JP2006312669A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition which has excellent flame retardancy, good appearance and high flowability, does not have a fear to produce a halogen-containing gas on combustion, because of not using a conventional halogen-containing flame retardant, is also extremely excellent from the aspect of environmental harmony, can suitably be used for various large or thin molded articles or various flame-retardant industrial parts, because of having excellent flowability, and has a very high industrial utilization value. <P>SOLUTION: This flame-retardant polycarbonate resin composition is characterized by comprising 100 pts.wt. of a resin component comprising 80 to 99.5 wt.% of a polycarbonate resin (A) and 0.5 to 20 wt.% of a terpene resin (B), 0.005 to 2 pts.wt. of an organic metal chloride, 0.01 to 3 pts.wt. of a silicone compound (D) whose main chain is a branched structure and whose organic functional groups contained therein comprise aromatic groups or aromatic groups and hydrocarbon groups (excluding the aromatic groups), 0.05 to 2 pts.wt. of a fiber-forming type fluorine-containing polymer (E), and 0 to 50 pts.wt. of an inorganic filler (F). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant polycarbonate resin composition. More specifically, a terpene resin, an organometallic salt compound, a silicone compound having a specific structure, a fiber-forming fluorine-containing polymer, and a flame retardant having a good appearance and high fluidity containing a specific amount of an inorganic filler as required. The present invention relates to a polycarbonate resin composition. 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 light and thin, and in order to satisfy design and design requirements, in addition to the above-mentioned performance such as impact resistance and heat resistance, There has been a demand for a material having high flame retardancy and high fluidity (moldability) without using a phosphorus-based flame retardant.

  The inventors of the present invention incorporated a specific amount of a terpene resin, an organometallic salt compound, a silicone compound having a specific structure, a fiber-forming fluorine-containing polymer, and, if desired, an inorganic filler into a polycarbonate resin, thereby producing halogen, phosphorus, etc. The present inventors have found that a polycarbonate resin composition having extremely excellent flame retardancy, fluidity, and appearance can be obtained synergistically without using a conventional flame retardant containing.

  That is, the present invention relates to a resin component comprising a polycarbonate resin (A) 80 to 99.5% by weight and a terpene resin (B) 0.5 to 20% by weight (hereinafter referred to as a mixture of components (A) and (B). The resin component may be referred to as “resin component.”) In an amount of 0.005 to 2 parts by weight of the organometallic salt compound (C), the main chain is a branched structure, and the organic functional group contained is an aromatic group. Or 0.01 to 3 parts by weight of a silicone compound (D) comprising an aromatic group and a hydrocarbon group (excluding aromatic groups), and 0.05 to 2 parts by weight of a fiber-forming fluorine-containing polymer (E) In addition, the present invention provides a flame retardant polycarbonate resin composition having a good appearance and high fluidity, characterized by comprising 0 to 50 parts by weight of an inorganic filler (F).

  The flame retardant polycarbonate resin composition of the present invention is excellent in flame retardancy, has a good appearance and a high fluidity, and does not use a conventional flame retardant containing halogen, so a gas containing halogen during combustion There is no concern about the occurrence of environmental problems, and it is extremely excellent in terms of environmental harmony. Furthermore, since it is excellent in fluidity, it can be suitably used as various large-sized or thin-walled molded products and various flame-retardant industrial component materials, and has a very high industrial utility value.

  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) 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 as a raw material, a terpene compound and an aromatic compound (the polymer is referred to as an aromatic modified terpene resin), a terpene compound and a phenol compound (the polymer is referred to as a phenol modified terpene resin) are used. 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 0.5-20 weight% in 100 weight part of resin components, Preferably it is 1-10 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 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, 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 silicone compound (D) used in the present invention, the main chain is a branched structure and the organic functional group is an aromatic group, or the aromatic group is a hydrocarbon group (excluding the aromatic group). Is as shown in the following general formula (1).
General formula (1)

  Here, R1, R2, and R3 represent main chain organic functional groups, and X represents a terminal functional group.

That is, it has a T unit (RSiO _1.5 ) and / or a Q unit (SiO _2.0 ) as a branch unit. These preferably contains more than 20 mol% of the total siloxane units _{(R 3~0 SiO 2~0.5).} (R represents an organic functional group.) The silicone compound (D) preferably contains 20 mol% or more of aromatic groups among the organic functional groups contained.

  The aromatic group contained is phenyl, biphenyl, naphthalene or a derivative thereof, but a phenyl group can be preferably used.

  Of the organic functional groups in the silicone compound (D) attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Further, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.

  The average molecular weight (weight average) of the silicone compound (D) is preferably 3000 to 500000, and more preferably 5000 to 270000.

  The compounding quantity of a silicone compound (D) is 0.01-3 weight part with respect to 100 weight part of resin components. When the blending amount is out of the range, it is not preferable because a sufficient flame retardant effect cannot be obtained in any case. More preferably, it is 0.05 to 1 part by weight.

  The fiber-forming fluorine-containing polymer (E) used in the present invention is preferably one that forms a fiber structure (fibril structure) in the resin component, such as polytetrafluoroethylene or 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 compounding amount of the fiber-forming fluoropolymer (E) 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.

  It is sufficient to blend the terpene resin (B), the organometallic salt compound (C), the silicone compound (D), and the fiber-forming fluorine-containing polymer (E) alone with respect to the polycarbonate resin (A). Does not show flame retardancy. That is, a synergistic effect is obtained by blending the terpene resin (B), the organometallic salt compound (C), the silicone compound (D), and the fiber-forming fluoropolymer (E) with the polycarbonate resin (A). It is possible to provide a flame-retardant polycarbonate resin composition that is self-extinguishing without dripping, has excellent workability and surface appearance during granulation processing, and also has sufficient consideration for environmental impact. .

  In addition to this, when the inorganic filler (F) 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 (F) 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 (F) is 0-50 weight part with respect to 100 weight part of resin components. When the inorganic filler (F) 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 (A) is reduced during granulation, which hinders 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 (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.), impact modifiers, 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 various pellets.

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”)
Silicone compound: (hereinafter abbreviated as “silicone compound”)
The silicone compound was produced according to a general production method. That is, an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof is dissolved in an organic solvent, hydrolyzed by adding water, and partially condensed. A silicone compound was formed, and triorganochlorosilane was further added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural characteristics of the silicone compound synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first included in the T unit in the silicone containing the T unit, and the remaining phenyl group is included in the D unit. When a phenyl group is attached to the D unit, the one attached is preferred.
If two phenyl groups remain, two are attached. Except for the terminal group, all the organic functional groups are methyl groups except for the phenyl group.
**: Weight average molecular weight is two significant digits.
Fiber-forming fluorine-containing polymer:
Made by Daikin, Polyflon FA-500
(Polytetrafluoroethylene, hereinafter abbreviated as “PTFE”)
Inorganic filler:
Fine powder mica (Yamaguchi mica, A-41, hereinafter abbreviated as “inorganic filler”)

The evaluation method is as follows.
(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. The test piece for flame retardancy evaluation (125 × 13 × 0.8 mm and 125 × 13 × 1.2 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.

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。

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.
Each evaluation result is 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 flame-retardant polycarbonate resin composition having the constituent requirements of the present invention exhibits an extremely large fluidity improving effect while maintaining high flame retardancy.
On the other hand, as shown in Comparative Examples 1 to 5, in the case where the constituent requirements of the present invention were not satisfied, there were some drawbacks.
In Comparative Example 1, although the terpene resin content was less than the lower limit of the specified range, the flame retardancy and fluidity were rejected.
In contrast, Comparative Example 2 was a case where the blending amount of the terpene resin exceeded the upper limit of the specified range, but the appearance and flame retardance were rejected.
Although the comparative example 3 is a case where a silicone compound is further less than the minimum of a prescription | regulation range, a flame retardance was also rejected.
In Comparative Example 4, the silicone compound exceeded the upper limit of the specified range, but the flame retardancy did not satisfy the standard.
Although the comparative example 5 is a case where the compounding quantity of an inorganic filler exceeds the upper limit of a prescription | regulation range, the stable granulation could not be performed but the sample could not be obtained.

Claims (4)

0.005 to 2 weights of organometallic salt compound (C) with respect to 100 parts by weight of the total resin component comprising 80 to 99.5 weight% of polycarbonate resin (A) and 0.5 to 20 weight% of terpene resin (B) Part, main chain is branched structure, and the organic functional group contained is an aromatic group, or a silicone compound (D) 0.01 to 3 consisting of an aromatic group and a hydrocarbon group (excluding an aromatic group) A flame-retardant polycarbonate resin composition, comprising 0.05 parts by weight of a fiber-forming fluoropolymer (E) and 0-50 parts by weight of an inorganic filler (F). 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 flame retardant polycarbonate resin composition according to claim 1, wherein the organic metal salt compound (C) is a metal salt of an aromatic sulfonic acid or a metal salt of a perfluoroalkanesulfonic acid.