WO1997017403A1

WO1997017403A1 - Flame-retardant polycarbonate resin composition

Info

Publication number: WO1997017403A1
Application number: PCT/JP1996/003287
Authority: WO
Inventors: Katsutoyo Fujita; Yoshitaka Ono
Original assignee: Kaneka Corporation
Priority date: 1995-11-09
Filing date: 1996-11-08
Publication date: 1997-05-15

Abstract

A flame-retardant polycarbonate resin composition prepared by blending 100 parts by weight of a resin component (R) comprising a polycarbonate resin (A) and a thermoplastic resin (B) at a weight ratio of 95/5 to 50/50 with 1 to 20 parts by weight of a brominated diphenylalkane compound (C) of general formula (I) (wherein R is C1-C6 alkylene; and m and n are each an integer of 1 to 5, the sum of m and n being 6 to 10). The above composition is excellent in pin-gate moldability, heat stability during residence, mold release properties, thermal deformation resistance and chemical resistance and can suitably be used for electrical and electronic components, housings of electrical and electronic appliances, moldings for the components of OA machines and AV apparatus, automobile parts, general merchandise, and so on.

Description

Damage-Flame retardant polycarbonate resin composition

The present invention relates to air * electronic components, air 'electronic product housing, OA equipment-

Suitable for moldings for AV equipment parts, automobile parts, sundries, etc., excellent in pin gate formability, retention heat stability, moldability, heat deformation resistance, chemical resistance, and flame retardancy. The present invention relates to a flame-retardant polycarbonate resin composition comprising a carbonate resin and a thermoplastic polyester. Background art

In recent years, demand for strong cost reductions has led to the integration of components and upsizing of electrical and electronic components, electrical and electronic product housings, molded products for OA and AV equipment components, and automotive parts. ing. Due to the integration of parts and the enlargement of parts, higher levels of adaptability to pin gate molding, stable heat retention, and mold releasability are being demanded.

Generally, the molding processability of flame-retardant resins is inferior to non-flame-retardant resins compared to resins. The same applies to the polycarbonate-based resin composition. In order to improve this, Japanese Patent Application Laid-Open No. H04-3636358 states that in a polymer blend of a polycarbonate resin / polyester resin, the flame retardant is limited to a plain phenolic resin. It is described that a higher moldability can be obtained as compared with a system using a flame retardant, such as a brominated polystyrene or a fluorinated polycarbonate, which is known to other companies. In addition, due to the integration of parts and the increase in size, resin is used for each part as necessary. ―, _M

PCT / JP96 / 03287 It is no longer possible to divide, so the various characteristics required of the material must be adjusted to the highest level among the integrated and large-sized parts, which means that A higher calendar level is being required.

However, as described above, as the integration of parts and the enlargement of the parts are progressing, more advanced molding workability and various characteristics are described in the above-mentioned Japanese Patent Application Laid-Open No. H04-3636358. Even with the composition, it cannot be said that the bin gate moldability, the retention heat stability, the moldability, the heat deformation resistance and the chemical resistance are sufficient, and further improvement is required.

An object of the present invention is to provide a flame retardant polycarbonate comprising the above-mentioned bin gate moldability, retention heat stability, mold release, heat deformation resistance, chemical resistance, and flame retardancy. The present invention provides a resin composition. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that (A) a polycarbonate resin, (B) a thermoplastic polyester resin, and (C) a brominated diphenylalkane compound. The flame retardant resin composition excels in pin gate moldability, retention heat stability, moldability, heat deformation resistance, and flame retardancy. Further, by adding an epoxy compound (D), the retention is further improved. A resin composition comprising a polycarbonate resin and a thermoplastic polyester having excellent heat stability and chemical resistance can be obtained. Furthermore, a resin composition comprising (E) an olefin unit and a (meth) acrylic ester unit. By adding a predetermined copolymer, a resin composition comprising a polycarbonate resin and a thermoplastic polyester, which is more excellent in layer, pin gate moldability and chemical resistance, is obtained. Found that to be, led to the completion of the present invention (Brief description of drawings

FIG. 1 is a schematic diagram for explaining a method for measuring shochu ripening deformability.

FIG. 2 is a schematic diagram for explaining a method for measuring chemical resistance. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a resin composition comprising (A) a polycarbonate resin and (B) a thermoplastic polyester resin, wherein the component (A) and the component (B) have a weight ratio of 95/5 to 50/50. (R) 100 parts by weight,

(C) The following general formula (I):

(In the formula, R is an alkylene group having 1 to 6 carbon atoms, m.n is an integer of 1 to 5, and m + n is 6 to 10)

1-20 parts by weight of a brominated diphenylalkane compound represented by

The flame-retardant polycarbonate resin composition (Claim 1), which further comprises the flame-retardant polycarbonate resin composition according to Claim 1,

(D) a flame-retardant polycarbonate resin composition comprising 0.01 to 15 parts by weight of an epoxy compound (Claim 2),

3. The flame-retardant polycarbonate resin composition according to claim 1 or 2, further comprising: (E) at least one (meth) acrylate having at least one olefin unit and 1 to 10 carbon atoms. Unit and 4 0 /

A flame-retardant polycarbonate resin composition comprising 0.5 to 15 parts by weight of a copolymer contained in a weight ratio of 60 to 95/5 (Claim 3), _TO

PCT / JP96 / 03287 Flame-retardant polycarbonate resin obtained by further adding 0.05 to 0 parts by weight of (F) an antimony compound to the flame-retardant polycarbonate-based resin composition according to claim 1, 2 or 3. A resin composition (Claim 4),

A flame-retardant polycarbonate resin composition obtained by further adding (G) 0.01 to 5 parts by weight of a fluororesin to the flame-retardant polycarbonate resin composition according to claim 1, 2, 3, or 4. Object (Claim 5),

A molded article for OA equipment or AV equipment parts, comprising the flame-retardant polycarbonate resin composition according to claim 1,

Respectively.

The polycarbonate resin as the component (A) used in the present invention is obtained by reacting at least one divalent or more phenol compound with at least one divalent carbonate such as phosgene or difluorocarbonate. It is a thermoplastic polycarbonate resin obtained by the above method.

Specific examples of the divalent phenol compound among the above-mentioned divalent or higher phenol compounds include hydroquinone, 4.4′-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl) propane, 2.2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, 4,4'-dihydroxy-opened xidiphenyl ether, etc. Can be Among them, 2.2-bis (4-hydroxyphenyl) propane is preferable because it is already industrially mass-produced.

Specific examples of the trivalent or higher phenol compound of the divalent or higher phenol compound include 1,1,1 tris (4-hydroquinphenyl) ethane and the like.

The phenol compounds may be used alone or in combination of two or more. In order to increase the flame retardancy, a polymer obtained by copolymerizing a phosphorus compound or a polymer terminated with a phosphorus compound may be used.In order to enhance weather resistance, a benzotriaryl group may be used. A polymer obtained by copolymerizing a divalent phenol having the same may be used.

The polycarbonate-based resin (A) as described above preferably has an average molecular weight of 100 000 to 600 000, more preferably 150 000 to 450 000, and especially 180 000 ~ 3500 is preferred. When the viscosity average molecular weight is less than 1000, the strength and heat deformation resistance of the obtained resin composition tend to decrease, and when it exceeds 600, the moldability tends to decrease. is there. The thermoplastic polyester resin as the component (B) used in the present invention is obtained by polycondensing a divalent or higher aromatic sulfonic acid component with a divalent or higher alcohol and / or phenol component. It is a plastic polyester resin.

Examples of the dihydric or higher alcohol and Z or phenol components include aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms. Examples thereof include compounds having two or more hydroxyl groups in the molecule, and derivatives thereof having ester forming ability. Specific examples of these include ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4- Dihydric alcohol or phenol components such as hydroxyphenyl) propane, 2,2'-bis (4-hydroxycycl σ-hexyl) propane and hydroquinone and their derivatives capable of forming esters; trivalent compounds such as glycerin and pentaerythritol The above-mentioned alcohols or phenol components and derivatives thereof having an ester-forming ability can be mentioned. These may be used alone or in combination of two or more. Among them, ethylene glycol and butanediol are preferably used from the viewpoints of easy handling, easy reaction, and good properties of the obtained resin.

Examples of the divalent or higher valent aromatic carboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (ρ-carbophenyl) methanane anthracene dicarboxylic acid, 4-4 ′ diphenyl dicarboxylic acid, 2-bis (phenoxy) carboxylic acid such as 4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid, pyromellitic acid, etc. and derivatives having ester forming ability thereof These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferably used from the viewpoint of ease of handling, ease of reaction, physical properties of the obtained resin, and the like.

In addition to the above components, the thermoplastic polyester resin (B) includes, in addition to the above components, a divalent or higher valent aliphatic carboxylic acid having 4 to 12 carbon atoms, a divalent or higher valent alicyclic carboxylic acid having 8 to 15 carbon atoms, Carboxylic acids other than aromatic carboxylic acids and their ester-forming derivatives may be partially copolymerized.

Specific examples of the carboxylic acids other than the aromatic carboxylic acids include adipic acid, sebacic acid, azelaic acid, dodecandionic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. And dicarboxylic acids, and derivatives thereof having an ester-forming ability.

Also, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid and their ester-forming derivatives, and cyclic esters such as ε-force prolactone can be used as the copolymerization component. In addition, polyethylene glycol, polypropylene glycol, polyethylene (ethylene oxide. Propylene oxide) blocks and / or random copolymers, Polyalkylene glycol units such as bisphenol A copolymerized polyethylene oxide addition polymerization, propylene oxide addition polymer, tetrahydrofuran addition polymer, polytetramethylene glycol, etc.

—Partially copolymerized ones can also be used.

The copolymerization amount of carboxylic acids other than the aromatic sulfonic acid, oxyacid, cyclic ester, and the like is generally 20% or less, preferably 15% or less, more preferably 1 or less.

The thermoplastic polyester resin (Β) has a polyalkylene terephthalate rate of preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more from the viewpoint of heat deformability. It is.

The inherent viscosity (IV) of the thermoplastic polyester resin (Β) measured at 25 in a phenol-tetrachloroethane = 1/1 (weight ratio) mixed solvent is preferably 0.35 dl Zg or more, More preferably, it is 0.40 to 1.80 d1 / g, and further preferably, it is 0.50 to 1.60 d1 / g. When the intrinsic viscosity is less than 0.35 d1 / g, the flame retardancy and mechanical strength of the molded body tend to decrease, and when the intrinsic degree exceeds 1.8 d1 / g, the molded product has fluidity during molding. However, there is a tendency that problems such as failure occur. The thermoplastic poly (ester) resin (B) may be used alone, or two or more kinds of different copolymer components or different intrinsic viscosities may be used in combination.

Specific examples of the thermoplastic polyester resin (B) as described above include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene methylene terephthalate, polycyclohexadimethylene terephthalate, and polyethylene terephthalate. Ethylene naphthalate, polybutylene naphthalate and the like can be mentioned, and these are used alone or in combination of two or more. The proportions of the polycarbonate resin (A) and the thermoplastic polyester resin (B) are as follows: (A) component Z (B) component in a weight ratio of 95/5 to 50/50, preferably 85/15 to It is 55 no 45. If the weight ratio of component (A) / component (B) is less than 50/50, the resulting molded article will have reduced flame retardancy and heat deformation resistance, and if it exceeds 95 Z5, will have reduced chemical resistance.

The (C) brominated diphenyl alkane compound used in the present invention is a component used for the purpose of imparting flame retardancy, pin gate moldability, retention heat stability, hybrid moldability, and heat deformation resistance. Formula (I):

(Where R is an alkylene group having 1 to 6 carbon atoms, m and n are each an integer of 1 to 5, and m + n is 6 to 10)

It is a compound represented by these.

—Cross-type (I) containing a group other than an alkylene group having 1 to 6 R is insufficient in bingate formability and heat retention stability, and also has a m. If m + n is less than 6 to 10 with an integer of 6, sufficient flame retardancy cannot be obtained.

Specific examples of the R include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an amylene group, an isoamylene group, a hexylene group, and an isohexylene group. Of these, those having an ethylene group are preferred because they have already been industrially mass-produced.

Specific examples of the brominated diphenylalkane-based compound (C) include decap π-modiphenylmethane, nonabromodiphenylmethane, otatab 乇 diphenylmethane, heptabodidiphenylmethane, and hexabromodiphenylmethane. Phenylmethane, decabromodiphenylethane, nonab mouth modifenylethane, octabidifendiphenyl, hebutabodifendiphenylethane, hexabromodiphenylethane, decabromodiphenylpropane, nonab mouth diphenylpropane, octabutane乇 diphenylpropane, hebutab mouth modiphenylpropane, hexab mouth modiphenylpropane, decab mouth modiphenylbutane, nonabromodiphenylbutane, octab mouth modiphenylbutane, hebutabromodiphenylbutane, hexabromodiphenylbutane , Modafu diphenyl pentane, Nonabromodiphenyl pentane, Moda diphenyl octane, Heptabromodiphenyl pentane, Hexabromodiphenyl hexane, Moda diphenyl hexane, Nonab mouth modifil hexane, octab mouth modifil hexane, heptab mouth modifil hexane, hex sub mouth modifil J1nil hexane, and the like. Among them, dekabu didiphenyl is preferred since it has a large flame-retardant effect and is already mass-produced industrially. These may be used alone or in combination of two or more. These brominated difuunylalkane compounds (C) are produced by a known method. The production method is not particularly limited, but is disclosed in Japanese Patent Application Laid-Open Nos. Hei 4-26 1, 28-28, Hei 4-2161, 129, Hei 05-43 497, Hei 06- It is disclosed in, for example, Japanese Patent Publication No. 5671/19.

The amount of the brominated diphenylalkane compound (C) is from 1 to 20 parts by weight, preferably from 2 to 15 parts by weight, per 100 parts by weight of the component (A) + the component (B). is there. If the amount is less than 1 part by weight, no good effect of improving flame retardancy can be obtained, and if it exceeds 20 parts by weight, pin gate moldability, retention heat stability, and chemical resistance decrease.

Further, in the present invention, by adding an epoxy compound as the component (D), it is possible to further improve the retention heat stability and the chemical resistance. The epoxy compound is a compound having at least one or more epoxy groups in a molecule and containing no halogen in the molecule. Specifically, N-glycidyl phthalimide, N-glycidyl tetrahydrophthalimide , Phenyl glycidyl ether, p-butyl phenyl glycidyl ether, neohexenoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl Ether, polytetramethylene dalicol diglycidyl ether, bisphenol A-type epoxy compound, bisphenol S-type ethoxy compound, resorcinol-type ethoxy compound, pheno Lunovolak type epoxy compound, orthocresol novolak type epoxy compound, diglycidyl adipate, diglycidyl sebacate, diglycidyl phthalate, glycidyl methacrylate, glycidyl acrylate, ethylene glycidyl methacrylate And ethylene 'glycidyl methacrylate' vinyl acetate copolymer. These epoxy compounds are used alone or in combination of two or more.

The amount of the epoxy compound (D) to be added is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic resin (B). Is from 0.05 to 12 parts by weight, more preferably from 0.1 to 10 parts by weight. If the addition amount is 0.01 weight percent, the effect of improving the retention heat stability is small, and if it exceeds 15 parts by weight, the flame retardancy and the formability deteriorate.

Furthermore, in the present invention, as the component (E), at least one olefin unit and at least one (meth) acrylate unit having 1 to 10 carbon atoms are included in a ratio of 40/60 to 95/5. Copolymer by weight ratio of By adding it, the pin gate moldability, moldability, and chemical resistance can be further improved.

The copolymer (E) is generally a copolymer obtained by subjecting one or more kinds of olefins and one or more kinds of alkyl (meth) acrylate units to radical S-bonding in the presence of a radical initiator. Further, the polymerization method is not limited to this, and the polymerization can be carried out using various generally known polymerization methods. The copolymer may take any copolymer form such as a random copolymer, a block copolymer, a graft copolymer, and the like.

Specific examples of the olefins of the copolymer include ethylene, propylene, 1-butene, 11-pentene and the like. These α-olefins may be used alone or in combination of two or more. Particularly preferred is ethylene.

As the alkyl ester in the alkyl (meth) acrylate in the copolymer (II), one having 1 to 10 carbon atoms is used. Preferably it has 8 or less carbon atoms, and more preferably 6 or less carbon atoms. If the number of carbon atoms exceeds 10, the compatibility decreases, the dispersion becomes poor in the resin composition, and the effect of improving the chemical resistance decreases.

Specific examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, η-propyl acrylate, i-propyl acrylate, II-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, Examples thereof include n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate, and these are used alone or in combination of two or more. Of these alkyl (meth) acrylates, particularly preferred are methyl acrylate and ethyl acrylate.

In the copolymer, at least one olefin unit and 1 to 10

I 1 The ratio of at least one (meth) acrylate unit having at least one carbon atom is 40Z60 to 95/5, preferably 45Ζ65 to 90/10. When the ratio between the olefin unit and the alkyl (meth) acrylate unit is more than 955, the effect of improving the chemical properties of the shochu and the female mold is small, and when the ratio is less than 40/60, the moldability decreases.

The copolymer (Ε) may be used alone or in combination of two or more copolymer components having different Ml values.

The amount of the copolymer (E) to be added is 0.5 to 15 parts by weight based on 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Preferably, it is 1 to 12 parts by weight, more preferably 1.5 to 10 parts by weight. If the added amount is less than 0.5 part by weight, the effect of improving the chemical resistance and the moldability is small, and if it exceeds 15 parts by weight, the flame retardancy and the retention heat stability are lowered.

In the present invention, (F) an antimony compound or (G) a fluorine-based resin can be used alone or in combination for the purpose of further improving the flame retardancy.

Specific examples of the antimony compound (F) include antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony phosphate and the like.

When an antimony compound is used, it may be used alone or in combination of two or more. The amount used is 0.05 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). is there. If the amount of the antimony compound is less than 0.05 parts by weight, the effect of improving the flame retardancy is small, while if it exceeds 10 parts by weight, the chemical resistance, molding processability, mechanical strength are reduced, and decomposition occurs during injection molding. Foaming may occur, which is not preferable.

The fluororesin (G) is a resin having a fluorine atom in the resin. Ingredient Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. In addition, if necessary, the monomer used for producing the fluororesin and the copolymerizable monomer may be used in combination to polymerize, if necessary, to the extent that physical properties such as flame retardancy of the obtained molded article are not impaired. The obtained copolymer may be used. These fluororesins are used alone or in combination of two or more.

The molecular weight of the fluororesin is preferably from 1,000 to 200,000, more preferably from 200,000 to 1,000,000 from the viewpoint of flame retardancy. Regarding the method for producing these fluorine-based resins, they can be obtained by generally known methods such as emulsion polymerization, suspension S polymerization, bulk polymerization, and solution polymerization.

The amount used is 0.01 to 5 parts by weight, preferably 0.0, based on 100 parts by weight of the total amount of (Α) polycarbonate resin and (Β) thermoplastic polyester resin. 5 to 4 parts by weight, more preferably 0.1 to 3.5 parts by weight When the amount is less than 0.01, the effect of improving the flame retardancy is small. It is not preferable because the number of the components decreases.

In addition, the flame-retardant resin composition of the present invention may further contain any other thermoplastic or thermosetting resin within a range not impairing the present invention, for example, liquid crystal polyester resin, polyester ester elastomer, and the like. Resin, polyether ether elastomer resin, polyolefin resin, boriamid resin, polystyrene resin, boliphenylene sulfide resin, boliphenylene ether resin, polyacetal resin, bori sulfone resin, polyarylate resin Resins, rubbery elastic bodies, etc. may be added alone or in combination of two or more.

Further, in order to make the flame-retardant resin composition of the present invention more sophisticated, It is preferable to use an antioxidant such as a cellulose-based antioxidant, a thioether-based antioxidant, or the like, a heat stabilizer such as a phosphorus-based stabilizer, or the like, alone or in combination of two or more. Furthermore, if necessary, usually well-known stabilizers, lubricants, mold release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, belts Additives such as antioxidants, conductivity-imparting agents, dispersants, compatibilizers, and antibacterial agents can be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited.For example, after drying the above components, and other additives, resins, etc., by melt-kneading such as single-screw or twin-screw extrusion welding, It can be manufactured by a method of melting and mixing. When the mixture is a liquid, it can be produced by adding the mixture to a twin-screw extruder using a liquid supply bomb or the like.

The molding method of the thermoplastic resin composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, vacuum molding, press Molding, calendar molding, etc. can be applied.

The flame-retardant polycarbonate resin composition of the present invention is excellent in pin gate moldability, retention heat stability, moldability, heat deformation resistance, and shochu-chemical properties. It is suitably used for housings, molded products for OA / AV equipment parts, automobile parts, sundries and the like.

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto. In the following description, “parts” means parts by weight and “%” means parts by weight unless otherwise specified. The evaluation of the resin composition was performed by the following method.

Flame retardance:

The obtained pellet was dried at 13 O'C for 3 hours, and then subjected to 35 t injection molding. A 1.5 mm thickness bar was obtained at a mold temperature of 7 O'C with a cylinder temperature of 280, and the following evaluation was performed.

Bars with a thickness of 1.5 mm were evaluated for flame retardancy according to the UL-94 V standard.

Bingate formability:

After drying the obtained beret at 13 O'C for 3 hours, using a 360 t injection molding machine, at a cylinder temperature of 290 'C and a mold temperature of 70, the pin gate shape was 22.0 mm. A 2.0 mm thick, A4 size box-shaped product is molded at an injection speed of 60% (the shear rate of the bin gate is about 1500 / sec), and the surface appearance of the obtained molded product is visually observed. Was evaluated.

A: Good appearance.

B: Discolored slightly to yellow.

C: Discoloration to yellow, flash, silver, and poor surface properties due to gas are partially observed on the molded product surface.

D: Discoloration to yellow, poor surface properties due to flash, silver, and gas are observed on the entire molded product surface.

Retention heat stability:

The obtained pellets were dried at 13 O'C for 3 hours, and then retained at a cylinder temperature of 29 O'C for 20 minutes using a 75 t injection molding machine, and then a mold temperature of 70 ' A plate-shaped molded body of 120 mm X 120 mm X 3 mm was molded in C, and the surface appearance of the obtained molded article was visually evaluated.

A: Good appearance.

B: Discolored slightly to yellow.

C: Discoloration to yellow, poor surface properties due to flash, silver, and gas are partially observed on the molded product surface.

D: Discoloration to yellow, flash, silver, poor surface quality due to gas P96 / 03287

It is found on the entire molded product surface.

Hybridity:

The obtained pellets were dried at 130 ° C for 3 hours, and then, using a 75 t injection molding contact, at a cylinder temperature of 290 and a mold temperature of 70 ° C, 12 Omm x 12 O A plate-shaped compact of mm x 1 mm was formed, and the minimum cooling time (sec) at which mold release was possible was examined and evaluated.

Heat deformation resistance:

The obtained pellets were dried at 130 and dried for 3 hours, and the molded body shown in Fig. 1 was heated at a cylinder temperature of 280 at a mold temperature of 70 ° C using a 75-t injection molding machine. Evaluation was carried out.

The obtained molded body and the one that had been subjected to a heat treatment of 140 O'C x 100 hours were measured for flatness from the eight measurement points shown in Fig. 1 using a three-dimensional measuring device (Toyo Seimitsu Co., Ltd.) PJ-800 A).

Here, the flatness is the measurement point that deviates most from the plane in the space divided into two by the plane (least square plane) determined by the measurement points indicated by the triangles (hatched) in FIG. Expressed as the sum of distance (mm) to

From the flatness obtained by the above method, the amount of change in flatness of the heat-treated product was determined from the following equation. The larger the amount of change in flatness, the greater the dimensional change due to heat treatment, indicating that the thermal deformation resistance is poor.

In particular, those with a small amount of change can be said to be suitable for use as components for electronic devices, especially OA and AV devices, which require dimensional accuracy in actual use at high temperatures. . Flatness change (mm) = (flatness of heat-treated product)-(flatness of unheated product)

Durability: After drying the obtained pellets at 130 for 8 hours, using a 75 t injection molding contact, a cylinder temperature of 280 ° (: at a mold temperature of 70'C, a 1/8 inch bar-(width 1 A molded body (2 mm, length: 127 mm) was obtained and evaluated as follows: As shown in Fig. 2, a predetermined bending strain (0.59 mm, 1. After giving 0! ½), the molded body was put into a chemical, taken out at X 10 hours after the treatment at 23, and the appearance change of the molded body was observed, and evaluated according to the following criteria.

Chemicals used: Gasoline, detergent (Mipt: Kao brand name) Evaluation criteria A _: No change in appearance.

B: A craze-like pattern is confirmed on the surface.

C: Cracks are observed on the 袠 surface.

Example 1

Bisphenol A-type polycarbonate resin with an average molecular weight of about 220 00 (A 1) 90 parts by weight and intrinsic viscosity of about 0.75 dl Zg 10 parts by weight of polyethylene terephthalate resin (B 1) As a diphenyl hydride compound, decab mouth modiphenyl (C l) rs AYTEX 80 10 J (trade name of Albemarle Co., Ltd.) After pre-dry blending 15 parts by weight, set the cylinder temperature to 28 O'C The resin composition was obtained by supplying it to a hopper of a twin-screw extruder “TEX44J (trade name, manufactured by Nippon Steel Works, Ltd.)” and extruding it. Are shown in Table 1.

Examples 2 to 7

A resin composition was obtained in the same manner as in Example 1, except that the amount of each compounding agent was changed to the amount shown in Table 1. The following ingredients were used. Table 1 shows the evaluation results.

(A) Polycarbonate resin: Bisphenol A-type polycarbonate resin with an average molecular weight of about 28,800 (A2)

(B) Thermoplastic polyester resin:

Polyethylene terephthalate resin having an intrinsic viscosity of 0.85 d 1 / g (B 2)

Polybutylene terephthalate resin with an intrinsic viscosity of 0.85 dl Zg (B3)

(F) Antimony compound:

Antimony trioxide “Antimony oxide C” (Sumitomo Metal Mining Co., Ltd.

DO'S

Comparative Examples 1 to 6

(C) Brominated flame retardants other than the halofluorinated diphenylalkane compound: brominated phenolic resin (c 2) “YPB-43M” (trade name of Toto Kasei Co., Ltd.)

Brominated polystyrene resin (c 3) Pyro Chiyuk 6 8 PBj (Nissan F: trade name, manufactured by rguchi Organic Chemicals Co., Ltd.)

table 1

Example Example Ratio 铰 Example

L 0 Q 4 c

3 β 0 1 2 3 4 5 6

A y u O U ί U 7 0 7 0 40 99 80 8 0

<< 50 7 0 70 7 0

1 —

Tree 0 CO CD 1 0 20 60 1 20 20 Fat B 30 50 30 30 30 30

set

30

Success

Compound Brenyl refenyl compound (CI) 1 5 1 2 1 5 I 0 1 0 5 5 I 5 1 5 0.5 3 0

C Br-modified resin (c2) 1 5

Br-modified styrene resin (c3) 1 5

<<

F Antimony trioxide 2

Λ

Flame retardant v-o V-2 v-o V-2 V-2 V-2 V-l v-0 v-of

H B vt-0 H B v-Z no

Binge formability BD Λ no □ DDBDCD Retention heat stability BBBBBBBCDBCCD Moldability (sec) 1 2 I 2 1 3 I 4 1 1 1 3 1 3 20 23 25 1 4 I 4 1 4 Heat deformation (mm) 0.3 0.3 0.4 0.5 0.5 0.4 0.4 0.4 0.5 2,1 1.7 0.6 2.1 Vegetable resistance Kerosene 0.5% strain

BAAAAAAAACBC

1.0% distortion CCACCCCCA c CC wash 0.5% distortion AAAAAAAAA c AA 1.0% distortion AAAAAAAAA c AB

Examples 8 to 11

A resin composition was obtained in the same manner as in Example 1, except that the amount of each compounding agent was changed to the amount shown in Table 2. The following ingredients were used. Table 2 shows the evaluation results. For comparison, the results of Examples 1, 4 and 5 are also shown.

(D) Epoxy compound:

Epoxy compound (D 1) "ADK STAB EP-22" (trade name of Asahi Denka Kogyo Co., Ltd.)

Epoxy compound (D 2) "Bond First II" (trade name of ethylene-glycidyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd.)

Table 2

Examples 12 to 14

A resin composition was obtained in the same manner as in Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 3. Further, the following ingredients were used. Table 3 shows the evaluation results. For comparison, the results of Examples 1, 4 and 5 are also shown.

(E) containing at least one orffine unit and at least one (meth) acrylate unit having 1 to 10 carbon atoms in a weight ratio of 40/60 to 95/5. Copolymer:

Copolymer of ethylene and ethyl acrylate (E1) EVAFLE / JP96 / 03287

X—EEA A 7 13 J (trade name, manufactured by Sanpan DuPont Polychemicals Co., Ltd., ethyl acrylate content = 17 weight, MI value = 25 g / 10 minutes) Co-weight of ethylene and ethyl acrylate Combined (E 2) "EVAFLE X—EEA A 704" (trade name, manufactured by Mitsui Dupont Boli Chemical Co., Ltd., ethyl acrylate content 25 weight%, I = 275% / ¥ 0 min) Copolymer (E 3) rEVAFLE X—EEA A 709 ”(trade name, manufactured by Mitsui Dupont Boli Chemical Co., Ltd., ethyl acrylate content = 35% by weight, MI = 25 g 10 minutes)

Table 3

Example 1 5 1 8

A resin composition was obtained in the same manner as in Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 4. The following ingredients were used. Table 4 shows the evaluation results. For comparison, the results of Example 45 are also shown.

(D) Epoxy compound:

Epoxy compound (D 1) “ADK STAB EP-22” (trade name of Asahi Denka Kogyo Co., Ltd.) (E) a copolymer containing at least one olefin unit and at least one (meth) acrylate unit having 1 to 10 carbon atoms in a weight ratio of 40/60 to 955; Coalescing:

Copolymer of ethylene and ethyl acrylate (E 1) rEVAFLE X—EEA A 7 13 ”(trade name, manufactured by DuPont Mitsui Polychemicals, Inc., content of ethyl acrylate—17% by weight, 1 (Value = 25/10 minutes) Copolymer of ethylene and ethyl acrylate (Ε3) rEVAFLE X-EEA A 709 J (trade name of Mitsui Dupont Boli Chemical Co., Ltd., content of ethyl acrylate) = 35 weight ½, MI = 25 g / 10 minutes)

(G) Fluororesin: Polytetrafluoroethylene with a molecular weight of about 5 million "Borifuron FA500J (trade name, manufactured by Daikin Co., Ltd.)

Table 4

As shown in Table 1, as apparent from a comparison between Examples 1 to 7 and Comparative Examples 1 to 6, the resin compositions of the present invention all have pin gate moldability, retention heat stability, hybrid moldability, and heat resistance. Excellent in deformability, shochu chemical properties, and flame retardancy. As is clear from the comparison between Examples 6 and 7, the flame retardancy is further improved by adding a predetermined amount of the (F) antimony compound.

As shown in Table 2, by comparing Examples 8 to 11 with Examples 1, 4, and 5, it is clear that by adding a predetermined amount of (D) epoxy compound, In addition, retention heat stability and chemical resistance are improved. _

As shown in Table 3, when Examples 12 to 14 and Examples 4 and 5 are compared, it is clear that (E) at least one kind of olefin unit and 1 to 10 carbon atoms By adding a predetermined amount of a copolymer containing one kind of (meth) acrylic acid ester unit at a weight ratio of 40Z60 to 95/5, it is possible to further improve pin gate moldability, moldability, and chemical resistance. Is improved. As shown in Table 4, comparing Examples 15 to 18 with Example 4.5, it is clear that, by adding a predetermined amount of (G) fluororesin, the flame retardancy was further improved. Is done. Industrial applicability

The flame-retardant polycarbonate resin composition of the present invention is excellent in pin gate moldability, retention heat stability, moldability, heat deformation resistance, and chemical resistance, and is particularly suitable for electric and electronic parts, electric and electronic product housings. It is suitable for molded products for OA equipment and AV equipment parts, automobile parts, sundries and the like.

Claims

The scope of the claims

1. A resin composition comprising (A) a polycarbonate resin and (B) a thermoplastic polyester resin, wherein the (A) component / (B) component has a weight ratio of 95/5 to 50 to 50 ( R) For 100 parts by weight,

(C) The following one-leg type (I):

(Wherein, R is an alkylene group having a carbon violet number of 1 to 6, m and n are each an integer of〗 to 5, and m + n is 6 to 10)

A flame-retardant polycarbonate resin composition comprising 1 to 20 parts by weight of a brominated difuunylalkane compound represented by the formula:

2. The flame-retardant polycarbonate resin composition according to claim 1, further comprising:

(D) Epoxy compound 0.0 1 to 15 parts by weight

And a flame-retardant polycarbonate resin composition.

3. The flame-retardant polycarbonate resin composition according to claim 1 or 2, further comprising:

(Ii) A copolymer containing at least one olefin unit and at least one (meth) acrylate unit having 1 to 10 carbon atoms in a weight ratio of 40 比 60 to 95/5. 0.5 to 5 parts by weight

And a flame-retardant polycarbonate resin composition.

4. The flame-retardant polycarbonate resin composition according to claim 1, 2 or 3, further comprising:

(F) Antimony compound 0.05 to 10 parts by weight And a flame-retardant polycarbonate resin composition.

5. The flame-retardant polycarbonate resin composition according to claim 1, 2, 3, or 4, further comprising:

(G) Fluorine resin 0.0 1 to 5 parts by weight

And a flame-retardant polycarbonate-based resin composition.

6. A molded article for 0 A equipment or AV equipment parts, which is excellent in heat deformation resistance, comprising the flame-retardant polycarbonate resin composition according to claim 1.