JP5240752B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition, and more specifically, a specific amount of a terpene resin having a specific particle size, an organic metal salt compound, a fiber-forming fluorine-containing polymer, 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 halogen or 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 adding a flame retardant such as.

JP 07-179742 A JP 09-95610 A JP 2000-63651 A JP 2000-160724 A

  In contrast to these prior arts, the applicant of the present invention has found that flame retardancy is improved by combining a terpene resin and an organic metal salt in a polycarbonate resin, and has already filed a patent application. (See Patent Document 5)

JP 2005-206712 A

  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.

  In the composition comprising a polycarbonate resin, a terpene resin, an organometallic salt compound, and a fiber-forming fluorine-containing polymer, the inventors bring about excellent flame retardancy by adjusting the particle size of the terpene resin used. As a result, the present invention has been completed.

  That is, this invention contains polycarbonate resin (A) 80-98 weight% and terpene resin (B) 2-20 weight% so that it may become a total of 100 weight part, Furthermore, organometallic salt compound (C) 0.02 ~ 2 parts by weight, a fiber-forming fluoropolymer (D) 0.05 to 5 parts by weight and an inorganic filler 0 to 50 parts by weight (E), comprising the terpene resin (B Is a flame retardant polycarbonate resin composition characterized by comprising particles passing through a Japanese Industrial Standard standard sieve having a nominal size of 2000 μm.

  The flame-retardant polycarbonate resin composition of the present invention comprises a terpene resin having a specific particle size, an organometallic salt compound, a fiber-forming fluoropolymer, and, if desired, a specific amount of inorganic filler, It has excellent flame retardancy without using a conventional flame retardant containing phosphorus or the like. 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.

  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) 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, hydrogenated aromatic modified. Terpene resins, phenol-modified terpene resins, hydrogenated phenol-modified terpene resins and the like are 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.

Examples of such terpene resins include “YS resin PX” (terpene resin), “YS resin TO” (aromatic modified terpene resin), “YS resin TR” (aromatic modified terpene resin), “Clearon” manufactured by Yashara Chemical Co., Ltd. “(Hydrogenated terpene resin)”, “YS polyster” (phenol-modified terpene resin), “Mighty Ace” (phenol-modified terpene resin), and the like.

  The terpene resin (B) of the present invention is composed of particles passing through a Japanese Industrial Standard standard sieve having a nominal size of 2000 μm, so-called 2 mm mesh particles. Use of a terpene resin having a particle size exceeding this is not preferable because flame retardancy is reduced. More preferably, it is a terpene resin composed of particles passing through a Japanese Industrial Standard standard sieve having a nominal size of 1000 μm, that is, particles having a so-called 1 mm mesh pass.

  Moreover, as a method of obtaining the terpene resin (B) comprised from the particle | grains of the said 2 mm mesh pass, after stirring and grind | pulverizing commercially available terpene resin with a Henschel mixer, the Japanese Industrial Standards standard sieve with a nominal dimension of 2000 micrometers is used. And collecting only the particles that pass through the sieve.

  The blending amount of the terpene resin (B) of the present invention is 2 to 20% by weight, preferably 5 to 15% by weight, based on the resin component composed of the polycarbonate resin (A) and the terpene resin (B). 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 organic metal 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.

  The compounding amount of the organometallic salt compound (C) is 0.02 to 2 parts by weight, preferably 0.03 to 1 part by weight, more preferably 100 parts by weight of the resin component consisting of (A) and (B). 0.05 to 0.5 parts by weight. 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 fiber-forming fluorine-containing polymer (D) used in the present invention, one that forms a fiber structure (fibrillar structure) in the resin component consisting of (A) and (B) is preferable. Fluoroethylene, tetrafluoroethylene copolymer (eg, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymer as shown in US Pat. No. 4,379,910, and fluorinated diphenol Examples include polycarbonate. 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 compounding amount of the fiber-forming fluoropolymer (D) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin component composed of (A) and (B). 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 flame retardant is sufficient when only a specific terpene resin (B), an organometallic salt compound (C), and a fiber-forming fluoropolymer (D) are added to the polycarbonate resin (A). Absent. That is, a synergistic effect can be obtained by adding a specific terpene resin (B), an organometallic salt compound (C), and a fiber-forming fluoropolymer (D) to the polycarbonate resin (A), and dripping. It is possible to provide a flame-retardant polycarbonate resin composition that is self-extinguishing without causing defects, is excellent in workability and surface appearance at the time of granulation processing, and has sufficient consideration for the influence on the environment.

In addition, when the inorganic filler (E) is added, the shape-retaining property at the time of burning the molded product is remarkably increased, and further, the flame retardancy at a thin wall is excellent.
Examples of the inorganic filler (E) include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, and silica powder.

  The compounding quantity of an inorganic filler (E) is 0-50 weight part with respect to 100 weight part of resin components which consist of (A) and (B). 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 components in the flame-retardant polycarbonate resin composition of the present invention, and examples thereof include mixing with a known mixer such as a tumbler or ribbon blender, and melt kneading with an 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” and “%” are based on weight unless otherwise specified.

  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.
Polycarbonate resin:
Caliber 200-20 (viscosity average molecular weight 19000) manufactured by Sumitomo Dow
(Hereinafter abbreviated as “PC”)

Terpene resin:
Phenol-modified terpene resin (hereinafter abbreviated as “terpene resin-1”) composed of particles passing through a Japanese Industrial Standard standard sieve having a nominal size of 2000 μm.
The manufacturing method is as follows.
Phenol-modified terpene resin with a particle size of about 1 cm (Yasuhara Chemical Co.
After stirring Mighty Ace G-150 with a Henschel mixer for 10 minutes,
This was sieved with a Japanese Industrial Standard standard sieve having a nominal size of 2000 μm, and only the particles passing through the sieve were collected.
Commercially available phenol-modified terpene resin (Yasuhara Chemical Mighty Ace G-150, particle size of about 1 cm)
(Hereafter, abbreviated as “terpene resin-2”.)

Organometallic salt compounds:
Potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide (hereinafter abbreviated as “metal salt”)
Fiber-forming fluorine-containing polymer:
Polytetrafluoroethylene (Daikin Polyflon FA-500)
(Hereinafter abbreviated as “PTFE”)
Inorganic filler:
Fine powder mica (A-41 made by Yamaguchi Mica)
(Hereinafter abbreviated as “inorganic filler”)

After the various pellets obtained were dried at 105 ° C. for 4 hours, an injection molding machine (Japan Steel Works J-100SAII was used at 245 ° C. and an injection pressure of 1600 kg / cm ² was used as a flame retardant test piece (125 × 13 × 1.0 mm and 125 × 13 × 1.6 mm) were molded, and the appearance of the test piece was visually observed.

  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.

The various pellets obtained were dried at 105 ° C. for 4 hours, and then subjected to Archimedes spiral flow gold under conditions of 280 ° C. and injection pressure of 1600 kg / cm ^{2 using} an injection molding machine (J-100-E-C5 manufactured by Nippon Steel). The fluidity was measured using a mold (width 10 mm, thickness 1.0 mm).
The results are shown in Table 2.

For comparison, the same operations as in Examples 1 to 6 were performed with the formulations shown in Table 3. The results are shown in Table 3.

ＮＲ：Ｎｏ Ｒａｔｉｎｇの略。Ｖ−０、Ｖ−１、Ｖ−２の何れにも該当せず、難燃性に劣る。

NR: Abbreviation for No Rating. It does not correspond to any of V-0, V-1, and V-2 and is inferior in flame retardancy.

  As shown in Examples 1 to 6, by using the terpene resin composed of the particles of the present invention, a polycarbonate resin composition having higher flame retardancy (reduction in total combustion time) was obtained.

On the other hand, Comparative Examples 1 to 5 are examples that do not satisfy the requirements of the present invention, but each had the following drawbacks.
Although the comparative example 1 is an example using the terpene resin of this invention, since its usage-amount was small, it was inferior to a flame retardance and fluidity | liquidity.
Although the comparative example 2 is an example using the terpene resin of this invention, since the usage-amount was too much, it was inferior to the flame retardance and the external appearance of the molded article.
Comparative Examples 3 and 4 are examples using commercially available terpene particles having a particle diameter of about 1 cm other than the terpene resin composed of the specific particles of the present invention. It was inferior in terms.
Although the comparative example 5 is an example using the terpene resin of this invention, since there was too much usage-amount of an inorganic filler, not only the external appearance of the molded article but the flame retardance was also inferior.

Claims (3)

  It contains 80 to 98% by weight of polycarbonate resin (A) and 2 to 20% by weight of terpene resin (B) so that the total amount becomes 100 parts by weight, and further, 0.02 to 2 parts by weight of organometallic salt compound (C), fiber A composition comprising 0.05 to 5 parts by weight of a forming fluoropolymer (D) and 0 to 50 parts by weight (E) of an inorganic filler, wherein the terpene resin (B) has a nominal size of 2000 μm A flame retardant polycarbonate resin composition comprising particles passing through a Japanese Industrial Standard standard sieve.   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.