JP3401818B2 - Polyethylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyethylene resin composition having improved crystallinity.

[0002]

2. Description of the Related Art Polyethylene is excellent in electrical properties, mechanical properties, workability, etc., and is inexpensive, so it is widely used as a material for injection molding, blow molding, film, sheet, pipe, wire coating, compression molding and the like. Applied to various fields.

In recent years, higher performance and special performance have been demanded for the resin due to the expansion of its use and demand. Specific examples of such performance include strength, transparency, and high-speed processability.

Various attempts have been made to improve the crystallinity as a method for improving the above performance. For example,
A method of adding a resin modifier such as a metal salt of a carboxylic acid, a metal salt of an aromatic carboxylic acid, a metal salt of an aromatic phosphoric acid, an amine salt or a metal salt of an aliphatic dicarboxylic acid, or a sorbitol derivative is known. .

However, these compounds have an insufficient modifying effect, or the resin modifier itself has a low heat resistance.
Furthermore, it has problems such as promoting deterioration of the resin,
There is room for improvement.

[0006]

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

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, by adding an amide compound having a specific structure to polyethylene. It was found that the desired effect was obtained, and the present invention was completed based on such findings.

That is, the polyethylene resin composition according to the present invention comprises a polyethylene resin, a polycarboxylic acid amide compound represented by the general formula (1), and a polyamine amide compound represented by the general formula (2). And one or more amide compounds selected from the group consisting of polyamino acid amide compounds represented by the general formula (3).

[0009]

Embedded image R ¹ — (CONHR ² ) m (1) [In the formula, R ¹ represents a saturated or unsaturated aliphatic, alicyclic or aromatic carboxylic acid residue having 1 to 24 carbon atoms. R ² is
A linear or branched alkyl group having 4 to 18 carbon atoms ,
A cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group,

[Chemical 18]

[Chemical 19]

[Chemical 20] Or

[Chemical 21] Represents a group represented by. m shows the integer of 2-6. R ³ ,
R ⁵ and R ⁸ are the same or different and each represent an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a phenyl group, an alkoxyl group, an ester group, a halogen atom or a nitro group. R
⁶ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group,
Phenyl group, alkoxyl group, ester group or nitro group
Represents R ⁴ and R ⁷ represent a linear or branched alkylene group having 1 to 4 carbon atoms. n and p each represent an integer of 1 to 5. o and q each represent an integer of 0 to 5. ]

[0010]

Embedded image ^R 9 - a ^(NHCOR 10) r (2) [wherein, ^{R 9} is an alicyclic or aromatic amine residue of 1 to 28 carbon atoms (excluding alkoxy Rirenjiamin residues)
Represent r represents an integer of 2 to 6. R ¹⁰ has 1 to 1 carbon atoms
8 straight-chain or branched-chain alkyl group, having 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, naphthyl group, an
Trill group,

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25] Or

[Chemical formula 26] Represents a group represented by. m shows the integer of 2-6.
R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ are the same or different,
Alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups,
Nyl group, alkoxyl group, ester group, halogen atom or
Represents a nitro group. R ¹² and R ¹⁵ are direct groups having 1 to 4 carbon atoms.
It represents a chain or branched alkylene group. s and u are husbands
Each represents an integer of 1 to 5. t and v each represent an integer of 0 to 5
You ]

[0011]

Embedded image ^{(R 18 CONH) w-R} 17 - (CONHR 19) x (3) [ wherein, ^{R 17} is an aliphatic saturated or unsaturated 1 to 15 carbon atoms, alicyclic or aromatic Represents an amino acid residue. w, x
Each represents an integer of 1 to 5 (where w + x is 2 or more,
It is 6 or less. ). R ¹⁸ and R ¹⁹ are each of the general formula (2)
R ¹⁰ has the same meaning as R ¹⁰ and may be the same or different. ]

[0012] Further, the present invention is represented by the above general formula (1).
A polycarboxylic acid amide compound represented by the general formula (2)
A polyamine amide compound represented by the formula (3)
Selected from the group consisting of polyamino acid amide compounds
One or more amide compounds
To improve the crystallinity of the polyethylene resin composition.
It provides a way to do this.

The amide compound represented by the general formula (1) has the general formula (1a)

Embedded image R ¹ — (COOH) m (1a) [In the formula, R ¹ and m have the same meanings as described above. ] The aliphatic, alicyclic or aromatic polycarboxylic acid represented by or its anhydride, and general formula (1b)

Embedded image R ² —NH ₂ (1b) [wherein, R ² has the same meaning as described above. ] One or two or more kinds of aliphatic, alicyclic or aromatic monoamines represented by the above formula can be easily prepared by amidation according to a conventionally known method.

As the aliphatic polycarboxylic acid, malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, 1,12-dodecanedioic acid,
1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, citric acid, methanetricarboxylic acid, tricarballylic acid, propenetricarboxylic acid, pentanetricarboxylic acid, ethanetetracarboxylic acid, propanetetracarboxylic acid, pentanetetracarboxylic acid, Butanetetracarboxylic acid (particularly 1,2,3,4-butanetetracarboxylic acid, abbreviated as "BTC" hereinafter), dodecanetetracarboxylic acid, pentanepentacarboxylic acid, tetradecanehexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotria Acetic acid,
Ethylene glycol bis (β-aminoethyl ether)
N, N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamine-N,
N ', N'-triacetic acid, 1,3-diaminopropane-2-
All-N, N, N ', N'-tetraacetic acid, 1,2-diaminopropane-N, N, N', N'-tetraacetic acid, triethylenetetramine hexaacetic acid, nitrilotriapropionic acid, 1,6
Examples include -hexanediaminetetraacetic acid and N- (2-carboxyethyl) iminodiacetic acid.

The alicyclic polycarboxylic acid includes 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, Cyclohexane tetracarboxylic 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 lower alkyl substitution products thereof (for example, 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 their lower alkyl substitutions (eg 1
Position, 5, 6, or 7 methyl substitution), 2, 3,
Examples include 4,5,6,7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid.

As the aromatic polycarboxylic acid, p-phenylene diacetic acid, p-phenylene diethanoic acid, phthalic acid,
4-tert-butylphthalic acid, isophthalic acid, 5-tert-
Butyl isophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Diphenic acid, 3,3′-biphenyldicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-
Bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3′-sulfonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 3,3′-oxydibenzoic acid , 4,4'-oxydibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4 '
-Carbonyldibenzoic acid, 3,3'-thiodibenzoic acid,
4,4'-thiodibenzoic acid, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'-terephthaloyldibenzoic acid, dithiosalicylic acid, benzenetricarboxylic acid, Benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylmethanetetracarboxylic 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, benzenehexacarboxylic acid, glycerin-
Examples thereof include trimellitic acid triester.

As the aliphatic monoamine, n-butyl acetate is used.
Min, isobutylamine, secondary butylamine, tertiary butylamine, n-amylamine, tertiary amylamine, hexylamine, heptylamine, n-octylamine, 2
-Ethylhexylamine, tertiary octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, pentadecylamine, octadecylamine and the like are exemplified.

Examples of the alicyclic monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, aminodecalin, etc., and the general formula (4) or the general formula ( The compound represented by 5) is mentioned.

[0019]

[Chemical 29] [In the formula, R ³ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a phenyl group, an alkoxyl group, an ester group,
Represents a halogen atom or a nitro group. n shows the integer of 1-5. ]

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-amylcyclohexylamine, di-
tert-amylcyclohexylamine, dihexylcyclohexylamine, trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, triisopropylcyclohexylamine, tri-n-butylcyclohexylamine, tri-se
c-Butylcyclohexylamine, tri-tert-butylcyclohexylamine, methoxycyclohexylamine, ethoxycyclohexylamine, butoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxycyclohexylamine, di-sec-butoxycyclohexylamine. , Di-tert-butoxycyclohexylamine, trimethoxycyclohexylamine, tri-n-butoxycyclohexylamine, chlorocyclohexylamine, dichlorocyclohexylamine, methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine, tribromocyclohexylamine Amine, nitrocyclohexylamine, dinitrosic Hexylamine, methoxycarbonyl cyclohexylamine, ethoxycarbonyl cyclohexylamine, butoxycarbonyl cyclohexylamine and the like.

[0021]

[Chemical 30] [In the formula, R ⁴ represents a linear or branched alkylene group having 1 to ⁴ carbon atoms. R ⁵ has the same meaning as R ³ in formula (4). o represents an integer of 0 to 5. ]

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, 2-aminoanthracene and 9-aminoanthracene, compounds represented by the general formula (6) or the general formula (7) can be mentioned.

[Chemical 31] [In the formula, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, cycloalkyl
Alkyl group, phenyl group, alkoxyl group, ester group or
Represents a nitro group. p shows the integer of 1-5. ]

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, dimethylaniline, diethyl Aniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline,
Tripropylaniline, tri-tert-butylaniline,
Anisidine, ethoxyaniline, butoxyaniline , dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, nitroaniline
And dinitroaniline, aminobenzoic acid methyl ester, aminobenzoic acid ethyl ester, aminobenzoic acid propyl ester, aminobenzoic acid isopropyl ester, aminobenzoic acid butyl ester, aminobenzoic acid isobutyl ester and the like.

[0025]

[Chemical 32] [In formula, R < ⁷ > is synonymous with R < ⁴ > in General formula (5). R ⁸ has the same meaning as R ³ in formula (4). q
Represents an integer of 0 to 5. ]

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

[0027] Among the general formula (1) amide compounds represented by, as more effective compounds, adipic acid dicyclohexyl amide, adipic acid bis (2,6-dimethyl anilide), adipic acid bis (1-naphthylamide ),
Suberic acid bis (2,4,6-trimethylanilide),
4,4′-diphenyl ether dicarboxylic acid bis (n-
Octylamide), BTC tetracyclopentylamide, BTC tetracyclohexylamide, BTC tetra (2-methylcyclohexylamide), SMSD tetracyclohexylamide, TDA tetracyclohexylamide, TDA tetra (2-methylcyclohexylamide) and the like.

The polyamine amide compound represented by the general formula (2) has the following general formula (2a)

Embedded image R ⁹ — (NH ₂ ) r (2a) [In the formula, R ⁹ and r have the same meanings as described above. ] An alicyclic or aromatic polyamine represented by the general formula (2b)

Embedded image R ¹⁰ —COOH (2b) [wherein, R ¹⁰ has the same meaning as described above. ] One or two or more kinds of aliphatic, alicyclic or aromatic monocarboxylic acids represented by the above formula can be easily prepared by amidation according to a conventionally known method.

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.

The aromatic polyamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene and 3,4-diamino. Toluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine,
4,5-Dimethyl-o-phenylenediamine, 2,4-
Diaminomesitylene, 2,3-diaminopyridine, 2,
6-diaminopyridine, 3,4-diaminopyridine,
1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,7-diaminonaphthalene, 9,10-diaminophenanthrene, 3,
3 ', 5,5'-tetramethylbenzidine, 3,3'-
Dimethyl-4,4'-diaminobiphenyl, 3,3'-
Dimethoxy-4,4'-diaminobiphenyl, 4,4 '
-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylenedi-2,6-diethylaniline, 4,4'-diamino-
1,2-diphenylethane, 4,4'-diamino-2,
2'-dimethylbibenzyl, 4,4'-diaminostilbene, 3,4'-diamino-2,2-diphenylpropane, 4,4'-diamino-2,2-diphenylpropane, 4,4'-diaminodiphenyl ether , 3,4 '
-Diaminodiphenyl ether, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,
3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, o
-Tolidine sulfone, 2,7-diaminofluorene,
3,7-diamino-2-methoxyfluorene, bis-p
-Aminophenylaniline, 1,3-bis (4-aminophenylpropyl) benzene, 1,4-bis (4-aminophenylpropyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone , 9,9-bis (4-aminophenyl) fluorene, 1,2,4,5-tetraaminobenzene, 1,3,5-triaminobenzene, 1,
2,4-triaminobenzene, pararose aniline,
2,4,6-triaminophenol, 3,3'-diaminobenzidine, tris (4-aminophenyl) methane and the like are exemplified. However, xylylenediamine is excluded because it does not provide the desired effect.

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, and the like nonadecanoic acid.

Examples of the alicyclic monocarboxylic acid include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, methylcyclopentanecarboxylic acid, phenylcyclopentanecarboxylic acid and methylcycloheptane. In addition to the carboxylic acid, compounds represented by the general formula (8) or the general formula (9) may be mentioned.

[0033]

[Chemical 35] [In the formula, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a phenyl group, an alkoxyl group, an ester group, a halogen atom or a nitro group. s shows the integer of 1-5. ]

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, nitrocyclohexanecarboxylic acid, dimethoxycyclohexanecarboxylic acid, diethoxycyclohexanecarboxylic acid, dichlorocyclohexanecarboxylic acid, dibromocyclohexanecarboxylic acid, dinitrocyclohexanecarboxylic acid, trimethylcyclohexane Examples thereof include carboxylic acid, trimethoxycyclohexanecarboxylic acid, triethoxycyclohexanecarboxylic acid and tribromocyclohexanecarboxylic acid.

[0035]

[Chemical 36] [In the formula, R ¹² represents a linear or branched alkylene group having 1 to 4 carbon atoms. R R ¹³ in the general formula (8)
Synonymous with ¹¹ . t shows the integer of 0-5. ]

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

As the aromatic monocarboxylic acid, in addition to benzoic acid, 1-naphthoic acid, 2-naphthoic acid, 9-carboxyanthracene, the general formula (10) or the general formula (1)
The compound represented by 1) is mentioned.

[0038]

[Chemical 37] [In formula, R < ¹⁴ > is synonymous with R < ¹¹ > in General formula (8). u shows the integer of 1-5. ]

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, nitrobenzoic acid, dimethylbenzoic acid, di-tert-
Examples thereof include butylbenzoic acid, dimethoxybenzoic acid, diethoxybenzoic acid, dichlorobenzoic acid, dibromobenzoic acid, dinitrobenzoic acid, trimethylbenzoic acid, trimethoxybenzoic acid, triethoxybenzoic acid, tribromobenzoic acid and the like.

[0040]

[Chemical 38] [In formula, R < ¹⁵ > is synonymous with R < ¹² > in General formula (9). R ¹⁶ has the same meaning as R ¹¹ in formula (8). v shows the integer of 0-5. ]

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), more effective compounds include N, N'-bis (n-heptanoyl) -1,4-diaminocyclohexane and N, N'-bis. (4-methylbenzoyl) -1,4
-Diaminocyclohexane, N, N'-dicyclohexylcarbonyl-p-phenylenediamine, N, N'-dibenzoyl-4,4'-diaminodiphenylmethane and the like are exemplified.

The polyamino acid amide compound represented by the general formula (3) has the following general formula (3a)

Embedded image (H ₂ N) w−R ¹⁷ — (COOH) x (3a) [wherein, R ¹⁷ , w , x and w + x have the same meanings as described above. ] The aliphatic, alicyclic or aromatic polyamino acid represented by the general formula (3b)

Embedded image R ¹⁸ —COOH (3b) [wherein, R ¹⁸ has the same meaning as described above. ] One or more kinds of aliphatic, alicyclic or aromatic monoca represented by
Rubonic acid and general formula (3c)

Embedded image R ¹⁹ —NH ₂ (3c) [wherein, R ¹⁹ has the same meaning as described above. ] One or more kinds of aliphatic, alicyclic or aromatic monoa represented by
It can be readily prepared by amidating according to conventional methods and Min.

Examples of the aliphatic polyaminocarboxylic acid include aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid and 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,
11-aminoundecanoic acid, 12-aminododecanoic acid,
2-aminoadipic acid, arginine, asparagine, aspartic acid, cystine, glutamic acid, glutamine,
Examples include ornithine, creatine, S- (carboxymethyl) cystine, aminomalonic acid and the like.

As the alicyclic polyaminocarboxylic acid, 1
-Aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-
Examples thereof include norbornanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, 1-amino-1,3-cyclohexanedicarboxylic acid and the like.

Examples of the aromatic polyaminocarboxylic acid include α
-Aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3
-Amino-3-phenylpropionic acid, α-aminocinnamic acid, 2-amino-4-phenylbutyric acid, 4-amino-3-
Phenyl butyric 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, 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-naphthoic acid, 8-amino-2-naphthoic acid,
3,5-diaminobenzoic acid, 4,4'-diamino-3,
3'-dicarboxy diphenyl methane etc. are illustrated.

[0047] As the monoamine as a raw material of the amide compounds represented by the general formula (3), examples of the monoamine as a raw material of the amide compounds represented by the general formula (1)
Selected compounds, chloroaniline, dichloroaniline
, Trichloroaniline, bromoaniline, dibromoaniline
Niline and tribromoaniline are further exemplified. Also,
Monocarboxylic acid which is a raw material of the amide compound represented by the general formula (3) is the same as monocarboxylic acid which is a raw material of the amide compound represented by the general formula (2).

Among the amide compounds represented by the general formula (3), N-benzoylglutamic acid dianilide, 3,5-bis (N-cyclohexylcarbonylamino) benzoic acid cyclohexylamide and the like are exemplified as more effective compounds. To be done.

The polyethylene resin used in the present invention is a polymer having ethylene as a constituent component, and is an ethylene homopolymer, ethylene and other α-olefins,
Examples thereof include butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and the like, and copolymers with vinyl acetate and the like.

Density and melt flow rate of polyethylene component (hereinafter abbreviated as "MFR". JIS K 721)
0-1976) is appropriately selected depending on the molding method to be applied and the application, and usually has a density of 0.91 to 0.97 g / c.
m ^{3 is} about 0.91 to 0.94 g / cm ³ , and MFR is about 0.1 to 200 g / 10 minutes, preferably about 0.5 to 100 g / 10 minutes.

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 5 parts by weight, more preferably about 0.01 to 2 parts by weight, relative to 100 parts by weight of the polyethylene resin. is there. 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 5 parts by weight, a modifying effect commensurate with the blending amount cannot be expected, which is not practical. However, it is uneconomical and is not preferable in any case.

In the resin composition according to the present invention, if necessary, an antioxidant (phenolic compound, phosphite compound, etc.), an ultraviolet absorber (benzophenone compound, benzotriazole compound, etc.), heat Stabilizers, light stabilizers (hindered amine compounds, etc.), antistatic agents, antiblocking agents, flame retardants, lubricants, organic / inorganic pigments, fillers (talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, carbonic acid Calcium, glass fibers, etc.), foaming agents, elastomers, processing aids, nucleating agents, etc. can be added within a range that does not impair the effects of the present invention.

The polyethylene composition thus obtained is
Excellent formability, toughness, and excellent transparency.

The polyethylene composition of the present invention is prepared by mixing the predetermined components using a conventionally known mixing device (Henschel mixer, ribbon blender, Banbury mixer, etc.) and then melt-kneading with a uniaxial or biaxial extruder. The obtained resin composition is used for various containers, tableware, kitchen appliances, toys, sundries, containers, industrial parts, injection molded products such as automobile parts, food products, cosmetics, containers for chemicals, etc. Suitable for hollow molded products such as kerosene cans, insulating materials such as films, laminates, sheets, wire coatings, etc., resin materials such as pipes, drawn tapes, monofilaments, etc., and injection molding and extrusion molding depending on the intended products. , Blow molding,
It is molded by various methods such as compression molding.

[0055]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The crystallization temperature in the examples was measured according to the following method.

Preparation of resin composition : predetermined polyethylene 1
A predetermined amount of amide compound is mixed with 00 parts by weight, mixed with a Henschel mixer, and pelletized with a 20 mmφ uniaxial extruder.

Measurement of crystallization temperature : The pellets obtained above are molded into a sheet having a thickness of 0.5 mm by a press molding machine, and the crystallization temperature of the sheet is measured according to JIS K 7121.

Examples 1 to 38 low-pressure method low-density polyethylene (density = 0.926 g / cm
³ , MFR = 20 g / 10 minutes, hereinafter referred to as "resin 1". ) The crystallization temperature of a resin composition prepared by adding 0.2 part by weight of a predetermined amide compound to 100 parts by weight was measured. The results obtained are shown in Table 1.

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

[Table 1]

[Table 2]

Examples 39-44 High Pressure Method Low Density Polyethylene (Density = 0.918 g / cm
³ , MFR = 22 g / 10 minutes, hereinafter referred to as "resin 2". ) 100 parts by weight of the amide compounds shown in Table 2 below.
The crystallization temperature of the resin composition prepared by adding 2 parts by weight was measured. The results obtained are shown in Table 2.

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

[Table 3]

Examples 45-50 High Density Polyethylene (Density = 0.967 g / cm ³ , M
FR = 6.7 g / 10 minutes, hereinafter referred to as “resin 3”. ) 1
The crystallization temperature of the resin composition prepared by adding 0.2 parts by weight of the amide compound shown in Table 3 to 00 parts by weight was measured. The results obtained are shown in Table 3.

Comparative Example 3 The crystallization temperature of the resin 3 itself was measured. The results obtained are shown in Table 3.

[Table 4]

[0064]

By adding the amide compound according to the present invention, it is possible to obtain a polyethylene resin composition having significantly improved crystallinity.

Front page continuation (72) Inventor Sadamitsu Kiyo, 13 Yakura-cho, Yasushima-ku, Fushimi-ku, Kyoto-shi, Kyoto, Japan Shin-Nippon Rika Co., Ltd. (72) Masafumi Yoshimura, 13 Yakura-cho, Yajima-jima, Fushimi-ku, Kyoto-shi, Kyoto (72) Inventor, Hiroshi Kitagawa, 13 Japan, Yakura-cho, Fukumi-ku, Kyoto City, Shin-Nippon Rika Co., Ltd. (56) References JP-A-50-12134 (JP, A) JP-A-50-77441 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08

Claims (3)

(57) [Claims] 1. A polyethylene resin, a polycarboxylic acid amide compound represented by the general formula (1), a polyamine amide compound represented by the general formula (2), and a polyamine represented by the general formula (3). A polyethylene resin composition containing one or more amide compounds selected from the group consisting of amino acid amide compounds. Embedded image R ¹ — (CONHR ² ) m (1) [In the formula, R ¹ represents a saturated or unsaturated aliphatic, alicyclic or aromatic carboxylic acid residue having 1 to 24 carbon atoms. R ² is
A linear or branched alkyl group having 4 to 18 carbon atoms ,
Cycloalkyl group having 3 to 12 carbon atoms, phenyl group, naphthyl group, anthryl group, and [Chemical 3] [Chemical 4] Or [Chemical 5] Represents a group represented by. m shows the integer of 2-6. R ³ ,
R ⁵ and R ⁸ are the same or different and each represent an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a phenyl group, an alkoxyl group, an ester group, a halogen atom or a nitro group. R
⁶ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group,
Phenyl group, alkoxyl group, ester group or nitro group
Represents R ⁴ and R ⁷ represent a linear or branched alkylene group having 1 to 4 carbon atoms. n and p each represent an integer of 1 to 5. o and q each represent an integer of 0 to 5. ] Embedded image ^R 9 - a ^(NHCOR 10) r (2) [wherein, ^{R 9} is an alicyclic or aromatic amine residue of 1 to 28 carbon atoms (excluding alkoxy Rirenjiamin residues)
Represent r represents an integer of 2 to 6. R ¹⁰ has 1 to 1 carbon atoms
8 straight-chain or branched-chain alkyl group, having 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, naphthyl group, an
Tolyl group, ## STR00008 ## [Chemical 9] [Chemical 10] Or [Chemical 11] Represents a group represented by. m shows the integer of 2-6.
R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ are the same or different,
Alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups,
Nyl group, alkoxyl group, ester group, halogen atom or
Represents a nitro group. R ¹² and R ¹⁵ are direct groups having 1 to 4 carbon atoms.
It represents a chain or branched alkylene group. s and u are husbands
Each represents an integer of 1 to 5. t and v each represent an integer of 0 to 5
You ] Embedded image ^{(R 18 CONH) w-R} 17 - (CONHR 19) x (3) [ wherein, ^{R 17} is an aliphatic saturated or unsaturated 1 to 15 carbon atoms, alicyclic or aromatic Represents the amino acid residue of w , x
Each represents an integer of 1 to 5 (where w + x is 2 or more,
It is 6 or less. ). R ¹⁸ and R ¹⁹ are each of the general formula (2)
R ¹⁰ has the same meaning as R ¹⁰ and may be the same or different. ] 2. R ² in the general formula (1) has 3 to 3 carbon atoms.
12 cycloalkyl groups, phenyl groups, naphthyl groups,
Ntoriru group, [of 13] [Chemical 14] [Chemical 15] Or [Chemical 16] The polyethylene-based polymer according to claim 1, which is a group represented by
Resin composition. 3. Represented by the general formula (1) according to claim 1.
Polycarboxylic acid amide compound, represented by the general formula (2)
Represented by the general formula (3)
Selected from the group consisting of polyamino acid amide compounds
To contain one or more amide compounds
And improves the crystallinity of the polyethylene resin composition.
How to make.