JP3477787B2 - Polyamide resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin composition having excellent crystallinity.

[0002]

2. Description of the Related Art Polyamide resins are widely used as materials for automobile parts, electronic / electrical equipment parts and various industrial products because they have excellent heat resistance, mechanical properties, chemical resistance, wear resistance and the like. .

However, although this core resin has excellent physical properties, its moldability (particularly molding cycle) is poor, and in recent years,
From the viewpoint of productivity and economical efficiency, attempts have been made to improve moldability without impairing basic physical properties.

As one of them, there is a method of improving the crystallization temperature and the crystallization rate by adding a nucleating agent. Examples of such a nucleating agent include inorganic substances such as talc, clay, mica and kaolin, organic metal salts such as sodium phenylphosphonate, magnesium acetate and metal salts of diaryl phosphate, organic substances such as polyethylene glycol derivatives and the like. .

However, these compounds have problems such as insufficient improvement effect and deterioration of physical properties inherent to the resin. In particular, the inorganic or metal salt type nucleating agent has a drawback that the inorganic substance or metal salt remains in the molded product and cracks easily occur. Further, an organic nucleating agent does not provide a sufficient nucleating agent effect, and there is room for improvement.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems of the nucleating agent and propose a novel and useful polyamide resin composition having improved crystallinity.

[0007]

In view of the present situation, the present inventors have conducted diligent studies to solve the above problems, and as a result, blend an amide compound having a specific structure with a polyamide resin. As a result, they have found that the desired effects can be obtained, and have completed the present invention based on such findings.

Namely, the polyamide resin composition according to the present invention, polyamide resins, polycarboxylic acid-based amide compound represented by the sequence in formula (1), polyamine amide represented by the general formula (2) One or two or more amide compounds selected from the group consisting of compounds and polyamino acid amide compounds represented by the general formula (3) [ however,
Except those described in (A) to (E) . (A) In the general formula (1), a = 2, and R1
Is a saturated or unsaturated aliphatic polycarboxylic acid residue or aromatic polycarboxylic acid residue. (B) In the general formula (1), a = 2 and R1 is saturated.
Or an unsaturated alicyclic polycarboxylic acid residue,
And R 2 is an alkyl group or an alkenyl group
of. (C) In the general formula (2), f = 2, and R9
Is a saturated or unsaturated aliphatic polyamine residue or aromatic polyamine residue. (D) In the general formula (2), f = 2, and R9 is saturated.
Alternatively, it is an unsaturated alicyclic polyamine residue and R 10 is an alkyl group or an alkenyl group.
of. (E) In the general formula (3), g + h = 2, and R11
Is a saturated or unsaturated aliphatic amino acid residue or an aromatic amino acid residue, and R 12 and R 13 are the same or
Are different from alkyl groups, alkenyl groups, phenyl groups or Is a group represented by. Characterized in that it contains a.

[0009]

[Chemical 8] [Wherein R ¹ is a residue of a saturated or unsaturated aliphatic polycarboxylic acid having 2 to 30 carbon atoms, a residue of a saturated or unsaturated alicyclic polycarboxylic acid or a residue of an aromatic polycarboxylic acid. 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 9] ,

[Chemical 10] ,

[Chemical 11] Or

[Chemical 12] Represents a group represented by. R ³ , R ⁵ , R ⁶ and R ⁸ are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group,
It represents an alkoxy group, a cycloalkyl group, a phenyl group or a halogen atom. R ⁴ and R ⁷ are the same or different and each represent a linear or branched alkylene group having 1 to 4 carbon atoms.
a shows the integer of 2-6. b and d each represent an integer of 1 to 5. c and e each represent an integer of 0 to 5. ]

[0010]

[Chemical 13] [Wherein R ⁹ is a residue of a saturated or unsaturated aliphatic polyamine having 1 to 25 carbon atoms, a residue of a saturated or unsaturated alicyclic polyamine or a residue of an aromatic polyamine (provided that the number of carbon atoms is 1 ~ 6 except for the linear diamine residue and the xylylenediamine residue). R ¹⁰ has the same meaning as R ² described above. f shows the integer of 2-6. ]

[0011]

[Chemical 14] [In the formula, R ¹¹ represents a saturated or unsaturated aliphatic amino acid residue having 1 to 25 carbon atoms, a saturated or unsaturated alicyclic amino acid residue, or an aromatic amino acid residue. R ¹² , R
¹³ has the same meaning as R ² described above, and may be the same or different. g and h each represent an integer of 1 to 5. However,
6 ≧ g + h ≧ 2. ]

The polycarboxylic acid amide compound represented by the general formula (1) includes an aliphatic, alicyclic or aromatic polycarboxylic acid represented by the 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.

[0013]

[Chemical 15] [In the formula, R ¹⁴ has the same meaning as R ¹ and i has the same meaning as a. ]

[0014]

[Chemical 16] [In the formula, R ¹⁵ has the same meaning as R ² described above. ]

Examples of the aliphatic polycarboxylic acids, citric acid, methanesulfonic tricarboxylic acids, tricarballylic acid, propenoic tricarboxylic acid, pentanoic tricarboxylic acid, ethane tetracarboxylic acid, propanoic tetracarboxylic acid, pentanoic tetracarboxylic acid, butane tetracarboxylic acid ( Especially 1,
2,3,4-butanetetracarboxylic acid, hereinafter "BTC"
Is abbreviated. ), Dodecanetetracarboxylic acid, pentanepentacarboxylic acid, tetradecanehexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylene glycol bis (β-aminoethyl ether) 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, triethylenetetraminehexaacetic acid, nitrilotriapropionic acid, 1,6-hexanediamine Examples include tetraacetic acid and N- (2-carboxyethyl) iminodiacetic acid.

As the alicyclic polycarboxylic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, 5- (succinic acid ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid,
Cyclohexane hexacarboxylic acid, 5, 6, 9, 10
-Tetracarboxytricyclo [6.2.2.0 ^2,7 ]
Dodeca-2,11-diene and its lower alkyl-substituted products (for example, methyl-substituted products at 3-position, 8-position, 11-position or 12-position), 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 abbreviated as "TDA") and its lower alkyl. Substitutes (for example, methyl substitution products at 1-, 5-, 6- or 7-positions), 2,3,4,5,6,7,1
2,13-octahydrophenanthrene-3,4,5,5
Examples include 6-tetracarboxylic acid and the like.

As the aromatic polycarboxylic acid , benzenetricarboxylic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid (hereinafter abbreviated as “DSDA”). ), Phenylmethanetetracarboxylic acid, perylenetetracarboxylic acid, naphthalenetetracarboxylic acid, 4,
4'-dinaphthalic acid, benzidine-3,3'-dicarboxyl-N, N'-tetraacetic acid, diphenylpropane tetracarboxylic acid, anthracene tetracarboxylic acid, phthalocyanine tetracarboxylic acid, ethylene glycol-trimellitic acid diester, benzene hexa Examples thereof include carboxylic acid and glycerin-trimellitic acid triester.

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

Examples of the alicyclic monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclobutylamine, cyclooctylamine, cyclododecylamine, and the like, and are represented by the general formula (4) or the general formula (5). Examples of the compound include

[0020]

[Chemical 17] [In the formula, R ¹⁶ 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. j represents an integer of 1 to 5. ]

[0021]

[Chemical 18] [In the formula, R ¹⁷ represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ¹⁸ has the same meaning as R ¹⁶ described above. k
Represents an integer of 0 to 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-cyclohexylpropylamine , Γ-cyclohexyl Examples include propylamine 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) can be mentioned.

[0029]

[Chemical 19] [In the formula, R ¹⁹ has the same meaning as R ¹⁴ described above. l shows the integer of 1-5. ]

[0030]

[Chemical 20] [In the formula, R ²⁰ has the same meaning as R ¹⁷ described above. R ²¹ has the same meaning as R ¹⁶ described above. m shows the integer of 0-5. ]

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, dimethyl Aniline, diethylaniline, dipropylaniline, diisopropylaniline,
Di-n-butylaniline, di-sec-butylaniline,
Di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert-
Examples include butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, 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 amide compounds represented by the general formula (1) , 1,4-cyclohexanedicarboxylic acid derivative ,
Trimesic acid derivative, tricarballylic acid derivative, 1,
3,5-Pentanetricarboxylic acid derivative, DSDA derivative, TDA derivative, BTC derivative are recommended, and more specifically, compounds such as trimesic acid tricyclohexylamide are most recommended.

The polyamine amide compound represented by the general formula (2) is an aliphatic, alicyclic or aromatic polyamine represented by the following general formula (2a) and one kind represented by the general formula (2b). Alternatively, it can be easily prepared by amidating two or more kinds of aliphatic, alicyclic or aromatic monocarboxylic acid according to a conventionally known method.

[0035]

[Chemical 21] [In the formula, R ²² has the same meaning as R ⁹ and n has the same meaning as f. ]

[0036]

[Chemical formula 22] [In the formula, R ²³ has the same meaning as R ¹⁰ described above. ]

Examples of the aliphatic polyamines include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexamine, N, N'-bis-aminoethyl - hexamethylenediamine, N, N'-bis-aminoethyl - Ethylenediamine, N, N'-bisaminopropyl-ethylenediamine, N, N'-bisaminopropyl-hexamethylenediamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine , 1,6,11- Triaminoundecane, 4-aminomethyl-1,8-diaminooctane, N- (2-aminoethyl) -1,3-propanediamine, N, N'-dinitrosopentamethylenetetramine, 1,2,3-tri Aminopropane, 1, 2,
Examples include 3,4-tetraaminobutane and the like.

As the alicyclic polyamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexyl, 4,4'-
Diamino-3,3'-dimethyldicyclohexyl, 4,
4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane,
1,3-bis (aminomethyl) cyclohexane, 1,4
-Bis (aminomethyl) cyclohexane, isophoronediamine, mensendiamine, melamine, 2,4,6-
Triaminopyrimidine, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane,
Examples include 1,2,4,5-tetraaminocyclohexane and the like.

As the aromatic polyamine , 1,2,
4,5-tetraaminobenzene, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, pararose aniline, 2,4,6-triaminophenol,
Examples include 3,3′-diaminobenzidine, tris (4-aminophenyl) methane and the like.

Examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid,
Caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, 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, pivalic acid and the like.

Examples of the alicyclic monocarboxylic acid include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, methylcyclopentanecarboxylic acid and phenyl. In addition to cyclopentanecarboxylic acid, butylcyclohexenecarboxylic acid and methylcycloheptanecarboxylic acid, compounds represented by general formula (8) or general formula (9) are exemplified.

[0042]

[Chemical formula 23] [In the formula, R ²⁴ has the same meaning as R ¹⁶ described above. o represents an integer of 1 to 5. ]

[0043]

[Chemical formula 24] [In the formula, R ²⁵ has the same meaning as R ¹⁷ described above. R ²⁶ has the same meaning as R ²⁴ described above. p 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 exemplified.

[Chemical 25] [In the formula, R ²⁷ has the same meaning as R ²⁴ described above. q represents an integer of 1 to 5. ]

[0047]

[Chemical formula 26] [In the formula, R ²⁸ has the same meaning as R ²⁵ described above. R ²⁹ has the same meaning as R ²⁴ described above. r shows the integer of 0-5. ]

The aromatic monocarboxylic acid represented by the general formula (10) includes 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.

Among the amide compounds represented by the general formula (2) , 1,4-diaminocyclohexane derivative,
4,4'-diaminodicyclohexylmethane derivative, tris (4-aminophenyl) methane derivative, 3,3'-
Diaminobenzidine derivative, 1,6,11-triaminoundecane derivative, tris (2-aminoethyl) amine derivative, tris (3-aminopropyl) amine derivative,
4-aminomethyl-1,8-diaminooctane derivative,
A melamine derivative or the like is recommended, and more specifically , N,
Compounds such as N'-dibenzoyl-1,4-diaminocyclohexane, N, N'-dibenzoyl-4,4'-diaminodicyclohexylmethane are most recommended.

The polyamino acid amide compound represented by the general formula (3) is an aliphatic amide compound represented by the following general formula (3a),
Alicyclic or aromatic polyamino acid and general formula (3b)
One or more aliphatic, alicyclic or aromatic monoamines represented by and one or more aliphatic, alicyclic or aromatic monoamines represented by the general formula (3c) It can be easily prepared by amidation with a carboxylic acid according to a conventionally known method.

[0052]

[Chemical 27] [In the formula, R ³⁰ has the same meaning as R ¹¹ , s has the same meaning as g, and t has the same meaning as h. However, 6 ≧ s + t ≧ 2. ]

[0053]

[Chemical 28] [In the formula, R ³¹ has the same meaning as the above R ¹² . ]

[0054]

[Chemical 29] [In the formula, R ³² has the same meaning as R ¹³ described above. ]

Examples of the aliphatic polyamino acid include aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid, β-aminobutyric acid, γ-aminobutyric acid, α-amino- α-methylbutyric acid, γ-amino-α-methylenebutyric acid, α-aminoisobutyric acid, β-aminoisobutyric acid, α-amino-n-valeric acid, δ
-Amino-n-valeric acid, β-aminocrotonic acid, α-amino-β-methylvaleric acid, α-aminoisovaleric acid, 2-
Amino-4-pentenoic acid, α-amino-n-caproic acid, 6-aminocaproic acid, α-aminoisocaproic acid, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-aminocaprylic acid, 9 -Aminononanoic acid, 1
1-aminoundecanoic acid, 12-aminododecanoic acid, 2
-Aminoadipic acid, arginine, asparagine, aspartic acid, cystine, glutamic acid, glutamine, ornithine, creatine, S- (carboxymethyl) cystine, aminomalonic acid and the like are exemplified.

As the alicyclic polyamino acid, 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4
-Aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, 1-amino-1,3-cyclohexanedicarboxylic acid and the like are exemplified.

As the aromatic polyamino acid, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-aminocinnamic acid Acid, 2
-Amino-4-phenylbutyric acid, 4-amino-3-phenylbutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-
Amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4- Amino-3-methylbenzoic acid, 2-amino-
3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o- Aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butyric acid, 4-aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid Acid, p-aminocinnamic acid, p-aminohippuric acid, 2-
Amino-1-naphthoic acid, 3-amino-1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-
1-naphthoic acid, 8-amino-1-naphthoic acid, 1-amino-2-naphthoic acid, 3-amino-2-naphthoic acid,
4-amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-
Examples thereof include naphthoic acid, 8-amino-2-naphthoic acid, 3,5-diaminobenzoic acid, 4,4′-diamino-3,3′-dicarboxydiphenylmethane.

The monoamine which is a raw material of the amide compound represented by the general formula (3) is the same as the monoamine which is a raw material of the amide compound represented by the general formula (1). The monocarboxylic acid that is also the raw material is the same as the monocarboxylic acid that is the raw material for the amide compound represented by the general formula (2).

Among the amide compounds represented by the general formula (3), β-aminopropionic acid derivative, 8-aminocaprylic acid derivative, aspartic acid derivative, glutamic acid derivative, p-aminomethylcyclohexanecarboxylic acid derivative, 4 -Aminocyclohexanecarboxylic acid derivative, 3,5-diaminocyclohexanecarboxylic acid derivative, p-aminobenzoic acid derivative, 5-amino-1-naphthoic acid derivative, p-aminophenylacetic acid derivative, 3,5
-Diaminobenzoic acid derivative, 4,4'-diamino-3,
A 3'-dicarboxydiphenylmethane derivative or the like is recommended.

The polyamide resin used in the present invention means a polyamide resin such as a polycondensate of diamine and dicarboxylic acid, a polycondensate of ω-aminocarboxylic acid, a lactam polycondensate, or a copolymerized polyamide resin thereof. Blends and the like, for example, polyamide 6, 66, 610, 1
Homopolymer of 1, 12 etc., nylon 6/66, 6/1
2, 6 / 6T, 66/610, 66/612, 66/6
Copolymers such as T and inter-blends thereof. Furthermore, blends with other polymers (for example, polyester) mainly containing these polyamides are also included.

The compounding amount of the amide compound according to the present invention is
It is not particularly limited as long as a predetermined effect can be obtained and can be appropriately selected, but is usually about 0.001 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight, relative to 100 parts by weight of the polyamide resin. is there. When the amount is less than 0.001 part by weight, it is difficult to obtain a predetermined modifying effect, and even when the amount is more than 10 parts by weight, a remarkable improvement in the modifying effect cannot be expected, which is not only practical but also uneconomical. However, in any case, it is not preferable.

The resin composition according to the present invention may optionally contain other components such as pigments, dyes, heat resistance improvers, antioxidants, weather resistance improvers, lubricants, antistatic agents, stabilizers and fillers. Agents, reinforcing agents, 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 polyamide resin composition thus obtained has excellent moldability and various properties.

The method of blending 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 with 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 polyamide resin composition of the present invention can be applied to usual molding methods such as extrusion molding, injection molding, blow molding, vacuum molding, and molding of automobile parts, electric / electronic parts, films, sheets and the like. It can be an item.

[0066]

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

[Preparation of Resin Composition] Polyamide Resin 10
0.2 parts by weight of a predetermined amide compound is mixed with 0 parts by weight, mixed with a Henschel mixer, and pelletized with a uniaxial extruder of 20 mmφ to prepare sample pellets.

[Measurement of Crystallization Temperature] Sample pellets are molded into a sheet having a thickness of 0.5 mm by a press molding machine. After melting the obtained sheet using a DSC measuring device (trade name "DSC7", manufactured by PERKIN-ELMER), cooling at 20 ° C / min and measuring the peak temperature (crystallization temperature, Tc) of the exothermic curve To do. During the measurement, nylon 6 melted at 250 ° C and nylon 66 melted at 300 ° C.

[Measurement of Crystallization Rate] Sample pellets are molded into a sheet having a thickness of 0.5 mm by a press molding machine. 5 to 10 mg of the obtained sheet is set in the sample holder of the above DSC measuring device, melted for 2 minutes at a temperature 30 ° C higher than the melting point of the resin, and then cooled to a temperature 30 ° C lower than the melting point of the resin at 150 ° C / min. And perform isothermal crystallization. The crystallization rate is evaluated by the time (Tmax) from reaching the crystallization temperature to the peak of the crystallization exothermic curve. In addition, when the melting point of the applied resin was measured by DSC, nylon 6 had a melting point of 22.
The temperature was 0 ° C. and the temperature of nylon 66 was 262 ° C.

Examples 1 to 18 Nylon 6 (manufactured by Unitika Ltd., hereinafter referred to as "resin 1") 100 parts by weight was added with 0.2 parts by weight of a predetermined amide compound to prepare a resin composition, The crystallization temperature and crystallization rate of this product were measured. The results obtained are shown in Table 1.

Comparative Example 1 The crystallization temperature and crystallization rate of Resin 1 itself were measured. The results obtained are shown in Table 1.

[Table 1]

Examples 19 to 33 Nylon 66 (manufactured by Ube Industries, Ltd., hereinafter referred to as "resin 2") 100 parts by weight was added with 0.2 parts by weight of a predetermined amide compound to prepare a resin composition. The crystallization temperature and crystallization rate of this product were measured. The results obtained are shown in Table 2.

Comparative Example 2 The crystallization temperature and crystallization rate of Resin 2 itself were measured. The results obtained are shown in Table 2.

[Table 2]

[0074]

By adding the amide compound according to the present invention, a polyamide resin composition having excellent crystallinity can be easily obtained.

Front page continued (72) Inventor Sadamitsu Kiyo, 13 Yakura-cho, Yashimajima, Fushimi-ku, Kyoto-shi, Kyoto, Japan Shin-Nippon Rika Co., Ltd. (72) Masafumi Yoshimura 13, Yakura-cho, Yashima-cho, Fushimi-ku, Kyoto-shi, Kyoto (72) Inventor Naoki Ikeda, 13 Nikko Ryaku Co., Ltd., Yashima-cho, Fushimi-ku, Kyoto City, Kyoto Prefecture (56) References JP 57-119951 (JP, A) JP 53-137253 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 77/00-77/12

Claims (3)

(57) [Claims] 1. A polyamide resin and a general formula
One selected from the group consisting of a polycarboxylic acid amide compound represented by (1), a polyamine amide compound represented by general formula (2), and a polyamino acid amide compound represented by general formula (3) Alternatively, two or more kinds of amide compounds [provided that the following (A) to (E) are excluded. (A) In the general formula (1), a = 2, and R1
Is a saturated or unsaturated aliphatic polycarboxylic acid residue or aromatic polycarboxylic acid residue. (B) In the general formula (1), a = 2 and R1 is saturated.
Or an unsaturated alicyclic polycarboxylic acid residue,
And R 2 is an alkyl group or an alkenyl group
of. (C) In the general formula (2), f = 2, and R9
Is a saturated or unsaturated aliphatic polyamine residue or aromatic polyamine residue. (D) In the general formula (2), f = 2, and R9 is saturated.
Alternatively, it is an unsaturated alicyclic polyamine residue and R 10 is an alkyl group or an alkenyl group.
of. (E) In the general formula (3), g + h = 2, and R11
Is a saturated or unsaturated aliphatic amino acid residue or an aromatic amino acid residue, and R 12 and R 13 are the same or
Is different, an alkyl group, an alkenyl group, a phenyl group or ## STR1 ## Is a group represented by. ] The polyamide-type resin composition characterized by containing these. R ^1- (CONH-R ² ) a (1) [In the formula, R ¹ is a residue of a saturated or unsaturated aliphatic polycarboxylic acid having 2 to 30 carbon atoms, or a saturated or unsaturated alicyclic polycarboxylic acid. Represents an acid residue or an aromatic polycarboxylic acid residue. 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] Or [Chemical 5] Represents a group represented by. ^{R 3, R 5, R 6} , R 8 are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkoxy group, a cycloalkyl group, a phenyl group or a halogen atom. R ⁴ and R ⁷ are the same or different,
It represents a linear or branched alkylene group having 1 to 4 carbon atoms. a shows the integer of 2-6. b and d each represent an integer of 1 to 5. c and e each represent an integer of 0 to 5. ] R < ⁹ >-(NHCO-R < ¹⁰ >) f (2) [In formula, R < ⁹ > is the residue of a C1-C25 saturated or unsaturated aliphatic polyamine, the residue of a saturated or unsaturated alicyclic polyamine. A group or a residue of an aromatic polyamine (however,
Excludes linear diamine residues having 1 to 6 carbon atoms and xylylenediamine residues. ) Represents. R ¹⁰ has the same meaning as R ² and f represents an integer of 2 to 6. ^{] (R 12 -NHCO) g-} R 11 - (NHCO-
R ¹³ ) h [In the formula, R ¹¹ represents a residue of a saturated or unsaturated aliphatic amino acid having 1 to 25 carbon atoms, a residue of a saturated or unsaturated alicyclic amino acid, or a residue of an aromatic amino acid. .
R ¹² and R ¹³ have the same meaning as R ² described above, and may be the same or different. g and h each represent an integer of 1 to 5. However, 6 ≧ g + h ≧ 2. ] 2. The amide compound is trimesic acid trimesic acid.
Chlorohexylamide, N, N'- dibenzoyl-1,4
The polyamide resin composition according to claim 1, which is one or more amide compounds selected from the group consisting of -diaminocyclohexane and N, N'-dibenzoyl-4,4-diaminodicyclohexylmethane. 3. A amide according to claim 1, which is a polyamide resin.
A method for improving the crystallinity of a polyamide resin composition by containing a compound .