JP3430609B2 - Polyester resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester resin composition. More specifically, the present invention relates to a polyester resin composition containing an amide compound as a nucleating agent for increasing the crystallization rate and improving the moldability.

[0002]

2. Description of the Related Art Thermoplastic polyester resins are heat resistant,
Since it has excellent physical and mechanical properties including light resistance and chemical resistance, it is widely used as fibers, films and molded products.

However, some polyesters typified by polyethylene terephthalate are generally inferior in moldability, leaving problems for use as injection molded products and extrusion molded products. The reason is that the crystallization speed of these polyesters is slow, and it cannot be sufficiently crystallized at a low mold temperature of about 60 to 100 ° C., which is used for usual thermoplastic resin injection molding. As a result, it has been the current situation that a good molded product cannot be obtained.

In order to solve these drawbacks, it has been attempted to raise the mold temperature and lengthen the holding time (Japanese Patent Publication No. 45-18788), but this method lengthens the molding cycle and the molding cost. Is not practical because it increases.

On the other hand, there has been proposed a method of adding a nucleating agent in order to make the crystal nucleation of the crystalline polymer uniform and increase the crystallization rate. Examples of the nucleating agent include inorganic substances such as talc, clay, mica, kaolin (Japanese Patent Publication No.
-7542), organic carboxylic acid metal salt (Japanese Patent Publication No. 48-
No. 4097) and the like. However, these compounds have problems such as an insufficient effect of improving the crystallization rate and deterioration of the physical properties of the polyester itself, so that satisfactory moldability cannot be obtained.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems of the nucleating agent, to propose a novel and useful polyester resin composition having a high crystallization rate and excellent moldability. .

[0007]

In view of the present situation, the present inventors have conducted diligent studies to solve the above problems, and as a result, blended an amide compound having a specific structure with a polyester resin. It was found that the desired effect was obtained by the above, and the present invention was completed based on such knowledge.

That is, the polyester resin composition according to the present invention comprises a polyester resin, a polycarboxylic acid amide compound represented by the general formula (1) and a polycarboxylic acid amide compound represented by the general formula (2).
It is characterized by containing one or more amide compounds selected from the group consisting of polyamino acid amide compounds .

R ^1- (CONH-R ² ) k (1) [wherein R ¹ represents a saturated or unsaturated aliphatic, alicyclic or aromatic polycarboxylic acid residue having 1 to 25 carbon atoms] Represent
R ² is an alkyl group or alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, Or Represents a group represented by. ^{R 3, R 5, R 6} , R 8 are the same or different, each represent an alkyl or alkenyl group or an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or a halogen atom. R
⁴ and R ⁷ are the same or different and each represents a linear or branched alkylene group having 1 to 4 carbon atoms. k represents an integer of 3 to 6. l and n each represent an integer of 1 to 5. m and o each represent an integer of 0 to 5. However, when k = 3, R ¹ is fat
Group polycarboxylic acid residue, R ² is an alkyl group,
Kenyl group, phenyl group, naphthyl group, anthryl group,

[Chemical 4] Or

[Chemical 5] And R ¹ is an aromatic polycarboxylic acid residue
And R ² is an alkyl group or an alkenyl group
except for. ]

[0010]

(R ¹⁰ —NHCO) q—R ⁹ — (NHCO—R ¹¹ ) r (2) [wherein, R ⁹ is a saturated or unsaturated aliphatic, alicyclic or aromatic group having 1 to 25 carbon atoms. Represents a family of polyamino acid residues. R
^{10 9} and R ¹¹ have the same meaning as R ^{2 in} formula (1), and may be the same or different. q and r show the integer of 1-5. However, 6 ≧ q + r ≧ 3. ]

Of the amide compounds represented by the above general formulas, one or more amide compounds having at least one alicyclic group are particularly effective. In the amide compound having two or more alicyclic groups, the type of each alicyclic group may be the same or different.

The polycarboxylic acid amide compound represented by the general formula (1) includes an aliphatic, alicyclic or aromatic polycarboxylic acid represented by the following general formula (1a) or an anhydride thereof and a general formula (1). It can be easily prepared by amidating one or more kinds of aliphatic, alicyclic or aromatic monoamines represented by 1b) according to a conventionally known method.

[0014]

[Chemical 15] [In the formula, R ¹ and k are as defined above. ]

[0015]

[Chemical 16] [In the formula, R ² has the same meaning as described above. ]

As the aliphatic polycarboxylic acid, methanetricarboxylic acid, tricarballylic acid, propenetricarboxylic acid, pentanetricarboxylic acid, ethanetetracarboxylic acid, propanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid [particularly 1 , 2, 3, 4
-Butanetetracarboxylic acid (hereinafter abbreviated as "BTC")], dodecanetetracarboxylic acid, pentanepentacarboxylic acid, tetradecanehexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethyleneglycolbis (β-aminoethylether) N, N, N ', N'-
Tetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamine-N, N ', N'-triacetic acid, 1,
3-diaminopropan-2-ol-N, N, N ', N'
-Tetraacetic acid, 1,2-diaminopropane-N, N, N ',
N'-tetraacetic acid, triethylenetetramine hexaacetic acid, nitrilotripropionic acid, 1,6-hexanediaminetetraacetic acid,
Examples include N- (2-carboxyethyl) iminodiacetic acid and the like.

Examples of the alicyclic polycarboxylic acid include cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, 5- (succinic acid) -3-methyl-3- Cyclohexene-1,2-dicarboxylic acid (hereinafter abbreviated as "SMSD"), bicyclo [2.2.2] oct-7-ene-
2,3,5,6-tetracarboxylic acid, cyclohexanehexacarboxylic acid, 5,6,9,10-tetracarboxytricyclo [6.2.2.0 ^2,7 ] dodeca-2,11-
Diene and its lower alkyl-substituted compounds (eg, 3-position, 8-position)
Position, 11- or 12-position methyl substitution product), 1,2-cyclohexanediaminetetraacetic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid, 3,5,6-tricarboxynorbornene-2-acetic acid, thiobis (norbornene-2,3-dicarboxylic acid), bicyclo [4.2.0] octane-3,4,7,8-tetracarboxylic acid, 1,1 '
-Bicyclopropane-2,2 ', 3,3'-tetracarboxylic acid, 1,2-bis (2,3-dimethyl-2,3-dicarboxycyclobutyl) ethane, pyrazine-2,3.
5,6-Tetracarboxylic acid, tricyclo [4.2.2.
0 ^{2, 5} ] decane-9-ene-3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid (hereinafter “TDA”)
Is abbreviated. ) And its lower alkyl substitutions (eg,
1-position, 5-position, 6-position or 7-position methyl substitution product), 2, 3,
Examples include 4,5,6,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid.

Examples of the aromatic polycarboxylic acid include benzenetricarboxylic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylmethanetetracarboxylic acid and perylenetetracarboxylic acid. Acid, naphthalenetetracarboxylic acid, 4,4'-dinaphthalic acid, benzidine-3,3'-dicarboxyl-N, N'-tetraacetic acid, diphenylpropanetetracarboxylic acid, anthracenetetracarboxylic acid, phthalocyaninetetracarboxylic acid, ethylene Examples include glycol-trimellitic acid diester, benzenehexacarboxylic acid, and glycerin-trimellitic acid triester.

As the aliphatic monoamine, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-amylamine, te
rt-amylamine, hexylamine, heptylamine,
n-octylamine, 2-ethylhexylamine, tert
Examples include octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, pentadecylamine, octadecylamine, octadecenylamine and allylamine.

Examples of the alicyclic monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, etc., and the compounds represented by the general formula (4) or the general formula (5). The compounds represented are exemplified.

[0021]

[Chemical 17] [In the formula, R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an alkoxyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or a halogen atom. s is 1
Indicates an integer of 5. ]

[0022]

[Chemical 18] [In the formula, R ¹⁵ represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹⁶ has the same meaning as R ¹⁴ in formula (4). t shows the integer of 0-5. ]

Examples of the alicyclic monoamine represented by the general formula (4) include methylcyclohexylamine, ethylcyclohexylamine, propylcyclohexylamine, isopropylcyclohexylamine, tert-butylcyclohexylamine, n-butylcyclohexylamine and isobutylcyclohexylamine. , Sec-butylcyclohexylamine, n-amylcyclohexylamine, isoamylcyclohexylamine, sec-amylcyclohexylamine, tert-amylcyclohexylamine, hexylcyclohexylamine, heptylcyclohexylamine, octylcyclohexylamine, nonylcyclohexylamine, decylcyclohexylamine, un Decylcyclohexylamine, dodecylcyclohexylamine, cyclohexylcyclo Hexylamine, phenylcyclohexylamine,

Dimethylcyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, di-n-butylcyclohexylamine, di-sec-butylcyclohexylamine, di-tert-butylcyclohexylamine, di-n-amylcyclohexyl. Amine, di-tert-
Amylcyclohexylamine, dihexylcyclohexylamine,

Trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, triisopropylcyclohexylamine, tri-n-butylcyclohexylamine, tri-sec-butylcyclohexylamine, tri-tert-butylcyclohexylamine,

Methoxycyclohexylamine, ethoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxycyclohexylamine, di-sec-butoxycyclohexylamine, di-tert-butoxycyclohexylamine, trimethoxycyclohexylamine, trimethoxycyclohexylamine -N-butoxycyclohexylamine,

Examples include chlorocyclohexylamine, dichlorocyclohexylamine, methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine, tribromocyclohexylamine and the like.

Examples of the alicyclic monoamine represented by the general formula (5) include cyclohexylmethylamine, methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine and dimethoxycyclohexyl. Methylamine, chlorocyclohexylmethylamine, dichlorocyclohexylmethylamine,

Α-cyclohexylethylamine, β-cyclohexylethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine,
Chlorocyclohexylethylamine, dichlorocyclohexylethylamine,

Α-cyclohexylpropylamine, β-
Examples thereof include cyclohexylpropylamine, γ-cyclohexylpropylamine and methylcyclohexylpropylamine.

As the aromatic monoamine, aniline, 1
In addition to naphthylamine, 2-naphthylamine, 1-aminoanthracene and 2-aminoanthracene, compounds represented by the general formula (6) or the general formula (7) are exemplified.

[0032]

[Chemical 19] [In the formula, R ¹⁷ has the same meaning as R ¹⁴ in formula (4). u shows the integer of 1-5. ]

[0033]

[Chemical 20] [In formula, R < ¹⁸ > is synonymous with R < ¹⁵ > in General formula (5). R ¹⁹ has the same meaning as R ¹⁴ in formula (4). v
Represents an integer of 0 to 5. ]

The aromatic monoamine represented by the general formula (6) includes toluidine, ethylaniline, propylaniline, cumidine, tert-butylaniline, n-butylaniline, isobutylaniline, sec-butylaniline,
n-amylaniline, isoamylaniline, sec-amylaniline, tert-amylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, cyclohexylaniline, aminodiphenyl, aminostyrene,

Dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-
Butylaniline, di-sec-butylaniline, di-tert
-Butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline,
Examples include tri-n-butoxyaniline, chloroaniline, dichloroaniline, trichloroaniline, bromoaniline, dibromoaniline, tribromoaniline.

The aromatic monoamine represented by the general formula (7) includes benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, chlorobenzylamine, dichloro. Benzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine,
Dimethoxyphenylethylamine, chlorophenylethylamine, dichlorophenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-
Examples include phenylpropylamine and methylphenylpropylamine.

Among the polycarboxylic acid amide compounds represented by the general formula (1), BTC tetracyclohexylamide, BTC tetra (2-methylcyclohexylamide), TDA tetracyclohexylamide, TDA tetra (2-methylanilide) are particularly preferable. , SMSD tetracyclohexyl amide, trimesic acid trianilide, trimesic acid tri (2-methylanilide) and the like are recommended.

A polyamino acid-based compound represented by the general formula (2)
The amide compound is an aliphatic compound represented by the following general formula (2a),
Alicyclic or aromatic polyamino acid and general formula (2b)
Represented by one or more kinds of aliphatic, alicyclic or aromatic monoamines represented by and a general formula (2c)
One or more aliphatic, alicyclic or aromatic compounds
It can be easily prepared by amidation with a nocarboxylic acid according to a conventionally known method.

[0039] ^{_{(HOOC) q-R 9 -}} (NH 2) r (2a) [ wherein, ^R 9, q, r and q + r are as defined above. ]

R ¹⁰ —NH ₂ (2b) R ¹¹ —COOH (2c) [In the formula, R ¹⁰ and R ¹¹ have the same meanings as described above. ]

As the aliphatic polyamino acid, 2-amino is used.
Adipic acid, arginine, asparagine, asparagine
Acid, cystine, glutamic acid, glutamine, ortini
Creatine, S- (carboxymethyl) cystine,
Aminomalonic acid and the like are exemplified.

Examples of the alicyclic polyamino acid include 3,5-di
Aminocyclohexanecarboxylic acid, 1-amino-1,3
Examples thereof include cyclohexanedicarboxylic acid .

As the aromatic polyamino acid, 3,5-di
Aminobenzoic acid, 4,4'-diamino-3,3'-dica
Examples include ruboxydiphenylmethane .

A source of the amide compound represented by the general formula (2)
The monoamine which is a material is an amide represented by the general formula (1).
It is the same as the monoamine that is the raw material of the compound. The same
Among the monocarboxylic acids that are raw materials, the aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecyl acid. Examples thereof include acids, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, acrylic acid, crotonic acid, oleic acid, elaidic acid, sorbic acid, linoleic acid, linoleic acid and pivalic acid.

As the alicyclic monocarboxylic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, methylcyclopentanecarboxylic acid,
In addition to phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, methylcycloheptanecarboxylic acid, a compound represented by the general formula (8) or the general formula (9) Compounds are exemplified.

[0046]

[Chemical formula 23] [In the formula, R ²⁰ represents an alkyl group, an alkenyl group or an alkoxyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or a halogen atom. w represents an integer of 1 to 5. ]

[0047]

[Chemical formula 24] [In the formula, R ²¹ represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ²² has the same meaning as R ²⁰ in formula (8). x shows the integer of 0-5. ]

Examples of the alicyclic monocarboxylic acid represented by the general formula (8) include methylcyclohexanecarboxylic acid, ethylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, pentylcyclohexanecarboxylic acid and hexylcyclohexanecarboxylic acid. , Phenylcyclohexanecarboxylic acid, chlorocyclohexanecarboxylic acid, bromocyclohexanecarboxylic acid, dimethylcyclohexanecarboxylic acid, di-te
rt-Butylcyclohexanecarboxylic acid, methoxycyclohexanecarboxylic acid, ethoxycyclohexanecarboxylic acid, dimethoxycyclohexanecarboxylic acid, diethoxycyclohexanecarboxylic acid, dichlorocyclohexanecarboxylic acid, trimethylcyclohexanecarboxylic acid, trimethoxycyclohexanecarboxylic acid, triethoxycyclohexanecarboxylic acid, etc. Is exemplified.

Examples of the alicyclic monocarboxylic acid represented by the general formula (9) include cyclohexylacetic acid, methylcyclohexylacetic acid, methoxycyclohexylacetic acid, cyclohexylpropionic acid and cyclohexylbutyric acid.

Examples of the aromatic monocarboxylic acid include benzoic acid, 1-naphthoic acid, 2-naphthoic acid and 9-carboxyanthracene, as well as the general formula (10) or the general formula (1).
The compound represented by 1) is mentioned.

[0051]

[Chemical 25] [In the formula, R ²³ has the same meaning as R ²⁰ in formula (8). y shows the integer of 1-5. ]

[0052]

[Chemical formula 26] [In the formula, R ²⁴ has the same meaning as R ²¹ in formula (9). R ²⁵ has the same meaning as R ²⁰ in formula (8). z
Represents an integer of 0 to 5. ]

Examples of the aromatic monocarboxylic acid represented by the general formula (10) include methylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, p-tert-butylbenzoic acid, pentylbenzoic acid and hexylbenzoic acid. Acid, phenylbenzoic acid, cyclohexylbenzoic acid, chlorobenzoic acid, bromobenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, dimethylbenzoic acid, di-tert-butylbenzoic acid,
Dimethoxybenzoic acid, diethoxybenzoic acid, dichlorobenzoic acid, trimethylbenzoic acid, trimethoxybenzoic acid,
Examples are triethoxybenzoic acid and the like.

Examples of the aromatic monocarboxylic acid represented by the general formula (11) include phenylacetic acid, methylphenylacetic acid,
Examples include methoxyphenylacetic acid, phenylpropionic acid, phenylbutyric acid, and the like.

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

Among the polyamino acid amide compounds represented by the general formula (2) , N, N'-dicyclohexanecarbonyl-3,5-diaminobenzoic acid cyclohexylamide is particularly recommended.

The polyester resin used in the present invention is a polymer or copolymer mainly composed of dicarboxylic acid (or its ester-forming derivative) and diol and obtained by a polycondensation reaction, and has a predetermined effect. As long as
The structure is not particularly limited.

Examples of the dicarboxylic acid used herein include terephthalic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include diphenyl ether-4,4'-dicarboxylic acid. Especially, terephthalic acid is preferably used. These dicarboxylic acids may be used alone or in admixture of two or more.

Examples of the ester-forming derivative of dicarboxylic acid include the above-mentioned dimethyl ester of dicarboxylic acid.

Examples of the diol component include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol and the like and mixtures thereof.

Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate and the like.

The polyester resin used in the present invention has an intrinsic viscosity (o-chlorophenol solution, 25
C.) is preferably 0.3 dl / g or more.

The compounding amount of the amide compound according to the present invention is not particularly limited as long as a predetermined effect can be obtained, and can be appropriately selected. Usually, it is about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyester resin. , And more preferably 0.
It is about 1 to 5 parts by weight. When the amount is less than 0.001 part by weight, it is difficult to obtain a predetermined modifying effect, and when the amount is more than 10 parts by weight, the modifying effect commensurate with the compounding amount cannot be expected, which is not practical. Or uneconomical,
Either case is not preferable.

In the resin composition according to the present invention, various organic acid salts and inorganic compounds may be used in combination, if necessary.
It is preferable from the viewpoint of improving moldability.

Specific examples of the compounds used in combination are:
Examples thereof include sodium stearate, barium stearate, sodium salts and barium salts of partially saponified montanic acid esters, ionomers such as ethylene-sodium acrylate copolymer, sodium salts of phenols, sodium benzoate and talc.

Further, by using a conventionally known crystallization accelerator together with the resin composition of the present invention, the moldability can be further improved.

Specific examples of such a crystallization accelerator include:
Polyalkylene glycols such as polyethylene glycol and polypropylene glycol, carboxylic acid diesters thereof, α, ω-dialkyl etherified polypropylene glycols and other α, ω-dialkyl etherified polyalkylene glycols, and benzoic acid ester compounds such as neopentyl glycol dibenzoate. Examples thereof include epoxy compounds such as polyethylene glycol diglycidyl ether, and aliphatic polyesters such as polylactone and polyethylene adipate.

The resin composition according to the present invention may optionally contain other components such as pigments, dyes, heat-resistant agents, antioxidants,
Weathering agent, lubricant, antistatic agent, stabilizer, filler, reinforcing material,
Flame retardants, plasticizers, other polymers, other nucleating agents and the like can be added within a range that does not impair the effects of the present invention.

The polyester resin composition thus obtained has a high crystallization rate, excellent moldability, and good mechanical properties such as tensile strength and elastic modulus.

The blending method of the nucleating agent used in the present invention is not particularly limited, and it is a method of adding at the time of polymerization, a method of melt-kneading by an extruder, a method of adding at the time of injection molding, a method of dry blending, and a combination of these methods. Different methods are available. Usually, melt kneading with an extruder is preferred.

The polyester resin composition of the present invention can be applied to ordinary molding methods such as extrusion molding, injection molding, blow molding and vacuum molding, and molded articles such as automobile parts, electric / electronic parts, films and sheets. Can be

[0080]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples.

Example 1 After drying under reduced pressure at 110 ° C. for 7 hours, the intrinsic viscosity was 0.80 dl.
/ G (o-chlorophenol solution, 25 ° C) 100 parts by weight of polyethylene terephthalate to BTC tetra (2-
0.2 parts by weight of (methylcyclohexylamide) (main nucleating agent A) was mixed, mixed with a Henschel mixer, melt-mixed with a 20 mmφ uniaxial extruder set at 290 ° C., and pelletized.

The obtained polyethylene terephthalate composition was dried under reduced pressure at 110 ° C. for 5 hours and press-molded with a press-molding machine kept at 290 ° C. It was rapidly cooled with a water cooling press to obtain a sheet having a thickness of 0.5 mm. The crystallization temperature of the sheet during the temperature rising process and the temperature lowering process was measured with a DSC measuring device at a rate of 20 ° C./min, and the difference between the temperature falling crystallization temperature (Tcc) and the temperature rising crystallization temperature (Tch) ( ΔT = Tcc
−Tch) was calculated and the crystallinity was evaluated (the larger ΔT, the larger the crystallinity).

Next, the intrinsic viscosity (o-
A chlorophenol solution, 25 ° C.) was measured to evaluate the stability of the molecular weight of the polyester during the production of the resin composition. The results obtained are shown in Table 1.

Example 2 Tch and T were obtained in the same manner as in Example 1 except that TDA tetra (2-methylanilide) (main nucleating agent B) was applied as the nucleating agent.
The intrinsic viscosity of cc, ΔT and pellet was measured to evaluate the stability of crystallinity and molecular weight. The results obtained are shown in Table 1.

Example 3 Tch, T were obtained in the same manner as in Example 1 except that SMSD tetracyclohexylamide (the present nucleating agent C) was applied as the nucleating agent.
The intrinsic viscosity of cc, ΔT and pellet was measured to evaluate the stability of crystallinity and molecular weight. The results obtained are shown in Table 1.

Example 4 Tch and Tc were obtained in the same manner as in Example 1 except that BTC tetracyclohexylamide (main nucleating agent D) was applied as the nucleating agent.
The intrinsic viscosity of c, ΔT and pellets was measured to evaluate the stability of crystallinity and molecular weight. The results obtained are shown in Table 1.

Example 5 Tch and Tc were obtained in the same manner as in Example 1 except that TDA tetracyclohexylamide (the present nucleating agent E) was used as the nucleating agent.
The intrinsic viscosity of c, ΔT and pellets was measured to evaluate the stability of crystallinity and molecular weight. The results obtained are shown in Table 1.

Example 6 Tri (2-methylanilide) trimesic acid as a nucleating agent
T is the same as in Example 1 except that (the present nucleating agent F) is applied.
The intrinsic viscosity of ch, Tcc, ΔT and pellets was measured to evaluate the stability of crystallinity and molecular weight. The obtained results are first
Shown in the table.

Example 7 Tch, Tcc, ΔT and the intrinsic viscosity of pellets were measured in the same manner as in Example 1 except that trimesic acid trianilide (the present nucleating agent G) was used as the nucleating agent to determine the crystallinity and the molecular weight. Stability was evaluated. The results obtained are shown in Table 1.

[0090]

[0091]

Comparative Example 1 Tch, Tcc, ΔT and the intrinsic viscosity of pellets were measured in the same manner as in Example 1 except that talc (Comparative Nucleating Agent 1) was used as a nucleating agent, and stability of crystallinity and molecular weight was measured. Was evaluated.
The results obtained are shown in Table 1.

Comparative Example 2 Tch, Tcc, ΔT and the intrinsic viscosity of pellets were measured in the same manner as in Example 1 except that sodium benzoate (Comparative Nucleating Agent 2) was used as the nucleating agent to determine the crystallinity and the molecular weight. Stability was evaluated. The results obtained are shown in Table 1.

Comparative Example 3 In the same manner as in Example 1 except that the amide compound was not added,
The intrinsic viscosity of Tch, Tcc, ΔT and pellets was measured to evaluate the stability of crystallinity and molecular weight. The results obtained are shown in Table 1.

[Table 1]

Example 10 Pellets obtained as in Example 1 were treated at 110 ° C.
After vacuum drying for an hour, using an injection molding machine set at 280 ° C. (mold clamping pressure 40 tons, manufactured by Nissei Plastic Industry Co., Ltd.), injection time 15 seconds, cooling time 20 seconds, mold temperature 140 ° C. AS
A TM1 dumbbell test piece was molded. The releasability from the mold at this time was evaluated in the following three stages. ◯: Good releasability, Δ: Slightly bad releasability, ×: Poor releasability

Further, using the obtained dumbbell test piece, AS
Tensile strength was measured according to TM D-638. The results obtained are shown in Table 2.

Example 11 The mold releasability and tensile strength were measured in the same manner as in Example 10 except that the mold temperature was 110 ° C. Second result obtained
Shown in the table.

Example 12 The mold releasability and tensile strength were measured in the same manner as in Example 10 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

Example 13 "Nucleating agent B" was used as the nucleating agent, and the mold temperature was 110.
The mold releasability and tensile strength were measured in the same manner as in Example 10 except that the temperature was selected. The results obtained are shown in Table 2.

Example 14 The mold releasability and tensile strength were measured in the same manner as in Example 13 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

Example 15 "Nucleating agent C" was used as the nucleating agent, and the mold temperature was 110.
The mold releasability and tensile strength were measured in the same manner as in Example 10 except that the temperature was selected. The results obtained are shown in Table 2.

Example 16 The mold releasability and tensile strength were measured in the same manner as in Example 15 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

Comparative Example 4 "Comparative Nucleating Agent 1" was used as the nucleating agent, and the mold temperature was 11
Releasability and tensile strength were measured in the same manner as in Example 10 except that 0 ° C was selected. The results obtained are shown in Table 2.

Comparative Example 5 The mold releasability and tensile strength were measured in the same manner as in Comparative Example 4 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

Comparative Example 6 "Comparative Nucleating Agent 2" was used as the nucleating agent and the mold temperature was 11
Releasability and tensile strength were measured in the same manner as in Example 10 except that 0 ° C was selected. The results obtained are shown in Table 2.

Comparative Example 7 The mold releasability and tensile strength were measured in the same manner as in Comparative Example 6 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

Comparative Example 8 Releasability and tensile strength were measured in the same manner as in Example 10 except that the amide compound was not added. The results obtained are shown in Table 2.

Comparative Example 9 The mold releasability and tensile strength were measured in the same manner as in Comparative Example 8 except that the mold temperature was 80 ° C. The results obtained are shown in Table 2.

[Table 2]

[0109]

EFFECTS OF THE INVENTION The polyester resin composition of the present invention has a high crystallization rate and excellent moldability in a low temperature mold, so that the molding cycle can be shortened and the productivity by injection molding or the like is greatly improved. To do. Further, the obtained molded product has excellent mechanical properties and is useful as an electric / electronic component, an automobile component or other industrial component.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuyuki Kawahara 13 Yasumachi Yakura-cho, Fushimi-ku, Kyoto City, Kyoto Prefecture Shin-Nippon Rika Co., Ltd. Incorporated (72) Inventor Hiroshi Kitagawa 13 Yakura-cho, Yashima-cho, Fushimi-ku, Kyoto-shi, Shin-Nippon Rika Co., Ltd. (56) Reference JP-A-5-1218 (JP, A) JP-A-4-370124 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (3)

(57) [Claims] 1. A polyester resin, and a general formula (1)
In represented by a polycarboxylic acid-based amide compound and the general formula
A polyester resin composition containing one or more amide compounds selected from the group consisting of polyamino acid amide compounds represented by (2) . Embedded image R ¹ — (CONH—R ² ) k (1) [wherein, R ¹ is a saturated or unsaturated aliphatic, alicyclic or aromatic polycarboxylic acid residue having 1 to 25 carbon atoms. Represents
R ² is an alkyl group or alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, [Chemical 3] [Chemical 4] [Chemical 5] Represents a group represented by. R ³ , R ⁵ , R ⁶ and R ⁸ are the same or different and each represent an alkyl group, an alkenyl group or an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or a halogen atom. R
⁴ and R ⁷ are the same or different and each represents a linear or branched alkylene group having 1 to 4 carbon atoms. k represents an integer of 3 to 6. l and n each represent an integer of 1 to 5. m and o each represent an integer of 0 to 5. However, when k = 3, R ¹ is fat
Group polycarboxylic acid residue, R ² is an alkyl group,
Kenyl group, phenyl group, naphthyl group, anthryl group, Or [Chemical 5] And R ¹ is an aromatic polycarboxylic acid residue
And R ² is an alkyl group or an alkenyl group
except for. Embedded image (R ¹⁰ —NHCO) q—R ⁹ — (NHCO—R ¹¹ ) r (2) [wherein, R ⁹ is a saturated or unsaturated fatty acid having 1 to 25 carbon atoms]
It represents an aliphatic, alicyclic or aromatic polyamino acid residue. R
^{10, R 11} is a same meaning as ^{R 2} in each formula (1)
And may be the same or different. q and r are 1 to 5
Indicates a number. However, 6 ≧ q + r ≧ 3. ] 2. The polyester resin composition according to claim 1, wherein the amide compound is one or more amide compounds having at least one alicyclic group which are the same or different. 3. The amide compound is represented by the general formula (1).
The polycarboxylic acid amide compound according to claim 1.
Polyester resin composition.