JP4367919B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition, and more specifically, by blending a specific amount of a terpene resin, an organometallic salt compound, a fiber-forming fluoropolymer, and optionally an inorganic filler. The present invention relates to a flame retardant polycarbonate resin composition that exhibits excellent flame retardancy without using a conventional flame retardant containing phosphorus, and also has excellent fluidity and workability during granulation.

Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in fields such as electric / electronic / OA, machinery, automobiles, and building materials. Among these, in the field of electrical / electronic / OA, 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 blending a flame retardant such as.

JP 7-179742 A JP-A-9-95610 JP2000-63651 JP2003-160724

  An object of the present invention is to provide a flame retardant polycarbonate resin composition that does not contain halogen or phosphorus, exhibits excellent flame retardancy, and is extremely excellent in fluidity and workability during granulation. Since it does not contain halogen or phosphorus, it is desirable from the environmental point of view, and furthermore, because it is excellent in processability such as fluidity, it is suitable as various large-sized or thin-walled molded products and various flame-retardant industrial component materials.

The present inventors blended a specific amount of a terpene resin, an organometallic salt compound and a fiber-forming fluorine-containing polymer with respect to a polycarbonate resin without using a conventional flame retardant containing halogen or phosphorus. The present invention was completed by finding a synergistic effect that brings about excellent flame retardancy.
That is, this invention contains (A) polycarbonate resin 80-98 weight% and (B) terpene resin 2-20 weight% so that it may become a total of 100 weight part, and also (C) organometallic salt compound 0.02 A flame-retardant polycarbonate resin composition comprising ~ 2 parts by weight, (D) 0.05 to 5 parts by weight of a fiber-forming fluoropolymer, and (E) 0 to 50 parts by weight of an inorganic filler , The flame retardant polycarbonate resin composition in which the (C) organometallic salt compound is a metal salt of aromatic sulfonic acid or a metal salt of perfluoroalkanesulfonic acid .

  The flame-retardant polycarbonate resin composition of the present invention is a conventional composition containing a halogen, phosphorus, or the like by blending a specific amount of a terpene resin, an organometallic salt compound, a fiber-forming fluorine-containing polymer, and, if desired, an inorganic filler. It has excellent flame retardancy without using any flame retardant. For this reason, there is no concern about generation of a gas containing halogen or phosphorus due to the flame retardant during combustion, and the environment is excellent. Furthermore, since it is extremely excellent in fluidity and workability at the time of granulation, it can be used as various large or thin molded articles and various flame-retardant industrial component materials.

  The polycarbonate resin (A) used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. Typical examples include 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.

  (A) The viscosity average molecular weight of polycarbonate resin is usually 10,000-100000, Preferably it is 15000-35000, More preferably, it is 17000-28000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

The (B) terpene resin of 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 resin and the like. Is included.
The terpene resin is obtained from 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 is obtained by cationic polymerization of these terpene compounds under a Friedel-Craft catalyst. In addition to the terpene compound alone, terpene compounds and aromatic compounds (polymerized compounds are referred to as aromatic-modified terpene resins), terpene compounds and phenolic compounds (polymerized compounds are referred to as phenol-modified terpene resins) may be used as raw materials. . 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, for example, "YS resin PX" (terpene resin), "YS resin TO" (aromatic modified terpene resin), "YS resin TR" (aromatic modified terpene resin) from Yashara Chemical Co., Ltd., Examples include “Clearon” (hydrogenated terpene resin), “YS Polystar” (phenol-modified terpene resin), and “Mighty Ace” (phenol-modified terpene resin).

  (B) The compounding quantity of terpene resin is 2 to 20 weight% in 100 weight part of resin components, Preferably it is 5 to 15 weight%. If it is less than 2% 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, it is difficult to obtain flame retardancy due to the flammability of the terpene resin itself, which is not preferable.

  Examples of the organometallic salt compound (C) of 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 used.

  (C) The compounding amount of the organometallic salt compound is 0.02 to 2 parts by weight, preferably 0.03 to 1 part by weight, more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the resin component. It is. If the blending amount is less than 0.02 parts by weight, it is difficult to obtain a synergistic effect, so that flame retardancy is lowered, which is not preferable. On the other hand, if it exceeds 2 parts by weight, problems such as failure to obtain impact strength and flame retardancy and deterioration of the surface appearance are undesirable.

  As the (D) fiber-forming type fluorine-containing polymer used in the present invention, those that form a fiber structure (fibrillar structure) in the resin component consisting of A and B are preferable, such as polytetrafluoroethylene, tetra Fluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonates produced from fluorinated diphenols, and the like. It is done. 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.

  (D) The compounding quantity of a fiber formation type fluoropolymer is 0.05-5 weight part with respect to 100 weight part of resin components. 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, if the amount exceeds 5 parts by weight, granulation 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.

  (A) To the polycarbonate resin, the above-mentioned (B) terpene resin, (C) organometallic salt compound, and (D) the fiber-forming type fluorine-containing polymer are blended alone, and sufficient flame retardancy is exhibited. Absent. That is, by synthesizing (A) polycarbonate resin with (B) terpene resin, (C) organometallic salt compound, and (D) fiber-forming fluorine-containing polymer, a synergistic effect is obtained and dripping occurs. It is possible to provide a flame retardant polycarbonate resin composition that is not self-extinguishing, has excellent workability and surface appearance during granulation, and that is sufficiently considered for its environmental impact.

In addition, when (E) an inorganic filler is added, the shape-retaining property at the time of combustion of the molded product is remarkably increased, and further, the flame retardancy at a thin wall is excellent.
Examples of the (E) inorganic filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, and silica powder.
(E) The compounding quantity of an inorganic filler is 0-50 weight part with respect to 100 weight part of resin components. When the inorganic filler is added in an amount of 50 parts by weight or less, the shape retention during combustion of the thin molded article is remarkably increased, and the flame retardancy is improved. If the amount exceeds 50 parts by weight, the molecular weight of the polycarbonate resin is reduced during granulation, which is unfavorable for stable production. This amount is preferably in the range of 2 to 20 parts by weight, more preferably 3 to 15 parts by weight. In this range, the balance of granulation workability, flame retardancy, and moldability is further improved.

Furthermore, various heat stabilizers, antioxidants, colorants, fluorescent brighteners, mold release agents, softeners, antistatic agents, and other additives, impact modifiers, etc., as long as the effects of the present invention are not impaired. 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 limitations on the method of mixing the various blending components in the flame retardant resin composition of the present invention, and examples thereof include mixing with a known mixer such as a tumbler or ribbon blender, or melt kneading with an extruder.

  There is no restriction | limiting in particular as a method of shape | molding the flame-retardant 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.

Examples 1-10
Based on the ingredients and amounts shown in Table 2, various ingredients are mixed using a tumbler and melt kneaded at a cylinder temperature of 240 ° C. using a 37 mm diameter twin screw extruder (KTX-37 manufactured by Kobe Steel). Various pellets were obtained.
The compounding components used are as follows.
1. (A) Polycarbonate resin: Caliber 200-20 manufactured by Sumitomo Dow (viscosity average molecular weight 19000) (hereinafter abbreviated as “PC”)
2. (B) Terpene resin: Yashara Chemical Co., Ltd. Mighty Ace G-150 (phenol abbreviated terpene resin, hereinafter abbreviated as “terpene resin”)
3. (C) Organometallic salt compound: potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide (hereinafter abbreviated as “metal salt”)
4). (D) Fiber-forming fluorine-containing polymer: polytetrafluoroethylene (Daikin Polyflon FA-500) (hereinafter abbreviated as “PTFE”)
5. (E) Inorganic filler: Fine powder mica (A-41 made by Yamaguchi Mica) (hereinafter abbreviated as “inorganic filler”)

The various pellets obtained were dried at 105 ° C. for 4 hours, and then injected into an injection molding machine (at 245 ° C. using a J-100SAII manufactured by Nippon Steel Works at an injection pressure of 1600 kg / cm ²⁾ . 13 × 1.0 mm and 125 × 13 × 1.6 mm) were molded, and the appearance of the molded product of the test piece was visually observed.

残炎時間とは、着火源を遠ざけた後の試験片が、有炎燃焼を続ける時間の長さであり、ドリップによる綿の着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。 Flame-retardant according to UL94 test (flammability test of plastic materials for equipment parts) established by Underwriters Laboratories after leaving the specimen in a constant temperature room at 23 ° C and 50% humidity for 72 hours Was evaluated. The classes according to UL94 are shown in Table 1.

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.

＊ 評価結果の数値は５試料の残炎時間の合計（秒）を示す（表３も同じ）。 After drying the various pellets obtained at 105 ° C. for 4 hours, an injection molding machine (Japan Steel Works J-100-E-C5 was used under conditions of 280 ° C. and injection pressure 1600 kg / cm ² , Archimedes spiral flow gold. The fluidity was measured using a mold (width 10 mm, thickness 1.0 mm).
The results are shown in Table 2.

* The numerical value of the evaluation result indicates the total (seconds) of after flame time of 5 samples (the same applies to Table 3).

＊ ＮＲはどの難燃クラスにも属さないものを表す。 Comparative Examples 1-6
For comparison, the same operations as in Examples 1 to 10 were performed with the formulations shown in Table 3. The results are shown in Table 3.

* NR represents not belonging to any flame retardant class.

As shown in Examples 1 to 10, the polycarbonate resin composition having the requirements of the present invention exhibits a very large fluidity improving effect while maintaining high flame retardancy.
When the terpene resin is less than 2 parts (Comparative Example 1), there is no effect of improving flame retardancy and fluidity, and the effect is exhibited when the terpene resin is 2 parts or more. Further, when the terpene resin is blended in an amount exceeding 20 parts (Comparative Example 2), the fluidity improving effect is exhibited, but drip during the combustion test is performed and the flame retardancy is inferior to that when only the polycarbonate resin is used.
As shown in Examples 5 and 6 and Comparative Examples 3 and 4, the metal salt is a highly difficult composition due to a synergistic effect with the terpene resin because the composition containing the metal salt of the present invention in the range of 0.02 to 2 parts. Although it shows flammability, when less than 0.02 parts or more than 2 parts are blended, the synergistic effect with the terpene resin is not exhibited, and the flame retardant improvement effect is low.

As shown in Comparative Example 5, if PTFE is less than 0.05 part, the drip prevention effect at the time of combustion is not improved, and high flame retardancy (V-0 or V-1) is not exhibited. Moreover, although it tried to adjust the composition which added 6 parts of PTFE of this invention to the mixing | blending of Example 6, granulation became difficult and evaluation was not possible.
When an inorganic filler is blended (Examples 7 to 10), higher flame retardancy is exhibited without hindering fluidity, and high flame retardance is maintained even in a thin molded article. As shown in Comparative Example 6, when 55 parts by weight of the inorganic filler is blended, high flame retardancy is not exhibited.

  From the above results, the composition having the requirements of the present invention retains high flame retardancy V-0 or V-1, and is excellent in fluidity without impairing the surface layer peeling or appearance of the molded product. I will provide a.

Claims (3)

(A) 80 to 98% by weight of polycarbonate resin and (B) 2 to 20% by weight of terpene resin are added to a total of 100 parts by weight, and (C) 0.02 to 2 parts by weight of an organometallic salt compound. D) A flame-retardant polycarbonate resin composition comprising 0.05 to 5 parts by weight of a fiber-forming fluorine-containing polymer and (E) 0 to 50 parts by weight of an inorganic filler , the (C) organic metal A flame retardant polycarbonate resin composition, wherein the salt compound is a metal salt of aromatic sulfonic acid or a metal salt of perfluoroalkanesulfonic acid .
The flame retardant polycarbonate resin composition according to claim 1, wherein the (B) terpene resin is an aromatic modified terpene resin. The flame retardant polycarbonate resin composition according to claim 1, wherein the (B) terpene resin is a phenol-modified terpene resin.