JP5352568B2 - Polycarbonate resin molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin molded product, and more specifically, it is excellent in flame retardancy and transparency without impairing mechanical properties such as excellent impact resistance and the like of polycarbonate resin, and particularly in a molded product having a thick part. The present invention relates to a polycarbonate resin molded article that exhibits excellent transparency without causing any problems.

  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), 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. Thick molded products, for example optical molded products such as LED lenses, home appliances such as LCD TV frames and various housings, products that require high transparency and no cloudiness May cause defects.
This invention is made | formed in view of such a subject, and it aims at providing the polycarbonate resin molded product which has a thick-walled part which was excellent in the flame retardance without white turbidity.

  As a result of intensive studies to achieve the above-mentioned problems, the inventor has molded a polycarbonate resin containing a specific amount of a specific metal salt compound, particularly a molded product having a thick part having a thickness of 5 mm or more. The problem of white turbidity was solved, and it found out that it was excellent in a flame retardance, and came to complete this invention.

  That is, according to the first invention of the present invention, 2-5 mmol / sodium trifluoromethanesulfonate sodium (B-1) and / or sodium pentafluoroethanesulfonate (B-2) is added to the polycarbonate resin (A). There is provided a polycarbonate resin molded article having a thick part having a thickness of 5 mm or more, formed by molding a polycarbonate resin composition containing kg.

  According to a second aspect of the present invention, there is provided a polycarbonate resin molded product characterized in that, in the first invention, the polycarbonate resin molded product has a thick portion having a thickness of 10 mm or more.

  According to a third aspect of the present invention, there is provided a polycarbonate resin molded product according to the first or second invention, wherein the molded product has a haze of 5% or less.

  According to a fourth aspect of the present invention, there is provided a polycarbonate resin molded product characterized in that in any one of the first to third aspects, the polycarbonate resin composition contains a release agent.

  Furthermore, according to the fifth invention of the present invention, in any one of the first to fourth inventions, 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 is provided.

  According to the polycarbonate resin molded product of the present invention, the polycarbonate resin is excellent in flame retardancy and transparency without impairing mechanical properties such as impact resistance and the like, and white turbidity occurs in the molded product having a thick part. Thus, a polycarbonate resin molded product exhibiting excellent transparency can be obtained.

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]
The polycarbonate resin molded product of the present invention is a polycarbonate containing 2 to 5 mmol / kg of sodium trifluoromethanesulfonate (B-1) and / or sodium pentafluoroethanesulfonate (B-2) with respect to the polycarbonate resin (A). It is a polycarbonate resin molded product having a thick part having a thickness of 5 mm or more, formed by molding a resin composition.
Hereinafter, each component, molded body, molding method thereof, and the like constituting the resin composition used for the polycarbonate resin molded article of the present invention will be described in detail.

[2. Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) used in the polycarbonate resin composition include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, preferably an aromatic polycarbonate resin. 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, and resorcinol. 4,4-dihydroxydiphenyl and the like. 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) include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or a combination of 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. Polycarbonate resin. In the present invention, two or more polycarbonate resins may be used in combination as the polycarbonate resin (A).

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

  The production method of the polycarbonate resin (A) 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 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 (A) 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 polycarbonate resin with a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the molded product obtained can be suppressed, and a flame retardance 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 (A) in the polycarbonate resin composition used in 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, Usually, it is preferable to contain a certain proportion or more of a polycarbonate resin of 1.8 or less, preferably 1.7 or less, preferably an aromatic polycarbonate resin.
Thus, 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, dripping at the time of burning of the polycarbonate resin molded product Can be suppressed and 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 above 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 ηa in _a low shear region in which 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-hydroxyphenylheptene-3,1,3,5-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 used in the present invention, the polycarbonate resin (A) is a polycarbonate resin having the above-mentioned structural viscosity index N in a predetermined range (hereinafter, this polycarbonate resin may be referred to as “predetermined N polycarbonate resin”). ) In the polycarbonate resin is usually 20% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more. By combining with the predetermined N polycarbonate resin in this manner, the torque during extrusion is not increased more than necessary, so that the productivity is hardly lowered. That is, both formability and productivity can be exhibited remarkably.
In addition, there is no restriction | limiting in the upper limit of content of predetermined N polycarbonate resin in polycarbonate resin (A), Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less. is there.
Moreover, 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 (A) may contain 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.

  When the polycarbonate resin (A) 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. Moreover, it is more than 0 mass% normally, Preferably it is 10 mass% or more, More preferably, it is 15 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.

  The polycarbonate resin (A) is not limited to an embodiment including only one type of polycarbonate resin, and includes an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) 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.

  In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. 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 resin (A) may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). 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 recycled polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention. 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 (B-1), sodium pentafluoroethanesulfonate (B-2)]
The polycarbonate resin composition used in the present invention contains sodium trifluoromethanesulfonate (B-1) and / or sodium pentafluoroethanesulfonate (B-2).
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 romethanesulfonic acid or the sodium salt of pentafluoroethanesulfonic acid 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 or sodium pentafluoroethanesulfonate needs to be 2 to 5 mmol / kg with respect to the polycarbonate resin (A). When both are used together, the total amount is obtained. The preferred content is 2.2 to 4.8 mmol / kg, more preferably 2.3 to 4.7 mmol / kg, even more preferably 2.4 to 4.6 mmol / kg, especially 2.5 to 4.6 mmol / kg. It is.
When it is less than 2 mmol / kg, the flame retardancy of the molded product is deteriorated and the level is reduced to the V-2 level. If it exceeds 5 mmol / kg, the flame retardancy of the molded product is worsened and haze is worsened.

[4. Other additives]
The polycarbonate resin composition used in 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 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.

-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- (mesitylene 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 0.5 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.

-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.

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 part by mass or more, preferably 0.01 part by mass or more, and usually 2 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. 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] -benzo Triazole, 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], among others, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] is preferred, especially 2- (2-hydroxy-5-tert-octylphenyl) Benzotriazole is preferred.

  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, and the upper limit thereof is preferably 1 part by mass or less. More preferably, it is 0.5 parts by mass 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. 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 restriction | limiting in the manufacturing method of a polycarbonate resin composition, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, a polycarbonate resin (A), sodium trifluoromethanesulfonate (B-1), and / or pentafluoroethanesulfonic acid. Sodium (B-2) and other components blended as necessary are mixed in advance using various mixers such as a tumbler or a Henschel mixer, 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 molded product of the present invention can be produced 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.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, 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 Law. A molding method using a hot runner method can also be used.

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). The molded article only needs to have at least part of a thick part having a thickness of 5 mm or more, preferably 10 mm or more, and the other part may be a thin part less than 5 mm.
The molded product of the present invention is a molded product that solves the problem of cloudiness that occurs in the thick-walled part during the cooling process during molding and has excellent flame retardancy. As specifically defined in the examples, the haze of the molded body 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.

  The molding method applied to produce a polycarbonate resin molded article 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 method. Examples of the molding method include a molding method. Of these, the injection molding method is particularly preferable.

  The polycarbonate resin molded product 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 1-10, Comparative Examples 1-10)
[Polycarbonate resin (A)]
The following polycarbonate resins (A1) to (A3) were used as the polycarbonate resin.
(A-1):
Branched aromatic polycarbonate resin obtained by transesterification method “NOVAREX (registered trademark) M7027BF” manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 27,000, structural viscosity index N value 1.4
(A-2):
"Iupilon (registered trademark) H-4000N" made by Mitsubishi Engineering Plastics
Viscosity average molecular weight 16,000, structural viscosity index N value 1.0
(A-3):
"Iupilon (registered trademark) E-2000N" manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight 26,000, structural viscosity index N value 1.0

[Flame Retardant (B)]
(B-1): Sodium trifluoromethanesulfonate (CF ₃ SO ₃ Na)
(B-2): Sodium pentafluoroethanesulfonate (C ₂ F ₅ SO ₃ Na)

[Other flame retardants (C)]
The following were used as other flame retardants.
(C-1): Potassium trifluoromethanesulfonate (CF ₃ SO ₃ K)
(C-2): Potassium nonafluorobutanesulfonate (C ₄ F ₉ SO ₃ K) (trade name “Bayowet C4” manufactured by LANXESS)
(C-3): Sodium heptafluoropropane sulfonate (C ₃ F ₇ SO ₃ Na)
(C-4): Sodium nonafluorobutanesulfonate _{(C 4 F 9 SO 3 Na} )

[Release agent (D)]
The following were used as the release agent (D).
(D-1) Pentaerythritol tetrastearate (trade name “Roxyol VPG861” manufactured by Cognis Japan)
(D-2) Stearyl stearyl acid (trade name “Unistar M9676” manufactured by NOF Corporation)

[Production of resin composition pellets]
The components (A) to (D) described above were blended in the proportions shown in Tables 1 and 2 (parts by mass, but the amount of flame retardant added is also listed in mmol / kg), and tumbler for 20 minutes. After mixing, supply to a twin-screw extruder (TEX30HSST) made by Nippon Steel Works, equipped with one vent, knead under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., and extruded into a strand. The molten resin thus obtained was quenched in a water tank and pelletized using a pelletizer to obtain polycarbonate resin composition pellets.

[Fluidity evaluation]
After the pellets obtained as described above were dried at 120 ° C. for 4 hours or longer, JIS K7210
Using a high-load flow tester according to the method described in Appendix C, the outflow Q value of the composition per unit time 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 wall thickness of 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]
(2) Haze (3mm, 5mm, 12mm)
Using Nippon Steel Works' injection molding machine J50, the length is set at a relatively low pressure and low pressure with an injection pressure of 60 to 80 MPa and an injection speed of 20 to 40 mm / sec under conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C. Molded articles of 50 mm, width 50 mm, wall thickness 3 mm, 5 mm and 12 mm were obtained as test pieces. The measurement was performed on a molded product that was slowly cooled by being left at room temperature after being removed from the molding machine, and a molded product that was rapidly cooled by being immersed in ice water for 3 minutes immediately after molding, in accordance with JIS K-7136. Haze was measured with an NDH-2000 type haze meter manufactured by the company.
The above evaluation results are shown in Tables 1 and 2.

As is apparent from Table 1, the molded article of the example containing a predetermined amount of sodium trifluoromethanesulfonate (B-1) and / or sodium pentafluoroethanesulfonate (B-2) has excellent flame retardancy, Even a 12 mm thick slow-cooled molded product exhibits extremely good haze. In Example 10, a polycarbonate resin having a structural viscosity index N of less than 1.2 is used, but it is understood that the flame retardancy and the haze are slightly poor.
On the other hand, as is clear from Table 2, those containing a predetermined amount of sodium trifluoromethanesulfonate (B-1) and / or sodium pentafluoroethanesulfonate (B-2) of Comparative Example (Comparative Examples 7 to 10) Or what used other flame retardants shows that flame retardance is bad and a haze is very bad compared with the thing of an Example.

  The polycarbonate resin molded product of the present invention is excellent in flame retardancy and transparency, and does not cause white turbidity in a molded product having a thick part, and has excellent transparency. For example, in addition to incandescent bulbs, fluorescent lamps, etc. In addition, 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 (5)

  A polycarbonate resin composition containing 2 to 5 mmol / kg of sodium trifluoromethanesulfonate (B-1) and / or sodium pentafluoroethanesulfonate (B-2) is molded with respect to the polycarbonate resin (A). A polycarbonate resin molded product having a thick portion with a thickness of 5 mm or more.   The polycarbonate resin molded product according to claim 1, wherein the molded product is a polycarbonate resin molded product having a thick portion having a thickness of 10 mm or more.   The polycarbonate resin molded article according to claim 1 or 2, wherein the molded article has a haze of 5% or less.   The polycarbonate resin molded article according to any one of claims 1 to 3, wherein the polycarbonate resin composition contains a release agent.   The polycarbonate resin molded article according to any one of claims 1 to 4, 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.