JP2003138122A - Exterior material for vehicle and exterior for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an exterior material for vehicles having fluidity and thermal stability during molding and giving a molded article having excellent balanced impact resistance and high rigidity. SOLUTION: This exterior material for vehicles comprises 50-90 pts.wt. of a polycarbonate resin(A), 5-45 pt.wt. of a graft polymer (B) prepared by carrying out graft polymerization of 90-20 wt.% of a monomer mixture composed of 50-90 wt.% of an aromatic vinyl and 10-50 wt.% of a vinyl cyanide in the presence of 10-80 wt.% of a diene rubber, 0-30 pts.wt. of a copolymer (C) obtained by polymerizing 50-90 wt.% of the aromatic vinyl and 10-50 wt.% of the vinyl cyanide, 1-30 pts.wt. of talc (D) and 1-10 pts.wt. of a phosphoric ester compound (E) [with the proviso that the sum total of the components (A), (B), (C), (D) and (E) is 100 pts.wt.].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vehicle exterior material. More specifically, the present invention relates to a vehicle exterior material and a vehicle exterior component that have excellent balance of impact resistance and rigidity, as well as excellent fluidity and thermal stability.

[0002]

2. Description of the Related Art In recent years, various plastic materials have come to be used for outer panels, wheel caps, spoilers, bumpers and the like for vehicle applications, and the demand for these plastic materials has been further increasing.
For example, for outer panel, a high level of balance between impact resistance and rigidity is required. Further, these exterior parts are often subjected to urethane coating or melamine coating from the viewpoint of their designability, and thus good quality is also required for the smoothness of the surface of the molded product before coating. On the other hand, PC composed of PC (polycarbonate) resin which is a resin excellent in high impact resistance and heat resistance and ABS resin (acrylonitrile-butadiene-styrene copolymer resin) which is a resin excellent in impact resistance and moldability A blend of resin and ABS resin, PC / ABS alloy, has been proposed. However, in these PC / ABS alloys, if glass fibers, carbon fibers, etc. are added to improve the rigidity thereof, the impact resistance is lowered, and further the appearance of the molded product is extremely lowered. In addition, when talc having a fine particle shape is blended, the smoothness of the surface of the molded product is good, but the thermal stability decreases, and a defective appearance called silver occurs on the surface of the molded product in the injection molding process. There is a problem. Under such circumstances, therefore, there is a demand for a vehicle / exterior material for PC / ABS alloy, which has an excellent balance of impact resistance and rigidity, as well as excellent fluidity and thermal stability.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a vehicle exterior material which is excellent in balance between impact resistance and high rigidity, fluidity during molding, and thermal stability. is there.

[0004]

SUMMARY OF THE INVENTION The present invention is a PC / ABS
By adding talc to the alloy and further adding a phosphoric acid ester compound, the rigidity is improved without lowering the impact resistance, and the vehicle exterior material has excellent fluidity and thermal stability during molding. The present invention has been completed and the present invention has been completed. Further, in the present invention, impact resistance is further improved by using an agglomerated and enlarged rubber formed by aggregating small particle rubber having a specific particle diameter as a diene rubber component of a graft polymer which constitutes an ABS resin. It is possible to obtain a vehicle exterior material having an excellent balance of fluidity.

That is, the present invention relates to [1] 50 to 90 parts by weight of a polycarbonate resin (A) and 10 to 8 diene rubbers.
Grafted by graft polymerizing 90 to 20% by weight of a monomer mixture consisting of 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer in the presence of 0% by weight. Copolymer (C) obtained by polymerizing 5 to 45 parts by weight of polymer (B), 50 to 90% by weight of aromatic vinyl monomer and 10 to 50% by weight of vinyl cyanide monomer.
0-30 parts by weight, talc (D) 1-30 parts by weight, and phosphoric acid ester compound (E) 1-10 parts by weight [however, (A), (B), (C), (D) and (E) The total amount of which is 100 parts by weight], and [2] the graft polymer (B) is a small particle diene rubber latex having a weight average particle diameter of 0.05 to 0.20 μm. 50 to 90% by weight of an aromatic vinyl monomer in the presence of 10 to 80% by weight of a diene rubber latex (solid content) that has been coagulated and enlarged to have a weight average particle diameter of 0.20 to 0.8 μ.
And a graft polymer obtained by graft-polymerizing 90 to 20% by weight of a monomer mixture consisting of 10 to 50% by weight of a vinyl cyanide monomer, [1].
[3] A vehicle exterior component obtained by molding the vehicle exterior material according to [1] or [2].

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a dihydroxyaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. A polymer obtained by the transesterification method, and a typical example thereof is 2,2-
Bis (4-hydroxyphenyl) propane, a polycarbonate resin made from "bisphenol A".

Examples of the dihydroxydiaryl compound include bis (4-hydroxydiphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) butane, in addition to bisphenol A. , 2,2-bis (4-hydroxyphenyl)
Octane, bisbis (4-hydroxydiphenyl) phenylmethane, 2,2-bis (4-hydroxydiphenyl-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-3,5dibromophenyl) propane, 2,2-bis (4-hydroxy-)
Bis (hydroxyaryl) alkanes such as 3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4
Bis (hydroxyaryl) cycloalkanes such as -hydroxyphenyl) cyclohexane, 4,4'-
Dihydroxy diphenyl ethers, dihydroxy diaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfe Dihydroxydiaryl sulfides such as Fide, 4,4′-
Dihydroxy diaryl sulfoxides such as dihydroxy diphenyl sulfoxide, 4,4′-dihydroxy diphenyl sulfone, 4,4′-dihydroxy-3,
Examples thereof include dihydroxydiaryl sulfones such as 3′-dimethyldiphenyl sulfone. These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyls and the like may be mixed.

Further, the above-mentioned dihydroxydiaryl compound and the following trivalent or higher valent phenol compounds may be mixed and used. As trihydric or higher phenol, 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'-hydroxydiphenyl) cyclohexyl) -propane and the like can be mentioned.

The weight average molecular weight of the polycarbonate resin (A) used is usually 10,000 to 80,
000, preferably 15,000 to 60,000. In producing these polycarbonate resins, a molecular weight modifier, a catalyst and the like can be used if necessary.

The graft polymer (B) used in the present invention means 50 to 90% by weight of an aromatic vinyl monomer and 10 to 10% of a vinyl cyanide monomer in the presence of 10 to 80% by weight of a diene rubber. Monomer mixture 9 consisting of 50% by weight
It is a graft polymer obtained by graft polymerizing 0 to 20% by weight.

The diene rubber constituting the graft polymer (B) is a polymer obtained by polymerizing a monomer containing 50% by weight or more of a diene monomer typified by 1,3-butadiene. Other monomers copolymerizable with the diene monomer include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Examples of the monomer include unsaturated carboxylic acid alkyl ester monomers such as monomers, methyl acrylate, ethyl acrylate, and methyl methacrylate. Specifically, it is a polybutadiene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, or a butadiene-methylmethacrylate copolymer. The gel content of diene rubber (solvent: toluene) is not particularly limited, but preferably 60 to 95% by weight can be preferably used.

Examples of the aromatic vinyl-based monomer constituting the graft polymer (B) include styrene, α-methylstyrene, paramethylstyrene, chlorostyrene, bromostyrene, etc., and one kind or two or more kinds are used. be able to. Particularly, styrene and α-methylstyrene are preferable.
As the vinyl cyanide-based monomer, acrylonitrile,
Methacrylonitrile and the like can be mentioned, and one kind or two or more kinds can be used. Acrylonitrile is particularly preferable. Further, in the present invention, a part of the aromatic vinyl-based monomer is another copolymerizable vinyl-based monomer, such as maleimide, methylmaleimide, ethylmaleimide, N-.
Maleimide monomers such as phenylmaleimide and O-chloro-N-phenylmaleimide, unsaturated carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate. You may substitute.

In the present invention, in view of the balance between impact resistance and fluidity, heat resistance and rigidity, the diene rubber which constitutes the graft polymer (B) is a small particle having a specific particle diameter. It is preferable to use an agglomerated and enlarged rubber obtained by aggregating rubber. Specifically, it is possible to use a diene rubber latex obtained by coagulating and expanding a small particle diene rubber latex having a weight average particle diameter of 0.05 to 0.20 μ to a weight average particle diameter of 0.20 to 0.8 μ. preferable. As a method for coagulating and enlarging the above-mentioned small particle diene rubber latex, a conventionally known method, for example, a method of adding an acidic substance (Japanese Examined Patent Publication Nos. 42-3112 and 55-55).
19246, JP-B-2-9601, JP-A-63-117.
005, JP-A-63-132903, JP-A-7-157.
501, JP-A-8-259777), a method of adding an acid group-containing latex (JP-A-56-166201, JP-A-59-93701, JP-A-1-126301, JP-A-8-126301).
-59704) and the like can be adopted without any particular limitation.

The method for producing the above graft polymer is not particularly limited, and it can be polymerized by an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof, but the above-mentioned cohesive enlargement is particularly preferable. When a rubber latex is used, a usual emulsion polymerization method can be adopted, and known emulsifiers, initiators and various auxiliaries can be used without any limitation.

Copolymer (C) used in the present invention
Is a copolymer obtained by polymerizing 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer. As the aromatic vinyl-based monomer and the vinyl cyanide-based monomer that compose the copolymer (C), the same ones as exemplified in the section of the graft polymer (B) can be used. Further, in the present invention, a part of the aromatic vinyl-based monomer constituting the copolymer (C) is maleimide, methylmaleimide, ethylmaleimide, N.
-Maleimide monomers such as phenylmaleimide, N-cyclohexylmaleimide and O-chloro-N-phenylmaleimide, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and 2-ethylhexyl acrylate It may be replaced with a system monomer or the like. The reduced viscosity of the copolymer (C) is not limited,
It is preferably in the range of 0.3 to 1.2 dl / g.

In the production of the above-mentioned copolymer (C), known emulsion polymerization method, bulk polymerization method, suspension polymerization method, solution polymerization method can be adopted, and an emulsifier, an initiator, and As various auxiliaries, known ones can be used without any limitation. The reduced viscosity of the copolymer (C) may be appropriately adjusted depending on the polymerization temperature, the method of adding the monomers, the initiator used and the type and amount of the polymerization chain transfer agent such as t-dodecyl mercaptan. it can.

As the talc (D) used in the present invention, it is usually preferable to use one having an average particle size of 0.1 to 50 μm.

Examples of the phosphate compound (E) used in the present invention include compounds represented by the following general formula 1.

[0019]

[Chemical 1]

(R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent organic group, and at least _one of R ₁ , R ₂ , R ₃ and R ₄ is 1
One is a monovalent organic group. X is a divalent organic group,
k, l, m, and n are each independently 0 or 1, and N is an integer of 0-10). Examples of the monovalent organic group in the above general formula 1 include an optionally substituted alkyl group, an aryl group, and a cycloalkyl group. Examples of the substituent in the case of being substituted include an alkyl group, an alkoxy group, Examples thereof include an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a group in which these substituents are combined (arylalkoxyalkyl group, etc.), or these substituents are bonded by an oxygen, sulfur, or nitrogen atom. The combined group (arylsulfonylaryl group etc.) may be a substituent. Examples of the divalent organic group include groups derived from alkylene groups, phenylene groups which may have a substituent, polyhydric phenols, polynuclear phenols (bisphenols, etc.). Particularly preferred divalent organic groups are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p,
Examples include p'-dihydroxydiphenyl sulfone and dihydroxynaphthalene. These may be used alone or in combination of two or more. Specific examples of these phosphate compounds (B) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl. Phosphate, trixylenyl phosphate, hydroxyphenyl diphenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and further the following formula 2,
Examples thereof include compounds represented by Chemical formula 3 or Chemical formula 4.

[0021]

[Chemical 2]

[0022]

[Chemical 3] (In the formula, R represents hydrogen or a methyl group.)

[0023]

[Chemical 4]

The blending ratio of the polycarbonate resin (A), the graft polymer (B), the copolymer (C), the talc (D) and the phosphoric acid ester compound (E) in the present invention is 50 to 90% by weight of (A). Parts, (B) 5 to 45 parts by weight,
(C) 0 to 30 parts by weight, (D) 1 to 30 parts by weight and (E) 1 to 10 parts by weight [however, (A), (B), (C),
The total amount of (D) and (E) is 100 parts by weight], and outside this range, the composition aimed at by the present invention cannot be obtained, which is not preferable. From the viewpoint of the balance of physical properties of the composition, the content of diene rubber in the entire composition is 2
It is preferably in the range of ˜30% by weight.

The mixing order and the state of the polycarbonate resin (A), the graft polymer (B), the copolymer (C), the talc (D) and the phosphoric acid ester compound (E) are not particularly limited, and powder, Examples of the method include simultaneous simultaneous mixing of the components (A), (B), (C), (D) and (E) according to a form such as pellets, and a method of mixing the remaining components after pre-mixing the specific two components. . A Banbury mixer, a roll, an extruder or the like can be used for the melt-mixing. Upon mixing, if necessary, polybutylene terephthalate, polyethylene terephthalate,
Other thermoplastic resins such as polyphenylene ether, as well as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents,
Known additives such as lubricants, dyes, pigments, plasticizers, flame retardants, release agents, glass fibers, metal fibers, carbon fibers and metal flakes, reinforcing materials, fillers and the like can be added.

The vehicle exterior material according to the present invention is
For example, it is molded into various parts such as a door panel, a front fender, a rear fender, a tailgate panel, a wheel cap, a spoiler, a bumper, and a pillar, and is put to practical use as a vehicle exterior part. Further, the vehicle exterior component of the present invention is excellent in smoothness of the surface of the molded article thereof, so that it is possible to apply urethane coating or melamine coating if necessary.

Here, these various exterior parts can be molded by a conventionally known molding method such as injection molding, extrusion molding or blow molding. Further, when urethane coating or melamine coating is applied to these exterior parts, a paint generally used for steel plates for automobiles or exterior resin parts for automobiles can be used. For example, in the melamine coating, it is possible to use a paint whose main component is an acrylic melamine resin-based paint or a polyester melamine resin-based paint. In urethane coating, it is possible to use a coating material containing an acrylic urethane resin-based coating material as a main component. At the time of coating, it is also possible to use a non-crosslinking type primer containing a chlorinated polyolefin resin or a polyester urethane resin as a main component as a primer. Further, a conductive primer having conductivity for electrostatic coating may be used as the primer.

The present invention will be described in detail below.
The present invention is not limited to this. Further, both parts and% are shown on a weight basis.

Reference Example-1 In a pressure vessel, 100 parts of 1,3-butadiene, 0.3 part of t-dodecyl mercaptan, 0.25 part of potassium persulfate, and 2.5 parts of sodium rosinate were placed.
Parts, 0.1 part of sodium hydroxide and 170 parts of pure water were charged, and the temperature was raised to 80 ° C., and then polymerization was started. Polymerization is 10
Finished in time. The obtained diene rubber latex (b-) had a solid content of 37% and a weight average particle diameter of 0.1.
The gel content was 90% and the gel content was 90%. The gel content is
The latex was dried to form a film, and after weighing about 1 g, the film was immersed in toluene at 23 ° C. for 48 hours,
The insoluble matter was separated by filtration with a 100 mesh wire mesh and dried, and the weight% thereof was measured.

[Reference Example-2] 270 parts by weight of the diene rubber latex (b-) obtained in Reference Example-1 and 0.1 part of sodium dodecylbenzene sulfonate were added to a pressure vessel and stirred and mixed for 10 minutes. After that, 5% phosphoric acid aqueous solution 2
0 part was added over 10 minutes. Then, 10 parts of a 10% aqueous potassium hydroxide solution was added to the mixture, and the enlarged diene rubber latex (b) having a solid content of 34% and a weight average particle diameter of 0.3 μm (b
-1) was obtained.

[Reference Example-3] The enlarged diene rubber latex (b-1) 50 obtained in Reference Example-2 was placed in a pressure vessel.
Parts (solid content), sodium dodecylbenzenesulfonate (1.5 parts), potassium persulfate (0.3 parts), and 70 ° C
After the temperature was raised to 3, the monomer mixture consisting of 35 parts of styrene and 15 parts of acrylonitrile was continuously added over 5 hours to obtain a graft polymer latex B-1. After adding 1 part of a phenolic antioxidant (Sumitomo Chemical Co., Ltd .: Sumilizer BBM) and 2 parts of trisnonylphenyl phosphite as an antioxidant per 100 parts by weight of the obtained latex (solid content), sulfuric acid was used. Salting out, dehydration,
It was dried to obtain a graft polymer B-1. Further, in the above polymerization, the graft polymer B-was prepared in the same manner as above except that the amount of the diene rubber latex was changed to 60 parts (solid content), 28 parts of styrene and 12 parts of acrylonitrile.
Got 2.

Reference Example 4 120 parts of pure water and 0.3 part of potassium persulfate were charged in a pressure vessel and then heated to 65 ° C. with stirring. Then, 70 parts of styrene, 30 parts of acrylonitrile, and 0. t-dodecyl mercaptan.
30 parts of an emulsifier aqueous solution containing 3 parts of a mixed monomer solution and 2 parts of sodium dodecylbenzenesulfonate were continuously added over 5 hours, and then the polymerization system was heated to 70 ° C.
The temperature was raised to 1, and the mixture was aged for 3 hours to complete the polymerization. Then, salting out, dehydration and drying were performed using magnesium sulfate to obtain a copolymer C-1. The reduced viscosity of the obtained copolymer C-1 was 0.45.

Examples 1 to 4 and Comparative Examples 1 to 4 Polycarbonate resin (A), graft copolymers B-1 and B-2 produced in Reference Example, copolymer C-1, talc (D) and phosphoric acid. Ester-based compound (E) was mixed at the mixing ratio shown in Table 1, melt-mixed at 250 ° C. using a 40 mm twin-screw extruder to form pellets, and various test pieces were prepared with an injection molding machine to evaluate physical properties. did. The results are shown in Table 3. The polycarbonate resin (A) used in the examples and comparative examples was made by Sumitomo Dow, Caliber 200-20, and talc (D) was produced by Hayashi Kasei Co., Ltd., Micron White 5000S.
As the phosphoric acid ester-based compound (E), Adeka Stab FP-500 manufactured by Asahi Denka Kogyo Co., Ltd. under the trade name shown in Chemical formula 4 was used.

O Impact resistance: 60 obtained by injection molding machine
Place a flat plate of mm x 60 mm x 3 mm on a circular table with a diameter of 50 mm, drop a 5 kg falling weight from any height on the radius 1/4 inch of the strike center, and measure the energy value in the area where the flat plate does not break did. Drop weight impact value: 5 kg x drop weight height (J) [fall weight height: the maximum height at which the flat plate does not break, with 100 cm as the upper limit] oMFR: According to ASTM D-1238. 250 ° C x
5kg load. o Rigidity: According to ASTM D-790. o Thermal stability (silver property): 200mm with injection molding machine
A × 150 mm × 3 mmt flat plate was molded, and the state of silver generation on the surface of the molded product was visually determined. The setting temperature of the molding machine cylinder was 250 ° C., and the molding cycle was 60 seconds / one shot. Silver property; ○: No silver generation, ×: Silver generation

[0035]

[Table 1]

[0036]

As described above, the vehicle exterior material according to the present invention has an excellent balance of impact resistance and rigidity, as well as excellent fluidity and thermal stability during molding, and is particularly suitable for outer panel and wheel cap. It can be suitably used as a vehicle exterior component such as a vehicle, a spoiler, or a bumper.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 69/00 C08L 51:04 51:04 25:12 25:12) F term (reference) 3D023 AA01 AB05 AC01 AC04 AC05 AC25 AC27 AD02 4F071 AA12X AA22X AA34X AA50 AA76 AA77 AA88 AB30 AC15 AF20 AF23 AF43 AH11 BA01 BB05 4J002 BC063 BN142 CG011 CG021 CG031 DJ046 EW047 GN00

Claims (3)

[Claims] 1. Polycarbonate resin (A) 50-90
A monomer mixture 90 consisting of 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer in the presence of 10 to 80% by weight of a diene rubber.
5 to 45 parts by weight of a graft polymer (B) obtained by graft polymerization of 20 to 20% by weight, and an aromatic vinyl monomer 50 to 9
0 to 30 parts by weight of a copolymer (C) obtained by polymerizing 0% by weight and 10 to 50% by weight of a vinyl cyanide-based monomer, 1 to 30 parts by weight of talc (D), and a phosphate ester compound (E ) 1 to 10 parts by weight (however, (A), (B), (C),
The total of (D) and (E) is 100 parts by weight]. 2. A diene in which a graft polymer (B) is obtained by coagulating and enlarging a small particle diene rubber latex having a weight average particle diameter of 0.05 to 0.20 μm to a weight average particle diameter of 0.20 to 0.8 μm. A monomer mixture 90 to 20 comprising 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer in the presence of 10 to 80% by weight of a rubber latex (solid content). The vehicle exterior material according to claim 1, which is a graft polymer obtained by graft-polymerizing wt%. 3. A vehicle exterior component obtained by molding the vehicle exterior material according to claim 1 or 2.