phase was separated, diluted with dichloromethane, washed with water, and washed with hydrochloric acid to make the conductivity of the water phase almost the same as that of ion-exchanged water. Dichloromethane was evaporated from the dichloromethane solution to obtain a polycarbonate oligomer. The number average molecular weight was found to be 2,400 by the end group analysis of NMR.

(Component C; 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 with a sodium metal content of 9.8 ppm (manufactured by Riken Vitamin Co., Ltd.)

In addition, the above-mentioned sodium metal content can be measured by the method described in WO2006/025587 pamphlet. In addition, this stearic acid shows a main component, and is a mixture which uses vegetable fats and oils as a raw material.

(other ingredients)

ST-P1: Phosphonite-based heat stabilizer (Sandstab P-EPQ (trade name), manufactured by Clariant Co., Ltd.)

ST-P2: Phosphite-based heat stabilizer (Irgafos 168 (trade name), manufactured by Chiba Specialty Chemical Co., Ltd.)

ST-H1: Phenolic antioxidant (Irganox 1076 (trade name), manufactured by Chiba Specialty Chemical Co., Ltd.)

UVA: 2.2'-p-phenylene bis(3,1-benzoxazin-4-one) (CEI-P, manufactured by Bamboo Wood Oil Co., Ltd.)

BLM: blueing agent masterbatch, prepared by uniformly mixing a blueing agent (Macrorex Bioresto B, manufactured by Bayer Co., Ltd.) and the above-mentioned PC-2 with a super mixer to make the blueing agent 0.1% by weight.

From the comparison of Examples and Comparative Examples in Table 1, it can be seen that the resin composition of the present invention is excellent in transparency, fluidity, and durability represented by fatigue properties.

Furthermore, the pellets obtained in the above-mentioned Examples 1 to 4 were used in SG260M-HP manufactured by Sumitomo Heavy Industries Co., Ltd., at a cylinder temperature of 320°C, a mold temperature of 80°C, an injection speed of 50 mm/sec, and a molding cycle of 70 seconds. Under the condition of UL94 burning test with a thickness of 0.4mm. In all cases, transparent molded products free from injection short circuit, mold release failure and residual strain were obtained. The haze values were all 0.3 to 0.4.

Since the resin composition of the present invention has improved fluidity, transparency, and durability, it can be used on parts that have not been used in the past by utilizing these properties. Among them, it is particularly suitable for thin-walled injection molded products, especially for applications that require transparency and repeatedly receive external force. Specific examples of thin-walled injection molded products include various casing molded products such as battery cases, lens barrels, memory cards, horns, magnetic tape cassettes, surface emitters, micromachine parts, and molded products with hinges. Or molded products for hinges, light-transmitting and/or light-guiding buttons, touch panel parts, etc. Therefore, an extra industrial effect has been played.

Industrial Applicability

The resin composition of the present invention has excellent transparency and fluidity, so in addition to the above-mentioned applications, it can also be widely used in small lenses and lens units, optical card substrates, display screens, and various applications that require visual effects. Frames, game devices and circuit protection covers, sensor covers, medical devices, etc. In addition, the above-mentioned button molded product can also be applied to button molded products having a structure in which a plate-shaped member and a button are integrally injection-molded from a conventional structure in which a plate-shaped member is cut from a sprue. In this case, the thickness of the plate-shaped member is about 50 to 200 μm, which is suitable for injection-molded products having extremely thin-walled parts.

Claims (9)

1. A resin composition comprising a polycarbonate resin as component A and a polycarbonate oligomer as component B, wherein, relative to 100 parts by weight of component A, the content of component B is 0.1 to 20 parts by weight ; A component is composed of a polycarbonate-polyorganosiloxane copolymer containing a polyorganosiloxane unit represented by the following general formula (α1) as the A1 component, or is composed of the A1 component and a polycarbonate other than the A1 component. Ester composition, in 100% by weight of component A, the content of polyorganosiloxane units is 0.1 to 20% by weight,

In the general formula (α1), R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group or phenyl group having 1 to 6 carbon atoms, which are the same or different from each other; R ₅ represents a divalent compound derived from an aliphatic or aromatic compound. organic residues; n represents the repeating number of the units in the brackets, the average of which is 10 to 60, and the structural units in the brackets are a mixture of two or more or a single structure, Component B is a polycarbonate oligomer represented by the following general formula (β2),

In the general formula (β2), A represents

s and t represent 0, Z represents a straight chain or branched chain alkyl group with 1 to 9 carbon atoms, r represents 1, p represents an integer of 4 to 10, and in formula (i-5), R ₂₃ and R ₂₄ Each independently represents a hydrocarbon group having 1 to 10 carbon atoms. 2. The resin composition according to claim 1, wherein the polycarbonate-polyorganosiloxane copolymer as the component A1 has a structure of the following general formula (α2) as the general formula (α1): unit and has a structural unit represented by the following general formula (i),

In the general formula (α2), R ₁ , R ₂ , R ₃ , R ₄ and n are the same as defined in the above general formula (α1); R ₁₁ and R ₁₂ represent an alkylene group with 2 to 6 carbon atoms, which are the same as each other or different; Y represents a hydrogen atom or an alkoxy group substituted at different positions of R ₁₁ , R ₁₂ and oxygen atom (O) combined with the benzene ring,

In the general formula (i), A represents 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 any bond selected from the following formula (i-4); s and t are each independently an integer of 0 or 1 to 4; R ₁₃ and R ₁₄ each independently represent a halogen atom or a carbon atom Alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, aromatic group with 6 to 10 carbon atoms An organic residue selected from the group consisting of an aralkyl group with 7 to 20 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, and an aralkyloxy group with 7 to 20 carbon atoms,

In formula (i-1), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represent 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 with 1 to 3 carbon atoms, In the formula (i-3), u represents an integer of 4 to 11, and the plurality of R ₂₁ and R ₂₂ each independently represent a group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. group,

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. 3. The resin composition according to claim 1, wherein the viscosity-average molecular weight of the component A is 16,000 to 25,000. 4. The resin composition according to claim 1, wherein the viscosity average molecular weight of the component A1 is 16,000 to 25,000. 5. The resin composition according to claim 1, wherein, in the above-mentioned component A, the polyorganosiloxane unit content contained in 100% by weight of component A1 is 1 to 20% by weight, and in 100% by weight of component A The content of polyorganosiloxane units is 0.5-5% by weight. 6. The resin composition according to claim 1, wherein n in the general formula (α1) is 16-50. 7. The resin composition according to claim 1, wherein the haze value at a thickness of 2 mm measured by JIS K7105 is 0.3 to 20%. 8. A transparent resin molded article obtained by injection molding the resin composition according to claim 7. 9. The transparent resin molded article according to claim 8, wherein the wall thickness of the injection molded article is mainly composed of a portion of 0.05 to 0.5 mm.

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