WO2009014050A1

WO2009014050A1 - Flame-retardant resin composition

Info

Publication number: WO2009014050A1
Application number: PCT/JP2008/062868
Authority: WO
Inventors: Keiichiro Ino; Fumitaka Kondo; Kazuhiko Inoue; Makoto Soyama; Masatoshi Iji
Original assignee: Teijin Chemicals Ltd.; Nec Corporation
Priority date: 2007-07-24
Filing date: 2008-07-10
Publication date: 2009-01-29
Also published as: JP5323701B2; CN101790565A; CN101790565B; JPWO2009014050A1

Abstract

Disclosed is a resin composition having high flame retardancy, which enables to obtain a molded article improved in appearance such as occurrence of silver streaks. Specifically disclosed is a resin composition containing 100 parts by weight of a polycarbonate resin (component A), 10-70 parts by weight of an inorganic particle (component B) containing a composite body of silicon dioxide and aluminum oxide and having a D50 particle size of not more than 10 μm, 0.01-2 parts by weight of a fluorine resin (component C), 0.05-3 parts by weight of a dissolution inhibitor (component D), 1-20 parts by weight of a fluidity improver (component E), and 0.01-2 parts by weight of an acid-modified polyolefin wax (component F). Also specifically disclosed is a molded article of such a resin composition.

Description

Memorandum Flame retardant resin composition Technical field

The present invention relates to a resin composition containing a polycarbonate resin and inorganic particles. More specifically, the present invention relates to a resin composition that contains a polycarbonate resin and inorganic particles and becomes a molded article having excellent flame retardancy and appearance. Background art

Many proposals have already been made for plastic composite materials filled with inorganic particles to impart flame retardancy, and some have been put into practical use. Such plastics include polycarbonate resins.

For example, JP 2004-10825 A (Patent Document 1) discloses a resin composition in which inorganic particles such as silica particles are blended in a polycarbonate resin. This document proposes to improve the flame retardancy by devising the shape of the inorganic particles.

JP 2001-152030 A (Patent Document 2) discloses a resin composition containing particles having a particle diameter of 10 nm to 100 nm obtained by pulverizing an inorganic porous material. Specifically, a resin composition in which porous particles obtained by pulverizing silicon oxide or aluminum oxide are blended with a polycarbonate resin or a polypropylene resin has been proposed. When inorganic particles are thus contained in the polycarbonate resin, the flame retardancy of the resin composition can be improved. However, it is difficult to stably achieve a high level of flame retardancy.

Japanese Patent Application Laid-Open No. 2005-272808 (Patent Document 3) discloses a resin composition in which polycarbonate resin is mixed with particles containing a composite of silicon dioxide and aluminum oxide, particularly flash ash. . This resin composition has excellent flame retardancy, but there is room for improvement in the appearance of molded articles such as silver. (Patent Document 1) Japanese Unexamined Patent Application Publication No. 2004-10825

(Patent Document 2) Japanese Patent Application Laid-Open No. 2001-152030

(Patent Document 3) Japanese Unexamined Patent Publication No. 2005-272808 Disclosure of Invention

As described above, in the resin composition containing inorganic particles, no attempt has been made to achieve both high flame retardancy and good appearance of molded products. Accordingly, an object of the present invention is to provide a resin composition which has a high flame retardancy and gives a molded article having an improved appearance of a molded article such as silver.

As a result of intensive studies, the present inventors have found that polycarbonate particles (component A) contain a composite of silicon dioxide and aluminum oxide as inorganic particles, and D50 particle diameter is 1 or less (component B). And found that a resin composition containing a fluorine resin (C component), an elution inhibitor (D component), a flow modifier (E component) and an acid-modified polyolefin wax (F component) can achieve the above-mentioned problems. The present invention has been completed.

The object of the present invention is (A) 100 parts by weight of polycarbonate resin (component A),

(B) Inorganic particles (component B) containing 10 to 70 parts by weight of a composite of silicon dioxide and aluminum oxide and having a D50 particle size of 10 m or less,

(C) 0.01 to 2 parts by weight of a fluororesin (component C),

(D) 0.05 to 3 parts by weight of dissolution inhibitor (component D),

(E) 1-20 parts by weight of flow modifier (E component) and

(F) This is achieved by a resin composition containing 0.01 to 2 parts by weight of an acid-modified polyolefin wax (F component). The resin composition of the present invention provides a molded product having high flame retardancy and improved appearance of the molded product such as silver.

The inorganic particles (component B) are preferably fly ash.

The fluororesin (component C) is preferably a polytetrafluoroethylene resin having a fibril forming ability.

The dissolution inhibitor (component D) is preferably divalent and Z or trivalent iron ions and sulfur. A salt with an acid ion, more preferably ferrous sulfate · hydrate or Schwernite, and more preferably ferrous sulfate · 7hydrate. By using such a compound as component D, elution of heavy metals and arsenic contained in the inorganic particles can be further suppressed.

The flow modifier (E component) is preferably at least one selected from the group consisting of aliphatic polyester resins and trimellitic acid esters. By using these flow modifiers, the appearance of molded articles such as silver can be improved.

The acid-modified polyolefin wax (F component) is preferably an acid-modified polyolefin wax having a carboxyl group and Z or carboxyl anhydride. By using these waxes, the appearance of molded articles such as silver can be further improved.

Further, it is preferable to contain 0.002 to 1 part by weight of a phosphorus stabilizer (G component) per 100 parts by weight of the polycarbonate resin (component A). As the G component, a phosphorus stabilizer in which 50% by weight or more of its 10% by weight is a phosphate compound and Z or a phosphate compound is more preferable.

The polycarbonate resin (component A) is preferably bisphenol A type polycarbonate.

The present invention includes a molded article comprising the resin composition according to claim 1. Brief Description of Drawings

FIG. 1 is an evaluation photograph of the silver generation ratio of Example 4 and Comparative Example 4. BEST MODE FOR CARRYING OUT THE INVENTION

Details of the present invention will be described below.

(A component: polycarbonate resin)

The polycarbonate resin used as component A in the present invention is obtained by reacting divalent phenol with a carbonate precursor. As an example of the reaction method Examples thereof include an interfacial polymerization method, a melt transesterification method, a solid phase ester exchange method of a carbonate precursor, and a ring-opening polymerization method of a cyclic carbonate compound. Typical examples of dihydric phenols used here are hydroquinone, resorcinol, 4,4, -biphenol, 1,1-bis (4-hydroxyphenol) ethane, 2,2-bis (4-hydroxyphenol). Enyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-1-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1_bis (4-hydroxyphenyl) 1-phenylphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1,3-, 3-trimethylcyclohexane, 2,2-bis ( 4-hydroxyphenyl) pentane, 4, 4 'one (p-phenylene diisopropylidene) diphenol, 4, 4'-(m-phenylene diisopropylidene) dipheno 1, 1 bis (4-hydroxyphenyl) 4-1 isopropyl cyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Enyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred divalent phenol is a bis (4-hydroxyphenyl) alkane, and bisphenol A (hereinafter sometimes abbreviated as “BPA”) is particularly preferred because of its excellent toughness and deformation characteristics.

The component A is preferably a bisphenol A type polycarbonate. Bisphenol A type polycarbonate is a polycarbonate resin in which bisphenol A is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more of divalent phenol.

In the present invention, in addition to bisphenol A type polycarbonate which is a general-purpose polycarbonate, a special polycarbonate manufactured using other divalent phenols is used. Can be used as component A.

For example, as part or all of the divalent phenol component, 4, 4′-one (m-phenol di-diisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1, 1-bis (4- Hydroxyphenyl) cyclohexane, 1, 1 bis (4-hydroxyphenyl) — 3, 3, 5-trimethylcyclohexane (hereinafter sometimes referred to as “B is—TMC”), 9, 9 Polycarbonate (homopolymer or copolymer) using bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) Is suitable for applications where dimensional changes due to water absorption and the requirement for form stability are particularly severe. These bivalent phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the total divalent phenol component constituting the polycarbonate / bonnet.

In particular, when high rigidity and good hydrolysis resistance are required, the component A constituting the resin composition is preferably a copolymer polycarbonate (1) to (3) below. Yes.

(1) In 100 mol% of the divalent phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%). And a BCF component of 20 to 8 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).

(2) In 100 mol% of the divalent phenol component constituting the polycarbonate, the BP A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%). And a copolymerized polycarbonate containing 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%) of the BCF component.

(3) In 100 mol% of the divalent phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%). And B is— 20-80 mol% of TMC component (more preferred Copolymer polycarbonate which is preferably 25 to 60 mol%, more preferably 35 to 55 mol%.

These special polycarbonates may be used alone or in combination of two or more. These can also be used by mixing with a commonly used bisphenol A type polycarbonate.

The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. Are listed.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself. Since it is remarkably excellent in low warpage after intensive molding, it is particularly suitable in a field where shape stability is required.

(i) a polycarbonate having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.113% and Tg of 120 to 180, or

(ii) Ding 8 is 160 to 250, preferably 170 to 230, and the water absorption is 0.1 to 0.30%, preferably 0.13 to 0.30%, more preferably 0. Polycarbonate which is 14-0.27%.

Here, the water absorption rate of polycarbonate is a value obtained by measuring the moisture content after immersion in water at 23 according to I S062-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3. Omm. It is. Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JI S K7121. As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate, or the like is used, and specific examples include phosgene, diphenyl carbonate, or dihaloformate of divalent phenol.

In the production of polycarbonate resin by interfacial polymerization using the above divalent phenol and carbonate precursor, oxidation prevention to prevent oxidation of the catalyst, terminal terminator and divalent phenol as necessary. An agent or the like may be used. The present invention The polycarbonate resin (component A) used in the above is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, and an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Polymerized polyester carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with both difunctional carboxylic acid and bifunctional alcohol . Further, a mixture obtained by mixing two or more of the obtained polycarbonate resins may be used.

The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding, and blow molding based on its strong properties. As a result, a molded product obtained by these molding methods having superior dimensional accuracy can be obtained.

The trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include 4, 6-dimethyl-2, 4, 6- 卜 ris (4-hydroxydiphenyl) heptene 1, 2, 2, 4, 6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane 1, 1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane, 2, 6-bis (2-hydroxy-5_methylbenzyl) 1-4 methylphenol, and 4 1 {4-[1 , 1_bis (4-hydroxyphenyl) ethyl] benzene}-, α-dimethylbenzylphenol and the like are preferably exemplified. Other polyfunctional aromatic compounds include fluorodalcine, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4 monobis (4,4-dihydroxytriphenylmethyl) ), Benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof are exemplified. Of these, 1,1,1_ 卜 ris (4-hydroxyphenyl) evene and 1,1,1-tris (3,5_dimethyl-4-hydroxyphenyl) ethane are preferred, especially 1,1,1 tris (4— Hydroxyphenyl) ethane is preferred. The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 100 mol% in total of the structural unit derived from the divalent phenol and the structural unit derived from the polyfunctional aromatic compound. 03 to 1 mol%, preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%. Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived from a side reaction during a melt transesterification reaction without using a polyfunctional aromatic compound. There may be. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid. And alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid are preferred. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.

Furthermore, it is possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.

Reaction methods such as interfacial polymerization, which is a method for producing polycarbonate resin, melt transesterification, solid-phase transesterification of force-bonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds are various literatures and patent publications. This is a well-known method.

In producing the resin composition of the present invention, the viscosity average molecular weight (Μ) of the polycarbonate resin (樹脂 component) is preferably 1 X 10 ^{4 to} 5 X 10 ⁴ , more preferably 1.4 to 10 ^{4 to} 3 3 1 0 ⁴ , more preferably 1.4 × 10 ⁴ to 2.4 × 10.

Polycarbonate resins having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically sufficient toughness and crack resistance. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ generally has a high molding processing temperature. It is inferior in versatility because it requires a high degree or requires a special molding method. High molding temperature tends to cause deterioration of deformation and rheological properties of resin composition.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above value (5 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and the extrusion molding, foam molding and blow molding are based on such characteristics. Molding processability can be improved. This improvement effect is even better than the branched polycarbonate.

In a more preferred embodiment, the component A is a polycarbonate resin (A—3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ⁶ , and a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A—3—two components) and a viscosity average molecular weight of 1.6 X 10 ⁴ to 3.5 X 10 ⁴ (A_ 3 components) (hereinafter “high molecular weight component included”) Polycarbonate resin ”(sometimes referred to as“ polycarbonate resin ”) can also be used.

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 X 10 ^{4 to} 3 X 10 ⁵ , more preferably 8 X 10 ⁴ to 2 X 10. ^5, more preferably ^{1 X 1 0 5 ~2 X 1} 0 5, particularly preferably 1 X 1 0 ⁵ ~: I. a 6 X 10 ^5. The A- 3- 2 molecular weight of the component, rather preferably the ^{1 X 1 0 4 ~2. 5} X 10 4, more preferably ^{1. 1 X 1 0 4 ~2.} 4X 10 4, more preferably 1. ^{2 X 1 0 4 ~2. 4X} 1 0 4, particularly preferably 1. a ^{2 X 10 4 ~2. 3 X} 10 4.

High molecular weight component-containing polycarbonate resin (A-3 component) can be obtained by mixing the above A-3-1 component and A-3-2 component in various proportions and adjusting to satisfy the predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1-component is 2-40% by weight and the A-3-3 component is 60-98% by weight, more preferably A-3-1- The component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually the molecular weight distribution of polycarbonate resin is in the range of 2-3. Obedience Therefore, it is preferable that the A-3-1-component and the A-31-2 component of the present invention satisfy the range of the molecular weight distribution. The molecular weight distribution is expressed by the ratio (MwZMn) of the weight average molecular weight (Mw) to the number average molecular weight (M n) calculated by GPC (gel permeation chromatography) measurement. Mn and Mw are based on standard polystyrene.

The preparation method of the A-3 component is as follows: (1) A method in which the 8_3-1 component and the 8-3-2 component are polymerized independently and mixed, (2) Using a method of producing an aromatic polycarbonate resin exhibiting a plurality of polymer peaks in a molecular weight distribution chart by the GPC method, represented by the method disclosed in Japanese Patent No. 3 0 6 336, in the same system, such an aromatic polycarbonate A method for producing a resin to satisfy the conditions of the A-3 component of the present invention, and (3) an aromatic polycarbonate resin obtained by such a production method (the production method of (2)), and a separately produced A — 3 — 1 component and Z or A— 3— 2 components can be mixed.

The viscosity average molecular weight referred to in the present invention is as follows. First, a specific viscosity (r? _SP ) calculated by the following formula is 20 and a Ostwald viscometer is measured from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride. Using

Specific viscosity (7? _SP ) = (t-t ₀ ) / to

[t _Q is the drop time of methylene chloride, t is the drop time of the sample solution]

Viscosity average molecular weight M is calculated from the obtained specific viscosity (7 ^ _SP ) by the following formula.

r? _SP / c = [η] +0.45 Χ [η] ² c (where [] is the intrinsic viscosity)

[η] = 1. 23 X 1 0 -. 4 Μ 0 83

c = 0.7

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

(B component: inorganic particles)

Inorganic particles (component B) are particles containing a composite of silicon dioxide and aluminum oxide. This means particles comprising a silicon dioxide phase and an aluminum oxide phase. Specific examples thereof include particles containing a solid solution of silicon dioxide and aluminum oxide, and particles obtained by fusing silicon dioxide particles and aluminum oxide particles. Fly ash is a suitable example of a particle containing such a complex.

According to the study of the present inventor, by using the inorganic particles (component B) having such a configuration, excellent flame retardancy that cannot be obtained with silicon dioxide particles alone, aluminum oxide particles alone, or a mixture thereof. Can be realized.

It is preferable that the inorganic particles further include aluminum oxide particles and silicon dioxide particles in addition to the particles containing the composite. By using such inorganic particles containing a plurality of different types of particles, a resin composition having excellent flame retardancy can be stably obtained.

Examples of inorganic particles having such a structure include particles containing a composite oxide of silicon and aluminum, and inorganic particles made of a mixture of silica particles and alumina particles. The fly ash described later can also be cited as an example of inorganic particles containing a plurality of types of particles.

Examples of such inorganic particles that can be obtained at low cost include fly ash. While incineration ash obtained from garbage incinerators is combustion ash obtained by burning various miscellaneous things, fly ash is coal combustion ash from thermal power plants, so the identity of raw materials is clear The content of heavy metals other than silicon and aluminum is low compared to combustion ash. In addition, it is relatively easy to control the content of heavy metals and the like in fly ash. Therefore, fly ash also has the advantage that it does not adversely affect the environment when added as a filler to the material composition. In addition, when such inorganic particles are used, phosphorus-based flame retardants, halogen-based flame retardants, etc. Even if the compounding amount is reduced, a resin composition having sufficient flame retardancy can be obtained. It is preferable from the viewpoint of environmental protection that the amount of phosphorus flame retardant and halogen flame retardant is 0.

Hereinafter, the particle size of the inorganic particles (component B) will be described. D 50 particle diameter of inorganic particles in the present invention (50% diameter: median diameter) When the powder is divided into two from a certain particle diameter, the number of large diameter powder and the small diameter powder In the present invention, the number of particles having a particle size of 0.1 m or more is calculated.) Is preferably 1 tm or more, more preferably 2 m or more, most preferably 3; m or more. The D 50 particle size is 以下 Ο μ ιη or less, preferably 8 // m or less, more preferably 7 m or less.

When the D 50 particle size is 1; m or more, the flame retardancy of the resin composition is improved. In addition, a decrease in moldability of the resin composition can be suppressed. In addition, scattering of inorganic particles is suppressed, and workability and handling stability in the manufacturing process of the resin composition are improved. When the D 50 particle size is 3 / m or more, the flame retardancy of the resin composition is further improved. In addition, scattering of inorganic particles is further suppressed, and workability and handling stability in the manufacturing process of the resin composition are further improved. When the D 50 particle size is 10 m or less, the flame retardancy of the resin composition is improved. In addition, a decrease in moldability of the resin composition can be suppressed. When the D 50 particle size is 7 m or less, the carbonization of the polycarbonate resin is further promoted during combustion, and as a result, the flame retardancy of the resin composition is further improved.

Here, commercially available fly ash usually has a D 50 particle size exceeding 10 m. For this reason, in the present invention, it is preferable to use a fly ash having such a large particle size, which is not directly used, but whose particle size is controlled by classification or the like. As a result, the synergistic action of the polycarbonate resin (component A) and the inorganic particles (component B) is remarkably obtained, and excellent flame retardancy can be stably realized. In addition, the moldability of the resin composition is maintained well.

Examples of the method for controlling the particle size of the inorganic particles (component B) include classification using a sieve having a specific opening, classification using an airflow classifier, and the like.

Inorganic particle (component B) in the present invention is the above particle size defined by D 50 particle size In addition to satisfying the conditions, it is preferable to satisfy the following particle size conditions defined by the volume average particle size. The volume average particle diameter of the inorganic particles is preferably l; m or more, more preferably 3 m or more, preferably 10 xm or less, more preferably 7 m or less. The volume average particle size is the average particle size obtained by dividing the sum of the product of the volume of a particle of a certain particle size and the number of particles of that particle size by the total volume of the particle. Measured by scattering method. When the volume average particle diameter of the inorganic particles is 1 m or more, the flame retardancy of the resin composition is improved. In addition, the moldability of the resin composition is improved. In addition, scattering of inorganic particles is suppressed, and workability and handling stability in the manufacturing process of the resin composition are improved. When the volume average particle size of the inorganic particles is 3 // m or more, the flame retardancy of the resin composition becomes even better. In addition, scattering of inorganic particles is further suppressed, and workability and handling stability in the manufacturing process of the resin composition are further improved. When the volume average particle size of the inorganic particles is 10 m or less, the flame retardancy of the resin composition is improved. In addition, the moldability of the resin composition is improved. When the volume average particle diameter of the inorganic particles is 7 / m or less, the flame retardancy of the resin composition is further improved.

In addition, the inorganic particles (component B) in the present invention satisfy the particle size conditions defined as follows in addition to satisfying the particle size conditions defined by D 50 particle size or volume average particle size. Is desirable. That is, it is desirable that the inorganic particles contain particles having a particle size of 20 × m or less, preferably 70 cumulative% (number cumulative) or more, more preferably 90 cumulative% (number cumulative) or more. Here, the number of particles with a particle size of 0.1 m or more is calculated. Flame retardancy is improved when the proportion of particles with a particle size of 20 m or less is 70% cumulative (number cumulative) or more based on the whole inorganic particles. In addition, a decrease in moldability of the resin composition is suppressed. In addition, when the proportion of particles having a particle size of 20 or less is 90 cumulative% (several cumulative) or more, the flame retardancy of the resin composition becomes even better. In addition, a decrease in moldability of the resin composition is further suppressed.

The particle size of the inorganic particles (component B) can be measured by a method such as cross-sectional observation with an electron microscope of a molded product obtained using the resin composition. Specifically, an ultrathin section of the resin composition is observed using a transmission electron microscope, or a cut surface of the resin composition is observed using a scanning electron microscope, and a photograph is taken for observation. Resin group from photo For spherical particles in the composition, the diameter of each particle is measured. Furthermore, the particle size of the non-spherical particles is obtained by calculating the projected area S of each particle, and using S, let (4 S / π) X 0.5 be the particle size of each particle. The number of measurements shall be 100. Alternatively, the particle diameter of the inorganic particles can be measured by the following light scattering method. In other words, using a DH S 9200 PRO FR A type device manufactured by MI CRO TRAC, using 2 wt% sodium hexadium phosphate aqueous solution (refractive index 1.33) as a dispersion medium, and using ultrasonic waves (20 kHz 300 kW) 3 After pretreatment for 5 minutes, the particle size distribution can be measured by the light scattering method using an average of three measurements of 20 seconds.

As a pretreatment before measurement, a 2 g sample was placed in 30 ml of a 2 wt% aqueous solution of sodium hexaphosphate and subjected to ultrasonic dispersion (20 kHz, 300 kW, 3 minutes).

In the present invention, the content of the inorganic particles (component B) is 10 to 70 parts by weight, preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 35 to 45 parts by weight. If the content of inorganic particles (component B) is less than 10 parts by weight, sufficient flame retardancy of the resin composition cannot be obtained, and if the content of inorganic particles exceeds 70 parts by weight, the resin composition will deteriorate. It becomes more likely to generate silver. At the same time, it becomes difficult to obtain sufficient flame retardancy.

The flyash which is a more preferable inorganic particle in the present invention will be described below. As the inorganic particles in the present invention, fly ash is preferably used. Fly ash (hereinafter referred to as “FA” as appropriate) refers to finely pulverized coal ash produced at thermal power plants that burn coal using the pulverized coal combustion method.

Fly ash contains the following ingredients: Here, the amount of components is an example.

(a) Silicon dioxide: 44% to 80% by mass

(b) Aluminum oxide: 15% to 40% by weight

(c) Other components: a small amount of ferric oxide (Fe ₂ 〇 ₃₎ or titanium oxide (T I_〇 ₂₎ and magnesium oxide (Mg_〇) and calcium oxide (C aO-) or the like. Silicon dioxide: content (silica S I_〇 ₂₎ is preferably 4 4 mass% or more der is, more preferably 5 0% by mass or more. Further, it is preferably 85% by mass or less, more preferably 75% by mass or less. When the content of silicon dioxide is within this range, the flame retardancy improving effect of the resin composition can be stably obtained by the synergistic action of the inorganic particles and the polycarbonate resin.

The content of aluminum oxide (alumina: Al ₂ O ₃ ) is preferably 10% by mass or more, and more preferably 15% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less. When the aluminum oxide content is within this range, the flame retardancy improving effect of the resin composition can be stably obtained due to the synergistic action of the inorganic particles and the polycarbonate resin.

Of these components, the total content of silicon dioxide and aluminum oxide is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. It is. The total content of silicon dioxide and aluminum oxide is preferably 99% by mass or less, more preferably 95% by mass or less. When the total content of silicon dioxide and aluminum oxide is within this range, the flame retardancy improving effect of the resin composition can be stably obtained by the synergistic action of the inorganic particles and the polycarbonate resin.

Fly ash also includes particles that form complex oxides of silicon dioxide and aluminum oxide. Also included are particles in which silicon dioxide and aluminum oxide form a silicon dioxide phase and an aluminum oxide phase in the particles to form a multiphase structure. Note that components such as ferric (F e ₂ 〇 ₃₎ or titanium oxide oxide (T I_〇 ₂₎ and oxide magnesium © beam (M G_〇) and calcium oxide (C A_〇), if a small amount, The flame retardancy and moldability of the resin composition are not particularly reduced. In addition to these oxides, fly ash contains trace amounts of heavy metals, but the concentration of trace amounts of heavy metals is lower than incineration ash obtained from garbage incinerators. This is because incineration ash is combustion ash obtained by burning various miscellaneous things, whereas fly ash is coal combustion ash from thermal power plants.

In addition, since the identity of raw materials is clear, it is also possible to control the content of heavy metals, etc. It is relatively easy with Liash. In addition, as described later, by taking measures against elution of trace amounts of heavy metals, the environmental impact risk of the resin composition and its molded product can be further reduced.

Also, fly ash is a fine particle, and when viewed with an electron microscope, most of the particles are spherical. For this reason, when fly ash is used, flame retardancy can be improved while suppressing a decrease in moldability during molding of the resin composition. Since fly ash is generated in large quantities at thermal power plants, and most of it is industrial waste, it has the advantage of low procurement costs. Therefore, the manufacturing cost of the resin composition having flame retardancy can also be reduced. Further, since fly ash has relatively stable quality such as particle size and composition, a resin composition having flame retardancy can be obtained stably.

In the present invention, by classifying commercially available fly ash with a 20 m diameter sieve, the D δ 0 particle size of this fly ash can be controlled to 10 m or less. Therefore, flame retardancy can be stably realized by the synergistic action of the polycarbonate resin (component A) and the inorganic particles (component B). In addition, a decrease in moldability of the resin composition can be stably suppressed.

(C component: Fluorine resin)

The fluororesin (C component) used in the present invention is a fluorine-containing compound that prevents melting and dripping at the time of combustion and further improves flame retardancy, and is typically a polytetrafluoro having a fibril formation ability. Ethylene is mentioned. Hereinafter, polytetrafluoroethylene is sometimes simply referred to as PTFE. PTFE with fibril-forming ability has an extremely high molecular weight, and tends to bind to each other by an external action such as shearing force to become fibrous. The number average molecular weight determined from the standard specific gravity of PTFE is preferably 1 million to 10 million, more preferably 2 million to 9 million. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE with such fibril formation ability improves dispersibility in the resin, and in order to obtain better flame retardancy and mechanical properties, it is also possible to use a PTFE mixture in a mixed form with other resins It is. Commercially available PTFEs having such fibril formation ability include, for example, Teflon (registered trademark) 6 J from Mitsui Dubon Fluorochemical Co., Ltd., Polyflon MP A FA500 and F-201 L from Daikin Chemical Industries, Ltd. be able to. Commercially available PTFE aqueous dispersions include Fullon AD-1 and AD-936 manufactured by Asahi Ishii Ifluoro Polymers Co., Ltd. Fullon D-1 and D-2 manufactured by Daikin Industries, Ltd. A representative example is Teflon (registered trademark) 30 J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.

The mixed form of PTFE is as follows: (1) A method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263) And a method obtained by the method described in JP-A-63-154744). Further, (2) those obtained by a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (the method described in JP-A No. 4-272957) can be used. (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution, and simultaneously removing each medium from the mixture (Japanese Patent Laid-Open Nos. 06-220210 and 08-188 653). Can be used. Further, it is possible to use those obtained by (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583). (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained. Can be used.

Commercially available products of these mixed forms of PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty I Chemicals. it can.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. Achieving good dispersibility of PTFE when the proportion of PTFE is within this range be able to.

The content of the fluororesin (component C) is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 100 parts by weight of the polycarbonate resin (component A). Or 0.1 to 0.6 parts by weight.

(D component: elution inhibitor)

The resin composition of the present invention further contains an elution inhibitor (D component) that suppresses elution of components such as heavy metals and selenium / arsenic in the inorganic particles (B component). By containing an elution inhibitor, elution of heavy metals such as hexavalent chromium, lead, and mercury and selenium and arsenic from the inorganic particles can be suppressed while maintaining high flame retardancy. For this reason, the impact on the environment and the impact on the human body can be reduced.

An elution inhibitor (component D) is a substance supplemented by adsorbing heavy metal ions, etc. in inorganic particles (component B).

This elution inhibitor (component D) may be an adsorbent or an ion exchange resin that adsorbs the components in the inorganic particles. By including an adsorbent or ion exchange resin that adsorbs components in inorganic particles in this way, it is possible to efficiently adsorb components such as heavy metals such as hexavalent chromium, lead, and mercury and selenium arsenic in inorganic particles. It is possible to efficiently reduce the environmental impact and the impact on the human body.

The dissolution inhibitor (component D) is preferably a salt of divalent and Z or trivalent iron ions and sulfate ions. More preferred is ferrous sulfate hydrate or Schwertmannite. Still more preferred is ferrous sulfate heptahydrate. By containing a salt of divalent or trivalent iron ions and sulfate ions in this way, heavy metals such as hexavalent chromium, lead, and mercury, and components such as selenium and arsenic are stably adsorbed in the inorganic particles. Therefore, it is possible to stably reduce the impact on the environment and the impact on the human body.

In addition, the elution inhibitor (component D) is preferably ferrous sulfate heptahydrate having less adverse effects because it deteriorates the appearance of the molded product as in the case of inorganic particles.

The relative mass ratio of the dissolution inhibitor (component D) to the inorganic particles (component B) is, for example, 1 / \, 400 or more, preferably 1 100 or more. Relative dissolution inhibitor If the mass ratio is higher than these values, the effect of suppressing the elution of heavy metals such as hexavalent chromium, lead and mercury and components such as selenium and arsenic from inorganic particles while maintaining high flame retardancy will be improved. To do. The content of the dissolution inhibitor (component D) in the resin composition is 0.05 to 3 parts by weight, preferably 0.07 parts per 100 parts by weight of the polycarbonate resin (component A). ˜2 parts by weight, more preferably 0.1 to 1 part by weight. If the content of the dissolution inhibitor is within this range, the occurrence of silver during molding is suppressed, and the appearance characteristics of the molded product made of the resin composition are improved.

(E component: flow modifier)

The flow modifier (component E) used in the present invention is preferably at least one fluid modifier selected from the group consisting of aliphatic polyester resins and trimellitic acid esters. If an aliphatic polyester resin is incorporated with trimellitic acid ester, the behavior of the resin composition during combustion becomes stable. That is, the rank of U L 94 is comparable, but has the advantage of shortening the burning time.

Preferable examples of the aliphatic polyester include poly-strength prolactone. Here, poly force prolactone is a polymer of force prolactone, particularly ε-force prolactone. Part of the hydrogen atom or repeating unit of the methylene chain of the poly-strength prolactone may be substituted with a halogen atom or a hydrocarbon group. Moreover, the end of the polystrength prolacton may be subjected to end treatment such as esterification or etherification. The molecular weight of Po Li caprolactone need not be particularly limited, but is usually ^{5 X 1 0 3 ~4 X 1} 0 4 represents the number average molecular weight. Such poly-prolacton can be produced by ring-opening polymerization of proprolacton in the presence of a catalyst such as an acid, base, or organometallic compound.

Trimellitic acid esters include Tory (2-ethylhexyl) trimellitate (Τ〇ΤΜ), Tory (normalooctyl) trimellitate (Τ η〇ΤΜ), Tory (isonolyl) trimellitate (Τ Ι Ν ΤΜ) , Tree (isodecyl) trimellitate (TID TM) and the like. Preferable examples include 卜 (2-ethyl hexyl) trimellitate (Τ Ο ΤΜ).

ABS resin, AS resin, etc. can be used as flow modifiers wear. ABS resin means a thermoplastic graph copolymer (ABS copolymer) obtained by graph copolymerization of a vinyl rubber component and a vinyl cyanide compound and an aromatic vinyl compound, and the graft copolymer, cyan A mixture of a vinyl fluoride compound and an aromatic vinyl compound copolymer (AS copolymer). The copolymer of the vinyl cyanide compound and the aromatic vinyl compound is a resin made of a thermoplastic graft copolymer obtained by graft copolymerizing a cyanated vinyl compound and an aromatic vinyl compound to a gen-based rubber component. It may be a copolymer by-produced during production, or may be a vinyl compound copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. The weight average molecular weight of the copolymer comprising such a vinyl cyanide compound and an aromatic vinyl compound is preferably 3.0 X 1 in a value measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. 0 ⁴ to 2.0 in the range of X 10 ^5, more preferably 6. 0 X 1 0 ⁴ to 1. in the range of 4X 10 ^5, more preferably ^{9. 0 X 1 0 4 ~1.} 2 X 10 is in the range of ^5. In the ABS resin used in the present invention, the proportion of the Gen rubber component in 100% by weight of the ABS resin component is in the range of 40% by weight or less. Is in the range of ~ 35 wt%, more preferably in the range of 8-30 wt%, particularly preferably in the range of 9-25 wt%. The proportion of the component graphed in the gen-based rubber component is preferably 95 to 20% by weight, more preferably 92 to 50% by weight, based on 100% by weight of the ABS resin component.

AS resin is a resin made of the above-mentioned AS copolymer. The AS resin may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably produced by bulk polymerization or suspension polymerization. It is preferably produced by a bulk polymerization method, and the polymerization method is the most common in the industry. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The weight average molecular weight of the AS polymer is preferably 4 × 10 ⁴ to 2 × 10 ^{5 in} terms of standard polystyrene by GPC measurement. The lower limit is more preferably 5 × 10 ⁴ , and even more preferably 7 × 10 ⁴ . The upper limit is 1. 6X 10 ⁵ Gayori weight, more preferably 1. ⁵ X 10 5. (F component: acid-modified polyolefin wax)

The acid-modified polyolefin-based wax which is the F component of the present invention is an acid-modified having an acidic group represented by a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. Polyolefin wax. A preferred embodiment of the F component of the present invention is an acid-modified polyolefin wax having at least one of the acidic groups exemplified above, and particularly preferably has a carboxyl group and Z or a carboxylic anhydride group. It is an acid-modified polyolefin series. In the acid-modified polyolefin wax, the concentration of the acidic group is in the range of 0.05 to: LO me Q / g, more preferably in the range of 0.1 to 6 meq Z g, and more preferably in the range of 0.5 to It is in the range of 4 meq Z g.

Examples of olefin fin wax include paraffin wax, micro-criss phosphorus wax, Fischer-Tropsch wax, and a one-year-old olefin polymer as paraffin waxes.

Examples of a method for bonding carboxyl groups to such a polyolefin wax include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-aged refin monomer, and (b) a polyolefin wax. On the other hand, there may be mentioned a method of bonding or copolymerizing a compound or monomer having a carboxyl group. In the method (a), a living polymerization method can be employed in addition to a radical polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, it is possible to polymerize after once forming a macromonomer. The copolymer can be used as a copolymer in various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to a random copolymer. In the method (b) above, a radical generator such as peroxide or 2,3_dimethyl-2,3diphenylbutane (commonly called "dicumyl") is added to the polyolefin wax as necessary, and the reaction is carried out at a high temperature. Alternatively, a copolymerization method can be employed. Such a method is a method in which reactive active sites are thermally generated in polyolefin wax and a compound or monomer that reacts with the active sites is reacted. Other methods for generating the active sites required for the reaction include the application of external forces by mechanochemical techniques, such as irradiation with radiation or electron beams. Can be mentioned. Further, there may be mentioned a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in a polyolefin wax. Examples of active sites for the reaction include unsaturated bonds and peroxide bonds, and examples of a method for obtaining active sites include nitroxide-mediated radical polymerization represented by TEMP. Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, particularly maleic anhydride. Is preferred.

More preferable as the F component is that the carboxyl group is preferably in the range of 0.05 to 1 Ome qZg, more preferably in the range of 0.1 to 6 me qZg, per 1 g of the acid-modified polyolefin wax. More preferably, it is a carboxyl group-containing olefin-based wax contained in the range of 0.5 to 4 meqZg. Further molecular weight of Orefu in wax is preferably ^{^{1 X 10 3 ~1 X 10 4}} , 5X 10 3 ~1 X 10 4 is more preferable. The molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (Gel Permeation Chromatography).

As a preferred embodiment of the F component, there can be mentioned a copolymer of α-aged refin and maleic anhydride, and the copolymer further satisfies the above-mentioned carboxyl group content and molecular weight. Particularly preferred. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Preferred examples of α-olefin include those having an average carbon number of 10 to 60. More preferable examples of monoolefin include carbon having an average value of 16 to 60, and more preferably 25 to 55.

The content of the acid-modified polyolefin wax (component F) is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0 to 100 parts by weight of the polycarbonate resin (salt component). 1 to 0.7 parts by weight. If the content of the acid-modified polyolefin wax (F component) is within this range, a good appearance of the molded product can be obtained while maintaining a high flame retardant effect. (G component: Phosphorus stabilizer)

The resin composition of the present invention preferably further contains a phosphorus-based stabilizer (G component). Such phosphorus stabilizers greatly improve the thermal stability during production or molding. The result is improved mechanical properties, hue, and molding stability. Examples of the phosphorus stabilizer (G component) include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Of these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, phosphate compounds, and phosphate compounds are preferred. In particular, phosphate compounds and / or phosphite compounds are preferred. As the phosphate compound, a triorganophosphate compound and an acid phosphate compound are preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. All of the following exemplified compounds corresponding to the compound are similarly included.

Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, 卜 -listeryl phosphate, tricresyl phosphate, triphenyl phosphate, trichlor phosphate Examples include phenyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, and riboxetyl phosphate. Among these, trialkyl phosphate is preferable. The number of carbon atoms of the alkyl group of such trialkyl phosphate is preferably 1 to 22 and more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

Examples of acid phosphate compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxychetyl phosphate, octyl acid phosphate, decyl acid phosphate, lauryl phosphate, stearyl acid phosphate, phosphate Benenyl acid phosphate, phenyl acid phosphate Nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoloxyl phosphate, alkoxy polyethylene glycol phosphate, bisphenol A acid phosphate, and the like. Among these, a long-chain dialkyl acid phosphate having an alkyl group with 10 or more carbon atoms, more preferably 14 to 22 is effective in improving thermal stability, and the stability of the acid phosphate itself. Is preferable because it is high.

Other examples of phosphite compounds include trialkyl phosphites such as tridecyl phosphite, dialkyl monophenyl phosphites such as didecyl monophenyl phosphite, and monoalkyls such as monobutyl diphenyl phosphite. Examples are triaryl phosphites such as dialyl phosphite, triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite. In addition, distearyl pentaerythri] ^ One Rudiphosphia 卜, Bis (2, 4-di tert-butylphenyl) Pen Yu Erisri I ^ One Rudiphosphite, Bis (2, 4-dicumylphenyl) Pen Yue Eli! ^ Ludiphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) Penyu Erisri) ^ Erythriphosphite such as Luluphosphite. In addition, 2,2-methylenebis (4,6-ditert-butylphenyl) octyl phosphite and 2,2'-methylenebis (4,6-ditert-butylphenyl) (2,4-ditert-butylphenyl) phosphine Examples include fights.

Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenyl dirange phosphonite and bis (di-tert-butylphenyl) monophenyl phosphonite, and tetrakis (2,4-di-tert-butylphenyl) -biphenyl. More preferred are two-range phosphonai ビス and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonai compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Phosphonate compounds include benzene phosphonate, benzene phosphonate Examples include jetyl acid and dipropyl benzenephosphonate. An example of tertiary phosphine is triphenylphosphine.

The content of the phosphorus-based stabilizer (component G) is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 1 based on 100 parts by weight of the polycarbonate resin (component A). Parts by weight, more preferably 0.05 to 0.5 parts by weight. It is preferable that 50% by weight or more of the G component is a phosphate compound and Z or a phosphate compound. The G component is preferably a trialkyl phosphate and / or an acid phosphate compound in 50% by weight or more in 100% by weight. In particular, it is preferable that 50% by weight or more of the 100% by weight is a trialkyl phosphate.

(Other ingredients)

In the resin composition of the present invention, various additives, reinforcing agents, and other polymers that are blended in the polycarbonate resin can be further blended.

(Other polymers and elastomers)

In the resin composition of the present invention, another polymer or elastomer can be further blended within a range in which the effect of the present invention is exhibited. As a guideline for such a range, the total amount of other polymers and elastomers based on 100 parts by weight of component A is not more than 200 parts by weight, preferably not more than 100 parts by weight, more preferably not more than 50 parts by weight. In the following, it is particularly preferably 30 parts by weight or less.

Such other polymers include polyphenylene ether, polyacetal, aromatic polyester, aliphatic polyester, polyamide, polyarylate (amorphous polyarylate, liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone. Examples thereof include polyethersulfone, polyphenylene sulfide, and polyolefins such as polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin, styrene polymers, and acrylic polymers such as polymethyl methacrylate.

Examples of elastomers include olefin-based elastomers, acrylic elastomers, polyester-based elastomers, polyamide-based elastomers, and the like. And thermoplastic elastomers such as polyurethane elastomers. Further, a rubbery graft copolymer in which a graft chain is bonded to a rubber substrate is also preferably exemplified as an elastomer. The rubber substrate has a rubber elasticity and has a glass transition temperature of 10 or less, preferably −10 or less, more preferably 1 to 30 or less. It is a coalescence. Such rubber substrates include, for example, polybutadiene, polyisoprene, random copolymers or block copolymers of styrene monobutadiene, acrylonitrile monobutadiene copolymers, alkyl acrylates or alkyl methacrylates and butadiene. Copolymer, Copolymer of ethylene and a-year-old refin, Copolymer of ethylene and unsaturated carboxylic acid ester, Copolymer of ethylene and aliphatic vinyl, Ethylene, propylene and non-conjugated dienter Examples include polymers, acrylic rubbers, and silicone rubbers. Preferred examples of the monomer for deriving the graft chain of the rubbery graft copolymer include aromatic vinyl compounds, vinyl cyanide compounds, acrylate esters, and methacrylate esters.

Specific examples of rubber graft copolymers include SB (styrene butadiene styrene) polymer, ABS (acrylonitrile butadiene styrene) polymer, MBS (methyl methacrylate butadiene styrene) polymer, MA BS (methyl methacrylate). Toacrylonitrile-butadiene-styrene polymer, MB (methylmethacrylate-butadiene) polymer, ASA (acrylonitrile-styrene-acrylic rubber) polymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) polymer, MA (methyl methacrylate) Acrylate-acrylic rubber) polymer, MA S (methyl methacrylate-acrylic rubber-styrene) polymer, methyl methacrylate-to-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer And Mechirume evening Kurireto (Akuri Le Silicone I P N rubber), and the like polymers. The rubber substrate is more than 40% by weight in 100% by weight of the rubbery graph copolymer, preferably 50% by weight or more, and more preferably in the range of 55-85% by weight.

The styrenic polymer is polystyrene (PS) (syndiotactic). Tic polystyrene), AS (acrylonitrile-styrene) copolymer,

Examples thereof include MS (methyl methacrylate-styrene) copolymer and SMA (styrene monomaleic anhydride) copolymer. As the styrenic polymer, a mixture previously integrated with the above rubbery graft copolymer can be used. For example, a commercially available ABS resin can be used as a mixture of a commercially available AS copolymer and ABS copolymer. Such a copolymer includes a so-called transparent ABS resin. The styrenic polymer may be modified with various functional groups typified by epoxy groups and acid anhydride groups. These styrene polymers can be used in combination of two or more.

Aromatic polyesters include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene 1,6-naphthalate (PEN), polybutylene naphtha Polyethylene terephthalate (PBN), polyethylene 1,2-bis (phenoxy) 1,4'-dicarboxylate, polyethylene terephthalate copolymerized with 1,4-cyclohexane dimethyl alcohol ( Copolyesters such as so-called PET-G), poly (ethylene isophthalate) terephthalate, polybutylene terephthalate / isophthalate can also be used. Of these, PET, PBT, and PEN / PBN are preferred. Two or more of the above aromatic polyesters can be mixed. These aromatic polyesters are copolymers obtained by copolymerizing units derived from other aromatic dicarboxylic acids or units derived from other dallicols in an amount of 50 mol% or less, preferably 1 to 30 mol%. Polyester may be used. The molecular weight of the aromatic polyester is not particularly limited, but the intrinsic viscosity measured by 351: using o-chlorophenol as a solvent is 0.4 to 1.2, preferably 0. o to 1.1 o.

(Filler)

Various known fillers can be blended in the resin composition of the present invention as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler is fibrous (bar, needle, Or the shape in which the axis extends in a plurality of directions), and the plate-like filler is filled in a plate shape (including those having irregularities on the surface and those having a curved surface) It is a material. The granular filler is a filler having a shape other than these including an indefinite shape.

The above fiber and plate shapes are often clear from the observation of the filler shape. For example, the difference from the so-called indefinite shape is that the aspect ratio is 3 or more. It can be said to be plate-shaped.

As the plate-like filler, glass flakes, talc, my strength, kaolin, metal flakes, carbon flakes, and graphite, and a plate whose surface is coated with a different material such as metal or metal oxide for these fillers. Preferable examples are fillers. The particle size is preferably in the range of 0.1 to 300 m. This particle size is a value based on the median diameter (D 50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods, up to about 10 / m. In the 50 m region, the value by the median diameter (D 50) of the particle size distribution measured by the laser diffraction / scattering method is used. In the 50 to 300 am region, the value is obtained by the vibration sieving method. . Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents. Also, olefin-based resins, styrene-based resins, acrylic-based resins, polyesters. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins, epoxy resins, and urethane resins, and higher fatty acid esters.

The fiber diameter of the fibrous filler is preferably in the range of 0. The upper limit of the fiber diameter is preferably 13 im and more preferably 10 m. On the other hand, the lower limit of the fiber diameter is preferably 1 m.

The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is defined as the residue obtained by dissolving the molded product in a solvent, the residue collected after decomposing the resin with a basic compound, and the ashing residue collected after ashing with a crucible. It is a value calculated from an image observed with a scanning electron microscope. Examples of such fibrous fillers include glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, boric acid. Examples include fibrous inorganic fillers such as aluminum whisker, calcium carbonate whistle, titanium oxide whistle, wollastonite, zonotlite, palygorskite (ayu pulgite), and sepiolite. In addition, fibrous heat-resistant organic fillers typified by heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzthiazole fibers can be mentioned.

In addition, for example, fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. Examples of the filler whose surface is coated with a different material include metal coated glass fiber, metal coated glass flake, titanium oxide coated glass flake, and metal coated carbon fiber. The surface coating method for different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, melting plating, etc.), vacuum deposition method, ion plating method, C Examples include VD methods (eg, thermal CVD, MCVD, plasma C VD, etc.), PVD methods, and sputtering methods.

Here, the fibrous filler refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more. The upper limit of the aspect ratio is about 10 and 0,000, preferably 2 0 0. The aspect ratio of such a filler is a value in the resin composition. The fibrous filler may be surface-treated with various types of cutting agents as in the case of the plate-shaped filler, may be subjected to bundling treatment with various resins, and may be granulated by compression treatment.

The content of such filler is not more than 20.0 parts by weight, preferably not more than 100 parts by weight, more preferably not more than 50 parts by weight, particularly preferably 3 parts by weight based on 100 parts by weight of the component A. 0 parts by weight or less.

(Release agent) A release agent can be blended in the resin composition of the present invention as necessary. The resin composition of the present invention often requires high dimensional accuracy. Therefore, it is preferable that the resin composition is excellent in releasability. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound (E.g., fluorine oil represented by polyfluorinated alkyl ether), paraffin wax, and beeswax. Such a release agent is a resin composition 1

0.005 to 2% by weight of 00% by weight is preferred.

The fatty acid ester may be a partial ester or a total ester (full ester). In the fatty acid ester, the acid value is preferably 20 or less (can take substantially 0), the hydroxyl value is in the range of 0.1 to 30, and the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by the method defined in JI S K0070.

(Hindered phenol stabilizers and other antioxidants)

The hindered phenol-based stabilizer is effective in preventing the heat aging of the resin composition. Since the resin composition of the present invention may be used in a high heat atmosphere, it is particularly preferably blended in such a case.

Hindered phenolic stabilizers include octyldecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3'-tert-butyl-5 , —Methyl-2 ′ —hydroxybenzil) 1 4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis 1 3— (3 — Tert-Butyl _ 4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2 -— [3-— (3-tert-Butyl-4-hydroxy-1,5-methylphenyl) propionyloxy] — 1,1-dimethylethyl} 1,2,4,8,10-tetraoxaspiro [5,5] undecane, N, N'-hexamethylenebis (3,5-di-tert-butyl-1-hydroxyhydrocinna ), 1, 3, 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis Butyl-4-hydroxyphenyl) Probione] Examples include methane. All of these are readily available. Among these, octyldecyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate is preferably used.

In addition, other antioxidants than the hindered phenol stabilizers can be used. Examples of such other antioxidants include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di tert-butyl-furan-2-one and o-xylene (details of such stabilizers). Is described in Japanese Patent Application Laid-Open No. 7-2 3 3 1 60), and Penyu Erisri] ^ Irutetrakis (3-mercaptopropionate), Penyu Erisri!ィ -containing stabilizers such as monotetrakis (3-laurylthiopropionate) and glycerol-3-stearylthiopropionate. The above hindered phenol stabilizers can be used alone or in combination of two or more. The blending amount of these stabilizers is preferably 0.001 to 1% by weight, more preferably 0.05 to 0.5% by weight in 100% by weight of the resin composition.

(Hydrolysis improver)

Since the resin composition of the present invention may be used in a high-heat atmosphere, it may be required to improve its hydrolysis resistance. In such a case, a compound conventionally known as a polycarbonate resin hydrolysis improver can be blended within a range not impairing the object of the present invention. Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include alicyclic epoxy compounds represented by 3,4-epoxycyclohexylmethyl_3 ', 4'-epoxycyclohexylcarboxylate, and 3-glycidylpropoxy sheet triethoxysilane. A silicon atom-containing epoxy compound is preferably exemplified. Such a hydrolysis improver is composed of 1 layer in 100% by weight of the resin composition. It is preferable that the amount is not more than%.

(UV absorber)

When the resin composition of the present invention is required to have improved weather resistance and ultraviolet absorption, it is preferable to add an ultraviolet absorber. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyl triazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds. More specifically, for example, 2— (2 H _benzotriazole-2-yl) — p —cresol, 2— (2 H—benzotriazole-2-yl) 1 4 1 (1, 1 , 3, 3-tetramethylbutyl) phenol, 2- (2H-benzotriazole-2-yl) 1, 4-6-bis (1-methyl-1-phenylethyl) phenol, 2 H) —Benzotriazol-2-yl] —4-methyl-6- tert —butylphenol, 2, 2′-methylenebis [6— (2 H—benzotriazol 2-yl) _ 4 one (1, 1,, 3, 3-tetramethylbutyl) phenol], 2— (4, 6-diphenyl 2-, 1, 3-, 5-triazine-2-yl) 1 5 1 [(hexyl) oxy] phenol, 2, 2 '_ p-Phenylenebis (3, 1-benzoxazine 4-one), and 1, 3-bis [(2-Cyan 3, 3 - Jifue two Ruakuriroiru) Okishi] one 2, 2-bis [[(2-Shiano one 3, 3-di-phenylene Ruakuriroiru) Okishi] such as methyl] propane and the like. In addition, hindered amines such as bis (2, 2, 6, 6, 6-tetramethyl-4-piperidyl) Sebake, bis (1, 2, 2, 6, 6-penyumethyl-4-piperidyl) sebagate, etc. It is also possible to use other light stabilizers. The blending amount of the ultraviolet absorber and the light stabilizer is preferably from 0.01 to 5% by weight in 100% by weight of the resin composition.

(Antistatic agent)

The resin composition of the present invention may contain an antistatic agent. Examples of such antistatic agents include polyether ester amide, glycerin monostearate, naphthaline phosphonate formaldehyde highly condensed alkali (earth) metal salt, alkali dodecylbenzenesulfonate (earth) metal salt, dodecyl Benzenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid phosphonium salt, maleic anhydride And acid monoglyceride and maleic anhydride diglyceride. The blending amount of the antistatic agent is preferably 0.5 to 20% by weight in 100% by weight of the resin composition.

(Other additional ingredients)

The resin composition of the present invention includes a sliding agent (for example, PTFE particles and high molecular weight polyethylene particles), a coloring agent (for example, a pigment such as carbon black and titanium oxide, and a dye), an inorganic phosphor (for example, aluminum). Phosphors using acid salts as mother crystals), inorganic or organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers (ATO fine particles, ITO fine particles, lanthanum boride fine particles) , Tungsten boride fine particles, phthalocyanine metal complexes, etc.), photochromic agents, and fluorescent brighteners.

(Manufacture of resin composition)

The resin composition of the present invention can be produced by melt-kneading the A component, the B component and other components using a twin screw extruder.

As a typical example of a twin screw extruder, ZSK (trade name, manufactured by Werenr & Pfle i der er, Inc.) can be mentioned. Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (trade name, manufactured by Kobe Steel, Ltd.), etc. Can be mentioned. In addition, melt kneaders such as FCM (Farre 1 company, product name), Ko-Kneader (Buss company, product name), and DSM (Krauss—Maffei, product name) are also examples. As an example. Among them, the evening typified by Z SK is more preferable. In such a Z SK type twin screw extruder, the screw is a complete mesh type, and the screw has various screw segments with different lengths and pitches, and various kinds of needing discs with different widths (and corresponding kneading discs). Segment).

A more preferable embodiment in the twin screw extruder is as follows. The screw shape can be 1, 2, or 3 screw screws, and the 2-thread screw is particularly preferred because it has a wide range of applications for both molten resin transport and shear kneading capabilities. Can be used. The ratio (LZD) between the length (L) and the diameter (D) of the screw in the twin screw extruder is preferably 20 to 50, more preferably 28 to 42. When L ZD is large, uniform dispersion is likely to be achieved, while when it is too large, resin degradation is likely to occur due to thermal degradation. The screw needs to have at least one kneading zone composed of a double disc segment (or a kneading segment corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed to efficiently discharge generated moisture and volatile gas to the outside of the extruder. In addition, water, an organic solvent, a supercritical fluid, or the like may be added in order to enhance the dispersibility of the inorganic particles or to remove impurities in the resin composition as much as possible. Furthermore, a screen for removing foreign substances mixed in the extrusion raw material can be installed in the zone in front of the extruder die to remove the foreign substances from the resin composition. Examples of such screens include wire meshes, screen changers, and sintered metal plates (such as disk filters).

The feeding method of B component to F component, optional G component and other additives (simply referred to as “additive” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified. . (I) A method in which the additive is fed into the extruder independently of the polycarbonate resin. U i) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. (Ii) A method of pre-melting and kneading an additive and a polycarbonate resin into a master pellet.

One of the above methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. Another method is a method in which a mass agent containing a high concentration of additives is prepared, and the master agent is separately or further premixed with the remaining polycarbonate resin or the like and then supplied to the extruder. is there. The mass agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Also other premixing means For example, there are now Yuichi mixers, V-type blenders, Henschel mixers, mechanochemical devices, and extrusion mixers, and high-speed stirring mixers such as Henschel mixers are preferred. Still another premixing method is, for example, a method in which a polycarbonate resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming a strand, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for optical disk polycarbonate resin are used to narrow the pellet shape distribution, reduce miscuts, and generate fine powder during transportation or transportation. And reduction of bubbles (vacuum bubbles) generated in the strands and pellets can be appropriately performed. These prescriptions can increase the molding cycle and reduce the rate of defects such as silver. The pellet may have a general shape such as a cylinder, a prism, or a sphere, but more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

As described above, according to the present invention, B component 10 to 70 parts by weight, C component 0.01 to 2 parts by weight, D component 0.05 to 3 parts by weight per 100 parts by weight of component A , And E component 1 to 20 parts by weight, F component 0.0 1 to 2 parts by weight, and optionally G component 0.0 0 1 to 2 parts by weight are mixed. The The details of the components A to G used in this production method are as described above. For such mixing, as described in the method for producing a resin composition, a vent type twin screw extruder can be most suitably used. In such melt-kneading, the cylinder temperature is preferably set to 2 5 0 to 3 2 0 t: more preferably 2 7 0 to 3 1 0 ° C, and the screw speed is preferably 6 0 to 5 0 0 Set to rpm, more preferably from 70 to 200 rpm. (Molding)

The resin composition of the present invention can usually produce various molded products by injection molding the pellets produced as described above. Furthermore, the resin composition melt-kneaded by a twin screw extruder can be directly made into a sheet, film, profile extrusion molded product, direct blow molded product and injection molded product without going through pellets.

In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by supercritical fluid injection), insert molding, depending on the purpose as appropriate. Molded products can be obtained using injection molding methods such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either a cold runner one-way method or a hot runner method can be selected. More preferable are injection compression molding and injection press molding which can be molded at a low injection speed.

In addition, the resin composition of the present invention can be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, the inflation method, the calendar method, and the casting method can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention may be formed into a molded product by rotational molding or blow molding.

Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electric plating, electroless plating, melting plating, etc.), painting, coating, printing, etc. The method used for ordinary resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

Applications of the molded article of the present invention include, for example, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), Examples include display devices (LCD, organic EL, electronic paper, plasma display, projector, etc.) and power transmission components (represented by the housing of a dielectric coil power transmission device).

Examples include printing, copying machines, scanners, and fax machines (including these multifunction devices). Examples include precision equipment such as VTR cameras, optical film cameras, digital still cameras, camera lens units, security devices, and mobile phones. In particular, the molded product of the present invention is suitably used for a housing, a cover, and a frame of a digital information processing apparatus such as a personal computer.

The molded products of the present invention include medical equipment such as massage machines and high oxygen therapy equipment, video recorders (so-called DVD recorders, etc.), audio equipment, home appliances such as electronic musical instruments, amusement devices such as pachinko machines and slot machines, precision It is also suitable for parts such as home robots equipped with various sensors.

The molded product of the present invention includes various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, and electronic parts. Transport containers (such as IC magazine cases, silicon wafer containers, glass substrate storage containers, and carrier tapes), antistatic or charge removal parts (such as charging rolls for electrophotographic photosensitive devices), various mechanical parts (gears) , Including turntables, low evenings, and screws, including mechanical parts for micromachines). Example

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. The following items were evaluated.

(I) Evaluation items

(1-1) Flame resistance

A combustion test was conducted at a thickness of 1.5 mm in accordance with UL standard 94V.

(1 -2) silver

With the following manufacturing conditions, a 1mm square gate with a radius of 20mm and a thickness of 1mm The photograph of the circular molded product was processed with two gradations, and the white part was converted as the silver area for the judgment. The silver generation ratio on the surface was evaluated according to the following criteria, and a score of 3 or more was rated. The silver generation ratio was calculated by rounding off one decimal place.

1 Fortune-telling Silver-100% -76

2 Occupation Silva-Generated area 75-51% of total area

3 points-Silver-Generation area is 50- 26% of the total area

4 points -Silver- -The total area is 25% to 1%

5 points: Silver--Total area-0%

(1 -3) Soil dissolution test

The dissolution test method for heavy metals, etc., was based on the dissolution test for soil environmental standards (Environment Agency Notification No. 46, August 23, 1991). The sample was made by collecting and crushing pellets of the resin composition and sieving with a 2 mm sieve. The sample solution consists of a sample (unit: g) and a solvent (hydrochloric acid aqueous solution with a hydrogen ion concentration index of 5.8 or more and 6.3 or less) (unit: ml) mixed at a ratio of 10% by weight / volume. The mixed solution was set to 500 m 1 or more. The dissolution test is performed for 6 hours using a shaker of the prepared sample solution at room temperature and normal pressure (the shaking frequency is adjusted to about 200 times per minute and the shaking width is adjusted to 4 cm or more and 5 cm or less in advance). We continued shaking.

For the test solution, the sample solution obtained by the above operation was allowed to stand for 30 minutes, then centrifuged at approximately 3 000 rpm for 20 minutes, and the supernatant was filtered through a membrane filter with a pore size of 0.45 zm. The amount required for quantification was accurately measured. The amount of arsenic and selenium contained in the obtained test solution was measured by the atomic absorption method as shown in Environment Agency Notification No. 46.

(I I) Manufacture of resin compositions and molded products

A resin composition having the blending ratio shown in Table 14 was prepared as follows. The explanation will be made according to the symbols in Table 14 below. The ingredients listed in Table 14 were mixed in a V-type blender to make a mixture. In addition, a small amount of additives other than the component A was prepared using a super mixer with a premix having a content of 10% by weight. A plurality of such premixtures were uniformly mixed with the remaining PC in a V-type blender. Using a vent type twin screw extruder (Nippon Steel Works TEX-3O XSST) with a screw diameter of 30 mm, the mixture from the V-type blender was fed to the first inlet at the end. Such an extruder has a kneading zone with a needing disk between the first supply port and the second supply port, and is provided with a vent port opened immediately thereafter. The length of the ventro was about 2 D with respect to the screw diameter (D). A side feeder was installed after the vent port, and a kneading zone with a kneading disk and a vent port following the kneading disc were further provided after the side feeder. The length of the vent port in this part is about 1.5 D, and a vacuum pump is used in that part to reduce the pressure to about 3 kPa. Extrusion was performed at a cylinder temperature of 2500 to 30000 (almost evenly rising from the barrel at the root of the screw to the die), a screw speed of 180 rpm, and a discharge rate of 20 kg per hour. . The extruded strand was cooled in a water bath, then cut with a pelletizer and pelletized.

The obtained pellets were dried at 120 ° C. for 5 hours in a hot air circulating drier, and then using a spray molding machine, the cylinder temperature was 2 80, the mold temperature was 80, and the shooting speed was 20 mm. The test pieces for the above evaluation items were prepared under the conditions of / sec and a molding cycle of about 60 seconds.

An evaluation photograph of the silver generation ratio of Example 4 and Comparative Example 4 is attached as FIG. The raw materials used in the above examples and comparative examples are as follows.

(A component: polycarbonate resin)

PC-1: Linear aromatic polycarbonate resin with a viscosity average molecular weight of 2 2,500 (Panlite L _ 1 2 2 WP (trade name) manufactured by Teijin Chemicals Ltd.)

PC-2: heat-resistant polycarbonate resin having a glass transition temperature of 17 I and a water absorption of 0.2% by weight produced by the following method

PC—3: Bisphenol A, p_tert-butylphenol as end-stopper, and 1,1,1 tris (4-hydroxyphenyl) chain as a branching agent (based on 100 mol% of bisphenol A) 0.3 mol%), and an aromatic polycarbonate resin having a viscosity average molecular weight of 24,500 synthesized from the phosgene by the interfacial polycondensation method PC-4: A linear aromatic polycarbonate resin synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene, with a viscosity average molecular weight of 15,200. 80,000 parts by weight, 23,700, and 10 parts by weight of 120,000 are melt-blended aromatic polycarbonate resin pellets with a viscosity average molecular weight of 29,500

(PC-2 production method)

A reactor equipped with a thermometer and a stirrer was charged with 19, 580 parts of ion-exchanged water and 3,850 parts of 48.5 wt% aqueous sodium hydroxide, and 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene ( BCF) 1,175 parts and bisphenol A (BPA) 2,835 parts and hydrosulfite 9 parts were dissolved, then methylene chloride 13,210 parts were added and stirred vigorously at 15 with phosgene 2, 000 parts were blown and reacted for about 40 minutes. After completion of the phosgene blowing, the mixture was raised to 28 mm and emulsified by adding 94 parts of p-tert-butylphenol and 640 parts of sodium hydroxide, and then 6 parts of triethylamine was added and stirring was continued for 1 hour to carry out the reaction. finished. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. Was evaporated to obtain 4,080 parts of colorless powder having a molar ratio of BCF to BP A of 20:80. The viscosity average molecular weight of this aromatic polycarbonate powder was 20,300.

(B component)

B—1 fly ash (manufactured by Yoden Business Co., Ltd .: Fineash FA20, Dδ 0 particle size: 5)

Β— 2 fly ash (D 50 particle size larger than 10 m)

(C component)

PTFE: Polytetrafluoroethylene (Daikin Industries, Ltd. Polyflon M P FA500

(D component) D-1: Ferrous sulfate heptahydrate (Fuji Titanium Industry Co., Ltd.)

D-2: Ferrous sulfate monohydrate (Fuji Titanium Industry Co., Ltd.)

D-3: Schwertmannite (manufactured by Zoffia: Azzle-S)

(E component)

E-1: AS resin (Nihon A & L "Litec-A BS-218"

E-2: ABS resin (Toyolac 700-314, manufactured by Toray, (trade name) Rubber component content: 12%)

E-3: Polycaprolactone ("Braxel HI P" (trade name) manufactured by Daicel Chemical Industries) E-4: Trimellitic acid ester ("TOTM" (trade name) manufactured by Daihachi Chemical)

(F component)

F-1: Acid-modified olefin wax that is a copolymer of maleic anhydride and α-olefin (Mitsubishi Chemical Corporation: Diacarna DC 30Μ)

(G component)

G-1: Trimethyl phosphate (Daihachi Chemical "TMP" (trade name))

G-2: Phosphite stabilizer (“Adekastab PEP—8” (trade name) manufactured by Ade force)

G-3: Phosphite stabilizer ("Adekastab PEP-24G" (trade)

ΠΡ ^ ΡNono

table 1

Table 2

Table 3

Table 4

The invention's effect

The resin composition of the present invention becomes a molded article having excellent flame retardancy and improved surface appearance. That is, the molded article of the present invention has excellent flame retardancy, and can achieve V-1 or V-0 in a combustion test having a thickness of 1.5 mm. Further, the molded article of the present invention has an excellent surface appearance with a low silver generation rate. Since the resin composition of the present invention contains an elution inhibitor (D component), there is little elution of heavy metals contained in the inorganic particles (B component). Industrial applicability

The resin composition of the present invention is extremely useful for various industrial applications such as the field of OA equipment and the field of electrical and electronic equipment.

Claims

The scope of the claims

1. (A) 100 parts by weight of polycarbonate resin (component A),

(B) inorganic particles (component B) containing 10 to 70 parts by weight of a composite of silicon dioxide and aluminum oxide and having a D50 particle size of 10 / m or less,

(C) 0.01 to 2 parts by weight of a fluororesin (component C),

(D) 0.05 to 3 parts by weight of dissolution inhibitor (component D),

(E) 1 to 20 parts by weight of flow modifier (E component) and

(F) A resin composition comprising 0.01 to 2 parts by weight of an acid-modified polyolefin wax (F component).

2. The resin composition according to claim 1, wherein the inorganic particles (component B) are fly ash.

3. The resin composition according to claim 1, wherein the fluororesin (component C) is a polytetrafluoroethylene resin having a fibril-forming ability.

4. The resin composition according to claim 1, wherein the elution inhibitor (component D) is a salt of divalent and / or trivalent iron ions and sulfate.

5. The resin composition according to claim 1, wherein the elution inhibitor (component D) is ferrous sulfate hydrate or Schwertmannite.

6. The resin composition according to claim 1, wherein the elution inhibitor (component D) is ferrous sulfate heptahydrate.

7. The resin composition according to claim 1, wherein the flow modifier (component E) is at least one selected from the group consisting of aliphatic polyester resins and trimellitic esters.

8. The resin composition according to claim 1, wherein the acid-modified polyolefin wax (F component) is an acid-modified polyolefin wax having a carboxyl group and Z or a carboxyl anhydride.

9. The resin composition according to claim 1, comprising 0.0001 to 2 parts by weight of a phosphorus stabilizer (G component) per 100 parts by weight of the polycarbonate resin (A component).

10. The resin composition according to claim 9, wherein 50% by weight or more of the phosphorus stabilizer (G component) is a phosphate compound and Z or a phosphite compound.

11. The resin composition according to claim 1, wherein the polycarbonate resin (component A) is bisphenol A-type polycarbonate.

12. A molded article comprising the resin composition according to claim 1.