JPS62179554A - Thermoplastic polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to weather and impact, consisting of a thermoplastic polyester resin, a specified impact modifier resin and a Ni-contg. ultraviolet stabilizer. CONSTITUTION:100pts.wt. thermoplastic polyester resin (A) (e.g., polyethylene terephthalate contg. an alkali metal hypophosphite blended therewith during polymn.) is blended with 0.1-120pts.wt. at least one impact modifier resin (B) selected from the group consisting of ethylene resins modified with a carboxylic acid (derivative) or a compd. having a glycidyl group, acrylic rubber, MBS resins and ABS resins, 0.01-5pts.wt. Ni-contg. ultraviolet stabilizer (C) of the formula (wherein X<1>, X<2>, X<3> and X<4> are each N, O or S; and R<1>, R<2>, R<3> and R<4> are each an org. residue and a plurality of them may form one org. residue when combined together) and optionally, an epoxy compd., a lubricant, an antioxidant, an ultraviolet absorber, a crystallization accelerator, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic polyester resin composition that has excellent weather resistance and zX resistance.

[Conventional technology]

Thermoplastic polyester, particularly polybutylene terephthalate (hereinafter abbreviated as PBT) resin, is widely considered as a raw material for automobile exterior parts because of its good heat resistance and dimensional stability. Among them, PBT resin, carboxylic acid or glycidyl group-modified ethylene resin, acrylic rubber or methacrylnitrile-butadiene-styrene resin (MBE+),
jr7ri') Lonitrile-butadiene-styrene resin 7
Compositions containing (ABs) have excellent impact resistance, and are therefore attracting attention as a material for automobile bumpers, fenders, etc. Since good weather resistance is required for these uses, benzotriazole-based ultraviolet absorbers are usually added. However, when the amount is 0.7 to 0.5% of the amount used for ordinary PBT, the effect of improving weather resistance is insufficient and discoloration and poor gloss occur. If the blending amount is 7% or more, the impact resistance deteriorates, and the impact resistance for the above-mentioned applications is no longer maintained.

[Invention tries to solve! IF1 Problem] As mentioned above, there is a demand for a thermoplastic polyester resin composition that has both weather resistance and impact resistance.

[Means for solving problems]

In order to solve the above problems, the composition of the present invention has the following advantages:
(a) Thermoplastic polyester resin (1) Selected from ethylene resins, acrylic rubbers, MBS and ABIII resins modified with carboxylic acids, their derivatives or glycidyl-containing compounds. At least/an impact-improving resin for foodstuffs and (0) a general formula (where This is a thermoplastic polyester resin composition consisting of a nickel-containing ultraviolet stabilizer represented by:

The thermoplastic polyester resin used in the present invention is a polyalkylene terebutanate obtained by a polycondensation reaction between a dialkyl ester of terephthalic acid and an aliphatic glycol, or a copolymer mainly composed of this. ,
Typical examples include polyethylene terephthalate,
Examples include polybutylene terephthalate.

Examples of the aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol,
Examples include hexamethylene glycol, but together with these aliphatic glycols, other diols or polyhydric alcohols, such as cyclohexanediol, cyclohexane dimetatool, xylylene, in an amount of 30% by weight or less based on the aliphatic glycols. Glycol, 2, λ-bis(Hiro-hydro-tetraxyphenyl)furopane, 2,2-bis(4t
-hydroxy-j,j-dibromphenyl)propane,
! ,,2-bis(Hiro-hydroxyethoxyphenyl)propane, 2-bis(Hiro-hydroxyethoxy-3,
A mixture of 5-dibromphenyl)propane, glycerin, pentaerythritol, etc. may be used.

In addition, terephthalic acid may contain other dibasic acids, polybasic acids, or their alkyl esters together with its dialkyl esters, such as phthalic acid, isophthalic acid,
A mixture of naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, adipic acid, sepaconic acid, trimesic acid, trimellitic acid, and alkyl esters thereof may be used. PBT is preferable from the viewpoint of ease of molding and impact resistance, and PBT is preferable because of its ease of molding and impact resistance.
BT is preferred.

Carboxylic acid or its derivative or glycidyl group-modified ethylene resin This is a resin made by randomly or graft copolymerizing (indicated by f) a compound having a functional group of carboxylic acid or its derivative or glycidyl group, mainly consisting of ethylene.

For example, etele/-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-sodium acrylate copolymer, ethylene-acrylic rRZn neutralized copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene −? -Maleic anhydride copolymer, ethylene-butene-? -Maleic anhydride copolymer, ethylene-butene-?
-Tetrahydrofurfuryl acrylic acid copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-
Vinyl acetate-glycidyl methacrylate copolymer, ethylene-propylene-? -glycidyl methacrylate copolymer, etc., and known ones can be used.

Acrylic rubber is a rubber-like elastic material obtained by polymerization of acrylic ester, and copolymerization mainly consisting of acrylic ester. A typical example is a polymer obtained by polymerizing an acrylic acid ester such as butyl acrylate and a small amount of a crosslinkable monomer such as butylene diacrylate, and a graft polymerizable monomer such as methyl methacrylate. Rubber-like polymers obtained by For example, it is commercially available as Metaprene (trademark) manufactured by Mitsubishi Rayon ■, Acryloid (trademark) manufactured by Rohm & 9 Haas, etc.

MBB or Ir1ABS resin has a butadiene rubber component/θ
~rs*41c%1 Preferably 30 to 70118% contains methyl, ethyl or butyl ester of methacrylic acid or acrylic acid, or acrylonitrile, and a vinyl aromatic octagroup compound such as styrene, vinyltoluene, α-methylstyrene, etc. as a graft component. /! ~90% by weight is preferably a graft copolymer using 30 to 70''.The MBS resin is Metaprene C (trademark) manufactured by Mitsubishi Rayon ■, etc., and the AB8 resin is manufactured by Mitsubishi Monosand, Japan Synthetic Rubber, Mitsubishi Rayon. It is widely available commercially from companies such as

Among these impact-improving resins, modified ethylene resins are preferred in terms of thermal stability.

The blending amount of these impact-improving resins (1,) is 0.0 for the thermoplastic polyester resin (a) / 00 N placement part.
The amount is 5 to 120 parts by weight, preferably 2 to 700 parts by weight. If the amount is too small, there will be no impact improvement effect, and if the amount is too large, the rigidity will be too low, making it unsuitable for use as exterior parts for automobiles, and in general, compatibility is poor, and R is an organic residue. Furthermore, R
A plurality of 1 to 4 may constitute 7 organic residues). Specifically, n-butylamine-nickel-,2'-thio-bis(9 is one yearly octyl felt), nickel-bis(('r''-thio-bis('r''-thio-bis(9))
9L-tert-octyl phthalate)], Nickel-dibutyldithiocarbamate Nickel-bis[di-isopropylamine-dithiophosphate], Nickel-bis-(3,j-di-tert-butyl-p-hydroxybenzyl) phosphonic acid Monoethyl (t or butyl) ester and the like.

Formulated aFi thermoplastic polyester (a) / 00!
0.0 for Okabe / ~ 5-layered base, preferably 0.0
,! r^λ parts by weight. If the blending amount is small, there is no effect of improving weather resistance. On the other hand, if the amount is too large, the gR resistance will be reduced and the thermal stability will be deteriorated, making it easier for silver etc. to occur during molding.

In addition to these ingredients, epoxy compounds, lubricants, antioxidants, ultraviolet absorbers, crystallization accelerators, and the like may be appropriately added to improve the performance.

That is, bisphenol A diglycidyl ether, 3-
Epoxy compounds such as mono-epoxycyclohexylmethyl-3, Hiro-epoxycyclohexane carboxylate, or lubricants such as ethylene bisstearamide, stearyl stearate, etc., aid in dispersing the impact-modifying resin. Pentaerythrityltetrakis (J-(p'-hydroxy-7
', j'-ditertiarybutylphenyl) globiomate, diracrylthiodiprobiomate, tris(2,
Antioxidants such as u-ditertiarybutylphenol) phosphite, 2-(,2'-hydroxy-5'-octylphenyl)penzotriazole, bis(2,2,
Incorporation of UV absorbers such as t,l tetramethyl-piperidinyl-prone sebacate promotes improved weather resistance. The content of these organic substances is usually 0.10742 parts by weight, preferably 0.05 to 7 parts by weight.

Further, depending on the required strength and rigidity, fillers such as glass fiber, carbon fiber, mica, talc, wollastonite, and glass peas may be added. When using these, it is effective to use an epoxy-based silane treatment agent in combination.

Also polycarbonate, polyester carbonate l's
Other resins such as Ho'J ester ether elastomer, nylon, polystyrene, polyphenylene oxide, polyphenylene sulfide, and polysulfone may also be blended.

〔Example〕

Hereinafter, a more specific explanation will be given using examples.

In addition, "parts" in the examples indicate "parts by weight."

After mixing the compositions shown in Example/~Hiro and Comparative Example 7~/Hiro table-/, a twin-screw vent extruder (
(manufactured by Nakatani) at a temperature of -60 to 2/θ°C and pelletized. After drying the obtained pellet, 3. 50 oz. injection molding@(Toshiba Machine Gunko 57spNll)
φ disc and //♂ inch XzoeL impact test piece at resin temperature, Obtained at JO-270°C, whole mold temperature Ifto°C. Impact tests were performed on Izod stamp specimens according to ASTM Dλ56. Further, in order to determine the change in color tone before and after the 4Ljθ time test in a weather resistance test using a Sunshine Weather-Ometer, the color difference ΔE was measured using a Tokyo Denshoku Color Ace TO-technique.

The results are shown in Table-/.

In addition, the ethylene used in Examples/and Comparative Examples/~3
Butene-/-? -Maleic anhydride-2-tetrahydrofurfuryl acrylate was produced by the following method.

Ethylene-butene-/copolymer (crystallinity 20%, MI
3. Otsu, butene-/content/%Lmolti) ioo part α, α'
- Bis-t-butylperoxycoupe p-diisopropylbenzene (dissolved in a small amount of acetone) OoOS part Maleic anhydride / part After blending the raw materials with the above composition, extrusion at 200°C using a 30φ twin screw extruder (manufactured by Nakatani Kikai) , the amount of grafted maleic anhydride produced by pelletizing O0a weight f, the crystallinity λO x, M
Maleic anhydride grafted ethylene-butene-
/ 700 parts of the copolymer, α,α'-bis-t-butylperoxy-p-diisopropylbenzene (a small amount dissolved in 10 parts of acetone), θ, os parts, and tetrahydrofurfuryl methadimethacrylate parts were mixed in the same manner as above. It was then extruded and pelletized.

The crystallinity of this ethylene-butene/copolymer grafted with two types of functional groups is 20q6, MI 2,2, maleic anhydride 90.3%, tetrahydrofurfuryl methacrylate 0.17% (respectively) ethylene-butene-/
(for copolymers).

〔Effect of the invention〕

As described above, according to the present invention, a polyester resin composition having excellent weather resistance and impact resistance can be obtained.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney: Yo Hase - 7 others Penumbra 7: Ne713 perfect circle (spontaneous) 1. Indication of the case: 1985 Patent Application No. 20409 2. Name of the invention: Thermoplastic polyester resin Composition (59G) Mitsubishi Chemical Industries, Ltd. Mei 1 [ILLLl "Detailed description of the invention" column 6 Contents of amendment

Claims (2)

[Claims] (1) (a) Thermoplastic polyester resin (b) Ethylene resin modified with carboxylic acid, its derivative or glycidyl group-containing compound, acrylic rubber, M
At least one type of impact-improving resin selected from BS and ABS resins and (c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, X^1^~^4 are N, O, S R^2^~^6 are atoms selected from the elements and are organic residues. Note that multiple R^1^~^4 may constitute one organic residue) A thermoplastic polyester resin composition comprising a nickel-containing UV stabilizer. (2) A patent claim consisting of 0.5 to 120 parts by weight of an impact improving resin (b) and 0.01 to 5 parts by weight of a nickel-containing ultraviolet stabilizer (c) to 100 parts by weight of a thermoplastic polyester resin (a). range 1
The thermoplastic polyester resin composition described in .