JP6004064B2 - Reinforced polycarbonate composite resin composition - Google Patents

Description

The present invention relates to a polycarbonate composite resin composition, and more specifically, by compounding a polycarbonate resin with a silane-modified polyethylene resin copolymerized with an ethylenically unsaturated silane compound, chemical resistance, thermal stability and appearance, Furthermore, it is related with the polycarbonate composite resin composition excellent in impact resistance.
The present invention also relates to a method for producing such a polycarbonate composite resin composition and a polycarbonate composite resin molded article obtained by injection molding the polycarbonate composite resin composition.

  Polycarbonate resins, particularly aromatic polycarbonate resins, are excellent in impact resistance, heat distortion resistance, rigidity, dimensional stability, etc., and are therefore used in a wide range of applications such as electrical equipment, communication equipment, precision machinery, and automobile parts. However, since polycarbonate resin has low chemical resistance, various attempts have been made to combine it with polyethylene in order to improve chemical resistance.

  When a polycarbonate resin and incompatible polyethylene are combined with a polycarbonate resin, a two-phase structure having a polycarbonate resin as a matrix and polyethylene as a domain is formed. At this time, when high crystallinity polyethylene with high crystallinity is used as the polyethylene, the molding shrinkage of the polyethylene occurs after the polycarbonate resin is solidified in the molding process, and a void is formed between the polycarbonate resin matrix and the polyethylene domain. Is done. The void formed in this way not only lowers the impact strength but also scatters incident light.For example, in the case of a molded product colored black by blending carbon black or the like, the blackness decreases due to the whitening phenomenon, There is a drawback that the appearance is significantly impaired.

  In addition, when polyethylene with low fluidity is used with respect to the polycarbonate resin as a matrix, the chemical resistance is not sufficiently improved due to lower dispersibility, and conversely when polyethylene with high fluidity is used. Forms a domain that is greatly stretched in the vicinity of the surface layer of the molded product, which causes problems such as delamination.

  On the other hand, by selecting low density polyethylene having appropriate fluidity, it is possible to improve the dispersibility of polyethylene in the polycarbonate resin and to suppress shrinkage during molding of the polyethylene domain. The problems as described above are improved.

  In addition, polycarbonate resin is generally added with various inorganic fillers for the purpose of improving strength or suppressing linear expansion (controlling the shrinkage rate during molding to improve dimensional accuracy). . However, a technique for ensuring the appearance and thermal stability of a molded product when an inorganic filler is blended has not been proposed in the past, and a decrease in appearance and / or thermal stability is a problem.

  That is, among inorganic fillers, glass (glass fiber, milled glass fiber, flake glass, etc.) hardly deteriorates the polycarbonate resin, but on the surface of the molded product, there are significant irregularities, resulting in poor appearance. On the other hand, inorganic minerals (talc, wollastonite, mica, etc.) have a good appearance of the molded product, but decompose the polycarbonate resin, that is, impair the thermal stability of the resin, and the mechanical strength of the obtained molded product. Will be reduced.

Patent Document 1 proposes blending a silane-modified polyethylene resin for the purpose of improving the wear resistance when an inorganic filler is blended with a polycarbonate resin.
In Patent Document 1, a high-density silane-modified polyethylene resin obtained by graft-polymerizing an ethylenically unsaturated silane compound on a high-density polyethylene having a density of 0.930 to 0.965 g / cm ³ is used as the silane-modified polyethylene resin. Yes.

Patent Document 2 proposes blending a silane-modified polyethylene resin for the purpose of improving the slidability of a thermoplastic resin such as a polycarbonate resin.
In Patent Document 2, is a silane-modified polyethylene resin of density 0.945~0.965g / cm ³ is preferred, wherein the density is inferior in heat resistance with a silane-modified polyethylene resin of less than 0.945 g / cm ³ Has been.

JP-A-8-100114 Japanese Patent Laid-Open No. 5-247236

  By blending a polycarbonate resin with a high-density silane-modified polyethylene resin as described in Patent Documents 1 and 2, improvements in thermal stability, impact resistance, and chemical resistance are recognized, but not particularly, especially There is a problem that the appearance (blackness) of the molded product is significantly impaired.

  An object of the present invention is to solve the above-mentioned conventional problems and to provide a polycarbonate composite resin composition having improved chemical resistance, further thermal stability and impact resistance of a polycarbonate resin without impairing the appearance. .

  Another object of the present invention is to provide a method for producing such a polycarbonate composite resin composition and a polycarbonate composite resin molded product obtained by injection molding the polycarbonate composite resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have blended a specific low-density silane-modified polyethylene resin with a polycarbonate resin, without impairing the appearance, and with chemical resistance, further heat stability, It has been found that impact resistance can be improved.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] Silane-modified polyethylene resin 1 having a density of 0.85 to 0.92 g / cm ³ obtained by copolymerizing an ethylenically unsaturated silane compound with polyethylene as a resin main component and 85 to 99% by mass of polycarbonate resin. -15% by mass, the content of the silane-modified polyethylene resin in the resin component is 10% by mass or less, and with respect to 100 parts by mass of the resin component, glass fiber, milled glass fiber, wollastonite, talc, and one or more inorganic filler-reinforced polycarbonate composite resin composition characterized Rukoto such containing 15 parts by weight selected from mica.

[2] A reinforced polycarbonate composite resin composition according to [1], which contains 50 parts by mass or less of a polyolefin-based resin with respect to 100 parts by mass of the resin main component.

[3] A reinforced polycarbonate composite resin composition according to [1] or [2], wherein the silane-modified polyethylene resin has a melt flow rate (MFR) at 190 ° C. of 0.1 to 50 g / 10 min.

[4] In [2] or [3], the polyolefin resin is one or more selected from high density polyethylene, low density polyethylene, linear low density polyethylene, and polypropylene. A reinforced polycarbonate composite resin composition.

[5] [1] to A method according to any one of [4], the inorganic filler, reinforced polycarbonate composite, characterized in that at least one member selected from among wollastonite, talc, and mica Resin composition.

[ 6 ] In any one of [1] to [ 5 ], the resin component further contains one or more selected from polyethylene terephthalate, polybutylene terephthalate, polystyrene, ABS resin, and AS resin. A reinforced polycarbonate composite resin composition.

[ 7 ] In any one of [ 1 ] to [ 6 ], the MFR change rate calculated by the following formula is 10% or less, and a reinforced polycarbonate composite resin composition.
MFR change rate = (R ₂₀ −R ₅ ) / R ₅ × 100
(However, R ₅ is the MFR value (280 ° C., 21.18 N) (unit: g / 10 min) when the composition is held at 280 ° C. for 5 minutes, and R ₂₀ is ₂₀ % of the composition at 280 ° C. MRF value (280 ° C., 21.18 N) (unit: g / 10 min) when held for a minute.)

[ 8 ] A reinforced polycarbonate composite resin molded article obtained by injection molding the reinforced polycarbonate composite resin composition according to any one of [1] to [ 7 ].

  According to the present invention, by blending a specific low-density silane-modified polyethylene resin with a polycarbonate resin, the chemical resistance and impact resistance of the polycarbonate resin can be effectively improved without impairing the appearance, and further inorganic filling can be performed. A decrease in thermal stability that occurs when a material is added can be greatly suppressed.

In other words, chemical resistance can be improved by blending polyethylene into polycarbonate resin, but with high-density polyethylene, impact resistance is reduced due to voids between the polycarbonate resin matrix and the polyethylene domain, resulting in poor appearance. In addition, there is also a problem of reduction in mechanical strength such as impact resistance due to delamination between the polycarbonate resin matrix and the polyethylene domain. On the other hand, low-density polyethylene improves this problem, but has a problem of nacreous appearance due to the diffracted light of the polyethylene domain.
Further, when an inorganic mineral is blended as an inorganic filler, there is a problem of decomposition of the polycarbonate resin, but this problem cannot be solved by blending polyethylene.

According to the present invention, by blending a silane-modified polyethylene resin, the chemical resistance is further improved compared with the case of blending a low density polyethylene, and then the above low density polyethylene is blended. Can be improved.
That is, when an inorganic mineral is added as an inorganic filler, the silane-modified polyethylene resin having higher affinity surrounds the surface of the inorganic mineral and prevents contact between the inorganic mineral and the polycarbonate resin, thereby suppressing the decomposition of the polycarbonate resin.

  When a high-density silane-modified polyethylene resin as described in Patent Documents 1 and 2 is used as the silane-modified polyethylene resin, a polycarbonate resin matrix is formed due to crystallization shrinkage of the domain phase derived from the high-density silane-modified polyethylene resin during molding. -Voids are formed between the silane-modified polyethylene domains, resulting in poor appearance and further reduced impact resistance and chemical resistance. By reducing the density of the silane-modified polyethylene resin, The formation can be prevented, the appearance can be maintained well, and the impact resistance and chemical resistance can be further improved.

  In producing such a polycarbonate composite resin composition of the present invention, according to the method for producing a polycarbonate composite resin composition of the present invention in which an inorganic filler is post-added after the melt-kneading process of the resin component, A polycarbonate composite resin composition exhibiting good mechanical strength and residence heat stability by suppressing degradation and degradation of the polycarbonate resin due to the inorganic filler and also suppressing degradation (damage, alteration, etc.) of the inorganic filler itself. Can be manufactured.

  The polycarbonate composite resin molded product of the present invention obtained by injection molding of the polycarbonate composite resin composition of the present invention is excellent in mechanical properties such as impact resistance, etc., which is inherent to polycarbonate resin, and also in chemical resistance. It is a quality polycarbonate composite resin molded product.

  Such a polycarbonate composite resin molded article of the present invention is useful for various uses such as electric / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure goods and miscellaneous goods, and in particular, vehicles. Expected to be applied to exterior and exterior parts and vehicle interior parts.

Examples of vehicle exterior / skin parts to which the polycarbonate composite resin molded product of the present invention is applied include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, Garnish, wheel caps, food bulges, fuel lids, various spoilers, motorbike cowls, etc.
Examples of vehicle interior parts include inner door handles, center panels, instrument panels, console boxes, luggage floor boards, display housings for car navigation, etc. , But not limited to these.

It is a schematic diagram which shows the evaluation test method of chemical resistance, (a) A figure is a side view which shows the state which loaded the test piece into bending, (b) A figure is the same top view, (c) A figure is the bottom face part is there.

  Embodiments of the present invention are described in detail below. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Polycarbonate resin]
Examples of the polycarbonate resin blended in the polycarbonate composite resin composition of the present invention include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, and preferably an aromatic polycarbonate resin.

  The aromatic polycarbonate resin is a linear or branched thermoplastic polymer obtained by using an aromatic dihydroxy compound and a carbonate precursor as raw materials, or using a small amount of a polyhydroxy compound in combination therewith, or It is a copolymer.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetra Bromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ) Octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis ( , 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1- Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, bis such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane And (hydroxyaryl) alkanes.

  Moreover, as aromatic dihydroxy compounds other than the above, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Cardo structure-containing bisphenols exemplified by methylphenyl) fluorene; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; '-Dihydroxydiphenyl sulfide, 4,4'-dihydride Dihydroxy diaryl sulfides exemplified by xy-3,3′-dimethyldiphenyl sulfide; dihydroxy exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Diaryl sulfoxides; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Is mentioned.

  Among the above, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. Two or more aromatic dihydroxy compounds may be used in combination.

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate and the like. Specific examples thereof include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl such as dimethyl carbonate and diethyl carbonate. Carbonates; dihaloformates of dihydric phenols and the like. Two or more of these carbonate precursors may be used in combination.

  The aromatic polycarbonate resin used in the present invention may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, In addition to polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7 -Dichloro isatin, 5-bromo isatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably based on the aromatic dihydroxy compound. 0.1 to 2 mol%.

  Examples of the method for producing the polycarbonate resin include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Although there is no restriction | limiting in the manufacturing method of the polycarbonate resin used by this invention, Interfacial polymerization method or a melt transesterification method is advantageous industrially.

  The molecular weight of the polycarbonate resin used in the present invention is usually 10,000 to 50,000 from the viewpoint of mechanical strength and fluidity (ease of moldability) as a viscosity average molecular weight (Mv) converted from the solution viscosity. Preferably it is 12,000-40,000, More preferably, it is 14,000-35,000, Most preferably, it is 16,000-32,000. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed to adjust the viscosity average molecular weight. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

Here, the viscosity average molecular weight (Mv) is methylene chloride as a solvent, an Ubbelohde viscometer is used, the intrinsic viscosity ([η]) at a temperature of 20 ° C. (unit dl / g) is determined, and Schnell's Viscosity formula: means a value calculated from the formula η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity ([η]) is a value calculated by the following equation by measuring the specific viscosity (ηsp) at each solution concentration (C) (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin used in the present invention is usually 1000 ppm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, further 30 ppm or more, and particularly preferably 40 ppm or more. By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the heat resistance and residence heat stability of the resin composition tend to be further improved.

  In addition, the unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the polycarbonate resin, and the measuring method is a colorimetric determination by the tetrachlorotitanium / acetic acid method (Macromol. Chem. 88215 (1965)). Method).

  In addition, the polycarbonate resin used in the present invention may contain a polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The viscosity average molecular weight (Mv) of the polycarbonate oligomer is usually 1,500 to 9,500, preferably 2,000 to 9,000. The usage-amount of an aromatic polycarbonate oligomer is 30 mass% or less normally with respect to polycarbonate resin.

  Furthermore, in the present invention, as the polycarbonate resin, not only a virgin resin but also a polycarbonate resin regenerated from a used product, that is, a so-called material recycled polycarbonate resin may be used. Used products include, for example, optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, etc.・ Construction materials such as corrugated sheet. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The used proportion of the regenerated polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, based on the virgin resin.

[Silane-modified polyethylene resin]
In the present invention, the silane-modified polyethylene resin blended to improve the chemical resistance of the polycarbonate resin is obtained by copolymerizing an ethylenically unsaturated silane compound with polyethylene, and has a density of 0.85 to 0.92 g / cm. ^Three .

When the density of the silane-modified polyethylene resin is higher than the above upper limit, molding shrinkage increases, so that voids are formed between the matrix and the domain, resulting in poor appearance and impact resistance. The physical properties (for example, impact resistance, heat resistance, etc.) of the obtained resin composition are lowered.
The density of the silane-modified polyethylene resin is more preferably 0.86 to 0.91 g / cm ³ , and particularly preferably 0.87 to 0.90 g / cm ³ . At this time, two or more types of silane-modified polyethylene resins or polyethylene resins having different densities can be used in combination and adjusted to the above-mentioned density suitable range.

  Here, the density of the silane-modified polyethylene resin is a value measured according to the ISO 1183 D method.

Moreover, it is preferable that the melt flow rate (MFR) in 190 degreeC of a silane modified polyethylene resin is 0.1-50 g / 10min. When the MFR of the silane-modified polyethylene resin is less than 0.1 g / 10 min, the dispersibility is poor, and it becomes easy to form a large domain, so that whitening is likely to occur. When the MFR is greater than 50 g / 10 min, the domain is greatly stretched. Therefore, the mechanical strength is likely to decrease due to delamination.
The more preferable MFR of the silane-modified polyethylene resin is 0.2 to 30 g / 10 min. At this time, two or more types of silane-modified polyethylene resins or polyethylene resins having different densities can be used in combination, and adjusted to the suitable range of the MFR.

  Here, the MFR is a value measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with ISO 1133.

  There is no restriction | limiting in particular as polyethylene which copolymerizes an ethylenically unsaturated silane compound, Of the thing illustrated as polyethylene of the polyolefin resin which the polycarbonate composite resin composition of this invention may contain, the silane modified polyethylene resin obtained The density of the silane modified polyethylene resin is more preferably within the above preferable range, and more preferably the MFR of the obtained silane-modified polyethylene resin is within the above preferable range.

As a polyethylene from which such a density, and further, an MFR silane-modified polyethylene resin can be obtained, the density itself is about 0.80 to 0.98 g / cm ³ and the MFR is about 0.1 to 100 g / 10 min. Examples include polyethylene.

Examples of the ethylenically unsaturated silane compound copolymerized with polyethylene include silane compounds represented by the following general formula.
RSiR ' _n Y _3-n
(Here, R represents an ethylenically unsaturated hydrocarbon group or oxyhydrocarbon group, R ′ represents an aliphatic saturated hydrocarbon group or phenyl group, Y is a hydrolyzable organic group, and n is 0, 1) Or 2.

  Specifically, in the above general formula, R is vinyl, acrylic, isopropenyl, butenyl, cyclohexenyl, γ- (meth) acryloyloxypropyl group or the like, and R ′ is methyl, ethyl, decyl, phenyl group or the like. , Y is methoxy, ethoxy, formyloxy, acetoxypropionyloxy, alkyl or arylamino group, and preferably trialkoxysilane in which R is vinyl or γ- (meth) acryloyloxypropyl group.

  The amount of the ethylenically unsaturated silane compound copolymerized with polyethylene is 0.01 to 15 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of polyethylene. preferable. If the copolymerization ratio of the ethylenically unsaturated silane compound is too small, the above-mentioned effect due to the silane modification of polyethylene cannot be sufficiently obtained, and if too large, the dispersibility decreases due to the increase in the crosslinking density and the appearance. Defects and chemical resistance decrease.

  The silane-modified polyethylene resin used in the present invention can be obtained, for example, by graft-polymerizing an ethylenically unsaturated silane compound to polyethylene in the presence of a radical generator.

  As the radical generator, any compound that can generate a free radical site in polyethylene under graft reaction conditions and has a sufficiently short half-life at the graft reaction temperature can be used. These radical generators are not particularly limited, but typical radical generators include organic peroxides such as dicumyl peroxide, t-butylperoxyoctate, benzoyl peroxide, azoisobutyronitrile, methylazol. Examples include azo compounds such as isobutyrate.

  The graft reaction of the ethylenically unsaturated silane compound onto polyethylene is carried out by using 0.01 to 15 parts by weight, preferably about 0.5 to 10 parts by weight of the ethylenically unsaturated silane compound relative to 100 parts by weight of the polyethylene, radical generator. In an amount of 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, and kneading at a temperature at which decomposition of the used radical generator occurs, generally about 150 to 200 ° C. . For the kneading, an ordinary kneading machine such as a single-screw or multi-screw kneading extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader or the like can be used.

  In addition, as such a silane modified polyethylene resin, a commercial item can also be used.

  As the silane-modified polyethylene resin, one kind may be used alone, or two or more kinds having different ethylenically unsaturated silane compounds or different densities may be used in combination.

  In general, a silane-modified polyethylene resin molded into a product is water-crosslinked in the presence of a silanol condensation catalyst. In the present invention, sufficient chemical resistance, thermal stability and impact resistance are improved even in the absence of a catalyst, but a silanol condensation catalyst may be used as necessary. By using a silanol condensation catalyst, an inorganic filler and a resin component come to adhere more firmly. Such silanol condensation catalysts generally include carboxylates of metals such as tin, zinc, iron, lead, cobalt, organic bases, inorganic acids, and organic acids. Specifically, for example, dibutyltin dilaurate , Carboxylates such as dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, etc., organics such as ethylamine, dibutylamine, hexylamine, pyridine Examples include bases, inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as toluenesulfonic acid, acetic acid, stearic acid and maleic acid. These silanol condensation catalysts may be used individually by 1 type, and may use 2 or more types together.

  When the silanol condensation catalyst is used, the amount used is usually about 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the silane-modified polyethylene resin. When the amount of the silanol condensation catalyst is less than 0.001 part by mass, it is not sufficient for catalyzing the crosslinking reaction. When the amount exceeds 10 parts by mass, the crosslinking reaction proceeds excessively, so that the silane-modified polyethylene resin flows. The appearance is lost and the physical properties are deteriorated due to the formation of large domains.

As a method for allowing the silanol condensation catalyst to exist, for example, the following method can be used.
(1) A masterbatch is prepared by kneading a silanol condensation catalyst in the same polyethylene used for silane modification with an extruder or the like, and the masterbatch is dry blended with a silane-modified polyethylene resin before molding. How to do.
(2) A method in which a product (molded product) containing no silanol catalyst is immersed in an aqueous solution or emulsion of silanol catalyst.

  Products in which the silanol condensation catalyst is introduced by these methods can be cross-linked by moisture in the atmosphere even when left in the air, but the product is generally at room temperature to about 200 ° C., usually from room temperature to 100 ° C. The water may be cross-linked by contact with water (liquid or vapor) of about 10 seconds to 1 week, usually about 1 minute to 1 day.

[Polyolefin resin]
The polycarbonate composite resin composition of the present invention may contain a polyolefin resin in addition to the polycarbonate resin and the silane-modified polyethylene resin, and the fluidity and physical properties can be adjusted by blending the polyolefin resin.

  Examples of polyolefin resins include polyethylene resins and polypropylene resins. Examples of polyethylene resins include high density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, ethylene- A glycidyl (meth) acrylate copolymer etc. are mentioned. Examples of the polypropylene resin include polypropylene resin, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like.

  These polyolefin resin may be used individually by 1 type, and may use 2 or more types together.

  Among these polyolefin-based resins, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and polypropylene resin are preferable because particularly high chemical resistance can be imparted.

  Below, polyethylene-type resin is demonstrated among polyolefin-type resins.

  The polyethylene-based resin is a copolymer of ethylene and a monomer copolymerizable with ethylene, and the copolymerizable monomer is not particularly limited. For example, propylene, 1-butene, 1-pentene, Α-olefins such as 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene, monocarboxylic acids such as vinyl acetate, isoprene, butadiene, acrylic acid, and methacrylic acid, or esters thereof, malee Examples thereof include one or more of dicarboxylic acids such as acids, fumaric acid and itaconic acid, or acid anhydrides thereof, and these may be copolymerized in the main chain. It may be polymerized.

  These polyethylene resins can be produced by ordinary methods.

  Among these, a preferable polyethylene-based resin is a copolymer of ethylene and one or more of α-olefins having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, an ethylene-propylene copolymer, Ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene Examples include a -1-heptene copolymer and an ethylene-1-octene copolymer, and a linear polyethylene resin in which a copolymer component is introduced into the main chain is particularly preferable.

  When the content of ethylene in such a polyethylene resin is too small, handling deteriorates due to a decrease in melting point and cost increases, and when it is too large, whitening occurs due to molding shrinkage due to crystallization. Therefore, the ethylene content in the polyethylene resin is preferably 90 to 40 mol%, particularly 85 to 50 mol%.

The polyethylene resin used in the present invention is a polyethylene resin as described above, and is preferably a low-density polyethylene resin having a density of 0.85 to 0.92 g / cm ³ . When the density of the polyethylene resin exceeds 0.92 g / cm ³ , there are problems of whitening due to domain voids, delamination, and deterioration of chemical resistance due to poor dispersion of polyethylene. By using a low-density polyethylene resin having a density of 0.92 g / cm ³ or less, the crystallinity is reduced, the shrinkage rate at the time of molding is close to the shrinkage rate of the polycarbonate resin, and void formation is suppressed. Since the formation of is suppressed, impact resistance is improved.
However, if the density of the polyethylene resin is smaller than 0.85 g / cm ³ , the physical properties are lowered. Therefore, a polyethylene resin having a density of 0.85 g / cm ³ or more is used. The density of the polyethylene resin is particularly preferably 0.86 to 0.92 g / cm ³ , and particularly preferably 0.88 to 0.90 g / cm ³ .

  Here, the density of the polyethylene resin is a value measured according to the ISO 1183 D method.

  In addition, such a low-density polyethylene-based resin has a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.3 to 4.0. Is preferred. When the molecular weight distribution (Mw / Mn) is larger than 4.0, there is a problem that impact resistance is lowered, and when it is smaller than 1.3, the moldability is inferior. A more preferable molecular weight distribution (Mw / Mn) of the polyethylene resin is 1.5 to 3.5.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene-based resin are measured by gel permeation chromatography (GPC: Gel Permeation Chromatography). Specifically, it is as described in the section of Examples described later.

The polyethylene resin preferably has a melt flow rate (MFR) at 190 ° C. of 0.1 to 50 g / 10 min. When the MFR of the polyethylene resin is less than 0.1 g / 10 min, the dispersibility is poor, and it is easy to form a large domain, so that whitening is likely to occur. When the MFR is greater than 50 g / 10 min, the domain is greatly stretched. For this reason, appearance defects, delamination and deterioration of physical properties are likely to occur due to pearl luster.
The more preferable MFR of the polyethylene resin is 0.2 to 30 g / 10 min.

  Here, the MFR is a value measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with ISO 1133.

[Other resins]
In the polycarbonate composite resin composition of the present invention, as the resin component, resins other than the above polycarbonate resin, silane-modified polyethylene resin and polyolefin resin, for example, polyethylene terephthalate, polybutylene terephthalate, polystyrene, ABS resin, and AS resin are used. 1 type or 2 types or more chosen from among these can be contained, and the following effects are produced by including these other resins.
Polyethylene terephthalate: improved chemical resistance Polybutylene terephthalate: improved chemical resistance, improved fluidity polystyrene: improved fluidity ABS resin: improved fluidity, improved impact resistance AS resin: improved fluidity

[Resin component]
The polycarbonate composite resin composition of the present invention comprises a polycarbonate resin and a silane-modified polyethylene resin as resin components (in the present invention, the polycarbonate resin and the silane-modified polyethylene resin are referred to as “resin main component”, and the polycarbonate resin and the silane-modified polyethylene resin are Including other resins such as polyolefin resin and ABS resin blended as necessary, it is referred to as “resin component”.) If necessary, other resins such as polyolefin resin and ABS resin are further included. But its content is
Polycarbonate resin: 85-99% by mass
Silane-modified polyethylene resin: 1 to 15% by mass
The polyolefin resin is preferably 0 to 50 parts by mass and the other resins are preferably 0 to 40 parts by mass with respect to 100 parts by mass of the resin main component.

  When the polycarbonate resin is more than the above upper limit and the silane-modified polyethylene resin is less than the above lower limit, the effect of the present invention due to the use of the silane-modified polyethylene resin cannot be sufficiently obtained. Conversely, the polycarbonate resin is more than the above lower limit. However, when the amount of the silane-modified polyethylene resin is larger than the above upper limit, appearance defects and physical properties are reduced due to an increase in polyethylene domain size.

  Further, when the content of the polyolefin-based resin is higher than the above upper limit, poor appearance, delamination and physical properties are deteriorated, and when the content of other resins is higher than the upper limit, impact resistance and heat resistance are reduced.

  When the polycarbonate composite resin composition of the present invention contains only a polycarbonate resin and a silane-modified polyethylene resin as resin components, the content is 85 to 99% by mass of the polycarbonate resin and 1 to 15% by mass of the silane-modified polyethylene resin, preferably Is 90-98% by mass of polycarbonate resin and 2-10% by mass of silane-modified polyethylene resin.

  Further, when the polycarbonate composite resin composition of the present invention includes a polycarbonate resin, a silane-modified polyethylene resin and a polyolefin resin as resin components, the preferred content is 70 to 98% by mass of the polycarbonate resin, 1 to 1 of the silane-modified polyethylene resin 1 15 mass%, polyolefin resin 1-15 mass%, more preferably polycarbonate resin 80-96 mass%, silane-modified polyethylene resin 2-10 mass%, polyolefin resin 2-10 mass%.

  Moreover, when the polycarbonate composite resin composition of this invention contains a polycarbonate resin, a silane modified polyethylene resin, and other resin as a resin component, the suitable content is 40-98 mass% of polycarbonate resins, the silane modified polyethylene resin 1 -15 mass%, other resin 1-45 mass%, more preferably 60-96 mass% polycarbonate resin, 2-10 mass% silane-modified polyethylene resin, and 2-30 mass% other resin.

  Furthermore, when the polycarbonate composite resin composition of the present invention contains a polycarbonate resin, a silane-modified polyethylene resin, a polyolefin-based resin, and other resins as resin components, the preferred content is 25 to 97% by mass of polycarbonate resin, silane 1 to 15% by mass of modified polyethylene resin, 1 to 15% by mass of polyolefin resin, and 1 to 45% by mass of other resins, more preferably 50 to 94% by mass of polycarbonate resin, and 2 to 10% by mass of silane-modified polyethylene resin. And 2-10% by mass of polyolefin resin and 2-30% by mass of other resins.

[Inorganic filler]
The polycarbonate composite resin composition of the present invention may be a reinforced polycarbonate composite resin composition containing an inorganic filler. By blending the inorganic filler, the elastic modulus is controlled and the shrinkage at the time of molding is suppressed to achieve a dimensional accuracy. Improvements can be made.

  Examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), milled glass fibers (short glass fibers), glass flakes, and glass beads; carbon fillers such as carbon fibers, short carbon fibers, carbon nanotubes, and graphite; Whisker such as potassium titanate and aluminum borate; silicate compounds such as wollastonite, talc, mica, kaolinite, zonotlite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. Preferred are glass fiber, milled glass fiber, wollastonite, talc, mica, and the like. Among these, wollastonite and talc are preferable for achieving both the appearance and the stability of residence heat. These inorganic fillers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The shape of the inorganic filler is preferably fibrous, needle-like, plate-like, or spherical, and when considering the reduction in molding shrinkage or linear expansion, fibrous, needle-like, or plate-like inorganic fillers are more preferred.

  As a size of the inorganic filler, the minor axis diameter is 0.01 to 100 μm, more preferably 0.05 to 50 μm, and still more preferably 0.1 to 10 μm. If the minor axis diameter of the inorganic filler is smaller than 10 nm, the polyethylene domain shape cannot be sufficiently broken and pearly luster remains in the molded product. Moreover, since it will become large between inorganic fillers when larger than 100 micrometers, pearl luster will remain between inorganic fillers. As will be described later, in particular, the short axis diameter of the inorganic filler is preferably the same as the short axis diameter of the polyethylene domain in order to effectively eliminate pearl luster.

  Here, the minor axis diameter of the inorganic filler is the length of the portion where the interval between the parallel plates is the smallest when the inorganic filler is sandwiched between two parallel plates. If it is fibrous, it corresponds to the fiber diameter, if it is plate-like, it corresponds to the plate thickness, and if it is spherical, it corresponds to the diameter.

  The minor axis diameter (average minor axis diameter) of the inorganic filler was determined by observing a cross section in the injection direction of the obtained injection molded product with a scanning electron microscope (SEM), and selecting the minor axis of 50 inorganic fillers arbitrarily selected. Although it can also obtain | require as a number average value of the measured value of a diameter, the average fiber diameter as a product specification of the fibrous inorganic filler supplied as a product can also be made into a short axis diameter, for example. The same applies to plate-like and spherical inorganic fillers.

  The aspect ratio of the inorganic filler (= major axis diameter / minor axis diameter. The major axis diameter is the portion of the portion where the interval between the parallel plates is widest when the inorganic filler is sandwiched between two parallel plates. If the inorganic filler is fibrous, it corresponds to the fiber length, if it is plate-like, it corresponds to the major axis of the plate surface, and if it is spherical, it corresponds to the diameter.) Although it is not, it is preferable that it is 2-500. If the aspect ratio of the inorganic filler is too large, the difference in molding shrinkage between the orientation direction of the inorganic filler and the direction perpendicular thereto becomes too large, and thus distortion is likely to occur, and if it is too small, the effect of suppressing linear expansion is not sufficient.

  As for the aspect ratio, as with the short axis diameter, the short axis diameter and the long axis diameter of the inorganic filler are measured by SEM observation, the aspect ratio is calculated for each inorganic filler, and the number average value is obtained. However, it is also possible to adopt an aspect ratio as a product standard of the inorganic filler supplied as a product.

  The blending amount of the inorganic filler is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and further preferably 3 to 15 parts by mass with respect to 100 parts by mass of the resin component. If the blending amount of the inorganic filler is less than the above lower limit, optimization of the molding shrinkage rate is insufficient and the dimensional accuracy cannot be sufficiently increased, and if it exceeds the upper limit, problems such as deterioration of moldability and embrittlement occur. .

[Other ingredients]
The polycarbonate composite resin composition of the present invention contains various other additives contained in the normal polycarbonate resin composition in addition to the above-described resin component and inorganic filler, as long as the effects of the present invention are not impaired. You may do it.

  Various additives that can be contained include antioxidants, heat stabilizers, mold release agents, UV absorbers, dyes and pigments, flame retardants, reinforcing agents, impact modifiers, antistatic agents, antifogging agents, lubricants, Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like can be mentioned. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the resin composition according to the present invention will be specifically described.

  Examples of the antioxidant include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4 6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like. Two or more of these may be used in combination.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  Content of antioxidant is 0.001-1 mass part normally with respect to 100 mass parts of resin components, Preferably it is 0.01-0.5 mass part. When the content of the antioxidant is less than 0.001 part by mass, the effect as an antioxidant is insufficient, and when it exceeds 1 part by mass, the effect reaches a peak and is not economical.

  The heat stabilizer used in the present invention includes a phosphite compound (a) in which at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. ), Phosphorous acid (b), and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).

  Specific examples of the phosphite compound (a) include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4 -Di-tert-butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl Phosphite, distearyl pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Rudiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Examples include erythritol diphosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in combination of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

  Content of a heat stabilizer is 0.001-1 mass part normally with respect to 100 mass parts of resin components, Preferably it is 0.01-0.5 mass part. When the content of the heat stabilizer is less than 0.001 part by mass, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by mass, the hydrolysis resistance may deteriorate.

  The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  Content of a mold release agent is 0.001-2 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.01-1 mass part. When the content of the release agent is less than 0.001 part by mass, the effect of releasability may not be sufficient. When the content exceeds 2 parts by mass, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

  Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  Content of a ultraviolet absorber is 0.01-3 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.1-1 mass part. When the content of the ultraviolet absorber is less than 0.01 parts by mass, the effect of improving the weather resistance may be insufficient, and when it exceeds 3 parts by mass, a problem such as mold deposit may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the resin component. When the content of the dye / pigment exceeds 5 parts by mass, the impact resistance may not be sufficient.

  Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  Content of a flame retardant is 1-30 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 3-25 mass parts, More preferably, it is 5-20 mass parts. When the content of the flame retardant is less than 1 part by mass, the flame retardancy may not be sufficient, and when it exceeds 30 parts by mass, the heat resistance may decrease.

  Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  Content of a dripping inhibitor is 0.02-4 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 0.03-3 mass parts. When the compounding amount of the dripping inhibitor exceeds 5 parts by mass, the appearance of the molded product may be deteriorated.

[Method for producing polycarbonate composite resin composition]
Regarding the kneading conditions for producing the polycarbonate composite resin composition of the present invention, the polycarbonate resin and silane-modified polyethylene resin used, the physical properties and blending ratio of other resin components, the type and blending ratio of the inorganic filler used, and other Depending on the presence or absence of additives, etc. and cannot be generally stated, for example, the following conditions can be adopted.

  A resin component, an inorganic filler, an additive, and the like are blended, and the blended composition is kneaded at a cylinder temperature of 200 to 300 ° C. and a screw rotation speed of 80 to 400 rpm. As a method for adding the inorganic filler, the resin component and the inorganic filler may be kneaded by batch supply to the kneader, but in the case of a fibrous or needle-like inorganic filler such as glass fiber or wollastonite, a strong need The needle-like inorganic filler may be broken by the ring, and the performance as the filler may be reduced. In addition, inorganic mineral-based inorganic fillers such as talc, wollastonite, and mica cause degradation and degradation of the polycarbonate resin by increasing the time of contact with the polycarbonate resin under heating.

  In the present invention, the degradation degradation of the polycarbonate resin is suppressed by blending the silane-modified polyethylene resin, but in order to further suppress the degradation degradation of the polycarbonate resin, the melt kneading time of the resin component and the inorganic filler is short. Is preferred.

  Therefore, the inorganic filler is preferably added in the middle of kneading to the resin component that has been previously melt-kneaded using the side feed method, and then extruded as a strand through a light kneading zone. The extruded strand is cooled, cut and pelletized.

  When kneading, the screw rotation speed and the discharge amount are balanced, the resin pressure in the die is set to about 1 to 50 MPa, and the resin pressure is kept constant, so that the shearing stress is effectively applied, and the polyethylene domain in the polycarbonate resin. And the dispersibility of the inorganic filler is improved. Even if the resin is not filled in the cylinder, sufficient shear stress is not applied, polyethylene tends to form large domains, and inorganic fillers are not uniformly dispersed, resulting in variations in physical properties and poor appearance. It becomes easy.

[Production method of polycarbonate composite resin molded product]
The molding method for producing a polycarbonate composite resin molded product from the polycarbonate composite resin composition of the present invention includes a general injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a multicolor injection molding method, and a multicolor injection compression method. Molding method, gas-assisted injection molding method, molding method using heat insulation mold, molding method using high-speed heating / cooling mold, insert molding method, IMC (in-mold coating) molding method, extrusion molding method, sheet molding method, Examples thereof include a thermoforming method, a rotational molding method, a lamination molding method, and a press molding method.
Of these, the polycarbonate composite resin molded product of the present invention is particularly obtained by injection molding.
In the present invention, the polycarbonate composite resin composition of the present invention can be subjected to multicolor composite molding with another thermoplastic resin composition to form a composite molded product.

[Thermal stability of polycarbonate composite resin composition]
The polycarbonate composite resin composition of the present invention preferably has an effect of suppressing the decomposition of the polycarbonate resin by blending the silane-modified polyethylene resin with the polycarbonate resin, and preferably includes an inorganic filler as an indicator of thermal stability. Good thermal stability with an MFR change rate calculated by the following formula of 10% or less is shown. This MFR change rate indicates the degree of increase in fluidity due to the decomposition of the polycarbonate resin and the decrease in molecular weight under melt residence, and the smaller the MFR change rate, the better the thermal stability.

MFR change rate = (R ₂₀ −R ₅ ) / R ₅ × 100
(However, R ₅ is the MFR value (280 ° C., 21.18 N) (unit: g / 10 min) when the composition is held at 280 ° C. for 5 minutes, and R ₂₀ is ₂₀ % of the composition at 280 ° C. MRF value (280 ° C., 21.18 N) (unit: g / 10 min) when held for a minute.)

  When the MFR change rate of the polycarbonate composite resin composition of the present invention exceeds 10%, the residence heat stability is insufficient, and the mechanical strength such as impact resistance of the obtained molded product is also lowered.

  In particular, when the polycarbonate composite resin composition of the present invention does not contain an inorganic filler, the MFR change rate is preferably 3% or less, particularly preferably 2% or less.

  Further, when the polycarbonate composite resin composition of the present invention contains an inorganic filler having a small decomposing action on the polycarbonate resin such as glass fiber and milled fiber, the MFR change rate is preferably 5% or less, particularly preferably 3% or less. .

  Even when the polycarbonate composite resin composition of the present invention contains an inorganic filler having a large decomposing action on polycarbonate resin such as talc and wollastonite, the MFR change rate is 10% or less, particularly 5% or less. Preferably there is.

  Such excellent thermal stability is achieved by blending the low-density silane-modified polyethylene resin according to the present invention and, as described above, post-adding an inorganic filler to the polycarbonate resin that has undergone the melt-kneading process. .

[Chemical resistance of polycarbonate composite resin molded products]
The polycarbonate composite resin molded article of the present invention preferably has a breaking elongation retention measured by the following chemical resistance evaluation test of 70% or more, particularly 80% or more.

<Chemical resistance evaluation test>
A tensile test piece (ISO 3167 type A) having a thickness of 4 mm is annealed at 120 ° C. for 2 hours in order to remove residual strain during molding. Then, in a state loaded with deflection of the deformation rate 0.94%, isopropanol was applied as the test drug, relative elongation at break E _x of the test piece was held for 48 hours in this state, similarly without applying chemicals The retention rate (%) (E _x / E _o × 100) with respect to the breaking elongation E _o of the test piece loaded with the same deflection for the same time is calculated.

  If the above-mentioned breaking elongation retention is less than the above lower limit, the chemical resistance improvement effect intended in the present invention cannot be sufficiently obtained.

  Here, the details of the chemical resistance evaluation test are as described in Examples below.

Hereinafter, the present invention will be described more specifically with reference to Examples , Reference Examples, and Comparative Examples. However, the present invention is not limited to these Examples unless it exceeds the gist.

  In addition, in the following, the measuring method of the physical property of the used resin is as follows.

<MFR of polyethylene resin or silane-modified polyethylene resin>
In accordance with ISO 1133, the measurement was performed at a temperature of 190 ° C. and a load of 21.18 N.

<Density of polyethylene resin or silane-modified polyethylene resin>
The measurement was performed according to ISO 1183 D method.

<Weight average molecular weight Mw, number average molecular weight Mn of polyethylene resin>
The molecular weight distribution Mw / Mn of the polyethylene resin was determined by measuring the weight average molecular weight Mw and the number average molecular weight Mn by gel permeation chromatography (GPC). The GPC was measured according to “Gel Permeation Chromatography” published by Takeuchi and published by Maruzen. That is, standard polystyrene (monodispersed polystyrene manufactured by Toyo Soda) with a known molecular weight was used, and converted to a number average molecular weight (Mn) and a weight average molecular weight (Mw) by a universal method, and the value of Mw / Mn was determined. The measurement used “150C-ALC / GPC” manufactured by Waters, and three columns “AD80M / S” manufactured by Showa Denko were used. As a sample, 200 μl of polyethylene resin diluted to 0.2% by mass in o-dichlorobenzene was used. The measurement was performed at 140 ° C. and a flow rate of 1 ml / min.

<Measurement of viscosity average molecular weight Mv of polycarbonate resin>
The viscosity average molecular weight (Mv) of the polycarbonate resin was determined by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity ([η]) at a temperature of 20 ° C. (unit: dl / g). Formula: Calculated from the formula [η] = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity (ηsp) at each solution concentration (C) (g / dl).

<Hydroxyl value of polycarbonate resin>
By colorimetric determination by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88215 (1965)).

Moreover, the compounding component of the resin composition used in the Example , the reference example, and the comparative example is as follows.

Polycarbonate resin: Mixed resin of the following polycarbonate resin A 81% by mass and the following polycarbonate resin B 19% by mass. Polycarbonate resin A: A product of Mitsubishi Engineering Plastics Co., Ltd. Aromatic polycarbonate resin “trade name: Iupilon (registered trademark) S-3000 "
Viscosity average molecular weight 22000, terminal hydroxyl group concentration 180ppm
Polycarbonate resin B: Mitsubishi Engineering Plastics Co., Ltd. Aromatic polycarbonate resin "Product name: Iupilon (registered trademark) H-4000"
Viscosity average molecular weight 16000, terminal hydroxyl group concentration 150ppm

Silane-modified polyethylene A: Mitsubishi Chemical Corporation low-density silane-modified polyethylene resin “trade name: XLE815N”, density 0.915 g / cm ³ , MFR 0.5 g / 10 min

Silane-modified polyethylene B: Mitsubishi Chemical Corporation high-density silane-modified polyethylene resin “trade name: XHE650N”, density 0.947 g / cm ³ , MFR 0.4 g / 10 min

Polyethylene A: Nippon Polyethylene Co., Ltd. product Low density ethylene-propylene copolymer “trade name: Kernel KF282”, ethylene content 80-85 mol%, density 0.915 g / cm ³ , Mw / Mn 2.6, MFR2. 2g / 10min

Polyethylene B: Nippon Polyethylene Co., Ltd. Product High-density ethylene-propylene copolymer “trade name: HF350”, ethylene content 98 mol%, density 0.950 g / cm ³ , Mw / Mn22, MFR 2.5 g / 10 min

  ABS: Technopolymer Co., Ltd. ABS resin “trade name: DP615” 50 mass% and AS resin “trade name: 290FC” 50 mass% mixed resin

  Glass fiber: “trade name: ECS03T-127” manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 13.5 μm, average aspect ratio 220)

  Milled glass fiber: “EPG70M-99S” manufactured by Nippon Electric Glass Co., Ltd. (average fiber diameter 13.5 nm, average aspect ratio 5)

  Wollastonite: “Product name: NYGLOS4W” manufactured by NYCO minerals Co., Ltd. (average fiber diameter 4.5 μm, average aspect ratio 11)

Colorant: Koshigaya Kasei Co., Ltd. carbon black "Product name: ROYAL BLACK 904G"

  Antioxidant: “Trade name: Irganox 1076” (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) manufactured by Ciba Specialty Chemicals Co., Ltd.

  Thermal stabilizer: “Brand name: Irgafos 168” (Tris (2,4-di-tert-butylphenyl) phosphite) manufactured by Ciba Specialty Chemicals Co., Ltd.

  In addition, evaluation methods for various physical properties and characteristics are as follows.

<Thermal stability>
The cylinder temperature of the melt indexer (manufactured by Toyo Seiki Co., Ltd.) was set at 280 ° C. and the load was 21.18 N. The pellet of the sample to be measured was placed in the cylinder, and the MFR value after heating for 5 minutes (R ₅ ) and The MFR value (R ₂₀ ) of the sample was measured, and MFR change rate = (R ₂₀ −R ₅ ) / R ₅ × 100 was calculated.
The obtained MFR change rate was used as an index for thermal stability evaluation. That is, the greater the MFR change rate, the lower the thermal stability, and the smaller the MFR change rate, the higher the thermal stability.

<Impact resistance>
Using an ISO standard multipurpose test piece (ISO 3167 type A) with a notching machine (“Torch Sewing Tool A-4” manufactured by Toyo Seiki Co., Ltd.), single-tooth V cutter (45 °, R = 0.25 mm), notch rotation speed 300 rpm The notch was cut twice, and at the same time, the center part was cut out by 80 mm with a slicer. A Charpy impact test was performed in accordance with ISO 179 using the obtained notched Charpy test piece. The measurement was performed using a Charpy impact tester (“DG-CB” manufactured by Toyo Seiki Co., Ltd.) with a hammer capacity of 4.0 J and a measurement temperature of 23 ° C.

<Chemical resistance>
An ISO standard tensile test piece (ISO 3167 type A) was annealed at 120 ° C. for 2 hours in order to remove residual strain during molding. Thereafter, as shown in FIGS. 1 (a), (b), and (c), using the spacer 2 and the support columns 4a and 4b, the test was performed with the fixed frame 3 loaded with the deformation rate shown in Table 1. Isopropanol (2-propanol 99.9 +% (cGC), manufactured by Wako Pure Chemical Industries, Ltd.) was applied as a chemical to the convex side of the test piece 1 (X part in FIG. 1 (c)), and this state was applied for 48 hours. , 25 ° C., allowed to stand at a constant temperature and humidity conditions of 50% humidity, then by ISO527 tensile test to measure the elongation at break _{E x.}
Separately, except that no coating isopropanol After you load deflection under the same conditions as described above was left in the same conditions, to measure the elongation at break E _o by ISO527 tensile test.
(E _x / E _o × 100) was calculated as a retention rate (%) with respect to the breaking elongation E _o .

Here, the deformation rate refers to the deformation rate, where L is the linear distance connecting the test piece 1 and the contacts A and B with the cylinders 4a and 4b supporting the test piece 1, the thickness of the test piece is a, and the deflection amount is δ. = 6aδ / L ² is calculated.
The deflection amount δ is calculated by the following equation.
δ = ([the height of the supporting cylinder] + [the thickness of the test piece] − [the height of the spacer])
The distance L between the jig support points is 101 mm, the thickness a of the test piece 1 is 4 mm, the height of the spacer 2 is 11 mm, and the height (diameter) of the support columns 4a and 4b is 10 mm.

<Appearance evaluation>
(Blackness)
The appearance of the test piece was visually observed, and the blackness was evaluated in the following four stages.
A: Completely black without any whitening.
○: Some whitening is slightly observed, but almost black.
Δ: Overall whitening slightly.
X: Overall whitening is observed.
(With or without pearl luster)
The appearance of the test piece was visually observed, and the degree of pearl luster was evaluated in the following four stages.
A: No pearl luster is observed.
○: Partially pearly luster is observed.
Δ: A slight pearly luster is seen overall.
X: Significant pearl luster is observed as a whole.
(Surface roughness)
The appearance of the test piece was visually observed, and the surface roughness was evaluated in the following four stages.
A: It has a very smooth and glossy surface.
○: It has a mat-like surface due to very fine irregularities.
(Triangle | delta): It has the surface which can confirm the shape of a filler by fine unevenness | corrugation.
X: It has the surface which can confirm the shape of a filler by a large unevenness | corrugation.

[Examples 2 to 8, Reference Example 1, Comparative Examples 1 to 7]
Among the blending components shown in Table 1, components other than the post-added inorganic filler were mixed in the proportions shown in Table 1, and in a twin screw extruder (“TEX30α” manufactured by Nippon Steel Works, Ltd., L / D = 52.5, cylinder diameter = 32 mm, cylinder temperature = 200 to 280 ° C., screw rotation speed 200 rpm, provided with a vent downstream of the kneading, kneading while removing decomposition products etc. by reducing the pressure with a vacuum pump, The kneaded product was extruded as a strand with a resin pressure in the die of 10 to 15 MPa and a discharge rate of 30 kg / h.When adding an inorganic filler by post-addition, it was added in the middle of kneading using the side feed method and added. After that, it was gently kneaded and extruded.
The extruded strand was cooled by applying cooling water using a cooling belt conveyor, cut to a length of 3 to 6 mm, and pelletized.
Thermal stability was evaluated using this pellet.

Further, using the obtained pellets, an injection molding machine (“NADEM2000” manufactured by MEIKI) was used, cylinder temperature 260 ° C., mold temperature 90 ° C., back pressure 5 MPa, screw rotation speed 100 rpm, injection speed 6%, holding pressure 30 MPa. Then, injection molding was performed under the conditions of a clamping time of 35 seconds (injection / holding time of 15 seconds, cooling time of 20 seconds), and an ISO standard multipurpose test piece (ISO 3167 type A) was molded.
The test piece was used for impact resistance, chemical resistance, and appearance evaluation.

  The evaluation results are shown in Table 1.

Table 1 shows the following.
In Comparative Example 1 in which no silane-modified polyethylene resin is used, thermal stability, impact resistance, and chemical resistance are inferior compared to Reference Example 1 in which a silane-modified polyethylene resin is blended.
Even if the silane-modified polyethylene resin is used, the density of the silane-modified polyethylene resin is as high as 0.947 g / cm ^3. Properties, impact resistance, and chemical resistance are poor, and in particular, blackness is inferior due to formation of voids between the polycarbonate resin matrix and the silane-modified polyethylene resin domain.

In Comparative Example 3 in which this high-density silane-modified polyethylene resin is used and an inorganic filler is further blended, the thermal stability is further inferior and the impact resistance is poor.
In Comparative Example 3, all evaluations were inferior to Example 4 of the same composition except that a low density silane modified polyethylene resin having a density of 0.915 g / cm ³ was used instead of the high density silane modified polyethylene resin. Become.

  Of Comparative Examples 4 to 7 in which high-density polyethylene or low-density polyethylene is blended with polycarbonate resin without using silane-modified polyethylene resin, Comparative Examples 6 and 7 using high-density polyethylene use high-density silane-modified polyethylene resin. Comparative Examples 2 and 3 were not much different from Comparative Examples 2 and 3, and Comparative Examples 4 and 5 using low-density polyethylene were improved over Comparative Examples 6 and 7, but were not sufficient.

On the other hand, in Reference Example 1 and Examples 2 to 4 using a low-density silane-modified polyethylene resin, corresponding Comparative Examples 2 using high-density silane-modified polyethylene resin or polyethylene not modified with silane in the same composition, respectively. Compared with ˜7, a remarkable improvement effect is obtained.

  In Example 5, a part of the low-density silane-modified polyethylene resin of Example 4 was replaced with low-density polyethylene. Although the performance was slightly inferior to that of Example 4, a sufficiently practical effect was obtained. ing.

  In Example 6, the amount of the silane-modified polyethylene resin was increased as compared with Example 4, and the thermal stability and chemical resistance were improved, but the impact resistance and appearance were slightly inferior.

  In Example 7, a part of the polycarbonate resin was replaced with ABS resin and AS resin from the formulation of Example 4, and the impact resistance and chemical resistance were improved.

  In Example 8, wollastonite was used as an inorganic filler, which was added all at once. Compared to Example 4, the thermal stability and impact resistance were slightly inferior.

  Thus, according to the present invention, a polycarbonate composite resin molded article having excellent thermal stability and chemical resistance, and excellent appearance and impact resistance is provided.

1 Test piece 2 Spacer 3 Fixed frame 4a, 4b Support cylinder

Claims (8)

As a resin main component, polycarbonate resin 85-99 mass%, and the density | concentration of 0.85-0.92 g / cm < ³ > silane modified polyethylene resin 1-15 mass obtained by copolymerizing an ethylenically unsaturated silane compound to polyethylene % contained,
The content of the silane-modified polyethylene resin in the resin component is 10% by mass or less,
And 1-15 mass parts of 1 type, or 2 or more types of inorganic fillers chosen from glass fiber, milled glass fiber, wollastonite, talc, and mica are contained with respect to 100 mass parts of resin components. reinforced polycarbonate composite resin composition characterized such Rukoto. The reinforced polycarbonate composite resin composition according to claim 1, comprising 50 parts by mass or less of a polyolefin-based resin with respect to 100 parts by mass of the resin main component. The reinforced polycarbonate composite resin composition according to claim 1 or 2, wherein the silane-modified polyethylene resin has a melt flow rate (MFR) at 190 ° C of 0.1 to 50 g / 10 min. 4. The reinforced polycarbonate according to claim 2, wherein the polyolefin resin is one or more selected from high density polyethylene, low density polyethylene, linear low density polyethylene, and polypropylene. Composite resin composition. In any one of claims 1 to 4, the inorganic filler, wollastonite, talc, and reinforced polycarbonate composite resin composition, wherein the at least one selected from the group consisting of mica . In any one of claims 1 to 5, further polyethylene terephthalate as the resin component, polybutylene terephthalate, polystyrene, ABS resin, and reinforced polycarbonate, characterized in that it contains one or more selected from the AS resin Composite resin composition. In any one of claims 1 to 6, reinforced polycarbonate composite resin composition, wherein the MFR change rate calculated by the following equation is 10% or less.
MFR change rate = (R ₂₀ −R ₅ ) / R ₅ × 100
(However, R ₅ is the MFR value (280 ° C., 21.18 N) (unit: g / 10 min) when the composition is held at 280 ° C. for 5 minutes, and R ₂₀ is ₂₀ % of the composition at 280 ° C. MRF value (280 ° C., 21.18 N) (unit: g / 10 min) when held for a minute.) A reinforced polycarbonate composite resin molded article obtained by injection molding the reinforced polycarbonate composite resin composition according to any one of claims 1 to 7 .

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