KR20120099640A - Antistatic polycarbonate resin composition and molded article of same - Google Patents

Abstract

An object of the present invention is to provide an antistatic polycarbonate resin composition excellent in antistatic property, weather resistance, color, molding heat resistance, transparency, and impact resistance and a molded article thereof.
This invention contains 100 weight part of (A) polycarbonate resin (component A), 0.01-4 weight part of (B) low molecular weight sulfonate (component B), and 0.05-3 weight part of (C) ultraviolet absorber (component C). As the resin composition, the component C is at least one compound selected from the group consisting of a benzotriazole compound, a benzotriazine compound, a benzoxazine compound, a 2-cyanoacrylic acid compound, and a benzophenone compound. The 10% weight loss temperature in TGA (thermogravimetric analysis) is a resin composition which is a compound of 280 degreeC or more, and its molded article.

Description

Antistatic polycarbonate resin composition and molded article therefor {ANTISTATIC POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLE OF SAME}

The present invention relates to an antistatic polycarbonate resin composition and a molded article made thereof. More specifically, the present invention relates to an antistatic polycarbonate resin composition excellent in antistatic property, weather resistance, color, molding heat resistance, transparency, and impact resistance, and a molded article formed therefrom.

Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, flame retardancy, and the like, and are widely used in electric and electronic, mechanical, automotive, and medical applications. However, since polycarbonate resin is an insulator, the surface resistivity is large, and static electricity caused by contact or friction is hardly lost. Therefore, a molded article made of polycarbonate resin may cause problems such as adhesion of dust to the surface of the molded article, discomfort caused by electric shock to the human body, and further generation of noise or malfunction in electronic products. That is, the chargeability of polycarbonate resin may become a problem. Therefore, it has always been desired to impart antistatic properties to a resin composition containing a polycarbonate resin while maintaining the basic characteristics of the polycarbonate resin. That is, a resin composition having good antistatic properties and excellent in transparency, color, and impact resistance has been demanded.

As a method of preventing the charging of a polycarbonate resin, the method of mix | blending an ionic surfactant is known. As such an ionic surfactant, the alkali metal salt of sulfonic acid, the phosphonium salt of sulfonic acid (refer patent document 1, patent document 2), etc. are illustrated, for example, Especially this phosphonium salt is preferable which was excellent in transparency of a resin composition. It is widely known as a salt.

Polycarbonate resins are also used in outdoor applications such as sheet materials, window glass materials and automobile headlamp lenses. Moreover, it is used in the use of the organic device represented by the transparent member used by passing light from a light source, such as a pachinko, a slot machine, and a large game device for game centers. However, when the polycarbonate resin is used for a long time in the outdoors or in the presence of a light source, it is known that the resin is deteriorated by ultraviolet rays and the color, transparency, and mechanical properties are lowered. As a method for improving weather resistance, for example, a method of blending an ultraviolet absorber into a polycarbonate resin (see Patent Document 3), and a resin (polycarbonate resin or other acrylic resin, etc.) blended with an ultraviolet absorber may be used as the surface of the polycarbonate molded body. The lamination | stacking or coating method to this is known widely.

In recent years, since the demand for high value-added polycarbonate resin is strong, differentiation by the fusion of the prior art is examined. The development of the resin composition which modified the antistatic property and weather resistance of polycarbonate resin simultaneously is made | formed, and the technique which uses antistatic agent and a ultraviolet absorber together is examined.

As a technique of using an antistatic agent and an ultraviolet absorber together in polycarbonate resin, the method of using a benzotriazole type ultraviolet absorber together in the resin composition containing sulfonate phosphonium salt is known (refer patent document 4). Moreover, the method of using a benzotriazole type ultraviolet absorber together in stabilized antistatic resin composition is known (refer patent document 5). Moreover, although the method of using an oxanilide type ultraviolet absorber together is also known (refer patent document 6), it is hard to say that sufficient examination was made regarding both antistatic property and weather resistance.

However, in recent years, the transparent member for vehicles represented by a glazing material, a head lamp lens, etc., and the transparent member for organic devices represented by various display covers, cases, etc. are progressed in thickness reduction and enlargement, and further processed for the purpose of productivity improvement. There exists a tendency to make resin temperature of city high. Increasing the resin temperature during injection molding causes a problem that volatilized ultraviolet absorbers are deposited on the surface of the mold every time the molding is repeated, and a molded article having sufficient antistatic performance cannot be obtained due to the deposition of the deposit on the surface of the molded article. . Moreover, when manufacturing a sheet-like member, the ultraviolet absorber was similarly deposited on a cooling roll, and there existed a problem that the antistatic performance and surface appearance of a sheet were damaged.

As an additional high value-added polycarbonate resin composition, a resin composition that simultaneously satisfies antistatic performance and weather resistance at the same or higher processing temperatures is required. However, Patent Literature 5 and Patent Literature 6 do not focus on the point, and it is difficult to say that sufficient studies have been conducted to obtain such a resin composition. Examples of such fields in which there is such a demand include a garage or arcade cover, an outdoor mirror, a meter cover, a vending machine cover, a flat display device cover, a solar cell cover, and the like, as well as a transparent member for a vehicle and a transparent member for an organic device.

Japanese Laid-Open Patent Publication No. 62-230835 Japanese Laid-Open Patent Publication 2005-132853 Japanese Laid-Open Patent Publication No. 55-7292 Japanese Patent Application Laid-Open No. 11-106635 Japanese Patent Application Laid-Open No. 11-80532 Japanese Unexamined Patent Publication No. 2008-81708

An object of the present invention is to provide an antistatic polycarbonate resin composition excellent in antistatic properties, weather resistance, color, molding heat resistance, transparency, and impact resistance, and molded articles made thereof, in particular automotive transparent members, transparent members for organic devices, and transparent It is providing a sheet-like member.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, polycarbonate resin (A component), low molecular weight sulfonate (B component), and a benzotriazole type compound, a benzotriazine type compound, a benzoxazine type compound, 2 By blending at least one species selected from the group consisting of cyanoacrylic acid compounds and benzophenone compounds, a UV absorber (component C) having a 10% weight reduction temperature in TGA (thermogravimetric analysis) of 280 ° C or higher It found out that the resin composition conforming to the said objective was obtained, and earnestly examined further, and completed this invention.

According to the present invention,

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

(B) 0.01 to 4 parts by weight of a low molecular weight sulfonate (component B), and

(C) Ultraviolet absorber (component C) As a resin composition containing 0.05-3 weight part,

The C component is at least one compound selected from the group consisting of a benzotriazole compound, a benzotriazine compound, a benzoxazine compound, a 2-cyanoacrylic acid compound, and a benzophenone compound, and TGA (thermogravimetric analysis). The resin composition which is a compound with a 10% weight reduction temperature in () is 280 degreeC or more is provided.

The resin composition of the structure (1) has favorable antistatic property and weather resistance even when the processing temperature is higher than the conventional one, and is preferably used for a product having a strong tendency of thinning and increasing the size of the product.

According to this invention, as a preferable aspect, the resin composition of the said structure (1) whose 10% weight loss temperature in TGA (thermogravimetric analysis) of (2) C component is 300 degreeC or more is provided. The resin composition of the structure (2) is excellent in antistatic property and weather resistance even when the processing temperature is higher.

According to this invention, as a more preferable aspect, the resin composition of the said structure (1) or (2) whose 10% weight loss temperature in TGA (thermogravimetric analysis) of (3) C component is 320 degreeC or more is provided. The resin composition of the structure (3) is excellent in antistatic property and weather resistance even when processing temperature is higher.

Moreover, according to this invention, the resin composition of the said structures (1)-(3) whose MVR (melt volume rate) increase rate of a pellet by mix | blending (4) C component as a preferable aspect is 10% or less is provided. The resin composition of the structure (4) is especially excellent in antistatic property.

Moreover, according to this invention, as a more preferable aspect, (5) The said structure (1) whose low molecular weight sulfonate is a sulfonic acid phosphonium salt represented by following General formula (I), Preferably dodecylbenzene sulfonate tetrabutyl phosphonium salt is used. The resin composition of (4) is provided.

(In formula, A <^1> represents a C1-C40 alkyl group, a C6-C40 aralkyl group, or a C6-C40 aryl group, R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms)

The resin composition of the structure (5) is excellent in color and transparency.

Moreover, according to this invention, as a further preferable aspect, (6) (D) the polyether ester which has a sulfonate group, and / or the polyester (component D) which has a sulfonate group is 0.01-per 100 weight part of polycarbonate resins (component A) The resin composition of the said structure (1)-(5) which contains 5 weight part is provided.

Moreover, the resin composition of the structure (6) which is a preferable aspect has high shaping | molding heat resistance, without impairing weather resistance, a hue, or transparency. This effect is considered to be due to the low molecular weight sulfonate being stably present in the resin matrix by the sulfonate of a polymer type having relatively good compatibility with the polycarbonate resin.

One of the preferable aspects of this invention is (7) the polyether ester of component D substituted with the sulfonate group represented by the following general formula (II), the aromatic dicarboxylic acid component which does not have a (D1) sulfonate group, and (D2) The resin of the said structure (6) which is a polyether ester which consists of an aromatic dicarboxylic acid component, the (D3) glycol component of C2-C10, and the poly (alkylene oxide) glycol component of (D4) number average molecular weights 200-50,000. Composition.

(In the formula, Ar is a trivalent aromatic group having 6 to 20 carbon atoms, M ⁺ represents a metal ion or an organic onium ion)

One of the preferable aspects of this invention is the aromatic dicarboxylic acid component in which the polyester of (8) D component does not have a (D5) sulfonate group, and (D6) the aromatic substituted by the sulfonate group represented by the said general formula (II). It is the resin composition of the said structure (6) which is polyester which consists of a dicarboxylic acid component and the glycol component of (D7) C2-C10.

The resin compositions of the structures (7) and (8) are remarkably excellent in molding heat resistance and have good color. In addition, the "component" in a polyether ester and polyester represents the structural unit in these polymers derived from this compound or its ester formable derivative. For example, an aromatic dicarboxylic acid component represents the structural unit in the polyether ester or polyester derived from aromatic dicarboxylic acid or its ester forming derivative, and a glycol component is a glycol compound or its ester The structural unit in the polyether ester or polyester derived from a formation derivative is shown.

As said preferable aspect of this invention (9) (E)-0.001-0.5 weight part of phosphate ester (component E) represented by following General formula (III) per 100 weight part of polycarbonate resin (component A)-said structure (1)- The resin composition of (8) is provided.

(Wherein X represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 A divalent group derived from a compound selected from the group consisting of -hydroxyphenyl) ketone, and bis (4-hydroxyphenyl) sulfide, n is an integer from 0 to 5, or a mixture of phosphate esters with different n numbers Is an average of 0 to 5, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently substituted or unsubstituted alkyl groups having 1 to 40 carbon atoms and having 6 to 40 carbon atoms. Monovalent group derived from a compound selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group having 6 to 40 carbon atoms)

The resin composition of the structure (9) is more excellent in color and transparency.

One of the preferable aspects of this invention is the said structure (1)-which contains 0.01-2 weight part of (10) (F) hindered phenol type antioxidant (component F) per 100 weight part of polycarbonate resin (component A). It is the resin composition of (9). The resin composition of the structure (10) has the advantage that it contributes not only at the time of extrusion or shaping | molding but also to the color stability at the time of a weather test, and becomes a suitable molded article for the product which is easy to expose to high temperature.

One of the preferable aspects of this invention is the said structure (1)-(11) which contains 0.01-2 weight part of (11) (G) phosphite ester antioxidant (component G) per 100 weight part of polycarbonate resin (component A). The resin composition of 10). The resin composition of the structure (11) is more excellent in stability of color.

One of the preferable aspects of this invention is a smooth flat plate of thickness 2mm which has an arithmetic mean roughness (Ra) of (12) 0.03 micrometer or less WHEREIN: The said structure whose haze measured by JISK7105 is 0.1 to 1% (1). ) To (11). The resin composition of the structure (12) has the outstanding transparency and smoothness.

One of the preferable aspects of this invention is (13) adjusting the smooth flat plate of thickness 2mm which has an arithmetic mean roughness (Ra) of 0.03 micrometer or less in 1 week condition in the environment of the temperature of 23 degreeC, and 50% of a relative humidity, The resin composition of said structure (1)-(12) whose half life measured by the conditions of temperature 23 degreeC, 50% of a relative humidity, 10 kW of applied voltages, and 20 mm of electrode-samples is 500 second or less. Even if the resin composition of the structure (13) is stored in the air for a long time, dust or the like does not adhere well, and thus the transparency and appearance are not impaired.

One of the preferable aspects of this invention is a molded article formed by melt-molding the resin composition of the said structure (1)-(13). The molded article of the constitution 14 is excellent in antistatic property, weather resistance, color, molding heat resistance, transparency, and impact resistance.

One of the preferable aspects of this invention is the molded article of said (14) whose (15) molded article is a vehicle transparent member. Since the transparent member for vehicles represented by an automotive resin window, a head lamp lens, etc. has a strong tendency to enlarge and thin, it is assumed that the case processed at higher temperature will increase. Since the resin composition of this invention is excellent also in antistatic property, weather resistance, color, and transparency even when processed at high temperature, the vehicle transparent member which has these characteristics is provided by such a structure (15).

One of the preferable aspects of this invention is the molded article of said (14) whose (16) molded article is a transparent member for organic devices. The resin composition of the present invention can express various designs due to good color, and also has such a feature that such a design is maintained for a long time without disturbing adhesion of dust. Here, the cover for protecting the electronic circuit board of an organic device is also contained in such a transparent member for organic devices. By using the same material for the various members used in the front of the cover and the organic device, it is possible to manufacture the device more efficiently and reduce its cost. The cover for protecting an electronic circuit board requires antistatic performance especially in view of suppressing noise generation and malfunction from the circuit. Therefore, the transparent member and organic device for organic devices which have these advantages are provided by this structure 16. As shown in FIG.

One of the preferable aspects of this invention is the molded article of said (14) whose (17) molded article is a transparent sheet-like member. According to such a structure (17), the molded article suitable for various sheet members, such as a building material use especially where antistatic performance and weather resistance are required is provided.

The resin composition of the present invention is excellent in antistatic performance, weather resistance, color, molding heat resistance, transparency, and impact resistance.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a molded article of a transparent headlamp lens simulation type of an automobile molded in an embodiment. As shown, the lens is in the shape of a dome.
1-A shows the front view of the molded article (the figure projected on the platen surface at the time of molding. Therefore, this area becomes the maximum projection area).
1-B shows the AA line cross section in [1-A] of the said molded article.
2 is a front view of the cover molded article.

Hereinafter, the detail of this invention is demonstrated further.

<A component: Polycarbonate resin>

A component is polycarbonate resin which becomes a main component of the resin composition of this invention. Representative polycarbonate resins (hereinafter may be simply referred to as "polycarbonates") are obtained by reacting dihydric phenols with carbonate precursors. Examples of the reaction include interfacial polycondensation, melt transesterification, and solid esters of carbonate prepolymers. The exchange method, the ring-opening polymerization method of a cyclic carbonate compound, etc. are mentioned.

Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) Propane (collectively "bisphenol A"), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy Phenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2- Bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol, 1,1-bis ( 4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxy Nil) propane, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene And 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (henceforth abbreviated as "BPA") is common.

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

For example, 4,4 '-(m-phenylenediisopropylidene) diphenol (sometimes abbreviated as "BPM" hereafter) and 1,1-bis (4) as one part or all part of a bivalent phenol component. -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis Polycarbonate (single polymer or copolymer) using (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") Is suitable for applications in which dimensional change due to absorption and form stability requirements are particularly stringent. It is preferable to use dihydric phenols other than these BPA 5 mol% or more, especially 10 mol% or more of the whole dihydric phenol component which comprises this polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the A component constituting the resin composition is the copolymerized polycarbonate of the following (1) to (3).

(1) BPM is 20-80 mol% (more preferably 40-75 mol%, More preferably, 45-65 mol%) in 100 mol% of the bivalent phenol components which comprise this polycarbonate, and also BCF The copolymerized polycarbonate is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

(2) BPA is 10-95 mol% (more preferably 50-90 mol%, More preferably, 60-85 mol%) in 100 mol% of the bivalent phenol components which comprise this polycarbonate, and also BCF The copolymerized polycarbonate is 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).

(3) In 100 mol% of the bivalent phenol components which comprise this polycarbonate, BPM is 20-80 mol% (more preferably 40-75 mol%, More preferably, 45-65 mol%), and Bis -Copolymer polycarbonate whose TMC is 20-80 mol% (more preferably 25-60 mol%, More preferably, 35-55 mol%).

These special polycarbonates may be used alone or in combination of two or more thereof. Moreover, these can also be mixed and used with the polycarbonate of bisphenol-A type which is common.

About the manufacturing method and characteristic of these special polycarbonates, Unexamined-Japanese-Patent No. 6-172508, Unexamined-Japanese-Patent No. 8-27370, Unexamined-Japanese-Patent No. 2001-55435, and Unexamined-Japanese-Patent No. 2002-117580 are mentioned, for example. It is described in detail in the issue.

In addition, among the various polycarbonates mentioned above, adjusting the copolymerization composition and the like to adjust the water absorption rate and the Tg (glass transition temperature) to be within the following range is good in hydrolysis resistance of the polymer itself, and low after molding. Since it is remarkably excellent also in warpage property, it is especially preferable in the field | area where form stability is calculated | required.

(Iii) a polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180 ° C, or

(Ii) Polycarbonate whose Tg is 160-250 degreeC, Preferably it is 170-230 degreeC, and water absorption is 0.10 to 0.30%, Preferably it is 0.13 to 0.30%, More preferably, it is 0.14 to 0.27%.

Here, the water absorption of polycarbonate is the value which measured the moisture content after immersing in 23 degreeC water for 24 hours based on ISO62-1980 using the disk-shaped test piece of 45 mm in diameter and 3.0 mm in thickness. In addition, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK71121.

On the other hand, carbonyl halide, carbonate ester, haloformate, etc. are used as a carbonate precursor, Specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, etc. are mentioned.

In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, you may use a catalyst, an end terminator, an antioxidant for preventing a bivalent phenol from being oxidized if necessary. The polycarbonate may be a branched polycarbonate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. As a trifunctional or more than trifunctional aromatic compound used here, a 1,1,1- tris (4-hydroxyphenyl) ethane and a 1,1,1- tris (3, 5- dimethyl- 4-hydroxyphenyl) ethane Etc. can be mentioned.

When it contains the polyfunctional compound which generate | occur | produces branched polycarbonate, the quantity is 0.001-1 mol% is preferable in polycarbonate whole quantity, More preferably, it is 0.005-0.9 mol%, Especially preferably, it is 0.01-0.8 mol % to be. Moreover, especially in the case of the melt transesterification method, although a branched structure may generate | occur | produce as a side reaction, also in such a branched structure amount, in a polycarbonate whole quantity, Preferably it is 0.001-1 mol%, More preferably, it is 0.005-0.9 mol. %, Especially preferably, it is 0.01-0.8 mol%. Also it can be calculated by ¹ H-NMR measurement for the ratio of such branched structures.

Moreover, in the resin composition of this invention, the polycarbonate resin used as A component is polyester carbonate copolymerized with bifunctional carboxylic acid of aromatic or aliphatic (including alicyclic), and bifunctional alcohol (alicyclic) A copolymerized polycarbonate copolymerized with a polycarbonate and a polyester carbonate copolymerized with such a bifunctional carboxylic acid and a difunctional alcohol. Moreover, the mixture which blended 2 or more types of obtained polycarbonates may be sufficient.

As the aliphatic bifunctional carboxylic acid used herein, α, ω-dicarboxylic acid is preferable. Examples of the aliphatic difunctional carboxylic acid include, for example, linear saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecane diacid, tetradecane diacid, octadecane diacid and dichoic acid diacid. Alicyclic dicarboxylic acids, such as an acid and cyclohexanedicarboxylic acid, are mentioned preferably. As a bifunctional alcohol, an alicyclic diol is more preferable, For example, cyclohexane dimethanol, cyclohexanediol, tricyclodecane dimethanol, etc. are illustrated.

Moreover, in this invention, use of the polycarbonate polyorganosiloxane copolymer which copolymerized the polyorganosiloxane unit as A component is also possible.

The aromatic polycarbonate resin which becomes A component is two types of various polycarbonates, such as the polycarbonate from which the above-mentioned dihydric phenol differs, the polycarbonate containing a branching component, polyester carbonate, a polycarbonate polyorganosiloxane copolymer, etc. What mixes the above may be sufficient. Moreover, what mixed 2 or more types of polycarbonate from which a manufacturing method differs, polycarbonate from which a terminal stopper differs, etc. can also be used.

In the polymerization reaction of polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction of dihydric phenol and phosgene, and reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As an organic solvent, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, are used, for example. In order to promote the reaction, for example, catalysts such as tertiary amines such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds Can also be used. In that case, it is preferable to keep reaction temperature normally 0-40 degreeC, reaction time about 10 minutes-about 5 hours, and pH in reaction at 9 or more.

Moreover, in this polymerization reaction, a terminal terminator is used normally. Monofunctional phenols can be used as such terminal terminator. As monofunctional phenols, it is preferable to use monofunctional phenols, such as phenol, p-tert- butylphenol, and p-cumylphenol, for example. Moreover, as monofunctional phenols, it is nuclear-substituted by long-chain alkyl groups of 10 or more carbon atoms, such as decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol, and triacontyl phenol. A monofunctional phenol is mentioned, The phenol is effective in the improvement of fluidity | liquidity and the hydrolysis resistance. These terminal stoppers may be used independently or may be used together 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction of a dihydric phenol and a carbonate ester, mixed while heating the divalent phenol and a carbonate ester in the presence of an inert gas, and distilling the alcohol or phenol produced. It is done by the method to make it. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced and the like, in most cases in the range of 120 to 350 ° C. At the end of the reaction, the reaction system is depressurized to about 1.33 × 10 ³ to 13.3 kPa to easily distill the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

As said carbonate ester, ester, such as a C6-C10 aryl group which may have a substituent, an aralkyl group, or a C1-C4 alkyl group, is mentioned, Especially, diphenyl carbonate is preferable.

Moreover, a polymerization catalyst can be used in order to speed up a polymerization rate. As such a polymerization catalyst, For example, alkali metal compounds, such as sodium hydroxide, potassium hydroxide, the sodium salt of dihydric phenol, potassium salt; alkaline earth metal compounds, such as calcium hydroxide, barium hydroxide, magnesium hydroxide; tetramethylammonium hydroxide, Nitrogen-containing basic compounds, such as tetraethylammonium hydroxide, trimethylamine, and triethylamine, etc. can be used. Also used in esterification reactions and transesterification reactions of alkoxides of alkali (earth) metals, organic acid salts of alkali (earth) metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds and the like. Catalysts can be used. These catalysts may be used independently or may be used in combination of 2 or more type. The amount of the catalyst to be used is preferably 1 × 10 ^-9 to 1 × 10 ^-5 equivalents, more preferably 1 × 10 ^-8 to 5 × 10 ^-6 equivalents to 1 mole of the divalent phenol of the raw material. Is selected.

In the reaction by the melt transesterification method, for the purpose of reducing the phenolic end groups of the resulting polycarbonate, after or after the end of the polycondensation reaction, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, Compounds, such as 2-ethoxycarbonylphenylphenyl carbonate, can be added.

In the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. As the quantity of such deactivator, it is preferable to use in the ratio of 0.5-50 mol with respect to 1 mol of catalyst which remain | survive. Moreover, it is suitable to use it in the ratio of 0.01-500 ppm with respect to the polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, Especially preferably, it is 0.01-100 ppm. Examples of preferred deactivators include phosphonium salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

The viscosity average molecular weight of the polycarbonate resin which becomes A component is not limited. However, since a viscosity average molecular weight falls below 10,000, intensity | strength etc. fall, and when it exceeds 50,000, shaping | molding process characteristics will fall, the range of 10,000-50,000 is preferable, The range of 12,000-30,000 is more preferable, 15,000-28,000 The range of is more preferable. In this case, the polycarbonate whose viscosity average molecular weight is out of the said range can also be mixed in the range which moldability etc. are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight of greater than 50,000 may be blended.

The viscosity average molecular weight as used in this invention is calculated | required using the Ostwald viscometer first from the solution which melt | dissolved 0.7 g of polycarbonate resin in 100 ml of methylene chlorides at 20 degreeC, the specific viscosity ((eta) _SP ) computed by following Formula first,

Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀

[t ₀ is the number of drops of methylene chloride, t is the number of drops of sample solution]

The viscosity average molecular weight M is computed by following Formula from the calculated | required specific viscosity ((eta) _SP ).

η _SP / c = [η] + 0.45 × [η] ² c (where [η] is the ultimate viscosity)

[η] = 1.23 × 10 ^-4 M ^{0 .83}

c = 0.7

<Component B: Low Molecular Weight Sulfonate>

Component B is a low molecular weight sulfonate. Low molecular weight means a stoichiometric molecular weight here, 1,000 g / mol or less is preferable and 750 g / mol or less is more preferable.

As a cation component of such a low molecular weight sulfonate, alkali metals, such as potassium, sodium, cesium, and rubidium, an alkaline earth metal, phosphonium, ammonium, etc. are mentioned. Examples of the acid component include dodecylbenzenesulfonic acid, perfluoroalkanesulfonic acid, and the like. Among these, potassium sulfonate salt, cesium salt, rubidium salt, phosphonium salt, and ammonium salt are preferable, and sulfonate phosphonium salt is particularly preferable. These may be used independently and may be used in combination of 2 or more type. In combination, it is preferable to use sulfonate phosphonium salt and sulfonate alkali (earth) metal salt together.

Although it does not specifically limit as such sulfonate phosphonium salt, The sulfonate phosphonium salt represented by the following general formula (I) is illustrated preferably.

(In formula, A <^1> represents a C1-C40 alkyl group, a C6-C40 aralkyl group, or a C6-C40 aryl group, R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms)

The sulfonic acid phosphonium salt represented by the said general formula (I) is provided with the resin composition excellent in transparency and antistatic property by the point which is favorable in heat resistance and antistatic property, and also the compatibility with polycarbonate resin is comparatively favorable.

In the general formula (Ⅰ), the alkyl group in A ¹ is, for example, dodecyl group, there may be mentioned for the group, a butyl group, an ethyl group or the like, particularly preferably a dodecyl group, decyl group. The aralkyl group has 6 to 40 carbon atoms, and for example, a benzyl group and a phenethyl group are mentioned, and a phenethyl group is particularly preferable. Examples of the aryl group in A ¹ include an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, and the like. Some of these hydrogen atoms may be substituted by halogen atoms, such as a fluorine atom, and an aralkyl group and an aryl group may contain the hetero atom in these alkyl groups, an aralkyl group, and an aryl group. For example, a phenyl group, a naphthyl group, a tolyl group, and a dodecylphenyl group are mentioned, Especially a dodecylphenyl group is preferable.

In said general formula (I), R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aralkyl group, or a C6-C15 aryl group each independently. R <^1> , R <^2> , R <^3> and R <^4> may mutually be same or different.

As a C1-C20 alkyl group, what is necessary is just a linear or branched alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, de A practical group, a dodecyl group, a tetradecyl group, an octadecyl group, an eicosyl group etc. are mentioned.

Examples of the aralkyl group having 6 to 20 carbon atoms include a benzyl group, 2,6-dibutylbutyl-4-methylbenzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and 2-phenylisopropyl group.

Examples of the aryl group having 6 to 15 carbon atoms include a phenyl group, a tolyl group, a naphthyl group, and the like.

As R <^1> , R <^2> , R <^3> and R <^4> , a C1-C20 alkyl group is preferable among these, and a C4-C16 alkyl group is more preferable. Moreover, the aspect in which R <^1> , R <^2> , R <^3> and R <^4> is a butyl group or an octyl group is more preferable, and the aspect in which all are a butyl group, or any one is an octyl group and the remainder is a butyl group is preferable. Sulfonate phosphonium salts in which R ¹ , R ² , R ^3, and R ⁴ are all butyl groups are preferable in terms of ease of availability and good compatibility with polycarbonate resins, and sulfonic acid phosphes in which one is an octyl group and the other is a butyl group Phosphorus salt is preferable at the point which has little thermal degradation of antistatic performance. More preferable in practical use is sulfonic acid phosphonium salt in which R ¹ , R ² , R ³ and R ⁴ are all butyl groups.

Among them, aromatic sulfonic acid phosphonium salts are preferably used. Examples of the aromatic sulfonic acid used for the aromatic sulfonic acid phosphonium salt include sulfonic acids of aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of aromatic ethers, sulfonic acids of aromatic ethers, sulfonic acids of aromatic sulfonates, aromatic sulfonic acids, aromatic sulfonic sulfonic acids, And at least one acid selected from the group consisting of sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and styrene in which the hydrogen atoms of the benzene ring of styrene are substituted with sulfonic acid groups. These can be used 1 type or in combination or 2 or more types. In the sulfonate phosphonium salt, a part of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

As such sulfonic acid phosphonium salt, the dodecyl benzene sulfonate phosphonium salt is preferable, and the dodecylbenzene sulfonate tetrabutyl phosphonium salt is especially preferable.

<C component: ultraviolet absorber>

The C component is at least one compound selected from the group consisting of a benzotriazole compound, a benzotriazine compound, a benzoxazine compound, a 2-cyanoacrylic acid compound, and a benzophenone compound, and TGA (thermogravimetric analysis). It is a ultraviolet absorber whose 10% weight loss temperature in) is 280 degreeC or more.

(10% weight loss temperature)

The measurement of 10% weight loss temperature is measured condition which consists of temperature range from 23 degreeC to 900 degreeC, and the temperature increase rate of 20 degree-C / min in nitrogen gas atmosphere using a TGA measuring apparatus based on JISK7120. Under In this weight loss behavior, the temperature at which 10% weight loss is observed is 10% weight loss temperature.

In the TGA measuring device, the weight loss due to volatilization of the ultraviolet absorber or the weight loss due to pyrolysis can be confirmed. When the volatility of the ultraviolet absorbent is high, the volatilized ultraviolet absorbent is deposited on the mold and the cooling roll due to the temperature difference between the resin temperature and the cooling roll in the mold or sheeting in the injection molding. In the antistatic resin composition, an antistatic agent bleeding on the surface of a molded article adsorbs moisture in the air, forms a film such as a water film on the surface of the molded article, and exhibits antistatic properties. However, when such a deposit adheres to the surface of a molded article or sheet | seat, since the quantity of the antistatic agent which exists in the molded article surface reduces substantially, it not only reduces transparency or surface appearance, but also antistatic property. On the other hand, when the heat resistance of the ultraviolet absorbent is easy to thermally decompose, not only the color and transparency of the molded product are impaired under the influence of the thermally decomposed ultraviolet absorber, but the thermally decomposed ultraviolet absorber promotes thermal decomposition of polycarbonate resin or low molecular weight sulfonate, Or transparency is significantly reduced. Furthermore, since the thermal decomposition of polycarbonate resin and low molecular weight sulfonate is accelerated | stimulated, impact resistance and antistatic property are also reduced in many cases. Therefore, it is preferable that the 10% weight loss temperature of the ultraviolet absorber in TGA is high, and if it is 280 degreeC or more, a preferable resin composition will be obtained. Since the product using polycarbonate has the tendency of enlargement and thinning, the 10% weight loss temperature of the ultraviolet absorber in TGA becomes like this. Preferably it is 300 degreeC or more, More preferably, it is 320 degreeC or more.

(Benzotriazole compound)

As a ultraviolet absorber, the benzotriazole type compound whose 10% weight loss temperature in TGA is 280 degreeC or more is used. The benzotriazole-based compound has the advantage that the influence of color on the polycarbonate resin is relatively small, and also has good ultraviolet absorbing ability. Therefore, since sufficient weather resistance can be provided with respect to polycarbonate resin, it is a ultraviolet absorber which is suitable for the use of transparent members for vehicles, such as an automobile resin window and a head lamp lens.

As a benzotriazole type compound, 2- [2'-hydroxy-3 ', 5'-bis ((alpha), (alpha)-dimethylbenzyl) phenyl] benzotriazole and 2, 2- methylene bis [4- (1, 1 , 3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 6- (2-benzotriazolyl) -4-t-octyl-6'-t-butyl4 ' -Methyl-2,2'-methylenebisphenol, -polycaprolactone modified 2-hydroxyphenylbenzotriazole, etc. are illustrated. Especially, 2- [2'-hydroxy-3 ', 5'-bis ((alpha), (alpha)-dimethyl benzyl) phenyl] benzotriazole is preferable. The UV absorbers include TINUVIN 234 (trade name, manufactured by CIBA SPECIALTY CHEMICALS), EVERSORB 76 and EVERSORB 234 (trade name, manufactured by Everlight Chemical), CHEMSORB 234 (trade name, manufactured by Gosen Pharma Corp.), GRS Sorb 234 (trade name, GeReSo mbH company), and Adecastab LA-31 (brand name, product made by Adeka Corporation), and JAST-500 (brand name, product manufactured by Johoku Chemical Industry Co., Ltd.), and UVA103 (brand name, Daicel Chemical Industry Co., Ltd.), etc. are marketed. It can be used easily.

(Benzotriazine compound)

As a ultraviolet absorber, the benzotriazine type compound whose 10% weight reduction temperature in TGA is 280 degreeC or more is used. Since the benzotriazine-based compound efficiently absorbs and converts light in the vicinity of the wavelength of 290 nm, which has a great influence on the photodegradation of the polycarbonate resin, to heat, excellent weather resistance can be given to the polycarbonate resin.

Examples of the benzotriazine compounds include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-octyloxyphenol and 2- (4,6-diphenyl-1,3 , 5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- ( 4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol, 2- (4,6-dibiphenyl-1, 3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-dibiphenyl-1,3,5-triazin-2-yl) -5- (2-ethylhexyl jade C) phenol and the like are exemplified. Also, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol or 2- (4,6-bis (2,4) Examples of the compound in which the phenyl group is a 2,4-dimethylphenyl group, such as -dimethylphenyl) -1,3,5-triazin-2-yl) -5-octyloxyphenol, are exemplified. Among them, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-dibiphenyl-1,3,5-triazine 2-yl) -5- (2-ethylhexyloxy) phenol is preferable, such as TINUVIN 1577, TINUVIN 1577 FF (trade name, manufactured by CIBA SPECIALTY CHEMICALS), CGX-UVA006 (trade name, manufactured by CIBA SPECIALTY CHEMICALS), and the like. It is commercially available as and can be used easily.

(Benzoxazine type compound)

As a ultraviolet absorber, the benzoxazine type compound whose 10% weight loss temperature in TGA is 280 degreeC or more is used. The benzoxazine-based compound has the advantage that the volatility is low and the influence of color on the polycarbonate resin is very small, and since the benzoxazine compound has a good ultraviolet absorbing ability, a resin composition excellent in color can be obtained.

A benzoxazine type compound is represented by the following general formula (IV).

(Wherein Ar is a divalent aromatic hydrocarbon residue having 6 to 12 carbon atoms. Ar may contain a hetero atom. N represents 0 or 1)

As a benzoxazine type compound, 2,2'-bis (3,1-benzooxazin-4-one) (in the case of n = 0 in the said General formula (IV)), 2,2'-p-phenyl Renbis (3,1-benzooxazin-4-one), 2,2'-m-phenylenebis (3,1-benzooxazin-4-one), 2,2 '-(4,4' -Diphenylene) bis (3,1-benzooxazin-4-one), 2,2 '-(2,6-naphthalene) bis (3,1-benzooxazin-4-one), 2,2 '-(1,5-naphthalene) bis (3,1-benzooxazin-4-one), 2,2'-(2-methyl-p-phenylene) bis (3,1-benzooxazine-4 -One), 2,2 '-(2-nitro-p-phenylene) bis (3,1-benzooxazin-4-one), and 2,2'-(2-chloro-p-phenylene) Bis (3,1-benzooxazin-4-one) and the like. Among them, 2,2'-p-phenylenebis (3,1-benzooxazin-4-one) and 2,2 '-(4,4'-diphenylene) bis (3,1-benzooxazine 4-one), and 2,2 '-(2,6-naphthalene) bis (3,1-benzooxazin-4-one) are preferred, in particular 2,2'-p-phenylenebis (3 , 1-benzooxazin-4-one) is preferred. The said benzoxazine can be used individually or in combination of 2 or more types.

Such benzoxazines can be produced by various methods disclosed in the pamphlet of WO03 / 035735. That is, both the method of using isatosan anhydride (in particular, the method of using recrystallized isatosan anhydride) and the method of using anthranilic acid can be used as a raw material. These acid compounds and carboxylic acid chloride compounds can be reacted to obtain benzoxazine. These may be recrystallized after production, as disclosed in Japanese Patent Laid-Open No. 62-31027. As such a compound, it is marketed as CEi-P (brand name, the Takemoto oils and fats company), and CYASORB UV-3638 (brand name, the CYTEC company make), and can use it easily.

(2-Cyanoacrylic Acid Compound)

As a ultraviolet absorber, the 2-cyanoacrylic-acid compound whose 10% weight loss temperature in TGA is 280 degreeC or more is used. It is preferable that the 2-cyanoacrylic acid type compound is a polyfunctional 2-cyanoacrylic acid ester represented by the following general formula (V).

In the general formula (V), the lower limit of n is 4, while the upper limit of n is 8, preferably 6. This is because the larger the molecular weight is, the more preferable in terms of the resistance to volatility, while the lower one is preferable in terms of transparency and color. The molecular weight of the polyfunctional 2-cyanoacrylic acid ester is preferably 783 to 2200 g / mol, more preferably 1044 to 1700 g / mol. Moreover, although they can mix and use 2 or more types, the compound which consists of a single structure as much as possible is advantageous in terms of transparency and a color. In addition, it is preferable that the by-products and impurities at the time of synthesis are also reduced as much as possible.

In the general formula (V), X represents an ester-forming moiety derived from an aliphatic or alicyclic polyol having 3 to 20 carbon atoms, and specific examples of the polyol include glycerin, erythritol, xylitol, mannitol, Sorbitol, pentaerythritol, dipentaerythritol, polyglycerol (triglycerol to hexaglycerol), trimethylolethane, trimethylolpropane, trimethylolbutane, and 1-methyl-2,2,6,6-tetrahydroxymethyl Cyclohexane etc. are illustrated. Among these, preferred polyols are glycerin, trimethylolpropane, trimethylolbutane, pentaerythritol, and dipentaerythritol, and particularly preferably pentaerythritol. As a particularly preferable 2-cyanoacrylic acid type compound, 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano- 3,3-diphenylacryloyl) oxy] methyl] propane is illustrated, The compound is marketed as UVINUL3030 (brand name, the BASF Corporation make), and can be used easily.

(Benzophenone compound)

As a ultraviolet absorber of this invention, the benzophenone type compound whose 10% weight loss temperature in TGA is 280 degreeC or more is used.

Examples of the benzophenone compound include bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane. It is marketed as Castave LA-51 (trade name, manufactured by Adeka Corporation) and SEESORB 151 (trade name, manufactured by Cipro Chemical Co., Ltd.) and can be easily used.

Among the ultraviolet absorbers used in the present invention in terms of antistatic property, weather resistance, molding heat resistance and impact resistance, particularly preferable ultraviolet absorbers are 2- [2'-hydroxy-3 ', 5'-bis (α, α-). Dimethylbenzyl) phenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2,2'-p-phenylenebis (3,1-benzooxazin-4-one ) Is used. Among them, particularly preferred ultraviolet absorbers include 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole and 2,2'-p-phenylenebis. (3,1-benzooxazin-4-one) is used. In addition, a ultraviolet absorber can mix and use 2 or more types.

<D component: Polyether ester having sulfonate group and / or polyester having sulfonate group>

The resin composition of this invention exhibits the outstanding characteristic by using together the polyether ester which has a sulfonate group, and / or the polyester which has a sulfonate group together with the said sulfonate.

The sulfonic acid base is a group The protons of the sulfonic acid group (-SO ₃ H) is substituted for other cations, -SO ₃ ^- X ^{+ -} is a group represented by ^{(X +} is a counter ion of SO _3). More specifically, X ⁺ is a cation selected from metal ions and organic onium ions, particularly preferably metal ions. In addition, the cation may be a divalent or higher ion.

Moreover, polyether ester means the polymer which has a tri (or more) poly (alkylene oxide) glycol component in the repeating unit.

In addition, polyester is polyester which does not contain the poly (alkylene oxide) glycol component more than a trimer. In addition, the polyester may contain a diethylene glycol component.

The polyether ester and polyester of the component D may be polymerized by polymerizing a monomer substituted with a sulfonate group, or may be produced by modifying a polymer not substituted with a sulfonate group with a sulfonate group. In addition, below, the polyether ester which has the sulfonate group of D component is simply "polyetherester of D component", and the polyester which has the sulfonate group of D component may only be called "polyester of D component".

Specific examples of the sulfonate group (-SO ₃ ^- X ⁺ ) contained in the D component are as follows. Metal ions in such X ⁺ (hereinafter may be simply referred to as counter ions) are ions of alkali metals such as sodium, potassium, lithium, rubidium, and cesium, and ions of alkaline earth metals such as calcium and magnesium. , Zinc ions, and copper ions. The organic onium ions in such counter ions include, for example, ammonium ions, phosphonium ions, sulfonium ions, onium ions derived from a hetero aromatic ring, and the like. Moreover, although the primary, secondary, tertiary, and quaternary can be used as the organic onium ion, quaternary onium ions are preferable. The organic onium ions in such counter ions are more preferably organic phosphonium ions (e.g., tetrabutylphosphonium ions and tetramethylphosphonium ions, etc.), and organic ammonium ions (e.g., tetrabutylammonium ions and Tetramethylammonium ions and the like), and particularly preferably organic phosphonium ions. The counter ions in the sulfonate group contained in the D component are more preferably metal ions, still more preferably alkali metal ions, alkaline earth metal ions and zinc ions, and particularly preferably alkali metal ions. In the case of a monovalent metal ion, 1 mol of metal ions shall correspond with 2 mol of sulfonic acid groups.

It is preferable that a sulfonate group contains 2 or more of sulfonate groups in 1 molecule of polymers, More preferably, 3 or more, More preferably, 4 or more are contained. Moreover, 1,000 or more are preferable and, as for the number average molecular weight, 2,000 or more are more preferable. Moreover, as a density | concentration of the sulfonate group contained in D component, Preferably it is the range of 5 * 10 <^-7> mol / g-5 * 10 <^-2> mol / g, More preferably, it is 5 * 10 <^-6> -5 * 10. ^-3 mol / g.

(D component: polyether ester)

As polyether ester of D component, (D1) aromatic dicarboxylic acid component which does not have a sulfonate group, (D2) aromatic dicarboxylic acid component substituted by the sulfonate group represented by following General formula (II), (D3) The polyether ester which consists of a C2-C10 glycol component and the poly (alkylene oxide) glycol component of (D4) number average molecular weights 200-50,000 is preferable.

(In the formula, Ar is a trivalent aromatic group having 6 to 20 carbon atoms, M ⁺ represents a metal ion, organic onium ion)

As aromatic dicarboxylic acid (and its ester-forming derivative) which does not have a sulfonate group for inducing (D1), for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and And ester ester-forming derivatives thereof. Especially, the polyether ester containing a naphthalenedicarboxylic acid component and a biphenyl dicarboxylic acid component, especially a naphthalenedicarboxylic acid component makes the refractive index of this polyether ester close to the refractive index of a polycarbonate, and is higher. It is preferable at the point which becomes easy to obtain the molded article which has transparency. As naphthalenedicarboxylic acid and its ester-formable derivative, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl, 2 specifically, Diethyl, 6-naphthalenedicarboxylic acid, dimethyl 2,7-naphthalenedicarboxylic acid, diethyl 2,7-naphthalenedicarboxylic acid, and the like, and the hydrogen atoms of the aromatic rings of these compounds include alkyl groups and halogen atoms. Or the like may be substituted. The aromatic dicarboxylic acid component of (D1) may be contained alone or in polyether ester in combination of 2 or more types.

The aromatic dicarboxylic acid component substituted with the sulfonate group (D2) is represented by the said Formula (II). Ar in said Formula (II) is a C6-C20 trivalent aromatic group, Specifically, a trivalent benzene ring and a naphthalene ring are mentioned, These rings are substituents, such as an alkyl group, a phenyl group, a halogen, and an alkoxy group. You may have it.

In said Formula (II), M <^+> represents a metal ion or organic onium ion, As the specific example, the same thing as the said X <^+> can be shown, More preferably, it is a metal ion, More preferably, an alkali metal Ions, alkaline earth metal ions and zinc ions, and particularly preferably alkali metal ions. In the case of monovalent metal ions, 1 mol of metal ions shall correspond to 2 mol of sulfonic acid groups.

Examples of the aromatic dicarboxylic acid substituted with a sulfonate group and an ester forming derivative thereof for inducing such (D2) include 4-sodium sulfo-isophthalic acid, 5-sodium sulfo-isophthalic acid, and 4-potassium sulfo-isophthalic acid. , 5-potassium sulfo-isophthalic acid, 2-sodium sulfo-terephthalic acid, 2-potassium sulfo-terephthalic acid, 4-sulfo-isophthalic acid zinc salt, 5-sulfo-isophthalic acid zinc salt, 2-sulfo-terephthalic acid zinc salt, 4 -Sulfo-isophthalic acid tetraalkyl phosphonium salt, 5-sulfo-isophthalic acid tetraalkyl phosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5-sulfo-isophthalic acid tetraalkyl ammonium salt, 2-sulfo- terephthalic acid tetraalkyl Phosphonium salt, 2-sulfo-terephthalate tetraalkylammonium salt, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-sodium sulfo-2,7-naphthalenedicarboxylic acid, 4-potassium sulfo-2, 6-naphthalenedicarboxylic acid, 4-potassiumsulfo-2,7-naphthalenedicarboxylic acid, 4-sulfo-2,6 Naphthalenedicarboxylic acid zinc salt, 4-sulfo-2,7-naphthalenedicarboxylic acid zinc salt, 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkylammonium salt, 4-sulfo-2,7-naphthalenedica Tetraalkyl ammonium salt, 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkyl phosphonium-, 4-sulfo-2,7-naphthalenedicarboxylic acid tetraalkyl phosphonium salt, or dimethyl ester thereof And diethyl ester.

Among them, dimethyl ester or diethyl ester of aromatic dicarboxylic acid in which Ar is a benzene ring and M ⁺ is an alkali metal ion such as sodium and potassium is more preferable in view of polymerizability, antistatic property, mechanical properties, and color. Do. Specifically, for example, 4-sodium sulfo-isophthalate dimethyl, 5-sodium sulfo-isophthalate dimethyl, 4-potassium sulfo-isophthalate dimethyl, 5-potassium sulfo-isophthalate dimethyl, 2-sodium sulfo-terephthalate dimethyl And 2-potassium sulfo-terephthalate dimethyl. The aromatic dicarboxylic acid component of (D2) may be contained alone or in polyether ester in combination of 2 or more types.

The two acid components of the component (D1) and the component (D2) are 100 mol% of the total acid component, and 95 to 50 mol% of the aromatic dicarboxylic acid component having no (D1) sulfonate group and (D2) It is preferable that it is the ratio of 5-50 mol% of the aromatic dicarboxylic acid component substituted by the sulfonate group represented by said formula (II). When the ratio of such (D2) component is less than 5 mol%, the antistatic effect may not be enough. Moreover, when (D2) component exceeds 50 mol%, a polymerization reaction will become difficult and it may become difficult to obtain polyether ester of sufficient polymerization degree, or handleability may deteriorate. The more preferable ratio of the above-mentioned (D1) component and (D2) component is (D1) 92-65 mol% and (D2) 8-35 mol%, The more preferable ratio is (D1) 90-70 mol% and (D2) 10 to 30 mol%.

Moreover, as a C2-C10 glycol for inducing (D3) which is one of the structural components of the polyether ester of D component of this invention, specifically, ethylene glycol, 1, 4- butanediol, propylene glycol, 1, 6-hexanediol, 3-methyl-1,5-pentanediol, etc. can be illustrated. Such glycol may contain an ether bond like diethylene glycol and a thioether bond like thiodiethanol.

Such glycol may be used independently and may use 2 or more types together. Among these, it is preferable to use 1, 6- hexanediol mainly from an antistatic effect, and it is more preferable to use 1, 6- hexanediol and ethylene glycol together. The preferred ratio of the 1,6-hexanediol component and the ethylene glycol component is 95 to 50 mol% of the 1,6-hexanediol component and 5 to 50 mol% of the ethylene glycol component, more preferably in 100 mol% of the glycol component. 90 to 70 mol% of 1, 6- hexanediol components and 10 to 30 mol% of ethylene glycol components.

As a poly (alkylene oxide) glycol for inducing (D4) which is one of the structural components of the polyether ester of D component, the poly (alkylene oxide) glycol mainly consisting of poly (ethylene oxide) glycol is illustrated preferably. . The poly (alkylene oxide) glycol may contain other poly (alkylene oxide) glycol, such as poly (propylene oxide) glycol.

The number average molecular weight of the (D4) poly (alkylene oxide) glycol component is preferably in the range of 200 to 50,000. When this molecular weight is less than 200, the better antistatic effect is not obtained and the advantage of using a polyether ester may not fully be exhibited. Moreover, from a practical point of view, such a molecular weight is sufficient as about 50,000. The molecular weight of the poly (alkylene oxide) glycol is preferably 500 to 30,000, more preferably 1,000 to 20,000. The poly (alkylene oxide) glycol component of (D4) may be contained alone or in polyether ester in combination of 2 or more types.

Content of (D4) component is in 100 weight% of polyether ester of D component, Preferably it is 10-50 weight%, More preferably, it is 15-45 weight%, More preferably, it exists in the range of 20-40 weight%. to be. When less than 10 weight%, the antistatic effect which is an advantage of the polyether ester of D component may not be enough, and when more than 50 weight%, the refractive index of the polyether ester of D component will become low, and it mixes with polycarbonate resin It may be difficult to obtain a molded article having high transmittance and excellent transparency.

It is preferable that the reduced viscosity (concentration 1.2 g / kPa) measured at 30 degreeC in the mixed solvent of phenol / tetrachloroethane (weight ratio 40/60) of the polyether ester of D component is 0.3 or more. If the reduced viscosity is less than 0.3, it may cause heat resistance or mechanical property deterioration. Since the upper limit with respect to a reduced viscosity is such a linear polymer, since it is a linear polymer, it is more preferable also in terms of an antistatic effect and a mechanical property, but the upper limit of actual polymerization is about 4.0. The reduced viscosity is more preferably 0.4 or more, and still more preferably 0.5 or more.

The polyether ester of the component D is obtained by heating and melting the component (D1), the component (D2), the component (D3), and the component (D4) at 150 to 300 ° C in the presence of a transesterification catalyst, followed by a polycondensation reaction. Can be. The transesterification catalyst is not particularly limited as long as it can be used in a conventional transesterification reaction. Examples of such transesterification catalysts include antimony compounds such as antimony trioxide, tin compounds such as monotin acetate, dibutyltin oxide, and dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate, Calcium compounds, such as calcium acetate, and alkali metal salts, such as sodium carbonate and potassium carbonate, etc. can be illustrated. Of these, tetrabutyl titanate is preferably used. Moreover, as the usage-amount of the said catalyst, what is necessary is just the usage-amount in normal transesterification reaction, 0.01-0.5 mol% is preferable with respect to 1 mol of acid components generally used, and 0.03-0.3 mol% is more preferable.

Moreover, it is also preferable to use antioxidant together at the time of reaction. As such antioxidant, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3- stearylthio propionate , Triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Oxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylforce Fonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxa Spiro (5,5) undecane; etc. are mentioned. As for the usage-amount of these antioxidant, 0.001-0.5 weight part is preferable with respect to 100 weight part of polyether esters of D component.

As the temperature at which the components (D1) to (D4) are heated and melted and polycondensed, the effluent is distilled off from the effluent for several minutes to several decades for an esterification reaction and / or a transesterification reaction at 150 to 200 ° C as an initial reaction. After performing, the polymerization reaction which makes a reactant high molecular weight is performed at 180-300 degreeC. If the temperature is lower than 180 ° C, the reaction is less likely to proceed, and if the temperature is higher than 300 ° C, side reactions such as decomposition tend to occur, so the above temperature range is preferable. The polymerization reaction temperature is more preferably 200 to 280 ° C, and particularly preferably 220 to 260 ° C. Although the reaction time of this polymerization reaction changes with reaction temperature and a polymerization catalyst, it is usually about tens of minutes-about several tens of hours.

(D component: polyester)

As polyester used as a D component, (D5) aromatic dicarboxylic acid component which does not have a sulfonate group, (D6) aromatic dicarboxylic acid component substituted by the sulfonate group represented by the said General formula (II), and ( D7) The polyester which consists of a C2-C10 glycol component is preferable.

As aromatic dicarboxylic acid and its ester-forming derivative which do not have a sulfonate group for deriving (D5), for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and esters thereof Formable derivatives are mentioned. Among them, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and their ester-forming derivatives are preferable. In particular, the polyester containing an isophthalic acid component and a naphthalenedicarboxylic acid component is preferable because the crystallinity of the polyester falls and as a result it becomes easy to obtain a molded article having higher transparency. Moreover, the polyester is excellent in compatibility with polycarbonate resin, and crystallization is inhibited also by the influence of a polycarbonate resin. As a result, the fall in transparency in the dry heat test has the advantage of being further improved as compared with the case of the polyether ester. Specific examples of naphthalenedicarboxylic acid and its ester-forming derivatives include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl, 2, Diethyl 6-naphthalenedicarboxylic acid, dimethyl 2,7-naphthalenedicarboxylic acid, diethyl 2,7-naphthalenedicarboxylic acid, etc. are mentioned. The hydrogen atom in the aromatic ring of these compounds may be substituted with an alkyl group, a halogen atom, or the like. The aromatic dicarboxylic acid component of (D5) may be contained in polyether ester even if it is single or in combination of 2 or more type.

The aromatic dicarboxylic acid component substituted by the sulfonate group of (D6) is represented by said Formula (II). Moreover, the specific example and the more preferable specific example are the same as that of the case of (D2) component in the polyether ester of the said D component.

The two types of acid components of the component (D5) and the component (D6) constituting the polyester of the component D are 100 mol% of the total acid component, and the aromatic dicarboxylic acid component 99.9 having no (D5) sulfonate group. It is preferable that it is the ratio of 0.1-50.0 mol% of the aromatic dicarboxylic acid component substituted with the sulfonate group represented by said Formula (II). When the ratio of such (D6) component is less than 0.1 mol%, the antistatic effect may not be enough. Moreover, when (D6) component exceeds 50.0 mol%, a superposition | polymerization reaction becomes difficult and the problem that the transparency of the polycarbonate resin composition formed is inferior arises.

Moreover, as a C2-C10 glycol for inducing (D7), specifically, ethylene glycol, 1, 4- butanediol, propylene glycol, 1, 6- hexanediol, and 3-methyl- 1, 5- pentane Diol etc. can be illustrated. Such glycol may contain an ether bond like diethylene glycol and a thioether bond like thiodiethanol.

Such glycol may be used independently and may use 2 or more types together. Of these, 1,6-hexanediol, ethylene glycol, and neopentyl glycol are preferably used from the viewpoint of securing an antistatic effect and transparency, and more preferably using neopentyl glycol and ethylene glycol together. The preferred ratio of the neopentyl glycol component and the ethylene glycol component in the polyester of the D component is 90 to 10 mol% of the neopentyl glycol component and 10 to 90 mol% of the ethylene glycol component, more preferably in 100 mol% of the glycol component. Preferably it is 80-20 mol% of neopentylglycol components, and 20-80 mol% of ethylene glycol components.

It is preferable that the polyester of D component in this invention is 0.2 or more of the reduced viscosity measured at 30 degreeC in the mixed solvent of phenol / tetrahydrofuran (weight ratio 60/40). If the reduced viscosity is less than 0.2, it may cause heat resistance or mechanical property deterioration. Since the upper limit with respect to a reduced viscosity is such a linear polymer, since it is a linear polymer, it is more preferable also in terms of an antistatic effect and a mechanical property, but the upper limit of actual polymerization is about 3.0. The reduced viscosity is more preferably 0.3 or more, and still more preferably 0.35 or more.

The polyester of the D component of the present invention can be produced by a transesterification reaction in the same manner as the polyether ester of the D component, and at the time of such preparation, may contain the antioxidant.

By using the said preferable D component, the resin composition which is remarkably excellent in molding heat resistance and a favorable color can be obtained. By more stable molding heat resistance than before, yellowing and appearance defects during molding are remarkably improved, and this effect is particularly found in molding using a large molding machine or a hot runner mold in which molten resin tends to stay.

In addition, the polyether ester and polyester which are the said preferable D component may be individual, respectively, and may mix and use 2 or more types. Although the polyether ester is excellent in antistatic property, the heat resistance and transparency is slightly inferior, while the polyester is excellent in heat resistance and transparency, but it is easy to be commercialized with polycarbonate resin, but the antistatic ability is slightly inferior. Each defect can be compensated for by combination. Therefore, according to which characteristic is emphasized among these characteristics, the appropriate D component can be selected suitably. In this invention, polyester which has a sulfonate group is especially preferable as D component from the point which provides the resin composition especially suitable for the use which places specific gravity on color and transparency.

<E component: Phosphate ester>

As phosphate ester which is E component, 1 type, or 2 or more types of phosphate ester represented by following General formula (III) is mentioned.

(Wherein X represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 A divalent group derived from a compound selected from the group consisting of -hydroxyphenyl) ketone, and bis (4-hydroxyphenyl) sulfide, n is an integer from 0 to 5, or a mixture of phosphate esters with different n numbers Is an average of 0 to 5, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently substituted or unsubstituted alkyl groups having 1 to 40 carbon atoms and having 6 to 40 carbon atoms. Monovalent group derived from a compound selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group having 6 to 40 carbon atoms)

It is preferable that the resin composition of this invention contains 1 type, or 2 or more types of phosphate ester represented by the said General formula (III). Phosphate ester gives the resin composition of this invention the outstanding color, shaping | molding heat resistance, and transparency.

Among the phosphate esters, aliphatic monophosphate esters represented by the following general formula (VI) are preferably used in view of dispersibility to the polycarbonate resin and affinity of the ultraviolet absorbent (component C).

(In formula, R <^9> , R <^10> , R <^11> respectively independently represents a hydrogen atom and a C1-C20 alkyl group.)

Examples of the aliphatic monophosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate and tris (chloropropyl) phosphate. Although trimethyl phosphate, triethyl phosphate, and tributyl phosphate are more preferable at the point which is more excellent in dispersibility, trimethyl phosphate is preferable at the point which is especially excellent in transparency.

<F component: Hindered phenolic antioxidant>

In the resin composition of this invention, in order to further stabilize the color at the time of heat processing of a molded article, a hindered phenol type antioxidant can be used further.

Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, cinafil alcohol, vitamin E and n-octadecyl-3- (3,5-di-tert-butyl-4-hydride. Oxyphenyl) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 2,6-di-tert- Butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6 -tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4, 6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop Cypionate, 1,6-hexanediolbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Bis [2-tert-butyl-4-methyl6- (3 -tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4 , 4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl 4-hydroxybenzyl) sulfide, 4,4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert- Butylphenol), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio)- 6- (4-hydroxy-3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert- Butyl-4-hydroxyhydrocinamide), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane , 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxy Oxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4 -Hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [ 3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionyloxymethyl] methane and the like. These are all easy to obtain.

Among them, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 3,9-bis {2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4 , 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanu Preference is given to tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane.

In particular, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or 3,9-bis {2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred. A hindered phenol-type antioxidant (F component) can be used individually or in combination of 2 or more types.

<G component: phosphite ester antioxidant>

Phosphoric acid ester system antioxidant (G component) can be used for the resin composition of this invention further in order to stabilize the hue and molecular weight at the time of heat processing at the time of shaping | molding process.

Examples of such phosphite ester antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, and dioctyl. Monophenylphosphite, diisopropyl monophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butyl Phenyl) octylphosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butyl Phenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearylpentaerythritoldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritoldiphosphite, phenylbisphenol A pentaerythritoldiphosphite, bis (nonylphenyl) pentaerythritoldiphosphite, dicyclohexylpentaerythritoldipotho And the like.

Moreover, as another phosphite compound, what has a cyclic structure by reacting with bivalent phenols can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl- ) Phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

Among them, tris (2,4-di-tert-butylphenyl) phosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite are particularly preferable. You may use a phosphite ester antioxidant (G component) 1 type or in mixture of 2 or more types.

<About quantity of each component>

Next, the quantity of B component-G component is demonstrated.

The amount of the component B is in the range of 0.01 to 4 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.1 to 2.8 parts by weight, still more preferably 0.5 to 2.5 parts by weight based on 100 parts by weight of the polycarbonate resin of the component A. to be. If the amount of the B component is less than 0.01 part by weight, the antistatic effect of the resin composition tends to be insufficient, and if it exceeds 4 parts by weight, the color and transparency of the molded article deteriorate, which is not preferable.

Content of C component is 0.05-3 weight part with respect to 100 weight part of polycarbonate resin of A component, Preferably it is 0.1-2.5 weight part, More preferably, it is 0.15-1.5 weight part, More preferably, it is 0.15 ˜1.5 parts by weight. If the amount of the C component is less than 0.05 part by weight, the weather resistance of the resin composition tends to be insufficient, and if it exceeds 3 parts by weight, the color and transparency of the molded article deteriorate due to the color of the C component itself, which is not preferable.

Moreover, it is preferable that the MVR rise rate of the pellet by mix | blending a C component is the quantity which satisfy | fills 10% or less. In addition, the measurement of MVR (melt volume rate) in this invention used the MVR measuring apparatus which dried the pellet at 120 degreeC for about 5 hours based on ISO 1133, and made the moisture content in the pellet into 200 ppm or less. It is a value measured on 300 degreeC and the conditions of 1.2 kgf of loads. When the MVR rise rate exceeds 10%, it may be difficult to obtain a molded article having sufficient antistatic properties. This is considered to be for the following reasons. Since the molecular weight of the ultraviolet absorber is about 1000 or less and smaller than that of polycarbonate, the temperature at which the resin composition is processed (typically 240 ° C or more) is often higher than the melting point of the ultraviolet absorber. It becomes the state disperse | distributed to liquid state. If the ultraviolet absorber is dispersed in the liquid phase, the melt viscosity of the resin composition tends to be low, so that the viscosity difference between the antistatic agent and the resin composition is small. When this viscosity difference becomes below a fixed value, it is considered that the antistatic agent is less likely to bleed out on the surface of the molded article at the time of injection molding or sheeting, which makes it difficult to obtain a molded article having sufficient antistatic property. On the other hand, even when the melting point of the ultraviolet absorber is high, plasticization of the same molten resin is sometimes expressed, which is known to make the ultraviolet absorber easy to move the polycarbonate molecular chains. Also in this case, it is thought that the case where it becomes difficult to obtain the molded article which has sufficient antistatic property similarly to the above occurs. Moreover, 7% or less is more preferable, and, as for MVR rise rate, 5% or less is still more preferable.

The amount of the component D is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, still more preferably 0.2 to 3 parts by weight based on 100 parts by weight of the polycarbonate resin of the component A. If the amount of the D component is less than 0.01 part by weight, the effect of improving molding heat resistance and antistatic property is likely to be insufficient, and if it is more than 5 parts by weight, the transparency and color of the molded article are deteriorated.

As described above, the counter ions of the low molecular weight sulfonic acid of component B and the sulfonate group of component D may be either metal ions or organic onium ions such as organic phosphonium ions. However, in consideration of transparency, color, antistatic performance and the like, it is preferable that the counter ions of the sulfonic acid component B and the sulfonate group D component consist of both organic phosphonium ions and metal ions. In both of these ratios, the metal ion to 1 mol of the organic phosphonium ion is preferably 0.02 to 2 mol, more preferably 0.03 to 1 mol, even more preferably 0.04 to 0.5 mol. Therefore, it is preferable to adjust the ratio of B component and D component, and the ratio of the organic phosphonium ion and metal ion in B component and D component so that such conditions may be satisfied. In particular, it is preferable to mix | blend the polyether ester which has sulfonic-acid metal base and / or the polyester which has sulfonic-acid metal base as a D component with polycarbonate resin so that the said ratio may be satisfied.

The amount of the component E is preferably 0.001 to 0.5 parts by weight, more preferably 0.003 to 0.5 parts by weight, still more preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin of the component A. If the amount of the component E is less than 0.001 part by weight, the effect of improving the color of the resin composition tends to be insufficient, and if it exceeds 0.5 part by weight, the impact resistance and the antistatic property deteriorate, and the molecular weight also tends to decrease, which is not preferable.

The amount of the F component is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin of the A component. If it is less than 0.01 part by weight, the color of the molten molded article obtained from the resin composition or the resin composition and the color stability during heat treatment of the molded article are likely to be insufficient. This is not preferable because it deteriorates and further causes a cost increase.

The amount of the G component is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin of the A component. If it is less than 0.01 part by weight, stabilization of color and molecular weight at the time of heat treatment during molding processing tends to be insufficient, and if it exceeds 2 parts by weight, it becomes an excess amount, so that the heat resistance of the resin composition is lowered and the color and transparency of the molded product are also deteriorated. Not desirable The weight ratio (F / G) of the F component and the G component is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, still more preferably 7/3 to 3/7.

<About other additives>

The resin composition of this invention can contain various additives normally mix | blended with a polycarbonate resin other than said A component-G component.

(Iii) Phosphorus stabilizer

In order to improve the heat stability at the time of shaping | molding process, it is preferable that various phosphorus stabilizers other than the said phosphate ester are further mix | blended with the resin composition of this invention. Phosphoric acid, phosphorous acid, tertiary phosphine, etc. are illustrated as such a phosphorus stabilizer, These phosphorus stabilizers can mix and use not only 1 type but 2 types. Such phosphorus stabilizer is preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the A component.

(Ii) antioxidants

In the resin composition of this invention, in order to further stabilize the hue at the time of heat processing of a molded article, antioxidant other than the said hindered phenol type antioxidant and a phosphite ester type antioxidant can be used.

Such other antioxidants include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthioprop Sulfur-containing stabilizers, such as cypionate, are illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotational molding. The amount of such a sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight based on 100 parts by weight of the A component.

(Ⅲ) Blueing agent

In the resin composition of this invention, it is preferable to contain 0.05-3.0 ppm (weight ratio) of a bluing agent further in a resin composition. The use of a bluing agent is very effective to give a molded article a natural transparency. A bluing agent means the coloring agent which shows blue to purple by absorbing orange to yellow light rays, and dye is especially preferable here. By blending the bluing agent, the resin composition of the present invention obtains a better color. When the amount of the bluing agent is less than 0.05 ppm, the effect of improving the color may be insufficient. On the other hand, when the amount of the bluing agent exceeds 3.0 ppm, the light transmittance is lowered, which is not suitable. The more preferable amount of bluing agent is in the range of 0.2 to 2.0 ppm in the resin composition. Representative examples of the bluing agent include Bayer's Macro Rolex Violet B and Macro Rolex Blue RR, Clariant's Polysinterrene Blue RLS, Sand's Terrasol Blue RLS, and the like.

(V) release agent

It is preferable to mix | blend a mold release agent further with the resin composition of this invention for the purpose of the improvement of the productivity at the time of the shaping | molding, and the deformation | transformation of a molded article. As such a mold release agent, a well-known thing can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene waxes, 1-alkene polymers, and the like. Modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds (polyfluoride) Fluorine oils represented by roalkyl ether), paraffin wax, beeswax and the like. Such a mold release agent is preferably 0.005 to 2 parts by weight based on 100 parts by weight of the A component. Especially, a fatty acid ester is mentioned as a preferable mold release agent.

Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. As such monohydric alcohol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, triacontanol, etc. are illustrated, for example. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In fatty acid ester, polyhydric alcohol is more preferable.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. As the aliphatic carboxylic acid, for example, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid) Saturated aliphatic carboxylic acids, such as nonadecanoic acid, behenic acid, icosanoic acid, and docoic acid, and unsaturated such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenic acid, eicosapentaenoic acid, and cetoleic acid. Aliphatic carboxylic acid is mentioned. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms.

Especially, saturated aliphatic carboxylic acid is preferable. Stearic acid and palmitic acid are particularly preferred. Since the aliphatic carboxylic acids such as stearic acid and palmitic acid are usually made of natural fats and oils such as animal fats and oils represented by tallow and lard, and vegetable oils such as palm oil and sunflower oil, these aliphatic carboxylic acids are usually carbon atoms. It is a mixture containing different carboxylic acid components with different numbers. Therefore, also in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids, especially stearic acid and palmitic acid, which are made of such natural fats and oils and are in the form of a mixture containing other carboxylic acid components, are preferably used.

The fatty acid ester may be any of partial esters and all esters (full esters). However, in partial ester, since a hydroxyl value becomes high normally and it is easy to cause decomposition | disassembly of resin at the time of high temperature, it is more preferably full ester. In view of thermal stability, the acid value in the fatty acid ester is preferably 20 or less, more preferably in the range of 4 to 20, still more preferably in the range of 4 to 12. In addition, the acid value may take substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. In addition, the iodine number is preferably 10 or less. In addition, the iodine number may take substantially zero. These characteristics can be calculated | required by the method prescribed | regulated to JISK0070.

Content of a mold release agent is based on 100 weight part A components, Preferably it is 0.005-2 weight part, More preferably, it is 0.01-1 weight part, More preferably, it is 0.05-0.5 weight part. In such a range, the resin composition has good release property and rollability. In particular, these amounts of fatty acid esters provide a resin composition having good release properties and irrolability without compromising good color or transparency.

(Iii) dyestuffs

The resin composition of this invention can provide the molded article which contains various salt pigments further and expresses various designability. The resin composition of this invention is very preferable in the use which permeate | transmits light from the point which is excellent in transparency. Therefore, for example, by blending a fluorescent brightener, by providing a higher light transmittance and natural transparency to the resin composition of the present invention, and by combining a fluorescent brightener or a fluorescent dye that emits light other than that, by utilizing a light emitting color It is possible to give a good design effect. Furthermore, the resin composition which has the formation of subtle coloring by a very small amount of dye pigments, and high transparency can also be provided.

Examples of the fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, and xane. Ten fluorescent dyes, xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Of these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and have little deterioration in the molding process of the polycarbonate resin.

As dyes other than the said bluing agent and fluorescent dye, ferrocyanide, perinone dye, quinoline dye, such as a perylene type dye, a coumarin type dye, a thioindigo type dye, an anthraquinone type dye, a thioxanthone type dye, and a blue wire , Quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Moreover, the resin composition of this invention can mix | blend a metallic pigment and can obtain a more favorable metallic color. As a metallic pigment, what has a metal film or a metal oxide film in various plate-shaped fillers is preferable. 0.00001-1 weight part is preferable on the basis of 100 weight part A component, and, as for content of the said dye pigment, 0.00005-0.5 weight part is more preferable.

(Iv) other heat stabilizers

You may mix | blend other heat stabilizers other than the said phosphorus stabilizer and a hindered phenol type antioxidant with the resin composition of this invention. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably in combination with both. Such other thermal stabilizers include, for example, lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of these stabilizers JP-A-H7-233160) is preferably exemplified. Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compounds can be used. Moreover, the stabilizer which mixed this compound, various phosphite compounds, and a hindered phenol compound is marketed. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Also in this invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, and more preferably 0.001 to 0.03 parts by weight based on 100 parts by weight of the A component.

(Iii) a compound having heat ray absorption ability

The resin composition of this invention can contain the compound which has a heat ray absorption ability. The resin composition in which such a compound is compounded can suppress the high temperature of a room. Such a resin composition is especially preferable in the use of the vehicle resin window glass and the resin window glass. Such compounds include near-infrared absorbing ability of phthalocyanine-based near-infrared absorbers, ATO, ITO, iridium oxide and metal oxide-based near-infrared absorbers such as ruthenium oxide and tungsten oxide, and metal boride-based near infrared absorbers such as lanthanum boride, cerium boride and tungsten boride. These excellent various metal compounds and a carbon filler are illustrated preferably. As such a phthalocyanine type near-infrared absorber, MIR-362 by Mitsui Chemicals Co., Ltd. is commercially available and can be obtained easily. Examples of carbon fillers include carbon black, graphite (both natural and artificial, and also whiskers), carbon fibers (including those by vapor phase growth), carbon nanotubes, and fullerenes, and the like. Are carbon black and graphite. These can be used individually or in combination of 2 or more types. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, further preferably 0.001 to 0.07 parts by weight based on 100 parts by weight of the A component. In the resin composition of this invention, the range of 0.1-200 ppm (weight ratio) is preferable, and, as for content of a metal oxide type | system | group near-infrared absorber, a metal boride type | system | group near-infrared absorber, the range of 0.5-100 ppm is more preferable. .

(Iii) light diffusing agents

Since the resin composition of this invention is excellent in transparency and a hue, it becomes a resin composition which has favorable hue and light-diffusion by mix | blending a light-diffusion agent further. Examples of such light diffusing agents include polymer microparticles (preferably acrylic crosslinked particles and silicon crosslinked particles having a particle diameter of several micrometers), inorganic particles having low refractive index, and composites thereof. The shape is exemplified by a spherical shape (not necessarily a complete sphere, including those that are deformed), a disk shape, a columnar shape (including a cube), an irregular shape, and the like. A light-diffusing agent is preferable from the point which a spherical form is common and it is easy to obtain, and the particle diameter is so preferable that it is uniform. The amount of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the polycarbonate resin of the component A. In addition, a light diffusing agent can use 2 or more types together.

(Ⅸ) White pigment for optical high reflectance

Since the resin composition of this invention is excellent in transparency and a hue, it becomes a resin composition which has favorable hue and light reflectivity by mix | blending a light highly reflecting white pigment further. As the white pigment, titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicon) is particularly preferable. 1-25 weight part is preferable with respect to 100 weight part of polycarbonate resins of A component, and, as for the quantity of such optically reflective white pigment, 2-20 weight part is more preferable. In addition, a white pigment for optical high reflectance can use 2 or more types together.

(Ⅹ) flame retardant

Various compounds known as flame retardants for polycarbonate resins may be blended into the resin composition of the present invention.

Such flame retardants include (i) organometallic salt flame retardants other than the component B (for example, organic sulfonic acid alkali (soil) metal salts, boric acid metal salt flame retardants, tartaric acid metal salt flame retardants, and the like); Flame retardants, and (i) halogen flame retardants (e.g., brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (including oligomers), brominated polyacrylates, chlorinated polyethylenes, and the like).

(Iii-i) Organometallic Salt Flame Retardant

The organometallic salt-based flame retardant is advantageous in that heat resistance is almost maintained, and the antistatic property can be imparted at all. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound composed of an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of metal ions. As a more preferable specific example, the metal salt of fluorine-substituted organic sulfonic acid, the metal salt of fluorine-substituted organic sulfate ester, and the metal salt of fluorine-substituted organic phosphate ester are illustrated. A fluorine-containing organometallic salt compound can be used 1 type or in mixture of 2 or more types. Among them, metal salts of fluorine-substituted organic sulfonic acid are particularly preferred, and metal salts of sulfonic acid having a perfluoroalkyl group are particularly preferred. The range of 1-18 is preferable, as for carbon number of a perfluoroalkyl group, the range of 1-10 is more preferable, More preferably, it is the range of 1-8.

The metal constituting the metal ions of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metals include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. The preferred organometallic salt based flame retardant is therefore an alkali metal salt of perfluoroalkylsulfonic acid. Among these alkali metals, rubidium and cesium are preferred when the transparency is higher, while they are not general purpose and difficult to be purified, resulting in disadvantages in terms of cost. On the other hand, although it is advantageous in terms of cost and flame retardancy, lithium and sodium may be disadvantageous in terms of transparency. In view of these, alkali metals in the alkali metal salt of perfluoroalkylsulfonic acid can be used separately, but potassium perfluoroalkylsulfonic acid salt having excellent balance of properties is most preferred in all respects. You may use together the potassium salt and the perfluoroalkyl sulfonic-acid alkali metal salt which consists of another alkali metal.

Examples of such perfluoroalkyl sulfonic acid alkali metal salts include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, and perfluorobutane. Sodium sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonic acid Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, rubidium perfluorohexane sulfonate, and the like. These can be used 1 type or in combination or 2 or more types. Among them, potassium perfluorobutane sulfonate is particularly preferable.

The content of the fluorine-containing organometallic salt is preferably 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less, as measured by ion chromatography. The lower the fluoride ion content, the better the flame retardancy and the light resistance. Although the minimum of content of a fluoride ion can be made substantially 0, about 0.2 ppm is preferable practically from the balance of refinement | equation number and an effect. The perfluoroalkylsulfonic acid alkali metal salt of such fluoride ion content is refine | purified as follows, for example. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion exchanged water at 2 to 10 times the weight of the metal salt in the range of 40 to 90 ° C (more preferably 60 to 85 ° C). The perfluoroalkylsulfonic acid alkali metal salts are prepared by neutralizing perfluoroalkylsulfonic acid with carbonates or hydroxides of alkali metals or by neutralizing perfluoroalkylsulfonylfluorides with carbonates or hydroxides of alkali metals (more Preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 M? · Cm or more. The liquid which melt | dissolved the metal salt is stirred at the said temperature for 0.1 to 3 hours, More preferably, 0.5 to 2.5 hours. Then, the liquid is cooled to 0-40 degreeC, More preferably, it is 10 to 35 degreeC. Crystals precipitate by cooling. The precipitated crystals are taken out by filtration. This produces a preferred purified perfluoroalkylsulfonic acid alkali metal salt.

The compounding quantity of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, still more preferably 0.008 to 0.13 parts by weight based on 100 parts by weight of the A component. In such a preferable range, the effect (for example, flame retardance, antistatic property, etc.) anticipated by mix | blending a fluorine-containing organometallic salt is exhibited, and also the bad influence on the light resistance of a resin composition is reduced.

(Iii-ii) Silicone Flame Retardant

The silicone compound used as a silicone type flame retardant improves flame retardancy by the chemical reaction at the time of combustion. As the compound, various compounds conventionally proposed as flame retardants of aromatic polycarbonate resins can be used. The silicone compound is believed to impart a flame retardant effect to the polycarbonate resin by forming a structure by itself or by combining with a component derived from the resin at the time of combustion, or by a reduction reaction at the time of forming the structure. . Therefore, it is preferable to contain the group with high activity in such a reaction, and it is preferable to contain the predetermined amount at least 1 sort (s) of group chosen from the alkoxy group and the hydrogen (namely, Si-H group) more specifically. As content rate of such group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, The range of 0.12-1 mol / 100g is more preferable, 0.15-0.6 mol / 100 The range of g is more preferable. This ratio is calculated | required from the alkali decomposition method by measuring the quantity of hydrogen or alcohol which generate | occur | produced per unit weight of a silicone compound. In addition, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is comprised by arbitrarily combining four types of siloxane units shown below. In other words,

M _{unit: (CH 3) 3 SiO 1} /2, H (CH 3) 2 SiO 1/2, H 2 (CH 3) SiO 1/2, (CH 3) 2 (CH 2 = CH) SiO 1/2 _{, (CH 3) 2 (C} 6 H 5) SiO 1/2, (CH 3) (C 6 H 5) (CH 2 = CH) SiO 1/2 1 , such as functional siloxane units,

D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ = CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units, such as

T _{units: (CH 3) SiO 3/} 2, (C 3 H 7) SiO 3/2, HSiO 3/2, (CH 2 = CH) SiO 3/2, (C 6 H 5) SiO 3/2 , etc. , Trifunctional siloxane units,

Q unit: tetrafunctional siloxane unit is represented by SiO _2.

The structure of the silicone compound used for a silicone type flame retardant is specifically, as a _formula , D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _m D _n Q _q , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , D _n T _p Q _q . Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , M _m D _n Q _q , and more preferably, M _m D _n or M _m D _n T _p .

Here, the coefficients m, n, p, q in the above-mentioned formula are integers of 1 or more indicating the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferable range is, the better the flame retardancy is. Moreover, as mentioned later, in the silicone compound containing a predetermined amount of aromatic groups, it is excellent also in transparency and a hue.

In addition, when any of m, n, p, and q is two or more numerical values, the siloxane unit with the coefficient can be two or more types of siloxane units from which the hydrogen atom to which it couples, or an organic residue differs.

The silicone compound may be linear or may have a branched structure. Moreover, it is preferable that the organic residue couple | bonded with a silicon atom is an organic residue of C1-C30, More preferably, it is 1-20. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl group . More preferably, they are a C1-C8 alkyl group, alkenyl group, or an aryl group. As an alkyl group, especially C1-C4 alkyl groups, such as a methyl group, an ethyl group, and a propyl group, are preferable.

Moreover, it is preferable that the silicone compound used as a silicone type flame retardant contains an aryl group. More preferably, the ratio (aromatic group amount) in which the aromatic group represented by the following general formula (i) is contained is 10 to 70 weight% (more preferably 15 to 60 weight%).

(In formula (X), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. In the formula (X), when n is 2 or more, Each can take a different kind of X)

The silicone compound used as the silicone-based flame retardant may contain a reactor in addition to the Si-H group and the alkoxy group. Examples of such a reactor include an amino group, a carboxyl group, an epoxy group, a vinyl group, a mercapto group, and a methacryloxy group. Etc. are illustrated.

As a silicone compound which has a Si-H group, the silicone compound containing at least 1 or more types of structural units represented by the following general formula (VIII) and (VIII) is illustrated preferably.

(Formula (Ⅷ) and formula (Ⅸ) of, Z ¹ ~ Z ³ represents a compound represented by a monovalent organic residue, or the following general formula (Ⅹ) a hydrogen atom, a group having 1 to 20 carbon atoms independently. Α ¹ ~ α ³ each independently represents 0 or 1. m1 represents an integer of 0 or 1. In addition, in the formula (iii), the repeating units in the case where m1 is 2 or more may each have a plurality of different repeating units).

(In formula (i), Z ⁴ to Z ⁸ each independently represent a hydrogen atom and a monovalent organic residue having 1 to 20 carbon atoms. Α ⁴ to α ⁸ each independently represent 0 or 1. M2 is 0 or An integer greater than or equal to 1. In addition, in Formula (i), the repeating unit in case m2 is 2 or more can take several different repeating unit, respectively.)

In the silicone compound used for a silicone type flame retardant, at least 1 sort (s) of compound chosen from the compound represented by general formula (XI) and general formula (XII) is mentioned as a silicone compound which has an alkoxy group, for example.

(In formula (XI), (beta) ¹ represents a vinyl group, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, and a C6-C12 aryl group and an aralkyl group. (Gamma) ¹ , (gamma) ² , (gamma) ^3). , γ ^4, γ ^5, and γ ⁶ represents an aryl group and an aralkyl group having 1 to 6 carbon alkyl group and a cycloalkyl group and having 6 to 12, at least one group is an aryl group or an aralkyl group. δ ^1, δ ² and δ ³ represent an alkoxy group having 1 to 4 carbon atoms)

(Formula (XII) of, β ² and β ³ represents an aryl group and an aralkyl group of vinyl groups, having 1 to 6 carbon alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number of 6 to 12. Γ ^7, γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ¹³ and γ ¹⁴ represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least 1 Groups are an aryl group or an aralkyl group, δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms)

(x-iii) halogen-based flame retardants

As the halogen flame retardant, brominated polycarbonate (including oligomer) is particularly preferable. Brominated polycarbonate is excellent in heat resistance and can greatly improve flame retardancy. As for the brominated polycarbonate used by this invention, the structural unit represented by the following general formula (XIII) is at least 60 mol%, Preferably it is at least 80 mol% of all the structural units, Especially preferably, it is substantially the following general formula (XIII) It is a brominated polycarbonate compound which consists of a structural unit represented by).

(Formula (XIII), X is a bromine atom, R is an alkylidene group or -SO ₂ C 1 -C 4 alkylene group, having from 1 to 4 carbon atoms of - a)

In the formula (XIII), preferably R represents a methylene group, an ethylene group, an isopropylidene group, -SO _2- , and particularly preferably an isopropylidene group.

The brominated polycarbonate has few terminal chloroformate groups remaining, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. This amount of terminal chlorine dissolves a sample in methylene chloride, adds 4- (p-nitrobenzyl) pyridine to react with terminal chlorine (terminal chloroformate), and this is an ultraviolet visible spectrophotometer (U-3200 manufactured by Hitachi, Ltd.). It can be measured and obtained by. If the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the resin composition becomes more favorable, and high temperature shaping | molding is attained, As a result, the resin composition excellent in molding processability is provided.

Furthermore, it is preferable that the brominated polycarbonate has few residual hydroxyl groups. More specifically, it is preferable that the amount of terminal hydroxyl groups is 0.0005 mol or less with respect to 1 mol of structural units of a brominated polycarbonate, More preferably, it is 0.0003 mol or less. The amount of terminal hydroxyl groups can be calculated | required by dissolving a sample in heavy chloroform and measuring by <^1> H-NMR method. The amount of such terminal hydroxyl groups is preferable because the thermal stability of the resin composition is further improved.

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the formula for calculating the specific viscosity used when calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention described above.

(xi) anti-drip agent

The resin composition of this invention can contain a dripping inhibitor. By using such anti-dripping agent in combination with the flame retardant, better flame retardancy can be obtained. Examples of such antidropping agents include fluorine-containing polymers having fibril-forming ability, and such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene. Copolymers), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins prepared from fluorinated diphenols, and the like, but preferably polytetrafluoroethylene (hereinafter sometimes referred to as PTFE). to be.

Polytetrafluoroethylene (fibrillated PTFE) having fibril forming ability has a very high molecular weight and exhibits a tendency to bond PTFE to fibers by external action such as shear force. The number average molecular weight is in the range of 1.5 million to ten million. This lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 degreeC, as disclosed in Unexamined-Japanese-Patent No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, and preferably in the range of 10 ⁸ to 10 ¹² poise.

In addition to the solid form, such PTFE can also be used in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability may use a PTFE mixture in a mixed form with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties. In addition, as disclosed in Japanese Unexamined Patent Application Publication No. Hei 6-145520, the fibrillated PTFE is used as a core, and a structure having a low molecular weight polytetrafluoroethylene as an angle is also used. It is preferably used.

Commercially available products of fibrillated PTFE include Teflon (registered trademark) 6J manufactured by Mitsui-Dupont Floro Chemical Co., Ltd., Polypron MPA FA500, Daikin Chemical Industries, Ltd., F-201L, and the like. . As a commercial item of the aqueous dispersion of the fibrillated PTFE, Fluon AD-1, AD-936, manufactured by Asahi Aishi Floro Polymers, Inc., Fluon D-1, manufactured by Daikin Industries Co., Ltd. And Teflon (registered trademark) 30J manufactured by Mitsui DuPont Floro Chemical Co., Ltd. are mentioned as a representative.

As a fibrillated PTFE in a mixed form, (1) a method of coprecipitation by mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer to obtain a coagulated mixture (JP-A-60-258263 Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (method disclosed in Japanese Patent Laid-Open No. 4-272957), (3) A method of uniformly mixing an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution, and simultaneously removing each medium from this mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Laid-Open No. 08-08). 188653 or the like), (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE (method disclosed in JP-A-9-95583), and (5) the number of PTFE After homogeneously mixing the dispersion liquid and the organic polymer dispersion liquid, a polymer obtained by polymerizing a vinyl monomer in the mixed dispersion liquid and then obtaining a mixture can be used (the method described in JP-A-11-29679). have. Commercially available products of these blended fibrillated PTFE include `` Meta Bren A3700 '' (brand name) and `` Meta Bren A3800 '' (brand name) manufactured by Mitsubishi Rayon Co., Ltd., and `` BLENDEX B449 '' manufactured by GE Specialty Chemicals Co., Ltd. ) And the like.

In order to utilize the favorable color and transparency of the resin composition of this invention more effectively, it is preferable that the said fibrillated PTFE is undispersed as much as possible. As a means of achieving this microdispersion, the fibrillated PTFE in mixed form is advantageous. In addition, a method of directly supplying an aqueous dispersion form in the melt kneader is also advantageous for the microdispersion. However, in the form of an aqueous dispersion, it is necessary to consider that the color deteriorates slightly. As a ratio of the fibrillated PTFE in a mixed form, 10 to 80 weight% of fibrillated PTFE is preferable in 100 weight% of such mixtures, More preferably, it is 15 to 75 weight%. When the proportion of the fibrillated PTFE is in this range, good dispersibility of the fibrillated PTFE can be achieved.

The content in the resin composition of the fibrillated PTFE is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight based on 100 parts by weight of the A component.

(xii) acidity regulators

The acidity modifier which consists of a low molecular weight or a polymeric carboxylic acid compound and an anhydrous carboxylic acid compound can be mix | blended with the resin composition of this invention. The B component and the D component, particularly the B component, are usually decomposed at least in the temperature range where the polycarbonate resin is melt processed by a thermal decomposition reaction or an oxidation reaction. In addition, in the by-products generated by the decomposition reaction, there are coloring matters and substances which cause side reactions with the polycarbonate resin, so that when the product is melted by heat melting or heat history occurs in the molded article, color deterioration or molecular weight decrease due to discoloration of the molded article Etc. may occur. Color deterioration, molecular weight reduction, etc. are more likely to occur at a higher temperature, but in particular, since the nucleophilic reaction to the sulfonic acid group tends to occur easily in a basic atmosphere, it is considered that decomposition of these antistatic agents occurs easily. In order to suppress such decomposition | disassembly, the method of adjusting an acidity of resin by adding an acidity regulator to a resin composition as mentioned above is preferable. The acidity modifier is a compound having pk (log of the reciprocal of the dissociation constant of the acid) in the weakly acidic region, and the preferred range of pk is 4 to 7, particularly preferably 4.5 to 5.5. As the low-molecular acidity modifier, aliphatic monocarboxylic acids such as acetic acid, propionic acid, palmitic acid, stearic acid, and arachidic acid, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid, acetic anhydride, and succinic anhydride Acid anhydrides of aliphatic carboxylic acids, such as aromatic monocarboxylic acids, such as benzoic acid, aromatic dicarboxylic acids, such as isophthalic acid, etc. are illustrated. Examples of the acidity modifier on the polymer include styrene-acrylic acid copolymers, styrene-maleic anhydride copolymers, and the like. Such carboxylic acid compounds and anhydrous carboxylic acid compounds not only act on suppression of the nucleophilic decomposition reaction, but also may be stabilized by forming ester-like structures with benzenesulfonic acid derivatives, which are considered as decomposition by-products of the antistatic agent. It is thought that there is also an effect of suppressing decomposition of the polycarbonate resin and the antistatic agent due to side reactions. 0.0001-1 weight part is preferable with respect to 100 weight part of A components, and, as for the quantity of an acidity regulator, 0.001-0.5 weight part is more preferable. By mix | blending an acidity regulator, the resin composition of this invention can exhibit the favorable characteristic made into the objective also in the high temperature shaping | molding conditions.

(xiii) reinforced filler

Various fillers known as reinforcing fillers can be blended with the resin composition of the present invention. Since the resin composition of this invention has favorable color and transparency, a resin composition with favorable color can be obtained by mix | blending an appropriate reinforcement filler. As such a reinforcing filler, a silicate mineral filler or a glass filler with high whiteness is preferable. Such silicate mineral fillers are preferably exemplified by talc, muscobite mica, synthetic fluorine mica, smectite, and wollastonite. Glass-based fillers include glass fibers, glass flakes, glass milled fibers, and the like. The silicate mineral filler and the glass filler can also use fillers coated with metal oxides such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide on their surfaces.

The reinforcing filler may be surface-treated with various surface treatment agents in advance. Such surface treating agents include silane coupling agents (including alkylalkoxysilanes, polyorganohydrogensiloxanes, and the like), higher fatty acid esters, acid compounds (eg, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic anhydride). And the like) and may be surface treated with various surface treatment agents such as wax. Moreover, it may be granulated with various resins, higher fatty acid esters, and binding agents, such as a wax, and may be granular.

The reinforcing filler can be blended as an upper limit of 100 parts by weight based on 100 parts by weight of the A component. This upper limit is preferably 25 parts by weight, more preferably 20 parts by weight.

(xiv) other components other than the above

In the resin composition and the molded article of the present invention, other thermoplastic resins and inorganic phosphors (for example, aluminate as a mother crystal) are used in the range not impairing the object of the present invention in addition to the components B to G and the components described above. Various well-known resin additives, such as a fluorescent substance), a flow modifier, a crystal nucleating agent, an inorganic and organic antibacterial agent, a photocatalytic antifouling agent (for example, fine particle titanium oxide, a fine particle zinc oxide), and a photochromic agent, may be contained.

As another thermoplastic resin, For example, polyester resins (except D component), such as polyethylene terephthalate and polybutylene terephthalate, a polyamide resin, a polyimide resin, a polyetherimide resin, a polyurethane resin, and a silicone resin Polyolefin resins such as polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyethylene, polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), resins, such as a polymethacrylate resin, a phenol resin, and an epoxy resin, are mentioned. As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core shell elastomer MBS (methacrylic acid) Methyl / styrene / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, etc. are mentioned.

<About the manufacturing method of the resin composition>

In manufacture of the resin composition of this invention, the manufacturing method is not specifically limited. However, in the molded article, since it is important that the antistatic agent is homogeneously dispersed in the polycarbonate resin, the resin composition of the present invention is preferably produced by melt kneading the A component to the G component and other components. As a specific method of melt kneading, a Banbury mixer, a kneading roll, an extruder, etc. are mentioned. Especially, an extruder is preferable at the point of kneading | mixing efficiency, and multi-screw extruders, such as a twin screw extruder, are preferable. The more preferable aspect in such a twin screw extruder is as follows. The screw shape can use 1 set, 2 sets, and 3 sets of screw screws, and can use especially the 2 set screw which has a wide application range of both the conveyance ability of a molten resin, and shear kneading ability. 20-45 are preferable and, as for ratio (L / D) of the length L of a screw in a twin screw extruder, and the diameter D, 28-42 are preferable. The larger the L / D is, the easier the homogeneous dispersion is. On the other hand, if the L / D is too large, decomposition of the resin is likely to occur due to thermal degradation. It is necessary for the screw to have one or more kneading zones composed of kneading disc segments (or kneading segments corresponding thereto) for enhancing kneading, and preferably one to three kneading zones. Moreover, as an extruder, what has a vent which can degas | moisture the water in a raw material and the volatile gas which arises from molten kneading resin can be used preferably. From the vent, a vacuum pump is preferably provided for efficiently discharging the generated water or the volatile gas to the outside of the extruder. In addition, a screen for removing foreign matters and the like mixed in the extrusion raw material may be provided in the zone in front of the extruder die portion to remove foreign matters from the resin composition. Such screens include wire mesh, screen changers, sintered metal plates (disc filters, etc.) and the like.

Moreover, although the supply method of the antistatic agent to the extruder is not specifically limited, Since the antistatic agent used in this invention may be a comparatively viscous liquid, in such a case, the following method is also preferable. (Iii) A method of heating the antistatic agent to lower the viscosity and supplying the extruder with good accuracy using a liquid pouring device. (Ii) A method of pre-mixing the antistatic agent and the polycarbonate resin powder using a mixer such as a Henschel mixer (including a super mixer) and then feeding the extruder. (Iii) A method of master pelletizing by melt-kneading an antistatic agent and a polycarbonate resin in advance. One of the methods of the above (ii) is a method of premixing all necessary raw materials and feeding the extruder. Another method is a method of preparing a master agent in which an antistatic agent is mixed at a high concentration, pre-mixing the master agent independently or further with the remaining polycarbonate resin, etc., and then feeding the extruder. In addition, the master agent may be selected from powder form and compression granulation of the powder or both. Other premixing means also include, for example, a Nauter mixer, a V-type blender, a Henschel mixer (including a super mixer), a mechanochemical device, and an extrusion mixer, but with a high speed stirring type such as a Henschel mixer. Mixers are preferred. Moreover, another premixing method is a method of removing the solvent, for example, after making polycarbonate resin and an antistatic agent into the solution which disperse | distributed uniformly in the solvent.

The resin extruded from the twin-screw extruder can be directly cut and pelletized, or after forming the strands, these strands are pelletized by cutting with a pelletizer. Since the resin composition of this invention has antistatic property, the ratio to which dust adheres to the pellet is reduced. However, when it is necessary to further reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder. The extruded resin as described above is directly cut and pelletized, or after forming the strand, the strand is cut and pelletized by a pelletizer. The shape of the obtained pellets can take general shapes such as cylinders, prisms, and spheres, more preferably cylinders. The diameter of this cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.3 mm. On the other hand, the length of a cylinder becomes like this. Preferably it is 1-30 mm, More preferably, it is 2-5 mm, More preferably, it is 2.5-3.5 mm.

<Molded article consisting of the resin composition of the present invention>

The resin composition of this invention obtained as mentioned above can manufacture various products by injection-molding the pellet manufactured as mentioned above normally. In such injection molding, in addition to the usual molding method, depending on the purpose, injection compression molding, injection press molding, gas assist injection molding, foam molding (including by injection of supercritical fluid), insert molding, in-molding Molded articles can be obtained using injection molding methods such as de-coated molding, adiabatic mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra-fast injection molding. The advantages of these various molding methods are already well known. Molding can also be selected for both cold runner and hot runner methods. Moreover, the resin composition of this invention can also be used in the form of various release extrusion molded articles, a sheet | seat, a film, etc. by extrusion molding. In addition, the inflation method, the calender method, the casting method, etc. can also be used for shaping a sheet | seat and a film. Moreover, it can also shape | mold as a heat shrink tube by applying a specific extending | stretching operation. Moreover, the resin composition of this invention can also be made into a molded article by rotating molding, blow molding, etc.

Thereby, the molded article which maintained transparency, heat resistance, and mechanical strength which polycarbonate resin has is provided. That is, according to the present invention, 0.01 to 4 parts by weight of B component, 0.05 to 3 parts by weight of C component, more preferably 0.01 to 5 parts by weight of D component, and even more preferably 0.001 parts by weight of 100 parts by weight of A component. The molded article which melt-molded the resin composition which mix | blends -0.5 weight part, 0.01-2 weight part of F components, and 0.01-2 weight part of G components is provided.

According to the present invention, 0.01 to 4 parts by weight of B component, 0.05 to 3 parts by weight of C component, 0.01 to 5 parts by weight of D component, 0.001 to 0.5 parts by weight of E component and 0.01 to 2 parts by weight of F component The molded article which is remarkably excellent in the color which melt-molded the resin composition formed by mix | blending 0.01-2 weight part of G components and 0.05-3.0 ppm (weight ratio) bluing agent in a resin composition is provided.

As mentioned above, the resin composition of this invention is excellent in color and transparency, and as a result, the molded article of very favorable color and transparency can be obtained. More specifically, in the 2 mm-thick smooth plate which consists of the resin composition of this invention and has an arithmetic mean roughness (Ra) of 0.03 micrometer or less, haze measured by JISK7105 is 0.1 to 1% (more Preferably, the resin composition which satisfy | fills 0.1 to 0.5%) is provided.

Moreover, the smooth flat plate of thickness 2mm which has an arithmetic mean roughness (Ra) of 0.03 micrometer or less is state-controlled for 1 week in the environment of the temperature of 23 degreeC, and 50% of the relative humidity, and the temperature of 23 degreeC and a relative on a static one-meter. The resin composition which satisfies that the half life measured on conditions of 50% of humidity, 10 kPa of applied voltages, and 20 mm of electrode-samples is 500 second or less, Preferably it is 300 second or less, More preferably, it is 200 second or less.

Moreover, the resin composition which further satisfies that the YI value computed by measuring the 2 mm-thick molded board shape | molded at the cylinder temperature of 320 degreeC and the mold temperature of 80 degreeC from this resin composition based on ASTME1925 is the range of 0-3. This is provided. The resin composition which can provide the molded article which has such a haze value, withstand voltage half life, and YI value has very favorable transparency, antistatic property, and color, and is especially preferable for a head lamp lens or other automotive transparent members. Therefore, the molded article of the present invention not only has excellent mechanical properties such as impact resistance, but also has excellent quality in texture.

Examples of the molded article of the present invention include various transparent parts for vehicles (head lamp lens, winker lamp lens, tail lamp lens, resin window glass, meter cover, etc.), and transparent parts for organic devices (such as pachinko corrugators and game machines). And electronic circuit board covers and bases thereof, transparent sheet-like members (including film members), for example, resin window glass (especially for construction such as double chassis resin window glass), solar cell covers, lenses for display devices, and outdoor mirrors. , A cover of a vending machine, a cover for a flat display device, a touch panel, and the like), a lamp cover, and the like.

Moreover, various surface treatment can be given to the molded article which consists of the resin composition of this invention. Surface treatment here means forming a new layer on the surface layer of resin molded products, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dip plating, etc.), coating, coating, and printing, The method used for the conventional aromatic polycarbonate resin can be applied. Specific examples of the surface treatment include various surface treatments such as a hard coat, a water / oil repellent coat, an ultraviolet absorbent coat, an infrared absorber coat, and metallization (deposition, etc.). Hard coats are particularly preferred and are also a necessary surface treatment.

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

(B) 0.01 to 4 parts by weight of a low molecular weight sulfonate (component B), and

(C) UV absorber (component C) As a method of improving the weather resistance of the resin composition containing 0.05 to 3 parts by weight,

As the C component, it is at least one compound selected from the group consisting of a benzotriazole compound, a benzotriazine compound, a benzoxazine compound, a 2-cyanoacrylic acid compound, and a benzophenone compound, and TGA (thermogravimetric) The method characterized by using the compound whose 10% weight loss temperature in an analysis) is 280 degreeC or more.

Example

Embodiments of the present invention, which the present inventors consider to be the best at present, are those which have collected the preferred ranges of the above requirements. For example, the representative examples thereof are described in the following Examples. Of course, this invention is not limited to these forms.

An Example is given to the following and this invention is further demonstrated to it. In addition, the part in an Example is a weight part and% is weight% unless there is particular notice. In addition, evaluation was performed by the following method.

(I) Evaluation of UV Absorber

(I-I) 10% weight loss temperature: a thermogravimetric analyzer (TA) in accordance with JIS K 7120 after storing the powdery ultraviolet absorber for one week in the presence of drying silica gel in a desiccator and adjusting the condition. The TGA2950 Thermogravimetric Analyzer (manufactured by Instruments Co., Ltd.) was heated and measured in a temperature range from room temperature (23 ° C) to 900 ° C at a temperature increase rate of 20 ° C / min in a nitrogen gas atmosphere. The 10% weight loss temperature is the temperature at which 10% weight loss of the ultraviolet absorbent is observed. The higher the 10% weight reduction temperature, the higher the heat resistance of the ultraviolet absorber.

(II) Evaluation of Resin Composition

(II-I) Antistatic property: A smooth flat test piece having a length of 50 mm × width of 50 mm × thickness of 2.0 mm and arithmetic mean roughness (Ra) of 0.03 μm on a surface at a temperature of 23 ° C. and a relative humidity of 50%. After storing for one week and performing condition adjustment, the large-voltage half-life of these test pieces was measured with the static onest meter (The Shido-do static electricity company H-0110), and antistatic property was evaluated. The measurement was performed under conditions of a temperature of 23 ° C., a relative humidity of 50%, an applied voltage of 10 Hz, and an electrode-sample distance of 20 mm. The smaller the value of the large voltage half-life, the better the antistatic performance.

(II-II) Color (YI value): Spectroscopic formula of a smooth flat plate having a length of 50 mm × width of 50 mm × thickness of 2.0 mm and arithmetic mean roughness (Ra) of the surface of 0.03 μm. The transmitted light of the C light source and the 2 degree field of vision was measured using the colorimetric color-difference TC-1800 MK-II type | mold, and it computed from these X, Y, and Z values using the following formula based on ASTM-D1925. The larger the YI value, the stronger the yellow group of the molded plate is.

YI = [100 (1.28X-1.06Z)] / Y

(II-III) Weather resistance: A test plate on a smooth flat plate having a length of 50 mm × width of 50 mm × thickness of 2.0 mm and arithmetic mean roughness (Ra) of 0.03 μm on the surface of the sunshine weather meter (Suga Tester Co., Ltd. 300 Sunshine) Weather meter S300 type) was used. The difference (ΔYI value) between the color (YI) and the color (YI) before treatment was calculated after treatment for 2000 hours in a total 120-minute cycle of black panel temperature 63 ° C., 50% relative humidity, 18 minutes water spray and 102 minutes without spray. . Smaller ΔYI values indicate better weather resistance. The color of the test piece after weathering treatment was evaluated using the same method as the above (II-II).

ΔYI = YI (after weathering)-YI (before weathering)

(II-IV) Molding heat resistance: The difference (ΔYI value) between the color (YI) of the test piece obtained by continuous molding and the color (YI) of the test piece obtained by molding after the resin stayed in the molding machine cylinder for 10 min. Smaller ΔYI values indicate better molding heat resistance. The color of the test piece obtained by retention molding was evaluated using the same method as the above (II-II).

ΔYI = YI (stayed molded part)-YI (continuous molded part)

(II-V) Transparency (haze): The haze of the test piece of the smooth flat plate whose length is 50 mm x width 50 mm x thickness 2.0 mm, and whose arithmetic mean roughness (Ra) is 0.03 micrometer or less is a product of Murakami Color Research Institute. It measured with the reflection-transmittance meter HR-100 type. The larger the value of the haze, the larger the light diffusion and the inferior transparency.

(II-VI) Impact resistance (notched Izod impact strength): Test was conducted using a test piece having a thickness of 3.2 mm manufactured according to the standard according to ASTM standard D-256. Eight test pieces were prepared, the impact strength of each test piece was measured, the average value was computed from eight measured values, and the average value was made into the notch formation Izod impact strength.

(II-X) MVR (melt volume rate): Semi-auto melt indexer manufactured by Toyo Seiki Co., Ltd. according to ISO 1133, pellets were dried at 120 ° C. for about 5 hours and the water content in the pellets was 200 ppm or less. By 2A type, it measured on 300 degreeC and the conditions of 1.2 kgf of loads. Higher MVR values indicate lower melt viscosity.

(II-X) MVR increase rate: The increase of the MVR value of the pellet by containing an ultraviolet absorber (C component) was computed compared with the MVR of the pellet which does not contain an ultraviolet absorber (C component).

MVR Rising Rate = (MVR (with C component) ÷ MVR (without C component)-1) × 100

(III) Preparation of Resin Molded Article

(III-I) Preparation of Polyether Ester (Component D-1)

150.8 parts 2,6-naphthalenedicarboxylic acid dimethyl ester (component D1), 24.9 parts dimethyl 5-sodium sulfoisophthalate (component D2), 47.9 parts ethylene glycol (component D3-1), 74.6 parts 1,6- Hexanediol (component D3-2), 89.8 parts of polyethylene glycol (number average molecular weight 2000; component D4), and 0.14 parts of tetrabutyl titanate were placed in a reactor equipped with a rectifying tower and a stirring device, and then nitrogen-substituted in the vessel. It heated up to 200 degreeC under normal pressure, stirring. The methanol produced by the reaction was gradually warmed from 200 ° C to 230 ° C while distilling off the methanol, and the reaction was completed. Thereafter, the reaction mass was transferred to a reactor having a vacuum outlet system equipped with a stirring device, and stirred at a temperature of 230 ° C., after 60 minutes of 6.7 × 10 ² Pa, after 100 minutes of 1.3 × 10 ² Pa, and after 120 minutes of 0.67. The polyether ester copolymer was obtained by making the inside of a system into pressure reduction by x10 <^2> Pa gradually, and polymerizing-reacting distilling a reaction outflow. The reduced viscosity of the obtained polyether ester copolymer was 1.35 (in the mixed solvent of phenol / tetrachloroethane (weight ratio 40/60), it is the value measured at the concentration of 1.2 (g / dl) and 30 degreeC). Moreover, in the obtained polyether ester copolymer, the ratio of the D1 component and the D2 component is 85:15 (molar ratio), the ratio of the D3-1 component and the D3-2 component is 19:81 (molar ratio), and the content of the D4 component. Was 26% by weight.

Preparation of (III-II) Pellets

To 100 parts of polycarbonate resin powder prepared by interfacial polycondensation from bisphenol A and phosgene, a low molecular weight sulfonate, an ultraviolet absorber, and other additives were added in the compounding amounts shown in Tables 1 to 5, and the bluing agent (manufactured by Bayer Corporation: 0.0001 parts of Macrox Violet B) were blended and mixed in a blender, followed by melt kneading using a vented twin screw extruder to obtain pellets. An antistatic agent, which is a viscous liquid phase at room temperature, was prepared using a super mixer with a premix with polycarbonate resin powder whose proportion is 10% by weight. In addition, about the other stabilizers, the pre-mixture with the polycarbonate resin powder was prepared previously based on the density | concentration of 10-100 times of compounding quantity, respectively, and the whole mixing by a blender was performed. The vent type twin screw extruder was manufactured by Nihon Steel Co., Ltd .: TEX30α-31.5BW-2V (completely engaged, co-rotating, two screw screw). The kneading zone was one type in front of the vent. The extrusion conditions were discharge rate 20 kg / h, screw rotation speed 130 rpm, and the degree of vacuum of the vent of 3 kPa, and the extrusion temperature was 260 degreeC from the 1st supply port to the die part.

(Ⅲ-Ⅲ) Preparation of Test Piece

After drying the obtained pellets at 120 degreeC for 7 hours by the hot-air circulation type dryer, length 50 was carried out using the injection molding machine on the conditions of a cylinder temperature of 310 degreeC, a metal mold temperature of 80 degreeC, and a four-speed 20 mm / sec. The test piece on the smooth flat plate whose mm x width 50mm x thickness 2.0mm, and arithmetic mean roughness Ra of the surface is 0.03 micrometer, and the test piece for impact resistance evaluation were shape | molded. The injection molding machine used SG260M-HP by Sumitomo Heavy Machinery Co., Ltd.

(III-IV) Preparation of Injection Molded Member

After drying the obtained pellets by the same method as (III-III), the transparent head lamp lens molded article shown in FIG. 1 and the electronic circuit cover molded article shown in FIG. 20 mm in height and 1.5 mm in thickness) were injection molded to prepare an injection molded member. The injection molding machine used SG260M-HP by Sumitomo Heavy Machinery Co., Ltd. Evaluation of such a molded member was performed visually on the basis of judgment of transparency, opacity, and yellowing. That is, what was observed as colorless transparent was determined as "transparency", what was observed that transparency was inadequate, "opacity", and yellowing was observed as "yellowing".

(III-V) Fabrication of Sheet-like Member

After drying the obtained pellets by the same method as (III-III), it extruded from the T die of 250 mm width on the conditions of cylinder temperature of 280 degreeC and die temperature of 280 degreeC using the screw diameter of 40-mm single screw extruder, and thickness 200 micrometers of unstretched film were produced. Moreover, the temperature regulator was connected to the cooling roll, and it can control the cooling temperature freely, and the temperature of the cooling roll was adjusted to 30 degreeC which is the most stable in each film. Evaluation of such a sheet-like member was performed visually on the basis of the judgment of transparency, opacity and yellowing as in the case of the injection molded member.

Examples 1 to 31, and Comparative Examples 1 to 23

The pellet of the resin composition which consists of each component of Table 1-Table 5 was manufactured, and the test piece and the transparent member were manufactured by the said processing method. The evaluation results are shown in Tables 1 to 5.

(Component A)

A-1: Polycarbonate resin powder of viscosity average molecular weight 22,400 manufactured by bisphenol A and phosgene by interfacial condensation polymerization method (Tejin Chemical Co., Ltd. make: Panlite L-1225WP)

A-2: Polycarbonate resin powder of the viscosity average molecular weight 20,900 manufactured by interfacial polycondensation method from bisphenol A and phosgene (Tejin Chemical Co., Ltd. make: Panlite L-1225WS)

(Component B)

B-1: dodecyl benzene sulfonate tetrabutyl phosphonium salt (Takemoto Oils & Fats Co., Ltd. make: TCS-101)

B-2: Dodecylbenzenesulfonic Acid Potassium Salt (manufactured by Takemoto Fatty Oil Co., Ltd.)

B-3: dodecyl benzene sulfonate didodecyl methyl ammonium salt (Sanyo Chemical Co., Ltd. make: Chemisut 3112C-6)

(Component C)

C-1: 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole (manufactured by CIBA SPECIALTY CHEMICALS: TINUVIN 234). [10% Weight Loss Temperature in TGA: 314 ° C]

C-2: 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] (manufactured by ADEKA Co., Ltd.) -31). [10% Weight Loss Temperature in TGA: 378 ° C]

C-3: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-octyloxyphenol (manufactured by CIBA SPECIALTY CHEMICALS: TINUVIN 1577FF). [10% Weight Reduction Temperature in TGA: 335 ° C]

C-4: 2,2'-p-phenylenebis (3,1-benzooxazin-4-one) (Takemoto Oils & Fats Co., Ltd. make: CEi-P). [10% Weight Reduction Temperature in TGA: 351 ° C]

C-5: 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacrylo Yl) oxy] methyl] propane (manufactured by BASF Corporation: UVINUL 3030). [10% Weight Loss Temperature in TGA: 399 ° C]

C-6 (for comparison): 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (manufactured by Chemipro Chemical Co., Ltd .: Chemisorb 79). [10% Weight Loss Temperature in TGA: 230 ° C]

C-7 (for comparison): 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (manufactured by Cipro Chemical Co., Ltd .: Sisov 709). [10% Weight Loss Temperature in TGA: 229 ° C]

C-8 (comparative): 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine (manufactured by CIBA SPECIALTY CHEMICALS: TINUVIN 405). [10% Weight Reduction Temperature in TGA: 255 ° C]

C-9 (for comparison): ethyl-2-cyano-3,3'-diphenyl acrylate (manufactured by Cipro Chemical Co., Ltd .: SEESORB 501). [10% Weight Reduction Temperature in TGA: 265 ° C]

(Component D)

D-1: polyether ester copolymer prepared by the above method (reduction viscosity 1.35 dl / g, sodium sulfonate base is about 1.5 × 10 ^-4 mol / g)

D-2: Sodium sulfonate-modified polyester (Toyo Spinning Co., Ltd. make: Byron 280) (Polyethylene terephthalate / isophthalate copolymer containing 5-sodium sulfoisophthalic acid unit as a repeating unit, reduced viscosity 0.53 dl / g)

D-3: Sodium sulfonate modified polyester (Toyo Spinning Co., Ltd. make: Byron 240) (Polyethylene terephthalate / isophthalate copolymerization containing a 5-sodium sulfoisophthalic acid unit as a repeating unit, reduced viscosity 0.45 dl / g)

(E component)

E-1: trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)

E-2: Aromatic condensed phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741)

(F component)

F-1: 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5,5] undecane (ADEKA Co., Ltd. product: Adecastabu AO-80)

F-2: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals K. K .: Irganox 1076)

(G component)

G-1: bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (manufactured by ADEKA Corporation: Adecastave PEP-24G)

As is clear from the above table, it can be seen that the resin composition of the present invention obtains a molded article having excellent properties of all of antistatic property, weather resistance, color, molding heat resistance, transparency, and impact resistance. Moreover, it turns out that it is suitable for the vehicle transparent member, the electronic circuit board cover member, and the transparent sheet-like member which require transparency, antistatic performance, and weather resistance.

Industrial availability

The resin composition of the present invention is widely useful in buildings, building materials, agricultural materials, marine materials, vehicles, electrical and electronic equipment, machinery, and other various fields. Among them, moldings which are very useful for transparent members for automobiles including car headlamp lenses, decorative members for organic groups (such as pachinko corgi and game machines), transparent members for electronic circuit board covers including substrate covers, transparent sheets including building materials, and transparent film members By providing the present invention, the industrial effect of the present invention is very large.

1: headlamp lens body
2: Dome portion of the lens
3: outer peripheral part of the lens
4: gate of molded product (width 30 mm, thickness of gate part 4 mm)
5: Sprue (diameter 7 mmφ of gate part)
6: diameter of the outer peripheral portion of the lens (220 mm)
7: diameter of the dome portion of the lens (200 mm)
8: height of the dome portion of the lens (20 mm)
9: thickness of the lens molded product (4 mm)
11: cover molded product
12: gate of the cover molded article (four points, a 0.65 mm diameter pin gate, symmetrical about the symmetry axis 15 and the symmetry axis 16, respectively)
13: length of cover molded product (mold dimensions 200 mm)
14: width of the cover molded product (mold dimensions 100 mm)
15: axis of symmetry of the cover molding length direction
16: axis of symmetry of the cover molding width direction
17: position of the gate of the cover molded article (length from the symmetric axis 15, 35 mm in the mold dimensions)
18: position of the gate of the cover molded article (length from the symmetric axis 16, 60 mm in the mold dimensions)

Claims (16)

(A) 100 parts by weight of a polycarbonate resin (component A),
(B) 0.01 to 4 parts by weight of a low molecular weight sulfonate (component B), and
(C) Ultraviolet absorber (component C) As a resin composition containing 0.05-3 weight part,
The C component is at least one compound selected from the group consisting of a benzotriazole compound, a benzotriazine compound, a benzoxazine compound, a 2-cyanoacrylic acid compound, and a benzophenone compound, and TGA (thermogravimetric analysis). The resin composition which is a compound with a 10% weight loss temperature in 280 degreeC or more). The method of claim 1,
The resin composition whose 10% weight loss temperature in TGA (thermogravimetric analysis) of C component is 300 degreeC or more. The method according to claim 1 or 2,
The resin composition whose 10% weight loss temperature in TGA (thermogravimetric analysis) of C component is 320 degreeC or more. The method according to any one of claims 1 to 3,
The resin composition whose MVR (melt volume rate) increase rate of a pellet by containing C component is 10% or less. The method according to any one of claims 1 to 4,
The resin composition whose B component is a sulfonic acid phosphonium salt represented by the following general formula (I).

(In formula, A <^1> represents a C1-C40 alkyl group, a C6-C40 aralkyl group, or a C6-C40 aryl group, R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms) The method of claim 5, wherein
The resin composition whose sulfonic acid phosphonium salt is a dodecylbenzene sulfonic acid tetrabutyl phosphonium salt. 7. The method according to any one of claims 1 to 6,
(D) The resin composition which contains 0.01-5 weight part of polyether ester which has a sulfonate group, and / or polyester which has a sulfonate group (component D) per 100 weight part of polycarbonate resin (component A). The method of claim 7, wherein
Aromatic dicarboxylic acid component which D component does not have a (D1) sulfonate group, (D2) Aromatic dicarboxylic acid component substituted by the sulfonate group represented by following General formula (II), (D3) Glycol of 2-10 carbon atoms The resin composition which is a polyether ester which consists of a component and the poly (alkylene oxide) glycol component of (D4) number average molecular weights 200-50,000.

(In the formula, Ar is a trivalent aromatic group having 6 to 20 carbon atoms, M ⁺ represents a metal ion or an organic onium ion) The method of claim 7, wherein
Aromatic dicarboxylic acid component in which D component does not have a (D5) sulfonate group, (D6) the aromatic dicarboxylic acid component substituted by the sulfonate group represented by the said General formula (II), and (D7) C2-C10 The resin composition which is polyester which consists of glycol components. 10. The method according to any one of claims 1 to 9,
(E) The resin composition which contains 0.001-0.5 weight part of phosphate ester (component E) represented by following General formula (III) per 100 weight part of polycarbonate resin (component A).

(Wherein X represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 A divalent group derived from a compound selected from the group consisting of -hydroxyphenyl) ketone, and bis (4-hydroxyphenyl) sulfide, n is an integer from 0 to 5, or a mixture of phosphate esters with different n numbers Is an average of 0 to 5, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently substituted or unsubstituted alkyl groups having 1 to 40 carbon atoms and having 6 to 40 carbon atoms. Monovalent group derived from a compound selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group having 6 to 40 carbon atoms) 11. The method according to any one of claims 1 to 10,
(F) The resin composition which contains 0.01-2 weight part of hindered phenolic antioxidants (component F) per 100 weight part of polycarbonate resins (component A). 12. The method according to any one of claims 1 to 11,
(G) A resin composition containing 0.01 to 2 parts by weight of a phosphite ester antioxidant (component G) per 100 parts by weight of a polycarbonate resin (component A). 13. The method according to any one of claims 1 to 12,
The resin composition whose haze measured by JISK7105 is 0.1 to 1% in the smooth flat plate of thickness 2mm which has an arithmetic mean roughness (Ra) of 0.03 micrometer or less. 14. The method according to any one of claims 1 to 13,
The 2 mm-thick smooth plate which has an arithmetic mean roughness (Ra) of 0.03 micrometer or less is state-controlled for 1 week in the environment of the temperature of 23 degreeC, and 50% of the relative humidity, and the temperature of 23 degreeC and the relative humidity of 50 degree with a static onestometer. The resin composition whose half voltage withstand voltage measured on the conditions of%, the applied voltage of 10 mA, and the electrode-sample distance of 20 mm is 500 second or less. The molded article formed by melt-molding the resin composition of any one of Claims 1-14. The method of claim 15,
Molded article which is a transparent member for vehicles, a transparent member for organic machines, or a transparent sheet-like member.

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