JP5864345B2 - Polycarbonate resin composition for thick molded products - Google Patents

Description

  The present invention relates to a polycarbonate resin composition for thick-walled molded articles, and more specifically, a thick-walled molded article having no thick turbidity in a molded article having a thick-walled portion, excellent in flame retardancy, and excellent in heat discoloration. The present invention relates to a polycarbonate resin composition.

  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.

  Under such circumstances, in recent years, many metal salt compounds typified by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. When an organometallic salt compound is used as a flame retardant, the effect can be obtained in a relatively small amount, and it is difficult without impairing the mechanical properties such as impact resistance, heat resistance, and electrical properties inherent to the polycarbonate resin. This is because flammability can be imparted.

  Examples of the flame-retarding technology of polycarbonate using a metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkyl sulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), and perfluoroalkane sulfone having 1 to 3 carbon atoms. A method of imparting flame retardancy to an aromatic polycarbonate resin using an alkali metal salt compound of perfluoroalkanesulfonic acid, such as a method of blending an alkali metal salt of an acid (see Patent Document 2); Using an alkali metal salt compound of an aromatic sulfonic acid such as a method of containing an acid sodium salt (see Patent Document 3) and a method of containing a non-halogenated aromatic sulfonic acid potassium salt (see Patent Document 4) A technique for imparting flame retardancy to a polycarbonate resin composition has been proposed.

Japanese Patent Publication No. 47-40445 Japanese Patent Publication No.54-32456 JP 2000-169696 A JP 2001-181493 A

However, such a flame retardant with a metal salt compound is not necessarily sufficient depending on the purpose of use, and in particular, in the case of a molded product having a thick part, white turbidity occurs when the molded product is slowly cooled. There are problems, and thick molded products such as LED lenses, optical molded products such as LED lenses, home appliances such as LCD TV frames and various housings, etc. In this product, it becomes a defect.
The present invention has been made in view of such problems, and an object of the present invention is to provide a polycarbonate resin composition for a thick-walled molded article having no white turbidity, excellent flame retardancy, and excellent heat discoloration. .

As a result of intensive investigations to achieve the above-mentioned problems, the present inventor used a polycarbonate resin containing a high molecular weight polycarbonate resin and a low molecular weight polycarbonate resin in a specific quantitative ratio, and a flame retardant for this. A polycarbonate resin composition containing a specific amount of sodium trifluoromethanesulfonate and / or sodium pentafluoroethanesulfonate as a molded article having a thick part particularly having a thickness of 5 mm or more obtained by molding the polycarbonate resin composition, As a result, the present inventors have found that the thick-walled portion has no cloudiness, is excellent in flame retardancy, and is excellent in heat discoloration, and has completed the present invention.
The present invention provides the following polycarbonate resin composition for thick molded articles.

[1] 1 to 50 parts by weight of a polycarbonate resin (A1) having a viscosity average molecular weight (Mv) of 40,000 to 200,000 and a viscosity average molecular weight (100 parts by weight of (A1) and (A2)) 100 parts by mass of polycarbonate resin (A) containing 99-50 parts by mass of polycarbonate resin (A2) having Mv) of 7,000-35,000, sodium trifluoromethanesulfonate and / or sodium pentafluoroethanesulfonate A polycarbonate resin composition for a thick molded article, which is contained in an amount of 0.01 part by mass or more and less than 0.1 part by mass and has a thick part having a thickness of 5 mm or more.
[2] The polycarbonate resin composition for thick-walled molded products according to [1], which is for thick-walled molded products having a thick portion having a thickness of 10 mm or more.
[3] The polycarbonate resin composition for thick-walled molded products according to the above [1] or [2], wherein the maximum recrystallization peak temperature of sodium trifluoromethanesulfonate and sodium pentafluoroethanesulfonate is 150 ° C. or lower.
[4] Using a film gate test piece of 50 × 50 × 12 mm, molding temperature 280 ° C., mold temperature 80 ° C., injection speed 25 mm / sec, injection pressure 50 MPa, holding pressure 70 MPa, primary filling time 3 seconds, injection holding A 12 mm-thick multi-purpose test piece injection-molded under conditions of a pressure time of 15 seconds, a cooling time of 20 seconds, a screw rotation speed of 100 rpm, and a back pressure of 10 MPa has a haze change of 1% or less when held at 140 ° C. for 500 hours. Item 4. The polycarbonate resin composition for thick molded articles according to any one of Items 1 to 3.

When the polycarbonate resin composition for thick molded articles of the present invention is a molded article having a thick part of 5 mm or more, there is no problem of white turbidity in the thick part and it is difficult to achieve both excellent flame retardancy. At the same time, and further has an excellent effect of excellent heat discoloration.
The resulting thick molded article can be particularly suitably used for applications that require high transparency, flame retardancy, and heat discoloration, such as lighting members that are exposed to light heat.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In addition, in this-application specification, unless there is particular notice, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[1. Overview]
1-100 mass parts and viscosity average molecular weights of polycarbonate resin (A1) whose viscosity average molecular weight (Mv) is 40,000-200,000 with respect to a total of 100 mass parts of (A1) and (A2). Sodium trifluoromethanesulfonate and / or sodium pentafluoroethanesulfonate with respect to 100 parts by mass of the polycarbonate resin (A) containing 99-50 parts by mass of the polycarbonate resin (A2) having (Mv) of 7,000-35,000 Is a polycarbonate resin composition for thick molded articles having a thick part with a thickness of 5 mm or more.
Hereinafter, each component, molded body, molding method thereof, and the like constituting the polycarbonate resin composition for thick molded articles of the present invention will be described in detail.

[2. Polycarbonate resin (A)]
The polycarbonate resin (A) used for the polycarbonate resin composition has a viscosity average molecular weight (Mv) of 40,000 to 200,000 and a viscosity average molecular weight (Mv) of 7,000 to 35,000. Contains polycarbonate resin (A2).
Examples of the polycarbonate resin include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins. The polycarbonate resins (A1) and (A2) are preferably aromatic polycarbonate resins, specifically Is a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid.

  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 resins (A1) and (A2) 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.

The molecular weight of the polycarbonate resin (A1) is higher than that of the polycarbonate resin (A2) of 40,000 to 200,000 in terms of viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Has an average molecular weight. On the other hand, the molecular weight of the polycarbonate resin (A2) is from 7,000 to 35,000, which is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Has a low viscosity average molecular weight.
By setting the viscosity average molecular weights of the polycarbonate resins (A1) and (A2) within the above ranges and a predetermined content of sodium trifluoromethanesulfonate or sodium pentafluoroethanesulfonate, the thickness of the thick molded article is increased. It becomes possible to solve the problem of white turbidity at the time of cooling of the part, to be excellent in flame retardancy, and to exhibit excellent heat discoloration.

The molecular weight of the polycarbonate resin (A1) is preferably 45,000 or more, more preferably 50,000 or more, further preferably 55,000 or more, particularly preferably 60,000 or more, preferably 170,000 or less, more Preferably it is 150,000 or less, More preferably, it is 100,000 or less, Most preferably, it is 90,000 or less.
The molecular weight of the polycarbonate resin (A2) is preferably 9,000 or more, more preferably 11,000 or more, still more preferably 13,000 or more, particularly preferably 15,000 or more, preferably 34,000 or less. More preferably, it is 33,000 or less, More preferably, it is 30,000 or less, Most preferably, it is 29,000 or less.

  The production method of the polycarbonate resins (A1) and (A2) is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melt polymerization method (transesterification method) is also used. be able to. 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 melt-polymerization method.

  When the polycarbonate resins (A1) and (A2) contain 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, and usually more than 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more. By setting the content of the linear polycarbonate resin in the polycarbonate resin within the above range, an advantage that a polycarbonate resin excellent in flame retardancy and moldability is easily obtained can be obtained.

  Polycarbonate resins (A1) and (A2) are polycarbonate resins alone (polycarbonate resins alone are not limited to embodiments containing only one type of polycarbonate resin. For example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights are used. It may be used in the meaning including the aspect of inclusion.) Or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Moreover, in order to improve the external appearance and fluidity of the molded product, the polycarbonate resins (A1) and (A2) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resins (A1) and (A2) may be not only virgin raw materials but also polycarbonate resins regenerated from used products (so-called material-recycled polycarbonate resins). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins (A1) and (A2) contained in the polycarbonate resin composition of the present invention. More preferred. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[3. Sodium trifluoromethanesulfonate (B1), sodium pentafluoroethanesulfonate (B2)]
The polycarbonate resin composition of the present invention contains sodium trifluoromethanesulfonate (B1) and / or sodium pentafluoroethanesulfonate (B2).
Examples of organic sulfonic acid metal salts as flame retardants include aliphatic sulfonic acid metal salts such as perfluoroalkane sulfonic acid metal salts, and aromatic sulfonic acid metal salts such as perfluoroalkane sulfonic acid metal salts. The metal of the sulfonic acid metal salt includes alkali metals such as sodium, lithium, potassium, rubidium and cesium, and alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium. The sodium salt of lomethanesulfonic acid (B1) or the sodium salt of pentafluoroethanesulfonic acid (B2) is used.
Sodium trifluoromethanesulfonate and sodium pentafluoroethanesulfonate achieve a very low haze value of 2% or less even in thick wall molding while satisfying V-0 in the vertical combustion test in accordance with UL94. These organic sulfonic acid metal salts were found to be unable to achieve these.

The content of sodium trifluoromethanesulfonate (B1) and / or sodium pentafluoroethanesulfonate (B2) is 0.01 parts by mass or more and 0.1 parts by mass with respect to 100 parts by mass in total of the polycarbonate resins (A1) and (A2). It is necessary to be less than 1 part by mass. When both are used together, it is the total amount.
The content of sodium trifluoromethanesulfonate (B1) and / or sodium pentafluoroethanesulfonate (B2) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.03. The amount is not less than mass parts, preferably not more than 0.095 parts by mass, more preferably not more than 0.090 parts by mass, and still more preferably not more than 0.085 parts by mass.
When the amount is less than 0.01 parts by mass, the flame retardancy of the molded product is deteriorated and the level is reduced to the V-2 level. If the amount is 0.01 parts by mass or more, the flame retardancy of the molded product deteriorates or haze deteriorates.

  The maximum recrystallization peak temperature of sodium trifluoromethanesulfonate (B1) and sodium pentafluoroethanesulfonate (B2) is preferably a temperature close to the glass transition temperature of the polycarbonate resin, specifically 150 ° C. or less. . The recrystallization maximum peak temperature is preferably 150 ° C. or lower because it becomes difficult to become cloudy in the polycarbonate resin composition during molding.

The recrystallization maximum peak temperature is measured according to the DSC (Differential Scanning Calorimetry) method described in JIS K7121. Specifically, it is measured by the method described in the examples. When there are a plurality of recrystallization temperature peaks or more, the peak temperature is the highest temperature side.
The maximum recrystallization peak temperature depends on the crystallinity of the flame retardant used, and those having a temperature of 150 ° C. or lower can be selected from various sodium trifluoromethanesulfonates and sodium pentafluoroethanesulfonates. .

[4. Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include flame retardants other than sodium trifluoromethanesulfonate or sodium pentafluoroethanesulfonate, thermal stabilizers, antioxidants, mold release agents, ultraviolet absorbers, dyes and pigments, and optical brighteners. , Anti-dripping agent, antistatic agent, anti-fogging agent, lubricant, anti-blocking agent, fluidity improver, plasticizer, dispersant, antibacterial agent and the like.

-Heat stabilizer As a heat stabilizer, a phosphorus compound is mentioned, for example. 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.

  The content of the heat stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). Usually, it is 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less. 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.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example. 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.

  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 with respect to 100 parts by mass of the polycarbonate resin (A). .5 parts by mass 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.

-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 15,000, and polysiloxane silicone oils. It is done.

  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. The ester of the aliphatic carboxylic acid and the alcohol is preferably a full ester.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 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 5,000 or less.

  The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). 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.

UV absorbers Examples of UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, hindered amines Examples include organic ultraviolet absorbers such as compounds. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. 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 preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), and the upper limit thereof is preferably 1 part by mass. Part or less, more preferably 0.5 part by weight or less. 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.

-Anti-drip agent As an anti-drip agent, it is preferable to contain 0.01-1 mass part of fluororesins with respect to 100 mass parts of polycarbonate resin (A). By containing the fluororesin in this manner, the melting characteristics of the resin composition can be improved, and specifically, the dripping prevention property at the time of combustion can be improved.

  If the content of the fluororesin is less than 0.01 parts by mass, the effect of improving the flame retardancy due to the fluororesin tends to be insufficient. Decline is likely to occur. The lower limit of the content is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, and the upper limit of the content is more preferably 0. .75 parts by mass or less, more preferably 0.6 parts by mass or less, and particularly preferably 0.5 parts by mass or less.

Of these, fluoroolefin resins are preferred as the fluororesin. 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.
Moreover, as this fluororesin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Examples of the fluoroolefin resin having a fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” manufactured by Daikin Chemical Industries, Ltd. "," Polyflon (registered trademark) FA500 "and the like. Furthermore, as commercially available products of aqueous dispersions of fluoroolefin resins, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon ( Registered trademark) D-1 "and the like.

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. For example, a method for producing the same is mentioned.

The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p. -Methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4- Aromatic vinyl monomers such as dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Examples thereof include diene monomers such as butadiene, isoprene and dimethylbutadiene. In addition, these monomers can be used individually or in mixture of 2 or more types.

  Among them, as a monomer for producing an organic polymer covering a fluoroolefin resin, those having a high affinity with an aromatic polycarbonate resin are preferable from the viewpoint of dispersibility when blended with an aromatic polycarbonate resin. An aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded product tends to be excellent.

As such an organic polymer-coated fluoroolefin resin, specifically, “Metabrene (registered trademark) A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex (registered trademark) 449” manufactured by GE Specialty Chemical Co., Ltd., PIC Company "Poly TS AD001" manufactured by the company etc. are mentioned.
In addition, 1 type may contain fluorine-type resin, and 2 or more types may contain it by arbitrary combinations and a ratio.

[5. Production method of polycarbonate resin composition]
There is no limitation on the production method of the polycarbonate resin composition, and a wide variety of production methods of known polycarbonate resin compositions can be adopted. Polycarbonate resins (A1) and (A2), sodium trifluoromethanesulfonate (B1) and / or pentafluoroethane Sodium sulfonate (B2) and other ingredients blended as necessary are pre-mixed using various mixers such as tumblers and Henschel mixers, and then Banbury mixer, roll, Brabender, single-screw kneading extrusion And a melt kneading method using a mixer such as a machine, a twin-screw kneading extruder, or a kneader. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[6. Molding]
The polycarbonate resin composition of the present invention is suitably molded as a thick molded product having a thick part having a thickness of 5 mm or more.
In the present invention, the thickness of the molded product means the thickness (mm) in the plate-like portion, and the rod-like, spherical, and convex shapes mean the diameter or height (mm). In the present invention, the thick-walled molded article may have at least a part having a thickness of 5 mm or more, preferably 10 mm or more, and the other is a thin part less than 5 mm. Also good.
The molded product obtained by molding the resin composition of the present invention solves the problem of white turbidity generated in the thick part during the cooling process at the time of molding, and is excellent in flame retardancy and further in heat discoloration.

As specifically defined in the examples, the haze of the molded product is preferably 5% or less, more preferably 4% or less, and still more preferably measured as a slowly cooled product when the thickness is 12 mm. Is preferably 3% or less, particularly preferably 2% or less.
Further, the thick molded product obtained has little change in transparency before and after the heat treatment. Specifically, a film gate test piece of 50 × 50 × 12 mm is used, a molding temperature of 280 ° C., a mold temperature of 80 ° C., and an injection speed. 12mm thick multipurpose test injection molded under the conditions of 25mm / sec, injection pressure 50MPa, holding pressure 70MPa, primary filling time 3 seconds, injection holding time 15 seconds, cooling time 20 seconds, screw rotation speed 100rpm, back pressure 10MPa The haze change when holding the piece at 140 ° C. for 500 hours is preferably 1% or less, more preferably 0.95% or less.

The molded product can be manufactured by molding pellets obtained by pelletizing the above polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The molding method applied to produce a thick molded product having a thick part having a thickness of 5 mm or more is preferably an injection molding method, an extrusion molding method, a hollow molding method, an injection compression molding method, a transfer molding method, etc. The molding method is mentioned. Of these, the injection molding method is particularly preferable.

  The thick molded product obtained by molding the polycarbonate resin composition of the present invention can be suitably used in various fields. For example, in addition to incandescent bulbs and fluorescent lamps, it can be suitably used for parts of devices and instruments that directly or indirectly use light sources such as cold cathode tubes, LEDs, and organic EL. Specific examples include LED lenses, mobile phones, mobile terminals, cameras, watches, notebook computers, various displays, lighting equipment parts, signal equipment parts, automotive headlamps, tail lamps, and home appliance / OA equipment displays. Although parts etc. are mentioned, it is not limited to these.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.

(Examples 1-9, Comparative Examples 1-8)
The following polycarbonate resins (A1-1) to (A1-2) and (A2-1) to (A2-3) were used as the polycarbonate resin.
(A1-1):
Linear aromatic polycarbonate resin obtained by interfacial polymerization method based on Example 1 (synthesis of PC-1) of International Publication WO2011 / 132510 Viscosity average molecular weight 67,000
(A1-2):
Linear aromatic polycarbonate resin obtained by interfacial polymerization method based on Example 1 (synthesis of PC-1) of International Publication WO2011 / 132510 Viscosity average molecular weight 75,000
(A2-1):
Branched aromatic polycarbonate resin obtained by melt polymerization method “NOVAREX (registered trademark) M7027BF” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 27,000
(A2-2):
Linear aromatic polycarbonate resin obtained by interfacial polymerization method “Iupilon (registered trademark) H-4000” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 17,000
(A2-3):
Linear aromatic polycarbonate resin obtained by the interfacial polymerization method “Iupilon (registered trademark) E-2000” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 27,000

[Flame retardants (B1) and (B2)]
(B1): Sodium trifluoromethanesulfonate, manufactured by Mitsubishi Materials Denka Kasei Co., Ltd., trade name “F-top EF-13”
Recrystallization peak temperature 123, 163, 207 ° C (maximum peak temperature 207 ° C)
(B2): Sodium pentafluoroethane sulfonate manufactured by Mitsubishi Materials Electronic Chemicals, trade name “F-top EF-23”
Recrystallization peak temperature 146 ° C
The recrystallization temperature was increased from 50 ° C. to 300 ° C. at a rate of 30 ° C./min using a differential scanning calorimeter “DSC220U type” manufactured by Seiko Instruments Inc. and held for 3 minutes. The temperature is lowered to 50 ° C. at a rate of 10 ° C./minute, held for 3 minutes, then raised to 300 ° C. at a rate of 10 ° C./minute, held for 3 minutes, and then raised to 50 ° C. at a rate of 30 ° C./minute. It was obtained from the DSC curve measured.

[Other flame retardants]
The following were used as flame retardants other than the above.
(B3): Potassium nonafluorobutanesulfonate, manufactured by DIC, trade name “Megafac F114”
Recrystallization peak temperature 121,252, 271 ° C. (maximum peak temperature 271 ° C.)
(B4): Sodium heptafluoropropane sulfonate, trade name “F-top EF-33” manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
Recrystallization peak temperature 122, 193 ° C (maximum peak temperature 193 ° C)
(B5): Sodium nonafluorobutanesulfonate, trade name “F-top EF-43” manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
Recrystallization peak temperature 109, 132, 218 ° C (maximum peak temperature 218 ° C)
Moreover, the following polysilane was used as another flame retardant.
(E1) Decaphenylcyclopentasilane Product name “Ogsol SI-30” manufactured by Osaka Gas Chemical Co., Ltd.

[Release agent (C)]
The following were used as the release agent (C).
(C1) Pentaerythritol tetrastearate Product name “Roxyol VPG861” manufactured by Cognis Japan
(C2) Stearyl stearyl acid product name "Unistar M9676" manufactured by NOF Corporation
[Stabilizer (D)]
The following were used as the stabilizer (D).
(D1) Phosphorus stabilizer Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA, trade name “ADK STAB 2112”
(D2) Phenol-based antioxidant stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ADEKA, trade name “ADK STAB AO-50”

[Production of resin composition pellets]
Each component described above was blended in the proportions (all parts by mass) shown in Table 1 and Table 2, mixed for 20 minutes with a tumbler, and then a twin screw extruder (TEX30HSST) made by Nippon Steel Works, equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is quenched in a water tank, pelletized using a pelletizer, and polycarbonate resin composition A product pellet was obtained.

[Fluidity evaluation: Q value]
After the pellets obtained as described above were dried at 120 ° C. for 4 hours or longer, JIS K7210
Using a Koka flow tester according to the method described in Appendix C, the outflow Q value per unit time of the composition under the conditions of 280 ° C. and a load of 160 kgf / cm ² (unit: × 10 ⁻² cm ³ / 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.

[Flame Retardancy Evaluation (UL)]
For each resin composition obtained in the examples and comparative examples, using an injection molding machine J50 manufactured by Nippon Steel Works, injection molding was performed under the conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C., a length of 127 mm, Molded articles having a width of 12.7 mm, a thickness of 1.5 mm, 2 mm, and 3 mm were obtained as test pieces. About the obtained test piece, the vertical combustion test based on UL94V was done, the flammability result was set to V-0, V-1, V-2 from the favorable order, and the thing outside a specification was classified into NG.

[Haze (%)]
Using an injection molding machine J50 manufactured by Nippon Steel Co., Ltd., molding temperature 280 ° C., mold temperature 80 ° C., injection speed 25 mm / sec, injection pressure = 50 MPa, holding pressure = 70 MPa, primary filling time = 3 seconds, injection holding pressure Molded articles having a length of 50 mm, a width of 50 mm, a thickness of 3 mm, 5 mm, and 12 mm were obtained as test pieces under the conditions of time = 15 seconds, cooling time = 20 seconds, screw rotation speed 100 rpm, and back pressure = 10 MPa. .
Measurement is performed on NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7136 for molded products with thicknesses of 3 mm, 5 mm, and 12 mm that are slowly cooled by being left at room temperature after taking out from the molding machine. It was measured.

[Haze change (%)]
The molded product having a thickness of 12 mm was held at 140 ° C. for 500 hours, and the haze change (ΔHaze:%) before and after treatment was measured with a SE2000 type official color meter manufactured by Nippon Denshoku Industries Co., Ltd.
[YI value change]
Further, the above molded product having a thickness of 3 mm is held at 140 ° C. for 500 hours, and the Y2000 (Yellow Index) value is measured before and after the treatment by the transmission method using a SE2000 type partial colorimeter manufactured by Nippon Denshoku Industries Co., Ltd. Was measured. A smaller ΔYI is preferable because it shows less discoloration by the heat resistance test, that is, better heat discoloration.
The above evaluation results are shown in Tables 1 and 2.

From Examples 1 to 9, it can be seen that the polycarbonate resin composition of the present invention has no cloudiness in the thick part, is excellent in flame retardancy, and is excellent in heat discoloration.
On the other hand, in Comparative Example 1 using only the linear aromatic polycarbonate resin in the range of the viscosity average molecular weight defined in (A2) and Comparative Example 6 using polysilane as the flame retardant, the flame retardancy is poor (at 3 mm thickness). V-2) In Comparative Example 2 using a branched and linear aromatic polycarbonate mixture having a viscosity average molecular weight of A2, it can be seen that the hue (heat-resistant discoloration) after heat treatment is inferior.

Further, Comparative Examples 3 to 5 and 7 using a metal salt flame retardant different from sodium trifluoromethanesulfonate and sodium pentafluoroethanesulfonate of the present invention have a high haze at 12 mm (Comparative Example 7 has a thickness of 5 mm). However, it is understood that the transparency of the thick portion is inferior.
Furthermore, it can be seen that even in Comparative Example 8 in which the amount of the flame retardant of the present invention is too large, the haze at 12 mm thickness is high and the transparency of the thick part is inferior.

  The polycarbonate resin composition of the present invention has no thick turbidity in a molded product having a thick part, and is excellent in flame retardancy and further in heat-resistant discoloration. In addition to light bulbs and fluorescent lamps, it can be used very suitably for parts of equipment and appliances that directly or indirectly use light sources such as cold cathode fluorescent lamps, LEDs, and organic ELs, and have very high industrial applicability.

Claims (4)

  1 to 50 parts by mass and viscosity average molecular weight (Mv) of polycarbonate resin (A1) having a viscosity average molecular weight (Mv) of 40,000 to 200,000 with respect to 100 parts by mass of (A1) and (A2) in total. To 100 parts by mass of polycarbonate resin (A) containing 99 to 50 parts by mass of 7,000 to 35,000 polycarbonate resin (A2), 0.01% of sodium trifluoromethanesulfonate and / or sodium pentafluoroethanesulfonate is added. A polycarbonate resin composition for thick-walled molded articles, comprising a part having a thickness of at least 5 mm and a thickness of at least 5 mm.   The polycarbonate resin composition for thick-walled molded products according to claim 1, which is for thick-walled molded products having a thick part having a thickness of 10 mm or more.   The polycarbonate resin composition for thick-walled molded articles according to claim 1 or 2, wherein the maximum recrystallization peak temperature of sodium trifluoromethanesulfonate and sodium pentafluoroethanesulfonate is 150 ° C or lower.   Using a film gate test piece of 50 × 50 × 12 mm, molding temperature 280 ° C., mold temperature 80 ° C., injection speed 25 mm / sec, injection pressure 50 MPa, holding pressure 70 MPa, primary filling time 3 seconds, injection holding time 15 The haze change when a 12 mm-thick multipurpose test piece injection-molded under the conditions of second, cooling time 20 seconds, screw rotation speed 100 rpm, and back pressure 10 MPa is 1% or less when held at 140 ° C. for 500 hours is 1% or less. 4. A polycarbonate resin composition for thick molded articles according to any one of 3 above.