JP3515583B2 - Polycarbonate resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly, to flame retardancy, thermal stability when staying in a mold, impact resistance and dimensional stability. , Moldability (fluidity)
The present invention relates to a polycarbonate resin composition having excellent properties. 2. Description of the Related Art Polycarbonate resin (PC) is excellent in mechanical strength, electric properties and transparency, and is used as an engineering plastic in various fields such as electric / electronic devices and automobiles. Widely used in the field. And in the field of OA equipment chassis etc. where heat resistance, rigidity, dimensional stability, etc. are required,
Polycarbonate resin (hereinafter abbreviated as GF-PC) reinforced with glass fiber (GF) has been used as an alternative to bulk molding compounds and aluminum die cast. However, by blending GF,
GF-PC has a problem that the impact strength is greatly reduced as compared with a single PC, and the moldability (fluidity, mold release property) is deteriorated. As a technique for improving the impact resistance and moldability, for example, Japanese Patent Application Laid-Open No. 3-27052 discloses a technique of blending a styrene elastomer having excellent heat resistance. However, in the technology disclosed herein, there is a problem that the anisotropy in dimensional stability is not reduced and the flame retardancy is not yet sufficient. On the other hand, in the OA equipment field, there is a risk of ignition or the like due to overheating, and therefore, there is a demand for improvement in flame retardancy mainly for outer parts. [0003] Accordingly, the present inventors have proposed:
In view of the above situation, the disadvantages of the conventional method have been eliminated,
Thermal stability, impact resistance and dimensional stability when staying in the mold,
Intensive research was conducted to develop a polycarbonate resin composition having excellent moldability (flowability). As a result, GF-P
It has been found that a polycarbonate resin composition having desired properties can be obtained by blending C with a plate-like or spherical filler, a heat-resistant styrene-based elastomer and a halogenated polystyrene. The present invention has been completed based on such findings. That is, the present invention relates to (A) 50 to 90% by weight of a polycarbonate resin,
(B) 5 to 33% by weight of a fibrous filler and (C) a plate-like glass filler having an aspect ratio of 10 or more or a particle size of 1 to 1
100μm spherical glass filler 5 I to 17 wt%
That (A), (B) the total amount of the components and the component (C) 10
(D) styrene-hydrogenated butadiene-
Styrene triblock polymer, styrene-isoprene-styrene triblock polymer, styrene-hydrogenated isoprene-styrene triblock polymer, styrene-hydrogenated isoprene diblock polymer, styrene-isoprene diblock polymer and styrene-hydrogenated butadiene diblock polymer At least one heat-resistant styrene-based elastomer selected from the group: 3 to 10 parts by weight and (E)
An object of the present invention is to provide a polycarbonate resin composition comprising 1 to 8 parts by weight of a flame retardant made of halogenated polystyrene. First, in the present invention, the polycarbonate resin (PC) used as the component (A) constituting the resin composition is represented by the following general formula (I): [Wherein, X is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms. A and b may each be an integer of 1 to 4. And Y is
Single bond, alkylene group having 1 to 8 carbon atoms, alkylidene group having 2 to 8 carbon atoms, cycloalkylene group having 5 to 15 carbon atoms, cycloalkylidene group having 5 to 15 carbon atoms or -S
—, —SO—, —SO ₂ —, —O—, —CO— bond or the general formula (II): [0008] The bond represented by Can be easily produced by reacting the dihydric phenol represented by the formula (1) with phosgene or a carbonate compound. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or as in the case of dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a suitable carbonate precursor. Here, there are various dihydric phenols represented by the general formula (I), and 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Examples of the dihydric phenol other than bisphenol A include 1,1- (4-hydroxyphenyl) methane as bis (4-hydroxyphenyl) alkane other than bisphenol A; 1,1- (4-hydroxyphenyl) ethane; hydroquinone; , 4'-dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4
Bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; compounds such as bis (4-hydroxyphenyl) ketone or bis (3,4-hydroxyphenyl) sulfone; 5-dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane, and the like. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Next, in the present invention, as the fibrous filler of the component (B) constituting the resin composition, any of glass fibers made of alkali-containing glass, low-alkali glass, non-alkali glass or the like is preferable. Can be used. The length of this glass fiber is preferably 0.01 to 2 m
m, more preferably in the range of 0.05 to 1 mm. Since these glass fibers may break when kneading with the polycarbonate resin, the size when strengthening the kneading is generally 1 to 6 m in length.
Those in the range of m are preferred. The diameter of 1 to 20 μm is usually sufficient. The form of these glass fibers is not particularly limited, and any form such as roving, milled fiber, and chopped strand can be used. These glass fibers can be used alone or in combination of two or more. Further, these glass fibers are desirably subjected to a surface treatment with a surface treatment agent and then subjected to a sizing treatment with an appropriate sizing agent for the purpose of improving the adhesiveness with the polycarbonate resin. Here, as the surface treatment agent,
For example, silane-based such as aminosilane-based, epoxysilane-based, vinylsilane-based, and acrylsilane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and boron-based coupling agents can be used. Among these, silane coupling agents and titanate coupling agents, particularly silane coupling agents, are preferred. The method of treating the glass fiber with the surface treatment agent is not particularly limited, and any conventionally used method such as an aqueous solution method, an organic solvent method, and a spray method can be used. Examples of the sizing agent include, for example, urethane-based, acrylic-based, acrylonitrile-styrene-based copolymer-based, epoxy-based, and the like, and any of them can be used. There is no particular limitation on the method of sizing the glass fibers using these sizing agents, and methods conventionally used, for example, dip coating, roller coating, spray coating,
Any method such as flow coating and spray coating can be used. Examples of the fibrous filler other than the glass fiber include whiskers such as carbon fiber, potassium titanate, aluminum borate, boron fiber, and silicon nitride, and mineral fibers. [0010] In the present invention, a plate-like filler or a spherical filler is used as the component (C) constituting the resin composition. Here, specific examples of the plate-like filler include glass flake, mica, and talc. The long diameter of this plate-like filler is
Those having a size of 2,000 μm or less, preferably 0.5 to 1,000 μm, and an aspect ratio (the ratio of the major axis to the thickness of the filler) of 5 or more, preferably 10 or more are used. When the major axis of the plate-like filler exceeds 2,000 μm, classification occurs when compounded with the resin, which makes it difficult to uniformly mix with the resin, and may cause spots on the obtained molded product. Is not preferred. When the aspect ratio of the plate-like filler is less than 5, the reduction of anisotropy in the dimensional stability of the obtained molded article and the improvement of the heat distortion temperature are insufficient, and the impact strength tends to decrease. Is not preferred. On the other hand, specific examples of the spherical filler include glass beads, glass balloons, calcium carbonate and the like. The spherical filler is generally referred to as a spherical filler, but in the present invention, not only a true spherical shape but also an elliptical shape to some extent may be used. As such a spherical filler,
Particles having a particle size of 0.5 to 200 μm, preferably 1 to 100 μm are used. The glass beads mentioned here are
It is a glass sphere having a small diameter as described above. In the present invention, the respective proportions of the components (A), (B) and (C) constituting the resin composition are as follows: (A) 50 to 90% by weight of a polycarbonate resin;
(B) 5 to 33 % by weight, preferably 10% by weight of fibrous filler
To 33 % by weight and (C) 5 to 17 % by weight, preferably 10 to 17 % by weight of plate-like or spherical fillers.
If the proportion of the fibrous filler (B) is less than 5% by weight, mechanical properties such as strength and rigidity are insufficient. On the other hand, if the content exceeds 33 % by weight, the mechanical properties such as strength and rigidity have little effect of improving the compounding amount, and the impact strength is rather reduced. Then, the strand taking-up stability during kneading becomes unstable, which is not preferable. On the other hand, when the blending ratio of the plate-like filler or the spherical filler as the component (C) is less than 5% by weight, the strength and rigidity are high, but the anisotropy in dimensional stability becomes large. Also, 1
If it exceeds 7 % by weight, the moldability such as fluidity deteriorates and the impact strength decreases, which is not preferable. The resin composition of the present invention comprises the above (A),
(B) 3 to 10 parts by weight, preferably 3 to 6 parts by weight, of (E) halogen and (E) halogen with respect to 100 parts by weight of the components (B) and (C) blended in respective proportions. 1 to 8 parts by weight, preferably 2 to 6 parts by weight. First,
As the heat-resistant styrenic elastomer of the component (D),
Although various ones can be used, for example, a compound represented by the general formula (I
II) Q- (RQ) _n ... (III) or general formula (IV) (QR) _n ... (IV) wherein Q is a styrene-based polymer block, and represented by the formula (III) )), The degree of polymerization may be the same at both ends of the molecular chain, or may be different. R is at least one block selected from an isoprene polymerized block, a hydrogenated butadiene polymerized block, and a hydrogenated isoprene polymerized block. n is an integer of 1 or more. ] Is used. The content of the Q component in the block copolymer is 20 to 80% by weight.
Must be within the range. Here, the content is 20
If the amount is less than 80% by weight, the strength and rigidity are inferior. If the amount is more than 80% by weight, the moldability and the impact resistance are undesirably reduced. The number average molecular weight per block of the Q component is in the range of 5,000 to 200,000, and the number average molecular weight per block of the R component is 5,000 to 200,000.
000 is required. Here, when the number average molecular weight per single block of the Q component is less than 5,000, or when the number average molecular weight per block of the R component is 5,000.
If it is less than the above, the mechanical properties are insufficient. When the number average molecular weight per block of the Q component exceeds 200,000, or when the number average molecular weight per block of the R component is 2
If it exceeds 0.000, the moldability deteriorates. Further, the number average molecular weight of the entire block copolymer is 100,000
When the number average molecular weight is less than 10,000, the mechanical properties are inferior, and when the number average molecular weight is more than 400,000, the moldability deteriorates. As the heat-resistant styrene-based elastomer (D), a diblock type, a triblock type and a tetrablock type are mainly used. The general formula (III)
Examples of the styrene polymer block of Q in (IV) and (IV) include blocks such as styrene, α-methylstyrene, vinyltoluene, vinylxylene, and vinylnaphthalene. As the heat-resistant styrene-based elastomer of the component (D), specifically, for example, styrene-
Hydrogenated butadiene-styrene triblock polymer (SE
BS), styrene-isoprene-styrene triblock polymer, styrene-hydrogenated isoprene-styrene triblock polymer (SEPS), styrene-hydrogenated isoprene diblock polymer (SEP), styrene-isoprene diblock polymer, styrene-hydrogenated butadiene Diblock polymers and the like. These components (D) may be used alone or in combination of two or more. As described above, the component (D) is blended in an amount of 3 to 10 parts by weight, preferably 3 to 6 parts by weight, based on 100 parts by weight of the components (A), (B) and (C). You. Here, if the compounding amount is less than 3 parts by weight, the effects on the impact resistance and the moldability (fluidity, mold release property) are not exhibited. On the other hand, if it exceeds 10 parts by weight, the strength and rigidity are greatly reduced, and the flame retardancy is UL941 / 16 inch V.
The amount of flame retardant added must be increased to pass -O. Along with this, the retention heat stability greatly deteriorates. On the other hand, the effect of improving the impact resistance is not recognized in proportion to the compounding amount, which is not preferable. When the morphology of a sample in which the impact resistance is not improved because of a large amount of the elastomer is observed, the elastomer is connected in a network and an inter-penetrating network (Inter Penetrating Network) is formed.
s). On the other hand, in the sample having improved impact resistance, the elastomer is finely dispersed. It is considered that this difference in morphology affects the impact resistance. As the flame retardant comprising the halogenated polystyrene as the component (E), various flame retardants can be used. Specifically, for example, polychlorostyrene, polydibromostyrene, polytribromostyrene, etc. The polymer type aromatic halogen-based flame retardant is preferably used.
Those having a molecular weight of preferably 10,000 to 50,000 are preferred. And the content of halogen is 50 to 80%
Are preferred. Further, the average particle size is 1 to 3
0 μm. As described above, the component (E) is blended in an amount of 1 to 8 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the components (A), (B) and (C). You. Here, when the amount is less than 1 part by weight, the flame retardant effect is small. On the other hand, if it exceeds 8 parts by weight, the impact resistance is lowered, and further the retention heat stability is deteriorated. The present invention provides, as described above, a polycarbonate resin composition comprising the components (A), (B), (C), (D) and (E), and (A), (B)
And each component of (C) is (A) 40 to 90% by weight, (B) is 5 to 55% by weight, preferably 10 to 50% by weight.
% And (C) are 5 to 55% by weight, preferably 10 to
It is blended at a ratio of 50% by weight. A resin composition comprising 1 to 10 parts by weight of (D) and 1 to 8 parts by weight of (E) with respect to 100 parts by weight of (A), (B) and (C) having the above mixing ratio. It is. The resin composition of the present invention may contain, if necessary, the components (A), (B), (C), (D) and (E) as long as the object of the present invention is not impaired.
In addition, various additives, other synthetic resins, elastomers and the like can be blended. For example, as various additives, inorganic fillers such as calcium sulfate, barium sulfate, aluminum hydroxide, clay, silica, diatomaceous earth, montmorillonite, bentonite, zinc borate, barium metaborate, and antimony trioxide, or hindered Phenol type, phosphite type, phosphate type,
Antioxidants such as amines, ultraviolet absorbers such as benzotriazoles and benzophenones, light stabilizers such as hindered amines, internal lubricants such as aliphatic carboxylic acid esters, silicone oils, polyethylene waxes and paraffins, polytetrafluoroethylene And the like, a common flame retardant, a release agent, an antistatic agent, a coloring agent, and the like. In the various moldings using the polycarbonate resin composition of the present invention, the mixing and kneading methods for mixing and kneading the above components are not particularly limited, and generally used methods, for example, a ribbon blender, a Henschel mixer, a Banbury mixer , Drum tumbler, single screw extruder, twin screw extruder,
It can be performed by a method using a coneder, a multi-screw extruder or the like. The heating temperature during kneading is usually 2
It is selected in the range of 50 to 300 ° C. The polycarbonate resin composition thus obtained is known various molding methods,
For example, by applying injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, and the like, various molded products in the OA field, the electronic / electric field, the automobile field, and the like can be manufactured. Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The components used in the examples and comparative examples are as follows. (A) PC: polycarbonate resin “Toughlon A220”
0 "[Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 22,000
0] (B) GF: Glass fiber “ECS03T-509” [manufactured by NEC Corporation, 3 mm in length, 13 μm in diameter, chopped strand treated with urethane bundling agent, aminosilane surface treatment agent] (C) Glass flake: “REFG-101” [Nippon Sheet Glass Co., Ltd., average particle size 600 μm, thickness
(C) Glass beads: “EGB731A” [manufactured by Toshiba Barotini Co., Ltd., average particle size 30 to 40 μm]
m, treated with aminosilane surface treating agent] (D) Styrene-based elastomer 1) "H1051" [Tuff Tech H10, manufactured by Asahi Kasei Corporation]
51 (SEBS having a styrene content of 40%)] 2) "H1041" [Tuff Tech H10 manufactured by Asahi Kasei Corporation]
41 (SEBS with a styrene content of 30%)] 3) "KL1050" (Kuraray Co., Ltd., SEP Septon KL1050 (SEP with a styrene content of 50%)] 4) "KL2006" (Kuraray Co., Ltd., SEPS Septon) KL2006 (SEP with 35% styrene content)
S)] (E) Flame retardant 1) “68PB” [manufactured by Nissan Ferro-Organic Chemical Co., Ltd., Pyrocheck 68PB (polytribromostyrene, bromine content 68%, Mw 270,000)] 2) “BC52” [Great Grey Lakes B manufactured by Lakes
C52 (brominated bisphenol A oligomer type, bromine content 52%)] 3) "EP100" [Dai Nippon Ink Chemical Co., Ltd., Platherm EP100 (epoxy brominated bisphenol A oligomer type, bromine content 52%)] 4 ) "PDBS" [Great Lakes, Gletrax P
DBS (polydibromostyrene, bromine content 58-60)
%, Mw 80,000)] The following test items were measured as performance evaluations. 1) Flame retardant UL94 standard Vertical combustion test (1/16 inch wall thickness), V-0 target 2) Process stability Toshiba IS25EP injection molding machine, 300 ° C, 40 seconds standard molding cycle product (flat plate) The color difference (color change) from the molded product (plate) after 10 minutes and 20 minutes of residence was measured with an optical meter (SM-3, manufactured by Suga Test Instruments). The smaller the measured value, the better. 3) Izod impact strength conforms to JIS K-7110 1/8 inch thickness Measurement 23 ° C with notch 4) Flexural modulus conforms to JIS K-7203 5) Molding shrinkage 140mm at molding temperature 300 ° C, mold temperature 80 ° C × 14
A flat plate of 0 mm × 3 mm was injection molded and measured at a magnification of 20 times with a universal projector [Nikon Profile Projector V-24B manufactured by Nippon Kogaku Co., Ltd.]. It indicates that the anisotropy decreases as the value of MD / TD approaches 1. Examples 1 to 12 and Comparative Examples 1 to 12 According to the composition shown in Table 1, a predetermined amount of each component was dry-blended, and then a twin-screw extruder [TEM-35, manufactured by Toshiba Machine Co., Ltd.] And a fibrous, plate-like or spherical filler was injected from the side using a vibrating feeder and a screw feeder, kneaded, and pelletized.
The obtained pellets were molded at a molding temperature of 300 ° C. and a mold temperature of 80 ° C.
To produce a test piece. The test pieces obtained in each of the examples and comparative examples were measured for the test items as performance evaluations. Table 2 shows the measurement results of the examples, and Table 3 shows the measurement results of the comparative examples. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] As described above, according to the present invention, flame retardancy,
Thermal stability, impact resistance and dimensional stability when staying in the mold,
It turns out that it is a polycarbonate resin composition excellent in moldability (flowability) etc. Therefore, the polycarbonate resin composition of the present invention can be effectively used as a material for various molded articles widely used in the OA equipment field, electric / electronic equipment field, automobile field, and the like.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 25:10 C08L 53:02 53:02 25:18 25:18) (56) References JP-A-3-52946 (JP, A) JP-A-58-171422 (JP, A) JP-A-61-123082 (JP, A) JP-A-62-109855 (JP, A) JP-A-3-273052 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C08L 69/00 C08K 3/00-3/40 C08K ⁷ /00-7/28

Claims (1)

(57) [Claim 1] (A) Polycarbonate resin 50 to 90
Wt%, (B) 5 to 33 wt% of fibrous filler, and (C) plate glass filler having an aspect ratio of 10 or more or spherical glass filler 5 to 17 having a particle size of 1 to 100 μm.
Consisting wt% (A) component, (B) 100 parts by weight of the total amount of components and (C), (D) a styrene - hydrogenated butadiene - styrene triblock polymer, a styrene - isoprene - styrene triblock polymers Styrene-hydrogenated isoprene-styrene triblock polymer,
3 to 10 parts by weight of at least one heat-resistant styrenic elastomer selected from the group consisting of styrene-hydrogenated isoprene diblock polymer, styrene-isoprene diblock polymer and styrene-hydrogenated butadiene diblock polymer, and (E) halogenated polystyrene Flame retardant 1
What is claimed is: 1. A polycarbonate resin composition, which is blended in an amount of up to 8 parts by weight.