JP2003049055A - Polytrimethylene terephthalate resin composition with excellent heat resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polytrimethylene terephthalate having good moldability and capable of providing molded articles having slight deformation by warp, good appearance, high stiffness at high temperatures and resistance to heat aging, enabling their use at high temperatures. SOLUTION: This resin composition comprises (A) a polytrimethylene terephthalate and (B) a phosphite compound in an amount of 0.01-5 pts.wt. based on 100 pts.wt. component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polytrimethylene terephthalate resin composition suitably used for parts such as connectors in the electric and electronic fields, electrical parts such as connectors in the field of automobiles, and other useful parts materials. In particular, the present invention is a polytrimethylene terephthalate having good moldability, small warpage deformation of the molded product, good appearance of the molded product, high rigidity at high temperature, and additionally excellent heat aging resistance capable of being used at high temperature. It relates to a resin composition.

[0002]

2. Description of the Related Art Thermoplastic polyesters typified by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, chemical resistance and electrical properties, and are expected to be used in a wide range of fields such as automobile parts and electric / electronic parts. Has been done. With the diversification of the market, high performance, special performance according to application, and high quality are required.

For example, automobile parts for outdoor use, electricity,
In the case of electronic parts, there is a demand for a higher level of heat aging resistance, and there has been an urgent need to meet the demand. In this situation, polyethylene terephthalate and polybutylene terephthalate have been examined for their corresponding technologies, but they are not satisfactory. In the case of polyethylene terephthalate, there is a problem before imparting heat aging resistance, such as deformation of the molded product during mold release in normal molding such as injection molding, and the resulting molded product cannot realize the original mechanical properties. Can't answer.

On the other hand, in the case of polybutylene terephthalate,
JP-A-5-214220, JP-A-6-11737
Although the publication No. 1 etc. describes that the heat aging resistance is improved to some extent by the technology of imparting heat aging resistance, the warped deformation of the molded product is large and the appearance of the molded product is poor,
Moreover, the rigidity at high temperature is not sufficient, and it is not possible to satisfy the market demand. Further, although these prior arts have a description suggesting polytrimethylene terephthalate, they are merely general descriptions and do not disclose any specific and technical disclosure. There are no examples.

[0005]

SUMMARY OF THE INVENTION Mechanical properties, chemical resistance,
In addition to the electrical characteristics, the moldability is good, the warp deformation of the molded product is small, the appearance of the molded product is good, the rigidity at high temperature is high, and in addition, it has excellent heat aging resistance that can be used at high temperature It is an object of the present invention to provide a molding material that is sufficiently satisfactory.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present inventors, as a result of repeated studies for solving the problem, a polyester comprising trimethylene terephthalate as a main repeating unit, and a composition comprising a phosphite compound, polyethylene terephthalate and polybutylene terephthalate, respectively. And that the phosphite compound has a different action effect. Furthermore, they have found that the blending amount of the phosphite compound to be blended with the polyester resin containing trimethylene terephthalate as the main repeating unit requires a specific range.

That is, the present invention is as follows. A resin composition comprising polytrimethylene terephthalate and a phosphite compound, wherein the phosphite compound (B) is 0.01 to 5 parts by weight with respect to 100 parts by weight of (A) polytrimethylene terephthalate. 1. A characteristic resin composition, The component (A), polytrimethylene terephthalate, has a number average molecular weight of 5,000 to 100,000,
The resin according to the above item 1, which is polytrimethylene terephthalate having a molecular weight distribution (Mw / Mn) of 1.2 to 4.5 and containing 1 to 20% of molecules having a molecular weight of 100,000 or more. Composition,

3. The phosphite compound as the component (B) is tris (2,4-di-t-butylphenyl) phosphite or tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphos. A resin composition as described in 1 or 2 above, which is a fight,
And 4. As the component (C), a crystal nucleating agent is further added in an amount of 0.0 to 100 parts by weight of polytrimethylene terephthalate.
The resin composition according to any one of 1 to 3 above, which is blended in an amount of 01 to 5 parts by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. First, polytrimethylene terephthalate as the component (A) of the composition of the present invention will be described. In the present invention, polytrimethylene terephthalate (hereinafter referred to as "P
It may be abbreviated as "TT". ) Represents a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component. In the present invention, as trimethylene glycol, 1,3
-Propanediol, 1,2-propanediol, 1,
It is selected from 1-propanediol, 2,2-propanediol, or a mixture thereof, but 1,3-propanediol is particularly preferable from the viewpoint of stability.

Besides, aromatic dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyl ether, are used as acid components within a range that does not impair the object of the present invention. Dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylketone dicarboxylic acid, diphenylsulfonedicarboxylic acid, etc .; aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid; alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; Using oxydicarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid, ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene as the glycol component. Recall, octamethylene glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, may be copolymerized with such a part hydroquinone.

The amount of the copolymerization in the case of copolymerization is not particularly limited as long as the object of the present invention is not impaired, but is usually 20 mol% or less of the acid component or 2 of the glycol component.
It is preferably 0 mol% or less. Further, PTT may be a combination of two or more of these copolymerization components. Further, a branched component in the above polyester component, for example, tricarballylic acid, trimesic acid, trimellitic acid and the like, an acid having a trifunctional or tetrafunctional ester forming ability,
Alternatively, a trifunctional or tetrafunctional ester-forming alcohol such as glycerin, trimethylolpropane, or pentaerythritol may be copolymerized, in which case they are 1.0 mol% or less of the total dicarboxylic acid component, It is preferably 0.5 mol% or less, and more preferably 0.3 mol% or less.

The PTT of the present invention preferably has a number average molecular weight of 5,000 to 100,000,
It is more preferably 7,000 to 100,000, Mw / Mn showing a molecular weight distribution is preferably 1.2 to 4.5, and more preferably 1.5 to 4.5. Furthermore, it is preferable that 1 to 20% of molecules having a molecular weight of 100,000 or more are contained. If the number average molecular weight is less than 5,000, the mechanical strength may decrease, and if it exceeds 100,000, the fluidity may become a problem. If Mw / Mn deviates from the range of 1.2 to 4.5, the balance between moldability and mechanical properties may deteriorate. Especially important is molecular weight 100,000
If the content of the molecules is 0 or more, and if it is less than 1%, there is a concern that the mechanical strength may be reduced particularly under high temperature and high humidity. When it is 20% or more, the moldability is lowered and the molding time may be prolonged.

The method for producing PTT used in the present invention is as follows:
Although not particularly limited, for example, JP-A-51-
140992, JP-A-5-262862,
According to the method described in JP-A-8-311177, terephthalic acid or its ester-forming derivative (for example, lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or its ester-forming derivative, In the presence of a catalyst, the mixture is heated and reacted at a suitable temperature and for a time, and the glycol ester of terephthalic acid obtained is further reacted in the presence of a catalyst at a suitable temperature and
A method of conducting a polycondensation reaction to a desired degree of polymerization in time can be mentioned.

The number average molecular weight and the molecular weight distribution can be measured by, for example, the osmotic pressure method, the terminal quantification method or the GPC method (gel permeation chromatography). For example, Tohso Corp. HLC-8120, Showa Denko KK HFIP804-803 (two 30 cm columns) as a column, hexafluoroisopropanol (hereinafter referred to as “HFIP”) as a carrier, and Polymer Laboratory Co., Ltd. as a standard sample. Using PMMA made, temperature 4
It can be carried out at 0 ° C. and a flow rate of 0.5 ml / min.

The phosphite compound as the component (B) of the composition of the present invention is not particularly limited, but examples thereof include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, and tris isoform. Decylphosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2 , 4-Di-t-butylphenyl) phosphite, tris (2,4-di-t)
-Butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, tetratridecyl-
4,4'-butylidene bis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene-diphenolalkylphosphite (however,
Alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) 1,1. , 3-Tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl)-
4,4'-butylidene bis (3-methyl-6-t-butylphenol) diphosphite, tetra (C1-C15)
Mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tris (mono, di mixed nonylphenyl) phosphite, 4,4'-isopropylidene bis (2-t-butylphenol) .di (nonylphenyl)
Phosphite, 9,10-di-hydro-9-oxa-9
-Oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol poly Phosphite, bis (octylphenyl) -bis (4,4'butylidene bis (3
-Methyl-6-t-butylphenol))-1,6-hexaneol diphosphite, hexatridecyl-
1,1,3-tris (2-methyl-4-hydroxy-5)
-T-butylphenol) diphosphite, tris (4,4 'isopropylidene bis (2-t-butylphenol)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2,2-methylenebis (4,6- Di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,
6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-
Methylphenyl) -4,4′-biphenylene diphosphite, and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite,
Alternatively, mention may be made of a mixture thereof. Of these, tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphite are particularly preferable.

Further, a preferable phosphite compound is a pentaerythritol type phosphite compound. Specific examples of the pentaerythritol-type phosphite compound include 2,6-di-t-butyl-4-methylphenylphenyl pentaerythritol diphosphite and 2,6-di-t-butyl-4-. Methylphenyl
Methyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl-2-ethylhexyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl-isodecyl-
Pentaerythritol diphosphite, 2,6-di-t
-Butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-
4-Methylphenyl isotridecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-
Methylphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenylbenzyl・ Pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl butyl carbitol pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyloctylphenyl pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-
t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6 -Di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-
Di-t-butyl-4-methylphenyl.2,4-di-t
-Octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl.
2-Cyclohexylphenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol diphosphite, bis (2,6-di-t-amyl-4- Examples thereof include methylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite.

Among them, bis (2,6-di-t-butyl-
4-Methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl ) Pentaerythritol diphosphite, bis (2,6-di-
Examples thereof include t-octyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is particularly preferable.

In the present invention, 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, most preferably 0, of the phosphite compound is used with respect to 100 parts by weight of the polyester containing trimethylene terephthalate as a main repeating unit. 0.05 to 1 part by weight is compounded. If the blending amount of the phosphite compound is less than 0.01 parts by weight, the effect of the present invention cannot be sufficiently exerted, and if it exceeds 5 parts by weight, the excellent mechanical properties originally possessed by polytrimethylene terephthalate are impaired. Therefore, it is not preferable.

The composition of the present invention has the object of the present invention.
Combine various additives that are normally used within the range that does not damage
You can As the type of additive, phosphite
Antioxidants other than compounds, UV absorbers, crystal nucleating agents, compounds
Shape modifiers and release agents, plasticizers, colorants, etc.
Be done. A crystal nucleating agent as the component (C) of the composition of the present invention is used.
When blended with these, a composition more consistent with the object of the present invention can be obtained.
can get. As crystal nucleating agent (C), organic or inorganic substances
They can also be used. As the inorganic substance, Zn powder,
Simple substance such as Al powder, graphite, carbon black
, ZnO, MgO, Al₂O₃ , TiO₂, MnO₂, SiO₂, Fe ₃O_FourNa
Which metal oxide, aluminum nitride, silicon nitride, titanium nitride,
Boron nitride and other nitrides, Na₂CO₃, CaCO₃ , Mg
CO₃ , CaSO_Four , CaSiO₃, BaSO_Four , Ca₃(PO_Four) ₃ Such as inorganic
Clays such as salt, talc, kaolin, clay, clay etc.
They can be used alone or in combination of two or more. Also
As the equipment, calcium oxalate, sodium oxalate
, Calcium benzoate, calcium phthalate, tartaric acid
Calcium, magnesium stearate, polyacrylic
Organic salts such as acid salts, polyester, polyethylene, polyethylene
Polymers such as polypropylene and cross-linked polymers can be used individually or
Can be used as a mixture of two or more. Especially preferred
Boron Night Ride, Talc, Kaori
Clays such as clay, clay, and clay. These crystal nucleating agents
Regarding the amount of (C) added, with respect to 100 parts by weight of PTT,
0.001 to 5 parts by weight, but 0.01 to 3 parts by weight
The added amount is particularly preferable in terms of mechanical properties.

By further adding a moldability improver to the composition of the present invention, a resin composition more suitable for the purpose of the present invention can be obtained. Moldability improvers include phosphoric acid esters, phosphite esters, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amide compounds, polyalkylene glycol or terminal modified products thereof, low molecular weight Examples thereof include polyethylene or low-molecular-weight polyethylene oxides, substituted benzylidene sorbitols, polysiloxanes, and caprolactones. Particularly preferred are (a) higher fatty acids, (b) higher fatty acid metal salts, and (c) higher fatty acid esters. It is a kind. These moldability improvers will be described in detail below.

(A) Higher fatty acids As the higher fatty acids, higher saturated fatty acids, higher unsaturated fatty acids or mixtures thereof are preferably used. (A-1) Higher saturated fatty acids Higher saturated fatty acids include, for example, capric acid, uradecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, Examples thereof include behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid, and the like, or a mixture thereof.

(A-2) Higher Unsaturated Fatty Acids As the higher unsaturated fatty acids, unsaturated fatty acids having 6 to 22 carbon atoms are preferably used. Among them, more preferable ones are, for example, undecylenic acid and oleic acid. , Elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid, gadoleic acid, gadoelaidic acid, 11-eicosenoic acid and the like, or a mixture thereof can be mentioned.

(B) Higher fatty acid metal salts As the higher fatty acid metal salts, higher saturated fatty acid metal salts, higher unsaturated fatty acid metal salts or mixtures thereof are preferably used. (B-1) Higher saturated fatty acid metal salt The higher saturated fatty acid fatty acid is represented by the following general formula. _{CH 3 (CH 2) n COO} (M) where a n = 8 to 30, the metal element (M) is, 1A of the Periodic Table of the Elements, 2A, 3A group elements, zinc, and aluminum are preferably used . Among them, more preferred are, for example, capric acid, uradecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid,
Palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laccelic acid lithium salt, sodium salt, magnesium salt, calcium salt, zinc salt , Aluminum salts, etc., or a mixture thereof.

(B-2) Higher unsaturated fatty acid metal salt The higher unsaturated fatty acid metal salt has 6 to 22 carbon atoms.
Unsaturated fatty acids and metal salts of 1A, 2A and 3A elements of the periodic table of elements, zinc, aluminum and the like are preferably used, and among them, undecylenic acid, oleic acid, elaidic acid, cetrain are more preferable. Acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid, gadoleic acid, gadoelaidic acid, 11-eicosenoic acid Examples thereof include lithium salt, sodium salt, magnesium salt, calcium salt, zinc salt, aluminum salt, and the like, or a mixture thereof.

(C) Higher fatty acid ester As the higher fatty acid ester in the present invention, an ester of a higher alcohol and a higher fatty acid, an ester of a polyhydric alcohol and a higher fatty acid, or a mixture thereof is preferably used.

(C-1) Esters of higher alcohols and higher fatty acids As esters of higher alcohols and higher fatty acids, preferred are aliphatic alcohols having 8 or more carbon atoms and higher fatty acids having 8 or more carbon atoms. Esters. Preferred higher fatty acid esters include, for example, lauryl laurate, lauryl myristate, lauryl palmitate, lauryl stearate, lauryl behenate, lauryl lignocerate, lauryl melicate, myristyl laurate, myristyl myristate, myristyl stearate. , Myristyl behenate, myristyl lignocerate, myristyl melissate, palmityl laurate, palmityl myristate, palmityl stearate, palmityl behenate, palmityl lignocerate, palmityl melicate, stearyl laurate , Stearyl myristate, stearyl palmitate, stearyl stearate, stearyl behenate, stearyl arachinate, stearyl lignocerate, stearyl melissate, eye Shiruraureto, Aiko sill palmitate,
Aicosyl stearate, aicosyl behenate, aicosyl lignocerate, aicosyl melissate, behenyl laurate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl behenate,
Behenyl arachinate, behenyl melissate, tetracosanyl laurate, tetracosa palmitate, tetracosanyl stearate, tetracosanyl behenate, tetracosanyl lignocerate, tetracosanyl serrate, cerotinyl stearate. , Cerotinyl behenate,
Mention may be made of cerotinyl serotinate, melisyl laurate, melisyl stearate, melisyl behenate, melisyl merisate and the like, or mixtures thereof.

(C-2) Esters of Polyhydric Alcohol and Higher Fatty Acids Partial esters of polyhydric alcohols and higher fatty acids include polyhydric alcohols such as glycerin, 1,2,3-butanetriol and 1,2. , 3-pentanetriol, erythritol, pentaerythritol, trimethylolpropane, mannitol, sorbitol and the like are preferably used, and higher fatty acids include, for example, capric acid, uradecyl acid, lauric acid, tridecyl acid, myristic acid,
Pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid and the like are preferably used.

The esters of these polyhydric alcohols and higher fatty acids may be monoesters, diesters or triesters. More preferred are higher fatty acid monoglycerides such as glycerin monolaurate, glycerin monomyristate, glycerin monostearate, glycerin monobehenate, glycerin monolignocellate, glycerin monomerisate, pentaerythritol-mono or di-. Laurate, pentaerythritol-mono or di-
Laurate, pentaerythritol-mono or di-myristate, pentaerythritol-mono or di-palmitate, pentaerythritol-mono or di-stearate, pentaerythritol-mono or di-behenate, pentaerythritol-mono or di- Mono- or di-higher fatty acid esters of pentaerythritol, such as lignocerate, pentaerythritol-mono or di-merisate, trimethylolpropane-mono- or di-laurate, trimethylolpropane-mono-
Or di-myristate, trimethylolpropane-mono- or di-palmitate, trimethylolpropane-mono- or di-stearate, trimethylolpropane-mono- or di-behenate, trimethylolpropane-mono- or di-lignocerate , Trimethylolpropane-mono- or di-merisate, such as trimethylolpropane mono- or di-higher fatty acid esters, sorbitan-mono, di- or tri-laurate,
Sorbitan-mono, di- or tri-myristate, sorbitan-mono, di- or tri-stearate, sorbitan-mono, di- or tri-behenate, sorbitan-mono, di- or tri-lignocerate, sorbitan-mono, di- or tri- Sorbitan such as melissate-mono-, di- or tri-higher fatty acid ester, mannitan-
Mono, di or tri-laurate, mannitan-mono,
Di- or tri-myristate, mannitan-mono, di- or tri-palmitate, mannitan-mono, di- or tri-stearate, mannitan-mono, di- or tri-behenate, mannitan-mono, di- or tri-lignocerate, mannitan- Mentione-mono-, di- or tri-higher fatty acid esters such as mono-, di- or tri-mericerate, etc., or mixtures thereof may be mentioned.

The compounding amount of these (a) higher fatty acids, (b) higher fatty acid metal salts, and (c) higher fatty acid esters is 0.001 with respect to 100 parts by weight of PTT in the PTT resin composition of the present invention. It is preferably from 5 to 5 parts by weight, more preferably from 0.01 to 3 parts by weight. When the compounding amount of the moldability improver is less than 0.001 part by weight, the moldability is not improved until the object of the present invention is achieved, and when it exceeds 5 parts by weight. However, it is not preferable because it tends to generate silver on the surface of the molded product and deteriorates the mechanical properties of the molded product.

Further, in the composition of the present invention, various fillers which are usually used can be used within the range not impairing the object of the present invention. Examples of the type of filler include inorganic fillers such as glass fiber and carbon fiber. Further, in the composition of the present invention, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polystyrene resin (rubber reinforced polystyrene, acrylonitrile-butadiene-styrene resin, etc.) is added to the composition of the present invention within the range not impairing the object of the present invention. 1) or 2 or more types of the thermoplastic resin of 1) may be mixed.

The method for producing the composition of the present invention is not particularly limited, and the polyester and the phosphite compound having trimethylene terephthalate as the main repeating unit are melt-mixed by a uniaxial or biaxial extruder, a roll or a Banbury mixer. Method, melt mixing polyester and phosphite compound having trimethylene terephthalate as the main repeating unit to prepare a masterbatch, and then mixing with polyester having trimethylene terephthalate as the main repeating unit so that the phosphite compound has a predetermined amount How to do, etc. are used.

The masterbatch method is more effective in the composition of the present invention. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The properties described in Examples and Comparative Examples were evaluated by the following methods.

(Evaluation method) (1) Tensile strength (MPa): PS40 manufactured by Nissei Plastic Co., Ltd.
Using an E injection molding machine, a molded product was obtained under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 95 ° C., and the measurement was performed according to ASTM-D638. (2) Heat aging resistance: A test piece conforming to ASTM-D638 was subjected to a heat aging treatment in an oven at 180 ° C. for 10 days, and the change in color tone of the test piece was visually determined. Color tone judgment: ◎: pale yellowish white, ○: pale yellowish white, ×
Mark; yellowish white

(3) Warp Deformability: Deflection (mm) A flat plate injection-molded using a mold having a thickness of 3 mm and a side of 130 mm was placed on a horizontal plane, and the maximum gap distance from the horizontal plane was measured. (4) Appearance of molded body: Handy gloss meter IG32 manufactured by Horiba
0 was used to measure Gs 60 ° C. according to JIS-K7150. When the numerical value was 70 or more, it was evaluated as ◯, and when it was less than 70, it was evaluated as x.

Materials used in Examples and Comparative Examples are described below. (1) PTT: Polytrimethylene terephthalate Intrinsic viscosity [η] 1.01 × 10 ² cm ³ · g ⁻¹ Polytrimethylene terephthalate The intrinsic viscosity [η] was determined based on the following definition formula. [Η] = lim (1 / C) × (ηr−1) [C → 0] ηr in the defining formula is 35 ° C. of a dilute solution of polytrimethylene terephthalate dissolved in o-chlorophenol having a purity of 98% or more. Relative viscosity is defined as the value obtained by dividing the viscosity of the above-mentioned by the viscosity of the solvent itself measured at the same temperature. Further, C is a solute weight value in gram unit in 100 ml of the above solution. Number average molecular weight 9800, Mw / M
n = 2.5, occupancy ratio of 100,000 or more molecules is 5.8%
Met.

The molecular weight and molecular weight distribution of polytrimethylene terephthalate were measured by GPC (gel permeation chromatography). The measurement conditions are HLC-8120 manufactured by Tosoh Corporation and HFIP804-803 (30c, Showa Denko KK) as a column.
m column 2), HFIP was used as a carrier, the temperature was 40 ° C., and the flow rate was 0.5 ml / min. A calibration curve was created and measured using PMMA manufactured by Polymer Laboratory as a standard sample. The molecular weight of standard PMMA is 620, 1.
680, 3805, 7611, 13934, 2428
0, 62591, 186000 were used. PBT: Polybutylene terephthalate Polyplastics Co., Ltd. Duranex 2002 PET: Polyethylene terephthalate Polyethylene terephthalate with an intrinsic viscosity of 0.68

(2) Phosphite compound B-1: Irgaphos 168 manufactured by Ciba-Geigy <registered trademark> Tris (2,4-di-t-butylphenyl) phosphite B-2: Irgaphos P-EPQFF manufactured by Ciba-Geigy
<Registered trademark> Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite (3) Crystal nucleating agent Talc (Nihon Talc Co., Ltd. Microace K-1)

[0038]

[Examples 1 to 4] The ingredients shown in Table 1 were blended in the required amount in a tumbler type blender, melted and kneaded in an extruder set to a cylinder temperature of 260 ° C, and water-cooled as a strand. It cut with the cutter and obtained the pellet prepared below. The extruder has a screw diameter of 25
mm twin-screw extruder (ZSK-25 manufactured by Warner & Frydler Co., Ltd.). The composition pellet thus obtained was molded by an injection molding machine (N-70BII manufactured by Nippon Steel Co., Ltd.) to prepare a molded product. The evaluation was carried out according to the above-mentioned method with respect to tensile strength, heat aging resistance, warp deformability of the molded product, and appearance of the molded product. The results are shown in Table 1.

[0039]

Comparative Examples 1 to 4 Extrusion, granulation, preparation of pellets, and molding were carried out in the same manner as in Example 1 with the formulations shown in Table 1. The results are shown in Table 1. In Comparative Example 4 in which PET: polyethylene terephthalate was used, there was a problem in moldability such as mold release failure at the injection molding stage, and it was not possible to evaluate the physical properties.

[0040]

[Table 1]

[0041]

The polytrimethylene terephthalate resin composition containing the phosphite compound of the present invention has good moldability, small warp deformation of the molded product, good appearance of the molded product, high rigidity at high temperature, and It has excellent heat aging resistance that can be used at high temperatures.

Claims (4)

[Claims] 1. A resin composition comprising polytrimethylene terephthalate and a phosphite compound, which comprises (A)
To 100 parts by weight of polytrimethylene terephthalate,
(B) Phosphite compound is 0.01-5 weight part, The resin composition characterized by the above-mentioned. 2. The component (A), polytrimethylene terephthalate, has a number average molecular weight of 5,000 to 100,0.
00, molecular weight distribution (Mw / Mn) is 1.2 to 4.5, and 1 to 20% of molecules having a molecular weight of 100,000 or more.
The resin composition according to claim 1, wherein the resin composition is polytrimethylene terephthalate. 3. The phosphite compound as the component (B) is tris (2,4-di-t-butylphenyl) phosphite or tetrakis (2,4-di-t-butylphenyl) -4,4. The resin composition according to claim 1 or 2, wherein the resin composition is'-biphenylenediphosphite. 4. As the component (C), a crystal nucleating agent is further added to 100 parts by weight of polytrimethylene terephthalate in an amount of 0.
001 to 5 parts by weight are blended.
The resin composition according to any one of 3 above.