JP4877705B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition. More specifically, a flame retardant polycarbonate resin composition having a very high fluidity and impact strength, containing a specific amount of a terpene resin, an organometallic salt compound, a fiber-forming fluorine-containing polymer, and a specific rubbery elastic body. About. Furthermore, since a conventional flame retardant containing halogen or phosphorus is not used at all, a composition having extremely excellent environmental harmony can be obtained.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in the fields of electric / electronic / ITE, machine, automobile, building material and the like. Among these, in the fields of electric, electronic, and ITE, there are many parts that require high flame resistance (UL94V) and impact resistance, such as personal computer exterior parts. Polycarbonate resin is a highly flame-retardant plastic material with self-extinguishing properties. However, in order to meet safety requirements in the electric, electronic, and OA fields, it has higher flame resistance equivalent to UL94V-0 and V-1. Is required.

  Therefore, in order to improve the flame retardancy of the polycarbonate resin, conventionally, a method of blending a halogen compound or a phosphorus compound as a flame retardant has been adopted. Among these, particularly for halogen compounds such as bromine and chlorine, it is desired to use a flame retardant that does not contain them from the environmental viewpoint.

  On the other hand, terpene resins have been used for flame-retardant polycarbonate resins (Patent Documents 3 and 4), but terpene resins are not used as those that provide a flame-retardant effect. The flame retardant was achieved by adding a flame retardant such as.

Japanese Unexamined Patent Publication No. 7-179742 JP-A-9-95610 JP 2000-63651 A JP 2003-160724 A

  In recent years, products using polycarbonate resin have become increasingly lighter and thinner, and in addition to the above-mentioned excellent performance, halogen-based or phosphorus-based flame retardants are used in order to satisfy design and design requirements. There has been a need for a material having a high flame retardancy and a high fluidity (formability).

  The present inventors incorporated a specific amount of a terpene resin, an organometallic salt compound, a fiber-forming fluorine-containing polymer, and a rubber-like elastic body into a polycarbonate resin, thereby adding a conventional flame retardant containing halogen, phosphorus, or the like. It has been found that a polycarbonate resin composition having a balance of flame retardancy, fluidity, strength and appearance can be obtained synergistically without use, and the present invention has been completed.

That is, the present invention is based on a total of 100 parts by weight of the resin component consisting of 80 to 99.5% by weight of the polycarbonate resin (A) and 0.5 to 20% by weight of the terpene resin (B). And (B) may be referred to as “resin component”.), Metal salt of aromatic sulfonic acid or metal salt of perfluoroalkanesulfonic acid (C) 0.005 to 2 parts by weight, A flame retardant polycarbonate resin composition comprising 0.05 to 2 parts by weight of a fluoropolymer (D) and 0.1 to 5 parts by weight of a rubber-like elastic body (E) is provided.

  The flame retardant polycarbonate resin composition of the present invention has excellent fluidity, strength and appearance, and does not use a conventional flame retardant containing halogen, phosphorus, etc. There is no concern about occurrence, and it is extremely excellent in terms of environmental harmony. Furthermore, since it is excellent also in fluidity | liquidity, intensity | strength, etc., it can be used conveniently as various large sized or thin wall molded articles and various flame-retardant industrial component materials, and industrial utility value is very high.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These are used singly or as a mixture of two or more types, but are preferably not substituted with halogen from the viewpoint of preventing discharge of the gas containing halogen, which is concerned during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination.
Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 17,000 to 28,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

  The terpene resin (B) used in the present invention includes α-pinene resin, β-pinene resin, limonene resin, dipentene resin, β-pinene / limonene resin, hydrogenated limonene resin, aromatic modified terpene resin, phenol. Modified terpene resins and the like are included.

  The terpene resin (B) is obtained using a terpene compound as a raw material, and the terpene compound is generally a compound having a basic skeleton of a polymer of isoprene such as monoterpene, sesquiterpene, and diterpene. As a terpene compound, α-pinene, β-pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole , Α-terpineol, β-terpineol, γ-terpineol, sabinene, paramentadienes, and carenes, preferably α-pinene, β-pinene, dipentene, and d-limonene.

  The terpene resin (B) is obtained by cationically polymerizing these terpene compounds under a Friedel-Craft catalyst. In addition to the terpene compound alone, a terpene compound and an aromatic compound (the polymer is referred to as an aromatic-modified terpene resin), and a terpene compound and a phenol-based compound (the polymer is referred to as a phenol-modified terpene resin) are used as raw materials. Also good. Examples of the aromatic compound include styrene, α-methylstyrene, vinyl toluene, and divinyl toluene. Examples of the phenol compound include phenol, bisphenol A, cresol, and xylenol. Moreover, you may use what hydrogenated the obtained said terpene resin. Further, as the terpene resin, a terpene compound, and a combination of components such as a cyclic polyolefin and an acyclic monounsaturated olefin may be used.

  As such a terpene resin (B), for example, “YS Resin PX” (terpene resin), “YS Resin TO” (aromatic modified terpene resin), “YS Resin TR” (aromatic) manufactured by Yashara Chemical Co., Ltd. Modified terpene resin), “Clearon” (hydrogenated terpene resin), “YS polyster” (phenol-modified terpene resin), “Mighty Ace” (phenol-modified terpene resin), and the like are listed.

  The compounding quantity of terpene resin (B) is 0.5 to 20 weight% in a resin component, Preferably it is 1 to 10 weight%. If it is less than 0.5% by weight, it is difficult to obtain a synergistic effect, so that sufficient flame retardancy is not exhibited. On the other hand, if it exceeds 20% by weight, the terpene resin (B) itself is not flammable, so it is difficult to obtain flame retardancy.

  Examples of the organic metal salt compound (C) used in the present invention include aromatic sulfonic acid metal salts and perfluoroalkanesulfonic acid metal salts. Examples of the metal include alkali metals and alkaline earth metals. Preferably, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, paratoluenesulfonic acid Sodium, perfluorobutanesulfonic acid potassium salt and the like can be preferably used.

  The compounding amount of the organometallic salt compound (C) is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.015 to 0.3 parts by weight, with respect to 100 parts by weight of the resin component. Range. If the blending amount is less than 0.005 parts by weight, it is difficult to obtain a synergistic effect, so that the flame retardancy is lowered. On the other hand, when the amount exceeds 2 parts by weight, problems such as failure to obtain impact strength and flame retardancy and deterioration of the surface appearance may occur.

  As the fiber-forming fluorine-containing polymer (D) used in the present invention, those that form a fiber structure (fibril structure) in the resin component are preferable. Polytetrafluoroethylene, tetrafluoroethylene-based copolymer Examples thereof include a polymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer, etc.), a partially fluorinated polymer as shown in US Pat. No. 4,379,910, a polycarbonate produced from a fluorinated diphenol, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used.

  The amount of the fiber-forming fluoropolymer (D) is 0.05 to 2 parts by weight with respect to 100 parts by weight of the resin component. If the blending amount is less than 0.05 parts by weight, a synergistic effect is hardly obtained and the effect of preventing dripping at the time of combustion is inferior. On the other hand, when the amount exceeds 2 parts by weight, it is not preferable because granulation of the resin composition becomes difficult, which hinders stable production. This amount is preferably in the range of 0.1 to 1 part by weight, more preferably 0.2 to 0.5 part by weight. In this range, the balance between flame retardancy and moldability is further improved.

  The rubber-like elastic body (E) used in the present invention is not particularly limited, but in particular, a butadiene rubber-like elastic body having a core / shell structure, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate. A composite rubber-based graft copolymer in which one or two or more vinyl monomers are graft-polymerized to a composite rubber having a structure intertwined so that the rubber component cannot be separated is preferably used. It is done.

A butadiene rubber-like elastic body having a core / shell structure is a polymer comprising a polybutadiene polymer in the core part and a styrene polymer or a styrene / methyl methacrylate copolymer in the shell part. Examples include Paramex EXL2602 and EXL2603 manufactured by Rohm & Haas.

In order to obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more members, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane. Etc., and a latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a crosslinking agent and / or a grafting agent, and then an alkyl (meth) acrylate monomer, a crosslinking agent and a grafting agent are added to the polyorganosiloxane rubber. It is obtained by impregnating with a latex and polymerizing. Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate and 2-ethylhexyl methacrylate. Although methacrylate is mentioned, it is particularly preferable to use n-butyl acrylate. Examples of vinyl monomers to be graft polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic monomers such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. The average particle size of the composite rubber is preferably 0.08 to 0.6 μm. When the average particle size of the composite rubber is less than 0.08 μm, the impact resistance of the resulting resin composition is lowered, and when the average particle size exceeds 0.6 μm, the surface appearance of the molded product of the resulting resin composition is deteriorated. . Particularly preferred is a product marketed under the trade name of Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.

The compounding amount of the rubber-like elastic body (E) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin component. More preferably, it is the range of 1-3 weight part. If the blending amount is less than 0.1 parts by weight, the degree of improvement in impact strength is insufficient, such being undesirable. On the other hand, if the amount exceeds 5 parts by weight, the flame retardancy may decrease, which is not preferable.

  Furthermore, various heat stabilizers, antioxidants (phosphorous and phenolic antioxidants), ultraviolet absorbers, colorants, fluorescent brighteners, mold release agents, softening materials, as long as the effects of the present invention are not impaired. , Additives such as antistatic agents, spreading agents (epoxy soybean oil, liquid paraffin, etc.), and other polymers may be blended. Examples of the heat stabilizer include metal hydrogen sulfate such as sodium hydrogen sulfate, potassium hydrogen sulfate, and lithium hydrogen sulfate, and metal sulfate such as aluminum sulfate.

  There are no particular restrictions on the mixing order or mixing method of the various components in the flame-retardant polycarbonate resin composition of the present invention, and mixing with a known mixer such as a tumbler or ribbon blender is possible. It can be easily melt-kneaded by a normal single-screw or twin-screw extruder.

  There is no restriction | limiting in particular as a method of shape | molding the flame-retardant polycarbonate resin composition of this invention, A well-known injection molding method, injection / compression molding method, etc. can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Parts” are based on weight.

  Based on the blending components and blending amounts shown in Tables 2-3, various blending components were mixed using a tumbler, and the cylinder temperature was adjusted to 240 ° C using a 37 mm diameter twin screw extruder (KTX-37 manufactured by Kobe Steel). And kneaded to obtain pellets of various resin compositions.

The compounding components used are as follows.
Polycarbonate resin:
Sumitomo Dow Caliber 200-20
(Viscosity average molecular weight 19000, hereinafter abbreviated as “PC”)
Terpene resin:
Yashara Chemical Co., Mighty Ace G-150
(Phenol-modified terpene resin, hereinafter abbreviated as “terpene resin”)
Organometallic salt compounds:
Sodium paratoluenesulfonate (hereinafter abbreviated as “metal salt”)
Fiber-forming fluorine-containing polymer:
Made by Daikin, Polyflon FA-500
(Polytetrafluoroethylene, hereinafter abbreviated as “PTFE”)
Rubber elastic body:
Rohm & Haas, Paraloid, EXL2602
Butadiene rubbery elastic body with styrene polymer in the shell (hereinafter abbreviated as “rubbery elastic body 1”)
Mitsubishi Rayon Co., Ltd., Metabrene S-2001
(Hereinafter abbreviated as “rubber-like elastic body 2”)

(appearance)
The obtained pellets of various resin compositions were dried at 105 ° C. for 4 hours, and then used with an injection molding machine (J-100-E-C5 manufactured by Nippon Steel Works), with a melting temperature of 245 ° C. and an injection pressure of 1600 kg / cm ^2. A test piece for flame retardancy evaluation (125 × 13 × 1.6 mm) was molded under the above conditions, and the appearance of the molded product was visually observed.

(Flame retardance)
The above-mentioned test piece is left for 72 hours in a temperature-controlled room with a temperature of 23 ° C. and a humidity of 50%, and it is difficult to comply with the UL94 test (flammability test of plastic materials for equipment parts) established by Underwriters Laboratories. Flammability was evaluated. The classes according to UL94 are shown in Table 1.
V-0 was determined to be acceptable.

  The after flame time is the length of time that the test piece after the ignition source is moved away from the flame, and the ignition of the cotton by the drip is for the sign about 300 mm below the lower end of the test piece. Of cotton is ignited by a drip from the specimen.

(Liquidity)
The obtained pellets of various resin compositions were dried at 105 ° C. for 4 hours, and then subjected to conditions of a melting temperature of 280 ° C. and an injection pressure of 1600 kg / cm ^{2 using} an injection molding machine (J-100-E-C5 manufactured by Nippon Steel). The flow length (unit: mm) was measured using an Archimedes spiral flow mold (width 10 mm, thickness 1.0 mm). A flow length of 125 mm or more was regarded as acceptable.

(Impact strength)
After the pellets of the various resin compositions obtained were dried at 105 ° C. for 4 hours, using an injection molding machine (J-100SAII manufactured by Nippon Steel), a test piece for impact strength evaluation under the condition of a melting temperature of 270 ° C. 63 × 13 × 3.2 mm). And according to ASTM D256 standard, Izod impact strength with a notch was measured under the condition of 23 ° C. A value of 15 kg / cm / cm or more was considered acceptable.

  Each evaluation result was shown to Tables 2-3.

＊ ＮＲはどの難燃クラスにも属さないものを表す。

* NR represents not belonging to any flame retardant class.

  As shown in Examples 1 to 5, the polycarbonate resin composition having the constituent requirements of the present invention exhibits an extremely large fluidity improving effect and high impact strength while maintaining high flame retardancy.

On the other hand, as shown in Comparative Examples 1 to 6, in the case where the constituent requirements of the present invention were not satisfied, all had some drawbacks.
Comparative Examples 1 and 4 were cases where the blending amount of the rubber-like elastic material was further smaller than the lower limit of the specified range, and the impact strength was rejected.
In Comparative Examples 2 and 5, conversely, the amount of the rubber-like elastic material exceeded the upper limit of the specified range, and the flame retardancy and fluidity were rejected.
Comparative Examples 3 and 6 were cases where the blending amount of the terpene resin exceeded the upper limit of the specified range, and the flame retardancy, appearance, impact strength, etc. were rejected.

Claims (4)

Metal salt of aromatic sulfonic acid or perfluoroalkanesulfonic acid with respect to a total of 100 parts by weight of the resin component consisting of 80-99.5% by weight of polycarbonate resin (A) and 0.5-20% by weight of terpene resin (B) 0.005 to 2 parts by weight of a metal salt (C), 0.05 to 2 parts by weight of a fiber-forming fluoropolymer (D) and 0.1 to 5 parts by weight of a rubber-like elastic body (E) A flame retardant polycarbonate resin composition characterized by comprising: The flame retardant polycarbonate resin composition according to claim 1, wherein the terpene resin (B) is an aromatic modified terpene resin. The flame-retardant polycarbonate resin composition according to claim 1, wherein the terpene resin (B) is a phenol-modified terpene resin. The rubber-like elastic body (E) has a structure in which a butadiene-based rubber-like elastic body having a core / shell structure and / or a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. The flame-retardant polycarbonate resin composition according to claim 1, which is a composite rubber-based graft copolymer obtained by graft-polymerizing one or two or more vinyl-based monomers to the composite rubber.