JP5011412B2 - Flame retardant polycarbonate resin composition, method for producing resin composition, and molded article comprising the same - Google Patents

Description

  The present invention relates to a method for producing a flame retardant polycarbonate resin composition resin composition, and a molded article comprising the same, and more specifically, has excellent flowability at the time of molding without a problem of molecular weight reduction, and has high flame retardancy. The present invention relates to a flame retardant polycarbonate resin composition, a method for producing the same, and a molded product comprising the same.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there.
In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

On the other hand, metal salt compounds represented by organic alkali metal salt compounds and organic alkaline earth metal salt compounds such as alkali metal perfluoroalkanesulfonates and sodium aromatic sulfonates have been studied as useful flame retardants. (See Patent Documents 1 and 2).
Among them, perfluoroalkanesulfonic acid alkali metal salts are excellent flame retardants. In particular, perfluorobutanesulfonic acid alkali metal salts, that is, nonafluorobutanesulfonic acid alkali metal salts, have been widely used. It has a problem that it tends to cause a decrease in molecular weight.
Although the alkali metal perfluoroalkanesulfonate itself is an excellent flame retardant, it has been strongly desired to improve this point.

Japanese Patent Publication No. 47-40445 JP 2000-169696 A

  The object of the present invention is, in view of the above-mentioned problems of the prior art, particularly in a flame retardant polycarbonate resin composition containing potassium nonafluorobutane sulfonate, which has no problem of molecular weight reduction and has excellent fluidity at the time of molding. It is providing the flame-retardant polycarbonate resin composition which has a flame retardance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have included a specific amount of potassium octafluorobutane sulfonate in potassium nonafluorobutane sulfonate, so that there is no problem of molecular weight reduction during molding. It has been found that a flame-retardant polycarbonate resin material having excellent fluidity and high flame retardancy can be obtained, and the present invention has been completed.

  That is, according to the first aspect of the present invention, 0.01 to 1 part by mass of potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) with respect to 100 parts by mass of the polycarbonate resin (A). A flame-retardant polycarbonate resin composition comprising 0.00001 part by mass or more and less than 0.001 part by mass is provided.

  According to the second invention of the present invention, the flame retardant polycarbonate resin composition is characterized in that the polycarbonate resin (A) contains 20% by mass or more of a polycarbonate resin having a structural viscosity index N of 1.2 or more. Is provided.

  Moreover, according to the 3rd invention of this invention, the molded article formed by shape | molding the flame-retardant polycarbonate resin composition which concerns on the 1st or 2nd invention is provided.

Furthermore, according to the fourth aspect of the present invention, potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) are used at a specific surface area of 0.01 to ⁵ mm ² / g and 60 to 95. There is provided a method for producing a flame retardant polycarbonate resin composition according to the first invention, comprising a step of mixing a masterbatch blended with a polycarbonate resin granule having a particle size of 180 to 1700 μm in mass%. The

  According to the flame retardant polycarbonate resin composition of the present invention, a flame retardant polycarbonate resin composition having no problem of molecular weight reduction and excellent fluidity at the time of molding and having a high degree of flame retardancy and a molded article using the same Obtainable.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[1. Overview]
The flame-retardant polycarbonate resin composition of the present invention contains at least a specific amount of polycarbonate resin (A), potassium nonafluorobutanesulfonate (B), and potassium octafluorobutanesulfonate (C). It is characterized by doing.

[2. Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) of the resin material used in the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, preferably aromatic polycarbonate resins. A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetramethylbisphenol A, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, Resorcinol, 4,4′-dihydroxydiphenyl and the like can be mentioned. Further, as a part of the dihydroxy compound, when the above-mentioned aromatic dihydroxy compound is combined with one or more tetraalkylphosphonium sulfonates, or a polymer or oligomer containing both terminal phenolic OH groups having a siloxane structure, A highly flame-retardant polycarbonate resin can be obtained.

  Preferred examples of the polycarbonate resin (A) used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy. The polycarbonate resin which used the compound together is mentioned. In the present invention, two or more polycarbonate resins may be used in combination as the component (A).

  The molecular weight of the polycarbonate resin (A) used in the present invention is a viscosity average molecular weight calculated from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is usually 14,000 to 30,000, preferably 18, 000 to 29,000. When the viscosity average molecular weight is within this range, a resin composition can be obtained that gives a molded article having good moldability and high mechanical strength. The most preferable molecular weight range of the polycarbonate resin (A) is 22,000 to 28,000.

  The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, it is also preferable to use the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method.

The polycarbonate resin in the present invention preferably contains a certain percentage or more of a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of a melt as described in detail in the document “Rheology for chemists” (Chemical Doujin, 1982, pp. 15-16). . Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.

  In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved. However, in order to maintain the moldability of the obtained polycarbonate resin composition in a favorable range, the structural viscosity index N of the polycarbonate resin is preferably not excessively large.

Therefore, the polycarbonate resin in the polycarbonate resin composition of the present invention has a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less. It is preferable to contain a polycarbonate resin of 1.7 or less, preferably an aromatic polycarbonate resin in a certain ratio or more.
The high structural viscosity index N means that the polycarbonate resin has a branched chain. By containing the polycarbonate resin having a high structural viscosity index N in this way, the polycarbonate resin composition of the present invention burns. The dripping at the time can be suppressed and the flame retardancy can be improved.

The structural viscosity index N can also be expressed by Log η _a = [(1-N) / N] × Log γ + C, which is derived from the above equation, as described in, for example, JP-A-2005-232442. Is possible. In the formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and η _a in a low shear region where the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is obtained by a melting method (transesterification method) as described in JP-A-8-259687 and JP-A-8-245782, for example. When reacting an aromatic dihydroxy compound and a carbonic acid diester, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolytic stability can be obtained without adding a branching agent by selecting catalyst conditions or production conditions. be able to.

  An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more can also be produced by a method using a branching agent when produced by a phosgene method or a melting method (a transesterification method) according to a conventional method. . Specific examples of the branching agent include phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4-hydroxy). Phenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,1,1-tris (4-hydroxyphenyl) ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like. The amount used is in the range of 0.01 to 10 mol%, particularly preferably in the range of 0.1 to 3 mol%, based on the aromatic dihydroxy compound.

  The molecular weight of the aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is a viscosity average molecular weight in the range of 16,000 to 30,000 converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Is preferred.

In the polycarbonate resin composition of the present invention, the polycarbonate resin is a polycarbonate resin in which the structural viscosity index N described above is in a predetermined range (hereinafter, this polycarbonate resin may be referred to as “predetermined N polycarbonate resin”). In general, it is desirable to contain 20% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more. This is because the synergistic effect of potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate according to the present invention can be remarkably exhibited by combining with a predetermined N polycarbonate resin. In addition, there is no restriction | limiting in the upper limit of content of predetermined N polycarbonate resin in polycarbonate resin, Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.
In addition, 1 type may be used for predetermined N polycarbonate resin, and it may use 2 or more types together by arbitrary combinations and a ratio.

  Further, the polycarbonate resin may include a polycarbonate resin having a structural viscosity index N outside the above predetermined range, in addition to the above predetermined N polycarbonate resin. Although there is no restriction | limiting in the kind, A linear polycarbonate resin is preferable especially. By combining the predetermined N polycarbonate resin and the linear polycarbonate resin, there is an advantage that it is easy to balance the flame retardancy (anti-dripping property) and moldability (fluidity) of the obtained polycarbonate resin composition. From this viewpoint, it is particularly preferable that the polycarbonate resin is composed of a predetermined N polycarbonate resin and a linear polycarbonate resin. In addition, the structural viscosity index N of this linear polycarbonate resin is usually about 1-1.15. In general, if the structural viscosity index N is about 1 to 1.15, it may be considered that the structural viscosity index is substantially made of a linear polycarbonate resin.

  When the polycarbonate resin contains a linear polycarbonate resin, the proportion of the linear polycarbonate resin in the polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, Usually, it is more than 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more. By making the content of the linear polycarbonate resin in the polycarbonate resin within the above range, good dispersibility of potassium nonafluorobutanesulfonate, potassium octafluorobutanesulfonate and other additives can be easily obtained, and flame retardant The advantage is that it is easy to obtain a polycarbonate resin having excellent properties and moldability.

  Furthermore, the polycarbonate resin (A) used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin.

[3. Nonafluorobutane sulfonate potassium (B)]
The polycarbonate resin composition of the present invention contains 0.01 to 1 part by mass of potassium nonafluorobutanesulfonate with respect to 100 parts by mass of the polycarbonate resin. Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing potassium nonafluorobutanesulfonate.
The preferable content of potassium nonafluorobutanesulfonate is 0.05 parts by mass or more, and the upper limit is preferably 0.3 parts by mass or less.

[4. Potassium octafluorobutanesulfonate (C)]
The polycarbonate resin composition of the present invention contains 0.00001 parts by mass to less than 0.001 parts by mass of potassium octafluorobutanesulfonate with respect to 100 parts by mass of the polycarbonate resin. Thus, by containing potassium octafluorobutanesulfonate together with potassium nonafluorobutanesulfonate, a high degree of flame retardancy can be imparted without the problem of cloudiness even in the case of thick molding.

Potassium octafluorobutanesulfonate is in particular potassium 1,1,2,2,3,3,4,4-octafluorobutanesulfonate.
A preferable range of the content of potassium octafluorobutanesulfonate is 0.0002 parts by mass or more and less than 0.001 parts by mass, and a more preferable range is 0.0005 parts by mass or more and less than 0.001 parts by mass.
The ratio of potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) is mass ratio, and the ratio of (B) component / (C) component is 100 / 0.001-1. From the viewpoint of flame retardancy improving effect, it is preferable.

[5. Release agent (D)]
The polycarbonate resin composition of the present invention preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like.

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

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

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

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.

  The content of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, more preferably 1 with respect to 100 parts by mass of the polycarbonate resin. It is below mass parts. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[6. Other flame retardants (E)]
The polycarbonate resin composition of this invention can contain flame retardants other than the said (B) component and (C) component. Examples of such flame retardants include halogen flame retardants, phosphorus flame retardants, inorganic filler flame retardants, metal salt flame retardants other than (B) component and (C) component.
Among these, organic sulfonic acid metal salt compounds other than the component (B) and the component (C) are preferable, potassium diphenylsulfone-3-sulfonate, sodium benzenesulfonate, sodium (poly) styrenesulfonate, (poly) Aromatic potassium sulfonates such as potassium styrenesulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, sodium trichlorobenzenesulfonate are preferably used. it can.

  The content of the flame retardant is usually 0.01 parts by mass or more, preferably 0.03 parts by mass or more, preferably 10 parts by mass or less, particularly 1 part by mass with respect to 100 parts by mass of the polycarbonate resin. It is as follows. If the flame retardant content is less than or equal to the lower limit of the range, the flame retardancy improving effect may be insufficient, and if the flame retardant content exceeds the upper limit of the range, the transparency In addition, mechanical properties and thermal properties may be degraded.

[7. Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);

  Core / shell of styrene-butadiene rubber, isobutylene-isoprene rubber, ethylene-propylene rubber, acrylic elastomer, methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), etc. Type elastomers, elastomers such as polyester elastomers;

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin); and the like.

-Resin additives Examples of resin additives include anti-dripping agents, heat stabilizers, antioxidants, UV absorbers, dyes and pigments, light diffusing agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, and flow. Examples include property improvers, plasticizers, dispersants, antibacterial agents, and fillers. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition of this invention is demonstrated concretely.

-Anti-dripping agent Examples of the anti-dripping agent include fluoropolymers, among which fluoroolefin resins are preferred. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
As the fluoropolymer, those having fibril forming ability are particularly preferable, and specific examples thereof include fluoroolefin resins having fibril forming ability. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Commercially available fluoroolefin resins having fibril-forming ability include, for example, “Teflon (registered trademark) 6J” manufactured by Mitsui & DuPont Fluorochemical Co., Ltd. (Trademark) F103 ". Furthermore, as a commercial item of the aqueous dispersion of fluoroolefin resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon (registered trademark) D-1” manufactured by Daikin Chemical Industries, Ltd. and the like can be mentioned. .

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

As such an organic phosphite compound, specifically, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10”, manufactured by Adeka Co., Ltd., manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include “JP-351”, “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by Ciba Specialty Chemicals.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

.. Antioxidants Examples of antioxidants include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010” (registered trademark, the same shall apply hereinafter) manufactured by Ciba Specialty Chemicals, “Irganox 1076”, and “Adeka Stub” manufactured by Adeka. AO-50 "," ADK STAB AO-60 "and the like.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals , "Tinubin 326", "Tinubin 327", "Tinubin 328 Etc. The.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the polycarbonate resin. It is. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; quinoline, anthraquinone, heterocyclic and methyl dyes.

Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and the like are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

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

[8. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include the polycarbonate resin according to the present invention, potassium nonafluorobutane sulfonate and potassium octafluorobutane sulfonate, and other components blended as necessary, for example, a ribbon blender, a Henschel mixer, a Banbury. Examples thereof include a melt kneading method using a mixer, a drum tumbler, a single or twin screw extruder, a kneader and the like. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

<Polycarbonate-Potassium Nonafluorobutanesulfonate / Potassium Potassium Octafluorobutanesulfonate (Masterbatch)>
As described above, a predetermined amount of potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate are blended in the polycarbonate resin composition of the present invention, and potassium nonafluorobutanesulfonate in the resin composition and molded article and In order to improve the dispersibility of potassium octafluorobutanesulfonate and, as a result, obtain stable combustion properties, potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate have a specific surface area of 0.01 to ⁵ mm ^2. / G, 60 to 95% by mass of a powdery polycarbonate resin having a particle size of 180 to 1700 μm, and a larger amount of potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate than the final blending amount Containing polycarbonate It is preferable to obtain a potassium trifluorobutanesulfonate master batch and melt knead the master batch with a polycarbonate resin to obtain a polycarbonate resin composition.

As for the polycarbonate resin in the form of a granular material, it is preferable that 60 to 95% by mass thereof has a particle size distribution measured by a method in accordance with JIS K0069 (screening test method) in the range of 180 to 1700 μm. The particle size distribution is preferably 70% by mass or more, particularly preferably 80% by mass or more, preferably 92% by mass or less, and more preferably 90% by mass or less.
Further, the polycarbonate resin in the form of a granular material preferably has a specific surface area determined by the BET multipoint method of 0.01 mm ² / g or more, more preferably 0.1 mm ² / g or more, and still more preferably. and a 0.5 mm ² / g or more, preferably ^{5 mm} 2 / g or less, more preferably ^{3 mm} 2 / g, more preferably not more than ^{2 mm} 2 / g.

  Examples of a method for producing such a polycarbonate-potassium nonafluorobutanesulfonate / potassium octafluorobutanesulfonate masterbatch include a method of mixing using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, etc. Use is preferred. The preferred blending amount of potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate in the master batch is the total amount of potassium nonafluorobutanesulfonate and potassium octafluorobutanesulfonate, with respect to 100 parts by mass of the polycarbonate resin. 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, further preferably 1 part by mass or more, 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.

[9. Molded body]
The polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application.

  Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and particularly suitable for use in parts of electrical and electronic equipment.

  Examples of electrical and electronic equipment include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, and batteries. Packs, recording medium drives and readers, mice, numeric keys, CD players, MD players, portable radio / audio players, and the like.

  The manufacturing method of a molded article is not particularly limited, and a molding method generally adopted for a polycarbonate resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The measurement / evaluation methods used in the examples and comparative examples are as follows.

[Flame retardance evaluation]
The flame retardancy of each polycarbonate resin composition was evaluated by conditioning a test specimen for UL test obtained by the method described below for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. -Conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. In Table 3, “flame retardant” is indicated.

[Fluidity evaluation]
After drying the pellets obtained by the production method described later at 120 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 280 ° C. and a load of 160 kgf ( (Unit: × 10 ⁻² cc / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high. In Table 3, it is expressed as “fluidity”.

[Transparency evaluation (turbidity and transmittance)]
The turbidity was evaluated in accordance with JIS K-7136, using a thick color plate produced by the method described later as a test piece, and measured with a NDH-2000 type turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. Turbidity is used as a measure of the white turbidity of the resin, and the smaller the value, the better the transparency. In Table 3, it is expressed as “turbidity”.
The total light transmittance was evaluated according to JIS K-7361-1, using the same thick color plate as described above as a test piece, and measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The total light transmittance is used as a scale indicating the transparency of the resin, and the larger the value, the higher the transparency. In Table 3, it is expressed as “transmittance”.

(Examples 1-6 and Comparative Examples 1-4)
Each component described in Table 2 below was mixed in a tumbler for 20 minutes with the contents (mass%) described in Table 3 and Table 4 below, and then a twin screw extruder (TEX30XCT) manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. The molten resin composition kneaded under the conditions of a screw rotational speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 290 ° C., rapidly cooled in a water tank, pelletized using a pelletizer, and polycarbonate A pellet of the resin composition was obtained.

[Molding of color plate]
Next, after the pellets obtained above were dried at 120 ° C. for 5 hours, a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., injection was performed using a NEX80-9E type injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. A thick color plate having a thickness of 5 mm, a length of 65 mm, and a width of 45 mm was molded under the conditions of a speed of 50 mm / sec and a holding pressure of 20 MPa.

[Formation of combustion test piece]
Similarly, after the pellets obtained by the above-mentioned method were dried at 120 ° C. for 5 hours, they were injection-molded using a J50-EP type injection molding machine manufactured by Nippon Steel, 125 mm in length, 13 mm in width, 2 mm in thickness. And 3 mm UL test specimens were molded.
The measurement results for these test pieces are shown in Tables 3 and 4.

From Examples 1 to 6 shown in Tables 3 to 4, the polycarbonate resin composition containing a predetermined amount of potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) in the polycarbonate resin (A), It can be seen that there is no problem of molecular weight reduction, excellent fluidity during molding, and high flame retardancy.
On the other hand, the polycarbonate resin compositions of Comparative Examples 1 and 2 that do not contain potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) have better transparency than the examples, but are not flammable. It can be seen that the polycarbonate resin composition of Comparative Example 3 is insufficient in both flame retardancy and transparency.

(Examples 7 to 9)
The above-mentioned components in Table 2 and the master batch (MB) described below were mixed in a tumbler for 20 minutes with the content (mass%) shown in Table 5 below, and then a twin shaft manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. Supplied to an extruder (TEX30XCT), kneaded under the conditions of a screw rotational speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 290 ° C., the molten resin composition extruded in a strand is rapidly cooled in a water tank, and a pelletizer To obtain pellets of a polycarbonate resin composition. The results are shown in Table 5.

(MB) PC-potassium fluorosulfonate master batch:
A specific surface area of 1.24 mm ² / g, a particle diameter of 180 to 1700 μm of 83% by mass, a viscosity average molecular weight of 22,000 poly-4,4-isopropylidenediphenyl carbonate particles 98% by mass, and nonafluorobutanesulfonic acid What blended 1.986 mass% potassium and 0.014 mass% potassium octafluorobutanesulfonate for 1 minute with a Henschel mixer.

Examples 7 to 9 shown in Table 5 had no problem of molecular weight reduction and were excellent in fluidity during molding, as in Examples 1 to 5. In addition, about flame retardance, it was the same level as Examples 1-5 in UL94 standard, but the flame retardance of Examples 7-9 has few dispersion | variation in a flame retardance compared with Examples 1-5. It was.
When Example 2 and Example 6 in Tables 3 to 4 were also carried out by the same method using a master batch, it was confirmed that there was little variation in flame retardancy as in Examples 7 to 9.

  From the above Examples and Comparative Examples, it was confirmed that the effect of having no problem of lowering the molecular weight, excellent fluidity at the time of molding, and having a high degree of flame retardancy can be obtained for the first time by the configuration of the present invention. .

  According to the flame retardant polycarbonate resin composition of the present invention, a polycarbonate resin molding material having excellent flowability at the time of molding without a problem of molecular weight reduction and high flame retardancy can be obtained. It can be used in a wide range of fields such as parts, OA equipment, information terminal equipment, battery packs, machine parts, home appliances, vehicle parts, building components, various containers, leisure goods and miscellaneous goods, lighting equipment, and industrial utility. Is very expensive.

Claims (4)

  To 100 parts by mass of the polycarbonate resin (A), 0.01 to 1 part by mass of potassium nonafluorobutanesulfonate (B) and 0.00001 part by mass of potassium octafluorobutanesulfonate (C) to less than 0.001 part by mass A flame retardant polycarbonate resin composition comprising:   The flame-retardant polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains 20% by mass or more of a polycarbonate resin having a structural viscosity index N of 1.2 or more.   A polycarbonate resin molded product obtained by molding the flame retardant polycarbonate resin composition according to claim 1. Polycarbonate resin comprising potassium nonafluorobutanesulfonate (B) and potassium octafluorobutanesulfonate (C) having a specific surface area of 0.01 to ⁵ mm ² / g and a particle size of 60 to 95% by mass of 180 to 1700 μm. The method for producing a flame retardant polycarbonate resin composition according to claim 1, comprising a step of mixing a master batch blended in the powder.