JP4639187B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a resin composition containing an aromatic polycarbonate resin. More specifically, the present invention relates to a resin composition that is excellent in flame retardancy and thermal stability and excellent in releasability during molding. The resin composition of the present invention is suitably used for parts of weak electric devices (communication devices such as telephones and fax machines), electric equipment exterior parts, specifically, modular jacks, electric meter covers, and the like.

Aromatic polycarbonate resins have many excellent properties and are used in a wide range of fields. However, aromatic polycarbonate resins are flammable, and severe flame retardancy is required depending on applications. As a method for flame-retarding an aromatic polycarbonate resin, a method of blending an organic halogen compound is known.
For example, Patent Document 1 proposes a method in which a polycarbonate oligomer of tetrabromobisphenol A is blended so that the bromine concentration is 5 to 15% by weight. Patent Document 2 proposes a method of blending a copolymer polycarbonate of tetrabromobisphenol A and bisphenol A so that the bromine concentration is 5 to 9% by weight. However, when a flame retardant resin composition obtained by blending such a bromo flame retardant is molded, the molding machine or the processing machine is easily corroded, and this corrosion becomes more severe as the bromine concentration increases. .
A method of blending a non-halogen flame retardant with an aromatic polycarbonate resin is also known. Patent Document 3 proposes a method of blending potassium perfluoroalkanesulfonate (component B). According to this method, the generation of toxic gas is reduced. However, when the B component is added in such an amount that exhibits sufficient flame retardancy, the thermal stability of the resin composition is lowered. Further, the component B is easy to foam, and the amount of use must be reduced as much as possible.
In order to solve these problems, Patent Document 4 discloses a resin in which an aromatic polycarbonate resin (component A) is mixed with an alkali salt of perfluoroalkanesulfonic acid (component B) and a halogenated triaryl phosphate (component C). A composition is disclosed. The resin composition has been shown to achieve excellent flame retardancy and prevention of molding machine corrosion. According to the invention described in Patent Document 4, the amount of potassium perfluoroalkanesulfonate (component B) can be reduced while maintaining flame retardancy. However, the resin composition has a problem that even if a release agent is added, the release property at the time of injection molding is not sufficient, and the production efficiency of a molded product is lowered. Further, there is a problem that mechanical strength such as thermal stability and impact resistance is lowered depending on the type and content of the release agent. Therefore, even in the invention described in Patent Document 4, there is room for improvement in order to keep the flame retardancy, releasability, thermal stability and mechanical strength of the resin composition satisfactorily.

Japanese Examined Patent Publication No. 47-044537 Japanese Patent Publication No. 47-024660 Japanese Examined Patent Publication No. 47-040445 Japanese Patent Application Laid-Open No. 07-041653

An object of this invention is to provide the resin composition which has favorable flame retardance and was excellent in thermal stability.
An object of this invention is to provide the resin composition which is excellent in the mold release property at the time of a shaping | molding process, and has very little corrosion of a molding machine and a processing machine in that case.
An object of the present invention is to provide a resin composition having good flame retardancy, thermal stability, and releasability while maintaining the mechanical strength such as excellent impact properties of an aromatic polycarbonate resin.
As a result of diligent research to achieve the above object, the present inventors have found that an aromatic polycarbonate resin (A component) containing a release agent (E component), a perfluoroalkanesulfonic acid alkali salt as a flame retardant (B component), halogenated triaryl phosphate (C component) and a specific aromatic sulfonic acid metal salt (D component) are blended, and even if the amount of B component and C component used is small, it is excellent. It has been found that a resin composition having flame retardancy, excellent releasability and good thermal stability can be obtained, and the present invention has been completed.

That is, the present invention comprises (A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) Alkali perfluoroalkanesulfonic acid salt (component B) 0.005 to 0.5 parts by weight,
(C) 0.01 to 6 parts by weight of a halogenated triaryl phosphate (component C) represented by the following formula (1),

In the formula (1), Ar ¹ , Ar ² and Ar ³ are the same or different aromatic groups, and the aromatic groups are substituted with at least one halogen atom.
(D) Aromatic sulfonic acid metal salt represented by the following formula (2), aromatic sulfonic acid metal salt represented by the following formula (3), or a mixture thereof (component D) 0.05 to 2 parts by weight

In formulas (2) and (3), M ¹ , M ² and M ³ are the same or different and are alkali metals or alkaline earth metals, l, m and n are each 1 or 2, and (E) full ester le (E component) 0.005 parts by weight of an aliphatic polyhydric alcohol and aliphatic carboxylic acids,
Is a flame retardant resin composition.

  The resin composition of the present invention is excellent in flame retardancy due to the use of a very small amount of flame retardant, retains the original excellent physical properties of the aromatic polycarbonate resin, and has excellent thermal stability and releasability. The industrial effect is exceptional.

(Aromatic polycarbonate resin: Component A)
The A component aromatic polycarbonate resin can be obtained by reacting a dihydric phenol and a carbonate precursor by a solution polymerization method or a melt polymerization method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), bis (4-hydroxyphenyl) methane, and 2,2-bis (4-hydroxy-3,5-dimethyl). Phenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) For example, sulfone and the aromatic ring thereof substituted with, for example, an alkyl group or an aryl group may be used, and these may be used alone or in combination of two or more. Of these, bisphenol A is preferred.

Examples of the carbonate precursor include carbonyl halide, diaryl carbonate, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
In producing such an aromatic polycarbonate resin, an appropriate molecular weight regulator, a catalyst for promoting the reaction, and the like can be used as necessary.
The molecular weight of the aromatic polycarbonate resin is not particularly limited, but is usually 10,000 to 50,000, preferably 15,000 to 40,000 in terms of viscosity average molecular weight. Here, the viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation. .
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7
Further, the aromatic polycarbonate resin may be a branched polycarbonate resin copolymerized with a polyfunctional compound or a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, and two or more kinds of aromatic polycarbonate resins may be used. It may be a mixture of polycarbonate resins. For example, it may be a mixture of a normal molecular weight aromatic polycarbonate resin and an ultrahigh molecular weight aromatic polycarbonate resin having a viscosity average molecular weight of 50,000 or more.

(Perfluoroalkanesulfonic acid alkali salt: B component)
Component B is an alkali salt of perfluoroalkanesulfonic acid. Preferred perfluoroalkanesulfonic acid alkali salts are those having 1 to 8 carbon atoms and alkyl groups in which all carbons of the hydrocarbon group are fluorinated. Alkali salts are salts of alkali metals and alkaline earth metals, and potassium salts and sodium salts are particularly preferred.
Specific examples include potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, potassium perfluorooctanesulfonate, sodium perfluorooctanesulfonate, and potassium perfluorobutanesulfonate is particularly preferable.
If the content of the B component is too small, it becomes difficult to obtain a sufficient flame retardant effect even if a halogenated triaryl phosphate (C component) and an aromatic sulfonic acid metal salt (D component) described later are used in combination. The thermal stability and impact properties of the resulting resin composition are lowered, and the flame retardancy is also lowered. Accordingly, the content of the B component is in the range of 0.005 to 0.5 parts by weight, preferably 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the A component. If it is this range, a transparent resin composition will be obtained.

(Halogenated triaryl phosphate: component C)
Component C is a halogenated triaryl phosphate represented by the following formula (1).

In the formula (1), Ar ¹ , Ar ² and Ar ³ are the same or different aromatic groups, and at least one halogen atom is substituted on the aromatic groups. Examples of the aromatic group include a phenyl group and a naphthyl group. Examples of the halogen atom include a bromine atom and a chlorine atom. The aromatic group in formula (1) may be substituted with an alkyl group, an aryl group, an aralkyl group, or an aryloxy group in addition to a halogen atom. Specific examples of component C include tris (2,4,6-tribromophenyl) phosphate.

The component C is preferably one in which salts as impurities and phosphate ester halides are reduced as much as possible. When these impurities are large, the resulting resin composition becomes turbid and the transparency is lowered, or the hue deteriorates during melt molding due to the deterioration of heat resistance.
Examples of the salt as an impurity include alkali metal and alkaline earth metal halides such as sodium chloride and calcium chloride, alkali metal and alkaline earth metal salts of phosphoric acid such as sodium phosphate and calcium phosphate, and partial phosphorus. Examples thereof include alkali metal and alkaline earth metal salts of acid phenyl esters. Examples of phosphoric acid ester halides include phosphoric acid monophenyl ester and phosphoric acid diphenyl ester halides.
Commercially available halogenated triaryl phosphates contain a large amount of the above impurities, and when such phosphates are used, it is necessary to increase their purity by recrystallization or the like.
Content of C component is 0.01-6 weight part with respect to 100 weight part of A component, Preferably it is the range of 0.01-3 weight part. If the content of component C is less than 0.01 parts by weight, sufficient flame retardancy cannot be imparted to the resin composition, and if it exceeds 6 parts by weight, the thermal stability of the resulting resin composition is lowered and the hue is reduced. It is inferior and mechanical properties such as impact properties are impaired. In addition, flame retardancy is also reduced. In particular, when it is desired to suppress corrosion of the molding machine or processing machine, 0.01 to 2 parts by weight is preferable, and 0.01 to 1 part by weight is more preferable.

(Aromatic sulfonic acid metal salt: D component)
The component D is an aromatic sulfonic acid metal salt represented by the following formula (2), an aromatic sulfonic acid metal salt represented by the following formula (3), or a mixture thereof.

In formulas (2) and (3), M ¹ , M ² and M ³ are the same or different and are an alkali metal or an alkaline earth metal, and l, m and n are 1 or 2, respectively. Examples of the alkali metal include sodium and potassium. Examples of alkaline earth metals include magnesium and calcium.
Specific examples of component D include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3,3′-disulfonate, and the like. However, potassium diphenylsulfone-3-sulfonate and potassium diphenylsulfone-3,3′-disulfonate are preferable.
In the case of the mixture of the aromatic sulfonic acid metal salt represented by the formula (2) and the aromatic sulfonic acid metal salt represented by the formula (3), the ratio is the weight ratio {formula (2) / formula (3)}. And preferably in the range of 10/90 to 90/10, more preferably in the range of 30/70 to 90/10, and even more preferably in the range of 50/50 to 90/10.
D component is a mixture of an aromatic sulfonic acid potassium salt represented by the following formula (2-1) and an aromatic sulfonic acid potassium salt represented by the following formula (3-1), and the weight ratio thereof. It is preferable that {(2-1) / (3-1)} is 50/50 to 90/10.

In particular, potassium diphenylsulfone-3-sulfonate (compound 2K) and potassium diphenylsulfone-3,3′-disulfonate (compound 3K) are preferably used in combination, and the ratio is a weight ratio (compound 2K / compound 3K). And preferably in the range of 10/90 to 90/10, more preferably 30/70 to 90/10, and even more preferably in the range of 50/50 to 90/10.
Content of D component is 0.05-2 weight part with respect to 100 weight part of A component, Preferably it is the range of 0.05-1 weight part. If the content of the D component is too small, sufficient flame retardancy and releasability cannot be imparted to the resin composition, and if it is too much, the thermal stability of the resulting resin composition is lowered, impact properties, etc. The mechanical properties of the steel become impaired. In addition, flame retardancy is also reduced. In particular, when it is desired to suppress corrosion of a molding machine or a processing machine, 0.05 to 0.5 parts by weight is preferable, and 0.05 to 0.3 parts by weight is more preferable.
Moreover, in order to improve a flame retardance further to the resin composition of this invention, 0.005-1 weight part can be mix | blended with fluororesin with respect to 100 weight part of A component. As fluororesin, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, polyfluoride Examples thereof include vinylidene, polyvinyl fluoride, and vinylidene fluoride-hexafluoropropylene copolymer. By blending the fluororesin, drip at the time of combustion can be prevented and the flame retardancy can be further improved.

(Full ester of aliphatic polyhydric alcohol and aliphatic carboxylic acid: E component)
The release agent of component E is a full ester le of an aliphatic polyhydric alcohol and aliphatic carboxylic acids. By using such an E component, the releasability and thermal stability of the resin composition are improved. In the present invention, the full ester does not necessarily have an esterification rate of 100%, but may be 80% or more, and preferably 85% or more.
The valence (hydroxyl number) of the aliphatic polyhydric alcohol is preferably 3 to 8, more preferably 4 to 8, and further preferably 4 to 6. The number of carbon atoms is preferably 3 to 30, more preferably 5 to 30, and still more preferably 5 to 20. The aliphatic polyvalent alcohol may contain an ether bond in the carbon chain.
Specific examples of the aliphatic polyhydric alcohol include glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Of these, glycerin, pentaerythritol and dipentaerythritol are preferable, and pentaerythritol is particularly preferable.

The number of carbon atoms of the aliphatic carboxylic acid is preferably 5 to 30, more preferably 10 to 22, and still more preferably 14 to 20.
Specific examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid And saturated aliphatic carboxylic acids such as docosanoic acid and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setoleic acid. The aliphatic carboxylic acid is preferably a saturated aliphatic carboxylic acid, and preferably has 14 to 20 carbon atoms. In particular, stearic acid and palmitic acid are preferred.
The component E is preferably a full ester of a 3 to 8 valent aliphatic alcohol having 3 to 30 carbon atoms and an aliphatic carboxylic acid having 5 to 30 carbon atoms. More preferably, it is a full ester of a 3 to 8 valent aliphatic alcohol having 3 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. The component E is preferably a full ester of a tetravalent to octavalent aliphatic alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms.

It is preferable that the acid value of E component is 4-20. When the acid value of the E component is in the range of 4 to 20, a resin composition having excellent mold stability and thermal stability can be obtained. The acid value is more preferably in the range of 4-18, and still more preferably in the range of 5-15. The main component that expresses the acid value is a free aliphatic carboxylic acid contained in the fatty acid ester (hereinafter sometimes simply referred to as “free fatty acid”). Therefore, in the E component used in the present invention, free fatty acid, etc. Is present in an amount corresponding to its acid value.
Here, the acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids contained in 1 g of the sample, and can be determined by the method defined in JIS K 0070. The E component is a full ester of a 4 to 8 valent aliphatic alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms, and preferably has an acid value of 4 to 20.
The reason why the full ester having an acid value of 4 to 20 can reduce the releasing force (improving the releasing property) and improve the thermal stability is not clear, but is considered as follows. The object to be measured by the acid value is mainly unreacted free carboxylic acid, which is easily gasified at the time of molding due to its relatively low molecular weight. It is thought that it contributes to the improvement of property. Naturally, the volatile content will increase to some extent, but these are considered to be that the proportion of the volatile matter is relatively small, and the proportion remaining on the mold side at the time of mold release is small, so that the mold deposit generation does not increase. It is done.

The E component preferably satisfies a 250% to 360 ° C. 5% weight loss temperature (hereinafter sometimes simply referred to as “weight reduction temperature”) in TGA (thermogravimetric analysis) measurement.
When the weight reduction temperature satisfies 250 to 360 ° C., a resin composition having excellent release properties and thermal stability and excellent discoloration and cracking resistance can be obtained. The range of the weight reduction temperature is more preferably 280 to 360 ° C, further preferably 300 to 350 ° C, particularly preferably 310 to 340 ° C.
The weight reduction temperature is determined as a temperature at which a 5% weight reduction is observed in a measurement condition in which the temperature is increased from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a temperature increase rate of 20 ° C./min.
There is a certain degree of correlation between the acid value and the weight loss temperature. For example, when comparing fatty acid full esters of the same species, the weight reduction temperature decreases as the acid value increases. The component E is substantially composed of a full ester, thereby improving the slipping property between the polycarbonate molecules. Accordingly, even when the resin flow inside the mold becomes complicated, the resin flow becomes smooth, and it is considered that the distortion inside the molded product is reduced by winning the effect. That is, when the intermolecular frictional force is high, locally generated nonuniform frictional force disturbs the flow of the resin, but when the overall frictional force is low, it is expected that the influence is difficult to occur. Furthermore, it is presumed that the reason why the distortion due to the disturbance of the resin flow does not increase is that the ratio of the volatile matter is moderate and the component does not increase in a chain like the cracked gas.

In addition, the E component itself has good chemical resistance and is less aggressive against the polycarbonate resin. This is considered to improve the cracking resistance of the molded product. Moreover, it is thought that the effect which reduces the attack property to polycarbonate resin and suppresses deterioration of polycarbonate resin becomes more effective by using together with the phosphorus stabilizer (F component) mentioned later.
The E component includes not only the ester compound itself but also a mixture of the compound and a free aliphatic carboxylic acid. Furthermore, by utilizing the fact that the value of acid value and weight reduction temperature varies depending on the proportion of free aliphatic carboxylic acid as described above, an additional aliphatic carboxylic acid is added to a full ester having a low acid value or a high weight reduction temperature. Thus, it is possible to prepare a fatty acid ester having a target acid value and weight reduction temperature. Similarly, it is also possible to prepare a full ester satisfying the conditions of the present invention by mixing two or more fatty acid esters having different acid values and weight reduction temperatures.
The manufacturing method of E component is not specifically limited, A conventionally well-known various method can be utilized. Rather than complete the reaction of a theoretical equivalent of aliphatic polyhydric alcohol and aliphatic carboxylic acid over a sufficient amount of time, a slight excess of aliphatic carboxylic acid is reacted with the aliphatic polyhydric alcohol and compared. It is preferable to complete the reaction at an early stage.

Examples of the reaction catalyst include organic tin compounds such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and 2-ethylhexyltin. Is mentioned.
Aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil). Accordingly, an aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. In the production of the E component, stearic acid and palmitic acid which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used. The preferable aspect of the composition ratio of each component in this mixture is as follows.
That is, the aliphatic carboxylic acid constituting the full ester in the E component contains a palmitic acid component and a stearic acid component, and in the peak area in the pyrolysis methylated GC / MS (gas chromatography-mass spectrometry) method, palmitic acid is used. The total of the area (Sp) of the acid component and the area (Ss) of the stearic acid component is 80% or more in the total aliphatic carboxylic acid, and the area ratio (Ss / Sp) of both is 1.3 to 30 Those are preferred.

Here, pyrolysis methylation GC / MS method means that a fatty acid full ester as a sample and a reaction reagent methyl ammonium hydroxide are reacted on a pyrofil to decompose the fatty acid full ester and produce a methyl ester derivative of the fatty acid. This is a method of performing GC / MS measurement on such a derivative.
The total of Sp and Ss is preferably 85% or more, more preferably 90% or more, and still more preferably 91% or more in the total aliphatic carboxylic acid component. On the other hand, the total of Sp and Ss can be set to 100%, but is preferably 98% or less and more preferably 96% or less from the viewpoint of manufacturing cost. Moreover, said area ratio (Ss / Sp) has the preferable range of 1.3-30. The range of 1.3-10 is more preferable, the range of 1.3-4 is further more preferable, and the range of 1.3-3 is particularly preferable. These mixing ratios need not be satisfied with a single aliphatic carboxylic acid, but may be satisfied by mixing two or more aliphatic carboxylic acids.
Examples of the fats and oils that can be used as the raw material of the aliphatic carboxylic acid satisfying the above mixing ratio include animal fats and oils such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, peanut Mention may be made of vegetable oils such as oil, cottonseed oil, sesame oil and olive oil. Among these, animal fats and oils are preferable in view of containing more stearic acid, and beef tallow is more preferable. Furthermore, among the beef tallow, oleostearin containing a lot of saturated components such as stearic acid and palmitic acid is preferable.

The hydroxyl value of the E component is preferably low from the viewpoint of thermal stability and reduction of the release force, while too low is not preferable because the cost increases due to an increase in production time. The range of 0.1-30 is suitable for the hydroxyl value of E component, the range of 1-30 is preferable, and the range of 2-20 is more preferable. Here, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and can be determined by the method defined in JIS K 0070. .
The iodine value of the E component is preferably low from the viewpoint of thermal stability. The iodine value of the E component is preferably 10 or less, and more preferably 1 or less. The iodine value is an amount obtained by converting the amount of halogen to be bonded to the number of g of iodine when halogen is reacted with 100 g of a sample, and can be obtained by a method defined in JIS K0070.
The compounding quantity of E component is 0.005-2 weight part with respect to 100 weight part of A component, 0.01-1 weight part is preferable and 0.05-0.5 weight part is more preferable. If the E component is too small, the releasability is not sufficiently improved, and the crack resistance is also lowered. On the other hand, when there is too much E component, the transparency of a molded product is impaired, and crack resistance may also decrease conversely due to a decrease in thermal stability.

(Phosphorus stabilizer: F component)
The resin composition of the present invention preferably contains a phosphorus stabilizer (F component) in order to further improve thermal stability.
Examples of the phosphorus stabilizer (F component) include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples thereof include triphenyl phosphite and tris (nonylphenyl) phosphite. , Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl Monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaeri Ritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) ) Phosphite compounds such as pentaerythritol diphosphite and distearyl pentaerythritol diphosphite.

Also, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, benzenephosphonate dimethyl, benzenephosphonate diethyl, benzenephosphonate dipropyl, tetrakis (2, 4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4- Di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2 4-di -tert- butylphenyl) -3-phenyl - phenyl phosphonite, and the like.
Among them, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And particularly preferably tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphos It is honite.
The amount of component F used is preferably in the range of 0.01 to 2 parts by weight, more preferably in the range of 0.01 to 1 part by weight, and in the range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of component A. Further preferred. When the amount used is within the above range, sufficient thermal stability is imparted to the resin composition, and mechanical properties such as impact properties of the resin composition are good.

(Ultraviolet absorber: G component)
The resin composition of the present invention may contain an ultraviolet absorber (G component). The G component is preferably at least one ultraviolet absorber selected from the group consisting of benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds and cyclic imino ester compounds.
Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetra Hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-) 2-methoxyphenyl) methane, 2 -Hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified.

  Specific examples of the benzotriazole compounds include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2 -Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- ( 1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydride) Xy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazol -L, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1, 3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2′- Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl monomer copolymerizable with the monomer 2-hydroxyphenyl- such as a copolymer with a monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer Examples thereof include a polymer having a 2H-benzotriazole skeleton.

Among them, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) ) Phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol] is preferably used, and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole is particularly preferably used.
Specific examples of the hydroxyphenyltriazine compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 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-butyl Examples include oxyphenol. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups. Of these, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol is preferably used.
Specific examples of the cyclic imino ester compound include a cyclic imino ester compound represented by the following formula (4).

In the formula, Ar is a residue obtained by extracting two hydrogen groups on the aromatic ring of an aromatic hydrocarbon having 6 to 12 carbon atoms, and may contain a hetero atom. n represents 0 or 1.
Examples of the compound of the above formula (4) include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine- 4-one), and 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).

Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, and a cyclic iminoester skeleton in the ester substituent of (meth) acrylic acid ester.
Among the ultraviolet absorbers, benzotriazole compounds and hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable for meter cover applications. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the G component is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the A component. -0.5 part by weight is particularly preferred.

(Additive)
In addition, optional additives such as other mold release agents, antistatic agents, antioxidants, reinforcing agents, foaming agents, dyes and pigments, inorganic fillers and the like are added to the resin composition of the present invention as necessary. be able to.
In the resin composition of the present invention, as another mold release agent, a monoester of an aliphatic alcohol and an aliphatic carboxylic acid is preferably 0.002 to 0.9 parts by weight, more preferably 100 parts by weight of component A. May contain 0.002 to 0.5 parts by weight.
The number of carbon atoms of the aliphatic alcohol is preferably 3-30, more preferably 3-22, and even more preferably 3-20.
The number of carbon atoms of the aliphatic carboxylic acid is preferably 5 to 30, more preferably 10 to 22, and still more preferably 14 to 20.
Specific examples of monoesters of aliphatic alcohols and aliphatic carboxylic acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, stearic acid monoglyceride, stearic acid monosorbate, behenine Examples include acid monoglyceride, pentaerythritol monostearate, propylene glycol monostearate, sorbitan monostearate and the like.

Further, the resin composition of the present invention is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the component A, of the phenyl group-containing polysiloxane as another mold release agent. Can be included.
The phenyl group-containing polysiloxane contains a phenylsiloxane unit and a trialkylsiloxane unit, and the ratio of aliphatic hydrogen to aromatic hydrogen is preferably in the range of 2.4 to 5.0, and the viscosity at 25 ° C. is 1 to What is 2,000 cSt is preferable.
The “ratio of aliphatic hydrogen to aromatic hydrogen” can be easily measured by a ¹ H nuclear magnetic resonance measuring apparatus. “Ratio of aliphatic hydrogen to aromatic hydrogen” is the ratio of “number of hydrogen atoms in an aliphatic hydrocarbon group” to “number of hydrogen atoms in an aromatic hydrocarbon group”. In the case of a unit having one phenyl group, that is, a methylphenylsiloxane unit, 3/5, that is, 0.6.
The viscosity of the phenyl group-containing polysiloxane at 25 ° C. is preferably 5 to 500 cSt, particularly preferably 10 to 100 cSt.
Further, the phenyl group-containing polysiloxane preferably has a refractive index of 1.44 to 1.48 at 25 ° C.

As the phenyl group-containing polysiloxane, SH-556 manufactured by Toray Dow Corning Silicone Co., Ltd. (the ratio of aliphatic hydrogen to aromatic hydrogen is 2.8, the viscosity at 25 ° C. is 22.5 cSt, the refractive index is 1. 460, which does not contain dimethylsiloxane units) is commercially available.
Examples of the antistatic agent include ammonium dodecylbenzenesulfonate, phosphonium salt of dodecylbenzenesulfonate, high boron LB-120 (manufactured by Boron International), maleic anhydride mono- or diglyceride, graphite, metal powder, and the like. Preferably it is 0.1-10 weight part with respect to 100 weight part, More preferably, it can contain 0.3-8 weight part.
Antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester (Alkyl has 7 to 9 carbon atoms and has a side chain), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa- tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, ethylenebis (oxyethylene) [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. Preferably it is 0.001-10 weight part with respect to a weight part, More preferably, it can contain 0.01-5 weight part.

Examples of the reinforcing agent include metal fiber, glass fiber, carbon fiber, graphite fiber, alumina fiber, silicon nitride fiber, potassium titanate whisker, boron fiber, wholly aromatic polyamide fiber, wholly aromatic polyester fiber, and the like. Preferably it is 1-60 weight part with respect to 100 weight part, More preferably, it can contain 5-50 weight part.
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, the B component to the E component and the desired additive may be mixed in advance, or may be added to the A component in any order and mixed by, for example, a supermixer or a tumbler.
The obtained resin composition can be formed into pellets by ordinary injection molding, extrusion molding, compression molding, or the like after being pelletized with an extruder or as it is, and the molded article thus obtained is excellent. In addition to having flame retardancy, it retains the original excellent physical properties of aromatic polycarbonate resin.
The resin composition of the present invention is suitably used for weak electrical equipment parts (modular jacks for communication equipment such as telephones and fax machines), electrical equipment exterior parts (electric meter cover), and the like that require flame retardancy. The modular jack is easily cracked during molding because of its shape, and by using the resin composition of the present invention, the releasability is improved, cracking during molding is reduced, and accordingly the product yield is improved. The product is preferably used. In addition, the electric meter cover has transparency and impact properties, and is required to be given weather resistance for outdoor use, but by using the aromatic polycarbonate resin composition of the present invention, This resin composition has excellent thermal stability and is excellent in flame retardancy and weather resistance of the molded product, and also improves cracking during molding due to improved releasability, which in turn increases product yield. The product is preferably used.

  The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight. The evaluation was based on the following method.

(1) Flame retardancy: 20 test pieces (length 125 mm × width 13 mm × thickness 3 mm) were prepared at 290 ° C. using an injection molding machine and evaluated according to Subject 94 (UL-94) of Underwriters Laboratories. did.
(2) Thermal stability: Using an injection molding machine, the pellets were molded into a “color measurement plate before residence” (length 70 mm × width 50 mm × thickness 2 mm) at a molding temperature of 340 ° C. for 1 minute cycle. Further, after the resin was allowed to stay in the cylinder for 10 minutes, a “color measurement plate after retention” was obtained. The hue of the flat plate before and after the stay was measured with a color difference meter, and the color difference ΔE was determined by the following formula. A smaller value (ΔE) shown in the table indicates better thermal stability.
ΔE = {(L−L ′) ² + (aa ′) ² + (b−b ′) ² } ^1/2
Hue before staying: L, a, b
Hue after residence: L ′, a ′, b ′
(3) Releasability: A cup-shaped molded piece was molded using an injection molding machine, and the protruding load at the time of mold release was measured with a memorizer. It shows that it is excellent in the mold release property, so that this value is small.
(4) Weather resistance (ΔYI): Using an injection molding machine, pellets were molded into a “color measurement plate before residence” (length 70 mm × width 50 mm × thickness 2 mm) at a molding temperature of 340 ° C. for 1 minute cycle. A molded plate was prepared, and a sunshine weather meter test was performed according to JIS A1415 (using an open frame carbon arc lamp). The hue before the treatment and after the treatment for 1,000 hours was measured with SE-2000 made by Nippon Denshoku to determine the yellowing degree YI. A smaller ΔYI (difference between YI after treatment and YI before treatment) indicates a better weather resistance.

Examples 1-11, Comparative Examples 1-13
Alkali metal perfluoroalkanesulfonate was added to 100 parts of a granular aromatic polycarbonate resin (component A) having a viscosity average molecular weight of 22,000 obtained from bisphenol A, p-tert-butylphenol and phosgene as molecular weight regulators by interfacial polymerization. Salt (component B), halogenated triaryl phosphate (component C), aromatic sulfonic acid metal salt (component D), full ester of aliphatic polyhydric alcohol and aliphatic carboxylic acid (component E), phosphorus stabilizer (Component F) was added in the amount shown in Table 1, and 0.6 ppm of the blueing agent represented by the following formula (5) was further added. After mixing for 10 minutes with a tumbler, the cylinder temperature was 280 ° C. using a 30φ extruder. After pelletizing with, and drying the resulting pellet at 120 ° C. for 4 hours, flame retardancy, thermal stability and mold release It was evaluated with. The evaluation results are shown in Table 1.

Examples 12-22, Comparative Examples 14-26
Alkali metal perfluoroalkanesulfonate was added to 100 parts of a granular aromatic polycarbonate resin (component A) having a viscosity average molecular weight of 22,000 obtained from bisphenol A, p-tert-butylphenol and phosgene as molecular weight regulators by interfacial polymerization. Salt (component B), halogenated triaryl phosphate (component C), aromatic sulfonic acid metal salt (component D), full ester of aliphatic polyhydric alcohol and aliphatic carboxylic acid (component E), phosphorus stabilizer (F component), UV absorber (G component) was added in the amount shown in Table 2, and 0.6 ppm of a blueing agent represented by the following formula (5) was added, and after mixing for 10 minutes with a tumbler, Pelletized at a cylinder temperature of 280 ° C. with a 30φ extruder, and the obtained pellets were dried at 120 ° C. for 4 hours. , The thermal stability was evaluated releasability and weather resistance. The evaluation results are shown in Table 2.

In addition, the symbol in Table 1 and Table 2 used by each Example shows the following compound.
A component aromatic polycarbonate resin; granular aromatic polycarbonate resin having a viscosity average molecular weight of 22,000 (manufactured by Teijin Chemicals Ltd.)
B component flame retardant b: potassium perfluorobutane sulfonate (Dainippon Ink Chemical Co., Ltd.)
C component flame retardant c: Tris (2,4,6-tribromophenyl) phosphate (manufactured by Teijin Chemicals Ltd.)
D component flame retardant d-1: Mixture of 80:20 (weight ratio) of potassium diphenylsulfone-3-sulfonate and potassium diphenylsulfone-3,3′-disulfonate (manufactured by SEALSANDS)
Flame retardant d-2: Mixture of 70:30 (weight ratio) of potassium diphenylsulfone-3-sulfonate and potassium diphenylsulfone-3,3′-disulfonate (manufactured by METROPOLITAN)

E component
e-1 component release agent e-1: acid value 9, TGA5% weight loss temperature 322 ° C., and the total area of the stearic acid components and (Ss) and the area of the palmitic acid component (Sp) in GC / MS method 94% of the total aliphatic carboxylic acid component and the area ratio (Ss / Sp) of 1.44 is a full of pentaerythritol and aliphatic carboxylic acid (mainly stearic acid and palmitic acid) Esters (Riken Vitamin Co., Ltd .: Riquester EW-400, hydroxyl value 6, iodine value 0.4, the aliphatic carboxylic acid is derived from animal fats and oils)
e-2-component release agent e-2: acid number 1, TGA5% weight loss temperature 390 ° C., and the total of Ss and Sp is 91% in the total aliphatic carboxylic acid component, their area ratio (Ss / Full ester of pentaerythritol and aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (Sp) is 1.11 (manufactured by Cognis Japan KK: Roxyol VPG-861, hydroxyl value 7, iodine (Value 0, the aliphatic carboxylic acid is derived from vegetable oil)
e-3-component release agent e-3: higher alcohol fatty acid esters (having 10 to 20 carbon atoms monoalcohol esters of fatty acids having 10 to 20 carbon atoms) and triglycerides (of glycerin and fatty acids having 10 to 20 carbon atoms Full ester) and a mixture of 30:70 (weight ratio) (Riken Vitamin Co., Ltd .: Riquemar SL-900)
e-4-component release agent e-4 (for comparison): glycerol mono-fatty acid ester (manufactured by Riken Vitamin Co., Ltd.: Rikemal S-100A, acid value 0.8, hydroxyl value 327, iodine value 1.8, and TGA5% Weight reduction temperature 205 ° C)

F component
f-1 component thermal stabilizer f-1: 71:15:14 (weight ratio) mixture of the following f-1-a component, f-1-b component and f-1-c component (Sand sand Stub P-EPQ)
f-1-a component: tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′- Biphenylene diphosphonite and tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite 100: 50: 10 (weight ratio) mixture f-1-b component: bis (2 , 4-Di-tert-butylphenyl) -4-phenyl-phenylphosphonite and 5: 3 (weight ratio) mixture of bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite f -1-c component: Tris (2,4-di-tert-butylphenyl) phosphite
f-2 component thermal stabilizer f-2: tris (2,4-di-tert-butylphenyl) phosphite (Irgaphos 168 manufactured by Ciba Geigy)

G component ultraviolet absorber g: 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole (Chemipro Chemical Co., Ltd. Chemisorb 79)
Other component bluing agent; compound represented by the following formula (5) ("Macrolex Violet B" manufactured by Bayer)

The resin composition of the present invention is suitably used for weak electrical equipment parts (modular jacks for communication equipment such as telephones and fax machines), electrical equipment exterior parts (electric meter cover), and the like that require flame retardancy.

Claims (11)

(A) 100 parts by weight of an aromatic polycarbonate resin (component A),
(B) Alkali perfluoroalkanesulfonic acid salt (component B) 0.005 to 0.5 parts by weight,
(C) 0.01 to 6 parts by weight of a halogenated triaryl phosphate (component C) represented by the following formula (1),

In the formula (1), Ar ¹ , Ar ² and Ar ³ are the same or different aromatic groups, and the aromatic groups are substituted with at least one halogen atom.
(D) Aromatic sulfonic acid metal salt represented by the following formula (2), aromatic sulfonic acid metal salt represented by the following formula (3), or a mixture thereof (component D) 0.05 to 2 parts by weight

In formulas (2) and (3), M ¹ , M ² and M ³ are the same or different and are alkali metals or alkaline earth metals, l, m and n are each 1 or 2, and (E) full ester le (E component) 0.005 parts by weight of an aliphatic polyhydric alcohol and aliphatic carboxylic acids,
A flame retardant resin composition comprising: D component is a mixture of an aromatic sulfonic acid potassium salt represented by the following formula (2-1) and an aromatic sulfonic acid potassium salt represented by the following formula (3-1), and the weight ratio thereof. The composition according to claim 1, wherein {(2-1) / (3-1)} is 50/50 to 90/10.

Full esters of E Ingredient is octavalent aliphatic alcohols having 3 to 30 carbon atoms The composition of claim 1, wherein a full ester of an aliphatic carboxylic acid having 5 to 30 carbon atoms. Full esters of E Ingredient is 4-8 divalent aliphatic alcohol having 5 to 30 carbon atoms The composition of claim 1, wherein a full ester of an aliphatic carboxylic acid having 10 to 22 carbon atoms. The composition according to claim 4, wherein the acid value of component E is 4 to 20. The aliphatic carboxylic acid in the E component contains a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) shows the area (Sp) of the palmitic acid component and the stearic acid. The composition according to claim 1, wherein the total of the component area (Ss) is 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is 1.3-30. The composition according to claim 1, wherein the E component has a 5% weight loss temperature of 250 to 360 ° C in TGA (thermogravimetric analysis). The composition according to claim 1, further comprising 0.002 to 0.9 parts by weight of an ester of an aliphatic monoalcohol and an aliphatic carboxylic acid with respect to 100 parts by weight of the component A. The composition of Claim 1 which contains 0.01-2 weight part of phosphorus stabilizers (F component) further with respect to 100 weight part of A component. The composition according to claim 9, wherein the F component is tetrakis-2,4-di-t-butylphenyl-4,4'-biphenylenediphosphonite. The composition according to claim 1, further comprising 0.0005 to 3 parts by weight of an ultraviolet absorber (G component) with respect to 100 parts by weight of the A component.