JP3077732B2 - Thermoplastic resin composition with excellent weather resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for a molding material containing an aromatic polycarbonate resin and a thermoplastic polyester as main components, and particularly to a weather resistance, a chemical resistance, an impact resistance and a molding property. The present invention relates to a thermoplastic resin composition having excellent processability. The resin composition of the present invention provides materials suitable for automobile-related parts, OA equipment, home electric parts, medical care, miscellaneous goods, and the like.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate resins are:
It is widely used as a resin having excellent mechanical strength, impact resistance and heat resistance, but has disadvantages such as slightly inferior chemical resistance and fatigue resistance.

[0003] On the other hand, thermoplastic polyesters are excellent in chemical resistance and moldability (flowability), but have high impact resistance,
It has disadvantages such as dimensional stability, sink during molding, and easy warpage.

A polymer alloy of an aromatic polycarbonate resin and a thermoplastic polyester is known to compensate for each of these drawbacks.
Among devices, home electric parts, medical care, and miscellaneous goods, there is a limit in performance of those requiring weather resistance or light resistance.

[0005] Aromatic polycarbonate resin has a certain level of ultraviolet absorbing ability due to its chemical structure, but it has a limit to excessive ultraviolet rays, and thermoplastic polyesters are susceptible to cracking and crazing due to long-term exposure to ultraviolet rays. I do. As a method for improving weather resistance, there is generally a method of adding an ultraviolet absorber, but at present there is no satisfactory method.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition suitable for a molding material containing an aromatic polycarbonate resin and a thermoplastic polyester as main components, and particularly to a weather resistance, a chemical resistance and an impact resistance. Another object of the present invention is to provide a thermoplastic resin composition having excellent moldability.

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention has been studied variously, and a specific ultraviolet absorbent and a light-stable material are used for a molding material containing an aromatic polycarbonate resin and a thermoplastic polyester as a main component. It has been found that by blending the agent at a predetermined ratio, a thermoplastic resin composition excellent in expected weather resistance, chemical resistance, impact resistance and moldability can be obtained.

More specifically, the present invention relates to (a) 10 to 90% by weight of an aromatic polycarbonate resin, (b) 90 to 10% by weight of a thermoplastic polyester, and (c) 0 to 20% of an impact modifier.
With respect to 100 parts by weight of the resin composition consisting of
(D) a benzotriazole-based ultraviolet absorber represented by the general formula (1) and (e) a hindered amine-based light stabilizer represented by the general formula (2) in an amount of 0.01 to 3 parts by weight. The present invention relates to a thermoplastic resin composition having excellent weather resistance.

In the present invention, the combination of the above-mentioned components (d) and (e) has excellent weather resistance which cannot be achieved only by adding a conventional ultraviolet absorbent, and is an aromatic polycarbonate resin. This is a thermoplastic resin composition having the moldability and chemical resistance exhibited by the thermoplastic polyester by utilizing the characteristics of (1).

The aromatic polycarbonate resin in the present invention is an aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. In the reaction of the aromatic polycarbonate polymer, a branching agent may be used if necessary.

As the above aromatic dihydroxy compound,
Specifically, for example, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane [= tetramethylbisphenol A] 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane [= tetrabromobisphenol A], 2,2-bis (4-hydroxyphenyl) cyclohexane, 2,2
-Bis (4-hydroxyphenyl) sulfone, 2,2-
Bis (4-hydroxyphenyl) sulfide, 2,2-
Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl and the like are exemplified. Of these, bisphenol A is particularly preferred from the economical viewpoint.

In order to obtain a branched aromatic polycarbonate resin, chloroglycine, 4,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptene-
3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tris (4-
Polyhydroxy compounds exemplified by hydroxyphenyl) ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole [= isatin bisphenol], 5-chloroisatin bisphenol, 5,6-dichloroisatin bisphenol, For example, 5-bromoisatin bisphenol is substituted for a part of the dihydroxy compound, for example, 0.1 to 2 mol% with a polyhydroxy compound.

Further, a monovalent aromatic hydroxy compound is used as a molecular weight regulator. These are, for example, m-
And p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-long-chain alkyl-substituted phenol are preferably used.

As the aromatic polycarbonate resin, a bis (4-hydroxyphenyl) alkane-based compound, in particular, a polycarbonate containing bisphenol A as a main raw material is typically used. Further, two or more aromatic dihydroxy compounds may be used in combination. And a branched polycarbonate obtained by using a small amount of a trivalent phenolic compound in combination with the polycarbonate copolymer obtained by the above method. Further, the aromatic polycarbonate resin may be used as a mixture of two or more kinds.

The thermoplastic polyester in the present invention comprises:
A polymer obtained by reacting an aromatic dicarboxylic acid or a diester thereof with a glycol or an alkylene oxide by a known method. Polyethylene terephthalate, polytetramethylene terephthalate, obtained by reacting an aromatic dicarboxylic acid as a main component with ethylene glycol, butanediol, cyclohexane dimethanol or ethylene oxide, etc.
Examples thereof include polyethylene naphthalate and polytetramethylene naphthalate.

The thermoplastic polyester may be a copolymer, for example, cyclohexane dimethanol, a copolymer of ethylene glycol and terephthalic acid, and a copolymer of cyclohexane dimethanol and a copolymer of ethylene glycol and terephthalic acid. Can be mentioned. Other known thermoplastic polyesters can also be used.

The thermoplastic polyester used in the present invention has an intrinsic viscosity (intrinsic viscosity) of 0.4 or more measured at 30 ° C. in a mixed solvent obtained by mixing phenol and tetrachloroethylene at a weight ratio of 6: 4. It is preferably from 0.5 to 1.5, and if it is less than 0.4, the impact resistance and chemical resistance are not sufficiently improved, which is not preferable.

The benzotriazole-based ultraviolet absorber as the component (d) used in the present invention is a compound represented by the following general formula (1). In the present invention, it is important from the viewpoint of the weather resistance of the resin composition. One of the ingredients.

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(Where X is a phenyl group, a hydroxyl group or a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms;
R _{1 to} R _{4 each} represent a hydrogen atom, a halogen atom or a carbon atom
(Indicating an alkyl group of 4)

Various UV absorbers are known for use in aromatic polycarbonate resins. The benzotriazole-based compound is one of useful ultraviolet absorbers, and among these benzotriazole-based ultraviolet absorbers, particularly in the present invention, the compound represented by the general formula (1) is effective.

Specific examples of the benzotriazole type ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-
tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-
(Hydroxy-5-octylphenyl) benzotriazole and the like.

Among them, in the present invention, 2- (5-methyl-2-hydroxyphenyl) benzotriazole represented by the following formula (d-1) and the following formula (d-2) are particularly preferred. 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole is preferred.

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In the present invention, a hindered amine light stabilizer is used as the component (e). Amine compounds generally tend to promote the hydrolysis of aromatic polycarbonate resins, and their use is not preferred. However, in the present invention, hindered amine compounds having a specific structure represented by the following general formula (2) are preferred. A special effect is achieved when the light stabilizer is used in combination with the benzotriazole-based compound.

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(Wherein, R _{5 to} R ₈ represent a hydrogen atom or a methyl group)

The hindered amine light stabilizer which is the component (e) in the present invention is a compound having a structure represented by the general formula (2), and has a weather resistance when used in combination with the component (d). It can be further improved. Specific examples thereof include those shown in the following formulas (e-1) and (e-2).

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In the present invention, the compounding amount of the benzotriazole-based ultraviolet absorber as the component (d) is 0.01 to 100 parts by weight of the total amount of the aromatic polycarbonate resin, the thermoplastic polyester and the impact modifier. Used in the range of ~ 3 parts by weight. The amount of the component (d) used is 0.01
When the amount is less than 3 parts by weight, the effect is not improved.

The compounding amount of the hindered amine light stabilizer as the component (e) is a total amount of the aromatic polycarbonate resin, the thermoplastic polyester and the impact modifier of 10%.
It is used in the range of 0.01 to 3 parts by weight with respect to 0 parts by weight. If it is less than 0.01 part by weight, the weather resistance cannot be sufficiently improved. Further effects cannot be expected, and the appearance is poor due to bleed-out, and heat resistance and impact resistance are adversely affected.

In the present invention, the desired effect is not sufficiently achieved by using the component (d) or the component (e) individually, but the desired effect is obtained by using the component (d) and the component (e) together. Is achieved, and their mixing ratio is usually
The weight ratio is 98/2 to 50/50, preferably 96
/ 4 to 65/35.

The impact modifier in the present invention includes polyester elastomer, MBS resin, MAS resin, acrylate core-shell graft copolymer, polyolefin and polyolefin elastomer, styrene core-shell graft copolymer, SBR, Examples include SEBS and polyurethane-based elastomers, and one or more of these are used. In the present invention, among the above, the aromatic polycarbonate resin as a resin component, and compatibility with thermoplastic polyester, etc.,
From the viewpoint of heat resistance and the like, polyester elastomers, MAS resins, acrylate ester core-shell graft copolymers, styrene core-shell graft copolymers, and the like are particularly suitable.

As the above-mentioned polyester elastomer, for example, trade name “Perprene P30B” commercially available from Toyobo Co., Ltd. can be mentioned.

The MBS resin is prepared by subjecting a butadiene rubber-like polymer such as polybutadiene or a butadiene-styrene copolymer to bulk polymerization, suspension polymerization, Those obtained by graft polymerization by a method such as bulk / suspension polymerization, solution polymerization or emulsion polymerization are preferred.

The MAS resin has an alkyl group having 1 to 8 carbon atoms.
Of a rubber component (1) mainly composed of an alkyl ester of acrylic acid or methacrylic acid, and an aromatic hydrocarbon polymer or an aromatic hydrocarbon monomer and one or two vinyl or vinylidene monomers (2) wherein a part or all of the monomer of (2) is (1)
5-40% by weight of a polymer obtained by polymerization in the presence of
Those containing the rubber are preferred.

The acrylate-based core-shell graft copolymer is a polyfunctional polymerizable monomer having a conjugated diene double bond represented by an alkyl ester of acrylic acid having 2 to 12 carbon atoms in an alkyl group and butadiene. And a core comprising a crosslinked rubber copolymer obtained by copolymerization in the presence of a crosslinking agent by an emulsion polymerization method, a monomer mixture such as styrene, methyl methacrylate, acrylonitrile, and methacrylonitrile. Those obtained by graft polymerization can be mentioned. Such acrylate-based core-shell graft copolymers include, for example, trade names “HIA-15” and “HIA-” from Kureha Chemical Industry Co., Ltd.
28 "," HIA-30 "and the like.

Polyolefins include polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer,
Ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers and the like having a low glass transition temperature, particularly those having a glass transition temperature of -40 ° C or lower are suitable.

The crosslinked polyolefin elastomer is a main component of an ethylene-propylene copolymer, which is crosslinked with a diene compound using a peroxide as a catalyst. As such a crosslinked olefin-based elastomer, for example, an elastomer commercially available from Mitsui Petrochemical Industry Co., Ltd. under the trade name “Millastomer” can be mentioned.

The styrene-based core-shell graft polymer is a so-called multi-stage polymer, which is a multi-stage seed in which the polymer of the previous stage is successively coated with the polymer of the subsequent stage. It is a graft polymer obtained by an emulsion polymerization method. Examples of such a core-shell graft polymer include those marketed by Takeda Pharmaceutical Co., Ltd. under the trade name “STAFLOID”.

SBR is composed of a non-elastomeric polymer block containing a vinyl aromatic hydrocarbon polymer and an elastomeric polymer block containing a conjugated diene compound polymer, and their composition ratio is 10/90 to 10/90. 55/4
Those in the range of 5 are preferred. Examples of such an elastomer include those commercially available from Shell Chemical Co., Ltd. under the trade name “Califlex”.

SEBS is a hydrogenated ABA block copolymer, the central block B is a conjugated diene hydrocarbon compound, usually a butadiene block or an isoprene block, and the terminal block A is a vinyl aromatic hydrocarbon. It is a polymer block. Such hydrogenation AB-
The A-type block copolymer is available from, for example, Shell Chemical Co., Ltd. under the trade names “Clayton G1650” and “Clayton G1”.
651 "or" Clayton G1657 "or those commercially available from Kuraray Co., Ltd. under the trade names" Septon 2002 "," Septon 2003 "and" Septon 2023 ".

The polyurethane elastomer is obtained by combining a diisocyanate and a polyol as a base material with various chain extenders or crosslinking agents. These polyurethane elastomers include, for example, "Paraprene" (trade name) of Nippon Polyurethane Industry Co., Ltd. and "Elastoran" (trade name) of Takeda Badish Co., Ltd.

The resin composition of the present invention may further contain, if desired, a stabilizer known per se, which is usually added to the resin composition.
Various additives such as pigments, dyes, lubricants, etc., various fillers such as glass fiber, glass cloth, non-woven fabric, reinforcing material such as inorganic or organic fiber material such as carbon fiber, and glass beads can be blended. Further, other synthetic resins and the like can be blended as required.

In preparing the resin composition of the present invention, a conventionally known method is employed, and an extruder, a Banbury,
A method of kneading with a mixer, a roll, or the like is appropriately used.

Hereinafter, the resin composition of the present invention will be described in more detail with reference to examples. The present invention is not limited to these.

Examples (1) Components The aromatic polycarbonate resin was manufactured by Mitsubishi Gas Chemical Company, Inc.
Manufactured and trade name "Iupilon S-3000" (molecular weight 23,
000) was used.

As the thermoplastic polyester, polyethylene terephthalate manufactured by Mitsubishi Rayon Co., Ltd., trade name "Dianite PA200" was used.

As an impact resistance improving material, "STAFLOID MG1011" (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) was used.

As a benzotriazole-based ultraviolet absorber, trade name "Tinuvin P" [2-
(5-methyl-2-hydroxyphenyl) benzotriazole] (d-1), trade name "Tinuvin 326" [2- (3
-Tert-butyl-5-methyl-2-hydroxyphenyl) 5-chlorobenzotriazole] (d-2), and as a control, "Tinuvin 234" [2-
[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole] (d
-3) was used.

As a hindered phenolamine-based light stabilizer, Sankyo LS-2626 (trade name) manufactured by Sankyo Co., Ltd.
(e-1) [Compound represented by Chemical Formula 7], manufactured by Ciba-Geigy, trade name "Tinuvin 622 LD" [Compound represented by Chemical Formula 8] (e-2), as a control, Sankyo Co., Ltd. Product name "Sanol LS765" [bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) sebacate] (e-3).

In the table, M2112 is a phosphite-based antioxidant, trade name “ADK STAB 21”, manufactured by Asahi Denka Kogyo Co., Ltd.
12 ".

The above ingredients were mixed in a tumbler at the ratios shown in Tables 1 and 2 and extruded into pellets by a single-screw vented extruder. After drying, a test piece (ASTMM-1 dumbbell) for measuring physical properties was produced by injection molding at a resin temperature of 260 ° C.

In the table, the amounts of components (a), (b) and (c) are in% by weight, and components (d) and (e) are 100% by weight in total of components (a), (b) and (c). Parts by weight relative to parts.

The tensile strength is in accordance with ASTM D-638,
Izod impact strength was measured according to ASTM D-256, and load deflection temperature was measured according to ASTM D-648.

The exposure test was carried out using a sunshine weather tester manufactured by Suga Test Instruments Co., Ltd., with a black panel temperature of 63.
The composition was treated for 1000 hours under the conditions of ° C. and rain spraying of 18 minutes / 120 minutes, and the tensile strength, Izod impact strength, and color difference (ΔE) were measured. (Hereinafter the margin)

[Table 1]

[Table 2]

[0053]

EFFECT OF THE INVENTION The resin composition of the present invention can give a molded article having excellent physical properties such as weather resistance and impact resistance, and can be used as a molding material for automobile-related parts, OA equipment, home appliance parts, medical care, miscellaneous goods, etc. It is suitable as.

────────────────────────────────────────────────── (5) References JP-A-4-363357 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/04 C08L 69 / 00

Claims (1)

(57) [Claims] (A) Aromatic polycarbonate resin 10
(D) 90 to 10% by weight of a thermoplastic polyester, (c) 100 to 100 parts by weight of a resin composition comprising 0 to 20% by weight of an impact modifier, and (d) the following general formula (1)
Benzotriazole ultraviolet absorber 0.01 represented by
(E) a thermoplastic resin composition comprising 0.01 to 3 parts by weight of a hindered amine stabilizer having a structure represented by the following general formula (2). Embedded image (However, X is a phenyl group, a hydroxyl group or a group having 1 to 1 carbon atoms.
A phenyl group substituted with an alkyl group of 0, and R _{1 to} R ₄ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. (Wherein, R _{5 to} R ₈ represent a hydrogen atom or a methyl group)