JPH1087968A - Resin composition and molding product from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester composition slight in discoloration even in a high-temperature environment and excellent in crack resistance, and a molding product from the composition. SOLUTION: This resin composition contains (A) 100 pts.wt. of a polyester resin, (B) 0.001-2 pts.wt. of a phosphorus-based stabilizer compound, (C) 0.01-20 pts.wt. of titanium oxide and (D) 0.005-50 pts.wt. of an organopolysiloxane-based polymer containing a Si-H bond in the molecule. The resin composition is molded to give the objective molding product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent heat stability and a molded product obtained by molding the same, which is used at a high temperature such as a socket of an incandescent lamp (lamp). It is also suitable as a molded product of electric, electronic equipment parts, automobile parts, machine parts and the like.

[0002] Polyester resins have excellent heat resistance (heat-resistant deformation) and chemical resistance and are therefore used in various fields such as electric, electronic equipment parts, automobile parts, and mechanical parts.
However, when exposed for a long time in a high temperature environment, there is a problem that the surface is cracked due to discoloration and thermal oxidative deterioration.

[0003] For example, when a polyester resin is used as a socket material for a light bulb, the heat of the light bulb causes the socket portion to reach a considerably high temperature (for example, 200 ° C, partially higher). There has been a problem that cracks easily occur on the surface.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyester resin composition which exhibits little thermal discoloration even in a high temperature environment and has excellent crack resistance. It is to provide a molded article. In particular, an object of the present invention is to provide a polyester excellent in heat stability (discoloration and crack resistance).

[0005]

The object of the present invention is to provide a resin composition having the following constitution, that is, (B) a phosphorus-based stabilizer compound in an amount of 0.001 to 100 parts by weight of a (A) polyester-based resin. 2 parts by weight, (C) titanium oxide
(D) an organopolysiloxane polymer having a Si—H bond in the molecule, based on 0.01 to 20 parts by weight and 100 parts by weight of the titanium oxide as the component (C).
The problem is solved by a resin composition containing 50 parts by weight, and is further advantageously solved by a molded article molded using such a resin composition.

Here, the component A) polyester includes:
In the polyester of a diol (or an ester-forming derivative thereof) and a dicarboxylic acid (or an ester-forming derivative thereof), the following compounds may be used alone or in combination as the diol component and the dicarboxylic acid component. Further, a compound having a hydroxyl group and a carboxylic acid group in one molecule such as lactone may be combined.

The diol component includes ethylene glycol, propylene 1,2-glycol, propylene 1,3-glycol, 1,4-butanediol, 2,3-butanediol,
Hexane 1,6-diol, octane 1,8-diol, neopentyl glycol, decane 1,10-diol, diethylene glycol, triethylene glycol, etc., having 2 carbon atoms
To 15 aliphatic diols. Preferred aliphatic diols are ethylene glycol, 1,4-butanediol.

Also, 1,2-cyclohexanediol, 1,4-
Cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These alicyclic diols can be used in either the cis or trans configuration, or as a mixture of both. A preferred cycloaliphatic diol is 1,4-cyclohexanedimethanol.

Furthermore, aromatic dihydric phenols such as resorcinol, hydroquinone and naphthalene diol, polyethylene glycol having a molecular weight of 400 to 6000, polyglycols such as polypropylene glycol and polytetramethylene glycol, and bisphenol A such as
Bisphenols described in JP-A-203956 can also be mentioned. In addition, the diol component,
Diesters such as diacetate and dipropionate may be used.

The dicarboxylic acid component includes isophthalic acid, terephthalic acid, orthophthalic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 1,2-di (4-carboxyphenyl) ethane, adipic acid, Examples thereof include aliphatic and alicyclic dicarboxylic acids such as succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and cyclohexanedicarboxylic acid. Also,
The acid component may be an ester derivative, for example, an alkyl ester such as methyl or ethyl, or an aryl ester such as phenol or cresol.

Preferred dicarboxylic acids are terephthalic acid and naphthalenedicarboxylic acid. As the component B), these diols and dicarboxylic acids may be used alone, a compound having a hydroxyl group and a carboxyl group in one molecule such as caprolactone may be used, or two or more diols or dicarboxylic acids may be used. Acids may be used in combination. The obtained polyesters may be used alone or in combination.

The catalyst used for producing the polyester may be any of ordinary catalysts such as antimony compounds, titanium compounds, tin compounds and germanium compounds.

Polyesters, preferably polyesters of aromatic dicarboxylic acids and alkylene glycols, specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly 1,4-cyclohexylene methylene terephthalate, poly ( 1,4-cyclohexylenemethylene terephthalate-co-
Isophthalate), poly (1,4-butylene terephthalate)
(Co-isophthalate) and poly (ethylene-co-1,4-cyclohexylenemethylene terephthalate). Among them, polyethylene terephthalate and polybutylene terephthalate are particularly preferred.

Further, polyethylene terephthalate (PE)
It is particularly preferable to use a combination of T) and polybutylene terephthalate (PBT) in view of the balance between heat resistance and cycle time during molding. That is, PET
Has excellent heat deformation resistance due to its higher melting point than PBT,
Since the crystallization speed of PBT is higher than that of PET, the molding cycle time can be reduced.

As the component (B) phosphorus stabilizer compound used in the present invention, those commercially available from various stabilizer manufacturers as antioxidants and the like can be used. For example, triphenyl phosphite, diphenyl nonyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, tris nonyl phenyl phosphite, diphenyl isooctyl phosphite, 2,2′-methylene bis (4, 6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl phosphite, diphenylmono (tridecyl) phosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenol) fluorophosphite, phenyl Diisodecyl phosphite, phenyl di (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl)
Phosphite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis (2,4-di-t-
Butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropylidenediphenolalkyl (C12-C15) phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ) Di-tridecyl phosphite, bis (2,4-di-t-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-di
-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite, phenyl-bisphenol A
Pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite, 1,1,3-
Tris (2-methyl-4-di-tridecyl phosphite-5-
t-butylphenyl) butane, 3,4,5,6-dibenzo-
1,2-oxaphosphane-2-oxide and the like can be used.

As an example of an available product, ADK STAB
PEP-36, PEP-24, PEP-4C, PEP-
8 (trademark: manufactured by Asahi Denka Kogyo KK), Irgafos168 (trademark:
Ciba Geigy), Sandstab P-EPQ (trademark: Sandoz), Chelex L (trademark: Sakai Chemical Industry Co., Ltd.), 3P2S (trademark: Ihara Chemical Industry Co., Ltd.), Mark 329K (trademark) :
Asahi Denka Kogyo Co., Ltd.), Mark P (trademark: Asahi Denka Kogyo Co., Ltd.)
And Weston 618 (trademark: manufactured by Sanko Chemical Co., Ltd.).

More preferred phosphorus stabilizers include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol Diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, more preferably
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite.

The component (B) is used in an amount of 0.01 to 2 parts by weight, preferably 0.00, based on 100 parts by weight of the component (A).
5 to 1 part by weight, more preferably 0.01 to 0.5 part by weight is used. If the amount of the component (B) is less than the above range, the effects of the present invention will not be sufficiently exhibited, and if it is more than the above range, heat resistance will be impaired.

The component (C) titanium oxide used in the present invention has a particle size of 0.05 to 5 μm, preferably 0.1 to 1 μm.
Are preferably used. The surface of titanium oxide is composed of an organic silane compound (such as a silane coupling agent), zinc,
Those treated with aluminum, silica, or the like can be used.

The crystal structure is not particularly limited, but is preferably rutile type titanium. These titanium oxides are usually commercially available. For example, Ti-pure R960 (trademark) manufactured by DuPont, Taipaque R680 (trademark) manufactured by Ishihara Sangyo Co., Ltd., Titone R-27 (trademark) Sakai Chemical Industry Co., Ltd. )) Is a preferred example.

Here, since titanium oxide has a strong hiding power, it is effective in suppressing heat discoloration. In addition, there are many applications that require a high degree of light-shielding properties, such as applications such as light bulb sockets, and titanium oxide is also used for the purpose of imparting this light-shielding property.

The component (C) is used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the component (A). Preferably 0.05 to 12 parts by weight, more preferably 0.1 to 12 parts by weight.
1 to 6 parts by weight are used. If the amount of the component (C) is less than the above range, the effects of the present invention will not be sufficiently exhibited, and if it is more than the above range, the mechanical strength will be impaired.

Next, the resin composition of the present invention further comprises
(D) an organopolysiloxane-based polymer having a Si—H bond in the molecule. Alkyl as an organic group,
Particularly preferred is methyl, but it may be lower alkyl such as ethyl or propyl, or may contain two or more alkyls.

Examples of such a compound include an alkyl hydrogen siloxane homopolymer, a siloxane copolymer mainly containing a dialkyl siloxane unit and an alkyl hydrogen siloxane unit, and preferably one of the dimethyl siloxy units of polydimethyl siloxane. Examples thereof include those obtained by partially or entirely substituting a methylhydrogensiloxane unit. Such a compound is commercially available, for example, from Toshiba Silicone Co., Ltd. under the trademark TSF484.

The above component (D) is used in an amount of 0.005 to 50 parts by weight based on 100 parts by weight of the component (C). Preferably, 0.01 to 20 parts by weight, more preferably, 0.1 to 20 parts by weight.
05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.2 to 1 part by weight.

If the amount of component (C) is less than the above range, the effect of the present invention will not be sufficiently exhibited. If the amount is more than the above range, the cost will only increase, and even if the added amount is increased, the effect associated therewith will be further increased. Can't expect.

The surface of the component (C) titanium oxide is coated on the surface of the component (D) with an organopolysiloxane-based polymer having a Si—H bond (for example, TSF484 (trademark)).
And the like, which is previously processed by Toshiba Silicon Co., Ltd.). Such titanium oxides are usually commercially available, for example, RL91 ™ Rh
A preferred example is one manufactured by One Polanc.

Various resins such as polyphenylene sulfide resin, polycarbonate resin, polyetherimide resin, styrene resin, styrene-acrylonitrile copolymer, PM
MA or the like can be used.

Further, rubber-like substances such as ABS, MB
S, SBS, SEBS, acrylic rubber, silicon rubber,
Acrylic-silicone rubber (S2001 (trade name), manufactured by Mitsubishi Rayon Co., Ltd.) and other additives may be added.

As an additive, for example, as a stabilizer, BHT (trademark: manufactured by Takeda Pharmaceutical Co., Ltd.), Ionox100 (trademark: manufactured by Shell Chemical Company), Age Rite Superlite (trademark: Vander bilt)
Santonox R (trademark: Monsanto), Antioxida
nt ZKF (trademark: manufactured by Bayer), Irganox 1076 (trademark: manufactured by Ciba-Geigy), HYoechst VPOSPI (trademark: manufactured by Hoechst), Irganox 1010 (trademark: manufactured by Ciba-Geigy), hindered phenols, Cyasorb UV-5411 (trademark: ACC
Cyasorb UV-531 (trademark: ACC), Tinuvin326
(Trademark: Ciba-Geigy), Tinuvin 320 (Trademark: Ciba-Geigy), Tinuvin 234 (Trademark: Ciba-Geigy), Tinuvin 120 (Trademark: Ciba-Geigy), U
Examples include benzotriazole-based ultraviolet absorbers such as vinul D49 (trade name: GAF) and other epoxy-based, thiol-based, and metal salt-based stabilizers.

As the flame retardant, a halogen type, for example, a brominated polycarbonate and a brominated polycarbonate oligomer, a brominated epoxy and the like can be used.

Examples of the phosphorus-based flame retardant, specific examples of the phosphoric ester-based compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl phosphate. Zirphenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl)
-2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate, R
1, to R4 are alkoxy, such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy,
Examples thereof include polyphosphates such as bisphenol A bisphosphate, which is phenoxy and methyl (substituted) phenoxy, hydroquinone bisphosphate, resorcinol bisphosphate, and trioxybenzene triphosphate, and preferably triphenyl phosphate and various polyphosphates.

As the anti-drip agent, polytetrafluoroethylene (Teflon) or the like can be used. In addition, a silicon-based compound can be used for the purpose of further improving flame retardancy.

Other colorants such as pigments and dyes, release agents such as silicone oil, low molecular weight polyolefins and alkyl esters such as pentaerythritol tetrastearate and glycerin monostearate, glass fibers and carbon fibers, milled glass, glass Inorganic fillers such as beads, glass flakes, talc, clay, silica, mica, wollastonite, potassium titanate whiskers, acicular titanium oxide, calcium carbonate, barium sulfate, plasticizers such as polycaprolactone, polycarbonate oligomers, and sulfone Antistatic agents such as salt compounds of acids and alkali metals or alkyl phosphoniums, polyalkylene glycols such as polyethylene oxide and polypropylene oxide, crosslinked polyesters, crosslinked polyamides, crosslinked polymethylmethacrylates Organic particulate compounds such as and infrared absorber was granulated and the like, antibacterial agents, may be added to the crystal nucleating agent.

The method for producing the resin composition of the present invention is not particularly limited, and a usual method can be used. Generally, a melt mixing method is desirable. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Component A: A-1: Polybutylene terephthalate: Barox 315 (trade name) manufactured by GE Plastics Co., Ltd. A-2: Polyethylene terephthalate: Mitui PET J025 (trademark), Mitsui Petrochemical Industries, Ltd. Made

Component B: B-1: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite: ADK STAB PEP-36 (trademark), manufactured by Asahi Denka Kogyo KK

Component C: C-1: Titanium oxide: Taipaque R680 (trademark), manufactured by Ishihara Sangyo Co., Ltd. C-2: Titanium oxide: Titone R-27 (trademark), C-3, manufactured by Sakai Chemical Industry Co., Ltd. : Titanium oxide: RL91 (trade name, manufactured by Rhone Polanc Co.) Here, RL91 of C-3 is a component (C) which is an organopolysiloxane having a Si—H bond in the molecule of the component (D). It has been pre-treated with a polymer (polymethylhydrogensiloxane).

Component D: D-1: polymethyl hydrogen siloxane: TSF484 (trademark), manufactured by Toshiba Silicone Co., Ltd.

Optional component: E-1: glass fiber: TP-CHOP VCE2 (trademark), manufactured by Nippon Electric Glass Co., Ltd. E-2: talc: LMS200 (trademark), average particle size 1.5 to 1.8. μm, manufactured by Fuji Talc Kogyo Co., Ltd. E-3: carbon black: Black # 8500 (trademark), manufactured by Tokai Carbon Co., Ltd.

Kneading : The sample was kneaded with a 60 mm single screw extruder. Kneading conditions Cylinder set temperature 260 ° C, screw rotation speed 150 rpm

Injection molding : A test plate was prepared from the dried sample using an injection molding machine. Molding condition Cylinder set temperature 260 ° C, mold temperature 80 ° C

Discoloration : Injection molded square plate (50 mm ×
After heat aging in an air oven at 200 ° C. for 300 hours using a 3 mm × 3 mm), the discoloration compared to before aging was measured using a Hitachi CA-35 spectrophotometer (light source: D65). did. The greater the value of Delta E, the greater the discoloration.

Presence or absence of crack : Square plate (5
0 mm x 3 mm x 3 mm) and 30
After heat aging in an air oven for 0 hour, the surface condition was carefully observed to check for cracks. The component ratios and evaluation results in the examples and comparative examples are as shown in Table 1.

[0046]

[Table 1]

[0047]

The resin molded product obtained by the resin composition according to the present invention has little thermal discoloration and can prevent the occurrence of minute cracks on the surface of the molded product even in the state of use at high temperatures. . Therefore, it is possible to obtain a molded product suitable for a socket of an incandescent lamp or a discharge lamp, an electric component having a built-in electric heater, or the like.

Claims (4)

[Claims] 1. A (B) phosphorus-based stabilizer compound (0.001) based on 100 parts by weight of a polyester-based resin.
To 2 parts by weight, 0.01 to 20 parts by weight of (C) titanium oxide, and 100 parts by weight of titanium oxide of component (C), (D) an organopolysiloxane having a Si—H bond in the molecule. A resin composition comprising 0.005 to 50 parts by weight of a polymer. 2. (B) phosphorus-based stabilizer compound 0.001 to 100 parts by weight of (A) polyester resin
2 parts by weight, (C) 0.01 to 20 parts by weight of titanium oxide, and 100 parts by weight of titanium oxide as the component (C), (D) an organopolysiloxane polymer having a Si—H bond in the molecule. A molded article obtained by molding a resin composition containing 0.005 to 50 parts by weight. 3. The molded article according to claim 2, wherein the component (C) is subjected to a surface treatment with the component (D) in advance. 4. The molded article according to claim 2, wherein the molded article is a light bulb (lamp) socket of a lighting fixture.